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HK1230584A1 - Novel pyrazolyl-heteroarylamides as pesticides - Google Patents

Novel pyrazolyl-heteroarylamides as pesticides Download PDF

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Publication number
HK1230584A1
HK1230584A1 HK17104037.8A HK17104037A HK1230584A1 HK 1230584 A1 HK1230584 A1 HK 1230584A1 HK 17104037 A HK17104037 A HK 17104037A HK 1230584 A1 HK1230584 A1 HK 1230584A1
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Hong Kong
Prior art keywords
group
alkyl
methyl
spp
independently
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HK17104037.8A
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Chinese (zh)
Inventor
Hans-Georg Schwarz
Michael Maue
Kerstin Ilg
Ulrich Görgens
Andreas Turberg
Sebastian Horstmann
Johannes KÖBBERLING
Niels Lindner
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Bayer Animal Health Gmbh
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Publication of HK1230584A1 publication Critical patent/HK1230584A1/en

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Description

Novel pyrazolyl-heteroarylamides as pesticides
The present application relates to novel pyrazolyl heteroaryl amides, to processes for their preparation and to their use for controlling animal pests, in particular arthropods, especially insects, arachnids and nematodes.
Specific halogenated compounds are known to be herbicidally active (cf. J. org. chem. 1997, 62(17),5908-5919, J. heterocyclic. chem. 1998, 35(6), 1493-1499, WO 2004/035545, WO2004/106324, US 2006/069132, WO 2008/029084).
Specific halogenated compounds are also known to be pesticidally active (EP 1911751, WO 2010/051926, WO2012/069366, WO 2012/080376, WO 2012/107434, WO 2014/122083, WO 2014/135439 and WO 2014/135437).
Specific halogenated compounds are additionally known to have cytokine inhibitory activity (WO 2000/07980).
Modern plant protection compositions have to meet a number of requirements, for example in terms of their level, duration and spectrum of action and possible uses. Important problems relate to the toxicity and compatibility with other active substances or formulation auxiliaries, and the expenditure which must be expended to synthesize the active substances. In addition, resistance to drugs can occur. For all these reasons, the search for new plant protection compositions has never been considered to be complete and there is always a need for new compounds having improved properties compared to the known compounds at least in individual respects.
It is an object of the present invention to provide compounds which broaden the spectrum of pesticides in various aspects and/or improve their activity.
It has now been found, surprisingly, that certain pyrazolyl heteroaryl amides and their useNOxides and salts have biological properties and are particularly suitable for controlling animal pests and can therefore be used particularly well in the agrochemical industry and in the field of animal health.
Similar compounds are known from WO 2012/080376. This application describes 1,2, 3-triazolebenzoanilides as pesticidal compounds; other heteroaroylbenzanilides are not described.
SUMMARY
The invention relates to compounds of the general formula (Ic)
Wherein
R1Is hydrogen, optionally substituted C1-C6Alkyl radical, C3-C6-alkenyl, C3-C6-alkynyl, C3-C7-cycloalkyl, C1-C6-alkylcarbonyl group, C1-C6Alkoxycarbonyl, aryl (C)1-C3) Alkyl, heteroaryl (C)1-C3) -an alkyl group;
chemical moiety (Gruppierung)
A1Is CR2Or a nitrogen-containing compound,
A2is CR3Or a nitrogen-containing compound,
A3is CR4Or nitrogen, and
A4is CR5Or a nitrogen-containing compound,
but wherein the chemical moiety A1To A4Not more than three of which are simultaneously nitrogen;
R2、R3、R4and R5Independently of one another, hydrogen, halogen, cyano, nitro, optionally substituted C1-C6Alkyl radical, C3-C6-cycloalkyl, C1-C6-alkoxy groups,N-C1-C6-alkoxyimino-C1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N-C1-C6-alkylamino orN,N-di-C1-C6-an alkylamino group;
if A is2And A3None of the moieties being nitrogen, R3And R4May form, together with the carbon atom to which they are attached, a 5-or 6-membered ring containing 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and/or 0 or 1 sulfur atom, or
If A is1And A2None of the moieties being nitrogen, R2And R3May form, together with the carbon atom to which they are attached, a 5-or 6-membered ring containing 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and/or 0 or 1 sulfur atom;
W is oxygen or sulfur;
q is hydrogen, amino or the following optionally substituted moietyOne of them is: alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, heterocyclyl, cycloalkylalkyl, arylalkyl, heteroarylalkyl, alkoxycarbonyl, or isN-alkylamino, alkylamino,N-alkylcarbonylamino,N,N-a dialkylamino, alkylsulfonylamino moiety; or
Q is aryl optionally mono-to pentasubstituted with V, or heteroaryl optionally mono-to pentasubstituted with V, wherein
V is halogen, cyano, nitro, optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, or a pharmaceutically acceptable salt thereof,NAn alkoxyiminoalkyl group, an alkylsulfanyl group, an alkylsulfinyl group, an alkylsulfonyl group, a substituted aryl group,N,N-a dialkylamino group;
R6independently of one another, halogen, cyano, nitro, amino or optionally substituted C1-C6Alkyl radical, C1-C6-alkoxy, C1-C6-alkylcarbonyl group, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
n has a value of 0-2 (R when n = 0)6Accordingly, H);
Z1is optionally substituted alkyl and cycloalkyl, and
Z2is hydrogen, halogen, cyano, nitro, amino or optionally substituted alkyl, alkylcarbonyl, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, and
Z3Is hydrogen or optionally substituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl.
A preferred embodiment relates to compounds of the invention as described in the summary above, wherein
R1Is hydrogen or C optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl1-C6Alkyl radical, C3-C6-alkenyl, C3-C6-alkynyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C3Alkyl radical, C1-C6-alkylcarbonyl group, C1-C6Alkoxycarbonyl, aryl (C)1-C3) Alkyl, heteroaryl (C)1-C3) -an alkyl group;
chemical moieties
A1Is CR2Or a nitrogen-containing compound,
A2is CR3Or a nitrogen-containing compound,
A3is CR4Or nitrogen, and
A4is CR5Or a nitrogen-containing compound,
but wherein the chemical moiety A1To A4Not more than three of which are simultaneously nitrogen;
R2、R3、R4and R5Independently of one another, hydrogen, halogen, cyano, nitro or C which is optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl1-C6Alkyl radical, C3-C6-cycloalkyl, C1-C6-alkoxy groups,N-C1-C6-alkoxyimino-C1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N-C1-C6-alkylamino orN,N-di-C1-C6-an alkylamino group;
w is oxygen or sulfur;
q is hydrogen, amino or one of the following moieties optionally mono-to heptaly substituted independently of one another by hydroxy, nitro, amino, halogen, alkoxy, cyano, hydroxycarbonyl, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbamoyl, phenyl: c 1-C6-alkanesBase, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C2-C5-heterocyclyl radical, C1-C4-alkoxy, C1-C6-alkyl-C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6Alkyl radical, C1-C6Hydroxyalkyl, aryl (C)1-C3) Alkyl, heteroaryl (C)1-C3) Alkyl radical, C1-C4-an alkoxycarbonyl group,N-C1-C4-alkylamino, alkylamino,N-C1-C4-alkylcarbonylamino,N,N-di-C1-C4-alkylamino radical, C1-C4-an alkylsulfonylamino group; or
Q is hydrogen, amino or selected from C1-C6Alkyl radical, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, 5-or 6-membered heterocyclyl, C1-C6-alkyl-C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6Alkyl radical, C6-C10-aryl- (C)1-C3) -alkyl, 5-or 6-membered heteroaryl- (C)1-C3) Alkyl radical, C1-C4-one of the moieties of alkoxycarbonyl optionally substituted independently of each other by 1, 2, 3, 4, 5, 6 or 7 substituents selected from hydroxy, nitro, amino, halogen, oxo, benzyloxy, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6Haloalkoxy, cyano, hydroxycarbonyl, C1-C4Alkoxycarbonyl, C1-C6-alkylcarbamoyl, C3-C6-cycloalkylcarbamoyl radical,N,N-di-C1-C4-alkylamino, optionally substituted by 1, 2 or 3 substituents independently of one another, chosen from halogen, C1-C6-alkoxy, C1-C6-haloalkoxy and C1-C6Phenyl substituted by alkyl substituents, optionally substituted by 1, 2 or 3 substituents independently of one another selected from halogen, C 1-C6-alkoxy, C1-C6-haloalkoxy and C1-C6Phenylthio substituted by alkyl substituents, optionally substituted by 1, 2 or 3 substituents independently of one another selected from halogen, C1-C6-alkoxy, C1-C6-haloalkoxy and C1-C6Phenoxy substituted with substituents of alkyl, optionally substituted with 1, 2 or 3 substituents independently of one another selected from halogen, C1-C6-alkoxy, C1-C6-haloalkoxy and C1-C6A 5-or 6-membered heteroaryl group (e.g. pyrazolyl) substituted by a substituent consisting of an alkyl group, orN-C1-C4-alkylamino, alkylamino,N-C1-C4-alkylcarbonylamino,N,N-di-C1-C4-alkylamino radical, C1-C4-an alkylsulfonylamino moiety; or
Q is aryl substituted with 0, 1, 2, 3 or 4 substituents V or 5-or 6-membered heteroaryl substituted with 0, 1, 2, 3 or 4 substituents V, or
Q is a bicyclic heterocycle substituted with 0, 1, 2, 3, or 4V substituents or a bicyclic carbocycle substituted with 0, 1, 2, 3, or 4V substituents; wherein
V independently of one another is halogen, cyano, nitro or C which is optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C1-C6-haloalkyl group, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy,N-C1-C6-alkoxyimino-C1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C 1-C6-an alkylsulfonyl group,N,N-di- (C)1-C6-alkyl) amino;
R6independently of one another, halogen, cyano, nitro, amino or C optionally mono-to heptasubstituted by halogen1-C6Alkyl radical, C1-C6-alkoxy, C1-C6-alkylcarbonyl group, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
n has a value of 0-1;
Z1is C optionally mono-to heptasubstituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl1-C6Alkyl radical, C3-C6-a cycloalkyl radical, and
Z2is hydrogen, halogen, cyano, nitro, amino or C which is mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl1-C6Alkyl radical, C1-C6-alkylcarbonyl group, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
Z3is hydrogen or C optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl1-C6Alkyl radical, C3-C6-cycloalkyl, C3-C4-alkenyl, C3-C4-alkynyl or aryl and heteroaryl optionally mono-to penta-substituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl.
Another preferred embodiment relates to compounds of the invention as described in the summary above, wherein
R1Is hydrogen, C1-C4Alkyl radical, C3-C4-alkenyl, C3-C4-an alkynyl group;
Chemical moieties
A1Is CR2，
A2Is CR3Or a nitrogen-containing compound,
A3is CR4And is and
A4is CR5；
W is oxygen;
R6is C1-C4-an alkyl group;
n has a value of 0-1;
Z1is C which is in each case optionally mono-to heptaly substituted independently of one another by halogen or cyano1-C6-alkyl or C3-C6-a cycloalkyl group;
Z2is C which is in each case optionally mono-to heptaly substituted independently of one another by halogen or cyano1-C6-alkyl or C3-C6-a cycloalkyl group;
Z3is hydrogen or C1-C6-an alkyl group.
Another preferred embodiment relates to compounds of the invention as described in the summary above, wherein
R1Is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, more preferably hydrogen;
chemical moieties
A1Is CR2，
A2Is CR3Or a nitrogen-containing compound,
A3is CR4And is and
A4is CR5；
W is oxygen;
R6is hydrogen (n = 0);
Z1is C which is in each case optionally mono-to heptaly substituted independently of one another by halogen1-C6-an alkyl group;
Z2is C which is in each case optionally mono-to heptaly substituted independently of one another by halogen1-C6-an alkyl group;
Z3is C1-C6-an alkyl group.
Another preferred embodiment relates to compounds of the invention as described in the summary above, wherein
R2And R5Independently of one another, hydrogen, fluorine, chlorine, bromine, iodine, methyl and methoxy;
R3and R4Independently of one another, hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C 1-C4Alkyl radical, C1-C4-haloalkyl.
Another preferred embodiment relates to compounds of the invention as described in the summary above, wherein
R2And R5Independently of one another, hydrogen or fluorine;
R3is hydrogen; and is
R4Is hydrogen, fluorine, chlorine or methyl.
Another preferred embodiment relates to compounds of the invention as described in the summary above, wherein
Q is hydrogen;
or
C optionally substituted by 1, 2, 3 or 4 substituents1-C6-alkyl, the substituents being independently of each other selected from
Fluorine,
Chlorine,
Bromine,
Iodine,
A cyano group,
An oxo group,
Methoxy group,
Benzyloxy group,
Ethoxy, ethoxy,
N,N-di-C1-C4-alkylamino, alkylamino,
Phenylthio optionally substituted independently of one another by 1, 2, 3 or 4 substituents from the group consisting of fluorine, chlorine, bromine, iodine, methoxy, methyl and trifluoromethyl,
phenoxy which is optionally substituted independently of one another by 1, 2, 3 or 4 substituents from the group consisting of fluorine, chlorine, bromine, iodine, methoxy, methyl and trifluoromethyl,
phenyl optionally substituted independently of one another by 1, 2, 3 or 4 substituents selected from the group consisting of fluorine, chlorine, bromine, iodine, methoxy, methyl and trifluoromethyl,
thienyl optionally substituted independently of one another by 1, 2, 3 or 4 substituents selected from the group consisting of fluorine, chlorine, bromine, iodine, methoxy, methyl and trifluoromethyl,
Pyrazolyl which is optionally substituted, independently of one another, by 1,2, 3 or 4 substituents from the group consisting of fluorine, chlorine, bromine, iodine, methoxy, methyl and trifluoromethyl, and
C3-C6-a cycloalkyl group;
or
C optionally substituted by 1,2, 3 or 4 substituents3-C6-cycloalkyl, the substituents being independently of each other selected from
Methoxy group,
Fluorine,
Chlorine,
Bromine,
Iodine,
A cyano group,
Methyl, methyl,
Phenyl optionally substituted independently of one another by 1,2, 3 or 4 substituents selected from the group consisting of fluorine, chlorine, bromine, iodine, methoxy, methyl and trifluoromethyl;
or
Q is the following group substituted with 0, 1,2, 3 or 4V substituents: phenyl, naphthyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, pyridyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, imidazolyl, furanyl, thienyl, pyrrolyl, oxadiazolyl, thiadiazolyl, benzothienyl, benzofuranyl, [1,2,4] triazolo [1,5-a ] pyrimidinyl, 1, 3-benzodioxolyl or tetrahydronaphthyl, wherein
V is, independently of one another, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, propyl, butyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2,2, 2-tetrafluoroethyl, 1-chloro-1, 2,2, 2-tetrafluoroethyl, 2,2, 2-trichloroethyl, 2-chloro-2, 2-difluoroethyl, 1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, n-propoxy, 1-methylethoxy, fluoromethoxy, Difluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, trifluoromethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2, 2-difluoroethoxy, pentafluoroethoxy, n-ethyldifluoromethoxy, n-, NMethoxy imino methyl, 1-, (N-methoxyimino) ethyl, methylsulfanyl, methylsulfonyl, methylsulfinyl, trifluoromethylsulfonyl, trifluoromethylsulfinyl, trifluoromethylsulfanyl,N,N-di-C1-C4Alkylamino (e.g. alkylamino)N,N-dimethylamino group).
Another preferred embodiment relates to compounds of the invention as described in the summary above, wherein
Q is C optionally substituted with 1, 2, 3 or 4 substituents1-C6-alkyl, the substituents being independently of each other selected from
Fluorine,
An oxo group,
Methoxy group,
Benzyloxy group,
Ethoxy, ethoxy,
N,N-dimethylamino group,
A phenylthio group,
A phenoxy group,
C3-C6-a cycloalkyl group,
Phenyl optionally substituted independently of one another by 1, 2, 3 or 4 substituents selected from the group consisting of fluorine, chlorine and trifluoromethyl,
thienyl optionally substituted with 1, 2, 3 or 4 trifluoromethyl, and
pyrazolyl optionally substituted independently of one another by 1, 2, 3 or 4 substituents selected from methyl and trifluoromethyl;
or
C optionally substituted by 1, 2, 3 or 4 substituents3-C6-cycloalkyl, the substituents being independently of each other selected from
Methoxy group,
Chlorine,
A cyano group,
Methyl, methyl,
Phenyl optionally substituted independently of one another by 1, 2, 3 or 4 substituents selected from the group consisting of chlorine, methyl and trifluoromethyl;
Or
Q is the following group substituted with 0, 1,2, 3 or 4V substituents: phenyl, naphthyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, pyridyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, imidazolyl, furanyl, thienyl, pyrrolyl, oxadiazolyl, thiadiazolyl, benzothienyl, benzofuranyl, [1,2,4] triazolo [1,5-a ] pyrimidinyl, 1, 3-benzodioxolyl or tetrahydronaphthyl, wherein
V is, independently of one another, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, propyl, butyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2,2, 2-tetrafluoroethyl, 1-chloro-1, 2,2, 2-tetrafluoroethyl, 2,2, 2-trichloroethyl, 2-chloro-2, 2-difluoroethyl, 1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, n-propoxy, 1-methylethoxy, fluoromethoxy, Difluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, trifluoromethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2, 2-difluoroethoxy, pentafluoroethoxy, n-ethyldifluoromethoxy, n-, NMethoxy imino methyl, 1-, (N-methoxyimino) ethyl, methylsulfanyl, methylsulfonyl, methylsulfinyl, trifluoromethylsulfonyl, trifluoromethylsulfinyl, trifluoromethylsulfanyl,N,N-di-C1-C4Alkylamino (e.g. alkylamino)N,N-dimethylamino group).
Another preferred embodiment relates to compounds of the invention as described in the summary above, wherein the compound is a compound of formula (Ic-1)
。
Another preferred embodiment relates to compounds of the invention as described in the summary above, wherein the compound is a compound of formula (Ic-2)
。
The invention also provides the use of a compound of the invention (e.g. formula (Ic), (Ic-1) or (Ic-2)) for the control of insects, arachnids and nematodes; pharmaceutical compositions comprising at least one compound of the invention; a compound of the invention for use as a medicament; use of a compound of the invention for the manufacture of a pharmaceutical composition for controlling parasites in animals; a process for the manufacture of a plant protection composition comprising at least one compound of the invention and customary extenders and/or surface-active substances; a method for controlling pests, characterized by allowing the compounds of the present invention to act on pests and/or their living space; the use of the compounds of the invention for protecting plant propagation material.
Detailed description of the invention
The pyrazolyl heteroaryl amides of the invention are defined by the general formula (I)
Wherein
R1Is hydrogen, optionally substituted C1-C6Alkyl radical, C3-C6-alkenyl, C3-C6-alkynyl, C3-C7-cycloalkyl, C1-C6-alkylcarbonyl group, C1-C6Alkoxycarbonyl, aryl (C)1-C3) Alkyl, heteroaryl (C)1-C3) -alkyl, most preferably hydrogen;
chemical moieties
A1Is CR2Or a nitrogen-containing compound,
A2is CR3Or a nitrogen-containing compound,
A3is CR4Or nitrogen, and
A4is CR5Or a nitrogen-containing compound,
but wherein the chemical moiety A1To A4Not more than three of which are simultaneously nitrogen;
R2、R3、R4and R5Independently of one another, hydrogen, halogen, cyano, nitro, optionally substituted C1-C6Alkyl radical, C3-C6-cycloalkyl, C1-C6-alkoxy groups,N-C1-C6-alkoxyimino-C1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N-C1-C6-alkylamino orN,N-di-C1-C6-an alkylamino group;
if A is2And A3None of the moieties being nitrogen, R3And R4May form, together with the carbon atom to which they are attached, a 5-or 6-membered ring containing 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and/or 0 or 1 sulfur atom, or
If A is1And A2None of the moieties being nitrogen, R2And R3May form, together with the carbon atom to which they are attached, a 5-or 6-membered ring containing 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and/or 0 or 1 sulfur atom;
w is oxygen or sulfur;
q is hydrogen, amino or one of the following optionally substituted moieties: alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, heterocyclyl, cycloalkylalkyl, arylalkyl, heteroarylalkyl, alkoxycarbonyl, or is N-alkylamino, alkylamino,N-alkylcarbonylamino,N,N-a dialkylamino, alkylsulfonylamino moiety; or
Q is aryl optionally mono-to pentasubstituted with V, or heteroaryl optionally mono-to pentasubstituted with V, wherein
V is halogen, cyano, nitro, optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, or a pharmaceutically acceptable salt thereof,NAn alkoxyiminoalkyl group, an alkylsulfanyl group, an alkylsulfinyl group, an alkylsulfonyl group, a substituted aryl group,N,N-a dialkylamino group;
t is one of the 5-membered heteroaromatic compounds T1 to T10, wherein the bond to the pyrazolyl head group is indicated by an asterisk,
wherein
R6Independently of one another, halogen, cyano, nitro, amino or optionally substituted C1-C6Alkyl radical, C1-C6-alkoxy, C1-C6-alkylcarbonyl group, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
n has a value of 0-2;
Z1is optionally substituted alkyl and cycloalkyl, and
Z2is hydrogen, halogen, cyano, nitro, amino or optionally substituted alkyl, alkylcarbonyl, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, and
Z3is hydrogen or optionally substituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl.
Preferred are compounds of formula (I)
Wherein
R1Is hydrogen or C optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl 1-C6Alkyl radical, C3-C6-alkenyl, C3-C6-alkynyl, C3-C7-cycloalkyl, C1-C6-alkylcarbonyl group, C1-C6Alkoxycarbonyl, aryl (C)1-C3) Alkyl, heteroaryl (C)1-C3) -alkyl, most preferably hydrogen;
chemical moieties
A1Is CR2Or a nitrogen-containing compound,
A2is CR3Or a nitrogen-containing compound,
A3is CR4Or nitrogen, and
A4is CR5Or a nitrogen-containing compound,
but wherein the chemical moiety A1To A4Not more than three of which are simultaneously nitrogen;
R2、R3、R4and R5Independently of one another, hydrogen, halogen, cyano, nitro or C which is optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C3-C6-cycloalkyl, C1-C6-alkoxy groups,NAlkoxyiminoalkyl, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N-C1-C6-alkylamino, alkylamino,N ,N-di-C1-C6-an alkylamino group;
if A is2And A3None of the moieties being nitrogen, R3And R4May form, together with the carbon atom to which they are attached, a 5-or 6-membered ring containing 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and/or 0 or 1 sulfur atom, or
If A is1And A2None of the moieties being nitrogen, R2And R3May form together with the carbon atom to which they are attached a 6-membered ring containing 0, 1 or 2 nitrogen atoms;
w is oxygen or sulfur;
q is hydrogen, amino or optionally independently of one another by halogen, cyano, C1-C6-alkoxy or C1-C6-alkoxycarbonyl mono-to heptaly substituted C 1-C6Alkyl radical, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C2-C5-heterocyclyl radical, C1-C4-alkoxy, C1-C6-alkyl-C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6Alkyl radical, C6-aryl- (C)1-C3) -alkyl, 5-or 6-membered heteroaryl- (C)1-C3) Alkyl radical, C1-C4An alkoxycarbonyl moiety orN-C1-C4-alkylamino, alkylamino,N-C1-C4-alkylcarbonylamino,N,N-di-C1-C4-alkylamino radical, C1-C4-an alkylsulfonylamino moiety; or
Q is aryl substituted with 0, 1, 2, 3 or 4 substituents V or 5-or 6-membered heteroaryl substituted with 0, 1, 2, 3 or 4 substituents V, wherein
V independently of one another is halogen, cyano, nitro or C which is optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy groups,N-C1-C6-alkoxyimino-C1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkyl sulfinAcyl radical, C1-C6-an alkylsulfonyl group,N,N-di- (C)1-C6-alkyl) amino;
t is one of the 5-membered heteroaromatic compounds T1 to T10, wherein the bond to the pyrazolyl head group is indicated by an asterisk,
wherein
R6Independently of one another, halogen, cyano, nitro, amino or C optionally mono-to heptasubstituted by halogen1-C6Alkyl radical, C1-C6-alkoxy, C1-C6-alkylcarbonyl group, C 1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
n has a value of 0-1;
Z1is C1-C6-alkyl, C3-C6-cycloalkyl, optionally mono-to heptasubstituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl, and
Z2is hydrogen, halogen, cyano, nitro, amino or C which is optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C1-C6-alkylcarbonyl group, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
Z3is hydrogen or C optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C3-C6-cycloalkyl, C3-C6-alkenyl, C3-C6-alkynyl or is optionally mono-to penta-disubstituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonylA substituted aryl or heteroaryl group.
Preference is furthermore given to compounds of the formula (I)
Wherein
R1Is hydrogen or C optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C3-C6-alkenyl, C3-C6-alkynyl, C3-C7-cycloalkyl, C1-C6-alkylcarbonyl group, C1-C6Alkoxycarbonyl, aryl (C)1-C3) Alkyl, heteroaryl (C)1-C3) -alkyl, most preferably hydrogen;
chemical moieties
A1Is CR2Or a nitrogen-containing compound,
A2is CR3Or a nitrogen-containing compound,
A3is CR4Or nitrogen, and
A4is CR5Or a nitrogen-containing compound,
but wherein the chemical moiety A1To A4Not more than three of which are simultaneously nitrogen;
R2、R3、R4and R5Independently of one another, hydrogen, halogen, cyano, nitro or C which is optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C3-C6-cycloalkyl, C1-C6-alkoxy groups,NAlkoxyiminoalkyl, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N-C1-C6-alkylamino, alkylamino,N ,N-di-C1-C6-an alkylamino group;
if A is2And A3None of the moieties being nitrogen, R3And R4May form, together with the carbon atom to which they are attached, a 5-or 6-membered ring containing 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and/or 0 or 1 sulfur atom, or
If A is1And A2None of the moieties being nitrogen, R2And R3May form together with the carbon atom to which they are attached a 6-membered ring containing 0, 1 or 2 nitrogen atoms;
w is oxygen or sulfur;
q is hydrogen, amino or C which is optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C2-C5-heterocyclyl radical, C1-C4-alkoxy, C1-C6-alkyl-C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6Alkyl, aryl- (C) 1-C3) -alkyl, heteroaryl- (C)1-C3) Alkyl radical, C1-C4An alkoxycarbonyl moiety orN-C1-C4-alkylamino, alkylamino,N-C1-C4-alkylcarbonylamino,N,N-di-C1-C4-alkylamino radical, C1-C4-an alkylsulfonylamino moiety; or
Q is aryl optionally mono-to pentasubstituted with V, or heteroaryl optionally mono-to pentasubstituted with V, wherein
V independently of one another is halogen, cyano, nitro or C which is optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C2-C4-alkenyl, C2-C4-alkynyl radical、C3-C6-cycloalkyl, C1-C6-alkoxy groups,N-C1-C6-alkoxyimino-C1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N,N-di- (C)1-C6-alkyl) amino;
t is one of the 5-membered heteroaromatic compounds T1 to T10, wherein the bond to the pyrazolyl head group is indicated by an asterisk,
wherein
R6Independently of one another, halogen, cyano, nitro, amino or C optionally mono-to heptasubstituted by halogen1-C6Alkyl radical, C1-C6-alkoxy, C1-C6-alkylcarbonyl group, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
n has a value of 0-1;
Z1is optionally substituted C1-C6-haloalkyl group, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, and
Z2is hydrogen, halogen, cyano, nitro, amino or C which is optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl 1-C6Alkyl radical, C1-C6-alkylcarbonyl group, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
Z3is hydrogen or optionally independently of one another halogen, cyano, alkoxyOr alkoxycarbonyl mono-to heptaly substituted C1-C6Alkyl radical, C3-C6-cycloalkyl, C3-C6-alkenyl, C3-C6-alkynyl or aryl or heteroaryl optionally mono-to penta-substituted independently of each other by halogen, cyano, alkoxy and alkoxycarbonyl.
Particularly preferred are compounds of formula (I)
Wherein
R1Is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, prop-2-enyl, 2-methylprop-2-enyl, prop-2-ynyl, methoxymethyl, ethoxymethyl, propoxymethyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, sec-butylcarbonyl, tert-butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, cyanomethyl, 2-cyanoethyl, benzyl, 4-methoxybenzyl, pyridin-2-ylmethyl, pyridin-3-ylmethyl, pyridin-4-yl-methyl, 4-chloropyridin-3-yl-methyl, most preferably hydrogen;
chemical moieties
A1Is CR2Or a nitrogen-containing compound,
A2Is CR3Or a nitrogen-containing compound,
A3is CR4Or nitrogen, and
A4is CR5Or a nitrogen-containing compound,
but wherein the chemical moiety A1To A4Not more than three of which are simultaneously nitrogen;
R2and R5Independently of one another, hydrogen, fluorine, chlorine, bromine, iodine, methyl and methoxyAnd is
R3And R4Independently of one another, hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, fluoromethyl, difluoromethyl, chlorodifluoromethyl, trifluoromethyl, 2,2, 2-trifluoroethyl, methoxy, ethoxy, n-propoxy, 1-methylethoxy, fluoromethoxy, difluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, trifluoromethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2, 2-difluoroethoxy, pentafluoroethoxy, n-fluoroethoxy, n-chloroethoxy, 2-chloro-2, 2-difluoroethoxy, n-fluoroethoxy, n-chloroethoxy, n,NMethoxy imino methyl, 1-, (N-methoxyimino) ethyl, methylsulfanyl, trifluoromethylsulfanyl, methylsulfonyl, methylsulfinyl, trifluoromethylsulfonyl, trifluoromethylsulfinyl;
w is oxygen or sulfur;
q is hydrogen, methyl, ethyl, n-propyl, 1-methylethyl, 1-dimethylethyl, 1-methylpropyl, n-butyl, 2-methylpropyl, 2-methylbutyl, hydroxymethyl, 2-hydroxypropyl, cyanomethyl, 2-cyanoethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2, 2-tetrafluoroethyl, 1-trifluoromethylethyl, 2, 2-difluoropropyl, 3,3, 3-trifluoropropyl, 2, 2-dimethyl-3-fluoropropyl, cyclopropyl, 1-cyanocyclopropyl, 1-chlorocyclopropyl, 1-methylcyclopropyl, 1-methoxycarbonylcyclopropyl, 1- (R) cyclopropyl N-methylcarbamoyl) cyclopropyl, 1-, (N-cyclopropylcarbamoyl) cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-cyclopropylethyl, bis (cyclopropyl) methyl, 2-dimethylcyclopropylmethyl, 2-phenylcyclopropyl, 2-dichlorocyclopropyl, trans-2-chlorocyclopropyl, cis-2-chlorocyclopropyl, 2-difluorocyclopropyl, trans-2-fluorocyclopropyl, cis-2-fluorocyclopropyl, trans-4-hydroxycyclohexyl, 4-trifluoromethylcyclohexyl, prop-2-enyl, 2-methylprop-2-enyl, prop-2-ynyl, 1-dimethylbut-2-ynyl, 3-chloroprop-2-enyl, cyclopentyl, cyclohexyl, 1-cyclopropylethyl, bis (cyclopropyl) methyl, 2-difluorocyclopropyl, 2-chlorocyclopropyl, trans-2-fluorocyclopropyl, cis-2-fluorocyclopropyl, trans-4-hydroxycyclohexyl, 4-trifluoromethylcyclohexyl, prop-2-enyl, prop-2, 3, 3-dichloroprop-2-enyl, 3-dichloro-1, 1-dimethylprop-2-enyl, oxetan-3-yl, thietane-3-yl, 1-thietane-3-yl, 1-thietane-3-yl, isoxazol-3-ylmethyl, 3-methyloxetan-3-ylmethyleneA phenyl group, a benzyl group, a 2, 6-difluorophenylmethyl group, a 3-fluorophenylmethyl group, a 2, 5-difluorophenylmethyl group, a 1-phenylethyl group, a 4-chlorophenylethyl group, a 2-trifluoromethylphenylethyl group, a pyridin-2-ylethyl group, a pyridin-2-ylmethyl group, 5-fluoropyridin-2-ylmethyl, (6-chloropyridin-3-yl) methyl, pyrimidin-2-ylmethyl, methoxy, 2-ethoxyethyl, 2- (methylsulfanyl) ethyl, 1-methyl-2- (ethylsulfanyl) ethyl, 2-methyl-1- (methylsulfanyl) propan-2-yl, methoxycarbonyl, methoxycarbonylmethyl, NH. 2、N-an ethylamino group,N-allylamino group,N,N-dimethylamino group,N,N-diethylamino, methylsulfonylamino; or
Q is one of the following substituted with 0, 1,2, 3 or 4V substituents: phenyl, naphthyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, pyridyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, imidazolyl, furanyl, thienyl, pyrrolyl, oxadiazolyl, thiadiazolyl, wherein
V is, independently of one another, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2,2, 2-tetrafluoroethyl, 1-chloro-1, 2,2, 2-tetrafluoroethyl, 2,2, 2-trichloroethyl, 2-chloro-2, 2-difluoroethyl, 1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, n-propoxy, 1-methylethoxy, fluoromethoxy, difluoromethoxy, Chlorodifluoromethoxy, dichlorofluoromethoxy, trifluoromethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2, 2-difluoroethoxy, pentafluoroethoxy, m, NMethoxy imino methyl, 1-, (N-methoxyimino) ethyl, methylsulfanyl, methylsulfonyl, methylsulfinyl, trifluoromethylsulfonyl, trifluoromethylsulfinyl, trifluoromethylsulfanyl, N-dimethylamino;
t is one of the 5-membered heteroaromatic compounds T1 to T10, wherein the bond to the pyrazolyl head group is indicated by an asterisk,
wherein
R6Independently of one another, halogen, cyano, nitro, amino, methyl, ethyl, 1-methylethyl, tert-butyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, trifluoromethoxy, 2, 2-difluoroethoxy, 2,2, 2-trifluoroethoxy, methylcarbonyl, ethylcarbonyl, trifluoromethylcarbonyl, methylsulfanyl, methylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, and
n has a value of 0-1;
Z1is methyl, ethyl, 1-dimethylethyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, bromodichloromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 1-fluoro-1-methylethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2,2, 2-tetrafluoroethyl, 1-chloro-1, 2,2, 2-tetrafluoroethyl, 2,2, 2-trichloroethyl, 2-chloro-2, 2-difluoroethyl, 1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, cyclopropyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl, 1-bromocyclopropyl, 1-cyanocyclopropyl, 1-trifluoromethylcyclopropyl, cyclobutyl and 2, 2-difluoro-1-methylcyclopropyl, and
Z2Is hydrogen, halogen, cyano, nitro, amino, methyl, ethyl, 1-dimethylethyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, bromodichloromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 1-fluoro-1-methylethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2,2, 2-tetrafluoroethyl, 1-chloro-1, 2,2, 2-tetrafluoroethyl, 2,2, 2-trichloroethyl, 2-chloro-2, 2-difluoroethyl, 1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, hepta-fluoroethylFluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, methylsulfanyl, methylsulfinyl, methylsulfonyl, ethylthio, ethylsulfinyl, ethylsulfonyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfanyl, chlorodifluoromethylsulfinyl, chlorodifluoromethylsulfonyl, dichlorofluoromethylsulfanyl, dichlorofluoromethylsulfinyl, dichlorofluoromethylsulfonyl and
Z3is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, vinyl, 1-propenyl, 2-propenyl, 1-propynyl, 1-butynyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 1-fluoro-1-methylethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2, 5-dichlorophenyl, 2, 4-dichlorophenyl, 3, 4-dichlorophenyl, 2, 6-dichloro-4-trifluoromethylphenyl, 3-chloro-5-trifluoromethylpyridin-2-yl.
Particularly preferred are compounds of the formula (I), in which
Z1Is trifluoromethyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl or pentafluoroethyl;
Z2is trifluoromethyl, nitro, methylsulfanyl, methylsulfinyl, methylsulfonyl, fluoro, chloro, bromo, cyano or iodo;
Z3is methyl, ethyl, n-propyl or hydrogen;
R1is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, prop-2-enyl, 2-methylprop-2-enyl, prop-2-ynyl, methoxymethyl, ethoxymethyl, propoxymethyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, sec-butylcarbonyl, tert-butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, cyanomethylMethyl, 2-cyanoethyl, benzyl, 4-methoxybenzyl, pyridin-2-ylmethyl, pyridin-3-ylmethyl, pyridin-4-yl-methyl, 4-chloropyridin-3-yl-methyl;
A1and A2Each is CH;
A3is CR4And is
A4Is CR5；
R4Is hydrogen, fluorine, chlorine, bromine, iodine or cyano;
R5is hydrogen, fluorine, chlorine, bromine, iodine, methyl or methoxy;
t is one of the 5-membered heteroaromatic compounds T1 to T10, wherein the bond to the pyrazolyl head group is indicated by an asterisk,
Wherein
R6Is hydrogen (n = 0), methyl, ethyl, 2-methylethyl, 2-dimethylethyl, fluoro, chloro, bromo, iodo, nitro, trifluoromethyl, amino;
w is oxygen;
q is hydrogen, methyl, ethyl, n-propyl, 1-methylethyl, 1-dimethylethyl, 1-methylpropyl, n-butyl, 2-methylpropyl, 2-methylbutyl, hydroxymethyl, 2-hydroxypropyl, cyanomethyl, 2-cyanoethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2, 2-tetrafluoroethyl, 1-trifluoromethylethyl, 2, 2-difluoropropyl, 3,3, 3-trifluoropropyl, 2, 2-dimethyl-3-fluoropropyl, cyclopropyl, 1-cyanocyclopropyl, 1-chlorocyclopropyl, 1-methylcyclopropyl, 1-methoxycarbonylcyclopropyl, 1- (R) cyclopropylN-methylcarbamoyl) cyclopropyl, 1-, (N-cyclopropylcarbamoyl) cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-cyclopropylethyl, bis (cyclopropyl) methyl, 2-dimethylCyclopropylmethyl, 2-phenylcyclopropyl, 2-dichlorocyclopropyl, trans-2-chlorocyclopropyl, cis-2-chlorocyclopropyl, 2-difluorocyclopropyl, trans-2-fluorocyclopropyl, cis-2-fluorocyclopropyl, trans-4-hydroxycyclohexyl, 4-trifluoromethylcyclohexyl, prop-2-enyl, 2-methylprop-2-enyl, prop-2-ynyl, 1-dimethylbut-2-ynyl, 3-chloroprop-2-enyl, 3-dichloroprop-2-enyl, 3-dichloro-1, 1-dimethylprop-2-enyl, oxetan-3-yl, oxetanyl, 2-chlorocyclopropyl, 2-chlorocyclohexyl, 2-methylpropyl, 2-propenyl, 2, 1-dimethylbut-2-ynyl, 1-dimethylprop-2-enyl, oxetan-3, Thien-3-yl, 1-thien-3-yl, 1-thien-3-yl, isoxazol-3-ylmethyl, 3-methyloxetan-3-ylmethyl, benzyl, 2, 6-difluorophenylmethyl, 3-fluorophenylmethyl, 2, 5-difluorophenylmethyl, 1-phenylethyl, 4-chlorophenylethyl, 2-trifluoromethylphenylethyl, pyridin-2-ylethyl, pyridin-2-ylmethyl, 5-fluoropyridin-2-ylmethyl, (6-chloropyridin-3-yl) methyl, pyrimidin-2-ylmethyl, methoxy, 2-ethoxyethyl, methyl, isopropyl, isobutyl, 2- (methylsulfanyl) ethyl, 1-methyl-2- (ethylsulfanyl) ethyl, 2-methyl-1- (methylsulfanyl) prop-2-yl, methoxycarbonyl, methoxycarbonylmethyl, NH 2、N-an ethylamino group,N-allylamino group,N,N-dimethylamino group,N,N-diethylamino, methylsulfonylamino, most preferably hydrogen; or
Q is the following group substituted with 0, 1,2, 3 or 4V substituents: phenyl, naphthyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, pyridyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, imidazolyl, furanyl, thienyl, pyrrolyl, oxadiazolyl, thiadiazolyl, wherein
V is, independently of one another, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2,2, 2-tetrafluoroethyl, 1-chloro-1, 2,2, 2-tetrafluoroethyl, 2,2, 2-trichloroethyl, 2-chloro-2, 2-difluoroethyl, 1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, pentafluoro-isopropyl, pentafluoro-tert-butyl, dichlorofluoromethyl, chlorobutyl, dichlorofluoromethyl, trifluoromethyl, chlorobutyl, 2-fluoroethyl, 2-difluoroethyl, 2, 2-difluoroethyl, 1A group, nonafluoro-n-butyl group, cyclopropyl group, cyclobutyl group, methoxy group, ethoxy group, n-propoxy group, 1-methylethoxy group, fluoromethoxy group, difluoromethoxy group, chlorodifluoromethoxy group, dichlorofluoromethoxy group, trifluoromethoxy group, 2,2, 2-trifluoroethoxy group, 2-chloro-2, 2-difluoroethoxy group, pentafluoroethoxy group, n-propyloxy group, n-, NMethoxy imino methyl, 1-, (N-methoxyimino) ethyl, methylsulfanyl, methylsulfonyl, methylsulfinyl, trifluoromethylsulfonyl, trifluoromethylsulfinyl, trifluoromethylsulfanyl, N-dimethylamino.
Further particularly preferred are compounds of the formula (I), in which
Z1Is trifluoromethyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl or pentafluoroethyl;
Z2is trifluoromethyl, nitro, methylsulfanyl, methylsulfinyl, methylsulfonyl, fluoro, chloro, bromo, cyano or iodo;
Z3is methyl, ethyl, n-propyl or hydrogen;
R1is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, prop-2-enyl, 2-methylprop-2-enyl, prop-2-ynyl, methoxymethyl, ethoxymethyl, propoxymethyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, sec-butylcarbonyl, tert-butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, cyanomethyl, 2-cyanoethyl, benzyl, 4-methoxybenzyl, pyridin-2-ylmethyl, pyridin-3-ylmethyl, pyridin-4-yl-methyl, 4-chloropyridin-3-yl-methyl, most preferably hydrogen;
A1Is CH;
A2is nitrogen;
A3is CR4And is
A4Is CR5；
R4Is hydrogen, fluorine, chlorine, bromine, iodine or cyano;
R5is hydrogen, fluorine, chlorine, bromine, iodine, methyl or methoxy;
t is one of the 5-membered heteroaromatic compounds T1 to T10, wherein the bond to the pyrazolyl head group is indicated by an asterisk,
wherein
R6Is hydrogen (n = 0), methyl, ethyl, 2-methylethyl, 2-dimethylethyl, fluoro, chloro, bromo, iodo, nitro, trifluoromethyl, amino;
w is oxygen;
q is hydrogen, methyl, ethyl, n-propyl, 1-methylethyl, 1-dimethylethyl, 1-methylpropyl, n-butyl, 2-methylpropyl, 2-methylbutyl, hydroxymethyl, 2-hydroxypropyl, cyanomethyl, 2-cyanoethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2, 2-tetrafluoroethyl, 1-trifluoromethylethyl, 2, 2-difluoropropyl, 3,3, 3-trifluoropropyl, 2, 2-dimethyl-3-fluoropropyl, cyclopropyl, 1-cyanocyclopropyl, 1-chlorocyclopropyl, 1-methylcyclopropyl, 1-methoxycarbonylcyclopropyl, 1- (R) cyclopropylN-methylcarbamoyl) cyclopropyl, 1-, (N-cyclopropylcarbamoyl) cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-cyclopropylethyl, bis (cyclopropyl) methyl, 2-dimethylcyclopropylmethyl, 2-phenylcyclopropyl, 2-dichlorocyclopropyl, trans-2-chlorocyclopropyl, cis-2-chlorocyclopropyl, 2-difluorocyclopropyl, trans-2-fluorocyclopropyl, cis-2-fluorocyclopropyl, trans-4-hydroxycyclohexyl, 4-trifluoromethylcyclohexyl, prop-2-enyl, 2-methylprop-2-enyl, prop-2-ynyl, 1-dimethylbut-2-ynyl, 3-chloroprop-2-enyl, cyclopentyl, cyclohexyl, 1-cyclopropylethyl, bis (cyclopropyl) methyl, 2-difluorocyclopropyl, 2-chlorocyclopropyl, trans-2-fluorocyclopropyl, cis-2-fluorocyclopropyl, trans-4-hydroxycyclohexyl, 4-trifluoromethylcyclohexyl, prop-2-enyl, prop-2, 3, 3-dichloroprop-2-enyl, 3-dichloro-1, 1-dimethylprop-2-enyl, oxetan-3-yl, thietane-3-yl 1-thietane-3-yl oxide, 1-thietane-3-yl dioxide, isoxazol-3-ylmethyl, 3-methyloxetan-3-ylmethyl, benzyl, 2, 6-difluorophenylmethyl, 3-fluorophenylmethyl, 2, 5-difluorophenylmethyl, 1-phenylethyl, 4-chlorophenylethyl, 2-trifluoromethylphenylethyl, pyridin-2-ylethyl, pyridin-2-ylmethyl, 5-fluoropyridin-2-ylmethyl, (6-chloropyridin-3-yl) methyl, pyrimidin-2-ylmethyl, methoxy, 2-ethoxyethyl, 2- (methylsulfanyl) ethyl, methyl, ethyl, isopropyl, isobutyl, 1-methyl-2- (ethylsulfanyl) ethyl, 2-methyl-1- (methylthioalkyl) propan-2-yl, methoxycarbonyl, methoxycarbonylmethyl, NH2、N-an ethylamino group,N-allylamino group,N,N-dimethylamino group,N,N-diethylamino, methylsulfonylamino; or
Q is one of the following substituted with 0, 1,2, 3 or 4V substituents: phenyl, naphthyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, pyridyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, imidazolyl, furanyl, thienyl, pyrrolyl, oxadiazolyl, thiadiazolyl, wherein
V is independently fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2,2, 2-tetrafluoroethyl, 1-chloro-1, 2,2, 2-tetrafluoroethyl, 2, 2-trichloroethyl, 2-chloro-2, 2-difluoroethyl, 1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, n-propoxy, 1-methylethoxy, fluoromethoxy, difluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, dichlorofluoromethyl, 1,2,2, 2-tetrafluoroeth, Dichlorofluoromethoxy group, trifluoromethoxy group, 2,2, 2-trifluoroethoxy group, 2-chloro-2, 2-difluoroethoxy group, pentafluoroethoxy group, perfluoroethoxy group, NMethoxy imino methyl, 1-, (N-methoxyimino) ethyl, methylsulfanyl, methylsulfonyl, methylsulfinyl, trifluoromethylsulfonyl, trifluoromethylsulfinyl, tris (hydroxymethyl) sulfinylFluoromethylsulfanyl, N-dimethylamino.
Also particularly preferred are compounds each defined by one of the general formulae (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii) and (Ij), wherein A is1-A4、n、W、Q、R1And Z1-Z3The radicals are each as defined above.
。
Very particular preference is given to compounds of the formula (Ic) in which Z is1Is CF2CF3，Z2Is CF3，Z3Is CH3，R1、R6The radical is hydrogen (n = 0), A1、A2Is C-H, A3Is C-H, C-Cl, C-F, A4Is C-H, C-F, C-OMe, W is oxygen and Q is methyl, ethyl, cyclopropyl, 1-chlorocyclopropyl, 1-cyanocyclopropyl, 2,2, 2-trifluoroethyl, 1,2, 2-tetrafluoroethyl, phenyl, 4-fluorophenyl, 2-fluorophenyl, 3, 5-difluorophenyl, 2, 6-difluorophenyl, 2-thienyl, 3-chloro-3-thienyl, 1-methyl-4-pyrazolyl, 4-pyridyl, 3-chloro-2-pyridyl, 2-chloro-4-pyridyl, 3-fluoro-4-pyridyl-4-pyridyl, 2, 6-dichloro-4-pyridyl.
Very particular preference is given to compounds of the formula (Ic) in which Z is1Is CF2CF3，Z2Is CF3，Z3Is CH3，R1、R6The radical is hydrogen (n = 0), A 1Is CH, A2Is N, A3Is C-H, C-Cl, C-F, C-CH3，A4Is C-H, C-F, C-OMe, W is oxygen and Q is methyl, ethyl, cyclopropyl, 1-chlorocyclopropyl, 1-cyanocyclopropyl, 2,2, 2-trifluoroethyl, 1,2, 2-tetrafluoroethyl, phenyl, 4-fluorophenyl, 2-fluorophenyl, 3, 5-difluorophenyl, 2, 6-difluorophenyl, 2-thienyl, 3-chloro-3-thienyl, 1-methyl-4-pyrazolyl, 4-pyridyl, 3-chloro-2-pyridyl, 2-chloro-4-pyridyl, 3-fluoro-4-pyridyl, 2, 6-dichloro-4-pyridyl.
Very particular preference is given to compounds of the formula (Ih) in which Z is1Is CF2CF3，Z2Is CF3，Z3Is CH3，R1、R6The radical is hydrogen (n = 0), A1、A2Is C-H, A3Is C-H, C-Cl, C-F, A4Is C-H, C-F, C-OMe, W is oxygen and Q is methyl, ethyl, cyclopropyl, 1-chlorocyclopropyl, 1-cyanocyclopropyl, 2,2, 2-trifluoroethyl, 1,2, 2-tetrafluoroethyl, phenyl, 4-fluorophenyl, 2-fluorophenyl, 3, 5-difluorophenyl, 2, 6-difluorophenyl, 2-, 3-thienyl, 3-chloro-3-thienyl, 1-methyl-4-pyrazolyl, 4-pyridyl, 3-chloro-2-pyridyl, 2-chloro-4-pyridyl, 3-fluoro-4-pyridyl, 2, 6-dichloro-4-pyridyl.
Very particular preference is given to compounds of the formula (Ih) in which Z is 1Is CF2CF3，Z2Is CF3，Z3Is CH3，R1、R6The radical is hydrogen (n = 0), A1Is CH, A2Is N, A3Is C-H, C-Cl, C-F, C-CH3，A4Is C-H, C-F, C-OMe, W is oxygen and Q is methyl, ethyl, cyclopropyl, 1-chlorocyclopropyl, 1-cyanocyclopropyl, 2,2, 2-trifluoroethyl, 1,2, 2-tetrafluoroethyl, phenyl, 4-fluorophenyl, 2-fluorophenyl, 3, 5-difluorophenyl, 2, 6-difluorophenyl, 2-thienyl, 3-chloro-3-thienyl, 1-methyl-4-pyrazolyl, 4-pyridyl, 3-chloro-2-pyridyl, 2-chloro-4-pyridyl, 3-fluoro-4-pyridyl, 2, 6-dichloro-4-pyridyl.
Definition of
According to the invention, "alkyl" -alone or as part of a chemical group-represents a straight-chain or branched hydrocarbon preferably having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl, 1-dimethylpropyl, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylpropyl, 1, 3-dimethylbutyl, 1, 4-dimethylbutyl, 2, 3-dimethylbutyl, 1-dimethylbutyl, 2, 2-dimethylbutyl, 3-dimethylbutyl, 1, 2-trimethylpropyl, 1,2, 2-trimethylpropyl, 1-ethylbutyl and 2-ethylbutyl. Preference is likewise given to alkyl having from 1 to 4 carbon atoms, such as, in particular, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. The alkyl groups of the present invention may be substituted by one or more groups which may be the same or different.
According to the invention, "alkenyl" -alone or as part of a chemical group-represents a straight-chain or branched hydrocarbon preferably having 2 to 6 carbon atoms and at least one double bond, such as vinyl, 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1-dimethyl-2-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1-dimethyl-2-butenyl, methyl-3-pentenyl, methyl-2-pentenyl, ethyl-3-pentenyl, ethyl-4-pentenyl, ethyl-, 1, 1-dimethyl-3-butenyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3-dimethyl-2-butenyl, 2-dimethyl-3-butenyl, 2, 3-dimethyl-2-butenyl, 2, 3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, and 1-ethyl-2-methyl-2-propenyl. Preference is likewise given to alkenyl having from 2 to 4 carbon atoms, such as, in particular, 2-propenyl, 2-butenyl or 1-methyl-2-propenyl. The alkenyl groups of the present invention may be substituted by one or more groups which may be the same or different.
According to the invention, "alkynyl" -alone or as part of a chemical group-represents a straight-chain or branched hydrocarbon preferably having 2 to 6 carbon atoms and at least one triple bond, such as 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1-dimethyl-3-butynyl, 1, 2-dimethyl-3-butynyl, 2-dimethyl-3-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl and 2, 5-hexadiynyl. Preference is likewise given to alkynyl having from 2 to 4 carbon atoms, such as, in particular, ethynyl, 2-propynyl or 2-butynyl-2-propenyl. The alkynyl groups of the present invention may be substituted by one or more groups which may be the same or different.
According to the invention, "cycloalkyl" -alone or as part of a chemical group-represents a mono-, di-or tricyclic hydrocarbon preferably having 3 to 10 carbons, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl or adamantyl. Likewise preferred are cycloalkyl groups having 3, 4, 5, 6 or 7 carbon atoms, such as, in particular, cyclopropyl or cyclobutyl. The cycloalkyl groups of the present invention may be substituted by one or more groups which may be the same or different.
According to the invention, "alkylcycloalkyl" represents mono-, bi-or tricyclic alkylcycloalkyl preferably having from 4 to 10 or from 4 to 7 carbon atoms, such as ethylcyclopropyl, isopropylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. Preference is likewise given to alkylcycloalkyl having 4, 5 or 7 carbon atoms, such as, in particular, ethylcyclopropyl or 4-methylcyclohexyl. The alkylcycloalkyl groups of the present invention may be substituted by one or more identical or different groups.
According to the invention, "cycloalkylalkyl" represents mono-, bi-or tricyclic cycloalkylalkyl preferably having 4 to 10 or 4 to 7 carbon atoms, such as cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl and cyclopentylethyl. Likewise preferred are cycloalkylalkyl radicals having 4, 5 or 7 carbon atoms, such as, in particular, cyclopropylmethyl or cyclobutylmethyl. The cycloalkylalkyl groups of the present invention may be substituted with one or more groups which may be the same or different.
According to the invention, "halogen" represents fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine.
Halogen-substituted chemical groups of the invention, such as haloalkyl, halocycloalkyl, haloalkoxy, haloalkylsulfanyl, haloalkylsulfinyl or haloalkylsulfonyl, are mono-or multiply substituted with halogen up to the maximum possible number of substituents. In the case of multiple substitution by halogen, the halogen atoms may be the same or different and may all be bonded to one or more carbon atoms. In this context, halogen is especially fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine.
According to the invention, "halocycloalkyl" represents a mono-, bi-or tricyclic halocycloalkyl preferably having 3 to 10 carbon atoms, such as in particular 1-fluorocyclopropyl, 2-fluorocyclopropyl or 1-fluorocyclobutyl. Also preferred are halocycloalkyl groups having 3, 5 or 7 carbon atoms. The halocycloalkyl groups of the present invention may be substituted by one or more groups which may be the same or different.
According to the invention, "haloalkyl", "haloalkenyl" or "haloalkynyl" represents halogen-substituted alkyl, alkenyl or alkynyl preferably having 1 to 9 identical or different halogen atoms, for example monohaloalkyl, such as CH2Cl, CH2F, CHClCH3, CHFCH3, CH2Cl, CH 2F; perhaloalkyl, such as CCl3 or CF3 or CF2CF 3; polyhaloalkyl groups such as CHF2, CH2F, CH2CHFCl, CHCl2, CF2H, CH2CF 3. The same applies to haloalkenyl and other halogenated groups. Haloalkoxy is, for example, OCF3, OCHF2, OCH2F, OCF2CF3, OCH2CF3 and OCH2CH2 Cl.
Further examples of haloalkyl are chlorodifluoromethyl, dichlorofluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 2,2, 2-trichloroethyl, 2-chloro-2, 2-difluoroethyl, pentafluoroethyl and pentafluoro-tert-butyl. Preferred are haloalkyl groups having 1 to 4 carbon atoms and 1 to 9, preferably 1 to 5, identical or different halogen atoms selected from fluorine, chlorine and bromine. Particularly preferred are haloalkyl groups having 1 or 2 carbon atoms and having 1 to 5 identical or different halogen atoms selected from fluorine and chlorine, such as, in particular, difluoromethyl, trifluoromethyl or 2, 2-difluoroethyl.
According to the invention, "hydroxyalkyl" represents a linear or branched alcohol preferably having 1 to 6 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol. Preference is likewise given to hydroxyalkyl having 1 to 4 carbon atoms. The hydroxyalkyl groups of the present invention may be substituted by one or more groups which may be the same or different.
According to the invention, "alkoxy" represents a straight-chain or branched O-alkyl radical preferably having 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy. Also preferred are alkoxy groups having 1 to 4 carbon atoms. The alkoxy groups of the present invention are substituted with one or more groups which may be the same or different.
According to the invention, "haloalkoxy" represents halogenated straight-chain or branched O-alkyl preferably having 1 to 6 carbon atoms, such as, in particular, difluoromethoxy, trifluoromethoxy, 2, 2-difluoroethoxy, 1,2, 2-tetrafluoroethoxy, 2,2, 2-trifluoroethoxy and 2-chloro-1, 1, 2-trifluoroethoxy. Also preferred are haloalkoxy groups having 1 to 4 carbon atoms. The haloalkoxy groups of the present invention may be substituted with one or more groups which may be the same or different.
According to the invention, "alkylsulfanyl" represents a straight-chain or branched S-alkyl group preferably having 1 to 6 carbon atoms, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, and tert-butylthio. Also preferred are alkylsulfanyl groups having 1 to 4 carbon atoms. The alkylsulfanyl groups of the invention may be substituted by one or more of the same or different groups.
Examples of haloalkylthio, i.e. halogen-substituted alkylsulfanyl are especially difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, 1-fluoroethylthio, 2, 2-difluoroethylthio, 1,2, 2-tetrafluoroethylthio, 2,2, 2-trifluoroethylthio or 2-chloro-1, 1, 2-trifluoroethylthio.
According to the invention, "alkylsulfinyl" represents a linear or branched alkylsulfinyl group preferably having 1 to 6 carbon atoms, such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl and tert-butylsulfinyl. Preference is likewise given to alkylsulfinyl having 1 to 4 carbon atoms. The alkylsulfinyl groups of the present invention may be substituted by one or more groups which may be the same or different.
Examples of haloalkylsulfinyl, i.e. halogen-substituted alkylsulfinyl, are, in particular, difluoromethylsulfinyl, trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, 1-fluoroethylsulfinyl, 2, 2-difluoroethylsulfinyl, 1,2, 2-tetrafluoroethylsulfinyl, 2,2, 2-trifluoroethylsulfinyl and 2-chloro-1, 1, 2-trifluoroethylsulfinyl.
According to the invention, "alkylsulfonyl" represents straight-chain or branched alkylsulfonyl preferably having 1 to 6 carbon atoms, such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl and tert-butylsulfonyl. Also preferred are alkylsulfonyl groups having 1 to 4 carbon atoms. The alkylsulfonyl groups of the present invention may be substituted by one or more groups which may be the same or different.
Examples of haloalkylsulfonyl, i.e. halogen-substituted alkylsulfonyl, are especially difluoromethylsulfonyl, trifluoromethylsulfonyl, sulfonyl, chlorodifluoromethylsulfonyl, 1-fluoroethylsulfonyl, 2, 2-difluoroethylsulfonyl, 1,2, 2-tetrafluoroethylsulfonyl, 2,2, 2-trifluoroethylsulfonyl and 2-chloro-1, 1, 2-trifluoroethylsulfonyl.
According to the invention, "alkylcarbonyl" represents a straight-chain or branched alkyl group-C (= O) preferably having 2 to 7 carbon atoms, such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, sec-butylcarbonyl and tert-butylcarbonyl. Also preferred are alkylcarbonyl groups having 1 to 4 carbon atoms. The alkylcarbonyl groups of the invention may be substituted by one or more groups which may be the same or different.
According to the invention, "cycloalkylcarbonyl" represents a straight-chain or branched cycloalkylcarbonyl group preferably having 3 to 10 carbon atoms in the cycloalkyl moiety, such as cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cycloheptylcarbonyl, cyclooctylcarbonyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octylcarbonyl and adamantylcarbonyl. Also preferred are cycloalkylcarbonyl groups having 3, 5, or 7 carbon atoms in the cycloalkyl moiety. The cycloalkylcarbonyl groups of the present invention may be substituted with one or more groups which may be the same or different.
According to the invention, "alkoxycarbonyl" -alone or as part of a chemical group represents a linear or branched alkoxycarbonyl group preferably having 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkoxy moiety, such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, sec-butoxycarbonyl and tert-butoxycarbonyl. The alkoxycarbonyl groups of the present invention may be substituted by one or more identical or different groups.
According to the invention, "alkylaminocarbonyl" represents a linear or branched alkylaminocarbonyl group preferably having 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkyl moiety, such as methylaminocarbonyl, ethylaminocarbonyl, n-propylaminocarbonyl, isopropylaminocarbonyl, sec-butylaminocarbonyl and tert-butylaminocarbonyl. The alkylaminocarbonyl groups according to the invention can be substituted by one or more identical or different radicals.
According to the invention, "N, N-dialkylaminocarbonyl" represents a straight-chain or branched N, N-dialkylaminocarbonyl group, preferably having 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkyl moiety, such as N, N-dimethylaminocarbonyl, N-diethylaminocarbonyl, N-di (N-propylamino) carbonyl, N-di (isopropylamino) carbonyl and N, N-di (sec-butylamino) carbonyl. The N, N-dialkylaminocarbonyl groups of the invention may be substituted by one or more groups which may be the same or different.
According to the invention, "aryl" represents a mono-, bi-or polycyclic aromatic system, preferably having 6 to 14, in particular 6 to 10, ring carbon atoms, for example phenyl, naphthyl, anthryl, phenanthryl, preferably phenyl. In addition, aryl represents polycyclic systems such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenyl, where the bonding point is on an aromatic system. Also included are bicyclic carbocycles (containing only carbon as ring atoms), in which one ring is aryl and the second ring is not aryl, e.g. tetrahydronaphthyl (C) 10H11) Wherein the point of bonding may be on an aromatic or non-aromatic ring. The aryl groups of the present invention may be substituted by one or moreThe same or different groups.
Examples of substituted aryl are arylalkyl which may likewise be substituted by one or more identical or different radicals in the alkyl and/or aryl moiety. Examples of such arylalkyl groups include benzyl and 1-phenylethyl.
According to the invention, a "heterocycle", "heterocyclic ring" or "heterocyclic ring system" (heterocyclyl) represents a carbocyclic ring system having at least one ring in which at least one carbon atom has been replaced by a heteroatom, preferably a heteroatom selected from N, O, S, P, B, Si, Se and which is saturated or partially unsaturated and may at the same time be unsubstituted or substituted by another substituent (wherein the bonding point is located on a ring atom). Unless otherwise specified, the heterocyclic ring contains preferably 3 to 9 ring atoms, in particular 3 to 6 ring atoms, and one or more, preferably 1 to 4, in particular 1,2 or 3, heteroatoms in the heterocyclic ring, preferably selected from N, O and S, but wherein no two oxygen atoms are directly adjacent. The heterocyclic ring generally contains not more than 4 nitrogen atoms and/or not more than 2 oxygen atoms and/or not more than 2 sulfur atoms. If the heterocyclyl or heterocyclic ring is optionally substituted, it may be fused to other carbocyclic or heterocyclic rings. In the case of optionally substituted heterocyclyl radicals, the present invention also includes optionally substituted polycyclic, preferably bicyclic, heterocycles, such as 8-azabicyclo [3.2.1] octyl or 1-azabicyclo [2.2.1] heptyl, benzothienyl, for example benzothien-2-yl, benzofuranyl, for example benzofuran-2-yl, [1,2,4] triazolo [1,5-a ] pyrimidinyl, for example [1,2,4] triazolo [1,5-a ] pyrimidin-2-yl, 1, 3-benzodioxolyl, for example 1, 3-benzodioxol-5-yl. In the case of optionally substituted heterocyclyl, the invention also includes spiro ring systems, such as 1-oxa-5-azaspiro [2.3] hexyl.
Heterocyclyl groups according to the invention are, for example, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, pyrrolinyl, pyrrolidinyl, imidazolinyl, imidazolidinyl, thiazolidinyl, oxazolidinyl, dioxolanyl, dioxolyl, pyrazolidinyl, tetrahydrofuranyl, dihydrofuranyl, oxetanyl, azetidinyl, aziridinyl, oxazepanyl (Oxazinanyl), azepanyl, oxopyrrolidinyl, dioxopyrrolidinyl, oxopiperazinyl and Oxepanyl (Oxetapanyl).
Of particular interest are heteroaryl, i.e., heteroaromatic systems. According to the invention, the term "heteroaryl" represents a heteroaromatic compound, i.e. a fully unsaturated aromatic heterocyclic compound encompassed by the above definition of heterocycle. Preference is given to 5-to 7-membered rings having 1 to 3, preferably 1 or 2, heteroatoms which may be identical or different from those mentioned. Heteroaryl groups according to the invention are, for example, furyl, thienyl, pyrazolyl, imidazolyl, 1,2, 3-and 1,2, 4-triazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,3,4-, 1,2, 4-and 1,2, 5-oxadiazolyl, Azepinyl, pyrrolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-, 1,2, 4-and 1,2, 3-triazinyl, 1,2,4-, 1,3,2-, 1,3, 6-and 1,2, 6-oxazinyl, Oxepinyl (Oxepinyl), Thiepinyl (Thiepinyl), 1,2, 4-triazolonyl and 1,2, 4-Diazepinyl (Diazepinyl). The heteroaryl groups of the present invention may also be substituted by one or more groups which may be the same or different.
Substituted radicals, such as substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl, mean substituted radicals, for example, derived from unsubstituted basic structures, where the substituents are, for example, selected from the group consisting of halogen, oxo (O =), alkoxy, alkylsulfanyl, hydroxy, amino, nitro, carboxy or a group equivalent to carboxy, cyano, isocyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono-and N, N-dialkylaminocarbonyl, substituted amino, such as acylamino, mono-and N, N-dialkylamino, trialkylsilyl and optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted heterocyclyl, where the latter cyclic groups may also be bonded via a heteroatom or divalent function as is the case for the alkyl mentioned, and alkylsulfinyl (including both enantiomers of alkylsulfinyl), Alkylsulfonyl, alkylphosphinyl, alkylphosphonyl and, in the case of cyclic groups (= "cyclic base structures"), one or more, preferably 1, 2 or 3, groups of alkyl, haloalkyl, alkylsulfanyl, alkoxyalkyl, optionally substituted mono-and N, N-dialkylaminoalkyl and hydroxyalkyl.
The term "substituted radicals", such as substituted alkyl, cycloalkyl, aryl, heteroaryl and the like, in addition to the saturated hydrocarbon-containing radicals mentioned also includes the corresponding unsaturated aliphatic and aromatic radicals, such as in each case optionally substituted alkenyl, alkynyl, oxo (O =), alkoxy, alkenyloxy, alkynyloxy, aryloxy (for example phenoxy (phenyl-O-), benzyloxy (C)6H5-CH2-O-), alkylthio, alkenylthio, alkynylthio, arylthio (e.g. phenylthio (phenyl-S-)), alkenyloxycarbonyl, alkynyloxycarbonyl, alkenylcarbonyl, alkynylcarbonyl, mono-and N, N-dialkenylaminocarbonyl, mono-and dialkynylaminocarbonyl, mono-and N, N-dialkynylamino, trialkynylsilyl, trialkylsilyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heteroaryl, aryl such as phenyl, phenoxy and the like as substituents. In the case of substituted cyclic groups having aliphatic moieties in the ring, also included are cyclic systems having such substituents bonded to the ring by single bonds on the ring, double bonds on the ring, for example by an alkylidene such as a methylidene or ethylidene or oxo bridge, imino or substituted imino group, or cyclic systems having such substituents wherein the second ring is bonded to two different atoms of the cyclic group through two different atoms, for example naphthyl or tetrahydronaphthyl (e.g. 1,2,3, 4-tetrahydronaphthalen-1-yl).
If two or more radicals form one or more rings, these may be carbocyclic, heterocyclic, saturated, partially saturated, unsaturated, e.g. as well as aromatic and further substituted.
The substituents mentioned by way of example ("first substituent stage"), if they contain a hydrocarbon-containing moiety, may optionally be further substituted therein ("second substituent stage"), for example by one of the substituents as specified for the first substituent stage. Corresponding further substituent orders are possible. The term "substituted group" preferably comprises only one or two substituent steps.
Preferred substituents for these substituent classes are, for example
Amino, hydroxy, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, carboxy, carboxamide, SF5, aminosulfonyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, N-mono-alkylamino, N-dialkylamino, N-alkanoylamino, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryloxycarbonyl, alkanoyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, alkylsulfanyl, cycloalkylsulfanyl, alkenylthio, cycloalkenylthio, alkynylthio, alkylthio and alkylsulfinyl (including both enantiomers of alkylsulfinyl), alkylsulfonyl, N-monoalkylaminosulfonyl, N-dialkylaminosulfonyl, alkylphosphinyl, phosphinyl, alkoxycarbonyl, aminocarbonyl, alkoxycarbonyloxy, alkynyloxycarbonyl, aryloxycarbonyl, alkoxycarbonyloxy, aryloxycarbonyl, alkoxycarbonyl, alkenylcarbonyl, alkynylthio, arylcarbonyl, Alkylphosphono groups (including both enantiomers of alkylphosphono groups and alkylphosphono groups), N-alkylaminocarbonyl, N-dialkylaminocarbonyl, N-alkanoylaminocarbonyl, N-alkanoyl-N-alkylaminocarbonyl, aryl, aryloxy, benzyl, benzyloxy, benzylthio, arylthio, arylamino, benzylamino, heterocyclic groups and trialkylsilyl groups.
The substituent composed of a plurality of substituent groups is preferably alkoxyalkyl, alkylthioalkyl, alkylthioalkylalkoxy, alkoxyalkoxy, phenethyl, benzyloxy, haloalkyl, halocycloalkyl, haloalkoxy, haloalkylthioalkyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkanoyl, haloalkylcarbonyl, haloalkoxycarbonyl, haloalkoxyalkoxy, haloalkoxyalkylsulfanyl, haloalkoxyalkanoyl, haloalkoxyalkyl or haloalkoxyalkyl.
In the case of groups having carbon atoms, preference is given to those having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms. Preference is generally given to compounds selected from the group consisting of halogen, such as fluorine and chlorine, (C)1-C4) Alkyl, preferably methyl or ethyl, (C)1-C4) Haloalkyl, preferably trifluoromethyl, (C)1-C4) Alkoxy, preferably methoxy or ethoxy, (C)1-C4) Haloalkoxy, nitro and cyano. Particular preference is given to the substituents methyl, methoxy, fluorine and chlorine.
Substituted amino, such as mono-or di-substituted amino, is, for example, amino N-substituted with one or two identical or different groups selected from alkyl, hydroxy, amino, alkoxy, acyl and aryl; preferably N-mono-and N, N-dialkylamino (for example methylamino, ethylamino, N-dimethylamino, N-diethylamino, N-di-N-propylamino, N-diisopropylamino or N, N-dibutylamino), N-mono-or N, N-dialkoxyalkylamino (for example N-methoxymethylamino, N-methoxyethylamino, N-di (methoxymethyl) amino or N, N-di (methoxyethyl) amino), N-mono-and N, N-diarylamino, such as optionally substituted anilines, acylamino, N-diamido, N-alkyl-N-arylamino, N-alkyl-N-acylamino and saturated N-heterocycles; preferred are alkyl groups having 1 to 4 carbon atoms; aryl is preferably phenyl or substituted phenyl; acyl is as further defined below, preferably (C) 1-C4) An alkanoyl group. The same applies to substituted hydroxyamino or hydrazino groups.
According to the invention, the term "cyclic amino" includes heteroaromatic or aliphatic ring systems having one or more nitrogen atoms. The heterocyclic ring is saturated or unsaturated, is composed of one or more optionally fused ring systems and optionally contains further heteroatoms, for example one or two nitrogen, oxygen and/or sulfur atoms. In addition, the term also includes those groups having spiro or bridged ring systems. The number of atoms forming the cyclic amino group is arbitrary, and may be constituted, for example, by 3 to 8 ring atoms in the case of a monocyclic system, and 7 to 11 atoms in the case of a bicyclic system.
Examples of the cyclic amino group having a saturated and unsaturated monocyclic group containing a nitrogen atom as a hetero atom include 1-azetidinyl, pyrrolidinyl (pyrolidino), 2-pyrrolidin-1-yl, 1-pyrrolyl, piperidinyl (Piperidino), 1, 4-dihydropyrazin-1-yl, 1,2,5, 6-tetrahydropyrazin-1-yl, 1, 4-dihydropyridin-1-yl, 1,2,5, 6-tetrahydropyridin-1-yl, homopiperidinyl; examples of the cyclic amino group having saturated and unsaturated monocyclic groups having two or more nitrogen atoms as hetero atoms include 1-imidazolidinyl, 1-imidazolyl, 1-pyrazolyl, 1-triazolyl, 1-tetrazolyl, 1-piperazinyl, 1-homopiperazinyl, 1, 2-dihydropiperazin-1-yl, 1, 2-dihydropyrimidin-1-yl, perhydropyrimidin-1-yl, 1, 4-diazepan-1-yl; examples of cyclic amino groups having saturated and unsaturated monocyclic groups containing one or two oxygen atoms and one to three nitrogen atoms as heteroatoms are, for example, oxazolidin-3-yl, 2, 3-dihydroisoxazol-2-yl, isoxazol-2-yl, 1,2, 3-oxadiazin-2-yl, morpholinyl (Morpholino), examples of cyclic amino groups having saturated and unsaturated monocyclic groups containing one to three nitrogen atoms and one to two sulfur atoms as heteroatoms include thiazolidin-3-yl, isothiazolin-2-yl, thiomorpholinyl or dioxothiomorpholinyl; examples of the cyclic amino group having a saturated and unsaturated fused ring group include indol-1-yl, 1, 2-dihydrobenzimidazol-1-yl, perhydropyrrolo [1,2-a ] pyrazin-2-yl; examples of cyclic amino groups having a spiro group include 2-azaspiro [4.5] decan-2-yl; examples of cyclic amino groups having a bridged heterocyclic group include 2-azabicyclo [2.2.1] hept-7-yl.
Substituted amino groups also include quaternary ammonium compounds (salts) having four organic groups on the nitrogen atom.
The optionally substituted phenyl radical is preferably unsubstituted or selected from halogen, (C)1-C4) Alkyl, (C)1-C4) Alkoxy group, (C)1-C4) Alkoxy radical- (C1-C4) Alkoxy group, (C)1-C4) Alkoxy radical- (C1-C4) Alkyl, (C)1-C4) Haloalkyl, (C)1-C4) Haloalkoxy, (C)1-C4) Alkylsulfanyl group, (C)1-C4) Haloalkyl sulfanyl, cyano, isocyano and nitro are mono-or multiply substituted, preferably up to three-fold substituted, phenyl, for example o-, m-and p-tolyl, dimethylphenyl, 2-, 3-and 4-chlorophenyl, 2-, 3-and 4-fluorophenyl, 2-, 3-and 4-trifluoromethylphenyl, 2,4-, 3,5-, 2, 5-and 2, 3-dichlorophenyl, o-, m-and p-methoxyphenyl.
Optionally substituted cycloalkyl is preferably unsubstituted or selected from halogen, cyano, (C)1-C4) Alkyl, (C)1-C4) Alkoxy group, (C)1-C4) Alkoxy radical- (C1-C4) Alkoxy group, (C)1-C4) Alkoxy radical- (C1-C4) Alkyl, (C)1-C4) Haloalkyl and (C)1-C4) Identical or different radicals of haloalkoxy, especially by one or two (C)1-C4) Alkyl is mono-or multiply substituted, preferably up to three times substituted cycloalkyl.
The optionally substituted heterocyclic radical is preferably unsubstituted or selected from halogen, cyano, (C) 1-C4) Alkyl, (C)1-C4) Alkoxy group, (C)1-C4) Alkoxy radical- (C1-C4) Alkoxy group, (C)1-C4) Alkoxy radical- (C1-C4) Alkyl, (C)1-C4) Haloalkyl, (C)1-C4) The same or different radicals of haloalkoxy, nitro and oxo are mono-or multiply substituted, preferably up to three-fold substituted, in particular by radicals selected from halogen, (C)1-C4) Alkyl, (C)1-C4) Alkoxy group, (C)1-C4) The radicals haloalkyl and oxo are very particularly substituted by one or two (C)1-C4) Alkyl mono-or polysubstituted heterocyclyl.
Examples of alkyl-substituted heteroaryl groups are furylmethyl, thienylmethyl, pyrazolylmethyl, imidazolylmethyl, 1,2, 3-and 1,2, 4-triazolylmethyl, isoxazolylmethyl, thiazolylmethyl, isothiazolylmethyl, 1,2,3-, 1,3,4-, 1,2, 4-and 1,2, 5-oxadiazolylmethyl, azepinylmethyl, pyrrolylmethyl, pyridylmethyl, pyridazinylmethyl, pyrimidinylmethyl, pyrazinylmethyl, 1,3,5-, 1,2, 4-and 1,2, 3-triazinylmethyl, 1,2,4-, 1,3,2-, 1,3, 6-and 1,2, 6-oxazinylmethyl, oxepitrienylmethyl, thiepinyltrienylmethyl and 1,2, 4-diazepatrienylmethyl.
The salts of the compounds of the invention which are suitable according to the invention, for example salts with bases or acid addition salts, are all customary non-toxic salts, preferably agriculturally and/or physiologically acceptable salts. For example, a salt or acid addition salt with a base. Preference is given to salts with inorganic bases, for example alkali metal salts (for example sodium, potassium or cesium salts), alkaline earth metal salts (for example calcium or magnesium salts), ammonium salts or salts with organic bases, especially with organic amines, for example triethylammonium, dicyclohexylammonium, N' -dibenzylethylenediamine-diammonium, pyridinium, picolinium or ethanolammonium salts, salts with inorganic acids (for example hydrochlorides, hydrobromides, dihydrosulfates, trihydrosulfates or phosphates), salts with organic carboxylic acids or organic sulfonic acids (for example formates, acetates, trifluoroacetates, maleates, tartrates, methanesulfonates, benzenesulfonates or 4-toluenesulfonate salts). As is well known, tertiary amines, such as some of the compounds of the present invention, may form N-oxides, which are also salts of the present invention.
Depending on the nature of the substituents, the compounds of the invention may be in the form of geometrical and/or optically active isomers or corresponding isomer mixtures of different composition. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers. The present invention thus includes both the pure stereoisomers and any mixture of these isomers.
The compounds of the invention may optionally be present in different polymorphic forms or as a mixture of different polymorphic forms. The present invention provides both pure polymorphs and polymorph mixtures and may be used according to the present invention.
Aspect 1 relates to compounds of the general formula (I)
Wherein
R1Is hydrogen, optionally substituted C1-C6Alkyl radical, C3-C6-alkenyl, C3-C6-alkynyl, C3-C7-cycloalkyl, C1-C6-alkylcarbonyl group, C1-C6Alkoxycarbonyl, aryl- (C)1-C3) -alkyl, heteroaryl- (C)1-C3) -alkyl, most preferably hydrogen;
chemical moieties
A1Is CR2Or a nitrogen-containing compound,
A2is CR3Or a nitrogen-containing compound,
A3is CR4Or nitrogen, and
A4is CR5Or a nitrogen-containing compound,
but wherein the chemical moiety A1To A4Not more than three of which are simultaneously nitrogen;
R2、R3、R4and R5Independently of one another, hydrogen, halogen, cyano, nitro, optionally substituted C1-C6Alkyl radical, C3-C6-cycloalkyl, C1-C6-alkoxy groups,N-C1-C6-alkoxyimino-C 1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N-C1-C6-alkylamino radicalOrN,N-di-C1-C6-an alkylamino group;
if A is2And A3None of the moieties being nitrogen, R3And R4May form, together with the carbon atom to which they are attached, a 5-or 6-membered ring containing 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and/or 0 or 1 sulfur atom, or
If A is1And A2None of the moieties being nitrogen, R2And R3May form, together with the carbon atom to which they are attached, a 5-or 6-membered ring containing 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and/or 0 or 1 sulfur atom;
w is oxygen or sulfur;
q is hydrogen, amino or one of the following optionally substituted moieties: alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, heterocyclyl, cycloalkylalkyl, arylalkyl, heteroarylalkyl, alkoxycarbonyl, or isN-alkylamino, alkylamino,N-alkylcarbonylamino,N,N-a dialkylamino, alkylsulfonylamino moiety; or
Q is aryl optionally mono-to pentasubstituted with V, or heteroaryl optionally mono-to pentasubstituted with V, wherein
V is halogen, cyano, nitro, optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, or a pharmaceutically acceptable salt thereof,NAn alkoxyiminoalkyl group, an alkylsulfanyl group, an alkylsulfinyl group, an alkylsulfonyl group, a substituted aryl group, N,N-a dialkylamino group;
t is one of the 5-membered heteroaromatic compounds T1 to T10, wherein the bond to the pyrazolyl head group is indicated by an asterisk,
wherein
R6Independently of one another, halogen, cyano, nitro, amino or optionally substituted C1-C6Alkyl radical, C1-C6-alkoxy, C1-C6-alkylcarbonyl group, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
n has a value of 0-2;
Z1is optionally substituted alkyl or cycloalkyl, and
Z2is hydrogen, halogen, cyano, nitro, amino or optionally substituted alkyl, alkylcarbonyl, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, and
Z3is hydrogen or optionally substituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl.
Aspect 2 relates to the compound according to aspect 1, wherein
R1Is hydrogen or C optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl1-C6Alkyl radical, C3-C6-alkenyl, C3-C6-alkynyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C3Alkyl radical, C1-C6-alkylcarbonyl group, C1-C6Alkoxycarbonyl, aryl (C)1-C3) Alkyl, heteroaryl (C)1-C3) -alkyl, most preferably hydrogen;
chemical moieties
A1Is CR2Or a nitrogen-containing compound,
A2is CR3Or a nitrogen-containing compound,
A3is CR4Or nitrogen, and
A4is CR5Or a nitrogen-containing compound,
but wherein the chemical moiety A 1To A4Is not more than threeEach simultaneously being nitrogen;
R2、R3、R4and R5Independently of one another, hydrogen, halogen, cyano, nitro or C which is optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl1-C6Alkyl radical, C3-C6-cycloalkyl, C1-C6-alkoxy groups,N-C1-C6-alkoxyimino-C1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N-C1-C6-alkylamino orN,N-di-C1-C6-an alkylamino group;
w is oxygen or sulfur;
q is hydrogen, amino or one of the following moieties optionally mono-to heptaly substituted independently of one another by hydroxy, nitro, amino, halogen, alkoxy, cyano, hydroxycarbonyl, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbamoyl, phenyl: c1-C6Alkyl radical, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C2-C5-heterocyclyl radical, C1-C4-alkoxy, C1-C6-alkyl-C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6Alkyl radical, C1-C6Hydroxyalkyl, aryl (C)1-C3) Alkyl, heteroaryl (C)1-C3) Alkyl radical, C1-C4-an alkoxycarbonyl group,N-C1-C4-alkylamino, alkylamino,N-C1-C4-alkylcarbonylamino,N,N-di-C1-C4-alkylamino radical, C1-C4-an alkylsulfonylamino group; or
Q is aryl substituted with 0, 1, 2, 3 or 4 substituents V or 5-or 6-membered heteroaryl substituted with 0, 1, 2, 3 or 4 substituents V, wherein
V is independently halogen, cyano, nitro or C optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy groups,N-C1-C6-alkoxyimino-C1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N , N-di- (C)1-C6-alkyl) amino;
t is one of the 5-membered heteroaromatic compounds T1 to T10, wherein the bond to the pyrazolyl head group is indicated by an asterisk,
wherein
R6Independently of one another, halogen, cyano, nitro, amino or C optionally mono-to heptasubstituted by halogen1-C6Alkyl radical, C1-C6-alkoxy, C1-C6-alkylcarbonyl group, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
n has a value of 0-1;
Z1is C optionally mono-to heptasubstituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl1-C6Alkyl radical, C3-C6-a cycloalkyl radical, and
Z2is hydrogen, halogen, cyano, nitro, amino or C which is mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C1-C6-alkylcarbonyl group, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
Z3is hydrogen or C optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl 1-C6Alkyl radical, C3-C6-cycloalkyl, C3-C4-alkenyl, C3-C4-alkynyl, or aryl and heteroaryl optionally mono-to penta-substituted independently of each other by halogen, cyano, alkoxy and alkoxycarbonyl.
Aspect 3 relates to the compound according to aspect 1 or 2, wherein
R1Is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, prop-2-enyl, 2-methylprop-2-enyl, prop-2-ynyl, methoxymethyl, ethoxymethyl, propoxymethyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, sec-butylcarbonyl, tert-butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, cyanomethyl, 2-cyanoethyl, benzyl, 4-methoxybenzyl, pyridin-2-ylmethyl, pyridin-3-ylmethyl, pyridin-4-ylmethyl, 4-chloropyridin-3-ylmethyl, most preferably hydrogen;
chemical moieties
A1Is CR2Or a nitrogen-containing compound,
A2is CR3Or a nitrogen-containing compound,
A3is CR4Or nitrogen, and
A4is CR5Or a nitrogen-containing compound,
but wherein the chemical moiety A1To A4Not more than three of which are simultaneously nitrogen;
R2and R5Independently of one another are hydrogen, fluorine, chlorine, bromine, iodine, methyl and methoxy and
R3and R 4Independently of one another, hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, fluoromethyl, difluoromethyl, chlorodifluoromethyl, trifluoromethyl, 2,2, 2-trifluoroethyl, methoxy, ethoxy, n-propoxy, 1-methylethoxy, fluoromethoxy, difluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, trifluoromethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2, 2-difluoroethoxy, pentafluoroethoxy, n-fluoroethoxy, n-chloroethoxy, 2-chloro-2, 2-difluoroethoxy, n-fluoroethoxy, n-chloroethoxy, n,NMethoxy imino methyl, 1-, (N-methoxyimino) ethyl, methylsulfanyl, trifluoromethylsulfanyl, methylsulfonyl, methylsulfinyl, trifluoromethylsulfonyl, trifluoromethylsulfinyl;
w is oxygen or sulfur;
q is hydrogen, methyl, ethyl, n-propyl, 1-methylethyl, 1-dimethylethyl, 1-methylpropyl, n-butyl, 2-methylpropyl, 2-methylbutyl, hydroxymethyl, 2-hydroxypropyl, cyanomethyl, 2-cyanoethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2, 2-tetrafluoroethyl, 1-trifluoromethylethyl, 2, 2-difluoropropyl, 3,3, 3-trifluoropropyl, 2, 2-dimethyl-3-fluoropropyl, cyclopropyl, 1-cyanocyclopropyl, 1-chlorocyclopropyl, 1-methylcyclopropyl, 1-methoxycarbonylcyclopropyl, 1- (R) cyclopropyl N-methylcarbamoyl) cyclopropyl, 1-, (N-cyclopropylcarbamoyl) cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-cyclopropylethyl, bis (cyclopropyl) methyl, 2-dimethylcyclopropylmethyl, 2-phenylcyclopropyl, 2-dichlorocyclopropyl, trans-2-chlorocyclopropyl, cis-2-chlorocyclopropyl, 2-difluorocyclopropyl, trans-2-fluorocyclopropyl, cis-2-fluorocyclopropyl, trans-4-hydroxycyclohexyl, 4-trifluoromethylcyclohexyl, prop-2-enyl, 2-methylprop-2-enyl, prop-2-ynyl, 1-dimethylbut-2-ynyl, 3-chloroprop-2-enyl, cyclopentyl, cyclohexyl, 1-cyclopropylethyl, bis (cyclopropyl) methyl, 2-difluorocyclopropyl, 2-chlorocyclopropyl, trans-2-fluorocyclopropyl, cis-2-fluorocyclopropyl, trans-4-hydroxycyclohexyl, 4-trifluoromethylcyclohexyl, prop-2-enyl, prop-2, 3, 3-dichloroprop-2-enyl, 3-dichloro-1, 1-dimethylprop-2-enyl, oxetan-3-yl, thietane-3-yl, 1-thietane-3-yl, 1-Thien-3-yl, isoxazol-3-ylmethyl, 3-methyloxetan-3-ylmethyl, benzyl, 2, 6-difluorophenylmethyl, 3-fluorophenylmethyl, 2, 5-difluorophenylmethyl, 1-phenylethyl, 4-chlorophenylethyl, 2-trifluoromethylphenylethyl, pyridin-2-ylethyl, pyridin-2-ylmethyl, 5-fluoropyridin-2-ylmethyl, (6-chloropyridin-3-yl) methyl, pyrimidin-2-ylmethyl, methoxy, 2-ethoxyethyl, 2- (methylsulfanyl) ethyl, 1-methyl-2- (ethylsulfanyl) ethyl, 3-methyloxetan-3-ylmethyl, benzyl, 2-trifluoromethyloxetan-2-ylethyl, pyridin-2-ylmethyl, pyrimidin-2-ylmethyl, methoxy, 2-ethoxy, 2-methyl-1- (methylsulfanyl) propan-2-yl, methoxycarbonyl, methoxycarbonylmethyl, NH 2、N-an ethylamino group,N-allylamino group,N,N-dimethylamino group,N,N-diethylamino, methylsulfonylamino; or
Q is the following group substituted with 0, 1,2, 3 or 4V substituents: phenyl, naphthyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, pyridyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, imidazolyl, furanyl, thienyl, pyrrolyl, oxadiazolyl, thiadiazolyl, wherein
V is, independently of one another, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2,2, 2-tetrafluoroethyl, 1-chloro-1, 2,2, 2-tetrafluoroethyl, 2,2, 2-trichloroethyl, 2-chloro-2, 2-difluoroethyl, 1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, n-propoxy, 1-methylethoxy, fluoromethoxy, difluoromethoxy, Chlorodifluoromethoxy, dichlorofluoromethoxy, trifluoromethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2, 2-difluoroethoxy, pentafluoroethoxy, m, NMethoxy imino methyl, 1-, (N-methoxyimino) ethyl, methylsulfanyl, methylsulphonyl, methylsulphinyl, trifluoromethylsulphonyl, trifluoromethylsulphinyl, trifluoromethylsulfanyl, N-dimethylamideA group;
t is one of the 5-membered heteroaromatic compounds T1 to T10, wherein the bond to the pyrazolyl head group is indicated by an asterisk,
wherein
R6Independently of one another, halogen, cyano, nitro, amino, methyl, ethyl, 1-methylethyl, tert-butyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, trifluoromethoxy, 2, 2-difluoroethoxy, 2,2, 2-trifluoroethoxy, methylcarbonyl, ethylcarbonyl, trifluoromethylcarbonyl, methylsulfanyl, methylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, and
n has a value of 0-1;
Z1is methyl, ethyl, 1-dimethylethyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, bromodichloromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 1-fluoro-1-methylethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2,2, 2-tetrafluoroethyl, 1-chloro-1, 2,2, 2-tetrafluoroethyl, 2,2, 2-trichloroethyl, 2-chloro-2, 2-difluoroethyl, 1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, cyclopropyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl, 1-bromocyclopropyl, 1-cyanocyclopropyl, 1-trifluoromethylcyclopropyl, cyclobutyl and 2, 2-difluoro-1-methylcyclopropyl, and
Z2Is hydrogen, halogen, cyano, nitro, amino, methyl, ethyl, 1-dimethylethyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, bromodichloromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 1-fluoro-1-methylethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2,2, 2-tetrafluoroethyl, 1-chloro-1, 2,2, 2-tetrafluoroethyl, 2,2, 2-trichloro-ethylEthyl, 2-chloro-2, 2-difluoroethyl, 1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, methylsulfanyl, methylsulfinyl, methylsulfonyl, ethylthio, ethylsulfinyl, ethylsulfonyl, trifluoromethylsulfanyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfanyl, chlorodifluoromethylsulfinyl, chlorodifluoromethylsulfonyl, dichlorofluoromethylsulfanyl, dichlorofluoromethylsulfinyl, dichlorofluoromethylsulfonyl and
Z3is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, vinyl, 1-propenyl, 2-propenyl, 1-propynyl, 1-butynyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 1-fluoro-1-methylethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2, 5-dichlorophenyl, 2, 4-dichlorophenyl, 3-4-dichlorophenyl, 2, 6-dichlorophenyl, 2-6-dichloro-4-trifluoromethylphenyl, 3-chloro-5-trifluoromethylpyridin-2-yl.
Aspect 4 relates to a compound according to any one of aspects 1 to 3, wherein
Z1Is trifluoromethyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl or pentafluoroethyl;
Z2is trifluoromethyl, nitro, methylsulfanyl, methylsulfinyl, methylsulfonyl, fluoro, chloro, bromo, cyano or iodo;
Z3is methyl, ethyl, n-propyl or hydrogen;
R1is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, prop-2-enyl, 2-methylprop-2-enyl, prop-2-ynyl, methoxymethyl, ethoxymethyl, propoxymethyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, sec-butylcarbonyl, tert-butylcarbonyl, methoxycarbonyl, ethylcarbonylOxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, cyanomethyl, 2-cyanoethyl, benzyl, 4-methoxybenzyl, pyridin-2-ylmethyl, pyridin-3-ylmethyl, pyridin-4-ylmethyl, 4-chloropyridin-3-ylmethyl, most preferably hydrogen;
A1and A2Each is CH;
A3is CR4And is
A4Is CR5；
R4Is hydrogen, fluorine, chlorine, bromine, iodine or cyano;
R5is hydrogen, fluorine, chlorine, bromine, iodine, methyl or methoxy;
t is one of the 5-membered heteroaromatic compounds T1 to T10, wherein the bond to the pyrazolyl head group is indicated by an asterisk,
Wherein
R6Is hydrogen, methyl, ethyl, 2-methylethyl, 2-dimethylethyl, fluorine, chlorine, bromine, iodine, nitro, trifluoromethyl, amino;
w is oxygen;
q is hydrogen, methyl, ethyl, n-propyl, 1-methylethyl, 1-dimethylethyl, 1-methylpropyl, n-butyl, 2-methylpropyl, 2-methylbutyl, hydroxymethyl, 2-hydroxypropyl, cyanomethyl, 2-cyanoethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2, 2-tetrafluoroethyl, 1-trifluoromethylethyl, 2, 2-difluoropropyl, 3,3, 3-trifluoropropyl, 2, 2-dimethyl-3-fluoropropyl, cyclopropyl, 1-cyanocyclopropyl, 1-chlorocyclopropyl, 1-methylcyclopropyl, 1-methoxycarbonylcyclopropyl, 1- (R) cyclopropylN-methylcarbamoyl) cyclopropyl, 1-, (N-cyclopropylcarbamoyl) cyclopropyl, cyclopropylmethylA group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 1-cyclopropylethyl group, a bis (cyclopropyl) methyl group, a 2, 2-dimethylcyclopropylmethyl group, a 2-phenylcyclopropyl group, a 2, 2-dichlorocyclopropyl group, a trans-2-chlorocyclopropyl group, a cis-2-chlorocyclopropyl group, a 2, 2-difluorocyclopropyl group, a trans-2-fluorocyclopropyl group, a cis-2-fluorocyclopropyl group, a trans-4-hydroxycyclohexyl group, a 4-trifluoromethylcyclohexyl group, a prop-2-enyl group, a 2-methylprop-2-enyl group, a prop-2-ynyl group, a 1, 1-dimethylbut-2-ynyl group, a 3-chloroprop-2-enyl group, a 3, 3-dichloroprop-2-enyl group, a bis (cyclopropyl) methyl group, a 2, 2-dimethylcyclopropylmethyl group, 3, 3-dichloro-1, 1-dimethylprop-2-enyl, oxetan-3-yl, thietane-3-yl, 1-thietane-3-yl oxide, 1-thietane-3-yl, isoxazol-3-ylmethyl, 3-methyloxetan-3-ylmethyl, benzyl, 2, 6-difluorophenylmethyl, 3-fluorophenylmethyl, 2, 5-difluorophenylmethyl, 1-phenylethyl, 4-chlorophenylethyl, 2-trifluoromethylphenylethyl, pyridin-2-ylethyl, pyridin-2-ylmethyl, 5-fluoropyridin-2-ylmethyl, (6-chloropyridin-3-yl) methyl, pyrimidin-2-ylmethyl, methoxy, 2-ethoxyethyl, 2- (methylsulfanyl) ethyl, 1-methyl-2- (ethylsulfanyl) ethyl, 2-methyl-1- (methylsulfanyl) propan-2-yl, methoxycarbonyl, methoxycarbonylmethyl, NH 2、N-an ethylamino group,N-allylamino group,N,N-dimethylamino group,N,N-diethylamino, methylsulfonylamino; or
Q is the following group substituted with 0, 1,2, 3 or 4V substituents: phenyl, naphthyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, pyridyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, imidazolyl, furanyl, thienyl, pyrrolyl, oxadiazolyl, thiadiazolyl, wherein
V is, independently of one another, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2,2, 2-tetrafluoroethyl, 1-chloro-1, 2,2, 2-tetrafluoroethyl, 2,2, 2-trichloroethyl, 2-chloro-2, 2-difluoroethyl, 11-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, n-propoxy, 1-methylethoxy, fluoromethoxy, difluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, trifluoromethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2, 2-difluoroethoxy, pentafluoroethoxy, pentafluoroisopropyl, n-butyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, n-propoxy, 1-methylethoxy, fluoromethoxy, difluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, trifluoromethoxy, 2,2, NMethoxy imino methyl, 1-, (N-methoxyimino) ethyl, methylsulfanyl, methylsulfonyl, methylsulfinyl, trifluoromethylsulfonyl, trifluoromethylsulfinyl, trifluoromethylsulfanyl, N-dimethylamino.
Aspect 5 relates to a compound according to any one of aspects 1 to 4, wherein
Z1Is trifluoromethyl, 1-chlorocyclopropyl, 1-fluorocyclopropyl or pentafluoroethyl;
Z2is trifluoromethyl, nitro, methylsulfanyl, methylsulfinyl, methylsulfonyl, fluoro, chloro, bromo, cyano or iodo;
Z3is methyl, ethyl, n-propyl or hydrogen;
R1is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, prop-2-enyl, 2-methylprop-2-enyl, prop-2-ynyl, methoxymethyl, ethoxymethyl, propoxymethyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, sec-butylcarbonyl, tert-butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, cyanomethyl, 2-cyanoethyl, benzyl, 4-methoxybenzyl, pyridin-2-ylmethyl, pyridin-3-ylmethyl, pyridin-4-ylmethyl, 4-chloropyridin-3-ylmethyl, most preferably hydrogen;
A1Is CH;
A2is nitrogen;
A3is CR4And is
A4Is CR5；
R4Is hydrogen, fluorine, chlorine, bromine, iodine or cyano;
R5is hydrogen, fluorine, chlorine, bromine, iodine, methyl or methoxy;
t is one of the 5-membered heteroaromatic compounds T1 to T10, wherein the bond to the pyrazolyl head group is indicated by an asterisk,
wherein
R6Is hydrogen, methyl, ethyl, 2-methylethyl, 2-dimethylethyl, fluorine, chlorine, bromine, iodine, nitro, trifluoromethyl, amino;
w is oxygen;
q is hydrogen, methyl, ethyl, n-propyl, 1-methylethyl, 1-dimethylethyl, 1-methylpropyl, n-butyl, 2-methylpropyl, 2-methylbutyl, hydroxymethyl, 2-hydroxypropyl, cyanomethyl, 2-cyanoethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2, 2-tetrafluoroethyl, 1-trifluoromethylethyl, 2, 2-difluoropropyl, 3,3, 3-trifluoropropyl, 2, 2-dimethyl-3-fluoropropyl, cyclopropyl, 1-cyanocyclopropyl, 1-chlorocyclopropyl, 1-methylcyclopropyl, 1-methoxycarbonylcyclopropyl, 1- (R) cyclopropylN-methylcarbamoyl) cyclopropyl, 1-, (N-cyclopropylcarbamoyl) cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-cyclopropylethyl, bis (cyclopropyl) methyl, 2-dimethylcyclopropylmethyl, 2-phenylcyclopropyl, 2-dichlorocyclopropyl, trans-2-chlorocyclopropyl, cis-2-chlorocyclopropyl, 2-difluorocyclopropyl, trans-2-fluorocyclopropyl, cis-2-fluorocyclopropyl, trans-4-hydroxycyclohexyl, 4-trifluoromethylcyclohexyl, prop-2-enyl, 2-methylprop-2-enyl, prop-2-ynyl, 1-dimethylbut-2-ynyl, 3-chloroprop-2-enyl, cyclopentyl, cyclohexyl, 1-cyclopropylethyl, bis (cyclopropyl) methyl, 2-difluorocyclopropyl, 2-chlorocyclopropyl, trans-2-fluorocyclopropyl, cis-2-fluorocyclopropyl, trans-4-hydroxycyclohexyl, 4-trifluoromethylcyclohexyl, prop-2-enyl, prop-2, 3, 3-dichloroprop-2-enyl, 3 3-dichloro-1, 1-dimethylprop-2-enyl, oxetan-3-yl, thietane-3-yl, 1-thietane-3-yl oxide, 1-thietane-3-yl, isoxazol-3-ylmethyl, 3-methyloxetan-3-ylmethyl, benzyl, 2, 6-difluorophenylmethyl, 3-fluorophenylmethyl, 2, 5-difluorophenylmethyl, 1-phenylethyl, 4-chlorophenylethyl, 2-trifluoromethylphenylethyl, pyridin-2-ylethyl, pyridin-2-ylmethyl, 5-fluoropyridin-2-ylmethyl, (6-chloropyridin-3-yl) methyl, pyrimidin-2-ylmethyl, methoxy, 2-ethoxyethyl, 2- (methylsulfanyl) ethyl, 1-methyl-2- (ethylsulfanyl) ethyl, 2-methyl-1- (methylsulfanyl) propan-2-yl, methoxycarbonyl, methoxycarbonylmethyl, NH2、N-an ethylamino group,N-allylamino group,N,N-dimethylamino group,N,N-diethylamino, methylsulfonylamino; or
Q is the following group substituted with 0, 1, 2, 3 or 4V substituents: phenyl, naphthyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, pyridyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, imidazolyl, furanyl, thienyl, pyrrolyl, oxadiazolyl, thiadiazolyl, wherein
V is, independently of one another, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2,2, 2-tetrafluoroethyl, 1-chloro-1, 2,2, 2-tetrafluoroethyl, 2,2, 2-trichloroethyl, 2-chloro-2, 2-difluoroethyl, 1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, n-propoxy, 1-methylethoxy, fluoromethoxy, difluoromethoxy, Chlorodifluoromethoxy, dichlorofluoromethoxy, trifluoromethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2, 2-difluoroethoxy, pentafluoroethoxy, m,NMethoxy imino methyl, 1-, (N-methoxyimino) ethyl, methylsulfanyl, methylsulphonylAcyl, methylsulfinyl, trifluoromethylsulfonyl, trifluoromethylsulfinyl, trifluoromethylsulfanyl, and N, N-dimethylamino.
Aspect 6 relates to a compound according to any one of aspects 1 to 5, wherein the compound of general formula (I) is a compound of one of formulae (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii) and (Ij)
Wherein A is1-A4、n、W、Q、R1And Z1-Z3The groups are as defined according to any one of aspects 1 to 6.
Aspect 7 relates to a compound according to any one of aspects 1 to 7, wherein the compound of formula (I) is a compound of general formula (Ic)
Wherein
Z1Is CF2CF3，
Z2Is CF3，
Z3Is CH3，
R1、R6The radical is hydrogen (n = 0),
A1、A2is a C-H group, and the compound has the structure of,
A3is C-H, C-Cl, C-F,
A4is C-H, C-F, C-OMe,
w is oxygen and
q is methyl, ethyl, cyclopropyl, 1-chlorocyclopropyl, 1-cyanocyclopropyl, 2,2, 2-trifluoroethyl, 1,2, 2-tetrafluoroethyl, phenyl, 4-fluorophenyl, 2-fluorophenyl, 3, 5-difluorophenyl, 2, 6-difluorophenyl, 2-thienyl, 3-chloro-3-thienyl, 1-methyl-4-pyrazolyl, 4-pyridyl, 3-chloro-2-pyridyl, 2-chloro-4-pyridyl, 3-fluoro-4-pyridyl, 2, 6-dichloro-4-pyridyl.
Aspect 8 relates to the compound according to aspect 7, wherein
Z1Is CF2CF3，
Z2Is CF3，
Z3Is CH3，
R1、R6The radical is hydrogen (n = 0),
A1is a C-H group, and the compound has the structure of,
A2is the sum of the numbers of N,
A3is C-H, C-Cl, C-F, C-CH3，
A4Is C-H, C-F, C-OMe,
w is oxygen and
q is methyl, ethyl, cyclopropyl, 1-chlorocyclopropyl, 1-cyanocyclopropyl, 2,2, 2-trifluoroethyl, 1,2, 2-tetrafluoroethyl, phenyl, 4-fluorophenyl, 2-fluorophenyl, 3, 5-difluorophenyl, 2, 6-difluorophenyl, 2-thienyl, 3-chloro-3-thienyl, 1-methyl-4-pyrazolyl, 4-pyridyl, 3-chloro-2-pyridyl, 2-chloro-4-pyridyl, 3-fluoro-4-pyridyl, 2, 6-dichloro-4-pyridyl.
Aspect 9 relates to a compound of the formula (Ih)
Wherein
Z1Is CF2CF3,
Z2Is CF3，
Z3Is CH3，
R1、R6The radical is hydrogen (n = 0),
A1、A2is a C-H group, and the compound has the structure of,
A3is C-H, C-Cl, C-F,
A4is C-H, C-F, C-OMe,
w is oxygen and
q is methyl, ethyl, cyclopropyl, 1-chlorocyclopropyl, 1-cyanocyclopropyl, 2,2, 2-trifluoroethyl, 1,2, 2-tetrafluoroethyl, phenyl, 4-fluorophenyl, 2-fluorophenyl, 3, 5-difluorophenyl, 2, 6-difluorophenyl, 2-thienyl, 3-chloro-3-thienyl, 1-methyl-4-pyrazolyl, 4-pyridyl, 3-chloro-2-pyridyl, 2-chloro-4-pyridyl, 3-fluoro-4-pyridyl, 2, 6-dichloro-4-pyridyl.
Aspect 10 relates to a compound according to aspect 9, wherein
Z1Is CF2CF3，
Z2Is CF3，
Z3Is CH3，
R1、R6The radical is hydrogen (n = 0),
A1is a C-H group, and the compound has the structure of,
A2is the sum of the numbers of N,
A3is C-H, C-Cl, C-F, C-CH3，
A4Is C-H, C-F, C-OMe,
w is oxygen and
q is methyl, ethyl, cyclopropyl, 1-chlorocyclopropyl, 1-cyanocyclopropyl, 2,2, 2-trifluoroethyl, 1,2, 2-tetrafluoroethyl, phenyl, 4-fluorophenyl, 2-fluorophenyl, 3, 5-difluorophenyl, 2, 6-difluorophenyl, 2-thienyl, 3-chloro-3-thienyl, 1-methyl-4-pyrazolyl, 4-pyridyl, 3-chloro-2-pyridyl, 2-chloro-4-pyridyl, 3-fluoro-4-pyridyl, 2, 6-dichloro-4-pyridyl.
Aspect 11 relates to the use of compounds of general formula (I), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii) and (Ij) according to any one of aspects 1 to 10 for controlling insects, arachnids and nematodes.
Aspect 12 relates to a pharmaceutical composition comprising at least one compound according to any one of aspects 1 to 10.
Aspect 13 relates to a compound according to any one of aspects 1 to 10 for use as a medicament.
Aspect 14 relates to the use of a compound according to any one of aspects 1 to 10 for the manufacture of a pharmaceutical composition for controlling parasites in animals.
Aspect 15 relates to a process for the manufacture of a plant protection composition comprising a compound according to any one of aspects 1 to 10 and conventional extenders and/or surface-active substances.
Aspect 16 relates to a method for controlling pests, characterized in that a compound according to any one of aspects 1 to 10 is allowed to act on the pests and/or their living space.
Aspect 17 relates to the use of a compound according to any one of aspects 1 to 10 for the protection of plant propagation material.
A particularly preferred embodiment of the present invention relates in aspect 18 to compounds of formula (Ic)
Wherein
R1Is hydrogen or C optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl 1-C6Alkyl radical, C3-C6-alkenyl, C3-C6-alkynyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C3Alkyl radical, C1-C6-alkylcarbonyl group, C1-C6Alkoxycarbonyl, aryl (C)1-C3) Alkyl, heteroaryl (C)1-C3) -alkyl, most preferably hydrogen;
chemical moieties
A1Is CR2Or a nitrogen-containing compound,
A2is CR3Or a nitrogen-containing compound,
A3is CR4Or nitrogen, and
A4is CR5Or a nitrogen-containing compound,
but wherein the chemical moiety A1To A4Not more than three of which are simultaneously nitrogen;
R2、R3、R4and R5Independently of one another, hydrogen, halogen, cyano, nitro orC optionally mono-to heptaly-substituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl1-C6Alkyl radical, C3-C6-cycloalkyl, C1-C6-alkoxy groups,N-C1-C6-alkoxyimino-C1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N-C1-C6-alkylamino orN,N-di-C1-C6-an alkylamino group;
w is oxygen or sulfur;
q is hydrogen, amino or one of the following moieties optionally mono-to heptaly substituted independently of one another by hydroxy, nitro, amino, halogen, alkoxy, cyano, hydroxycarbonyl, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbamoyl, phenyl: c1-C6Alkyl radical, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C2-C5-heterocyclyl radical, C1-C4-alkoxy, C1-C6-alkyl-C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6Alkyl radical, C 1-C6Hydroxyalkyl, aryl (C)1-C3) Alkyl, heteroaryl (C)1-C3) Alkyl radical, C1-C4-an alkoxycarbonyl group,N-C1-C4-alkylamino, alkylamino,N-C1-C4-alkylcarbonylamino,N,N-di-C1-C4-alkylamino radical, C1-C4-an alkylsulfonylamino group; or
Q is hydrogen, amino or selected from C1-C6Alkyl radical, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, 5-or 6-membered heterocyclyl, C1-C6-alkyl-C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6Alkyl radical, C6-C10-aryl- (C)1-C3) -alkyl, 5-or 6-membered heteroaryl- (C)1-C3) Alkyl radical, C1-C4-one of the moieties of alkoxycarbonyl optionally substituted independently of each other by 1, 2, 3, 4, 5, 6 or 7 substituents selected from hydroxy, nitro, amino, halogen, oxo, benzyloxy, C3-C6-cycloalkyl, C1-C6Alkoxy, cyano, hydroxycarbonyl, C1-C4Alkoxycarbonyl, C1-C6-alkylcarbamoyl, C3-C6-cycloalkylcarbamoyl radical,N,N-di-C1-C4-alkylamino, optionally substituted by 1, 2 or 3 substituents independently of one another, chosen from halogen, C1-C6-alkoxy, C1-C6-haloalkoxy and C1-C6Phenyl substituted by alkyl substituents, optionally substituted by 1, 2 or 3 substituents independently of one another selected from halogen, C1-C6-alkoxy, C1-C6-haloalkoxy and C1-C6Phenylthio substituted by alkyl substituents, optionally substituted by 1, 2 or 3 substituents independently of one another selected from halogen, C 1-C6-alkoxy, C1-C6-haloalkoxy and C1-C6A 5-or 6-membered heteroaryl group (e.g. pyrazolyl) substituted by a substituent of an alkyl group, orN-C1-C4-alkylamino, alkylamino,N-C1-C4-alkylcarbonylamino,N,N-di-C1-C4-alkylamino radical, C1-C4-an alkylsulfonylamino moiety; or
Q is aryl substituted with 0, 1, 2, 3 or 4 substituents V or 5-or 6-membered heteroaryl substituted with 0, 1, 2, 3 or 4 substituents V, or
Q is a bicyclic heterocycle substituted with 0, 1, 2, 3, or 4V substituents or a bicyclic carbocycle substituted with 0, 1, 2, 3, or 4V substituents; wherein
V isIndependently of one another, halogen, cyano, nitro or C which is optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C1-C6-haloalkyl group, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy,N-C1-C6-alkoxyimino-C1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N,N-di- (C)1-C6-alkyl) amino;
R6independently of one another, halogen, cyano, nitro, amino or C optionally mono-to heptasubstituted by halogen1-C6Alkyl radical, C1-C6-alkoxy, C1-C6-alkylcarbonyl group, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
n has a value of 0-1;
Z1is C optionally mono-to heptasubstituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl1-C6Alkyl radical, C3-C6-a cycloalkyl radical, and
Z2is hydrogen, halogen, cyano, nitro, amino or C which is mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl1-C6Alkyl radical, C1-C6-alkylcarbonyl group, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
Z3is hydrogen or C optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl1-C6Alkyl radical, C3-C6-cycloalkyl, C3-C4-alkenyl, C3-C4-alkynyl or aryl and heteroaryl optionally mono-to penta-substituted independently of each other by halogen, cyano, alkoxy and alkoxycarbonyl.
Another preferred embodiment relates in aspect 19 to compounds of formula (Ic) according to aspect 18, wherein R is6Is hydrogen or C1-C6-alkyl and n is 0 or 1, more preferably wherein R6Is hydrogen.
Another preferred embodiment relates in aspect 20 to compounds of formula (Ic) according to aspect 18 or 19, wherein the chemical moiety
A1Is CR2，
A2Is CR3Or a nitrogen-containing compound,
A3is CR4And is and
A4is CR5Wherein
R2And R5Independently of one another, hydrogen, fluorine, chlorine, bromine, iodine, C1-C4Alkyl (e.g. methyl) and C 1-C4Alkoxy (e.g. methoxy) and R3And R4Independently of one another, hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C1-C4Alkyl (e.g. methyl), C1-C4-haloalkyl, more preferably wherein R2And R5Independently of one another are hydrogen, fluorine, methyl and methoxy and R3And R4Independently of one another, hydrogen, fluorine, chlorine, methyl.
Another preferred embodiment relates in aspect 21 to a compound of formula (Ic) according to any one of aspects 18 to 21, wherein the chemical moiety
A1Is CR2，
A2Is CR3，
A3Is CR4And is and
A4is CR5Wherein
R2Is hydrogen, R3Is hydrogen, R4Is hydrogen, fluorine, chlorine, bromine, iodine, methyl or ethyl and R5Is hydrogen, fluorine, chlorine, bromine or iodine, more preferably R2Is hydrogen, R3Is hydrogen, R4Is hydrogen, fluorine, chlorine or methyl and R5Is hydrogen or fluorine.
Another preferred embodiment relates in aspect 22 to compounds of formula (Ic) according to any one of aspects 18 to 21, wherein the chemical moiety
A1Is CR2，
A2Is a nitrogen-containing compound having a nitrogen-containing group,
A3is CR4And is and
A4is CR5Wherein
R2Is hydrogen, R4Is hydrogen, fluorine, chlorine, bromine, iodine, methyl or ethyl and R5Is hydrogen, fluorine, chlorine, bromine or iodine, more preferably R2Is hydrogen, R4Is hydrogen, fluorine, chlorine or methyl, preferably fluorine, chlorine or methyl and R5Is hydrogen or fluorine, preferably hydrogen.
Another preferred embodiment relates in aspect 23 to a compound of formula (Ic) according to any one of aspects 18 to 22, wherein W is oxygen.
Another preferred embodiment relates in aspect 24 to a compound of formula (Ic) according to any one of aspects 18 to 23, wherein
Z1Is C which is in each case optionally mono-to heptaly substituted independently of one another by halogen or cyano1-C6-alkyl or C3-C6-a cycloalkyl group;
Z2is C which is in each case optionally mono-to heptaly substituted independently of one another by halogen or cyano1-C6-alkyl or C3-C6-a cycloalkyl group;
Z3is hydrogen or C1-C6-an alkyl group,
more preferably, wherein
Z1Is C which is in each case optionally mono-to heptaly substituted independently of one another by halogen1-C6-an alkyl group;
Z2is C which is in each case optionally mono-to heptaly substituted independently of one another by halogen1-C6-an alkyl group;
Z3is C1-C6-an alkyl group,
even more preferably, wherein
Z1Is perfluoro-C1-C3Alkyl (e.g. C)2F5）；
Z2Is perfluoro-C1-C3Alkyl (e.g. CF)3）；
Z3Is C1-C4Alkyl (e.g. methyl).
A very particularly preferred embodiment relates in aspect 25 to compounds of the formula (Ic) according to any one of aspects 18 to 24, wherein Z1Is C2F5，Z2Is CF3And Z is3Is methyl.
Another preferred embodiment relates in aspect 26 to compounds of formula (Ic) according to any one of aspects 18 to 25, wherein Q is hydrogen, amino or C optionally mono-to heptaly substituted, independently of each other, by hydroxy, nitro, amino, halogen, alkoxy, cyano, hydroxycarbonyl, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbamoyl, phenyl 1-C6Alkyl radical, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C2-C5-heterocyclyl radical, C1-C4-alkoxy, C1-C6-alkyl-C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6Alkyl radical, C1-C6Hydroxyalkyl, aryl (C)1-C3) Alkyl, heteroaryl (C)1-C3) Alkyl radical, C1-C4-an alkoxycarbonyl group,N-C1-C4-alkylamino, alkylamino,N-C1-C4-alkylcarbonylamino,N,N-di-C1-C4-alkylamino radical, C1-C4One of the alkylsulfonylamino moieties or aryl which is substituted by 0, 1, 2, 3 or 4 substituents V or 5-or 6-membered heteroaryl which is substituted by 0, 1, 2, 3 or 4 substituents V, wherein V independently of one another are halogen, cyano, nitro or C which is optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl1-C6Alkyl radical, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy groups,N-C1-C6-alkoxyimino-C1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N,N-di- (C)1-C6-alkyl) amino.
Another more preferred embodiment relates in aspect 27 to compounds of formula (Ic) according to any one of aspects 18 to 25, wherein Q is
Hydrogen, amino or from C1-C6Alkyl radical, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, 5-or 6-membered heterocyclyl, C1-C6-alkyl-C3-C6-cycloalkyl, C3-C6-cycloalkyl-C 1-C6Alkyl radical, C6-C10-aryl- (C)1-C3) -alkyl, 5-or 6-membered heteroaryl- (C)1-C3) Alkyl radical, C1-C4-one of the moieties of alkoxycarbonyl optionally substituted independently of each other by 1, 2, 3, 4, 5, 6 or 7 substituents selected from hydroxy, nitro, amino, halogen, oxo, benzyloxy, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6Haloalkoxy, cyano, hydroxycarbonyl, C1-C4Alkoxycarbonyl, C1-C6-alkylcarbamoyl, C3-C6-cycloalkylcarbamoyl radical,N,N-di-C1-C4-alkylamino, optionally substituted by 1, 2 or 3 substituents independently of one another, chosen from halogen, C1-C6-alkoxy, C1-C6-haloalkoxy and C1-C6Phenyl substituted by alkyl substituents, optionally substituted by 1, 2 or 3 substituents independently of one another selected from halogen, C1-C6-alkoxy, C1-C6-haloalkoxy and C1-C6Phenylthio substituted by alkyl substituents, optionally substituted by 1, 2 or 3 substituents independently of one another selected from halogen, C1-C6-alkoxy, C1-C6-haloalkoxy and C1-C6Phenoxy substituted with substituents of alkyl, optionally substituted with 1, 2 or 3 substituents independently of one another selected from halogen, C1-C6-alkoxy, C1-C6-haloalkoxy and C1-C6-a 5-or 6-membered heteroaryl group substituted with a substituent for an alkyl group (e.g. pyrazolyl or thienyl), orN-C1-C4-alkylamino, alkylamino,N-C1-C4-alkylcarbonylamino, N,N-di-C1-C4-alkylamino radical, C1-C4-an alkylsulfonylamino moiety; or
Q is aryl substituted with 0, 1, 2, 3 or 4 substituents V or 5-or 6-membered heteroaryl substituted with 0, 1, 2, 3 or 4 substituents V, or
Q is a bicyclic heterocycle substituted with 0, 1, 2, 3, or 4V substituents or a bicyclic carbocycle substituted with 0, 1, 2, 3, or 4V substituents; wherein
V independently of one another is halogen, cyano, nitro or C which is optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy and alkoxycarbonyl1-C6Alkyl radical, C1-C6-haloalkyl group, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy,N-C1-C6-alkoxyimino-C1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N,N-di- (C)1-C6-alkyl) amino.
Another preferred embodiment relates in aspect 28 to compounds of formula (Ic) according to any one of aspects 18 to 25 or 27, wherein Q is
-hydrogen;
-C optionally substituted with 1, 2, 3 or 4 substituents1-C6-alkyl, the substituents being independently of each other selected from
Fluorine, chlorine, bromine, iodine, cyano, oxo, C1-C4-alkoxy, C1-C4-haloalkoxy, benzyloxy,N,N-di-C1-C4-alkylamino radical, C3-C6Cycloalkyl, optionally substituted independently of one another by 1, 2, 3 or 4 substituents selected from fluorine, chlorine, bromine, iodine, C 1-C4-alkoxy, C1-C4-alkyl and C1-C4Phenylthio substituted by substituents of haloalkyl, optionally independently of one another by 1,2, 3 or 4 substituents selected from fluorine, chlorine, bromine, iodine, C1-C4-alkoxy, C1-C4-alkyl and C1-C4Phenoxy substituted with substituents of haloalkyl, optionally independently of one another by 1,2, 3 or 4 substituents selected from fluorine, chlorine, bromine, iodine, C1-C4-alkoxy, C1-C4-alkyl and C1-C4Phenyl substituted with substituents of haloalkyl, optionally independently of one another by 1,2, 3 or 4 substituents selected from fluorine, chlorine, bromine, iodine, C1-C4-alkoxy, C1-C4-alkyl and C1-C4Pyrazolyl substituted by substituents of haloalkyl, optionally substituted independently of one another by 1,2, 3 or 4 substituents selected from fluorine, chlorine, bromine, iodine, C1-C4-alkoxy, C1-C4-alkyl and C1-C4-thienyl substituted with a substituent of haloalkyl;
-C optionally substituted with 1,2, 3 or 4 substituents3-C6-cycloalkyl, the substituents being independently of each other selected from
C1-C4Alkoxy, fluoro, chloro, bromo, iodo, cyano, C1-C4-alkyl, optionally substituted by 1,2, 3 or 4, independently of each other, selected from fluoro, chloro, bromo, iodo, C1-C4-alkoxy, C1-C4-alkyl and C1-C4-phenyl substituted with a substituent of haloalkyl; or
-is phenyl, naphthyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, pyridyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, imidazolyl, furyl, thienyl, pyrrolyl, oxadiazolyl, thiadiazolyl, benzothienyl, benzofuranyl, [1,2,4 ]Triazolo [1,5-a]Pyrimidinyl, 1, 3-benzodioxolyl or tetrahydronaphthyl, each of which is substituted by 0, 1, 2, 3 or 4 substituents V, where V is, independently of one another, fluorine, chlorine, bromine, iodine, cyano, nitro, C1-C4Alkyl radical, C1-C4-haloalkyl group, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy,N,N-di-C1-C4-an alkylamino group.
Another preferred embodiment relates in aspect 29 to compounds of formula (Ic) according to any one of aspects 18 to 25 or 27 to 28, wherein Q is
-C optionally substituted with 1, 2, 3 or 4 substituents1-C6-alkyl, the substituents being independently of each other selected from
Fluorine, chlorine, bromine, iodine, oxo, C1-C4-alkoxy, benzyloxy, benzyl,N,N-di-C1-C4-alkylamino radical, C3-C6Cycloalkyl, phenylthio, phenoxy, optionally substituted by 1, 2, 3 or 4 substituents independently of one another, selected from fluorine, chlorine, bromine, iodine, C1-C4-alkoxy, C1-C4-alkyl and C1-C4Phenyl substituted by a substituent of haloalkyl, optionally substituted by 1, 2, 3 or 4 substituents independently of one another selected from C1-C4-alkyl and C1-C4-substituted pyrazolyl and thienyl with haloalkyl;
-C optionally substituted with 1, 2, 3 or 4 substituents3-C6-cycloalkyl, the substituents being independently of each other selected from
C1-C4Alkoxy, fluoro, chloro, bromo, iodo, cyano, C 1-C4-alkyl, optionally substituted by 1,2, 3 or 4, independently of each other, selected from fluorine, chlorine, bromine, iodine and C1-C4-phenyl substituted with a substituent of alkyl; or
-is phenyl, pyrimidinyl, pyridinyl, pyrazolyl, oxazolyl, isoxazolyl, furanyl, thienyl, benzothienyl, benzofuranyl, [1,2,4]Triazolo [1,5-a]Pyrimidinyl, 1, 3-benzodioxolyl or tetrahydronaphthyl, each of which is substituted by 0, 1,2, 3 or 4 substituents V, where V is, independently of one another, fluorine, chlorine, cyano, nitro, C1-C4Alkyl radical, C1-C4-haloalkyl group, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy,N,N-di-C1-C4-an alkylamino group.
Another preferred embodiment relates in aspect 30 to compounds of formula (Ic) according to any one of aspects 18 to 25 or 27 to 29, wherein Q is
-C optionally substituted with 1,2, 3 or 4 substituents1-C4-alkyl, the substituents being independently of each other selected from
Fluorine, chlorine, bromine, iodine, oxo, C1-C4-alkoxy, benzyloxy, benzyl,N,N-di-C1-C4-alkylamino radical, C3-C6Cycloalkyl, phenylthio, phenoxy, optionally substituted by 1,2 or 3 substituents independently of one another, selected from fluorine, chlorine, bromine, iodine, C1-C4-alkoxy, C1-C4-alkyl and C1-C4Phenyl substituted by a substituent of haloalkyl, optionally substituted by 1 or 2 substituents independently of one another selected from C 1-C4-alkyl and C1-C4-substituted pyrazolyl and thienyl with haloalkyl;
-C optionally substituted with 1 or 2 substituents3-C6-cycloalkyl, the substituents being independently of each other selected from
C1-C4Alkoxy, fluoro, chloro, bromo, iodo, cyano, C1-C4-alkyl, optionally substituted by 1 or 2 substituents independently of one another, selected from fluorine, chlorine, bromine, iodine and C1-C4-phenyl substituted with a substituent of alkyl; or
-is phenyl, pyrimidinyl, pyridinyl, pyrazolyl, oxazolyl, isoxazolyl, furanyl, thienyl, benzothienyl, benzofuranyl, [1,2,3]Triazolo [1,5-a]Pyrimidinyl, 1, 3-benzodioxolyl or tetrahydronaphthyl, each of which is substituted by 0, 1,2 or 3 substituents V, where V is, independently of one another, fluorine, chlorine, cyano, nitro, C1-C4Alkyl radical, C1-C4-haloalkyl group, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy,N,N-di-C1-C2-an alkylamino group.
Another preferred embodiment relates in aspect 31 to compounds of formula (Ic) according to any one of aspects 18 to 25 or 27 to 30, wherein Q is
-C optionally substituted with 1,2,3 or 4 substituents1-C4-alkyl, the substituents being independently of each other selected from
Fluorine, oxo, C1-C4-alkoxy, benzyloxy, benzyl,N,N-di-C1-C4-alkylamino radical, C 3-C6Cycloalkyl, phenylthio, phenoxy, optionally substituted by 1,2 or 3 substituents independently of one another, selected from fluorine, chlorine, C1-C4-alkoxy, C1-C4-alkyl and C1-C4Phenyl substituted by a substituent of haloalkyl, optionally substituted by 1 or 2 substituents independently of one another selected from C1-C4-alkyl and C1-C4-substituted pyrazolyl and thienyl with haloalkyl;
-C optionally substituted with 1 or 2 substituents3-C6-cycloalkyl, the substituents being independently of each other selected from
C1-C4Alkoxy, chloro, cyano, C1-C4-alkyl, optionally selected from 1 or 2 independently of each other from chlorine and C1-C4-phenyl substituted with a substituent of alkyl; or
-is phenyl, pyrimidinyl, pyridinyl, pyrazolyl, oxazolyl, isoxazolyl, furanyl, thienyl, benzothienyl, benzofuranyl, [1,2,3]Triazolo [1,5-a]Pyrimidinyl, 1, 3-benzodioxolyl or tetrahydronaphthyl, each of which is substituted by 0, 1,2 or 3 substituents V, where V is, independently of one another, fluorine, chlorine, cyano, nitro, C1-C4Alkyl radical, C1-C4-haloalkyl group, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy,N,N-di-C1-C2-an alkylamino group.
Another preferred embodiment relates in aspect 32 to compounds of formula (Ic) according to any one of aspects 18 to 25 or 27 to 31, wherein Q is
-C optionally substituted with 1,2,3 or 4 substituents1-C6-alkyl, the substituents being independently of each other selected from
Fluorine, oxo, methoxy, ethoxy, benzyloxy,N,N-dimethylamino group, C3-C6Cycloalkyl, phenylthio, phenoxy, optionally substituted by 1,2 or 3 substituents independently of one another, selected from fluorine, chlorine, C1-C4-alkoxy, C1-C4-alkyl and C1-C4Phenyl substituted by a substituent of haloalkyl, optionally substituted by 1 or 2 substituents independently of one another selected from C1-C4-alkyl and C1-C4-substituted pyrazolyl and thienyl with haloalkyl;
-C optionally substituted with 1 or 2 substituents3-C6-cycloalkyl, the substituents being independently of each other selected from
C1-C4Alkoxy, chloro, cyano, C1-C2-alkyl, optionally selected from 1 or 2 independently of each other from chlorine and C1-C2-phenyl substituted with a substituent of alkyl; or
-is phenyl, pyrimidinyl, pyridinyl, pyrazolyl, oxazolyl, isoxazolyl, furanyl, thienyl, benzothienyl, benzofuranyl, [1,2,3]Triazolo [1,5-a]Pyrimidinyl, 1, 3-benzodioxolyl or tetrahydronaphthyl, each of which is substituted by 0, 1,2 or 3 substituents V, where V is, independently of one another, fluorine, chlorine, cyano, nitro, C1-C4Alkyl radical, C1-C2-haloalkyl group, C3-C6-cycloalkyl, C 1-C2-alkoxy, C1-C2-haloalkoxy,N,N-di-C1-C2-an alkylamino group.
Another preferred embodiment relates in aspect 33 to compounds of formula (Ic) according to any one of aspects 18 to 25 or 27 to 32, wherein Q is
Pyridyl optionally mono-or disubstituted independently of one another by fluorine, methyl, cyano, chlorine (e.g. 4-pyridyl, 3-F-4-pyridyl, 3-Cl-2-pyridyl, 2-Cl-4-pyridyl, 2, 6-Cl)2-4-pyridyl, 2-Cl-3-pyridyl, 2-Cl-6-Me-4-pyridyl, 3-F-5-pyridyl, 2-Me-4-pyridyl, 2-F-4-pyridyl, 2-CN-5-pyridyl, 2-Cl-5-pyridyl, 2-F-5-pyridyl, 2-CN-5-pyridyl),
-C optionally mono-substituted by Cl, methoxy, methyl or CN3-C6Cycloalkyl (e.g. cyclopropyl, 1-CN-cyclopropyl, 1-Cl-cyclopropyl, 4-methoxycyclohex-1-yl, 1-methylcyclohexyl, 1-methylcyclopropyl, cyclopentyl),
phenyl which is optionally mono-or di-or trisubstituted independently of one another by fluorine, methoxy, ethoxy, trifluoromethoxy, cyano, trifluoromethyl, dimethylamino, methyl, ethyl, propyl (e.g. phenyl, 2-F-phenyl, 3,5-F2-phenyl, 2,6-F2-phenyl, 4-F-phenyl, 3-methoxyphenyl, 3-CF 3-4-F-phenyl, 2, 6-bismethoxyphenyl, 4- (dimethylamino) phenyl, 2,4, 6-triisopropylphenyl, 3-CF3-phenyl, 4-Me-phenyl, 2,3-F2-phenyl, 2-ethoxyphenyl, 2- (trifluoromethoxy) phenyl, 3-cyanophenyl, 2, 3-dimethylphenyl, 4-CN-phenyl, 3, 4-dimethylphenyl, 3-Me, 4-F-phenyl, 3-F, 4-Me-phenyl, 3-MeO, 4-F-phenyl, 3-F, 4-MeO-phenyl, 4-Cl, 3-F-phenyl, 3-methoxy-4-Me-phenyl, 3-EtO-4-F-phenyl),
-C optionally mono-substituted with methoxy or ethoxy1-C6-alkyl or C1-C6Haloalkyl (e.g. CHF)2CF2-、CF3CH2-, methyl, ethyl, propyl, 1,2, 2-tetramethylethyl, (1, 1-dimethyl) -2-F-ethyl, methoxymethyl, 1-methylpropyl, 2-methoxyethyl, (R) -1-F-ethyl, 2-Me-propan-1-yl, butyl, 2, 2-dimethylpropan-1-yl, methyl, ethyl, propyl, 1,2, 2-tetramethylethyl, methyl, ethyl, propyl, ethyl,1, 1-dimethyl-2-ethoxyethyl),
pyrazolyl which is optionally mono-, di-or trisubstituted independently of one another by methyl, ethyl, propyl, butyl, nitro, such as 1-methyl-4-pyrazolyl, 1-methyl-3-tBu-4-NO2-a pyrazolyl group),
thiazolyl (e.g. 1-thiazolyl),
thienyl which is optionally monosubstituted by chlorine (e.g. 3-thienyl, 2-thienyl, 3-Cl-2-thienyl),
Pyrimidinyl (e.g. pyrimidin-3-yl, pyrimidin-2-yl),
-a [1,2,4] triazolo [1,5-a ] pyrimidin-2-yl group optionally mono-or disubstituted independently of each other by halomethyl, methyl (e.g. 7- (difluoromethyl) -5-methyl- [1,2,4] triazolo [1,5-a ] pyrimidin-2-yl),
benzothienyl optionally mono-or disubstituted independently of one another by chlorine, methyl (for example 3-Cl-benzothien-2-yl, 3-Cl-6-Me-benzothien-2-yl),
furyl optionally mono-or disubstituted independently of one another by methyl, trifluoromethyl (e.g. 3-Me-2-benzofuryl, 2-CF)3-4-Me-furan-2-yl, 2-Me-3-furyl),
thienyl (e.g. 5-Me-thiophen-2-yl) optionally mono-or disubstituted by methyl, trifluoromethyl,
isoxazolyl optionally mono-substituted with methyl (e.g. 5-methylisoxazol-4-yl),
1, 3-benzodioxolyl optionally mono-or disubstituted by fluorine (for example 2, 2-difluoro-1, 3-benzodioxol-5-yl or 1, 3-benzodioxol-5-yl).
Another embodiment relates in aspect 34 to a compound of formula (Ic) according to any one of aspects 18 to 25 or 27 to 32, wherein Q is phenylthiomethyl, 1-phenylethyl, phenylcyclopentylmethyl, benzyloxymethyl, phenoxyethyl, p-hexylmethyl, p-hexylphenyl, o-tolyl, o, 1-Me, 1- (3-Cl-Ph) -ethyl, 1- (4-Cl-Ph) -2-Me-propan-1-yl, 3-F-benzyl, 3-CF3-benzyl, 3-CF 3-4-Me-pyrazol-1-ylmethyl, rac-1-phenoxyethyl, 1-phenylpropan-1-yl, 2-phenylethyl, 2-Cl-4-F-benzyl or tetrahydronaphthyl, 1- (4-Me-Ph) -cyclohex-1-yl, 1-Ph-cycloprop-1-yl, 1- (4-Cl-Ph) -cyclobut-1-yl, 1- (4-Cl-Ph) -cyclopent-1-yl, 2-thienylmethyl, (Me)2NC(O)C(O)-。
Another preferred embodiment relates in aspect 35 to a compound of formula (Ic) according to any one of aspects 18 to 34, which is a compound of formula (Ic-1)
The compounds of the invention of formula (Ic-1) are those wherein W = O, A1= A2= CH、A3= CR4、A4= CR5And R is6Compounds of the general formula (Ic) of = H (i.e. n = 0).
Another preferred embodiment relates in aspect 36 to compounds of formula (Ic-1) according to aspect 35, wherein Q is
Pyridyl optionally mono-or disubstituted independently of one another by fluorine, methyl, cyano, chlorine (e.g. 4-pyridyl, 3-F-4-pyridyl, 3-Cl-2-pyridyl, 2-Cl-4-pyridyl, 2, 6-Cl)2-4-pyridyl, 2-Cl-3-pyridyl, 2-Cl-6-Me-4-pyridyl, 3-F-5-pyridyl, 2-Me-4-pyridyl, 2-F-4-pyridyl, 2-CN-5-pyridyl, 2-Cl-5-pyridyl, 2-F-5-pyridyl, 2-CN-5-pyridyl),
-C optionally mono-substituted by Cl, methoxy, methyl or CN3-C6Cycloalkyl (e.g. cyclopropyl, 1-CN-cyclopropyl, 1-Cl-cyclopropyl, 4-methoxycyclohex-1-yl, 1-methylcyclohexyl, 1-methylcyclopropyl, cyclopentyl),
-optionally substituted, independently of one another, by fluorine, methoxy, ethoxy, trifluoromethoxy, cyano, trifluoromethyl, diMethylamino, methyl, ethyl, propyl mono-or di-or trisubstituted phenyl (e.g. phenyl, 2-F-phenyl, 3, 5-F)2-phenyl, 2,6-F2-phenyl, 4-F-phenyl, 3-methoxyphenyl, 3-CF3-4-F-phenyl, 2, 6-bismethoxyphenyl, 4- (dimethylamino) phenyl, 2,4, 6-triisopropylphenyl, 3-CF3-phenyl, 4-Me-phenyl, 2,3-F2-phenyl, 2-ethoxyphenyl, 2- (trifluoromethoxy) phenyl, 3-cyanophenyl, 2, 3-dimethylphenyl, 4-CN-phenyl, 3, 4-dimethylphenyl, 3-Me, 4-F-phenyl, 3-F, 4-Me-phenyl, 3-MeO, 4-F-phenyl, 3-F, 4-MeO-phenyl, 4-Cl, 3-F-phenyl, 3-methoxy-4-Me-phenyl, 3-EtO-4-F-phenyl),
-C optionally mono-substituted with methoxy or ethoxy1-C6-alkyl or C1-C6Haloalkyl (e.g. CHF)2CF2-、CF3CH2-, methyl, ethyl, propyl, 1,2, 2-tetramethylethyl, (1, 1-dimethyl) -2-F-ethyl, methoxymethyl, 1-methylpropyl, 2-methoxyethyl, (R) -1-F-ethyl, 2-Me-propan-1-yl, butyl, 2, 2-dimethylpropan-1-yl, 1-dimethyl-2-ethoxyethyl),
Pyrazolyl which is optionally mono-, di-or trisubstituted independently of one another by methyl, ethyl, propyl, butyl, nitro, such as 1-methyl-4-pyrazolyl, 1-methyl-3-tBu-4-NO2-a pyrazolyl group),
thiazolyl (e.g. 1-thiazolyl),
thienyl which is optionally monosubstituted by chlorine (e.g. 3-thienyl, 2-thienyl, 3-Cl-2-thienyl),
pyrimidinyl (e.g. pyrimidin-3-yl, pyrimidin-2-yl),
-a [1,2,4] triazolo [1,5-a ] pyrimidin-2-yl group optionally mono-or disubstituted independently of each other by halomethyl, methyl (e.g. 7- (difluoromethyl) -5-methyl- [1,2,4] triazolo [1,5-a ] pyrimidin-2-yl),
benzothienyl optionally mono-or disubstituted independently of one another by chlorine, methyl (for example 3-Cl-benzothien-2-yl, 3-Cl-6-Me-benzothien-2-yl),
furyl optionally mono-or disubstituted independently of one another by methyl, trifluoromethyl (e.g. 3-Me-2-benzofuryl, 2-CF)3-4-Me-furan-2-yl, 2-Me-3-furyl),
thienyl (e.g. 5-Me-thiophen-2-yl) optionally mono-or disubstituted by methyl, trifluoromethyl,
isoxazolyl optionally mono-substituted with methyl (e.g. 5-methylisoxazol-4-yl),
1, 3-benzodioxolyl optionally mono-or disubstituted by fluorine (for example 2, 2-difluoro-1, 3-benzodioxol-5-yl or 1, 3-benzodioxol-5-yl).
Another preferred embodiment relates in aspect 37 to compounds of formula (Ic-1) according to aspect 35, wherein Q is
Phenylthiomethyl, 1-phenylethyl, phenylcyclopentylmethyl, benzyloxymethyl, phenoxyethyl, 1-Me, 1- (3-Cl-Ph) -ethyl, 1- (4-Cl-Ph) -2-Me-propan-1-yl, 3-F-benzyl, 3-CF3-benzyl, 3-CF 3-4-Me-pyrazol-1-yl-methyl, rac-1-phenoxyethyl, 1-phenylpropan-1-yl, 2-phenylethyl, 2-Cl-4-F-benzyl or tetrahydronaphthyl, 1- (4-Me-Ph) -cyclohex-1-yl, 1-Ph-cycloprop-1-yl, 1- (4-Cl-Ph) -cyclobut-1-yl, 1- (4-Cl-Ph) -cyclopent-1-yl, 2-thienylmethyl, (Me)2NC(O)C(O)-。
Another preferred embodiment relates in aspect 38 to a compound of formula (Ic-1) according to aspect 35, wherein Q is a group as shown in aspects 36 and 37.
Another preferred embodiment relates in aspect 39 to compounds of formula (Ic) according to aspect 35, wherein Q is 4-F-phenyl, 3-MeO-4-F-phenyl, 3-Cl-2-pyridyl, 2-CN-5-pyridyl, 4-pyridyl.
Another preferred embodiment relates in aspect 40 to compounds of formula (Ic-1) according to aspect 35, wherein Q is a group as shown in aspects 36, 37 and 38.
Another preferred embodiment relates in aspect 41 to a compound of formula (Ic) according to any one of aspects 18 to 34, which is a compound of formula (Ic-2)
The compounds of the invention of formula (Ic-2) are those wherein W = O, A1= CH、A2= N、A3= CR4、A4= CR5And R is6Compounds of the general formula (Ic) of = H (i.e. n = 0).
Another preferred embodiment relates to compounds of formula (Ic-2) according to aspect 41, wherein Q is 4-F-phenyl, 3-MeO, 4-F-phenyl, 3-Cl-2-pyridyl, 2-CN-5-pyridyl, 4-pyridyl.
The application is as follows:
the invention also relates to a method for controlling animal pests, in which a compound of the invention of general formula (I) is allowed to act on the animal pests and/or their living space. The compounds of the invention of the general formula (I) are used for controlling a large number of different pests, including, for example, harmful piercing and sucking insects, biting insects and other plant-parasitic pests, storage pests, pests destroying industrial materials and hygiene pests, including parasites in the field of animal health.
Crop protection
In view of good plant compatibility, favourable toxicity to warm-blooded animals and good environmental compatibility, the compounds according to the invention of the formula (I) are suitable for protecting plants and plant organs, for increasing harvest yields, for improving the quality of the harvest and for controlling animal pests, especially insects, arachnids, helminths, nematodes and molluscs, encountered in agriculture, horticulture, animal husbandry, aquaculture, forests, gardens and leisure facilities, in the protection of stored products and materials and in the hygiene sector. They are preferably used as plant protection compositions. They are effective against normally sensitive and resistant species and against all or individual developmental stages. The pests include:
Pests from the phyla arthropods, in particular from the class arachnids, such as acarina (Acarus spp.), acreria kuko, citrus gall mites (acaria sheldoni), Dermanyssus aculeatus (acalops spp.), Ceriporia spicata (Acarus spp.), Ceriporia (Acarus spp.), Acacia spp (Amblyomma spp.), Tetranychus crataegi (Amphitrychus viennensis), Arwidely Acacia spp (Argassp.), Boophilus spp.), Brevibacterium spp (Brevipypus spp.), Bryopyrax spp.), Bryolocated Binychus (Bryobia praetiosa), Deyophycus (Bryoid) Acarus sp, Ceratophycus sp (Dephyrophus spp.), Ceratophycus spp (Ceratophyceae spp.), Dephyrophus spp.), Deynaphus sp, Dephyceae spp (Hypopyrus spp.), Dephyceae spp., Pyrenopsis (Hydratus spp.), Dephycus spp (Hydratus spp.), Dephycus spp.), Dephyceae (Hydrae, Dephyrophus spp.), Dephymatodes sp., Euphyceae (Hydrae, Dephyceae spp.), Dephyceae (Hydrae, Dephyceae spp.), Dephytylodes (Hygrophyceae spp.), Dephyceae spps sp.), Euphyceae (Hygrophyceae, Euphyceae spts, Dephyceae (Hygrophyceae) and Dephyceae (Euphyceae, Dephyceae, Euphyceae, Euphy, Venomous (Latrodectus spp.), Loxosceles spp, Metatarnychus spp, Neurospora aurora spp, Nuphera spp, Oligonurus spp, pure Tetranychus spp, Ornithronosus spp, Panonychus spp, Citrus tsutuo (Phyllophora spp), Phyllophora citri, Platytephrocystis Tetranychus, Tarsonemus tarda, Rhynchus spp, Rhizophus spp, Rhizopus spp, Rhizophus spp, Stexophyromyces spp, Stereococcus spp;
Pests from the order Chilopoda, such as Geophilus spp, Scutigera spp;
pests from the order of the phylum Rhamnoidea or class, such as Onychiurus armatus (Onychiurus armatus);
pests from the order of the Diplopoda, such as Blaniulus guttulatus;
from the class entomophytes, for example pests from the order blattaria, for example periplaneta asia (Blattella asahinai), Blattella germanica (Blattella germanica), Blattella orientalis, madela germanica (leucorhagadereae), copaiba (Panchlora spp.), trichoderma (parachlorota spp.), periplaneta (periplaneta spp.), and periplaneta coida (periplaneta perps);
pests from the order coleoptera, such as, for example, acalyma vitratum, callosobruchus (acanthosperms obtectus), rhynchophylla (adorteus spp.), agrastica alni, click beetles (Agriotes spp.), black beetles (aphanita diasporis), potato gilles (ampherollin solsticalis), furniture larch (Anobium puncatum), star cattle (anophophora spp.), florists (anthromyces spp.), bark beetles (anthlem spp.), apium spicatum, Apogonia spium spp., Ataridia spp., fur coat (athagentia spp.), baryces cauliflora, brethrene spissus, echinoderma spissus, colophonium spp., echinoderma spp., salpinus spissus, colophon spossima, callorhiza spp, callorhodopsea, callorhinus spissus, callorhius spissus, callorhodopsea (callorhodopsis spp), callorhodopsis spissus spp, callorhodorhodopsis spp, callorhodopsis spp, callorhodelos spissus, callorhodopsis spp, callorhodeloides (callorhodorhodorhodorhodorhinus spp), callorhodopsis spp, callorhodorhodorhodorhode spp, callorhode spp, callorhodorhode spp, callorhodorhodorhodorhode spp, callorhode spp, callorhodorhodorhodorhodorhodorhodorhodorhode spp, callorhode spp, callorhodorhodorhodorhodorhode spp, pelorhodorhodorhodorhode spp, pelorhodorhodorhodorhodorhodorhode spp, pelorhode spp, pelorhodorhodorhodorhode spp, pelorhodorhodorhodorhodorhodorhodor, The genera Dichocrocis spp, diabrotica (Dicladispa armigera), diaboderus spp, calabash (Epilachna spp), flea beetle (Epitrix spp), Faustinus spp, Gymnoclada (gibbrophylloides), broad leaved beetle (gnocerus communis), cabbage borer (Hellula undalis), black-spotted sugarcane golden beetle (heterocarya erector), Heteronyx spp, Lamorpha elata, Calf. (Hypericum), purple leaf elephant (Hypericum), blue-green elephant (Hypericum sp), bark beetle (Hypericum spp), Lupus spp (Mexicana spp), Luciliella spp, Lucilium (Mexicana spp), Lucilium spp (Mexicana spp), Lucilium spp (Melothrix spp), Lucilium spp (Melothrix spp), Lucilium spp, Lupus spp, Lucili (Melothrix spp), Lucilium spp) Naupusaxanthoraphus, genus gongro (endochromia spp.), yellow spider (niptoluerus), rhinoceros (oricotes rhinoceros), grazing (oryzaephius suirinmensis), oryzaphalus (oryzaephius surrinameris), Oryzaphagus oryzagus, thiorrhinus spp, cochlearia farinosa, cuora spp (Phyllophaga spp.), phyllophallus leiocarpus, phyllocoptera (phyllotetra spp.), japanese beetle (podlia japonica), premotris spp., piscifolium spp., large grain beetle (proteus, phyllotopteria spp., dendroctonus spp, trichia spp, trich;
Pests from the order diptera, such as the genus Aedes (Aedes spp.), the genus agromycops (Agromyza spp.), the genus trypanosoma (Anastrepha spp.), the genus Anopheles (Anopheles spp.), the genus zanthoxylum (aspenylia spp.), the genus anthurium (Bactrocera spp.), the genus gardnerella garden (Bibio hornula), the genus callimastra (calliphryidae), the genus anthurius (calliphryidae), the genus Calliphora (calliphoropteris pallida), the genus Calliphora virgina, the species cerasus (Ceratitis capitata), the genus chironus (chironosus spp.), the genus chrysomyzilla (chrysomyzilla spp.), the genus gadfly (chrysomyzilla spp.), the genus chrysomyzilla (chrysomyzilla spp.), the strand, the genus chrysomyzilla (calli spp.), the genus callimastia, the genus calliphorina (calliphorina spp.), the genus calliphorina (calliphorina), the genus calliphorina (calli spp.), the genus euglena, the genus eupellics (calli), the genus euglena, the genus calli (calli), the genus calli (calliphorina, the genus euglena, the genus calli (calli), the genus calli (calliphorina, the genus calli), the genus calli (calli), the genus euglena, The species Drosophila (Fannia spp.), Gastrophila (Gastrophila spp.), Glossina spp.), Sargasus (Haematopota spp.), Hymenoptera (Hydrellia spp.), rice leaf fly (Hydrella griseola), seed fly (Hylemya spp.), pediculus fly (Hippoboca spp.), Pisca fly (Hypoderma spp.), Luria spp.), Lucilia (Liriomyza spp.), Lucilia fly (Lucilia spp.), Luomyzis (Lucomia spp.), Lupinus (Lumoma spp.), Manimania spp.), Musca fly (Musca spp.), Ostrophys fly (Ostrophys spp., Musca fly (Oscillus spp.), Musca fly (Osneit), paratanytarsus spp, Paranauterborn subincta, Spanish spp, Chrysomyelia (Pegomyia spp.), phleboptera (Phebotomus spp.), Phorbid spp, Phormia spp, Tyrosus (Piophilalaceae), Prodpolis spp, Psila rosae, Robushelus spp, Sarcophaga spp, Simplicus spp, Silybus spp, Sarcophaga spp, Simulium spp, Stomoxys spp, Tabanus spp (Tabanusspp spp), Tetopns spp, Large mosquito spp;
Pests from the order heteroptera, such as Lygus lucorum (Anasa Tristis), anthropopathies spp, boiseaspp, blisuss spp, calosporis spp, Campylomma livida, cavelius spp, stinorum spp, Cimex spp, collicia spp, crenitides dillutus, dysarthris, dichotoma, dicholomys hewetti, rudinid plant, Euschistus, eulygus bugs, euonymus spray, halomorpha harys, heliosporidium spp, horpiogliosis spp, hobalephyllalellus, rice marginatus (leucotrichia spp), leucotrichia spp, leidophora, trichoderma spp, leidae, leucotrichia spp, trichoderma harlygus, purpurea, leucotrichia, phyllorusum, phytophthora spp, leucotrichia spp, phytophora, phytophthora spp (purpura, phytophthora spp, euphala, phytophthora spp, eupatora spp, phytophthora spp, eupatora spp, phytophthora spp, euphala, phytophthora spp (phytophthora spp, eupatora spp, phytophthora spp, eupatora spp, phytophthora spp;
pests from the order homoptera, such as Acizzia acaciaebileyana, Acizzia dodonaea, Acizzia aucatoides, Acridia capitata (Acrida turita), Acyrthospon spp, Acrogenia spp, Aenola miaspp, Agonospora spp, Alyrodes proteella, Aleurolobius barodensis, Aleurothrix floricosus, Allocardial malaysis, Amrasca spp, Anurapichia sriscardui, Auoniella spp, Aphis persicae (Aphanoticola), Aphis spp, Arboria maculalis, Arthrobacter xylinus, Acridula spp, Calcilaria, California viridea, California, Choristia, Aleuropa, California, Choristia, Aleuropaea, Aleurotica, Aleurotis, California, Choriscus, California, Choriscus, Erythia, or Ebenaria, or Erythia, or Percifia, or Ebenaria, or Ebenomyia, or, Citrus psyllid (Diaphorina citri), pellago (diappiss spp.), paramecium (Drosicha spp.), Drosicha (Drosicha spp.), Dysaphis spp., poliomyelia (dysococcus spp.), leucotrichum (empoasca spp.), trichomonas (eriomonas spp.), trichophyma spp.), eudesmus (eriophyma spp.), trichophyma spp.), euphylum spp., hypochonium spp., ferrocharum spp., Geococcus comyces spp., glucophycus spp., glocosporus spp., euphorbia spp., euphylum spp., mucor spp., euphylum spp., mucococcus spp., euphorbia grandis (euphorbia spp.), euphylium sponospora spp, mucor cocci (euphorbia spp.), phyceae spp.), physalsa spp., mucophyceae, physalsa spp., euphorbia spp., euphylium spp., euphorbia spp., euphylum, euphorbia spp., mucor spp., euphorbia spp., euphylia (euphorbia spp.), euphylia spp., mucos spp., euphorbia spp., euphylia spp., euphorbia spp., euphylia spp., euphylum trichophysa, phylia spp., euphylia spp, euphorbia grandis, phylum euphorbia spp, phylum trichophysa, phylum euphorbia spp, phylum trichophyceae, phylum trichophysa (phylum trichophyceae), phylum trichophyceae, phylum peronospora spp), phylum trichophyceae, phylum peronospora spp, phylum trichophysa (phylum peronospora spp), phylum trichophyceae, phylum peronospora spp., mucos, phylum peronosum peronos, Parabethia myricae, Parathioza spp, Parapelyriasis genus (Paralatoria spp.), Plasmopara viticola (Pemphigus spp.), Cervus zeae (Peregrius maidis), Plasmodium filiformis (Phenococcus spp.), such as Phenococcus madeirensis, Phycomyces paserini, Phododon humuli, Rhizopus vitis (Phylloxelata spp.), Pinnapediococcus aspergillus, Plascococcus spp, Propodophylla flava, Protopulina varium, Phyllospora purpurea (Phyllospora spp.), Phyllospora purpurea, Phyllospora spp, Phyllospora purpurea, Phyllospora spp (Phyllospora spp.), Phyllospora purpurea, Phyllospora spp., Phyllospora spp (Phyllospora spp), Phyllospora spp, and Phyllospora spp The genus cornicerya (Unaspis spp.), Rhixomatous (Viteusvitifolii), Zygina spp;
Pests from the order hymenoptera, such as Acromymex spp, Athalia spp, Blastoma spp, Diprion spp, Blastoma spp, Hoplocampa spp, Blastoma spp, Solenopsis invicta, Tapinomasp, Urocerus spp, Vespa spp, Xeri spp;
pests from the order isopoda, such as Armadillidium vulgare, Oniscus asellus, Porcellio scaber;
pests from the order of the isoptera, such as the genera termites (coptottermes spp.), Cornitermes cumulans, sanded termites (Cryptotermes spp.), albizia (incosteritermes spp.), microttermes obesi, odontotermis obesi (odontottermes spp.), and Reticulitermes spp;
pests from the order lepidoptera, such as pyracantha parva (Achroia grisella), athyria sanguinea (Acronictamajor), athetia fusca (Adoxophyes spp.), Aedia leucoglobosa, athyria leucosporum (Agrotis spp.), Alabama spp, amylois trascena, athyria spp (Anarsia spp.), angelicae spp, argyrophylla spp, athyria brassicae (barathyria brassicae), indica butterfly (Borbo cunnarna), buclizia thunbergii, busere spongiosa, busere larvas (Bupalus pinius), burseola spp, caciae spp Ecytolopha aurantium, Elasmopalsluognosilus, Eldana saccharana, Pinctada punctata (Ephestia spp.), Sporidia spp (Ephingia spp.), Sporidia falcata (Epinotia spp.), Sporidia pomonella (Epiphora punctata), Sporidia pomifera (Epiphila punctata), Spodoptera legeliocapsa (Etiella spp.), Eulia spp., Eupoecilia ambigella, Flavobactea virescens (Euprotis spp.), Euxoa spp., Feltia, Ceratoptera pyralis (Galleria mellonella), Gracilaria spp, Microcardia (Graphola spp.), Hedyleptasa, Helicoverpa spp., Heliothis spp (Hellebia spp.), Sporidia spp Oiketicus spp, Oriaspp, Orthoga spp, Setaria spp, Helicoverpa spp, Phyllodendron spp, Phyllocnidia, Phyllodendron spp, Phyllocercospora spp, Pieris spp, Phylloptera spp, Phyllostachyta, Spodoptera spp, Spodoptera spp, Spodoptera, Acremova spp, Stomoptylexxservella, Pernychus spp, Synanthondon spp, Tecia solarivora, Thermeiagematalis, Tinea cloacaella, Chlamydomonas armyworms, Germinella bissula, Spodoptera tortricola, Trichophaga tapetum, Trichoplusia (Trichoplusia spp.), Tryporyza incertulas (Tryporyza incertulas), Tuabsoluta, Virata carolina spp;
Pests from the order orthoptera or from the order skipperiales, such as Acheta domesticus, dichloplus spp, mole cricket genera (Gryllotalpa spp.), Locusta spp, Locusta migratoria spp, melanophora spp, desert locust (schistosa gregaria);
pests from the order phthiraptera, for example, zoophthiris (Damalinia spp.), hematophthiris (haemantopinus spp.), Pediculus trichopterus (linogluchus spp.), Pediculus (pediocus spp.), phyllus (pediococcus spp.), phyllorea vastatrix, Phtirusspubis, and rodentia (trichoectes spp.);
pests from the order rodentia, such as Lepinotus spp, pediculosis spp;
pests from the order of siphonaptera, for example, the genera Ceratophyllus (Ceratophyllus), Ctenocephalides (Ctenocephalides spp.), human fleas (Pulex irritans), Periplaneta species (Tunga pendans), Xenopsylla cheopis;
pests from the order of the Thysanoptera, for example Amyrium zeae (Anathyrips obscurus), Thrips oryzae (Balothrix biformis), Drepanothrips reuteri, Enneatherrips flavens, Frankliniella spp (Frankliniella spp.), Thrips spp (Heliothrips spp.), Thrips greenhouse Thrips (Hercinothrips femoralis), Rhizophosthrips cruentus, Thrips spp (Scothrix spp.), Entiothrips cadamomi, Thrips spp (Thrips spp.);
Pests from the order Chlamydomonales (= Thysanoptera), such as Ctenolepisma spp, Chlamydomonas (Lepismasaccharia), Lepismodies inquinus, Chlamydomonas parvum (Thermobia domestica);
pests from the subclass, such as Scutigerella spp;
pests from the phylum mollusca, in particular from the class bivalves, such as the genus campylobacter (Dreissena spp.), and pests from the class gastropoda, such as the Arion spp, the genus umbilicus (biomhalaria spp.), the genus paulospira (Bulinus spp.), the genus deraceras spp, the genus cochlear (Galba spp.), the genus Lymnaea spp, the genus oncomelania spp (oncomelania spp.), the genus ampullaria spp (pomocea spp.), and the genus amber (Succinea spp.).
Preparation
The invention also relates to formulations as plant protection compositions and/or pesticides and to the use forms produced therefrom, such as irrigation, drip and spray liquids, which comprise at least one active substance according to the invention. The use forms optionally contain further plant protection agents and/or pesticides and/or synergistic adjuvants, such as penetrants, for example vegetable oils, for example rapeseed oil, sunflower oil, mineral oils, for example paraffin oil, alkyl esters of vegetable fatty acids, for example rapeseed oil methyl ester or soybean oil methyl ester, or alkanol alkoxylates, and/or spreading agents, for example alkylsiloxanes and/or salts, for example organic or inorganic ammonium or phosphonium salts, for example ammonium sulfate or diammonium phosphate, and/or retention aids, for example dioctyl sulfosuccinate or hydroxypropyl guar polymers, and/or wetting agents, for example glycerol, and/or fertilizers, for example ammonium-, potassium-or phosphorus-containing fertilizers.
Conventional formulations are, for example, water-Soluble Liquids (SL), Emulsion Concentrates (EC), aqueous Emulsions (EW), suspension concentrates (SC, SE, FS, OD), water-dispersible granules (WG), Granules (GR) and capsule Concentrates (CS); these and other formulation types are described, for example, in Crop Life International and in Pesticide Specifications, Manual on definition and use of FAO and WHO Specifications for pesticides, FAO Plant Production and protection Papers-173, FAO/WHO Joint Meeting on Pesticide Specifications, 2004, ISBN: 9251048576. Optionally, the formulations comprise further agrochemical active substances in addition to one or more active substances according to the invention.
Preference is given to formulations or use forms which comprise adjuvants, such as extenders, solvents, spontaneous promoters, carriers, emulsifiers, dispersants, antifreeze agents, antimicrobial agents, thickeners and/or further adjuvants, such as adjuvants. Adjuvants are herein components that improve the biological effect of the formulation but do not have a biological effect themselves. Examples of adjuvants are agents that promote retention, spreading characteristics, adhesion to leaf surfaces or penetration.
These formulations are manufactured in a known manner, for example by mixing the active substances with auxiliaries, for example extenders, solvents and/or solid carriers, and/or further auxiliaries, for example surface-active substances. These formulations are manufactured in a suitable device or prior to or during application.
The adjuvants used may be substances which are suitable for providing the active substances in their formulations or in the use forms prepared from these formulations, for example ready-to-use plant protection compositions, such as spray liquors or seed dressing products (Saatgutbeizen), with specific properties, such as specific physical, technical and/or biological properties.
Suitable extenders are, for example, water, polar and nonpolar organic chemical liquids, for example selected from aromatic and nonaromatic hydrocarbons (such as alkanes, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which may optionally also be substituted, etherified and/or esterified), ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly) ethers, unsubstituted (einfach) and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide).
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Useful liquid solvents include essentially: aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride or dichloromethane, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or ethylene glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water.
In principle, all suitable solvents can be used. Suitable solvents are, for example, aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic hydrocarbons or aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride or dichloromethane, aliphatic hydrocarbons, such as cyclohexane, paraffins, petroleum fractions, mineral and vegetable oils, alcohols, such as methanol, ethanol, isopropanol, butanol or ethylene glycol, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethyl sulfoxide, and water.
In principle, all suitable carriers can be used. Useful carriers include, inter alia: for example ammonium salts and natural rock flour, such as kaolin, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock flour, such as finely divided silica (Kieselsäure), alumina and natural or synthetic silicates, resins, waxes and/or solid fertilizers. Mixtures of such carriers may likewise be used. Carriers that can be used in granules include, for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic powders, and granules of organic materials such as sawdust, paper, coconut shells, corn cobs and tobacco stems.
Liquefied gas extenders or solvents may also be used. Particularly suitable are those extenders or carriers which are gases at standard temperature and at standard pressure, for example aerosol propellant gases such as halogenated hydrocarbons, and butane, propane, nitrogen and carbon dioxide.
Examples of emulsifiers and/or foam formers, dispersants or wetting agents of ionic or nonionic nature or mixtures of these surface-active substances are salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic or naphthalenesulfonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyoxyethylated (polyphenyliert) alcohols or phenols, fatty acid esters of polyhydric alcohols, and derivatives of compounds containing sulfuric, sulfonic and phosphoric esters, such as alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates, protein hydrolysates, lignosulfite waste liquors and methylcellulose. The presence of surface-active substances is advantageous when one of the active substances and/or one of the inert carriers is insoluble in water and when they are applied in water.
Further auxiliaries which may be present in the formulations and the use forms derived therefrom are dyes, such as inorganic pigments, for example iron oxide, titanium oxide and prussian blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and nutrients and micronutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
In addition, stabilizers, such as low temperature stabilizers, preservatives, antioxidants, light stabilizers or other agents that improve chemical and/or physical stability may also be present. In addition, foam formers or defoamers may be present.
In addition, the preparations and the use forms derived therefrom may also contain viscosity-increasing agents, such as carboxymethylcellulose, natural and synthetic powders, granules or latex-type polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids as additional adjuvants. Other adjuvants may be mineral and vegetable oils.
Optionally, further adjuvants may also be present in the formulation and the use forms derived therefrom. Such additives are, for example, perfumes, protective colloids, adhesives, mastics, thickeners, thixotropic agents, penetrating agents, retention aids, stabilizers, chelating agents, complexing agents, wetting agents, spreading agents. In general, the active substance can be combined with various solid or liquid additives commonly used for formulation purposes.
Useful retention aids include substances that reduce dynamic surface tension, such as dioctyl sulfosuccinate, or substances that increase viscoelasticity, such as hydroxypropyl guar polymer.
Penetrants which may be used in the present case are all those substances which are customarily used to improve the penetration of agrochemical active substances into plants. Penetrants are defined herein by their ability to penetrate the plant cuticle from a (usually aqueous) application liquid and/or from a spray liquid and thereby increase the mobility of the active substance in the cuticle. Methods described in the literature (Baur et al 1997, Pesticide Science 51, 131-152) can be used to determine this property. Examples include alcohol alkoxylates, such as cocoethoxylate (10) or isotridecyl ethoxylate (12), fatty acid esters, such as rapeseed oil methyl ester or soybean oil methyl ester, fatty amine alkoxylates, such as tallow based primary amine ethoxylate (15) or ammonium and/or phosphonium salts, such as ammonium sulfate or diammonium phosphate.
The formulations preferably contain from 0.00000001 to 98% by weight of active substance or more preferably from 0.01 to 95% by weight of active substance, more preferably from 0.5 to 90% by weight of active substance, based on the weight of the formulation.
The active substance content of the use forms (plant protection compositions) prepared from the preparations can vary within wide limits. The active substance concentration of the use forms can generally be from 0.00000001 to 95% by weight of active substance, preferably from 0.00001 to 1% by weight, based on the weight of the use form. Application is effected in a conventional manner suitable for the form of use.
Mixture of
The compounds of formula (I) may also be used in admixture with one or more suitable fungicides, bactericides, acaricides, molluscicides, nematicides, insecticides, microbial agents, beneficial microorganisms, herbicides, fertilizers, bird repellents, phytotoxins (phytonics), bactericides, safeners, semiochemicals and/or plant growth regulators to thereby, for example, broaden the spectrum of action, prolong the period of action, enhance the rate of action, prevent rejection or prevent development of resistance. Furthermore, such combinations of active substances may improve plant growth and/or tolerance to abiotic factors, such as high or low temperatures, drought or high water content or soil salt content. It may also improve flowering and fruiting performance, optimize germination capacity and root development, promote harvest and improve yield, affect maturation, improve the quality and/or nutritional value of the harvest, prolong shelf life and/or improve the processability of the harvest.
Furthermore, the compounds of the formula (I) can be present in admixture with other active substances or semiochemicals, such as attractants and/or bird repellents and/or plant activators and/or growth regulators and/or fertilizers. Likewise, the compounds of formula (I) may be used in admixture with agents that improve plant properties, such as growth, yield and quality of harvest.
In a particular embodiment of the invention, the compounds of the formula (I) are present in admixture with other compounds, preferably those described below, in formulations or use forms prepared from these formulations.
If one of the compounds mentioned below can exist in various tautomeric forms, these forms are also included if not explicitly mentioned in each case.
Mixtures with insecticides/acaricides/nematicides
The active substances mentioned herein under their "trivial names" are known and described, for example, in the pesticide handbook (the pesticide Manual, 16th ed., British Crop Protection Council 2012), or can be searched on the internet (for example http:// www.alanwood.net/pesticides).
(1) Acetylcholinesterase (AChE) inhibitors, such as carbamates, e.g., cotton boll-carbofuran, aldicarb, bendiocarb, benfuracarb, butocarbosulfan, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, varacetam, furacarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, monocarb, triazamate, methiocarb, XMC, and methiocarb; or organic phosphates, for example acephate, pirimiphos-methyl, ethoprophos-methyl, glutethion, cadusafos, phosphorus oxychloride, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-methyl, diazinon, dichlorvos/DDVP, chlormephos, dimethoate, chlorfenvinphos, ethoprophos, EPN, ethion, fenamiphos, vamephos, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, Imicyafos, isosulfothion, O- (methoxyaminothiophosphoryl) salicylate, isoxazolophos, malathion, triazophos, methamidophos, methidathion, monocrotophos, naled, omethoate, mesofos, parathion, methyl parathion, phenthophos, oryza, phorate, phosmet, phosphamidogen, phoxim, pirimiphos-methyl, pirimiphos-methyl, pirimiphos, pir, Prothioconazole, pyrazothion, pyridaphenthion, quinalphos, fenitrothion, butylpyrimidinophos, disulfoton, terbufos, chlorfenphos, phorate, triazophos, trichlorfon (Triclorfon) and aphid.
(2) GABA-controlled chlorine channel antagonists, for example cyclopentadienylorganochlorines, such as chlordane and endosulfan, or phenylpyrazole (Fiprole), such as ethiprole and fipronil.
(3) Sodium channel modulators/voltage-dependent sodium channel blockers, e.g., pyrethroids such as, for example, prallethrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin s-cyclopentenyl isomers, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [ (1R) -trans isomer ], deltamethrin, empenthrin [ (EZ) - (1R) isomer ], esfenvalerate, esprox, fenpropathrin, zeta-cypermethrin, Fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, benzoxyfen, prallethrin, thianthrin, Momfluorothrin, permethrin, phenothrin [ (1R) -trans isomer ], prallethrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin [ (1R) isomer ] ], tetrabromthrin and transfluthrin or DDT or methoxychlor.
(4) Nicotinic acetylcholine receptor (nAChR) agonists, such as neonicotinoids, for example acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam or nicotine or sulfoxaflor or Flupyradifurone.
(5) Allosteric activators of nicotinic acetylcholine receptors (nachrs), such as spinosyns (spinosines), e.g., spinetoram and Spinosad (Spinosad).
(6) Chloride channel activators such as avermectins/milbemycins, e.g., abamectin, emamectin benzoate, lepimectin, and milbemycins.
(7) Juvenile hormone mimics, such as juvenile hormone analogs, e.g. Hydroprene, methoprene (Kinoprene) and methoprene or fenoxycarb or pyriproxyfen.
(8) Active substances with unknown or unspecific mechanisms of action, such as alkyl halides, for example methyl bromide and other alkyl halides; or Chloropicrin or sulfuryl fluoride or borax or tartar.
(9) Selective antifeedants such as pymetrozine or flonicamid.
(10) Mite growth inhibitors, such as clofentezine, hexythiazox and flutenzine or etoxazole.
(11) Microbial disruptors of insect gut membranes, such as Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis kurstaki subspecies, Bacillus thuringiensis tenebrionis subspecies and BT plant proteins: cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Ab 1.
(12) Oxidative phosphorylation inhibitors, ATP disruptors, for example diafenthiuron or organotin compounds, for example azocyclotin, tricyclotin and hexafenbutatin oxide (Fenbutatin oxide) or propargite or dicofol.
(13) Oxidative phosphorylation uncouplers that interrupt the H proton gradient, such as chlorfenapyr, DNOC, and sulfluramid.
(14) Nicotinic acetylcholine receptor antagonists such as chlorfenapyr, cartap hydrochloride, thiocyclam and dimehypo.
(15) Chitin biosynthesis inhibitors, type 0, such as bistrifluron, chlorfluazuron, diflubenzuron, epoxiconazole, flufenoxuron, hexaflumuron, lufenuron, Novaluron, Noviflumuron, teflubenzuron and triflumuron.
(16) Chitin biosynthesis inhibitors, type 1, such as buprofezin.
(17) Molting inhibitors (especially for dipterans, i.e. dipterans), such as cyromazine.
(18) Ecdyson receptor agonists, such as chromafenozide, Halofenozide, methoxyfenozide, and tebufenozide.
(19) Octopamine (oktopamine) agonists, such as amitraz.
(20) complex-III electron transport inhibitors, such as hydramethylnon; or acequinocyl; or fluacrypyrim.
(21) complex-I electron transport inhibitors, for example METI acaricides, such as fenazaquin, fenpyroximate, pyriminostrobin, pyridaben, tebufenpyrad and tolfenpyrad or rotenone (Derris).
(22) Voltage-dependent sodium channel blockers, such as indoxacarb or metaflumizone.
(23) Acetyl-coa carboxylase inhibitors, such as tetronic acid (Tetronsäure) and tetramic acid (Tetramsäure) derivatives, such as spirodiclofen, spiromesifen and spirotetramat.
(24) Complex-IV electron transport inhibitors, for example phosphines, such as aluminum phosphide, calcium phosphide, phosphines and zinc phosphide or cyanides.
(25) Complex-II electron transport inhibitors, such as cyenopyrafen and cyflumetofen.
(28) Ryanodine receptor effectors such as diamides, for example chlorantraniliprole, cyantraniliprole and flubendiamide.
Other active substances with an unknown or undefined mechanism of action, such as, for example, Afidopyropen, Afox laner, azadirachtin, Benclothiaz, fenpyroximate, bifenazate, bromopropylate, mefenpyr, cryolite, Cyclaniliprole, cycloxaprid, Cyhalodiamide, Dicloromethiaz, diclomezotiz, flufenacet, Flometoquin, Fluerulfole, Imidamide, Fluomycoside, Butflufipronil (Flufiprole), Fluhexafon, Flupyramid, Fluraldaner, furazazide, Guadipyr, Heptafluthrin, imidaclothiz, iprodione, Ifluthrin, Paichopundin, Pychiazide, pyridalyl, Pyrifluquinazon, pyrifluquinazine, pyriminostrobin, Tetraflufenaminophen, Tetrathion, Tetrathiopyr, Tetraflumorphyrin, Tetraflumorphan, Triflufenox, and Timizapyr; and additionally a Bacillus firmus-based preparation (I-1582, BioNeem, Votivo) and the following known active compounds: 1- { 2-fluoro-4-methyl-5- [ (2,2, 2-trifluoroethyl) sulfinyl ] phenyl } -3- (trifluoromethyl) -1H-1,2, 4-triazol-5-amine (known from WO 2006/043635), {1'- [ (2E) -3- (4-chlorophenyl) prop-2-en-1-yl ] -5-fluorospiro [ indole-3, 4' -piperidin ] -1(2H) -yl } (2-chloropyridin-4-yl) methanone (known from WO 2003/106457), 2-chloro-N- [2- {1- [ (2E) -3- (4-chlorophenyl) prop-2-en-1-yl ] piperidin-4-yl } -4- (trifluoromethyl) phenyl ] isonicotinamide (known from WO 2006/003494), 3- (2, 5-dimethylphenyl) -4-hydroxy-8-methoxy-1, 8-diazaspiro [4.5] dec-3-en-2-one (known from WO 2009/049851), 3- (2, 5-dimethylphenyl) -8-methoxy-2-oxo-1, 8-diazaspiro [4.5] dec-3-en-4-yl ethyl carbonate (known from WO 2009/049851), 4- (but-2-yn-1-yloxy) -6- (3, 5-dimethylpiperidin-1-yl) -5-fluoropyrimidine (known from WO 2004/099160), 4- (but-2-yne-1-oxy) -6- (3-chlorophenyl) pyrimidine (known from WO 2003/076415), PF1364 (CAS number 1204776-60-2), methyl 2- [2- ({ [ 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazol-5-yl ] carbonyl } amino) -5-chloro-3-methylbenzoyl ] -2-methylhydrazinecarboxylate (known from WO 2005/085216), methyl 2- [2- ({ [ 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazol-5-yl ] carbonyl } amino) -5-cyano-3-methylbenzoyl ] -2-ethylhydrazinecarboxylate (known from WO2005 Known from/085216), methyl 2- [2- ({ [ 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazol-5-yl ] carbonyl } amino) -5-cyano-3-methylbenzoyl ] -2-methylhydrazinecarboxylate (known from WO 2005/085216), methyl 2- [3, 5-dibromo-2- ({ [ 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazol-5-yl ] carbonyl } amino) benzoyl ] -2-ethylhydrazinecarboxylate (known from WO 2005/085216), N- [2- (5-amino-1, 3, 4-thiadiazol-2-yl) -4-chloro-6-methylbenzene -3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide (known from CN 102057925), 8-chloro-N- [ (2-chloro-5-methoxyphenyl) sulfonyl ] -6- (trifluoromethyl) imidazo [1,2-a ] pyridine-2-carboxamide (known from WO 2010/129500), 4- [5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydro-1, 2-oxazol-3-yl ] -2-methyl-N- (1-oxathiolan-3-yl) benzamide (known from WO 2009/080250), N- [ (2E) -1- [ (6-chloropyridin-3-yl) methyl ] pyridinylidene-2 (1H) -yl ] -2,2, 2-trifluoroacetamide (known from WO 2012/029672), 1- [ (2-chloro-1, 3-thiazol-5-yl) methyl ] -4-oxo-3-phenyl-4H-pyrido [1,2-a ] pyrimidin-1-ium-2-ol-ate (known from WO 2009/099929), 1- [ (6-chloropyridin-3-yl) methyl ] -4-oxo-3-phenyl-4H-pyrido [1,2-a ] pyrimidin-1-ium-2-ol-ate (known from WO 2009/099929), 4- (3- {2, 6-dichloro-4- [ (3, 3-dichloroprop-2-en-1-yl) oxy ] phenoxy } propoxy) -2-methoxy-6- (trifluoromethyl) pyrimidine (known from CN 101337940), N- [2- (tert-butylcarbamoyl) -4-chloro-6-methylphenyl ] -1- (3-chloropyridin-2-yl) -3- (fluoromethoxy) -1H-pyrazole-5-carboxamide (known from WO 2008/134969), 3- [ benzoyl (methyl) amino ] -N- [ 2-bromo-4- [1,2,2, 2-tetrafluoro-1- (trifluoromethyl) ethyl ] -6- (trifluoromethyl) phenyl ] - 2-fluorobenzamide (known from WO 2010018714), [2- (2, 4-dichlorophenyl) -3-oxo-4-oxaspiro [4.5] dec-1-en-1-yl ] butyl carbonate (known from CN 102060818), 4- [5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4H-isoxazol-3-yl ] -N- [ (Z) -methoxyiminomethyl ] -2-methylbenzamide (known from WO 2007/026965), 3E) -3- [1- [ (6-chloro-3-pyridyl) methyl ] -2-pyridinylene ] -1,1, 1-trifluoropropan-2-one (known from WO 2013/144213), N- (methylsulfonyl) -6- [2- (pyridin-3-yl) -1, 3-thiazol-5-yl ] pyridine-2-carboxamide (known from WO 2012/000896), N- [3- (benzylcarbamoyl) -4-chlorophenyl ] -1-methyl-3- (pentafluoroethyl) -4- (trifluoromethyl) -1H-pyrazole-5-carboxamide (known from WO 2010/051926).
Mixtures with fungicides
The active substances mentioned herein under their "colloquial names" are known and described, for example, in "Pesticide Manual" or on the Internet (for example http:// www.alanwood.net/pesticides).
All fungicidal mixture partners listed in classes (1) to (15) can optionally form salts with the corresponding bases or acids if appropriate functional groups are present. Furthermore, if tautomerism is possible, the fungicidal mixed partners listed in classes (1) to (15) also include tautomeric forms.
1) Ergosterol biosynthesis inhibitors such as (1.01) Aldimorph, (1.02) azaconazole, (1.03) bitertanol, (1.04) bromuconazole, (1.05) cyproconazole, (1.06) benzchlorotriazol, (1.07) difenoconazole, (1.08) diniconazole, (1.09) diniconazole-M, (1.10) moroxydine, (1.11) moroxydine acetate, (1.12) epoxiconazole, (1.13) epoxiconazole, (1.14) fenarimol, (1.15) fenbuconazole, (1.16) fenhexamid, (1.17) fenpropidin, (1.18) butylbenzenestrobin, (1.19) fluquinconazole, (1.20) flurprimidol, (1.21) flusilazole, (1.22) flutriafol, (1.23) Furconazole, (1.24) Furconazole, (1.25) hexaconazole, (1.25) flusilazole-27.26) pyrizole sulfate, (1.28) imibenconazole, (1.29) ipconazole, (1.30) metconazole, (1.31) myclobutanil, (1.32) naftifine, (1.33) fluoropyrimidinol, (1.34) oxpoconazole, (1.35) paclobutrazol, (1.36) pefurazoate, (1.37) penconazole, (1.38) dichlofluanid, (1.39) prochloraz, (1.40) propiconazole, (1.41) prothioconazole, (1.42) barnyard grass-vos, (1.43) pyribenzoxim, (1.44) Quinconazol, (1.45) simeconazole, (1.46) spiroxamine, (1.47) tebuconazole, (1.48) terbinafine, (1.49) tetraconazole, (1.50) triadimefon, (1.51) triadimenol, (1.52) tridemorph, (1.53) fluconazole, (1.54) triflumizole, (1.56) Uniconazole, (1.58) Uniconazole, (1.51) Uniconazole, (1.58) Uniconazole, (1.59) voriconazole, (1.60) 1- (4-chlorophenyl) -2- (1H-1,2, 4-triazol-1-yl) cycloheptanol, (1.61) 1- (2, 2-dimethyl-2, 3-dihydro-1H-inden-1-yl) -1H-imidazole-5-carboxylic acid methyl ester, (1.62) N '- {5- (difluoromethyl) -2-methyl-4- [3- (trimethylsilyl) propoxy ] phenyl } -N-ethyl-N-methylacyliminocarboxamide, (1.63) N-ethyl-N-methyl-N' - { 2-methyl-5- (trifluoromethyl) -4- [3- (trimethylsilyl) propoxy ] phenyl } Imidocarboxamides, (1.64) O- [1- (4-methoxyphenoxy) -3, 3-dimethylbutan-2-yl ] -1H-imidazole-1-thiocarbamate, (1.65) pyribenzole oxazole (Pyresoxal), (1.66) 2- { [3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl ] methyl } -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.67) thiocyanic acid 1- { [3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl ] methyl } -1H-1,2, 4-triazol-5-yl ester, (1.68) 5- (allylsulfanyl) -1- { [3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl ] methyl } -1H-1,2, 4-triazole, (1.69) 2- [1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.70) 2- { [ rel (2R,3S) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl ] methyl } -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.71) 2- { [ rel (2R,3R) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl ] methyl } -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.72) thiocyanic acid 1- { [ rel (2R,3S) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl ] methyl } -1H-1,2, 4-triazol-5-yl ester, (1.73) thiocyanic acid 1- { [ rel (2R,3R) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl ] methyl } -1H-1,2, 4-triazol-5-yl ester, (1.74) 5- (allylsulfanyl) -1- { [ rel (2R,3S) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl ] methyl } -1H-1,2, 4-triazole, (1.75) 5- (allylsulfanyl) -1- { [ rel (2R,3R) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl ] methyl } -1H-1,2, 4-triazole, (1.76) 2- [ (2S,4S,5S) -1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.77) 2- [ (2R,4S,5S) -1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.78) 2- [ (2R,4R,5R) -1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.79) 2- [ (2S,4R,5R) -1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.80) 2- [ (2S,4S,5R) -1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.81) 2- [ (2R,4S,5R) -1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.82) 2- [ (2R,4R,5S) -1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.83) 2- [ (2S,4R,5S) -1- (2, 4-dichlorophenyl) -5-hydroxy-2, 6, 6-trimethylhept-4-yl ] -2, 4-dihydro-3H-1, 2, 4-triazole-3-thione, (1.84) 2- [4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl ] -1- (1H-1,2, 4-triazol-1-yl) propan-2-ol, (1.85) 2- [4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl ] -1- (1H-1,2, 4-triazol-1-yl) butan-2-ol, (1.86) 2- [4- (4-chlorophenoxy) -2- (trifluoromethyl) phenyl ] -1- (1H-1,2, 4-triazol-1-yl) pentan-2-ol, (1.87) 2- [ 2-chloro-4- (4-chlorophenoxy) phenyl ] -1- (1H-1,2, 4-triazol-1-yl) butan-2-ol, (1.88) 2- [ 2-chloro-4- (2, 4-dichlorophenoxy) phenyl ] -1- (1H-1,2, 4-triazol-1-yl) propan-2-ol, (1.89) (2R) -2- (1-chlorocyclopropyl) -4- [ (1R) -2, 2-Dichlorocyclopropyl ] -1- (1H-1,2, 4-triazol-1-yl) butan-2-ol, (1.90) (2R) -2- (1-chlorocyclopropyl) -4- [ (1S) -2, 2-dichlorocyclopropyl ] -1- (1H-1,2, 4-triazol-1-yl) butan-2-ol, (1.91) (2S) -2- (1-chlorocyclopropyl) -4- [ (1S) -2, 2-dichlorocyclopropyl ] -1- (1H-1,2, 4-triazol-1-yl) butan-2-ol, (1.92) (2S) -2- (1-chlorocyclopropyl) -4- [ (1R) -2, 2-dichlorocyclopropyl ] -1- (1H-1,2, 4-triazol-1-yl) butan-2-ol, (1.93) (1S,2R,5R) -5- (4-chlorobenzyl) -2- (chloromethyl) -2-methyl-1- (1H-1,2, 4-triazol-1-ylmethyl) cyclopentanol, (1.94) (1R,2S,5S) -5- (4-chlorobenzyl) -2- (chloromethyl) -2-methyl-1- (1H-1,2, 4-triazol-1-ylmethyl) cyclopentanol, (1.95) 5- (4-chlorobenzyl) -2- (chloromethyl) -2-methyl-1- (1H-1,2, 4-triazol-1-ylmethyl) cyclopentanol.
2) Respiratory chain inhibitors at complex I or II, for example (2.01) bispyribac-pyrim, (2.02) boscalid, (2.03) carboxin, (2.04) Diflumetoriom, (2.05) methylfuroamide, (2.06) fluopyram, (2.07) flutolamide, (2.08) fluxapyroxad, (2.09) furamectin, (2.10) pyrimethanil, (2.11) Isopyrazam (cis-epimeric racemate 1RS,4SR,9RS and anti-epimeric racemate 1RS,4SR,9 SR), (2.12) Isopyrazam (trans-epimeric racemate 1RS,4SR,9 SR), (2.13) Isopyrazam (trans-epimeric racemate 1R,4S, 9S), (2.14) Isopyrazam (trans-epimeric enantiomer 1S,4R, 9R), (2.14) Isopyrazam (trans-epimeric racemate 1RS, 4R,9 RS), (2.15) Isopyrazam (cis-epimeric racemate 1RS,4SR,9 RS), (2.16) Isopyrazam (cis-epimer 1R,4S, 9R), (2.17) Isopyrazam (cis-epimer 1S,4R, 9S), (2.18) mefenamide, (2.19) oxycarboxin (2.20) Penflufen, (2.21) penthiopyrad, (2.22) Sedaxan, (2.23) thifluzamide, (2.24) 1-methyl-N- [2- (1,1,2, 2-tetrafluoroethoxy) phenyl ] -3- (trifluoromethyl) -1H-pyrazole-4-carboxamide, (2.25) 3- (difluoromethyl) -1-methyl-N- [2- (1,1,2, 2-tetrafluoroethoxy) phenyl ] -1H-pyrazole-4-carboxamide, and mixtures thereof, (2.26) 3- (difluoromethyl) -N- [ 4-fluoro-2- (1,1,2,3,3, 3-hexafluoropropoxy) phenyl ] -1-methyl-1H-pyrazole-4-carboxamide, (2.27) N- [1- (2, 4-dichlorophenyl) -1-methoxypropan-2-yl ] -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide, (2.28) 5, 8-difluoro-N- [2- (2-fluoro-4- { [4- (trifluoromethyl) pyridin-2-yl ] oxy } phenyl) ethyl ] quinazolin-4-amine, (2.29) Benzovindifiupy, (2.30) N- [ (1S,4R) -9- (dichloromethylene) -1,2,3, 4-tetrahydro-1, 4-methanonaphthalen-5-yl ] -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide, (2.31) N- [ (1R,4S) -9- (dichloromethylene) -1,2,3, 4-tetrahydro-1, 4-methanonaphthalen-5-yl ] -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide, (2.32) 3- (difluoromethyl) -1-methyl-N- (1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl) -1H-pyrazole-4-carboxamide, (2.33) 1,3, 5-trimethyl-N- (1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl) -1H-pyrazole-4-carboxamide, (2.34) 1-methyl-3- (trifluoromethyl) -N- (1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl) -1H-pyrazole-4-carboxamide, (2.35) 1-methyl-3- (trifluoromethyl) -N- [ (3R) -1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl ] -1H-pyrazole-4-carboxamide, (2.36) 1-methyl-3- (trifluoromethyl) -N- [ (3S) -1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl ] -1H-pyrazole-4-carboxamide, (2.37) 3- (difluoromethyl) -1-methyl-N- [ (3S) -1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl ] -1H-pyrazole-4-carboxamide, (2.38) 3- (difluoromethyl) -1-methyl-N- [ (3R) -1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl ] -1H-pyrazole-4-carboxamide, (2.39) 1,3, 5-trimethyl-N- [ (3R) -1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl ] -1H-pyrazole-4-carboxamide, (2.40) 1,3, 5-trimethyl-N- [ (3S) -1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl ] -1H-pyrazole-4-carboxamide, (2.41) Puccinate, (2.42) 2-chloro-N- (1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl) pyridine-3-carboxamide, (2.43) Isofetamid, (2.44) 1-methyl-3- (trifluoromethyl) -N- [2'- (trifluoromethyl) biphenyl-2-yl ] -1H-pyrazole-4-carboxamide, (2.45) N- (4' -chlorobiphenyl-2-yl) -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide, (2.46) N- (2',4' -dichlorobiphenyl-2-yl) -3- (difluoromethyl) -1-methyl-1H-pyrazole- 4-carboxamide, (2.47) 3- (difluoromethyl) -1-methyl-N- [4'- (trifluoromethyl) biphenyl-2-yl ] -1H-pyrazole-4-carboxamide, (2.48) N- (2',5 '-difluorobiphenyl-2-yl) -1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carboxamide, (2.49) 3- (difluoromethyl) -1-methyl-N- [4' - (prop-1-yn-1-yl) biphenyl-2-yl ] -1H-pyrazole-4-carboxamide, (2.50) 5-fluoro-1, 3-dimethyl-N- [4'- (prop-1-yn-1-yl) biphenyl-2-yl ] -1H-pyrazole-4-carboxamide, (2.51) 2-chloro-N- [4' - (prop-1-yn-1-yl) biphenyl-2-yl ] nicotinamide, (2.52) 3- (difluoromethyl) -N- [4'- (3, 3-dimethylbut-1-yn-1-yl) biphenyl-2-yl ] -1-methyl-1H-pyrazole-4-carboxamide, (2.53) N- [4' - (3, 3-dimethylbut-1-yn-1-yl) biphenyl-2-yl ] -5-fluoro-1, 3-dimethyl-1H-pyrazole-4-carboxamide, (2.54) 3- (difluoromethyl) -N- (4 '-ethynylbiphenyl-2-yl) -1-methyl-1H-pyrazole-4-carboxamide, (2.55) N- (4' -ethynylbiphenyl-2-yl) -5-fluoro-1, 3-dimethyl-1H-pyrazole-4-carboxamide, (2.56) 2-chloro-N- (4 '-ethynylbiphenyl-2-yl) nicotinamide, (2.57) 2-chloro-N- [4' - (3, 3-dimethylbut-1-yn-1-yl) biphenyl-2-yl ] nicotinamide, (2.58) 4- (difluoromethyl) -2-methyl-N- [4'- (trifluoromethyl) biphenyl-2-yl ] -1, 3-thiazole-5-carboxamide, (2.59) 5-fluoro-N- [4' - (3-hydroxy-3-methylbut-1-yn-1-yl) biphenyl-2-yl ] -1, 3-dimethyl-1H-pyrazole-4-carboxamide, (2.60) 2-chloro-N- [4'- (3-hydroxy-3-methylbut-1-yn-1-yl) biphenyl-2-yl ] nicotinamide, (2.61) 3- (difluoromethyl) -N- [4' - (3-methoxy-3-methyl-but-1-yn-1-yl) biphenyl-2-yl ] nicotinamide Phenylbut-1-yn-1-yl) biphenyl-2-yl ] -1-methyl-1H-pyrazole-4-carboxamide, (2.62) 5-fluoro-N- [4'- (3-methoxy-3-methylbut-1-yn-1-yl) biphenyl-2-yl ] -1, 3-dimethyl-1H-pyrazole-4-carboxamide, (2.63) 2-chloro-N- [4' - (3-methoxy-3-methylbut-1-yn-1-yl) biphenyl-2-yl ] nicotinamide, (2.64) 1, 3-dimethyl-N- (1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl) -1H-pyrazole-4-carboxamide, (2.65) 1, 3-dimethyl-N- [ (3R) -1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl ] -1H-pyrazole-4-carboxamide, (2.66) 1, 3-dimethyl-N- [ (3S) -1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl ] -1H-pyrazole-4-carboxamide, (2.67) 3- (difluoromethyl) -N-methoxy-1-methyl-N- [1- (2,4, 6-trichlorophenyl) propan-2-yl ] -1H-pyrazole-4-carboxamide, (2.68) 3- (difluoromethyl) -N- (7-fluoro-1, 1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl) -1-methyl-1H-pyrazole-4-carboxamide, (2.69) 3- (difluoromethyl) -N- [ (3R) -7-fluoro-1, 1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl ] -1-methyl-1H-pyrazole-4-carboxamide, (2.70) 3- (difluoromethyl) -N- [ (3S) -7-fluoro-1, 1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl ] -1-methyl-1H-pyrazole-4-carboxamide.
3) Inhibitors of the respiratory chain at complex III, such as (3.01) ametoctradin, (3.02) Amisulbrom (Amisulbrom), (3.03) azoxystrobin, (3.04) cyazofamid, (3.05) coumoxystrobin (coumethoxystebinin), (3.06) coumoxystrobin, (3.07) dimoxystrobin, (3.08) enestroburin (enoxabin), (3.09) famoxadone, (3.10) fenamidone, (3.11) fluxastrobin, (3.12) fluoxastrobin, (3.13) kresoxim-methyl, (3.14) metominostrobin, (3.15) trifloxystrobin, (3.16) picoxystrobin, (3.17) pyraclostrobin, (3.18) pyraclostrobin, (3.19) pyraclostrobin, (3.20) pyrronicarb, (3.21) triclopyr), (3.22) fenamidoxim, (3.23) trifloxystrobin, (3.23) 2- (2-phenoxy) -2-6-phenyl-methyl-3- { [ phenoxy ] trifloxystrobin (3.3.3.3-6) trifloxystrobin ) -2- (methoxyimino) -N-methylacetamide, (3.24) (2E) -2- (methoxyimino) -N-methyl-2- (2- { [ ({ (1E) -1- [3- (trifluoromethyl) phenyl ] ethylidene } amino) oxy ] methyl } phenyl) acetamide, (3.25) (2E) -2- (methoxyimino) -N-methyl-2- {2- [ (E) - ({1- [3- (trifluoromethyl) phenyl ] ethoxy } imino) methyl ] phenyl } acetamide, (3.26) (2E) -2- {2- [ ({ [ (1E) -1- (3- { [ (E) -1-fluoro-2-phenylvinyl ] oxy } phenyl) ethylidene ] amino } the invention Oxy) methyl ] phenyl } -2- (methoxyimino) -N-methylacetamide, (3.27) Feraminostrabin, (3.28) 5-methoxy-2-methyl-4- (2- { [ ({ (1E) -1- [3- (trifluoromethyl) phenyl ] ethylidene } amino) oxy ] methyl } phenyl) -2, 4-dihydro-3H-1, 2, 4-triazol-3-one, (3.29) (2E) -2- {2- [ ({ cyclopropyl [ (4-methoxyphenyl) imino ] methyl } sulfanyl) methyl ] phenyl } -3-methoxyacrylate methyl (3.30) N- (3-ethyl-3, 5, 5-trimethylcyclohexyl) -3-carboxamido-2-hydroxybenzamide, (3.31) 2- {2- [ (2, 5-dimethylphenoxy) methyl ] phenyl } -2-methoxy-N-methylacetamide, (3.32) 2- {2- [ (2, 5-dimethylphenoxy) methyl ] phenyl } -2-methoxy-N-methylacetamide, (3.33) (2E,3Z) -5- { [1- (4-chlorophenyl) -1H-pyrazol-3-yl ] oxy } -2- (methoxyimino) -N, 3-dimethylpent-3-enamide.
4) Mitotic and cell division inhibitors, for example (4.01) benomyl, (4.02) carbendazim, (4.03) Chrofenazol, (4.04) diethofencarb, (4.05) ethaboxam, (4.06) fluopicolide, (4.07) fuberidazole, (4.08) pencycuron, (4.09) thiabendazole, (4.10) thiophanate-methyl, (4.11) thiophanate, (4.12) zoxamide, (4.13) 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4, 6-trifluorophenyl) [1,2,4] triazolo [1,5-a ] pyrimidine, (4.14) 3-chloro-5- (6-chloropyridin-3-yl) -6-methyl-4- (2,4, 6-trifluorophenyl) pyridazine.
5) Compounds capable of having a multipoint action, for example (5.01) Bordeaux mixture, (5.02) captafol, (5.03) captan, (5.04) chlorothalonil, (5.05) cupric hydroxide, (5.06) cupric naphthenate, (5.07) cupric oxide, (5.08) copper oxychloride, (5.09) cupric sulfate (2+), (5.10) dichlofluanim, (5.11) diazinon, (5.12) dodine, (5.13) dodine free base, (5.14) ferbamate, (5.15) fluorofurolpet, (5.16) captan, (5.17) iminoctadine, (5.18) iminoctadine acetate, (5.19) iminoctadine, (5.20) iminoctadine besylate, (5.21) iminoctadine triacetate, (5.22) manganin, (5.23) mancozeb, (5.24) iminoctadine acetate, (5.5.5) mancozeb, (5.25) quinacridide acetate, (5.5.25) quinacrine, (5.28) propamidine, (5.29) propineb, (5.30) sulphur and sulphur preparations including lime sulphur, thiram (5.31), tolylfluanid (5.32), zineb (5.33), ziram (5.34), and trichlorfon (5.35).
6) Compounds capable of inducing host defense responses, such as (6.01) Acibenzolar-S-methyl, (6.02) Isotianil (Isotianil), (6.03) thiabendazole, (6.04) tiadinil, and (6.05) laminarin.
7) Inhibitors of amino acid and/or protein biosynthesis, such as (7.01) Andoprim, (7.02) Blasticidin (Blasticidin-S), (7.03) cyprodinil, (7.04) kasugamycin, (7.05) kasugamycin hydrochloride hydrate, (7.06) mepanipyrim, (7.07) pyrimethanil, (7.08) 3- (5-fluoro-3, 3,4, 4-tetramethyl-3, 4-dihydroisoquinolin-1-yl) quinoline, (7.09) oxytetracycline, and (7.10) streptomycin.
8) Inhibitors of ATP production, for example (8.01) fentintin chloride, (8.02) fentinchloride, (8.03) fentin chloride, (8.04) Silthiofam.
9) Inhibitors of cell wall synthesis, such as (9.01) benthiavalicarb-isopropyl, (9.02) dimethomorph, (9.03) flumorph, (9.04) propineb, (9.05) mandipropamid, (9.06) polyoxin, (9.07) polyoxin, (9.08) validamycin A, (9.09) Valifenacat, (9.10) polyoxin B, (9.11) (2E) -3- (4-tert-butylphenyl) -3- (2-chloropyridin-4-yl) -1- (morpholin-4-yl) prop-2-en-1-one, (9.12) (2Z) -3- (4-tert-butylphenyl) -3- (2-chloropyridin-4-yl) -1- (morpholin-4-yl) prop-2-en-1-one.
10) Inhibitors of lipid and membrane synthesis, such as (10.01) biphenyl, (10.02) dicyclopentadienyl, (10.03) clonidine, (10.04) edifenphos, (10.05) clomazole, (10.06) Iodocarb, (10.07) iprobenfos, (10.08) isoprothiolane, (10.09) propamocarb, (10.10) propamocarb hydrochloride, (10.11) amproparb, (10.12) fenamiphos, (10.13) quintozene, (10.14) tetrachloronitrobenzene, (10.15) tolclofos-methyl.
11) Inhibitors of melanin biosynthesis, such as (11.01) cyclopropanamide, (11.02) diclorocyanide, (11.03) cyanamide, (11.04) phthalide, (11.05) pyroquilon, (11.06) tricyclazole, (11.07) { 3-methyl-1- [ (4-methylbenzoyl) amino ] butan-2-yl } carbamic acid 2,2, 2-trifluoroethyl ester.
12) Inhibitors of nucleic acid synthesis, for example (12.01) benalaxyl, (12.02) benalaxyl-M (Kiralaxyl), (12.03) bupirimate, (12.04) Clozylacon, (12.05) metidine, (12.06) ethirimol, (12.07) furalaxyl, (12.08) hymexazol, (12.09) metalaxyl, (12.10) metalaxyl-M (Mefenoxam), (12.11) meturamide, (12.12) oxadixyl, (12.13) oxolinic acid, (12.14) octreone.
13) Inhibitors of signal transduction such as (13.01) ethiprole, (13.02) fenpiclonil, (13.03) fludioxonil, (13.04) iprodione, (13.05) procymidone, (13.06) quinoxyfen, (13.07) vinclozolin, and (13.08) Proquinazid.
14) Compounds capable of acting as uncouplers, such as (14.01) binapacryl, (14.02) fenamipide (Dinocap), (14.03) azozone, (14.04) fluazinam, (14.05) Meptyldinocap.
15) Other compounds, for example, (15.001) thiocyanobenzene, (15.002) Bethoxazin, (15.003) carbamycin (capsomycin), (15.004) carvone, (15.005) mefenpyr, (15.006) Pyriofenone (Chlazafenone), (15.007) thiabendazole, (15.008) Cyflufenamid (Cyflufenamid), (15.009) cymoxanil, (15.010) Cyprosufamide, (15.011) dazomet, (15.012) imicarb (Debacarb), (5) dichlorophenol, (15.014) diclofenapyr, (15.015) delphin, (15.016) difenzoquat sulfate (Difenzoquat sulfate), (15.017) diphenylamine, (15.018) Ecomat, (15.019) Fenpyrazamine (Fenpzamine), (82 15.020) fluidester, (56) flutypyrad, (368653) Calcium sulfofenamide (Fotiazem 8427), (365737) Fosetyl (368658) Calcium hexachlorophene (368627), Calcium hexachlorophene (Folium 15.023), (15.028) Irumamycin, (15.029) sulbencarb, (15.030) methyl isothiocyanate, (15.031) metrafenone, (15.032) milomycin, (15.033) natamycin, (15.034) nickel dimethyldithiocarbamate, (15.035) phthalazinone (Nitroth-isoproyl), (15.036) Oxamocarb, (15.037) Oxyfenthin, (15.038) pentachlorophenol and salts, (15.039) phenothrin, (15.040) phosphorous acid and salts thereof, (15.041) Propamocarb-fosetylate, (15.042) Propanosine-Natrium, (15.043) Pyrimorph (Pyrimorph), (15.044) pyrolidin (Pyrrolitrin), (15.045) Tebuquiflon, (15.046) bisumyl, (15.047) Tolnidid, (15.048) Triazoxid, (15.049) trichlamide (28) cyanamid, (6863) fenpyrad-isopropyl-3, S-isoproxil-2, S-isopropyl-) - (3) pyridine (R-isopropyl-3-isopropyl-pyraclostrobin (3, 7) propanil-isopropyl, isopropyl-beta-isopropyl, isopropyl-beta 2-yl } carbonyl) amino ] -6-methyl-4, 9-dioxo-1, 5-dioxononan (dioxan) -7-yl ester, (15.052) 1- (4- {4- [ (5R) -5- (2, 6-difluorophenyl) -4, 5-dihydro-1, 2-oxazol-3-yl ] -1, 3-thiazol-2-yl } piperidin-1-yl) -2- [ 5-methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl ] ethanone, (15.053) 1- (4- {4- [ (5S) -5- (2, 6-difluorophenyl) -4, 5-dihydro-1, 2-oxazol-3-yl ] -1, 3-thiazol-2-yl } piperidin-1-yl) -2- [ 5-methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl ] ethanone, (15.054) Oxathiapiprolin, (15.055) 1H-imidazole-1-carboxylic acid 1- (4-methoxyphenoxy) -3, 3-dimethylbut-2-yl ester, (15.056) 2,3,5, 6-tetrachloro-4- (methylsulfonyl) pyridine, (15.057) 2, 3-dibutyl-6-chlorothieno [2,3-d ] pyrimidin-4 (3H) -one, (15.058) 2, 6-dimethyl-1H, 5H- [1,4] dithiino [2,3-c:5,6-c' ] dipyrrole-1, 3,5,7(2H,6H) -tetraone, (15.059)2- [ 5-methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl ] -1- (4- {4- [ (5R) -5-phenyl-4, 5-dihydro-1, 2-oxazol-3-yl ] -1, 3-thiazol-2-yl } piperidin-1-yl) ethanone, (15.060) 2- [ 5-methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl ] -1- (4- {4- [ (5S) -5-phenyl- ] -piperidin-1-yl -4, 5-dihydro-1, 2-oxazol-3-yl ] -1, 3-thiazol-2-yl } piperidin-1-yl) ethanone, (15.061) 2- [ 5-methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl ] -1- {4- [4- (5-phenyl-4, 5-dihydro-1, 2-oxazol-3-yl) -1, 3-thiazol-2-yl ] piperidin-1-yl } ethanone, (15.062) 2-butoxy-6-iodo-3-propyl-4H-chromen-4-one, (15.063) 2-chloro-5- [ 2-chloro-1- (2, 6-difluoro-4-methoxyphenyl) -4-methyl-1H-imidazol-5-yl ] pyridine, (15.064) 2-phenylphenol and salts, (15.065) 3- (4,4, 5-trifluoro-3, 3-dimethyl-3, 4-dihydroisoquinolin-1-yl) quinoline, (15.066) 3,4, 5-trichloropyridine-2, 6-dicarbonitrile, (15.067) 3-chloro-5- (4-chlorophenyl) -4- (2, 6-difluorophenyl) -6-methylpyridazine, (15.068) 4- (4-chlorophenyl) -5- (2, 6-difluorophenyl) -3, 6-dimethylpyridazine, 15.068), (15.069) 5-amino-1, 3, 4-thiadiazole-2-thiol, (15.070) 5-chloro-N '-phenyl-N' - (prop-2-yn-1-yl) thiophene-2-sulfonylhydrazide, (15.071) 5-fluoro-2- [ (4-fluorobenzyl) oxy ] pyrimidin-4-amine, (15.072) 5-fluoro-2- [ (4-methylbenzyl) oxy ] pyrimidin-4-amine, (15.073) 5-methyl-6-octyl [1,2,4] triazolo [1,5-a ] pyrimidin-7-amine, (15.074) (2Z) -3-amino-2-cyano-3-phenylpropenoic acid ethyl ester, and, (15.075) N' - (4- { [3- (4-chlorobenzyl) -1,2, 4-thiadiazol-5-yl ] oxy } -2, 5-dimethylphenyl) -N-ethyl-N-methyloimidocarboxamide, (15.076) N- (4-chlorobenzyl) -3- [ 3-methoxy-4- (prop-2-yn-1-yloxy) phenyl ] propanamide, (15.077) N- [ (4-chlorophenyl) (cyano) methyl ] -3- [ 3-methoxy-4- (prop-2-yn-1-yloxy) phenyl ] propanamide, (15.078) N- [ (5-bromo-3-chloropyridin-2-yl) methyl ] -2, 4-dichloronicotinamide, (15.079) N- [1- (5-bromo-3-chloropyridin-2-yl) ethyl ] -2, 4-dichloronicotinamide, (15.080) N- [1- (5-bromo-3-chloropyridin-2-yl) ethyl ] -2-fluoro-4-iodonicotinamide, (15.081) N- { (E) - [ (cyclopropylmethoxy) imino ] [6- (difluoromethoxy) -2, 3-difluorophenyl ] methyl } -2-phenylacetamide, (15.082) N- { (Z) - [ (cyclopropylmethoxy) imino ] [6- (difluoromethoxy) -2, 3-difluorophenyl ] methyl } -2-phenylacetamide, (15.083) N' - {4- [ (3-tert-butyl-4-cyano-1, 2-thiazol-5-yl) oxy ] -2-chloro-5-methylphenyl } -N-ethyl-N-methylimidocarboxamide, (15.084) N-methyl-2- (1- { [ 5-methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl ] acetyl } piperidin-4-yl) -N- (1,2,3, 4-tetrahydronaphthalen-1-yl) -1, 3-thiazole-4-carboxamide, (15.085) N-methyl-2- (1- { [ 5-methyl-3- (trifluoromethyl) -1H-pyrazol-1- Yl ] acetyl } piperidin-4-yl) -N- [ (1R) -1,2,3, 4-tetrahydronaphthalen-1-yl ] -1, 3-thiazole-4-carboxamide, (15.086) N-methyl-2- (1- { [ 5-methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl ] acetyl } piperidin-4-yl) -N- [ (1S) -1,2,3, 4-tetrahydronaphthalen-1-yl ] -1, 3-thiazole-4-carboxamide, (15.087) {6- [ ({ [ (1-methyl-1H-tetrazol-5-yl) (phenyl) methylene ] amino } oxy) methyl ] pyridin-2-yl } carbamic acid pentyl ester, (15.088) phenazine-1-carboxylic acid, (15.089) quinolin-8-ol, (15.090) quinolin-8-ol sulfate (2:1), (15.091) {6- [ ({ [ (1-methyl-1H-tetrazol-5-yl) (phenyl) methylidene ] amino } oxy) methyl ] pyridin-2-yl } carbamic acid tert-butyl ester, (15.092) (5-bromo-2-methoxy-4-methylpyridin-3-yl) (2,3, 4-trimethoxy-6-methylphenyl) methanone, (15.093) N- [2- (4- { [3- (4-chlorophenyl) prop-2-yn-1-yl ] oxy } -3-methoxyphenyl) ethyl ] -N2- (methylsulfonyl) valinamide, (15.094) 4-oxo-4- [ (2-phenylethyl) amino ] butanoic acid, (15.095) {6- [ ({ [ (Z) - (1-methyl-1H-tetrazol-5-yl) (phenyl) methylidene ] amino } oxy) methyl ] pyridin-2-yl } carbamic acid but-3-yn-1-yl, (15.096) 4-amino-5-fluoropyrimidin-2-ol (tautomeric form: 4-amino-5-fluoropyrimidin-2 (1H) -one), (15.097) propyl 3,4, 5-trihydroxybenzoate, (15.098) [3- (4-chloro-2-fluorophenyl) -5- (2, 4-difluorophenyl) -1, 2-oxazol-4-yl ] (pyridin-3-yl) methanol, (15.099) (S) - [3- (4-chloro-2-fluorophenyl) -5- (2, 4-difluorophenyl) -1, 2-oxazol-4-yl ] (pyridin-3-yl) methanol, (15.100) (R) - [3- (4-chloro-2-fluorophenyl) -5- (2, 4-difluorophenyl) -1, 2-oxazol-4-yl ] (pyridin-3-yl) methanol, (15.101) 2-fluoro-6- (trifluoromethyl) -N- (1,1, 3-trimethyl-2, 3-dihydro-1H-inden-4-yl) benzamide, and pharmaceutically acceptable salts thereof, (15.102) 2- (6-benzylpyridin-2-yl) quinazoline, (15.103) 2- [6- (3-fluoro-4-methoxyphenyl) -5-methylpyridin-2-yl ] quinazoline, (15.104)3- (4, 4-difluoro-3, 3-dimethyl-3, 4-dihydroisoquinolin-1-yl) quinoline, (15.105) abscisic acid, (15.106) N '- [ 5-bromo-6- (2, 3-dihydro-1H-inden-2-yloxy) -2-methylpyridin-3-yl ] -N-ethyl-N-methylacyliminocarboxamide, (15.107) N' - { 5-bromo-6- [1- (3, 5-difluorophenyl) ethoxy ] -2-methylpyridin-3-yl } -N-ethyl-N-methylimidocarboxamide, (15.108) N ' - { 5-bromo-6- [ (1R) -1- (3, 5-difluorophenyl) ethoxy ] -2-methylpyridin-3-yl } -N-ethyl-N-methylimidocarboxamide, (15.109) N ' - { 5-bromo-6- [ (1S) -1- (3, 5-difluorophenyl) ethoxy ] -2-methylpyridin-3-yl } -N-ethyl-N-methylimidocarboxamide, (15.110) N ' - { 5-bromo-6- [ (cis-4-isopropylcyclohex-yclohexyl) -cis-3-yl ] -2-methylpyridin-3-yl } -N-ethyl-N-methylimidocarboxamide Yl) oxy ] -2-methylpyridin-3-yl } -N-ethyl-N-methylimidazolinecarboxamide, (15.111) N' - { 5-bromo-6- [ (trans-4-isopropylcyclohexyl) oxy ] -2-methylpyridin-3-yl } -N-ethyl-N-methylimidazolinecarboxamide, (15.112) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N- (2-isopropylbenzyl) -1-methyl-1H-pyrazole-4-carboxamide, (15.113) N-cyclopropyl-N- (2-cyclopropylbenzyl) -3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole -4-carboxamide, (15.114) N- (2-tert-butylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.115) N- (5-chloro-2-ethylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.116) N- (5-chloro-2-isopropylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.117) N-cyclopropyl-3- (difluoromethyl) -N- (2-ethyl-5-fluorobenzyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.118) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N- (5-fluoro-2-isopropylbenzyl) -1-methyl-1H-pyrazole-4-carboxamide, (15.119) N-cyclopropyl-N- (2-cyclopropyl-5-fluorobenzyl) -3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.120) N- (2-cyclopentyl-5-fluorobenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.121) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N- (2-fluoro-6-isopropylbenzyl) -1-methyl-1H-pyrazole-4-carboxamide, (15.122) N-cyclopropyl-3- (difluoromethyl) -N- (2-ethyl-5-methylbenzyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.123) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N- (2-isopropyl-5-methylbenzyl) -1-methyl-1H-pyrazole-4-carboxamide, (15.124) N-cyclopropyl-N- (2-cyclopropyl-5-methylbenzyl) -3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.125) N- (2-tert-butyl-5-methylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.126) N- [ 5-chloro-2- (trifluoromethyl) benzyl ] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.127) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-N- [ 5-methyl-2- (trifluoromethyl) benzyl ] -1H-pyrazole-4-carboxamide, (15.128) N- [ 2-chloro-6- (trifluoromethyl) benzyl ] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.129) N- [ 3-chloro-2-fluoro-6- (trifluoromethyl) benzyl ] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.130) N-cyclopropyl-3- (difluoromethyl) -N- (2-ethyl-4, 5-dimethylbenzyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.131) N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N- (2-isopropylbenzyl) -1-methyl-1H-pyrazole-4-carbothiocarboxamide, (15.132) N '- (2, 5-dimethyl-4-phenoxyphenyl) -N-ethyl-N-methyloimidocarboxamide, (15.133) N' - {4- [ (4, 5-dichloro-1, 3-thiazol-2-yl) oxy ] -2, 5-dimethylphenyl } -N-ethyl-N-methyloimidocarboxamide, (15.134) N- (4-chloro-2, 6-difluorophenyl) -4- (2-chloro-4-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (15.135) 9-fluoro-2, 2-dimethyl-5- (quinolin-3-yl) -2, 3-dihydro-1, 4-benzoxepin (Benzoxazepin), (15.136) 2- { 2-fluoro-6- [ (8-fluoro-2-methylquinolin-3-yl) oxy ] phenyl } propan-2-ol, (15.137) 2- {2- [ (7, 8-difluoro-2-methylquinolin-3-yl) oxy ] -6-fluorophenyl } propan-2-ol, (15.138) 4- (2-chloro-4-fluorophenyl) -N- (2-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (15.139) 4- (2-chloro-4-fluorophenyl) -N- (2, 6-difluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (15.140) 4- (2-chloro-4-fluorophenyl) -N- (2-chloro-6-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (15.141) 4- (2-bromo-4-fluorophenyl) -N- (2-chloro-6-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (15.142) N- (2-bromo-6-fluorophenyl) -4- (2-chloro-4-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (15.143) 4- (2-bromo-4-fluorophenyl) -N- (2-bromophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (15.144) 4- (2-bromo-4-fluorophenyl) -N- (2-bromo-6-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (15.145) 4- (2-bromo-4-fluorophenyl) -N- (2-chlorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (15.146) N- (2-bromophenyl) -4- (2-chloro-4-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (15.147) 4- (2-chloro-4-fluorophenyl) -N- (2-chlorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (15.148) 4- (2-bromo-4-fluorophenyl) -N- (2, 6-difluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (15.149) 4- (2-bromo-4-fluorophenyl) -N- (2-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (15.150) N' - (4- {3- [ (difluoromethyl) sulfanyl ] phenoxy } -2, 5-dimethylphenyl) -N-ethyl-N-methyliminocarboxamide, (15.151) N ' - (2, 5-dimethyl-4- {3- [ (1,1,2, 2-tetrafluoroethyl) sulfanyl ] phenoxy } phenyl) -N-ethyl-N-methyliminocarboxamide, (15.152) N ' - (2, 5-dimethyl-4- {3- [ (2,2, 2-trifluoroethyl) sulfanyl ] phenoxy } phenyl) -N-ethyl-N-methyliminocarboxamide, (15.153) N ' - (2, 5-dimethyl-4- {3- [ (2,2,3, 3-tetrafluoropropyl) sulfanyl ] phenoxy } phenyl) -N-ethyl-N-methyliminocarboxamide, and mixtures thereof, (15.154) N '- (2, 5-dimethyl-4- {3- [ (pentafluoroethyl) sulfanyl ] phenoxy } phenyl) -N-ethyl-N-methylimidocarboxamide, (15.155) N' - (4- { [3- (difluoromethoxy) phenyl ] sulfanyl } -2, 5-dimethylphenyl) -N-ethyl-N-methylimidocarboxamide, (15.156) N '- (2, 5-dimethyl-4- { [3- (1,1,2, 2-tetrafluoroethoxy) phenyl ] sulfanyl } phenyl) -N-ethyl-N-methylimidocarboxamide, (15.157) N' - (2, 5-dimethyl-4- { [3- (2,2, 2-trifluoroethoxy) phenyl ] sulfanyl } phenyl) -N-ethyl-N-methylimidocarboxamide, (15.158) N '- (2, 5-dimethyl-4- { [3- (2,2,3, 3-tetrafluoropropoxy) phenyl ] sulfanyl } phenyl) -N-ethyl-N-methylimidocarboxamide, (15.159) N' - (2, 5-dimethyl-4- { [3- (pentafluoroethoxy) phenyl ] sulfanyl } phenyl) -N-ethyl-N-methylimidocarboxamide, (15.160) 2- [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] -1- [4- (4- {5- [2- (prop-2-yne- 1-yloxy) phenyl ] -4, 5-dihydro-1, 2-oxazol-3-yl } -1, 3-thiazol-2-yl) piperidin-1-yl ] ethanone, (15.161) 2- [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] -1- [4- (4- {5- [ 2-fluoro-6- (prop-2-yn-1-yloxy) phenyl ] -4, 5-dihydro-1, 2-oxazol-3-yl } -1, 3-thiazol-2-yl) piperidin-1-yl ] ethanone, (15.162) 2- [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] -1- [4- (4- {5- [ 2-chloro-6- (prop-2-yn-1-yloxy) phenyl ] -4, 5-dihydro-1, 2-oxazol-3-yl } -1, 3-thiazol-2-yl) piperidin-1-yl ] ethanone, (15.163) methanesulfonic acid 2- {3- [2- (1- { [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] acetyl } piperidin-4-yl) -1, 3-thiazol-4-yl ] -4, 5-dihydro-1, 2-oxazol-5-yl } phenyl ester, (15.164) methanesulfonic acid 2- {3- [2- (1- { [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] acetyl } piperidin-4-yl) -1, 3-thiazol-4-yl ] -4, 5-dihydro-1, 2-oxazol-5-yl } -3-chlorophenyl (15.165) 2- [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] -1- [4- (4- { (5S) -5- [2- (prop-2-yn-1-yloxy) phenyl ] -4, 5-dihydro-1, 2-oxazol-3-yl } -1, 3-thiazol-2-yl) piperidin-1-yl ] ethanone, a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable carrier, (15.166) 2- [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] -1- [4- (4- { (5R) -5- [2- (prop-2-yn-1-yloxy) phenyl ] -4, 5-dihydro-1, 2-oxazol-3-yl } -1, 3-thiazol-2-yl) piperidin-1-yl ] ethanone, (15.167) 2- [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] -1- [4- (4- { (5S) -5- [ 2-fluoro-6- (prop-2-yn-1-yloxy) phenyl ] -4, 5-dihydro-1, 2-oxazol-3-yl } -1, 3-thiazol-2-yl) piperidin-1-yl ] ethanone, (15.168) 2- [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] -1- [4- (4- { (5R) -5- [ 2-fluoro-6- (prop-2-yn-1-yloxy) phenyl ] -4, 5-dihydro-1, 2-oxazol-3-yl } -1, 3-thiazol-2-yl) piperidin-1-yl ] ethanone, (15.169) 2- [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] -1- [4- (4- { (5S) -5- [ 2-chloro-6- (prop-2-yn-1-yloxy) phenyl ] -4, 5-dihydro-1, 2-oxazol-3-yl } -1, 3-thiazol-2-yl) piperidin-1-yl ] ethanone, (15.170) 2- [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] -1- [4- (4- { (5R) -5- [ 2-chloro-6- (prop-2-yn-1-yloxy) phenyl ] -4, 5-dihydro-1, 2-oxazol-3-yl } -1, 3-thiazol-2-yl) piperidin-1-yl ] ethanone, (15.171) methanesulfonic acid 2- { (5S) -3- [2- (1- { [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] acetyl } piperidin-4-yl) -1, 3-thiazol-4-yl ] -4, 5-dihydro-1, 2-oxazol-5-yl } phenyl ester, (15.172) methanesulfonic acid 2- { (5R) -3- [2- (1- { [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] acetyl } piperidin-4-yl) -1, 3-thiazol-4-yl ] -4, 5-dihydro-1, 2-oxazol-5-yl } phenyl ester, (15.173) methanesulfonic acid 2- { (5S) -3- [2- (1- { [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] acetyl } piperidin-4-yl) -1, 3-thiazol-4-yl ] -4, 5-dihydro-1, 2-oxazol-5-yl } -3-chlorophenyl ester, (15.174) methanesulfonic acid 2- { (5R) -3- [2- (1- { [3, 5-bis (difluoromethyl) -1H-pyrazol-1-yl ] acetyl } piperidin-4-yl) -1, 3-thiazol-4-yl ] -4, 5-dihydro-1, 2-oxazol-5-yl } -3-chlorophenyl ester.
Biopesticides as mixed counterparts
The compounds of formula (I) may be combined with biopesticides.
Biopesticides include, inter alia, bacteria, fungi, yeasts, plant extracts and such products formed by microorganisms, including proteins and secondary metabolites.
Biopesticides include, inter alia, bacteria, such as Blastomyces spp, root-colonizing (Wurzelbesiedelnd) bacteria, and bacteria that act as biopesticides, fungicides, or nematicides.
Examples of such bacteria used as or as biopesticides are:
bacillus amyloliquefaciens, strain FZB42 (DSM 231179) or Bacillus cereus, in particular Bacillus cereus strain CNCM I-1562 or Bacillus firmus, strain I-1582 (accession number CNCM I-1582) or Bacillus pumilus, in particular strain GB34 (accession number ATCC 700814) and strain QST2808 (accession number NRRL B-30087), or Bacillus subtilis, in particular strain GB03 (accession number ATCC SD-1397), or Bacillus subtilis strain T713 (accession number NRRL B-21661) or Bacillus subtilis strain OST 30002 (accession number NRRL B-50421), Bacillus thuringiensis, in particular Bacillus thuringiensis subspecies trypticae (serotype H-14), strain AM65-52 (accession number ATCC 1276), or Bacillus thuringiensis subspecies aizawai, in particular strain ABTS-1857 (Bacillus thuringiensis-1852), or Bacillus thuringiensis strain HD-1371, or Bacillus thuringiensis subspecies tenebrionis strain NB 176 (SD-5428), Pasteuria pendrans, Pasteuria spp (reniform nematodes) -PR3 (accession number ATCC SD-5834), Streptomyces microflavus strain AQ6121 (= QRD 31.013, NRRLB-50550), Streptomyces fulvus strain AQ 6047 (accession number NRRL 30232).
Examples of fungi and yeasts used as or as biopesticides are:
beauveria bassiana, in particular strain ATCC 74040, Chaetomium minitans (Coniothyrium minitans), in particular strain CON/M/91-8 (accession number DSM-9660), Lecanicillium spp, in particular strain HRO LEC 12, Verticillium lecanii (formerly Verticillium lecanii), in particular strain KV01, Metarhizium anisopliae, in particular strain F52 (DSM 3884/ATCC 90448), Methchnikowia fructicola, in particular strain NRRL Y-30752, Paecilomyces fumonis (Paecilomyces fumosoroseus) (now: Isaria fumosorosea), in particular strain IFPC 200613 or Apoka 97 (Accesion number ATCC 20874), Paecilomyces lilacinus, in particular Paecilomyces lilacinus violaceus 251 (AGAL 89/03089/030550), in particular Thermomyces flavus strain 36117, in particular strain CCt 1, in particular Trichoderma reesei strain 12282, strain CBanfaecium viride 1, strain 39, Trichoderma reesei (CBra strain 0882).
Examples of viruses used as or as biopesticides are:
spodoptera frugiperda (Adoxophyes orana) (apple shell leaf roller (Apfelschlecler)) Granulosis Virus (GV), codling moth (Cydia pomonella) (apple leaf roller (Apfelwort)) Granulosis Virus (GV), Heliothis armigera (Helicoverpa armigera) (cotton bollworm) Nuclear Polyhedrosis Virus (NPV), Spodoptera exigua (Spodoptera virucigua) (Spodoptera exigua) mNPV, Spodoptera frugiperda (Spodoptera frugiperda) (fall armywurn) mNPV, Spodoptera littoralis (African cotton leafworm) NPV.
Also included are bacteria and fungi that are added to plants or plant parts or plant organs as "inoculants" and that use their specific properties to promote plant growth and plant health. Examples include:
agrobacterium, Azotobacter (Azorhizobium caulinodans), Azotospira, Azotobacter, Mesorhizobium, Burkholderia, especially Burkholderia cepacia (formerly Pseudomonas cepacia), Burkholderia or Gigaspora monosporum, Gliocladium, Cerama, Lactobacillus buchneri, Gliocladium, Pisolithustinotrus, Pseudomonas, Rhizobium, especially Rhizobium trifolium, Phycomyces, Scleroderma spp.
Examples of plant extracts and such products formed by microorganisms, including proteins and secondary metabolites, which are used as or can be used as biopesticides, are:
garlic (Allium sativum), wormwood (Artemisia absinthium), azadirachtin, biokeepers WP, Cassia nigricans, celastrol (Celastrus angustifolia), Chenopodium album, chitin, Armour-Zen, european Dryopteris filix-mas, Equisetum arvense, fortuneum azar, fungaltop, Heads Up (quinoa saponin extract), pyrethrum/pyrethrin, quasiamarara, oak (Quercus), Quillaja (Quillaja), Regalia, "requisit insecticides", rotenone, ryanodine/pennisdin, comfrey (syfitinib), Artemisia chrysanthemi (taraxacum), thyme (taraxacum), thymol, zeaxanthin, mustard powder, especially brassica sativa powder 70.
Safeners as hybrid counterparts
The compounds of formula (I) may be admixed with safeners, for example, cloquintocet-mexyl (-mexyl), chloranil (cyclometril), cyprosulfamide, dichlormid, fenchlorazole (-ethyl ester), fenclorim, fluxofenan, furazolazole, bisbenzoxazolic acid (-ethyl ester), pyrazololytic acid (-diethyl ester), naphthalic anhydride, oxabetrinil, 2-methoxy-N- ({4- [ (methylcarbamoyl) amino ] phenyl } sulfonyl) benzamide (CAS 129531-12-0), 4- (dichloroacetyl) -1-oxa-4-azaspiro [4.5] decane (CAS 71526-07-3), 2, 5-trimethyl-3- (dichloroacetyl) -1, 3-oxazolidine (CAS 52836-31-4) combinations.
Plants and plant parts
All plants and plant parts can be treated according to the invention. Plants are understood herein to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants may be plants which are obtainable by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or by combinations of these methods, including the transgenic plants and including the plant varieties which may or may not be protected by variety protection. Plant parts are to be understood as meaning all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, flowers, fruit bodies, fruits and seeds and tubers, roots and rhizomes. Plant parts also include harvests and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, shoots and seeds.
The treatment of the plants and plant parts with the active substances according to the invention is carried out directly or by acting on their surroundings, living space or storage space by customary treatment methods, for example by dipping, spraying, evaporating, fogging, scattering, spreading (Aufstreichen), pouring and, in the case of propagation material, in particular in the case of seeds, also by applying one or more coatings.
As already mentioned above, all plants and their parts can be treated according to the invention. In a preferred embodiment, plant species and plant varieties and parts thereof, wild or obtained by conventional biological breeding methods (e.g. crossing or protoplast fusion), are treated. In a further preferred embodiment, transgenic plants and plant varieties (genetically modified organisms) and parts thereof obtained by genetic engineering methods, optionally in combination with conventional methods, are treated. The terms "part" and "part of a plant" or "plant part" have been explained above. It is particularly preferred according to the invention to treat plants of the respective commercial or in-use plant variety. Plant variety is understood to mean plants which have novel properties ("traits") and which have been obtained by conventional breeding, mutagenesis or recombinant DNA techniques. They may be cultivars, species, biotypes or genotypes.
Transgenic plants, seed treatment and integration events (integrative seregnisse)
Depending on the plant species or plant species, their location and growth conditions (soil, climate, growth period, nutrition), the treatment of the invention may also lead to superadditive ("synergistic") effects. For example, the following effects are possible in excess of the actually expected effect: reducing the application rates and/or widening the spectrum of action and/or improving the action of the substances and compositions which can be used according to the invention, better plant growth, improved tolerance to high or low temperatures, improved tolerance to drought or to water or soil salt content, improved flowering performance, easier harvesting, accelerated maturation, higher yields, higher quality and/or higher nutritional value of the harvested products, improved shelf life and/or processability of the harvested products.
Transgenic plants or plant varieties which are preferably treated according to the invention (obtained by genetic engineering) include all plants which have been genetically modified to obtain genetic material which confers particularly advantageous useful properties ("traits") on these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher yield, higher quality and/or higher nutritional value of the harvested product, better shelf life and/or processability of the harvested product. Examples of such properties which are further and particularly emphasized are better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and increased tolerance of the plants to specific herbicidal active substances. Examples of transgenic plants include important crop plants, such as cereals (wheat, rice), maize, soybean, potato, sugar beet, tomato, pea and other vegetable types, cotton, tobacco, oilseed rape and fruit plants (such as the fruits: apples, pears, citrus fruits and grapes), with particular emphasis on maize, soybean, potato, cotton, tobacco and oilseed rape. Traits which are particularly emphasized are the increased defence of the plants against insects, arachnids, nematodes, slugs and snails by toxins produced in the plants, in particular those toxins which are formed in the plants by genetic material from Bacillus thuringiensis, for example by the genes CryIA (a), CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and combinations thereof (hereinafter referred to as "Bt plants"). Properties ("traits") which are also particularly emphasized are the increased defence of the plants against fungi, bacteria and viruses by Systemic Acquired Resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. A further property of particular emphasis ("trait") is the increased tolerance of the plants to specific herbicidal active substances, for example imidazolinones, sulfonylureas, glyphosate or glufosinate (for example the "PAT" gene). Genes conferring the relevant desired properties ("traits") can also be present in combination with one another in transgenic plants. Examples of "Bt plants" include the corn varieties, cotton varieties, soybean varieties and potato varieties sold under the tradenames YIELD GARD (e.g., corn, cotton, soybean), KnockOut (e.g., corn), StarLink (e.g., corn), Bollgard (cotton), Nucotn (cotton) and NewLeaf (potato) Kengyu (TM). Examples of herbicide tolerant plants include corn varieties, cotton varieties and soybean varieties sold under the tradenames Roundup Ready @ (resistant to glyphosate, e.g., corn, cotton, soybean), Liberty Link @ (resistant to glufosinate, e.g., oilseed rape), IMI @ (resistant to imidazolinone) and STS @ (resistant to sulfonylurea, e.g., corn). Herbicide tolerant plants (grown in a conventional manner for herbicide tolerant) also include the varieties sold under the name of Clearfield @ (e.g., corn). These statements of course also apply to plant varieties which have these genetic properties ("traits") still to be developed and which are to be developed and/or marketed in the future.
The plants listed can be treated according to the invention with compounds of the general formula (I) and/or active substance mixtures according to the invention in a particularly advantageous manner. The preferred ranges indicated above for the active substances or mixtures also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or mixtures specifically mentioned herein.
Transgenic plants, seed treatment and integration events
Transgenic plants or plant varieties which are preferably treated according to the invention (obtained by genetic engineering) include all plants which have been genetically modified to obtain genetic material which confers particularly advantageous useful properties ("traits") on these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher yield, higher quality and/or higher nutritional value of the harvested product, better shelf life and/or processability of the harvested product. Further and particularly emphasized examples of such properties are the production of toxins by e.g. plants, in particular those toxins formed in plants by genetic material from Bacillus thuringiensis, for example by the genes CryIA (a), CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and combinations thereof, to animal and microbial pests such as insects, arachnids, nematodes, mites, snails, and increased resistance of plants to phytopathogenic fungi, bacteria and/or viruses, for example by Systemic Acquired Resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins, and increased tolerance of the plants to specific herbicidal active substances, such as imidazolinones, sulfonylureas, glyphosate or glufosinate (e.g. "PAT" gene). Genes conferring the relevant desired properties ("traits") can also be present in combination with one another in transgenic plants. Examples of transgenic plants include important crop plants, such as cereals (wheat, rice, triticale, barley, rye, oats), maize, soybean, potato, sugar beet, sugarcane, tomato, pea and other types of vegetables, cotton, tobacco, oilseed rape and fruit plants (such as the fruits apple, pear, citrus fruits and grapes), with particular emphasis on maize, soybean, wheat, rice, potato, cotton, sugarcane, tobacco and oilseed rape. A particularly emphasized property ("trait") is the increased resistance of the plant to insects, arachnids, nematodes and snails.
Type of crop protection-treatment
The treatment of plants and plant parts with the compounds of the invention of the formula (I) is carried out directly or by acting on their surroundings, living space or storage space by customary treatment methods, for example by dipping, spraying, atomizing, irrigating, evaporating, dusting, fogging, broadcasting, foaming, painting, spreading, pouring (drenching), drip irrigation and, in the case of propagation material, in particular in the case of seeds, also by dry seed dressing (beizen), wet seed dressing, serum dressing, encrusting, coating with one or more coats and the like. The active substances can also be applied by the ultra-low-volume method or the active substance preparation or the active substance itself can be injected into the soil.
A preferred direct treatment of plants is foliar application, i.e. the compounds of the invention of the formula (I) are applied to the leaves, wherein the frequency of treatment and the application rate can be adjusted depending on the respective pathogen, pest or weed infestation pressure.
In the case of systemically active compounds, the compounds of the invention of the formula (I) also enter the plant via the root system. The plants are then treated by the action of the compounds of the invention of the formula (I) on the living space of the plants. This can be achieved, for example, by drenching or by mixing into soil or nutrient solutions, i.e. by impregnating the plant locus with a liquid form of the compound of the invention of formula (I) (e.g. soil or hydroponic systems), or by soil application, i.e. by introducing the compound of the invention of formula (I) into the plant locus in solid form (e.g. in granular form). In the case of rice crops, this can also be achieved by metering the compounds of the formula (I) in solid application form (e.g.granules) into the irrigated paddy field.
Seed treatment
The control of animal pests by treating plant seeds has long been known and is the subject of constant improvement. However, the treatment of seeds brings with it a series of problems which cannot always be solved in a satisfactory manner. It is therefore desirable to develop methods for protecting seeds and germinating plants which omit or at least significantly reduce the additional application of plant protection compositions during storage, after sowing or after emergence of the plants. It is further desirable to optimize the amount of active substance used to provide optimal protection of seeds and germinating plants from animal pests without the active substance used damaging the plants themselves. In particular, the seed treatment methods should also take into account the inherent insecticidal or nematicidal properties of the insect-resistant or resistant transgenic plants to achieve optimal protection of the seeds and the germinating plants with a minimum of plant protection compositions.
The present invention therefore also relates in particular to a method for protecting seeds and germinating plants from attack by pests by treating the seeds with the compounds of the invention of the formula (I). The method of the invention for protecting seeds and germinating plants from attack by pests comprises a method for simultaneous or sequential treatment of seeds with an active substance of formula I and a mixed counterpart in one operation. It also includes a method of treating seeds with the active agent of formula I and the mixed pair at different times.
The invention also relates to the use of the compounds of the invention of formula (I) for treating seeds to protect the seeds and the plants produced therefrom from animal pests.
The invention also relates to seeds which have been treated with the compounds of the invention of formula (I) to protect against animal pests. The invention also relates to seeds which have been treated simultaneously with an active substance of formula (I) and a mixed counterpart. The invention also relates to seeds which have been treated with the active substances of the formula (I) and the mixed counterparts at different times. In the case of seeds which have been treated at different times with the active substance of formula (I) and the mixed counterpart, the individual active substances in the composition according to the invention can be present on the seed in different layers. In this case, the layers comprising the active substance of formula (I) and the mixed partner may optionally be separated by an intermediate layer. The invention also relates to seeds to which the active substances of formula (I) and the mixed counterparts have been applied as part of a coating or as additional layer(s) in addition to a coating.
The invention also relates to seeds which are film-coated after treatment with the compounds of the invention of formula (I) in order to prevent dust abrasion on the seeds.
One of the advantages of the present invention is that, due to the specific systemic nature of the compositions of the invention, the treatment of the seeds with these compositions protects not only the seeds themselves, but also the plants obtained after emergence from animal pests. This makes it possible to dispense with the direct treatment of the crop at the time of sowing or shortly thereafter.
Another advantage is that the treatment of seeds with the compounds of the invention of formula (I) can enhance the germination and emergence of the treated seeds.
It is also considered advantageous that the compounds of the invention of the formula (I) are also particularly useful in transgenic seed.
It should also be mentioned that the compounds of the invention of formula (I) may be used in combination with signal technology compositions, which bring about better colonization and/or optimized nitrogen fixation, for example by commensals, such as rhizobia, mycorrhiza and/or endophytic bacteria or fungi.
The compositions of the invention are suitable for protecting the seed of every plant species used in agriculture, greenhouse, forestry or horticulture. This is in particular the seeds of cereals (e.g. wheat, barley, rye, millet and oats), maize, cotton, soybean, rice, potatoes, sunflower, coffee, tobacco, Canola (Canola), oilseed rape, sugar beet (e.g. sugar beet and fodder beet), peanuts, vegetables (e.g. tomato, cucumber, beans, cruciferous vegetables (Kohlgewächse), onions and lettuce), fruit plants, lawns and ornamental plants. Of particular importance is the treatment of seeds of cereals (such as wheat, barley, rye and oats), maize, soya beans, cotton, canola, rape and rice.
As already mentioned above, the treatment of transgenic seed with the compounds of the invention of the formula (I) is also of particular importance. This relates to plant seeds which usually contain at least one heterologous gene controlling the expression of a polypeptide having in particular insecticidal and/or nematicidal properties. The heterologous gene in the transgenic seed may be derived from a microorganism such as Bacillus (Bacillus), Rhizobium (Rhizobium), Pseudomonas (Pseudomonas), Serratia (Serratia), Trichoderma (Trichoderma), Corynebacterium (Clavibacter), Glomus (Glomus) or Gliocladium (Gliocladium). The invention is particularly useful for treating transgenic seed containing at least one heterologous gene derived from Bacillus. More preferably, the heterologous gene is derived from Bacillus thuringiensis.
In the present invention, the compounds of the invention of formula (I) are applied to the seed, either alone or in suitable formulations. The seeds are preferably treated in a sufficiently stable state so that no damage occurs during the treatment. The seed can generally be treated at any time between harvest and sowing. Seeds are typically used from which the cob, husk, stalk, pod, fluff or pulp has been separated and removed from the plant. For example, seeds that have been harvested, washed and dried to a moisture content that allows storage may be used. Alternatively, seeds which have been treated, for example, with water after drying and then dried, for example priming (priming), can also be used.
In general, when treating seeds, care must be taken to select the amount of the composition of the invention and/or other additives applied to the seeds so as not to impair germination of the seeds and not to impair plants growing therefrom. This must be taken into account in particular in the case of active substances which may exhibit phytotoxic effects at certain application rates.
The composition of the invention can be applied directly, i.e. without further components and without dilution. It is generally preferred to apply the composition to the seed in a suitable formulation. Formulations and methods suitable for treating seeds are known to the person skilled in the art and are described, for example, in the following documents: US 4,272,417A, US 4,245,432A, US 4,808,430A, US 5,876,739A, US 2003/0176428A 1, WO 2002/080675A 1, WO 2002/028186A 2.
The compounds of the formula (I) used according to the invention can be converted into customary seed dressing formulations, such as solutions, emulsions, suspensions, dusts, foams, slurries or other coatings for seeds and ULV formulations.
These formulations are prepared in a known manner by mixing the compounds of the formula (I) with the customary additives, such as customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins and water.
The dyes which may be present in the seed dressing formulations which can be used according to the invention are all dyes conventionally used for this purpose. Pigments that are sparingly soluble in water may be used, as well as dyes that are soluble in water. Examples include dyes named rhodamine B, c.i. pigment red 112, and c.i. solvent red 1.
Wetting agents which may be present in the seed dressing formulations which can be used according to the invention are all substances which promote wetting and are customarily used for formulating agrochemical actives. Alkyl naphthalene sulfonates such as diisopropyl or diisobutyl naphthalene sulfonate can be preferably used.
Dispersants and/or emulsifiers which may be present in the seed dressing formulations which can be used according to the invention are all nonionic, anionic and cationic dispersants conventionally used for formulating agrochemical active substances. It may be preferred to use a non-ionic or anionic dispersant, or a mixture of non-ionic or anionic dispersants. Suitable nonionic dispersants include, in particular, ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristyrylphenol polyglycol ethers and their phosphorylated or sulfated derivatives. Suitable anionic dispersants are, in particular, lignosulfonates, polyacrylates and aryl sulphonate/formaldehyde condensates.
Antifoams which may be present in the seed dressing formulations which can be used according to the invention are all foam-suppressing substances conventionally used for formulating agrochemical actives. Silicone antifoam and magnesium stearate may preferably be used.
Preservatives which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for this purpose in agrochemical compositions. Examples include bischlorophenol and benzyl alcohol hemiformal.
The secondary thickeners which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for this purpose in agrochemical compositions. Cellulose derivatives, acrylic acid derivatives, xanthan gum, modified clays and finely divided silica may be considered preferably.
The adhesives which may be present in the seed dressing formulations which can be used according to the invention are all customary adhesives which can be used in seed dressing products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose (Tylose).
Gibberellins which may be present in the seed dressing formulations which can be used according to the present invention are preferably gibberellins a1, A3 (= gibberellic acid), a4 and a 7; gibberellic acids are particularly preferably used. Gibberellins are known (see R. Wegler, "Chemie der Pflanzenschutz-und Schädlingsbekämpfungstel", Vol.2, Springer Verlag,1970, pp.401-412).
The seed dressing formulations which can be used according to the invention can be applied to different types of seed either directly or after prior dilution with water. For example, the concentrates or the preparations obtainable therefrom by dilution with water can be used for dressing seeds of cereals, such as wheat, barley, rye, oats and triticale, and also of maize, rice, oilseed rape, peas, beans, cotton, sunflowers, soybeans and sugar beets or vegetable seeds of various natures. The seed dressing formulations which can be used according to the invention or their diluted formulations can also be used for dressing seeds of transgenic plants. In this case, it is also possible for an additional synergistic effect to occur in the interaction with the substance formed by expression.
For the treatment of seeds with the seed dressing formulations which can be used according to the invention or with formulations made therefrom by addition of water, all mixing devices which can be conventionally used for seed dressing are available. In particular, the seed dressing procedure is to load the seeds into a mixer in a discontinuous or continuous operation, add the respectively desired amount of the seed dressing formulation (as such or after prior dilution with water), and mix until the formulation is distributed uniformly on the seeds. Optionally, a drying operation follows thereafter.
The application rates of the seed dressing preparations which can be used according to the invention can be varied within wide limits. Depending on the respective content of the compounds of the invention of the formula (I) in the formulation and the seed. The compounds of formula (I) are generally applied in amounts of from 0.001 to 50 g/kg of seed, preferably from 0.01 to 15 g/kg of seed.
Animal health
In the field of animal health, i.e. in the field of veterinary medicine, the active substances of the invention are active against animal parasites, in particular ectoparasites or, in another embodiment, endoparasites. The term "endoparasite" includes in particular helminths, such as cestodes, nematodes or trematodes, and protozoa, such as coccidia. Ectoparasites are generally and preferably arthropods, especially insects such as flies (biting and licking), parasitic fly larvae, lice, hair lice (Haarling), feather lice, fleas, and the like; or acarids (Acarid), such as ticks, e.g., hard or soft ticks, or mites, such as itch mites, chiggers, bird mites, and the like, as well as aquatic ectoparasites, such as copepods.
In the veterinary medicine field, compounds of the formula (I) having advantageous toxicity in warm-blooded animals are suitable for controlling parasites which occur in useful animals, breeding stock, zoo animals, laboratory animals and domestic animals in animal breeding and stock farming. They are effective against all or individual developmental stages of the parasite.
Agriculturally useful animals include, for example, mammals such as sheep, goats, horses, donkeys, camels, water buffalo, rabbits, reindeer, fallow deer, in particular cattle and pigs; birds, such as turkeys, ducks, geese, especially chickens; fish and crustaceans, for example in aquaculture, and insects, such as bees.
Domesticated animals include, for example, mammals such as hamsters, guinea pigs, rats, mice, chinchillas, ferrets, particularly dogs, cats, caged birds, reptiles, amphibians, and aquarium fish.
In a preferred embodiment, the compound of formula (I) is administered to a mammal.
In another preferred embodiment, the compound of formula (I) is administered to birds, i.e. cage birds, in particular poultry.
The use of the compounds of formula (I) for controlling animal parasites should reduce or prevent diseases, cases of death and performance degradation (in terms of meat, milk, wool, leather, eggs, honey etc.) in order to achieve a more economical and simpler animal feeding and to achieve a better animal welfare.
With respect to the field of animal health, the term "control" means that the compounds of formula (I) are effective in reducing the incidence of the respective parasite in animals infected to an innocuous extent with such parasites. More specifically, "controlling" means herein that the compound of formula (I) can kill, inhibit the growth of, or inhibit the proliferation of the respective parasite.
These parasites include:
from the order of the Anoplura, for example the genera Siphonius (Haematopinus spp.), pediculosis (Linogathus spp.), pediculosis (Pediculus spp.), Phthirus spp, and Aphidius (Solenoptes spp.); specific examples are: linogathus setosus, Linogathus vituli, Linogathus ovillus, Linogathus sovirformis, sheep paw (Linogathus pedalia pedalis), Linogathus stenopsis, Haematopinassi macrocephalus, bovine blood louse (Haematopinus eurterus), porcine blood louse (Haematopinus surus), head louse (Pediculus humanus carpitis), somatic louse (Pediculus humanus coproris), Phylera vatrix, crab louse (Phthirus pudius), and Calophyllum aquaticum (Solarius capitus);
From the order trichoviridae and from the suborder ambycrina and Ischnocerina, for example Trimenopon spp, avicularis (Menopon spp), duck lice (Trinoton spp), bovine lupulus (Bovicola spp), werneckiesellas, lepiketron spp, Damalina spp, rodentia (trichomes spp), catlice (Felicola spp); specific examples are: bovicola bovis, wool lice (Bovicola ovis), Bovicolleimbata, Damalina bovis, Canarius canicola (Trichoderma canis), Felicola subrostratus, Bovicola caprae, Lepikentron ovis, Werneckiella eque;
from the sub-orders Diptera and Long Angle (Nematococcus) and short Angle (Brachyserina), such as, for example, the genera Aedes (Aedes spp.), Anopheles (Anopheles spp.), Culex (Culex spp.), Schigna (Simulium spp.), Eumulus spp.), phleboptera (Phlebomes spp.), Lutzomyzia (Lutzomyzia spp.), Culicoides spp.), Tabanus (Chrysomyia spp.), Odaglipa, Wilhelmia spp., Wilhelminthia spp., Herculella (Hyborura spp.), Tab., Tamaria, Tachys spp., Tachytrix, Haemophilus spp (Tachypodia spp.), Tachys spp., Mucora spp., Haemophilus spp., Mucora fly, Haemophilus spp Dermomycota (Hypoderma spp.), gastromyza (Gasterophilus spp.), pediculus (hippopasca spp.), Lipoptena spp., ticking spp., rhinestone spp., and macromosquitos (Tipula spp.); specific examples are: aedes aegypti (Aedes aegypti), Aedes albopictus (Aedes albopictus), Aedes coracoid (Aedes taeniorirhynchus), Anopheles gambiae (Anopheles gambiae), Anopheles quinquefolia (Anopheles maculipennis), Calliptera erythropolis (Calliptera erythrocepha), Chrysozoapluvialis, Culex fatiquefolia (Culex quinquestatus), Culex pipiens acutifolius (Culex tarsalis), Fannaceae trichoderma, Sarcophaga autoeclipta (Sarcophaga), Sarcophaga gallica (Stomopsis calvaria), Sarcophaga great deal Europe (Tipula papulosa), Lucilitica cupricius (Lucilia), Mucorata sericea (Callicaria, Haemaria, Haematococcus, Haematococculus, Haemaria, Haematococcus, Haemaria, Hydrotaea albicans, Chrysomya chloropyga, Chrysomya beziana, Musca caprina (Oestrus ovis), Musca bovis (Hypoderma bovis), Musca striata (Hypoderma lineatum), Przhevalskina silenus, Musca hominis (Dermatopia hominis), Musca caprae (Melophagus ovinus), Lipopeptotheca capreoli, Lipopeptotheca cervi, Hippobocacavariegata, Hippoboca quinana, Gasterophilus intestinalis, Gasterophilus morrorrhiza, Gasterophilus inermis, nasal flies (Gasterophilus nasalis), Gasterophilus niloticus, Gasterophilus copelus, Brasterophilus gastrula;
From the order of the Siphonaptera, for example, Siphonaptera (Pulex spp.), Ctenocephalides (Ctenocephalides spp.), Dinophyides (Tungaspp.), Dinophyides (Xenopsylla spp.), and Siphonaptera (Ceratophyllus spp.); specific examples are: ctenocephalides canis (Ctenocephalides canis), Ctenocephalides felis (Ctenocephalides felis), human fleas (Pulexirritans), Tunga peltata (Tunga peltata), Xenopsylla cheopis;
from the order of heteroptera, for example, the genera Cimex spp, Triatoma spp, Rhodnius spp, and panargyrum spp.
From the order of the Blattaria, such as Blatta orientalis, Periplaneta americana, Blatta germanica and Supella spp (e.g. Blatta palmeriana (Supelalongipalpa));
from the subclasses Acarini (Acarina) and the subclasses Negroda and Mesotimata, such as, for example, the genera Argasp (Argas spp.), Iridaceae (Ornithodoros spp.), Otopyrium (Otobius spp.), hard tick (Ixodes spp.), Orblyomma spp.), Rhipicephalus (Rhipicephalus spp.), Dermacentor Spp, Haemophysalis spp., Hyalomma spp., Dermanyssus spp., Rhipiceus (Dermanyssus spp.), Rhipicephalus (Rhipicephalus spp.), Rhipicephalus spp., original Acrophagus spp. (original Acetophys spp.), Orthospos, Vaspops, Vasonophorus spp.; specific examples are: periosphaeus (Argas persicus), Oryza sativa (Argas reflexus), Ornithodoros moubata), Otobius megini (Ornithodoros moubata), Boophilus microplus (Rhipicephalus) microplus, Rhipicephalus (Rhipicephalus) Decoloratus, Rhipicephalus orbiculatus (Rhipicephalus) Annulus, Rhipicephalus orbiculatus (Rhipicephalus), Rhipicephalus cephalotus (Boophilus), Hyalomma anatosus, Orthomma Agrocybe (Hyalomma americanus), Hyalomus nerus, Hyalomus marinus, Hyalomus traies, Rhipicephalus everus (Rhipicephalus evertus), Rhizophora sclerosus (Ixococcus neospora), Hexaphycus (Hexaphymus), Haemarrhalis (Haemaphycus), Haemaphycus, Haemarrhythrophus nilotis (Haemarrhynchus, Haemaphycus), Haemaphycus (Haemarrhythus, Haemarrhythrophus, Haemarrhythemarrhythus, Haemarrhythus (Haemarrhythemarrhythemarrhythus), Haemarrhythemarrhythemarrhythemarrhythus, Haemarrhythus, Haemarrhythemarrhythus, Haemarrhythemarrhythemarrhythemarrhythus, Haemarrhythemarrhythus, Haemarrhythemarrhythemarrhythemarrhythemarrhythus, Haemarrhythus, Haemarrhythemarrhythemarrhythemarrhythemarrhythemarrhythemarrhythemarrhythemarrhythus, Haemarrhythemarrhythemarrhythemarrhythemarrhythemarrhythemarrhythus, Haemarrhythus, Haemarrhythemarrhythemarrhythus, Haemarrhythemarrhythus, Haemarrhythus, Haemarrhythemarrhythemarrhythemarrh, Dermatopteris variabilis (Dermacentor variabilis), Hyaloma mauritanicum, Rhipicephalus sanguineus (Rhipicephalus sanguineus), Rhipicephalus capsulatus (Rhipicephalus bursa), Rhipicephalus capitis (Rhipicephalus sanguineus), Rhipicephalus capsulatus (Rhipicephalus capsulatus), Rhipicephalus capsulatus penicillius, Rhipicephalus tubani, Rhipicephalus zambeziensis, Amblyomma americanus (Amblyomma americanum), Amblyomma variegatum, Amyomma americanum, Amblyomma variegatum, Amblyomma hebracum huberculum (Amblyomma hebraeum), Amblyomma cajejunnense, Dermanyssus gallinarum, Ornitysbushiza, Ornithobium woodchuck (Orinobrunaeus), Valonia mangium arboricus (Orinobrunaeus), and Varroa bee;
From the orders of the radiata (phylum anterior) and the order of the dermatophagoides (phylum airless), for example, the genera fagaconis (Acarapis spp.), hemimelena (cheyletellla spp.), avicularis (ornithococcales spp.), sarcophagostoma (Myobia spp.), dermatophagoides (Psoroptes spp.), Demodex spp.), tsugaku (Demodex spp.), tsutsutsugami (trombia spp.), trichoderma spp.), tsutsugaku (trichoderma spp.), trichoderma spp., trichum (trichoderma spp.), dermatophagoides spp., pterus spp., pteropis spp., dermatophagoides (trichoderma spp.), dermatophagoides spp., psorales (trichoderma spp.), dermatophagoides spp., acarina spp.), dermatophagoides spp., psorales (trichophytes, dermatophagoides pteronyx (manges, psorales (manges), acarina spp.); specific examples are: cheylectiella yasgugri, Hypocrea bruguiensis (Cheylectiella blakei), Demodex canis (Demodex cantis), Demodex bovina (Demodex bovis), Demodex ovis (Demodex ovis), Demodex capri (Demodex caprae), Demodex equine Demodex equi, Demodex bailli, Demodex suis (Demodex suis), Neotrophula aurora aurutum, Neotrophula desaleri, Neoschonospora heterothermobia, Red trombone acarus (Trombicula akushi), Elapirus procumbens (Sarodeces cyotis), Catharynus auritus (Eurodex subcateum cati), Sarcoptis, Sarcophagus scabies (Psyctes), Sarcoptes mange (Psyctes psorales), Sarcoptes mange, Sarcoptes Psoroptes (Psyctes), Sarcoptes mange acarus (Psychus praecodonsis), Sarcoptes Psoroptes sinensis (Psyctes psorales, Psychus praecodonsis), Sarcoptes mange.
From the subclass copepodae, of the order Siphonostomatoida, in particular the genera Lepeophus scabiosus and Bemisia sp (Caligus); mention may be made, by way of example and with particular preference, of the species Lepeoptheiriussalmonis, Caligus elongatus and Caligus clemenseni.
In general, the active substances of the invention can be used directly when used for treating animals. They are preferably used in the form of pharmaceutical compositions which may contain pharmaceutically acceptable excipients and/or adjuvants known in the art.
In the animal health sector and animal husbandry, the active substances are administered (= administered) in a manner known per se by enteral administration in the form of, for example, tablets, capsules, drinks, infusions, granules, pastes, pills, feed-through methods and suppositories, by parenteral administration (for example by injection (in particular intramuscular, subcutaneous, intravenous, intraperitoneal)), by implantation, by nasal administration, by transdermal administration in the form of, for example, dipping or bathing, spraying, pouring (and spotting), washing and dusting powders, and by means of mouldings containing active substances, such as collars, ear tags, tail tags, limb straps, halters, marking devices, etc. The active may be formulated as a shampoo or suitable formulation for aerosol or unpressurized spraying, such as pump spraying and atomizer spraying.
In the case of use for useful animals, poultry, domestic animals and the like, the active substances according to the invention can be used as formulations (e.g. dusts, dusting powders [ wettable powders, "WP" ], emulsions, emulsion concentrates [ "EC" ], free-flowing compositions, homogeneous solutions and suspension concentrates [ "SC" ]) containing the active substances in an amount of from 1% to 80% by weight, either directly or after dilution (e.g. 100-to 10000-fold dilution), or they can be used as chemical baths.
In the case of use in the animal health sector, the active substances according to the invention can be used in combination with suitable synergists, repellents or other active substances, such as acaricides, insecticides, anthelmintics, antiprotozoals, in order to broaden the spectrum of action. Possible mixed partners of the compounds of the invention of the formula (I) may, in the case of use in animal health, be one or more compounds selected from the classes (INS-1) to (INS-25).
(INS-1) acetylcholinesterase (AChE) inhibitors, such as carbamates, e.g. boll-carbofuran, aldicarb, bendiocarb, benfuracarb, butocarbosulfan, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, varroamidine, furametprocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, monocarb, triazamate, oxamyl, XMC and methomyl; for use against ectoparasites, particularly preferred here are bendiocarb, carbaryl, methomyl, Promacyl and propoxur; or
Organophosphates, for example acephate, azamethiphos, (methyl, ethyl) glutathione, cadusafos, phosphorus oxychloride, chlorfenvinphos, chlormephos, (methyl) chlorpyrifos, coumaphos, cyanophos, methamphos, diazinon, dichlorvos/DDVP, chlormephos, dimethoate, chlorfenvinphos, EPN, ethion, fenamiphos, vamephos, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, isosulfothion, O- (methoxyaminothiophosphoryl) isopropyl salicylate, isoxazolophos, malathion, methidathion, monocrotophos, naled, methamphetan, (methyl) parathion, phenthoate, phorate, phosmet, phosphamidon, phoxim, (methyl) pyrimidophos, profenofos, prothromophos, prothioconazole, prothiocarpon, foscarnivorubin, dimeth-p, fos, Pyrazofos, pyridaphenthion, quinalphos, fenitrothion, butylpyrimidine phosphine, temephos, fenthion, chlorfenvinphos, methyl ethosulfan, triazophos, trichlorfon and aphid-methomyl; for use against ectoparasites, particular preference is given here to pirimiphos-methyl, chlorfenphos, chlorpyrifos, coumaphos, methidathion, diazinon (dipirophos), dichlorvos (DDVP), chlormephos, dimethoate, ethion (Diethion), vamephos (sulfamophos), fenitrothion, fenthion (MPP), heptenophos, malathion, dibromophos, phosmet (PMP, Phtalofos), phoxim, amphetahos, parathion, Chlorfenapyr (CVMP) and trichlorphon/metrophos.
(INS-2) GABA-controlled chloride channel antagonists, such as organochlorines, for example chlordane (Bromocyclene), (α -) chlordane and endosulfan, heptachlor, lindane and toxaphene; for use against ectoparasites, particularly preferred here are (α -) endosulfan and linden; or
Fiprole (phenylpyrazole), such as Acetoprole (Acetoprole), ethiprole, fipronil, Pyrafluprole, Pyriprole, Rizazole; for use against ectoparasites, fipronil and Pyriprole are particularly preferred here; or
Arylisoxazolines, arylpyrrolines, arylpyrrolidines, such as Fluralananer (known from WO2009/2024541, example 11-1; and compounds from WO2012007426, WO2012042006, WO2012042007, WO2012107533, WO2012120135, WO2012165186, WO2012155676, WO 2012012017359, WO2012127347, WO2012038851, WO2012120399, WO2012156400, WO2012163959, WO2011161130, WO 073444, WO 20112287, WO2011075591, WO2011157748, WO 2007/075459, WO 2007/125984, WO 2005/085216, WO 2009/002809), Affoxo 2011laner (e.g. in WO 20112011 749) and structurally related arylpyrrolines (e.g. WO 2009/217436727, WO 2010020522, WO2005, WO 6748363, WO2011, WO201 2009072621, WO 2012018620120186201869, WO 20020150563350577, WO 20050563250567, WO 2005056327378, WO 2005056324350567, WO 20050563290, WO 20150567, WO 20050563290, WO 20050567, WO 20150563290, WO 20150567, WO 20050567, WO 20050563290, WO 20050567, WO; for use against ectoparasites, preference is given here to Afxolaner and Fluaralaner.
(INS-3) sodium channel modulators/voltage-dependent sodium channel blockers, e.g. pyrethroids, e.g. bifenthrin, allethrin (d-cis-trans, d-trans), bifenthrin, bioallethrin-S-cyclopentenyl, biocethrin, cycloprothrin, (β -) cyfluthrin, (α -, lambda-) cyhalothrin, (alpha-, β -, theta-, zeta-) cypermethrin, cyphenothrin [ (1)R)-Trans isomer]Deltamethrin, transfluthrin, empenthrin [ (R) ((R))EZ)-(1R) Isomers]Fenvalerate, efeprinim, fenpropathrin, fenvalerate, flucythrinatePentothrin, flumethrin, (tau-) fluvalinate, benzoxim, imiprothrin, metofluthrin, permethrin, phenothrin [ (1)R) -trans isomer]Prallethrin, Profluthrin, pyrethrin (pyrethrum), resmethrin, RU 15525, silafluofen, tefluthrin, tetramethrin [ (1)R) Isomers]]tetrabromthrin, transfluthrin and ZXI 8901, for use against ectoparasites, particular preference is given here to pyrethroid allethrin type I, bioallethrin, permethrin, phenothrin, resmethrin, tetramethrin and pyrethroid type II (alphacyanopyrethrid) α -cypermethrin, (β -) cyfluthrin, (lambda-) cyhalothrin, (α -, zeta-) cypermethrin, deltamethrin, fenvalerate, flucythrinate, flumethrin, (tau-) fluvalinate and ester-free pyrethroid-etofenprox and silafluosilate, or organochloride compounds, such as DDT or methoxydi-n.
(INS-4) nicotinic acetylcholine receptor agonists, such as neonicotinoids, for example acetamiprid, clothianidin, dinotefuran, imidacloprid, Imidaclothiz, nitenpyram, thiacloprid, thiamethoxam; for use against ectoparasites, preference is given here in particular to clothianidin, dinotefuran, imidacloprid, nitenpyram and thiacloprid; or nicotine.
(INS-5) allosteric acetylcholine receptor modulators (agonists), such as spinosyns, e.g., spinetoram and spinosyns; for use against ectoparasites, spinosyns and spinetoram are particularly preferred here.
(INS-6) chloride channel activators, such as avermectins/milbemycins, such as abamectin, doramectin, emamectin benzoate, eprinomectin, ivermectin, Latidectin (Latidectin), lepimectin, milbeoxime, milbemycin, moxidectin and selamectin; indole terpenes, such as Nodulisporinsäure derivatives, in particular Nodulisporinsäure a; for use against ectoparasites, particular preference is given here to doramectin, eprinomectin, ivermectin, milbemycin oxime, moxidectin, selamectin and Nodulisporinsäure A.
(INS-7) juvenile hormone analogues, such as Hydroprene (S-), methoprene (Kinoprene), methoprene (S-); or fenoxycarb; pyriproxyfen; for use against ectoparasites, methoprene (S-) and pyriproxyfen are particularly preferred here.
(INS-8) mite growth inhibitors, such as clofentezine, flutenzine, hexythiazox, etoxazole; for use against ectoparasites, etoxazole is particularly preferred here.
(INS-9) Slo-1 and latrophin receptor agonists, such as cyclic depsipeptides, for example Emodepsid and its starting compound PF1022A (known from EP 382173, compound I); for use against ectoparasites, Emodepsid is particularly preferred here.
(INS-10) oxidative phosphorylation inhibitors, ATP disruptors, e.g. diafenthiuron.
(INS-12) nicotinic acetylcholine receptor antagonists such as chlorfenapyr, cartap (hydrochloride), Thiocylam and bisultap (sodium).
(INS-13) chitin biosynthesis inhibitors, type 0, such as benzoylureas, for example bistrifluron, chlorfluazuron, diflubenzuron, cyclofluazuron, flufenoxuron, hexaflumuron, lufenuron, Novaluron (Novaluron), Noviflumuron (Noviflumuron), teflubenzuron and triflumuron; for use against ectoparasites, diflubenzuron, tebufenozide, lufenuron and triflumuron are particularly preferred here.
(INS-14) chitin biosynthesis inhibitors, type 1, such as buprofezin.
(INS-15) molt-inhibiting actives such as cyromazine and Dicyclanil (Dicyclanil); for use against ectoparasites, especially preferred here are cyromazine and dicyclanil.
(INS-16) Ecdyson agonists/interferents, for example dihydrazides, such as chromafenozide, Halofenozide, methoxyfenozide and tebufenozide.
(INS-17) octopamine agonists such as amitraz, Cymiazole, chlordimeform and Demidraz; for use against ectoparasites, particular preference is given here to amitraz, Cymiazole and Demiditraz.
(INS-18) Complex-III Electron transport inhibitors, such as hydramethylnon; miticidal quinones; fluacrypyrim.
(INS-19) complex-I electron transport inhibitors, e.g. selected from METI acaricides, e.g. fenazaquin, fenpyroximate, pyriminostrobin, pyridaben, tebufenpyrad, tolfenpyrad; for use against ectoparasites, fenpyroximate, pyriminobac-methyl and tolfenpyrad are particularly preferred here.
(INS-20) voltage-dependent sodium channel blockers, such as indoxacarb and metaflumizone; for use against ectoparasites, indoxacarb and metaflumizone are particularly preferred here.
(INS-21) acetyl-coa carboxylase inhibitors, for example tetronic acid derivatives, such as spirodiclofen and spiromesifen; or tetramic acid derivatives, such as spirotetramat.
(INS-22) Complex-II Electron transport inhibitors, such as cyenopyrafen.
(INS-23) ryanodine receptor effectors, such as diamides, for example flubendiamide, chlorantraniliprole (Rynaxypyr), cyantranilide (Cyazypyr) and 3-bromo-N- { 2-bromo-4-chloro-6- [ (1-cyclopropylethyl) carbamoyl ] phenyl } -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide (known from WO 2005/077934) or methyl 2- [3, 5-dibromo-2- ({ [ 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazol-5-yl ] carbonyl } amino) benzoyl ] -1, 2-dimethylhydrazinecarboxylate (known from WO 2007/043677), and 1- (3-chloropyridin-2-yl) -N- [ 4-cyano-2-methyl-6- (methylcarbamoyl) phenyl ] -3- [ [5- (trifluoromethyl) -2H-tetrazol-2-yl ] methyl ] -1H-pyrazole-5-carboxamide (CAS number 1229654-66-3-mixture may also contain 1- (3-chloro-2-pyridyl) -N- [ 4-cyano-2-methyl-6- [ (methylamino) carbonyl ] phenyl ] -3- [ [5- (trifluoromethyl) -1H-tetrazol-1-yl ] methyl ] -1H-pyrazole-5-carboxamide, CAS number 1229656-17-0).
(INS-24) other active substances with unknown mechanism of action, e.g. azadirachtin, Amidoflumet, fenpyroximate, bifenazate, Dermatolanil, cryolite, cyflumetofen, dicofol, Fluensulfone (5-chloro-2- [ (3,4, 4-trifluorobut-3-en-1-yl) sulfonyl group]-1, 3-thiazole), pyrimethanil, pyridalyl and Pyrifluquinazon; and additionally a Bacillus firmus-based preparation (I-1582, BioNeem, Votivo) and the following known active compounds: 4- { [ (6-Bromopyridin-3-yl) methyl](2-fluoroethyl) amino } furan-2 (5H) -one (known from WO 2007/115644), 4- { [ (6-fluoropyridin-3-yl) methyl](2, 2-Difluoroethyl) amino } furan-2 (5H) -one (known from WO 2007/115644), 4- { [ (2-chloro-1, 3-thiazol-5-yl) methyl](2-fluoroethyl) amino } furan-2 (5H) -one (known from WO 2007/115644), 4- { [ (6-chloropyridin-3-yl) methyl](2-fluoroethyl) amino } furan-2 (5H) -one (known from WO 2007/115644), 4- { [ (6-chloropyridin-3-yl) methyl](2, 2-Difluoroethyl) amino } furan-2 (5H) -one (known from WO 2007/115644), 4- { [ (6-chloro-5-fluoropyridin-3-yl) methyl](methyl) amino } furan-2 (5H) -one (known from WO 2007/115643), 4- { [ (5, 6-dichloropyridin-3-yl) methyl ](2-fluoroethyl) amino } furan-2 (5H) -one (known from WO 2007/115646), 4- { [ (6-chloro-5-fluoropyridin-3-yl) methyl](cyclopropyl) amino } furan-2 (5H) -one (known from WO 2007/115643), 4- { [ (6-chloropyridin-3-yl) methyl](cyclopropyl) amino } furan- 2(5H) -one (known from EP-A-0539588), 4- { [ (6-chloropyridin-3-yl) methyl](methyl) amino } furan- 2(5H) -one (known from EP-A-0539588), [ (6-chloropyridin-3-yl) methyl](methyl) oxy-. lambda.4Sulfanylidene (sulfonidene) cyanamide (known from WO 2007/149134), [1- (6-chloropyridin-3-yl) ethyl](methyl) oxy-. lambda.4Sulfanylidenecyanamide (known from WO 2007/149134), [ (6-trifluoromethylpyridin-3-yl) methyl](methyl) oxy-. lambda.4Sulfanylcyanamide (known from WO 2007/095229), sulfoxaflor (likewise known from WO 2007/149134), 11- (4-chloro-2, 6-dimethylphenyl) -12-hydroxy-1, 4-dioxa-9-azadispiro [4.2.4.2]Tetradec-11-en-10-one (known from WO 2006/089633), 3- (4' -fluoro-2, 4-dimethylbiphenyl-3-yl) -4-hydroxy-8-oxa-1-azaspiro [ 4.5%]Dec-3-en-2-one (known from WO 2008/067911), 1- [ 2-fluoro-4-methyl-5- [ (2,2, 2-trifluoroethyl) sulfinyl group ]Phenyl radical]-3- (trifluoromethyl) -1H-1,2, 4-triazol-5-amine (known from WO 2006/043635), cyclopropanecarboxylic acid [ (3S,4aR,12R,12aS,12bS) -3- [ (cyclopropylcarbonyl) oxy]-6, 12-dihydroxy-4, 12 b-dimethyl-11-oxo-9- (pyridin-3-yl) -1,3,4,4a,5,6,6a,12,12a,12 b-decahydro-2H, 11H-benzo [ f]Pyrano [4,3-b ]]Chromen-4-yl group]Methyl ester (known from WO 2006/129714), 2-cyano-3- (difluoromethoxy) -N-ethyl-benzenesulfonamide (known from WO 2005/035486), N- [1- (2, 3-dimethylphenyl) -2- (3, 5-dimethylphenyl) ethyl]-4, 5-dihydro-2-thiazolamine (known from WO 2008/104503); penigequinolone A (known from EP 2248422 (Compound I) and WO 2009/060015 (Compound No. 11)).
(INS-25) suitable synergists where used with ectoparasiticides include MGK264 (INS-25)N-octylbicycloheptenecarboxamide), Piperonyl Butoxide (PBO) and synergized acetylenic ethers; particularly preferred herein are piperonyl butoxide and MGK 264.
In addition to these categories, short-term repellents may also be used in mixtures or in combination applications. Examples are DEET (N, N-diethyl-3-methylbenzamide), Excaritin (1-piperidinecarboxylic acid), (1S, 20S) -2-methylpiperidinyl-3-cyclohexene-1-carboxamide (SS 220), deetholone (3, 4-dihydro-2, 2-dimethyl-4-oxo-2H-pyran-6-carboxylic acid butyl ester), dihydronepetalactone, nootkatone, IR3535 (3- [ N-butyl-N-acetyl ] -aminopropionic acid ethyl ester), 2-ethylhexyl-1, 3-diol, (1R,2R,5R) -2- (2-hydroxypropan-2-yl) -5-methyl-cyclohex-1-ol, benzene-1, 2-dicarboxylic acid dimethyl ester, dodecanoic acid, undecane-2-one, N-diethyl-2-phenylacetamide and essential oils or other plant components with known repellency, such as borneol, Callicarpenal, 1, 8-eucalyptol (eucalyptol), carvacrol, β -citronellol, α -copaene, coumarin (or synthetic derivatives thereof known from US 20120329832). Escitretin, delphine and IR3535 (3- [ N-butyl-N-acetyl ] -aminopropionic acid ethyl ester) are particularly preferred for combating ectoparasites.
Among the above-mentioned classes (INS-1) to (INS-25), the following classes are preferred as mixed partners: (INS-2), (INS-3), (INS-4), (INS-5), (INS-6), (INS-17), and (INS-25).
Particularly preferred examples of insecticidally or acaricidally active compounds, synergists or repellents as mixed partners of the compounds of the invention of the formula (I) are Afaxolaner, allethrin, amitraz, bioallethrin, Chlothridin, (beta-) cyfluthrin, (lambda-) cyhalothrin, Cymiazole, (alpha-, zeta-) cypermethrin, cyphenothrin, deltamethrin, Demidiraz, dinotefuran, doramectin, eprinomectin, esprox, fenvalerate, fipronil, acetamiprid, flucythrinate, flumethrin, Fluralane tau, (-) fluvalinate, Ecatin, Imidacloprid, ivermectin, MGK264, milbemycin, moxidectin, nitenpyram, permethrin, phenothrin, piperonyl butoxide, pyriproxyfen, proferin, flusilafluosilate, spinetoram, doxycycline, Tetramethrin and thiacloprid.
Vector control
The compounds of formula (I) may also be used for vector control. In the present invention, the vector is an arthropod, particularly an insect or arachnid, capable of transmitting a pathogen, such as a virus, a worm, a unicellular organism and a bacterium, from an infectious source (plant, animal, human, etc.) to a host. The pathogen may be transmitted to the host mechanically (e.g., by sand eyes of non-biting flies) or after piercing (e.g., by plasmodium of mosquitoes).
Examples of vectors and their transmitted diseases or pathogens are:
1) mosquito (Mosquitoes)
-anopheles: malaria, filariasis;
-culex: japanese encephalitis, filariasis, other viral diseases, transmission of worms;
-aedes: yellow fever, dengue fever, filariasis, other viral diseases;
-gnat: worm transmission, particularly the coccinella discoidea (Onchocerca volvulus);
2) lice: skin infection, typhus (epidemic typhus);
3) fleas: pestilence, endemic typhus;
4) fly: narcolepsy (trypanosomiasis); cholera, other bacterial diseases;
5) mite: ticking disease, typhus, rickettsialpox, tularemia, St.Louis encephalitis, viral meningitis (FSMS), Crimeria Congo hemorrhagic fever, typhus, borreliosis;
6) tick: borrelia diseases (Borelliosen), such as, for example, Treponema pallidum (Borrelia guttoni), tick-borne encephalitis (Fruhommer-Meningoencephalitis), Q fever (Rickettsia berghei), Babesia disease (Babesia canis).
Examples of vectors are in the present invention insects which can transmit plant viruses to plants, such as aphids, flies, leafhoppers or thrips. Other vectors capable of transmitting plant viruses are spider mites (spinenmibile), lice, beetles and nematodes.
Further examples of vectors in the present invention are insects and arachnids which can transmit pathogens to animals and/or humans, such as mosquitoes, especially aedes, anopheles, e.g. anopheles gambiae, anopheles arabica, a. funestus, anopheles macrorhynchus (malaria) and culex, lice, fleas, flies, mites and ticks.
If the compounds of formula (I) break the resistance (Resistenz-breche d), vector control is also possible.
The compounds of the invention are useful in the prevention of disease and/or pathogen transmission by vectors. Thus, a further aspect of the invention is the use of the compounds of the invention for vector control, for example in agriculture, horticulture, forestry, gardening and leisure facilities, and in the protection of stored products and materials.
Protection of industrial materials
The compounds of the invention of the formula (I) are suitable for protecting industrial materials against attack or destruction by insects, for example from the orders coleoptera, hymenoptera, isoptera, lepidoptera, psocida and chlamydomonas.
Industrial material is herein understood to mean non-living material, preferably such as plastics, glues, sizing agents, paper and cardboard, leather, wood processing products and coating compositions. The invention is particularly preferably used for protecting wood.
In one embodiment of the invention, the composition or product of the invention further comprises at least one additional insecticide and/or at least one fungicide.
In another embodiment, the composition of the invention is a ready-to-use composition, i.e. it can be applied to the corresponding material without further modification. Useful additional insecticides or fungicides include those mentioned above.
It has also been found that, surprisingly, the active substances and compositions according to the invention can be used for protecting objects which come into contact with salt water or brackish water, in particular ship hulls, screens, nets, buildings, wharfs and signalling systems, against fouling (Bewuchs). It is likewise possible to use the active substances and compositions according to the invention as antiscalants, alone or in combination with other active substances.
Animal pest control in the health sector
The compounds of the invention of formula (I) are suitable for controlling animal pests in the hygiene sector. The invention is particularly useful for household protection, hygiene protection and stored product protection, in particular for controlling insects, arachnids and mites encountered in enclosed spaces, such as houses, factory halls, offices, vehicle cabins. For controlling animal pests, the active substance or composition can be used alone or in combination with other active substances and/or adjuvants. They are preferably used in domestic pesticide products. The active substances according to the invention are effective against sensitive and resistant species and against all developmental stages.
These pests include, for example, pests from the order arachnida, from the order scorpions, arachnida and ceylonida (opiones), from the order cheilopsis and bipoda, from the order entomomycete blattaria, from the order coleoptera, dermaptera, diptera, heteroptera, hymenoptera, isoptera, lepidoptera, phthiraptera, rodentia, saltriana or orthoptera, siphonaptera and leptomyidae and from the order triandra and the like.
For example in aerosols, unpressurized sprays, such as pump and atomizer sprays, automatic atomization systems, atomizers, foams, gels, evaporator products with evaporator sheets made of cellulose or plastic, liquid evaporators, gel and film evaporators, propellant-driven evaporators, non-energetic or passive evaporation systems, moth-proof papers, moth-proof bags and moth-proof gels, as granules or powders, in baits or in bait stations.
Preparation method
The compounds of the present invention can be prepared by conventional methods known to those skilled in the art.
Reaction scheme 1 shows general preparation method A of Compound (I-1) of the present invention.
Reaction scheme 1
A1-A4、Q、W、R1And Z1-Z3The radicals are each as defined above. The five-membered ring composed of E1-E3, carbon and nitrogen is a 5-membered heterocyclic ring defined under T. X is halogen. When M is boronic acid, boronic ester or trifluoroborate, U is bromo, iodo or trifluoromethanesulfonate. When M is bromo, iodo or triflate, U is boronic acid, boronic ester or trifluoroboronic ester.
The compounds of the invention of the general structure (I-1) can be prepared by methods known in the literature from the reactants 4 and 5 by means of palladium-catalyzed reactions [ WO 2005/040110; WO 2009/089508 ]. The compounds of general structure 5 are commercially available or can be prepared by methods known to those skilled in the art. Compounds of general structure 4 can be prepared from the corresponding starting materials 2 and 3 by nucleophilic substitution on aromatic compounds (X = chloro or fluoro) by methods known in the literature [ WO 2007/107470; tetrahedron Letters 2003, 44, 7629-7632] or by transition metal catalyzed reactions (X = bromine or iodine) [ WO 2012/003405; WO 2009/158371] preparation.
Alternatively, the compound (I-1) of the present invention can be prepared by the general preparation method B (reaction scheme 2).
Reaction scheme 2
A1-A4、Q、R1And Z1-Z3The radicals are each as defined above. The five-membered ring composed of E1-E3, carbon and nitrogen represents a 5-membered heterocyclic ring defined under T. X is halogen; x1Is halogen or OH. When M is boronic acid, boronic ester or trifluoroborate, U is bromo, iodo or trifluoromethanesulfonate. When M is bromo, iodo or triflate, U is boronic acid, boronic ester or trifluoroboronic ester.
The compounds of the invention of the general structures (I-1) and (I-1-1) can be prepared analogously to peptide coupling methods known in the literature from the reaction of starting materials 8 or 10 with 9 [ WO 2010/051926 or WO 2010/133312 ]. The compounds of general structure 8 can be prepared by general methods similar to those known in the literatureReduction of Compounds of Structure 7 [ WO 2012/080376]Or by a direct coupling route from general structure 4. The compounds of general structure 7 can be prepared by palladium-catalyzed reactions analogously to methods known in the literature [ WO 2005/040110; WO 2009/089508]. The compounds of the invention of the general structure (I-1) can be prepared by alkylation of amides of the structure (I-1-1) with alkylating agents 11, which are sufficiently known to the person skilled in the art, preferably in the presence of basic reaction auxiliaries. Alternatively, intermediates of general structure 8 can be reacted with suitably substituted (R) under reducing conditions1a、R1b) Reaction of ketone or aldehyde 12 to produce a compound of general structure 10 [ WO 2012/080376]In order to subsequently resemble peptide coupling methods known in the literature [ WO 2012/080376]The compound of the present invention of the general structure (I-1) was obtained.
The compounds of the present invention of the general structure (I-2) can be synthesized by preparation method C shown in reaction scheme 3.
Reaction scheme 3
A1-A4、Q、R1And Z1-Z3The radicals are each as defined above. The five-membered ring composed of E1-E3, carbon and nitrogen represents a 5-membered heterocyclic ring defined under T.
The compounds of the invention of general structure (I-2) can be prepared from the compounds of general structure (I-1) in analogy to methods known in the literature [ WO 2012/056372; WO 2003/066050 ].
Compounds of general structure 2 are commercially available or can be prepared by or analogously to methods known to those skilled in the art [ WO 2010/051926; WO 2011/131615; WO 2006/018725; WO 2012/065932; WO 2007/077961; US 2012-0115903; WO 2010/017902; WO 2010/127856; tetrahedron Letters 2011,44, 8451-8457 ].
Compounds of general structure 3 are commercially available or can be prepared by or in analogy to methods known to those skilled in the art [ WO 2009/155527; WO2007/138072 ].
Compounds of general structure 5 are commercially available or can be prepared by or analogously to methods known to those skilled in the art [ WO 2005/041904 ].
The compounds of general structure 6 are commercially available or can be prepared by methods known to those skilled in the art or analogously thereto [ Journal of Organic Chemistry 2013, 78(5), 1923-1933 ].
Reaction scheme 4 shows general preparation D of compound (Ih) of the present invention.
Reaction scheme 4
Z in the above formulas 2, 14, 15, 16, 17 and 181、Z2、Z3、A1、A2、A3、A4The groups are each as defined in the general term as hereinbefore defined with reference to the group of formula (Ih) or formula (I); this applies in particular to the preferred or particularly preferred radical definitions of the formula (Ih).
Starting from pyrazoles with leaving group X = halogen or X = mesylate (2), the corresponding pyrazolylacetylene 14 can be prepared optionally under transition metal catalysis [ US 2011/275628A ].
The compounds of general structure 17 are synthesized by [3+2] cycloaddition of acetylene 14 with the corresponding (hetero) aryl azide 16 [ analogous to Tetrahedron Letters, 2006, 47, (19) 3209-3212 ], followed by reduction to amine/aniline 18 and conversion to the compounds of the invention (Ih). Alternatively, the compounds (Ih) of the invention can be synthesized directly from acetylene 14 and the corresponding (hetero) arylazide 15 in a [3+2] cycloaddition process.
Oxidizing agents for Oxidizing alcohol groups are known (see, for example, Oxidizing agents in Organic Synthesis by Oxidation with Metal Compounds, Mijs, de Joge, Plenum Verlag, New York, 1986; Manganese Compounds as Oxidizing Agens in Organic Chemistry, Arndt, Open Courtpublishing Company, La Salle, IL, 1981; The Oxidation of Organic Compounds by Permanation Ion and Hexavalent Chromium, Lee, Open Court Publishing Company, La Salle, IL, 1980). The oxidation can be carried out, for example, in the presence of permanganates (e.g. potassium permanganate), metal oxides (e.g. manganese dioxide, chromium oxide, which are used as corins reagent in, for example, chromium (VI) bipyridyl oxide (see j. c. collins et al Tetrahedron lett. 30, 3363-3366, 1968)). Also in the presence of pyridinium chlorochromate (e.g., Corey reagent) (see also R.O. Hutchins et al, Tetrahedron Lett. 48, 4167-4170, 1977; D. Landini et al Synthesis 134-136, 1979) or Ruthenium tetroxide (see S. -I.Murahashi, N. Komiya Ruthenium-catalyzed Oxidation of Alkenes, Alcohols, Amines, Amides, β -Lactams, Phenols and Hydrocarbon, model Oxidation methods, Baeckvall, Jan-Erling (eds.), Wiley-VCH-Verlag GmbH & Co. KGaA, 2004). Also suitable are ultrasound-induced oxidation reactions and the use of potassium permanganate (see J. Yamawaki et al, chem. Lett. 3, 379-380, 1983).
For the deblocking/cleavage of the protecting group (SG), all known suitable acidic or basic reaction auxiliaries can be used by means of the methods described in the literature. When a protecting group is used for an amino group of a carbamate type, it is preferable to use an acidic reaction auxiliary. When a tert-butyl carbamate protecting group (BOC group) is used, for example, a mixture of an inorganic acid, such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid or an organic acid, such as benzoic acid, formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid, and a suitable diluent, such as water and/or an organic solvent, such as tetrahydrofuran, dioxane, dichloromethane, chloroform, ethyl acetate, ethanol or methanol, is used. Preference is given to mixtures of hydrochloric acid or acetic acid with water and/or organic solvents, such as ethyl acetate.
Some reactions and preparation processes are known to proceed particularly well in the presence of diluents or solvents and basic or acidic reaction auxiliaries. Mixtures of diluents and solvents may also be used. The diluent and the solvent are advantageously used in such amounts that the reaction mixture has good stirrability throughout the process.
Diluents or solvents which can be used for carrying out the process according to the invention include in principle all organic solvents which are inert under the particular reaction conditions. Examples include: halogenated hydrocarbons (e.g. chlorinated hydrocarbons such as tetraethylene, tetrachloroethane, dichloropropane, dichloromethane, dichlorobutane, chloroform, carbon tetrachloride, trichloroethane, trichloroethylene, pentachloroethane, difluorobenzene, 1, 2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene), alcohols (e.g. methanol, ethanol, isopropanol, butanol), ethers (e.g. ethyl propyl ether, methyl tert-butyl ether, n-butyl ether, anisole, phenetole, cyclohexylmethyl ether, dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, dichlorodiethyl ether and polyethers of ethylene oxide and/or propylene oxide), amines (e.g. trimethyl-, triethyl-, tripropyl-, tributylamine, N-methylmorpholine, pyridine and tetramethylenediamine), nitrohydrocarbons (e.g., nitromethane, nitroethane, nitropropane, nitrobenzene, chloronitrobenzene, o-nitrotoluene; nitriles, such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, m-chlorobenzonitrile), tetrahydrothiophene dioxide, dimethyl sulfoxide, tetramethylene sulfoxide, dipropyl sulfoxide, benzyl methyl sulfoxide, diisobutyl sulfoxide, dibutyl sulfoxide, diisoamyl sulfoxide, sulfones (for example dimethyl-, diethyl-, dipropyl-, dibutyl-, diphenyl-, dihexyl-, methylethyl-, ethylpropyl-, ethylisobutyl-and pentamethylene sulfone), aliphatic, cycloaliphatic or aromatic hydrocarbons (for example pentane, hexane, heptane, octane, nonane and technical (technisch) hydrocarbons), and also so-called "white spirit" containing components having a boiling point of, for example, from 40 ℃ to 250 ℃, p-cymene, gasoline fractions having a boiling point in the range from 70 ℃ to 190 ℃, cyclohexane, methylcyclohexane, tetrahydrothiophene dioxide, dimethylene sulfoxide, p-isopropyltoluene, dimethylene sulfoxide, and mixtures thereof, Petroleum ether, crude gasoline, octane, benzene, toluene, chlorobenzene, toluene, methanol, ethanol, Bromobenzene, nitrobenzene, xylene, esters (e.g., methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate, dimethyl carbonate, dibutyl carbonate and ethylene carbonate); amides (e.g. hexamethylenephosphoric triamide, formamide, N-methylformamide,N,N-dimethylformamide,N,N-dipropylcarboxamide,N ,NDibutylformamide, N-methylpyrrolidine, N-methylcaprolactam, 1, 3-dimethyl-3, 4,5, 6-tetrahydro-2 (1H) -pyrimidine, octylpyrrolidone, octylcaprolactam, 1, 3-dimethyl-2-imidazolidinedione, N-formylpiperidine, N-acetylformamide, N-acetylpyrrolidone, N-,N,N' -1, 4-diformylpiperazine) and ketones (e.g. acetone, acetophenone, methyl ethyl ketone, methyl butyl ketone).
The basic reaction auxiliary used for carrying out the process according to the invention can be any suitable acid-binding agent. Examples include: alkaline earth metal or alkali metal compounds (e.g. hydroxides, hydrides, oxides and carbonates of lithium, sodium, potassium, magnesium, calcium and barium), amidine or guanidine bases (e.g. 7-methyl-1, 5, 7-triazabicyclo [ 4.4.0)]Dec-5-ene (MTBD); diazabicyclo [4.3.0]Nonene (DBN), diazabicyclo [2.2.2]Octane (DABCO), 1, 8-diazabicyclo [5.4.0]Undecylene (DBU), cyclohexyl tetrabutyl guanidine (CyTBG), cyclohexyl tetramethyl guanidine (CyTMG), N ,N,N ,NTetramethyl-1, 8-naphthalenediamine, pentamethylpiperidine) and amines, especially tertiary amines (e.g. triethylamine, trimethylamine, tribenzylamine, triisopropylamine, tributylamine, tricyclohexylamine, tripentylamine, trihexylamine, pentanediamine, penta,N ,N-dimethylaniline,N ,N-dimethyltoluidine,N ,N-dimethyl-p-aminopyridine, N-methylpyrrolidine, N-methylpiperidine, N-methylimidazole, N-methylpyrazole, N-methylmorpholine, N-methylhexamethylenediamine, pyridine, 4-pyrrolidinopyridine, 4-dimethylaminopyridine, quinoline, α -methylpyridine, β -methylpyridine, isoquinoline, pyrimidine, acridine, pyridine,N ,NN ', N' -tetramethylenediamine,N ,NN ', N' -tetraethylenediamine, quinoxaline, N-propyldiisopropylamine, N-ethyldiisopropylamine,N ,N' -dimethylcyclohexylamine, 2, 6-lutidine, 2, 4-lutidine or triethylenediamine).
Acidic reaction auxiliaries which are used for carrying out the process according to the invention include all inorganic acids (for example hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid, and also sulfuric acid, phosphoric acid, phosphorous acid, nitric acid), lewis acids (for example aluminum (III) chloride, boron trifluoride or its etherate, titanium (V) chloride, tin (V) chloride and organic acids (for example formic acid, acetic acid, propionic acid, malonic acid, lactic acid, oxalic acid, fumaric acid, adipic acid, stearic acid, tartaric acid, oleic acid, methanesulfonic acid, benzoic acid, benzenesulfonic acid or p-toluenesulfonic acid).
If protecting groups are considered in the reaction scheme, all known protecting groups can be used. In particular those described in Greene T.W., Wuts P.G.W. in Protective Groups in Organic Synthesis, John Wiley & Sons, Inc. 1999, "Protection for the hydroxyl group inclusion 1, 2-and 1, 3-diols".
Other suitable protecting groups are
Substituted methyl ether type(e.g., methoxymethyl ether (MOM), methyl sulfide (MTM), (phenyldimethylsilyl) methoxymethyl ether (SNOM-OR), benzyloxymethyl ether (BOM-OR), p-methoxybenzyloxymethyl ether (PMBM-OR), p-nitrobenzyloxymethyl ether, o-nitrobenzyloxymethyl ether (NBOM-OR), (4-methoxyphenoxy) methyl ether (p-AOM-OR), guaiacol methyl ether (GUM-OR), t-butoxymethyl ether, 4-pentoxymethyl ether (POM-OR), siloxymethyl ether, 2-methoxyethoxymethyl ether (MEM-OR), 2,2, 2-trichloroethoxymethyl ether, bis (2-chloroethoxy) methyl ether, 2- (trimethylsilyl) ethoxymethyl ether (SEM-OR), Methoxymethyl ether (MM-OR));
substituted ethyl ether type(e.g., 1-ethoxyethyl ether (EE-OR), 1- (2-chloroethoxy) ethyl ether (CEE-OR), 1- [2- (trimethylsilyl) ethoxy ]Ethyl ether (SEE-OR), 1-methyl-1-methoxyethyl ether (MIP-OR), 1-methyl-1-benzyloxyethyl ether (MBE-OR), 1-methyl-1-benzyloxy-2-fluoroethyl ether (MIP-OR), 1-methyl-1-phenoxyethyl etherPhenyl ether, 2, 2-trichloroethyl ether, 1, 1-dianisol-2, 2, 2-trichloroethyl ether (DATE-OR), 1,1,1,3,3, 3-hexafluoro-2-phenylisopropyl ether (HIP-OR), 2-trimethylsilylethyl ether, 2- (benzyl) ethyl sulfide, 2- (phenyl) ethylselenide), ethers (e.g. tetrahydropyranyl ether (THP-OR), 3-bromotetrahydropyranyl ether (3-BrTHP-OR), tetrahydrothiopyranyl ether, 1-methoxycyclohexyl ether, 2-and 4-pyridylmethyl ether, 3-methyl-2-pyridylmethyl-N-oxide ether, 2-quinolinylmethyl ether (Qm-OR), 1-pyrenylmethyl ether, diphenylmethyl ether (DPM-OR), p ' -dinitrodiphenylmethyl ether (DNB-OR), 5-dibenzocycloheptyl ether, triphenylmethyl ether (Tr-OR), α -naphthyldiphenylmethyl ether, p-methoxyphenyldiphenylmethyl ether (Tr-OR), di-p-dinitrodiphenylmethyl ether (MMM-OR), p-dinitrodiphenylmethyl ether (TMB-OR), tri-bromophenylimino-4- (4, 4-phenyl) methyl) ether (TMTr-4, 4' -phenyl) phenyl-N ' -benzoyloxy (TMOR), tri-bromophenyloxy) phenyl-4, 4-bromobenzoyl ether (TMR-methyl ether) ]Trityl ether (IDTr-OR), 4' -dimethoxy-3 ' ' - [ N- (imidazolylethyl) carbamoyl]Trityl ether (IETr-OR), 1-bis (4-methoxyphenyl) -1' -pyrenyl methyl ether (Bmpm-OR), 9-anthryl ether, 9- (9-phenyl) xanthenyl ether (Pixyl-OR), 9- (9-phenyl-10-oxo) anthryl (Tritylone ether), 4-methoxytetrahydropyranyl ether (MTHP-OR), 4-methoxytetrahydrothiopyranyl ether, 4-methoxy-tetrahydrothiopyranyl-S, S-dioxide, 1- [ (2-chloro-4-methyl) phenyl thiopyranyl-S, S-dioxide]-4-methoxypiperidin-4-yl ether (CTMP-OR), 1- (2-fluorophenyl) -4-methoxypiperidin-4-yl ether (Fpmp-OR), 1, 4-dioxan-2-yl ether, tetrahydrofuryl ether, tetrahydrothiofuranyl ether, 2,3,3a,4,5,6,7,7 a-octahydro-7, 8, 8-trimethyl-4, 7-methanobenzofuran-2-yl ether (MBF-OR), tert-butyl ether, allyl ether, propargyl ether, p-chlorophenyl ether, p-methoxyphenyl ether, p-nitrophenyl ether, p-2, 4-dinitrophenyl ether (DNP-OR), 2,3,5, 6-tetrafluoro-4- (trifluoromethyl) phenyl ether, Benzyl ether (Bn-OR));
substituted benzyl radicalEther type(e.g., p-methoxybenzyl ether (MPM-OR), 3, 4-dimethoxybenzyl ether (DMPM-OR), o-nitrobenzyl ether, p-halobenzyl ether, 2, 6-dichlorobenzyl ether, p-aminoacylbenzyl ether (PAB-OR), p-azidobenzyl ether (Azb-OR), 4-azido-3-chlorobenzyl ether, 2-trifluoromethylbenzyl ether, p- (methylsulfinyl) benzyl ether (Msib-OR));
Silyl ether type(e.g., trimethylsilyl ether (TMS-OR), triethylsilyl ether (TES-OR), triisopropylsilyl ether (TIPS-OR), dimethylisopropylsilyl ether (IPDMS-OR), diethylisopropylsilyl ether (DEIPS-OR), dimethylhexylsilyl ether (TDS-OR), tert-butyldimethylsilyl ether (TBDMS-OR), tert-butyldiphenylsilyl ether (TBDPS-OR), tribenzylsilyl ether, tri-p-xylylsilyl ether, triphenylsilyl ether (TPS-OR), diphenylmethylsilyl ether (DPMS-OR), di-tert-butylmethylsilyl ether (DTBMS-OR), tri (trimethylsilyl) silyl ether (Sisyl ether), di-tert-butylmethylsilyl ether (DTBMS-OR), Tris (trimethylsilyl) silyl ether (Sisyl ether), (2-hydroxystyryl) dimethylsilyl ether (HSDMS-OR), (2-hydroxystyryl) diisopropylsilyl ether (HSDIS-OR), tert-butylmethoxyphenylsilyl ether (TBMPS-OR), tert-butoxydiphenylsilyl ether (DPTBOS-OR));
ester type(e.g., formate, benzoylformate, acetate (Ac-OR), chloroacetate, dichloroacetate, trichloroacetate, trifluoroacetate, (TFA-OR), methoxyacetate, triphenylmethoxyacetate, phenoxyacetate, p-chlorophenoxyacetate, phenylacetate, diphenylacetate (DPA-OR), nicotinate, 3-phenylpropionate, 4-pentanoate (Pentaate), 4-oxopentanoate (Oxopentotoate) (levulinate) (Lev-OR) 4,4- (ethylenedithio) pentanoate (LevS-OR), 5- [ 3-bis (4-methoxyphenyl) hydroxymethoxyphenoxyphenoxyacetate (LevS-OR) ]Levulinic acid estersPivalate (Pv-OR), 1-adamantanoate, crotonate, 4-methoxycrotonate, benzoate (Bz-OR), p-phenylbenzoate, 2,4, 6-trimethylbenzoate (Mesitoat), 4- (Methylthiomethoxy) butyrate (MTMB-OR), 2- (methylthiomethoxymethyl) benzoate (MTMT-OR),
ester type(e.g., methyl carbonate, methoxymethyl carbonate, 9-fluorenylmethyl carbonate (Fmoc-OR), ethyl carbonate, 2,2, 2-trichloroethyl carbonate (Troc-OR), 1-dimethyl-2, 2, 2-trichloroethyl carbonate (TCBOC-OR), 2- (trimethylsilyl) ethyl carbonate (TMS-OR), 2- (phenylsulfonyl) ethyl carbonate (Ps-OR), 2- (triphenylphosphino) ethyl carbonate (Peoc-OR), tert-butyl carbonate (Boc-OR), isobutyl carbonate, ethylene carbonate, allyl carbonate (Alloc-OR), p-nitrophenyl carbonate, benzyl carbonate (Z-OR), p-methoxybenzyl carbonate, 3, 4-dimethoxybenzyl carbonate, o-nitrobenzyl carbonate, P-nitrobenzyl carbonate, 2-dansyl ethyl carbonate (Dnseoc-OR), 2- (4-nitrophenyl) ethyl carbonate (Npeoc-OR), 2- (2, 4-dinitrophenyl) ethyl carbonate (Dnpeoc)), and
Type of sulfate ester(e.g., allyl sulfonate (Als-OR), methanesulfonate (Ms-OR), benzylsulfonate, tosylate (Ts-OR), 2- [ (4-nitrophenyl) ethyl)]Sulfonate ester (Npes-OR)).
Catalysts suitable for the catalytic hydrogenation in the process according to the invention are all customary hydrogenation catalysts, for example platinum catalysts (e.g. platinum sheet, platinum sponge, platinum black, colloidal platinum, platinum oxide, platinum wire), palladium catalysts (e.g. palladium sponge, palladium black, palladium oxide, palladium-carbon, colloidal palladium, palladium-barium sulfate, palladium-barium carbonate, palladium hydroxide), nickel catalysts (e.g. reduced nickel, nickel oxide, raney nickel), ruthenium catalysts, cobalt catalysts (e.g. reduced cobalt, raney cobalt), copper catalysts (e.g. reduced copper, raney copper, Ullmann copper). Preference is given to using noble metal catalysts, such as platinum and palladium or ruthenium catalysts, rhodium catalysts, for example tris (triphenylphosphine) rhodium (I) chloride in the presence of triphenylphosphine, optionally applied to a suitable support, such as carbon or silicon. Furthermore, "chiral hydrogenation catalysts" (e.g. those containing chiral diphosphine ligands, such as (2S,3S) - (-) -2, 3-bis (diphenylphosphino) butane [ (S, S) -chiralphos ] or (R) - (+) -2,2' -or (S) - (-) -2,2' -bis (diphenylphosphino) -1,1' -binaphthyl [ R (+) -BINAP or S (-) -BINAP ]) can be used which increase the content of one isomer in the isomer mixture or almost completely prevent the formation of the other isomer.
Salts of the compounds of the invention are prepared by standard methods. Representative acid addition salts are those formed, for example, by reaction with an inorganic acid, for example sulfuric acid, hydrochloric acid, hydrobromic acid, phosphoric acid or an organic carboxylic acid, such as acetic acid, trifluoroacetic acid, citric acid, succinic acid, butyric acid, lactic acid, formic acid, fumaric acid, maleic acid, malonic acid, camphoric acid, oxalic acid, phthalic acid, propionic acid, glycolic acid, glutaric acid, stearic acid, salicylic acid, sorbic acid, tartaric acid, cinnamic acid, valeric acid, picric acid, benzoic acid or an organic sulfonic acid, such as methanesulfonic acid and 4-toluenesulfonic acid.
When the compound of formula (I) has a structural element suitable for forming such a salt, salts of the compound of the present invention formed from an organic base such as pyridine or triethylamine or those formed from an inorganic base such as a hydride, hydroxide or carbonate of sodium, lithium, calcium, magnesium or barium are also representative.
Synthetic methods for preparing heterocyclic N-oxides and tertiary amines are known. They can be obtained with peroxy acids (e.g. peracetic and metachloroperbenzoic acid (MCPBA), hydrogen peroxide), alkyl hydroperoxides (e.g. tert-butyl hydroperoxide), sodium perborate, and ketone peroxides (e.g. dimethyl ketone peroxide). For example, T.L. Gilchrist, Comprehensive Organic Synthesis, Vol.7, pp.748-750, 1992, S.V. Ley, (Ed.), Pergamon Press; m, Tisler, B, Stanovnik in Comprehensive heterocyclic chemistry, volume 3, pages 18-20, 1984, A.J. Boulton, A. McKillop, (ed.), Pergamon Press; M.R. Grimett, B.R.T. Keene in Advances in heterocyclic chemistry, Vol.43, p.149-163, 1988, A.R. Katritzky, (Ed.), Academic Press; m, Tisler, B, Stanovnik in Advances in Heterocyclic Chemistry, Vol.9, p.285-291, 1968, A.R. Katritzky, A.J. Boulton (eds.), Academic Press; these methods are described in Advances in Heterocyclic Chemistry, Vol.22, p.390-392, 1978, A.R. Katritzky, A.J. Boulton, (eds.), Academic Press, by G.W. H.Cheeseman, E.S.G.Werstuk.
Preparation examples
1H NMR data
Recording was carried out with Bruker Avance 400 equipped with a flow cell (volume 60. mu.l) or with Bruker AVIII 400 equipped with a 1.7 mm Kryo-CPTCI sampling head or with Bruker AVII 600 (600.13 MHz) equipped with a 5 mm Kryo-TCI sampling head or with Bruker AVIII 600 (601.6 MHz) equipped with a 5 mm Kryo-CPMNP sampling head1H NMR data. This used tetramethylsilane as reference (0.0 ppm) and CD3CN、CDCl3Or D6-DMSO was performed as deuterated solvent.
Synthesis of N- {3- [2' -methyl-5 ' - (pentafluoroethyl) -4' - (trifluoromethyl) -2' H-1,3' -bipyrazol-4-yl ] phenyl } isonicotinamide
Stage 1
4-bromo-2 ' -methyl-5 ' - (pentafluoroethyl) -4' - (trifluoromethyl) -2' H-1,3' -bipyrazole
8 g (27.9 mmol) of 5-fluoro-1-methyl-3- (pentafluoroethyl) -4- (trifluoromethyl) -1H-pyrazole (Nippon Kagaku Kaishi, 1985, (10), 1995-2000), 4.11 g (27.9 mmol) of 4-bromopyrazole and 7.73 g (55.9 mmol) of potassium carbonate are stirred in 140 ml of THF at reflux for 12 hours. Subsequently, the potassium carbonate is filtered off, the solvent is distilled off on a rotary evaporator and chromatographed using silica gel (cyclohexane/ethyl acetate (esiester) gradient). 6.83 g (55.3% of theory) were isolated as a waxy solid.
Stage 2
2' -methyl-4- (3-nitrophenyl) -5' - (pentafluoroethyl) -4' - (trifluoromethyl) -2' H-1,3' -bipyrazole
5.5 g (13.3 mmol) of bipyrazole from stage 1 and 2.22 g (13.3 mmol) of 3-nitrophenylboronic acid are initially loaded in 110 ml of 1, 4-dioxane and 0.98 g (1.33 mmol) of 1,1' -bis (diphenylphosphino) ferrocene palladium (II) chloride and 86.5 ml of 2M Na are added2CO3An aqueous solution. The formulation was stirred at 100 ℃ until the conversion was complete. After the reaction mixture had cooled, the entire formulation was concentrated on silica gel on a rotary evaporator and then chromatographed using silica gel (cyclohexane/ethyl acetate gradient). 5.21 g (78.4% of theory) are obtained as a colorless solid.
Stage 3
3- [2' -methyl-5 ' - (pentafluoroethyl) -4' - (trifluoromethyl) -2' H-1,3' -bipyrazol-4-yl ] aniline
4.9 g (10.7 mmol) of the nitro compound from stage 2 are dissolved in 36 ml of isopropanol and 6.3 g (27.9 mmol) of tin (II) chloride dihydrate are added at room temperature. The reaction mixture was cooled to 0 ℃ and then 9 ml of concentrated HCl was slowly added dropwise and then stirred under reflux for 2 hours. After the reaction was complete, the volume of the reaction mixture was concentrated to 2/3 on a rotary evaporator, then 500 ml of water were added, and the aqueous mixture was then adjusted to pH 8-9 with 30% NaOH. The aqueous mixture is extracted repeatedly with ethyl acetate, the combined organic phases are dried over magnesium sulfate, filtered and concentrated, and the residue is chromatographed on silica gel (cyclohexane/ethyl acetate gradient). 3.2 g (68.2% of theory) of a pale yellow oil are obtained.
Stage 4
N- {3- [2' -methyl-5 ' - (pentafluoroethyl) -4' - (trifluoromethyl) -2' H-1,3' -bipyrazol-4-yl ] -phenyl } isonicotinamide
300 mg (0.7 mmol) of the aniline from stage 3 are dissolved in 2 ml of THF, 126 mg (0.7 mmol) of isonicotinoyl chloride hydrochloride and 86 mg (0.84 mmol) of triethylamine are added at room temperature and stirred under reflux, monitored by thin layer, until the reaction is complete. After cooling, 5 ml of water were added and the mixture was extracted repeatedly with dichloromethane. The combined organic phases are dried over magnesium sulfate, filtered and concentrated, and the residue is chromatographed on silica gel (cyclohexane/ethyl acetate gradient). 300 mg (80.2% of theory) of the target compound are obtained in the form of a pale yellow oil.
The compounds listed in tables 1a, 1b and 2 were prepared by the above-described preparation method.
TABLE 1a
The compounds of the invention of formula (Ic-1) are those wherein W = O, A1= A2= CH、A3= CR4、A4= CR5And R is6Compounds of the general formula (Ic) of = H (i.e. n = 0).
Particularly preferred compounds of formula (Ic-1) are also represented by the formula Z in Table 1a1、Z2、Z3、R1、R4、R5And any combination of the radical definitions recited for Q.
TABLE 1b
The compounds of the invention of formula (Ic-1) are those wherein W = O, A1= A2= CH、A3= CR4、A4= CR5And R is6Compounds of the general formula (Ic) of = H (i.e. n = 0).
Particularly preferred compounds of formula (Ic-1) are also represented by the formula Z in Table 1b1、Z2、Z3、R1、R4、R5And any combination of the radical definitions recited for Q.
TABLE 2
The compounds of the invention of formula (Ic-2) are those wherein W = O, A1= CH、A2= N、A3= CR4、A4= CR5And R is6Compounds of general formula (Ic) with = H (i.e. n = 0).
Example numbering Z1 Z2 Z3 R1 R4 R5 Q
2-001 CF2CF3 CF3 CH3 H Cl H 4-F-phenyl
2-002 CF2CF3 CF3 CH3 H Cl H 3-Cl-2-pyridinyl
2-003 CF2CF3 CF3 CH3 H CH3 H 4-F-phenyl
2-004 CF2CF3 CF3 CH3 H CH3 H 4-pyridyl group
2-005 CF2CF3 CF3 CH3 H F H 4-pyridyl group
2-006 CF2CF3 CF3 CH3 H Cl H 4-pyridyl group
2-007 CF2CF3 CF3 CH3 H Cl H 3-MeO, 4-F-phenyl
2-008 CF2CF3 CF3 CH3 H Cl H 2-CN-5-pyridyl
2-009 CF2CF3 CF3 CH3 CH3 Cl H 2-CN-5-pyridyl
Particularly preferred compounds of formula (Ic-2) are also represented by the formula Z in Table 21、Z2、Z3、R1、R4、R5And any combination of the radical definitions recited for Q.
Analyzing data
NMR Peak Listing method
To be provided with1Form of H NMR Peak List selected examples were recorded1H NMR data. For each signal peak, the values in ppm are listed first, followed by the signal intensities in parentheses. The values of the different signal peaks-signal intensity value pairs-are listed separately from each other by a semicolon.
The form of the peak list for one embodiment is thus:
1(strength)1)；2(strength)2)；……；i(strength)i)；……；n(strength)n)。
The intensity of the sharp signal is highly correlated with the signal in centimeters in the printed example of the NMR spectrum and shows the true ratio of the signal intensities. In the case of a broad signal, multiple peaks or signal midpoints and their associated intensities can be displayed in comparison with the strongest signal in the spectrum.
To calibrate the chemical shifts of the 1H NMR spectrum, we used the chemical shifts of tetramethylsilane and/or the solvent, especially in the case of spectra measured in DMSO. Thus, tetramethylsilane peaks may, but need not, appear in the NMR peak list.
1List of H NMR peaks similar to the conventional1H NMR output, and therefore typically contains all the peaks listed in the conventional NMR interpretation.
Furthermore, similar to the conventional1H NMR outputs, which may show peaks of solvent signals, signals of stereoisomers of the target compounds that also form the subject of the present invention and/or impurities.
In the description of the signals of the compounds in the solvent and/or water ranges, our1Common solvent peaks are shown in the list of H NMR peaks, e.g. DMSO-D6The peak of DMSO and the peak of water in (1), which generally have high intensity on average.
The peaks of stereoisomers of the target compound and/or impurity peaks typically have on average a lower intensity than the peaks of the target compound (e.g. >90% purity).
Such stereoisomers and/or impurities may be typical of the respective preparation process. Their peaks therefore help in this case to identify the reproducibility of our preparation process with reference to the "by-product fingerprint (fingerlbdrucken).
If desired, a practitioner who calculates the peaks of the target compound by known methods (MestreC, ACD simulation, also using empirically assessed expected values) may optionally separate the peaks of the target compound using an additional intensity filter. This separation is similar to conventional1Correlation peak extraction in H NMR interpretation.
1Further details of the H NMR peak list can be found in Research Disclosure Database Number 564025.
LC-MS data
Method M1:
the instrument is a Waters ACQUITY SQD UPLC system; a Waters Acquity UPLC HSS T31.8 mu m 50x 1 mm; eluent A is 1 l of water and 0.25ml of 99% formic acid, eluent B is 1 l of acetonitrile and 0.25ml of 99% formic acid; gradient 0.0 min 90% A → 1.2 min 5% A → 2.0 min 5% A; the furnace is at 50 ℃; the flow rate is 0.40 ml/min; UV detection: 208-.
Method M2:
the instrument is Agilent MS Quad 6150; HPLC, Agilent 1290; a Waters Acquity UPLC HSST 31.8 mu m 50x 2.1 mm; eluent A is 1 l of water and 0.25ml of 99% formic acid, eluent B is 1 l of acetonitrile and 0.25ml of 99% formic acid; gradient 0.0 min 90% A → 0.3 min 90% A → 1.7 min 5% A → 3.0 min 5% A; the furnace is at 50 ℃; the flow rate is 1.20 ml/min; UV detection at 205-305 nm.
Method M3:
instrument MS: Waters SQD; instrumental HPLC, Waters UPLC; column Zorbax SB-Aq (Agilent), 50mm x 2.1 mm, 1.8 μm; eluent A is water and 0.025 percent formic acid, eluent B is acetonitrile (ULC) and 0.025 percent formic acid; gradient, 0.0 min 98% A-0.9 min 25% A-1.0 min 5% A-1.4 min 5% A-1.41 min 98% A-1.5 min 98% A; the furnace is operated at 40 ℃; the flow rate is 0.600 ml/min; DAD is detected by UV; 210 nm.
Method M4:
the instrument is a Waters ACQUITY SQD UPLC system; a Waters Acquity UPLC HSS T31.8 mu m 50x 1 mm; eluent A is 1 l of water and 0.25 ml of 99% formic acid, eluent B is 1 l of acetonitrile and 0.25 ml of 99% formic acid; gradient 0.0 min 95% A → 6.0 min 5% A → 7.5 min 5% A; the furnace is at 50 ℃; the flow rate is 0.35 ml/min; UV detection at 210-400 nm.
Intermediates
The compounds of the invention of the formula (INT-c-1) are wherein A1= CH、A3= CR4、A4= CR5And E1= N、E2= E3General formula 7 of = CH (Y = NO)2) Or 8 (Y = NH)2) The compound of (1).
Analytical data for intermediates
List of NMR peaks of intermediate
LC-MS data for intermediates
Example numbering Method of producing a composite material Residence time [ min ]] M+H
INT-014 M1 1.20 462
INT-015 M1 1.09 445
INT-016 M1 0.80 441
Biological examples
In vitro contact assay of Ctenocephalides felis with adult Ctenocephalides felis
To coat the tubes, 9 mg of active substance are first dissolved in 1 ml of acetone (for analysis) and then diluted with acetone (for analysis) to the desired concentration. 250 microliters of this solution was evenly distributed on the inside wall and bottom of a 25 ml test tube by tumbling and pouring on an orbital shaker (shaking at 30 rpm for 2 hours). An area dose of 5 micrograms/square centimeter was achieved with a uniform distribution at 900 ppm of active solution and 44.7 square centimeters of inner surface.
After the solvent has evaporated, the tube is filled with 5-10 adult cat fleas: (Ctenocephalides felis) Colonisation, sealed with a perforated plastic lid and incubated in a horizontal position at room temperature and ambient humidity. After 48 hours, the efficacy was determined. For this purpose, the test tube is erected and fleas are knocked to the bottom of the test tube. Fleas that remain immobile or move in an uncoordinated manner at the bottom are considered dead or dying.
A substance exhibits good resistance if at least 80% efficacy is achieved in this test at an application rate of 5 micrograms/square centimeterCtenocephalides felisEfficacy. 100% efficacy means that all fleas die or dying. 0% efficacy means that there is no harm to any fleas.
In this test, for example, the following compounds from the preparation examples show a efficacy of 100% at an application rate of 5 micrograms/square centimeter (500 g/ha): 1-001, 1-003, 1-004, 1-006, 1-010, 1-012, 1-013, 1-016, 1-022, 1-023, 1-024, 1-025, 1-026, 1-027, 1-028, 1-031, 1-034, 1-036, 1-037, 1-040, 1-041, 1-049, 1-058, 1-064, 1-066, 1-068, 1-069, 1-073, 1-076, 1-081, 1-085, 1-086, 1-087, 1-088, 1-089, 1-091, 1-094, 1-095, 1-096, 1-097, 1-098, 1-099, 1-100, 1-101, 1-127, 2-005 and 2-006.
In this test, for example, the following compounds from the preparation examples show 80% efficacy at an application rate of 5 micrograms/square centimeter (500 g/ha): 1-039, 1-060 and 1-083.
In this test, for example, the following compounds from the preparation examples show 80% efficacy at an application rate of 1 microgram per square centimeter (100 g/ha): 1-014.
In vitro contact test of Rhipicephalus sanguineus and adult brown dog ticks
To coat the tubes, 9 mg of active substance are first dissolved in 1 ml of acetone (for analysis) and then diluted with acetone (for analysis) to the desired concentration. 250 microliters of this solution was evenly distributed on the inside wall and bottom of a 25 ml test tube by tumbling and pouring on an orbital shaker (shaking at 30 rpm for 2 hours). An area dose of 5 micrograms/square centimeter was achieved with a uniform distribution at 900 ppm of active solution and 44.7 square centimeters of inner surface.
After the solvent had evaporated off, the tube was treated with 5-10 adult dog ticks (Rhipicephalus sanguineus) Colonisation, sealed with a perforated plastic lid and incubated in the dark at room temperature and ambient humidity. After 48 hours, the efficacy was determined. For this purpose, ticks were knocked onto the bottom of the test tube and incubated on a hot plate at 45-50 ℃ for up to 5 minutes. Ticks that remain immobile or move in an uncoordinated manner at the bottom so that they cannot intentionally escape the heat by climbing upward are considered dead or moribund.
A substance exhibits good resistance if at least 80% efficacy is achieved in this test at an application rate of 5 micrograms/square centimeterRhipicephalus sanguineusEfficacy. 100% efficacy means that all ticks die or moribund. 0% efficacy means that no ticks were injured.
In this test, for example, the following compounds from the preparation examples show a efficacy of 100% at an application rate of 5 micrograms/square centimeter (500 g/ha): 1-001, 1-002, 1-003, 1-004, 1-007, 1-008, 1-009, 1-010, 1-012, 1-013, 1-014, 1-016, 1-017, 1-022, 1-023, 1-024, 1-025, 1-026, 1-027, 1-028, 1-029, 1-031, 1-032, 1-034, 1-036, 1-038, 1-040, 1-041, 1-042, 1-048, 1-049, 1-054, 1-058, 1-060, 1-064, 1-066, 1-068, 1-069, 1-073, 1-075, 1-076, 1-077, 1-078, 1-081, 1-085, 1-086, 1-088, 1-089, 1-090, 1-091, 1-092, 1-093, 1-094, 1-095, 1-096, 1-097, 1-099, 1-100, 1-101, 1-117, 1-121, 1-127, 2-001 and 2-003.
In this test, for example, the following compounds from the preparation examples show 80% efficacy at an application rate of 5 micrograms/square centimeter (500 g/ha): 1-011, 1-015, 1-030, 1-035, 1-055, 1-061, 1-070, 1-084, 1-087, 1-098 and 2-006.
In this test, for example, the following compounds from the preparation examples show a efficacy of 100% at an application rate of 1 microgram per square centimeter (100 g/ha): 1-033.
In this test, for example, the following compounds from the preparation examples show 80% efficacy at an application rate of 1 microgram per square centimeter (100 g/ha): 1-043, 2-005 and 2-007.
Hibernation tick (Amblyomma hebaraeum) test
The solvent is dimethyl sulfoxide.
To produce a suitable active substance preparation, 10 mg of active substance are mixed with 0.5 ml of dimethyl sulfoxide and the concentrate is diluted with water to the desired concentration.
Tick nymph (Hibernation ticks) Placed in a perforated plastic cup and soaked in the desired concentration for 1 minute. Ticks were transferred on filter paper to petri dishes and stored in a climatic chamber.
After 42 days, the kill rate in% was determined. 100% means that all ticks were killed; 0% means that no ticks were killed.
In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 100 ppm: 1-022, 1-024, 1-025, 1-038, 1-040, 1-041 and 1-088.
In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 100 ppm: 1-087.
Boophilus microplus-dipping test
The test animal is cattle tick (Little cattle tick)Parkhurst strain, SP resistance
The solvent is dimethyl sulfoxide.
10 mg of active substance are dissolved in 0.5 ml of dimethyl sulfoxide. To produce a suitable formulation, the active substance solution is diluted with water to the concentration required in each case.
This active preparation is pipetted into a vial. 8-10 adult female cattle ticks saturated with blood (c)Boophilus microplus) Transferred to another perforated tube. The tube was dipped into the active agent preparation and all ticks were completely soaked. Following liquid flood, ticks were transferred on filter discs to plastic dishes and stored in a climate controlled room.
Efficacy was assessed after 7 days by production of fertilized eggs. Eggs that are not significantly fertile are stored in a climatic chamber until the larvae hatch after about 42 days. 100% efficacy means that none of the ticks lay fertilized eggs; 0% means that all eggs are fertile.
In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 100 ppm: 1-004, 1-022, 1-024, 1-025, 1-026, 1-027, 1-038, 1-040, 1-041, 1-049, 1-060, 1-073, 1-080, 1-087, 1-088, 1-089, 1-094, 1-098, 1-099 and 1-100.
In this test, for example, the following compounds from the preparation examples show an effectiveness of 95% at an application rate of 100 ppm: 1-001.
In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 100 ppm: 1-010 and 1-042.
In this test, for example, the following compounds from the preparation examples show an effectiveness of 80% at an application rate of 100 ppm: 1-037 and 2-001.
Boophilus microplus-injection test
The solvent is dimethyl sulfoxide.
To produce a suitable active substance preparation, 10 mg of active substance are mixed with 0.5 ml of solvent and the concentrate is diluted with solvent to the desired concentration.
Injection of 1 microliter of active substance solution into 5 adult, saturated female cattle ticks (Boophilus microplus) In the abdomen of (c). Animals were transferred to dishes and stored in a climatic chamber.
Efficacy was assessed after 7 days by production of fertilized eggs. Eggs that are not significantly fertile are stored in a climatic chamber until the larvae hatch after about 42 days. 100% efficacy means that none of the ticks lay fertilized eggs; 0% means that all eggs are fertile.
In this test, for example, the following compounds from the preparation examples show a efficacy of 100% at an application rate of 20 μ g/animal: 1-001, 1-002, 1-003, 1-004, 1-005, 1-006, 1-007, 1-008, 1-009, 1-010, 1-011, 1-012, 1-013, 1-014, 1-015, 1-016, 1-017, 1-018, 1-019, 1-020, 1-022, 1-023, 1-024, 1-025, 1-026, 1-027, 1-028, 1-029, 1-030, 1-031, 1-032, 1-033, 1-034, 1-035, 1-036, 1-037, 1-038, 1-040, 1-041, 1-042, 1-043, 1-046, 1-047, 1-007, 1-048, 1-049, 1-050, 1-052, 1-054, 1-055, 1-057, 1-058, 1-059, 1-060, 1-061, 1-062, 1-063, 1-064, 1-065, 1-066, 1-067, 1-068, 1-069, 1-070, 1-071, 1-073, 1-075, 1-076, 1-077, 1-078, 1-079, 1-080, 1-081, 1-082, 1-084, 1-085, 1-086, 1-087, 1-088, 1-089, 1-091, 1-092, 1-093, 1-094, 1-095, 1-096, 1-097, 1-094, 1-095, 1-097, 1-098, 1-099, 1-100, 1-101, 1-107, 1-108, 1-110, 1-114, 1-115, 1-116, 1-117, 1-118, 1-119, 1-121, 1-123, 1-124, 1-125, 1-126, 1-127, 2-001, 2-002, 2-003, 2-004, 2-005, 2-006, 2-007.
In this test, for example, the following compounds from the preparation examples show a 95% efficacy at an application rate of 20 μ g/animal: 1-112.
In this test, for example, the following compounds from the preparation examples show a potency of 90% at an application rate of 20 μ g/animal: 1-074.
In this test, for example, the following compounds from the preparation examples show 80% efficacy at an application rate of 20 μ g/animal: 1-083, 1-109 and 1-111.
Ctenocephalides felis-oral test
The solvent is dimethyl sulfoxide.
To produce a suitable active substance preparation, 10 mg of active substance are mixed with 0.5 ml of dimethyl sulfoxide. Dilution with citrated bovine blood produced the desired concentration.
About 20 starved adult feline fleas (A), (B), (C), (DCtenocephalides felis) Placed in a chamber closed at the top and bottom by gauze. A metal cylinder closed at the bottom with parafilm was placed over the chamber. The cylinder contains a blood/active substance product into which fleas can be sucked through the parafilm.
After 2 days, the kill rate in% was determined. 100% means that all fleas are killed; 0% means that no fleas are killed.
In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 100 ppm: 1-001, 1-002, 1-003, 1-004, 1-005, 1-006, 1-007, 1-008, 1-009, 1-010, 1-011, 1-012, 1-013, 1-014, 1-015, 1-016, 1-017, 1-019, 1-022, 1-023, 1-024, 1-025, 1-026, 1-027, 1-028, 1-029, 1-030, 1-031, 1-032, 1-033, 1-034, 1-035, 1-036, 1-037, 1-038, 1-040, 1-041, 1-042, 1-04053, 1-047, 1-049, 1-055, 1-8, 1-037, 1-040, 1-041, 1-04053, 1-04059, 1-055, 1-8, 1-007, 1-022, 1-023, 1-060, 1-061, 1-062, 1-064, 1-066, 1-067, 1-068, 1-069, 1-070, 1-073, 1-075, 1-076, 1-077, 1-081, 1-084, 1-085, 1-086, 1-087, 1-088, 1-089, 1-091, 1-092, 1-093, 1-094, 1-095, 1-096, 1-097, 1-098, 1-099, 1-100, 1-101, 1-116, 1-117, 1-121, 1-126, 1-127, 2-001, 2-003, 2-004, 2-005, 2-006, 2-007.
In this test, for example, the following compounds from the preparation examples show an effectiveness of 95% at an application rate of 100 ppm: 1-020, 1-048, 1-057, 1-079 and 1-080.
In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 100 ppm: 1-052, 1-063, 1-065, 1-071, 1-082, 1-115 and 1-123.
In this test, for example, the following compounds from the preparation examples show an effectiveness of 80% at an application rate of 100 ppm: 1-021 and 1-078.
Lucilia cuprina test
The solvent is dimethyl sulfoxide.
To produce a suitable active substance preparation, 10 mg of active substance are mixed with 0.5 ml of dimethyl sulfoxide and the concentrate is diluted with water to the desired concentration.
About 20 of Australian gold sleeping flies (Schlafgoldfriege) ((ii))Lucilia cuprina (Roxb.) Kuntze) The L1 larvae were transferred to test containers containing minced horse meat and the active substance preparation at the desired concentration.
After 2 days, the kill rate in% was determined. 100% means that all larvae are killed, 0% means that none of the larvae are killed.
In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 100 ppm: 1-001, 1-002, 1-003, 1-004, 1-005, 1-006, 1-007, 1-008, 1-009, 1-010, 1-011, 1-012, 1-013, 1-014, 1-015, 1-016, 1-017, 1-019, 1-022, 1-023, 1-024, 1-025, 1-026, 1-027, 1-028, 1-029, 1-030, 1-031, 1-032, 1-033, 1-034, 1-035, 1-036, 1-037, 1-038, 1-040, 1-041, 1-042, 1-043, 1-046, 1-047, 1-049, 1-050, 050, 1-052, 1-054, 1-055, 1-057, 1-058, 1-060, 1-062, 1-064, 1-067, 1-068, 1-069, 1-070, 1-071, 1-073, 1-075, 1-077, 1-078, 1-079, 1-081, 1-084, 1-085, 1-086, 1-087, 1-088, 1-089, 1-091, 1-092, 1-093, 1-094, 1-095, 1-096, 1-097, 1-098, 1-099, 1-100, 1-101, 1-116, 1-117, 1-119, 1-121, 1-126, 1-127, 2-001, 1-127, 2-003, 2-004, 2-005, 2-006 and 2-007.
In this test, for example, the following compounds from the preparation examples show an effectiveness of 95% at an application rate of 100 ppm: 1-048 and 1-076.
In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 100 ppm: 1-020.
In this test, for example, the following compounds from the preparation examples show an effectiveness of 80% at an application rate of 100 ppm: 1-065, 1-066 and 1-115.
Housefly test
The solvent is dimethyl sulfoxide.
To produce a suitable active substance preparation, 10 mg of active substance are mixed with 0.5 ml of dimethyl sulfoxide and the concentrate is diluted with water to the desired concentration.
Containers containing sponges treated with sugar solution and active substance preparation of the desired concentration 10 adult houseflies (c)Housefly)And (4) colonization.
After 2 days, the kill rate in% was determined. 100% means that all flies were killed; 0% means that none of the flies were killed.
In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 100 ppm: 1-001, 1-002, 1-003, 1-004, 1-006, 1-007, 1-010, 1-019, 1-024, 1-025, 1-027, 1-028, 1-034, 1-035, 1-036, 1-040, 1-055, 1-068, 1-075, 1-077, 1-084, 1-086, 1-087, 1-089, 1-094, 1-099, 1-100, 1-127, 2-001 and 2-003.
In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 100 ppm: 1-013, 1-014, 1-026, 1-037, 1-073, 1-096, 1-126, 2-005 and 2-006.
In this test, for example, the following compounds from the preparation examples show an effectiveness of 80% at an application rate of 100 ppm: 1-031, 1-032, 1-047, 1-049, 1-058, 1-071, 1-119, 2-004.
Myzus persicae-spray test
Solvent 78 parts by weight of acetone
1.5 parts by weight of dimethylformamide
Emulsifier is alkyl aryl polyglycol ether.
To produce a suitable active substance preparation, 1 part by weight of active substance is dissolved using the stated parts by weight of solvent and supplemented with water containing 1000 ppm of emulsifier concentration until the desired concentration is reached. To make other test concentrations, dilute with emulsifier-containing water.
Spraying all stages of green peach aphids with the desired concentration of active substance preparation (Myzus persicae) Infected leaf of Chinese cabbage: (Chinese cabbage）。
At 6 days, the efficacy in% was determined. 100% means that all aphids are killed; 0% means that no aphids were killed.
In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 500 g/ha: 1-016 and 1-031.
In this test, for example, the following compounds from the preparation examples show a 100% efficacy at an application rate of 100 g/ha: 1-001, 1-006, 1-009, 1-010, 1-025, 1-026, 1-027, 1-036, 1-040, 1-041, 1-064, 1-076, 1-081, 1-086, 1-098, 1-099 and 1-100.
In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 100 g/ha: 1-003, 1-012, 1-017, 1-019, 1-033, 1-048, 1-087 and 1-089.
Horseradish cochleariae-spray assay
Solvent 78.0 parts by weight of acetone
1.5 parts by weight of dimethylformamide
Emulsifier is alkyl aryl polyglycol ether.
To produce a suitable active substance preparation, 1 part by weight of active substance is dissolved using the stated parts by weight of solvent and supplemented with water containing 1000 ppm of emulsifier concentration until the desired concentration is reached. To make other test concentrations, the formulation was diluted with water containing the emulsifier.
Spraying the leaf of Chinese cabbage with the active substance preparation of the required concentrationChinese cabbage) And after drying, using horse radish simian beetle: (Horseradish Siape insect) Colonization of larvae.
After 7 days, the efficacy in% was determined. 100% means that all beetle larvae are killed; 0% means that no beetle larvae have been killed.
In this test, for example, the following compounds from the preparation examples show a 100% efficacy at an application rate of 500 g/ha: 1-009, 1-016, 1-018 and 1-031.
In this test, for example, the following compounds from the preparation examples show an efficacy of 83% at an application rate of 500 g/ha: 1-029.
In this test, for example, the following compounds from the preparation examples show a 100% efficacy at an application rate of 100 g/ha: 1-001, 1-002, 1-003, 1-004, 1-005, 1-006, 1-007, 1-010, 1-011, 1-012, 1-013, 1-014, 1-015, 1-017, 1-019, 1-022, 1-023, 1-024, 1-025, 1-026, 1-027, 1-028, 1-034, 1-035, 1-036, 1-037, 1-038, 1-039, 1-040, 1-041, 1-042, 1-043, 1-047, 1-050, 1-054, 1-055, 1-060, 1-064, 1-067, 1-068, 1-069, 1-071, 1-3, 1-073, 1-050, 1-055, 1-074, 1-036, 1-078, 1-069, 1-071, 1-076, 1-081, 1-084, 1-085, 1-086, 1-087, 1-088, 1-089, 1-090, 1-091, 1-092, 1-093, 1-094, 1-095, 1-096, 1-097, 1-098, 1-099, 1-100, 1-101, 1-116, 1-121, 1-126, 1-127, 2-001, 2-003, 2-004, 2-005, 2-006, 2-007.
In this test, for example, the following compounds from the preparation examples show an efficacy of 83% at an application rate of 100 g/ha: 1-033.
Spodoptera frugiperda-spray test
Solvent 78.0 parts by weight of acetone
1.5 parts by weight of dimethylformamide
Emulsifier is alkyl aryl polyglycol ether.
To produce a suitable active substance preparation, 1 part by weight of active substance is dissolved using the stated parts by weight of solvent and supplemented with water containing 1000 ppm of emulsifier concentration until the desired concentration is reached. To make other test concentrations, dilute with emulsifier-containing water.
Spraying corn leaves with the desired concentration of active substance preparationZea mays) And after drying, using armyworm (Grass land Spodoptera littoralis) The colonization of the caterpillars.
After 7 days, the efficacy in% was determined. 100% means that all caterpillars are killed; 0% means that none of the caterpillars were killed.
In this test, for example, the following compounds from the preparation examples show a 100% efficacy at an application rate of 500 g/ha: 1-009, 1-016, 1-018, 1-029, 1-030 and 1-031.
In this test, for example, the following compounds from the preparation examples show a 100% efficacy at an application rate of 100 g/ha: 1-001, 1-003, 1-004, 1-005, 1-006, 1-007, 1-010, 1-012, 1-013, 1-014, 1-015, 1-017, 1-019, 1-022, 1-023, 1-024, 1-025, 1-026, 1-027, 1-028, 1-034, 1-035, 1-036, 1-037, 1-038, 1-039, 1-040, 1-043, 1-052, 1-054, 1-055, 1-064, 1-067, 1-068, 1-069, 1-071, 1-073, 1-076, 1-078, 1-081, 1-084, 1-086, 1-087, 1-088, 1-089, 1-091, 1-092, 1-093, 1-095, 1-096, 1-097, 1-098, 1-099, 1-100, 1-101, 1-117, 1-121, 1-127, 2-001, 2-003, 2-004, 2-005 and 2-006.
In this test, for example, the following compounds from the preparation examples show an efficacy of 83% at an application rate of 100 g/ha: 1-002, 1-057, 1-058, 1-060, 1-085, 1-094 and 1-116.
Tetranychus urticae-spray test, OP resistance
Solvent 78.0 parts by weight of acetone
1.5 parts by weight of dimethylformamide
Emulsifier is alkyl aryl polyglycol ether.
To produce a suitable active substance preparation, 1 part by weight of active substance is dissolved using the stated parts by weight of solvent and supplemented with water containing 1000 ppm of emulsifier concentration until the desired concentration is reached. To make other test concentrations, dilute with emulsifier-containing water.
Spraying all stages of the spider mites of general mite stage(s) with the desired concentration of active substance preparationTetranychus urticae Koch) Infected Bean leaves: (Bean food）。
After 6 days, the efficacy in% was determined. 100% means that all spider mites were killed; 0% means that any spider mites were not killed.
In this test, for example, the following compounds from the preparation examples show a 100% efficacy at an application rate of 500 g/ha: 1-009 and 1-016.
In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 500 g/ha: 1-031.
In this test, for example, the following compounds from the preparation examples show a 100% efficacy at an application rate of 100 g/ha: 1-001, 1-003, 1-004, 1-006, 1-010, 1-012, 1-013, 1-015, 1-017, 1-019, 1-022, 1-023, 1-024, 1-025, 1-026, 1-027, 1-028, 1-029, 1-033, 1-034, 1-035, 1-038, 1-039, 1-040, 1-041, 1-042, 1-043, 1-046, 1-047, 1-048, 1-081, 1-053, 1-054, 1-058, 1-060, 1-063, 1-064, 1-065, 1-0717, 1-071, 1-073, 1-078, 1-085, 1-087, 1-088, 1-089, 1-091, 1-092, 1-093, 1-094, 1-095, 1-096, 1-097, 1-098, 1-099, 1-100, 1-101, 1-108, 1-121, 2-001, 2-003, 2-004 and 2-006.
In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 100 g/ha: 1-007, 1-011, 1-014, 1-018, 1-055, 1-068, 1-069, 1-076 and 1-086.
In this test, for example, the following compounds from the preparation examples show a 100% efficacy at an application rate of 20 g/ha: 2-005.
Anopheles test (ANPHGB surface treatment)
Solvent acetone + 2000 ppm rapeseed oil methyl ester (RME).
To produce a suitable active substance preparation, the active substance is dissolved in a solvent (2 mg/ml). After pipetting the active substance preparation onto a glazed brick and drying, adult mosquitoes of the anopheles RSPH gate (kdr homozygote) of the genus anopheles were placed on the treated brick. The exposure time was 30 minutes.
Mortality in% was determined after 24 hours after contact with the treated surface. 100% means that all mosquitoes were killed; 0% means that no mosquitoes were killed.
In this test, for example, the following compounds from the preparation examples exhibit an efficacy of 90 to 100% at an application rate of 100 mg/m: 1-001, 1-023, 1-024, 1-036 and 1-040.
In this test, for example, the following compounds from the preparation examples exhibit an efficacy of 90 to 100% at an application rate of 20 mg/m: 1-024 and 1-127.
Anopheles test (ANPHFU surface treatment)
Solvent acetone + 2000 ppm rapeseed oil methyl ester (RME).
To produce a suitable active substance preparation, the active substance is dissolved in a solvent (2 mg/ml). After pipetting the active substance preparation onto the glazed tile and drying, adult mosquitoes of the FUMOZ-R phylum Anopheles (Anopheles funestus) (Hunt et al, Med Vet entomol. 2005 Sep; 19(3): 271-5) were placed on the treated tile. The exposure time was 30 minutes.
Mortality in% was determined after 24 hours after contact with the treated surface. 100% means that all mosquitoes were killed; 0% means that no mosquitoes were killed.
In this test, for example, the following compounds from the preparation examples exhibit an efficacy of 90 to 100% at an application rate of 100 mg/m: 1-001, 1-022, 1-023, 1-024, 1-025, 1-036, 1-037, 1-040 and 1-073.
In this test, for example, the following compounds from the preparation examples exhibit an efficacy of 90 to 100% at an application rate of 20 mg/m: 1-001, 1-022, 1-023, 1-024, 1-025, 1-026, 1-027, 1-036, 1-040, 1-081 and 1-127.
Aedes test (AEDSAE surface treatment)
Solvent acetone + 2000 ppm rapeseed oil methyl ester (RME).
To produce a suitable active substance preparation, the active substance is dissolved in a solvent (2 mg/ml). The active preparation was pipetted onto the glazed tile and after drying, adult mosquitoes of the genus moneim of the genus aedes aegypti were placed on the treated tile. The exposure time was 30 minutes.
Mortality in% was determined after 24 hours after contact with the treated surface. 100% means that all mosquitoes were killed; 0% means that no mosquitoes were killed.
In this test, for example, the following compounds from the preparation examples exhibit an efficacy of 90 to 100% at an application rate of 100 mg/m: 1-001, 1-002, 1-003, 1-006, 1-010, 1-012, 1-013, 1-014, 1-016, 1-017, 1-019, 1-022, 1-023, 1-024, 1-025, 1-026, 1-027, 1-034, 1-035, 1-036, 1-037, 1-073, 1-081, 1-085, 1-094, 1-099, 1-100, 1-127 and 2-001.
In this test, for example, the following compounds from the preparation examples exhibit an efficacy of 90 to 100% at an application rate of 20 mg/m: 1-001, 1-002, 1-003, 1-006, 1-010, 1-012, 1-013, 1-014, 1-016, 1-017, 1-019, 1-022, 1-023, 1-024, 1-025, 1-026, 1-027, 1-034, 1-035, 1-036, 1-037, 1-040, 1-073, 1-081, 1-086, 1-094, 1-099, 1-100, 1-127 and 2-001.

Claims (17)

1. A compound of the formula (Ic)
Wherein
R1Is hydrogen, optionally substituted C1-C6Alkyl radical, C3-C6-alkenyl, C3-C6-alkynyl, C3-C7-cycloalkyl, C1-C6-alkylcarbonyl group, C1-C6Alkoxycarbonyl, aryl (C)1-C3) Alkyl, heteroaryl (C)1-C3) -an alkyl group;
chemical moieties
A1Is CR2Or a nitrogen-containing compound,
A2is CR3Or a nitrogen-containing compound,
A3is CR4Or nitrogen, and
A4is CR5Or a nitrogen-containing compound,
but wherein the chemical moiety A1To A4Not more than three of which are simultaneously nitrogen;
R2、R3、R4and R5Independently of one another, hydrogen, halogen, cyano, nitro, optionally substituted C1-C6Alkyl radical, C3-C6-cycloalkyl, C1-C6-alkoxy groups,N-C1-C6-alkoxyimino-C1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N-C1-C6-alkylamino orN,N-di-C1-C6-an alkylamino group;
if A is2And A3None of the moieties being nitrogen, R3And R4May form, together with the carbon atom to which they are attached, a 5-or 6-membered ring containing 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and/or 0 or 1 sulfur atom, or
If A is1And A2None of the moieties being nitrogen, R2And R3May form, together with the carbon atom to which they are attached, a 5-or 6-membered ring containing 0, 1 or 2 nitrogen atoms and/or 0 or 1 oxygen atom and/or 0 or 1 sulfur atom;
w is oxygen or sulfur;
q is hydrogen, amino or one of the following optionally substituted moieties: alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, heterocyclyl, cycloalkylalkyl, arylalkyl, heteroarylalkyl, alkoxycarbonyl, or is N-alkylamino, alkylamino,N-alkylcarbonylamino,N,NDialkylamino, alkylA alkylsulfonylamino moiety; or
Q is aryl optionally mono-to pentasubstituted with V, or heteroaryl optionally mono-to pentasubstituted with V, wherein
V is halogen, cyano, nitro, optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, or a pharmaceutically acceptable salt thereof,NAn alkoxyiminoalkyl group, an alkylsulfanyl group, an alkylsulfinyl group, an alkylsulfonyl group, a substituted aryl group,N,N-a dialkylamino group;
R6independently of one another, halogen, cyano, nitro, amino or optionally substituted C1-C6Alkyl radical, C1-C6-alkoxy, C1-C6-alkylcarbonyl group, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
n has a value of 0-2;
Z1is optionally substituted alkyl or cycloalkyl, and
Z2is hydrogen, halogen, cyano, nitro, amino or optionally substituted alkyl, alkylcarbonyl, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, and
Z3is hydrogen or optionally substituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl.
2. A compound according to claim 1, wherein
R1Is hydrogen or C optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C 3-C6-alkenyl, C3-C6-alkynyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C3Alkyl radical, C1-C6-alkylcarbonyl group, C1-C6Alkoxycarbonyl, aryl (C)1-C3) Alkyl, heteroaryl (C)1-C3) -an alkyl group;
chemical moieties
A1Is CR2Or a nitrogen-containing compound,
A2is CR3Or a nitrogen-containing compound,
A3is CR4Or nitrogen, and
A4is CR5Or a nitrogen-containing compound,
but wherein the chemical moiety A1To A4Not more than three of which are simultaneously nitrogen;
R2、R3、R4and R5Independently of one another, hydrogen, halogen, cyano, nitro or C which is optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C3-C6-cycloalkyl, C1-C6-alkoxy groups,N-C1-C6-alkoxyimino-C1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N-C1-C6-alkylamino orN,N-di-C1-C6-an alkylamino group;
w is oxygen or sulfur;
q is hydrogen, amino or one of the following moieties which are optionally mono-to heptaly substituted independently of one another by hydroxy, nitro, amino, halogen, alkoxy, cyano, hydroxycarbonyl, alkoxycarbonyl, alkylcarbamoyl, cycloalkylcarbamoyl or phenyl: c1-C6Alkyl radical, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C2-C5-heterocyclyl radical, C1-C4-alkoxy, C1-C6-alkyl-C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6Alkyl radical, C1-C6Hydroxyalkyl, aryl (C) 1-C3) Alkyl, heteroaryl (C)1-C3) Alkyl radical, C1-C4-an alkoxycarbonyl group,N-C1-C4-alkylamino, alkylamino,N-C1-C4-alkylcarbonylamino,N,N-di-C1-C4-alkylamino radical, C1-C4-an alkylsulfonylamino group; or
Q is hydrogen, amino or selected from C1-C6Alkyl radical, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, 5-or 6-membered heterocyclyl, C1-C6-alkyl-C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6Alkyl radical, C6-C10-aryl- (C)1-C3) -alkyl, 5-or 6-membered heteroaryl- (C)1-C3) Alkyl radical, C1-C4-one of the moieties of alkoxycarbonyl optionally substituted independently of each other by 1, 2, 3, 4, 5, 6 or 7 substituents selected from hydroxy, nitro, amino, halogen, oxo, benzyloxy, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6Haloalkoxy, cyano, hydroxycarbonyl, C1-C4Alkoxycarbonyl, C1-C6-alkylcarbamoyl, C3-C6-cycloalkylcarbamoyl radical,N,N-di-C1-C4-alkylamino, optionally substituted by 1, 2 or 3 substituents independently of one another, chosen from halogen, C1-C6-alkoxy, C1-C6-haloalkoxy and C1-C6Phenyl substituted by alkyl substituents, optionally substituted by 1, 2 or 3 substituents independently of one another selected from halogen, C1-C6-alkoxy, C1-C6-haloalkoxy and C1-C6Phenylthio substituted by alkyl substituents, optionally substituted by 1, 2 or 3 substituents independently of one another selected from halogen, C 1-C6-alkoxy, C1-C6-haloalkoxy and C1-C6Phenoxy substituted with substituents of alkyl, optionally substituted with 1, 2 or 3 substituents independently of one another selected from halogen, C1-C6-alkoxy, C1-C6-haloalkoxy and C1-C65-or 6-membered heteroaryl substituted with a substituent of-alkyl (examples)Such as pyrazolyl); or isN-C1-C4-alkylamino, alkylamino,N-C1-C4-alkylcarbonylamino,N,N-di-C1-C4-alkylamino radical, C1-C4-an alkylsulfonylamino moiety; or
Q is aryl substituted with 0, 1, 2, 3 or 4 substituents V or 5-or 6-membered heteroaryl substituted with 0, 1, 2, 3 or 4 substituents V, or
Q is a bicyclic heterocycle substituted with 0, 1, 2, 3, or 4V substituents or a bicyclic carbocycle substituted with 0, 1, 2, 3, or 4V substituents; wherein
V independently of one another is halogen, cyano, nitro or C which is optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C1-C6-haloalkyl group, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy,N-C1-C6-alkoxyimino-C1-C3Alkyl radical, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group,N,N-di- (C)1-C6-alkyl) amino;
R6independently of one another, halogen, cyano, nitro, amino or C optionally mono-to heptasubstituted by halogen 1-C6Alkyl radical, C1-C6-alkoxy, C1-C6-alkylcarbonyl group, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
n has a value of 0-1;
Z1is C optionally mono-to heptasubstituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C3-C6-a cycloalkyl radical, and
Z2is hydrogen, halogen, cyano, or,Nitro, amino or C mono-to heptasubstituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C1-C6-alkylcarbonyl group, C1-C6Alkyl sulfanyl, C1-C6-alkylsulfinyl, C1-C6-an alkylsulfonyl group, and
Z3is hydrogen or C optionally mono-to heptaly substituted independently of one another by halogen, cyano, alkoxy or alkoxycarbonyl1-C6Alkyl radical, C3-C6-cycloalkyl, C3-C4-alkenyl, C3-C4-alkynyl or aryl and heteroaryl optionally mono-to penta-substituted independently of each other by halogen, cyano, alkoxy and alkoxycarbonyl.
3. A compound according to claim 1 or 2, wherein
R1Is hydrogen, C1-C4Alkyl radical, C3-C4-alkenyl, C3-C4-an alkynyl group;
chemical moieties
A1Is CR2，
A2Is CR3Or a nitrogen-containing compound,
A3is CR4And is and
A4is CR5；
W is oxygen;
R6is C1-C4-an alkyl group;
n has a value of 0-1;
Z1is C which is in each case optionally mono-to heptaly substituted independently of one another by halogen or cyano 1-C6-alkyl or C3-C6-a cycloalkyl group;
Z2is C which is in each case optionally mono-to heptaly substituted independently of one another by halogen or cyano1-C6-alkyl or C3-C6-a cycloalkyl group;
Z3is hydrogen or C1-C6-an alkyl group.
4. A compound according to claim 1, 2 or 3, wherein
R1Is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl;
chemical moieties
A1Is CR2，
A2Is CR3Or a nitrogen-containing compound,
A3is CR4And is and
A4is CR5；
W is oxygen;
R6is hydrogen;
Z1is C which is in each case optionally mono-to heptaly substituted independently of one another by halogen1-C6-an alkyl group;
Z2is C which is in each case optionally mono-to heptaly substituted independently of one another by halogen1-C6-an alkyl group;
Z3is C1-C6-an alkyl group.
5. A compound according to any preceding claim, wherein
R2And R5Independently of one another, hydrogen, fluorine, chlorine, bromine, iodine, methyl and methoxy;
R3and R4Independently of one another, hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C1-C4Alkyl radical, C1-C4-haloalkyl.
6. A compound according to any preceding claim, wherein
R2And R5Independently of one another, hydrogen or fluorine;
R3is hydrogen; and is
R4Is hydrogen, fluorine, chlorine or methyl.
7. A compound according to any preceding claim, wherein
Q is hydrogen;
or
C optionally substituted by 1, 2, 3 or 4 substituents 1-C6-alkyl, the substituents being independently of each other selected from
Fluorine,
Chlorine,
Bromine,
Iodine,
A cyano group,
An oxo group,
Methoxy group,
Benzyloxy group,
The ethoxy group is a group of one or more selected from the group consisting of an ethoxy group,
N,N-a dimethylamino group,
phenylthio optionally substituted independently of one another by 1, 2, 3 or 4 substituents from the group consisting of fluorine, chlorine, bromine, iodine, methoxy, methyl and trifluoromethyl,
phenoxy which is optionally substituted independently of one another by 1, 2, 3 or 4 substituents from the group consisting of fluorine, chlorine, bromine, iodine, methoxy, methyl and trifluoromethyl,
phenyl optionally substituted independently of one another by 1, 2, 3 or 4 substituents selected from the group consisting of fluorine, chlorine, bromine, iodine, methoxy, methyl and trifluoromethyl,
thienyl optionally substituted independently of one another by 1, 2, 3 or 4 substituents selected from the group consisting of fluorine, chlorine, bromine, iodine, methoxy, methyl and trifluoromethyl,
pyrazolyl which is optionally substituted, independently of one another, by 1, 2, 3 or 4 substituents from the group consisting of fluorine, chlorine, bromine, iodine, methoxy, methyl and trifluoromethyl, and
C3-C6-a cycloalkyl group;
or
C optionally substituted by 1, 2, 3 or 4 substituents3-C6-cycloalkyl, the substituents being independently of each other selected from
Methoxy group,
Fluorine,
Chlorine,
Bromine,
Iodine,
A cyano group,
Methyl, methyl,
Phenyl optionally substituted independently of one another by 1, 2, 3 or 4 substituents selected from the group consisting of fluorine, chlorine, bromine, iodine, methoxy, methyl, trifluoromethyl;
Or
Q is the following group substituted with 0, 1,2, 3 or 4V substituents: phenyl, naphthyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, pyridyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, imidazolyl, furanyl, thienyl, pyrrolyl, oxadiazolyl, thiadiazolyl, benzothienyl, benzofuranyl, [1,2,4] triazolo [1,5-a ] pyrimidinyl, 1, 3-benzodioxolyl or tetrahydronaphthyl, wherein
V is, independently of one another, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, propyl, butyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2,2, 2-tetrafluoroethyl, 1-chloro-1, 2,2, 2-tetrafluoroethyl, 2,2, 2-trichloroethyl, 2-chloro-2, 2-difluoroethyl, 1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, n-propoxy, 1-methylethoxy, fluoromethoxy, Difluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, trifluoromethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2, 2-difluoroethoxy, pentafluoroethoxy, n-ethyldifluoromethoxy, n-, NMethoxy imino methyl, 1-, (N-methoxyimino) ethyl, methylsulfanyl, methylsulfonyl, methylsulfinyl, trifluoromethylsulfonyl, trifluoromethylsulfinyl, trifluoromethylsulfanyl, N-dimethylamino.
8. A compound according to any preceding claim, wherein
Q is C optionally substituted with 1,2, 3 or 4 substituents1-C6-alkyl, the substituents being independently of each other selected from
Fluorine,
An oxo group,
Methoxy group,
Benzyloxy group,
Ethoxy, ethoxy,
N,N-dimethylamino group
A phenylthio group,
A phenoxy group,
C3-C6-a cycloalkyl group,
Phenyl which is optionally substituted independently of one another by 1,2, 3 or 4 substituents from the group consisting of fluorine, chlorine and trifluoromethyl,
Thienyl optionally substituted with 1,2, 3 or 4 trifluoromethyl, and
pyrazolyl optionally substituted independently of one another by 1,2, 3 or 4 substituents selected from methyl and trifluoromethyl;
or
C optionally substituted by 1,2, 3 or 4 substituents3-C6-cycloalkyl, the substituents being independently of each other selected from
Methoxy group,
Chlorine,
A cyano group,
Methyl, methyl,
Phenyl optionally substituted independently of one another by 1,2, 3 or 4 substituents selected from the group consisting of chlorine and methyl and trifluoromethyl;
or
Q is the following group substituted with 0, 1,2, 3 or 4V substituents: phenyl, naphthyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, pyridyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, imidazolyl, furanyl, thienyl, pyrrolyl, oxadiazolyl, thiadiazolyl, benzothienyl, benzofuranyl, [1,2,4] triazolo [1,5-a ] pyrimidinyl, 1, 3-benzodioxolyl or tetrahydronaphthyl, wherein
V is, independently of one another, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, propyl, butyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trifluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 1,2,2, 2-tetrakisfluoroethylFluoroethyl, 1-chloro-1, 2,2, 2-tetrafluoroethyl, 2,2, 2-trichloroethyl, 2-chloro-2, 2-difluoroethyl, 1-difluoroethyl, pentafluoroethyl, pentafluoro-tert-butyl, heptafluoro-n-propyl, heptafluoro-isopropyl, nonafluoro-n-butyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, n-propoxy, 1-methylethoxy, fluoromethoxy, difluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, trifluoromethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2, 2-difluoroethoxy, pentafluoroethoxy, n-fluoroethoxy, pentafluoroethyl, n-propyl, heptafluoro-n-butyl, cyclopropyl, cyclobutyl, methoxy, ethoxy, 1-methylethoxy, fluoromethoxy,Nmethoxy imino methyl, 1-, (N-methoxyimino) ethyl, methylsulfanyl, methylsulfonyl, methylsulfinyl, trifluoromethylsulfonyl, trifluoromethylsulfinyl, trifluoromethylsulfanyl, N-dimethylamino.
9. A compound according to any preceding claim, wherein the compound is of formula (Ic-1)
。
10. A compound according to any one of the preceding claims, wherein the compound is of formula (Ic-2)
。
11. Use of compounds of general formula (I), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii) and (Ij) according to any of claims 1 to 10 for controlling insects, arachnids and nematodes.
12. A pharmaceutical composition comprising at least one compound according to any one of claims 1 to 10.
13. A compound according to any one of claims 1 to 10 for use as a medicament.
14. Use of a compound according to any one of claims 1 to 10 for the manufacture of a pharmaceutical composition for controlling parasites in animals.
15. A process for the manufacture of plant protection compositions comprising a compound according to any one of claims 1 to 10 and conventional extenders and/or surface-active substances.
16. A method for controlling pests, characterized in that a compound according to any one of claims 1 to 10 is allowed to act on the pests and/or their living space.
17. Use of a compound according to any one of claims 1 to 10 for the protection of plant propagation material.
HK17104037.8A 2014-01-03 2014-12-30 Novel pyrazolyl-heteroarylamides as pesticides HK1230584A1 (en)

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Application Number Priority Date Filing Date Title
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