[go: up one dir, main page]

EP1341776A1 - Benzazolonylcarbonyl cyclohexenones et utilisation en tant qu'herbicides - Google Patents

Benzazolonylcarbonyl cyclohexenones et utilisation en tant qu'herbicides

Info

Publication number
EP1341776A1
EP1341776A1 EP01985385A EP01985385A EP1341776A1 EP 1341776 A1 EP1341776 A1 EP 1341776A1 EP 01985385 A EP01985385 A EP 01985385A EP 01985385 A EP01985385 A EP 01985385A EP 1341776 A1 EP1341776 A1 EP 1341776A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
alkoxy
haloalkoxy
diyl
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01985385A
Other languages
German (de)
English (en)
Inventor
Guido Mayer
Ulf Misslitz
Ernst Baumann
Wolfgang Von Deyn
Steffen Kudis
Michael Hofmann
Thorsten Volk
Matthias Witschel
Cyrill Zagar
Andreas Landes
Klaus Langemann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1341776A1 publication Critical patent/EP1341776A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to cyclohexenone derivatives of benzazolones (benzazolonylcarbonylcyclohexenones), agents containing such compounds and the use of the cyclohexenone derivatives or agents containing them for controlling harmful plants.
  • the invention relates to benzazolone carboxylic acids, which are important intermediates for the preparation of such cyclohexenone derivatives.
  • Cyclohexane-1,3-diones are known from EP-A 283 261, in which the cyclohexenone ring is substituted in the 2-position with a heteroaromatic radical bonded via a carbonyl group.
  • 5-ring or 6-ring heterocycles containing sulfur, nitrogen and / or oxygen are mentioned as heteroaromatic radicals.
  • WO 96/05182 discloses saccharin derivatives with herbicidal activity which are substituted on the benzene nucleus of the saccharin skeleton with a (2-cyclohexane-1,3-dione) carbonyl radical.
  • cyclohexane-1,3-diones with herbicidal activity which have a benzo-condensed sulfur heterocycle in the 2-position, e.g. B. have a thiochroman or a benzodehydrothiophene radical which is bonded via a carbonyl group.
  • WO 00/20408 describes u. a. Herbicides based on cyclohexenone derivatives of the general formula (a)
  • R is a methyl group
  • X is a hydrogen atom, a halogen atom or the like
  • G represents a 3- to 5-membered chain, which together with the two carbon atoms of the benzene ring to which G is linked, a 5- to 7th -linked, saturated or unsaturated condensed ring
  • Z 1 represents a halogen atom or the like
  • m is an integer between zero and four and q is either one or two.
  • PCT / EP 00/04042 discloses benzoheterocyclylcyclohexenones.
  • heterocyclic radicals include benzoxazolyl, benzidiazolyl, benzothiazolyl and benzotriazinyl.
  • the compounds have herbicidal activity.
  • the present invention is therefore based on the object of providing new compounds with herbicidal activity which preferably have a higher activity than the herbicidal substances of the prior art and / or better selectivity towards harmful plants.
  • the present invention relates to cyclohexenone derivatives of benzo-condensed, unsaturated 5-ring nitrogen heterocycles of the general formula I,
  • R 1 is halogen, C ⁇ -C4 alkyl, C] .- C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C ⁇ -C 4 alkoxy-C -C 4 -alkyl, C 4 -haloalkoxy-C ⁇ -C 4 alkyl, -C-C 4 haloalkylthio-C ⁇ -C 4 alkyl,
  • R 2 is hydrogen, hydroxy, nitro, amino, Ci-C ⁇ -alkylamino,
  • R 3 are hydrogen, C 4 -alkyl, C haloalkyl, C ⁇ -C 4 -alcohol xy-C ⁇ -C 4 alkyl, C 1 -C 4 -haloalkoxy-C ⁇ -C 4 alkyl or halogen;
  • R 4 C ⁇ -C 6 -alkyl, C 6 haloalkyl, C ⁇ -C 6 -alkoxy-C ⁇ -C 6 - alkyl, C ⁇ -C 6 haloalkoxy-C ⁇ -C 6 alkyl, C 2 -C 6 - alkenyl, C 2 -C 6 haloalkenyl, C ⁇ -C 6 haloalkoxy-C 2 -C 6 -alke- nyl, C ⁇ -C 6 -alkoxy-C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C ⁇ -C 6 haloalkoxy-C 2 -C 6 -alki- nyl, C ⁇ -C 6 -alkoxy-C 2 -C 6 alkynyl;
  • R a , R 4b independently of one another can have the meanings given for R 4 and R 4b can stand for hydrogen;
  • R 5 independently of one another are hydrogen, C 6 alkyl, Ci-C ö haloalkyl, C ⁇ -C 6 -alkoxy-C ⁇ -C 6 -alkyl, (Cx-Ce-HalogenalkoxyJ-C ⁇ -alkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C ⁇ -C 6 haloalkyl-C 2 -C 6 -alke- nyl, C ⁇ -C 6 haloalkoxy-C 2 -C 6 alkenyl,
  • R6 is hydrogen, Ci-Ci-alkyl, C 1 -C 4 haloalkyl,
  • R 9 , R 11 , R 13 independently of one another are hydrogen or C 1 -C 4 alkyl
  • R 10 is hydrogen, halogen, hydroxy, Cx-C ⁇ alkyl
  • R 9 and R 11 or R 11 and R 13 together form a ⁇ bond or a Ci-Cs-alkylene chain, which can carry one, two or three radicals from the following group: halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or -CC 4 alkoxycarbonyl;
  • R 9 and R 13 together form a C ⁇ -C 4 -alkyl chain which may carry one, two or three radicals from the following group: gene halo, cyano, C 4 -alkyl, C 4 haloalkyl or C ⁇ - C-alkoxycarbonyl;
  • R 10 and R 11 together form a -0- (CH 2 ) p -0-, -0- (CH 2 ) p -S-, -S- (CH 2 ) p -S-, -0- (CH 2 ) q - or -S- (CH 2 ) q chain, in which p is 2, 3, 4 or 5, and q is 2, 3, 4, 5 or 6, and by one, two or three radicals the group may be substituted: halogen, cyano, C 4 -alkyl, C 4 haloalkyl or C ⁇ -C 4 alkoxycarbonyl; or
  • R 10 and R 11 together with the carbon to which they are attached form a carbonyl group
  • R 15 Ci-Cg-alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or C 3 -C 6 cycloalkyl, where the four radicals mentioned can be partially or completely halogenated and / or one, two or can carry three of the following groups: cyano, -CC 4 alkoxy, -C-C 4 -haloalkoxy, -C-C 4 -alkylthio, -C-C-haloalkylthio, -C-C 4 -alkylcarbonyl, -C-C 4 - Alkoxycarbonyl or C 1 -C 4 haloalkoxycarbonyl,
  • R 16 , R 17 independently of one another are hydrogen, hydroxy
  • R 18 is hydrogen, -CC 6 alkyl, C 3 -C 6 alkenyl,
  • R 19 is hydrogen, C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; means
  • herbicidal compositions which contain cyclohexenone derivatives of the formula I and have a very good herbicidal action.
  • methods for combating undesired plant growth using the cyclohexenone derivatives of the formula I have been found.
  • the compounds of the formula I can contain one or more chirality centers and are then present as enantiomers or mixtures of diastereomers.
  • the invention relates both to the pure enantiomers or diastereomers and to their mixtures.
  • the compounds of the formula I can also be present in the form of their agriculturally useful salts, the type of salt generally not being important. In general, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the herbicidal activity of the compounds I
  • the cations used are in particular ions of the alkali metals, preferably lithium, sodium and potassium, the alkaline earth metals, preferably calcium and magnesium, and the transition metals, preferably manganese, copper, zinc and iron, and ammonium, where if desired one to four hydrogen atoms by C x —C 4 —alkyl, hydroxy-C ⁇ -C 4 -alkyl, C ⁇ -C 4 -alkoxy-C ⁇ -C 4 -alkyl, hydroxy-C ⁇ -C 4 -alkoxy-C ⁇ -C 4 -alkyl, phenyl or benzyl can, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2- (2-hydroxyeth-1-ox) eth-1-ylairanoniu,
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogenphosphate, hydrogenphospha, nitrate, hydrogencarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C ⁇ C 4 -alkane acids, preferably formate, acylate , Propionate and butyrate.
  • Ila also represents the tautomeric forms Ila ', Ila''andIla'''.
  • Ilb also represent the tautomeric forms I b ', Ilb "and Ilb'".
  • - C ⁇ -C 4 alkyl for: z.
  • B methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl;
  • - C ⁇ - ⁇ C 4 -haloalkyl a C ⁇ -C 4 -alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine,
  • Bromine and / or iodine is substituted, ie z.
  • B chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl,
  • 2-chloro-2-fluoroethyl 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2, 2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl, 3,3,3-tri- chloropropyl, 2, 2,3, 3, 3-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, l- (bromomethyl) -2-bromomethyl, 4-
  • C ⁇ -C-alkylthio (C ⁇ -C 4 -alkylsulfanyl: C ⁇ -C 4 -alkyl-S-) and the alkylthio parts of C ⁇ -C 4 -alkylthio-C ⁇ -C 4 -alkyl for: e.g. methylthio, ethylthio, propylthio, 1-methylethylthio, butthio, 1-methylpropylthio, 2-methylpropylthio or 1,1-dimethyleththio;
  • C ⁇ ⁇ C 4 alkylthio, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethio, bromodifluoromethylthio, 2 — fluoroethylthio, 2-chloroethylthio, 2 Bromethylthio, 2-iodoethylthio, 2,2-difluoroethylthio,
  • C ⁇ -Cg-alkylsulfinyl C ⁇ -C 4 -alkylsulfinyl, as mentioned above, as well as pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2, 2-dimeth-propylsulfinyl, 1-ethylpropylsulfinyl, 1, 1-dimethyl 1,2-dimethylpropylsulfinyl, hexylsulfinyl, 1-ethpentylsulfinyl,
  • C ⁇ ⁇ C 4 alkylsulfinyl, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethyl, bromodifluoromethyl Fluoroethylsulfinyl, 2-chloroethylsulfiny1, 2-bromoethylsulfiny1, 2-odethylsulfinyl, 2, 2-difluoroethylsulfinyl, 2,2, 2-trifluoroethylsulfinyl, 2,2, 2-trichloroethylsulfinyl, 2-chloro-2-fluoro
  • C ⁇ -C 6 haloalkylsulfinyl C ⁇ -C 4 haloalkylsulfinyl, as mentioned above, and 5 — fluoropentylsulfinyl, 5 — chloropentylsulfinyl, 5 — bromopentylsulfinyl,
  • C ⁇ -C 6 -alkylsulfonyl C ⁇ -C 4 -alkylsulfonyl as mentioned above, and pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, sulfonyl , 1-ethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1, 1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2-sulfon
  • haloalkylsulfonyl is a C ⁇ ⁇ C 4 —alkylsulfonyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, and for the haloalkylsulfonyl of ConylC 4 —haloalkylsulfonyl- C ⁇ - C 4 alkyl for: e.g. B.
  • fluoromethylsulfonyl difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl,
  • 2,2,2-richloroethylsulfonyl pentafluoroethylsulfonyl, 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 2, 2-difulfonyl, 3-fluorophenyl, 3-fluorophenyl, Dichloropropylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3-trichloropropylsulfonyl, 2,2,3,3,3-pentafluoropropylsulfonyl, heptafluoropropylsulfonyl, 1- (fluoromethyl) -2-fluoroethylsulfonyl
  • 6-fluorohexylsulfonyl 6-bromohexylsulfonyl, 6-iodohexylsulfonyl or dodecafluorohexylsulfonyl;
  • - C ⁇ -Cg-alkylamino methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1,1-dimethylethylamino, pentylamino, 1-methylbutylamino, 2-methylbutlamino, 3-meth lbutylamino, 2 , 2-dimethylpropylamino, 1-ethylpropylamino, hexylamino, 1, 1-dimethylpropylamino, 1,2-dimethylpropylamino, 1-methylpentylamino, 2-methylpentylamino, 3-methylpentylamino, 4-methpentylamino, 1, 1-dimethylbutylamino, 1,2- Dimethylbutylamino, 1, 3-dimethylbutylamino, 2, 2-dimethylbutylamino, 2,3-dimethylbutylamin
  • Di- (C ⁇ -C 4 -alkyl) amino for example N, N-dimethylamino, N, N-di-ethylamino, N, N-dipropylamino, N, N-di— (1-methylethyl) amino, N, N-dibutlamino, N, N-di- (1-meth lpropy1) amino, N, N-di- (2-methylprop 1) a ino, N, N-di- (1,1-dimethylethyl) amino, N -Ethyl-N-methylamino, N-methyl-N-propylamino, N-methyl-N- (1-methylethyl1) amino, N-butyl-N-methylamino, N-methyl-N- (1-methylpropy1) amino, N -Meth 1-N- (2-met ylpropy1) amino, N- (1, 1-dimethylethyl) -N-methylamino, N-ethy
  • Di- (C ⁇ -Cg-alkyl) amino Di- (C ⁇ -C 4 -alkyl) amino as mentioned above, and N, N-dipentylamino, N, N-dihexylamino, N-methyl1-N-pentylamino, N-ethyl1 -N-pentylamino, N-methyl-N-hexylamino or N-ethyl-N-hexylamino;
  • C 4 -C 4 -alkylcarbonyl for example methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-ethylethylcarbonyl, butylcarbonyl, 1-methylpropyIcarbonyl, 2-methylpropylcarbonyl or 1, 1-dimethylethylcarbonyl;
  • C ⁇ -Cg-alkylcarbonyl and the alkylcarbonyl radicals of C-Cg-alkylcarbonylamino: C ⁇ -C 4 —alkylcarbonyl, as mentioned above, and z.
  • 6-fluorohexylcarbonyl 6-chlorohexyl carbonyl, 6-bromohexyl carbonyl or perfuorhexyl carbonyl;
  • - C ⁇ ⁇ C 4 -haloalkoxycarbonyl a C ⁇ ⁇ C 4 alkoxycarbonyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethoxycarbonyl, difluoromethoxycarbonyl, trifluoromethoxycarbonony1, chlorodifluoromethoxycarbonyl, bromodifluoryl, bromodifluoryl, bromodifluoryl —Fluoroethoxycarbonyl, 2 — chloroethoxycarbonyl, 2 — bromoethoxycarbonyl, 2 — iodoethoxycarbonyl, 2, 2 — difluoroethoxycarbonyl, 2,2, 2 — trifluoroethoxycarbonyl, 2 — chloro — 2 — fluoroethoxycarbonyl, 2 — chloro-2,2, -ifluoroethoxycarbonyl,
  • 2,2,2-trichloroethoxycarbonyl penta fluorethoxycarbonyl, 2-fluoropropoxycarbonyl, 3-fluoropropoxycarbonyl, 1,2-chloropropoxycarbonyl, 3-chloropropoxycarbonyl, 2-bromopropoxycarbonyl, 3-bromopropoxycarbonyl, 2,2-difluoropropoxycarbonyl, 2,3-difluorocarbonyl
  • C ⁇ -Cg-haloalkoxycarbonyl a C ⁇ -C 4 -haloalkoxycarbonyl radical as mentioned above, and 5-fluoropentoxycarbonyl, 5-chloropentoxycarbonyl, 5-bromopentoxycarbonyl, 6-fluorohexoxycarbonyl, 6-chlorohexoxycarbonyl or 6-bromohexoxycarbonyl;
  • - (Cx - C 4 - alkyl) carbonyloxy acetyloxy, ethylcarbonyloxy, propylcarbonyloxy, 1 - methylethylcarbonyloxy, butyl lc arbony lox, 1 - ethyl lpropy lc arbony lox, 2 - methylpropylcarbonyloxy or 1, 1 - dimethylethylcarbonyloxy;
  • - (Cx-C4-alkylamino) carbonyl for example methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl,
  • N-methyl-N-1-methylbutyl) aminocarbonyl N-methyl-N-2-methylbutyl) aminocarbon 1, N-methyl-N-3-methylbutyl) aminocarbonyl, N-methyl-N-2,2- dimethylpropyl) aminocarbonyl, N-methyl-N-1-ethylpropyl) aminocarbonyl,
  • N-butyl-N-pentylaminocarbonyl N, -dipentylaminocarbonyl, N-ropyl-N-hexylaminocarbonyl, N-butyl-N-hexylaminocarbonyl, N-pentyl-hexylaminocarbonyl or N, N-dihexylaminocarbonyl;
  • Di- (C ⁇ -Cg-alkyl) aminothiocarbonyl e.g.
  • N-methyl-N-1-methyl butyl) -aminothiocarbonyl N-methyl-N-2-methylbuty1) -aminothiocarbonyl, N-methyl-N-3-methylbutyl) -aminothiocarbonyl, N-methyl-N-2,2- dimethylpropyl) aminothiocarbonyl, N-methyl-N-1-ethylpropyl) aminothiocarbonyl,
  • C ⁇ -Cg-hydroxyalkyl C ⁇ -Cg-alkyl substituted by one to three OH groups, e.g. B hydroxyethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1,2-bishydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 2,2-dimethyl-3-hydroxypropyl;
  • Phenyl-C ⁇ -Cg-alkyl C ⁇ -Cg-alkyl substituted by a phenyl radical, e.g. B. benzyl, 1-phenylethyl and 2-phenylethyl, where the phenyl radical may be partially or completely halogenated in the manner indicated or may have one to three of the substituents indicated above for phenyl;
  • a phenyl radical e.g. B. benzyl, 1-phenylethyl and 2-phenylethyl, where the phenyl radical may be partially or completely halogenated in the manner indicated or may have one to three of the substituents indicated above for phenyl;
  • Heterocyclyl-C ⁇ -Cg-alkyl accordingly represents a C ⁇ -Cg-alkyl substituted by a heterocyclyl radical
  • C ⁇ -C 6 -alkoxy-C ⁇ -Cg-alkyl C ⁇ -C 6 -alkoxy, as mentioned above, substituted C ⁇ -C 6 -alkyl, e.g. methoxymethyl, ethoxymethyl, propoxymethyl, (1-methylethoxy) methyl, butoxymethyl, (1-methylpropoxy) methyl, (2-methylpropoxy) methyl, (1, 1-dimethylethox) methyl, 2- (methoxy) ethyl, 2- (ethoxy) ethyl, 2- (propoxy) ethyl, 2- (l- Methylethoxy) ethyl, 2- (butoxy) ethyl,
  • C ⁇ ⁇ Cg-alkoxy-C ⁇ ⁇ Cg-lkoxycarbonyl C ⁇ -Cg-alkoxy, as mentioned above, substituted C ⁇ -Cg-alkoxy, e.g.
  • C 3 -C 6 alkenyl and the alkenyl parts of C 3 -C 6 alkenylcarbonyl, C 3 -Cg -alkenox, C 3 -Cg-alkenyloxycarbonyl, C 3 -Cg-alkenylaminocarbonyl, N- (C 3 -Cg —Alkenyl) —N— (C ⁇ -C 6 alkyl) aminocarbonyl, N— (C 3 -Cg — alkenyl) —N— (C ⁇ -C 6 alkoxy) aminocarbonyl: e.g. B. Prop-2-en-1-y1, prop-1-en-3-l, but-1-en-4-l,
  • C 2 -C 6 alkenyl and the alkenyl parts of C 2 -Cg alkenylcarbonyl, phenyl C 2 -Cg alkenylcarbonyl and heterocyclyl-C 2 -Cg alkenylcarbonyl: C 3 -Cg alkenyl as mentioned above, and ethenyl ;
  • C 3 -Cg haloalkenyl a C 3 -Cg alkenyl radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 2-chloroallyl, 3-chloroallyl, 2,3 -Dichlorallyl, 3,3-dichlorallyl, 2,3,3-ri-chlorallyl, 2,3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl, 2,3-dibromoallyl, 3,3-dibromoallyl, 2 , 3,3-tribromoallyl or 2,3-dibromobut-2-enyl; C 3 -Cg alkynyl, and the alkynyl parts of C 3 -Cg alkyne Icarbonyl, C 3 -C 6 alkynyloxy,
  • C 2 -C 6 alkynylcarbonyl C 3 -Cg alkynyl as mentioned above, and ethynyl;
  • - C 3 -C 6 -haloalkynyl a C 3 -C 6 -alkynyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine; B.
  • C ⁇ -C 6 -alkanediyl methanediyl, ethane-1, 1-diyl, ethane-1, 2-diyl, propane-1, 1-diyl, propane-1, 2-diyl, propane-1, 3-diyl, propane -2,2-diyl, butane-1, 1-diyl, butane-1, 2-diyl, butane-1, 3-diyl, butane-1, 4-diyl, 2-methyl-propane-1, 3-diyl , 2-methyl-propane-l, 2-diyl, 2-methyl-propane-l, 1-diyl, 1-methyl-propane-l, 2-diyl, l-methyl-propane-2, 2-diyl, 1 -Methyl-propane-l, 1-diyl, pentane-1, 1-diyl, pentane-1, 2-diyl, pentane-l,
  • C 2 -C 6 -alkenediyl ethene-1, 1-diyl, ethene-1, 2-diyl, 1-propene-1, 1-diyl, 1-propene-1, 2-diyl, 1-propene-1, 3-diyl, 2-propene-1, 1-diyl, 2-propene-1,2-diyl, 2-propene-1,3-diyl, 1-butene-1, 1-diyl, 1-butene-1, 2-diyl, 1-butene-1, 3-diyl, 1-butene-l, 4-diyl, 2-butene-1, 1-diyl, 2-butene-1, 2-diyl,
  • C 2 -C 6 alkadiene diyl 1,3-butadiene-l, 1-diyl, 1, 3-butadiene-1,2-diyl, 1, 3-butadiene-1, 3-diyl, 1,3-but adiene-1,4-diyl, 1,3-pen-tadiene-l, 1-diyl,
  • C 2 -C 6 alkynediyl ethyne-1,2-diyl, 1-propyne-1,3-diyl, 2-propyne-1,1-diyl, 2-propyne-1,3-diyl, 1-butyne l, 3-diyl, 1-butyne-l, 4-diyl, 2-butyne-1, 1-diyl, 2-butyne-l, 4-diyl, l-methyl-2-propyne-l, 1-diyl, l-methyl-2-propyne-l, 3-diyl, 1-pentyne-l, 3-diyl, 1-pentyne-l, 4-diyl, 1-pentyne-l, 5-diyl,
  • C 3 -Cg cycloalkyl as well as the cycloalkyl parts of C 3 -C 6 cycloalkylamino and C 3 -Cg cycloalkylcarbonyl: eg cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
  • Aryl means carbocyclic aromatic compounds such as phenyl or naphthyl
  • B. C-linked 5-membered rings such as:
  • C-linked 5-membered rings such as: Tetrahydrofuran-2-y1, tetrahydrofuran-3-yl, tetrahydrothiene-2-yl, tetrahydrothiene-3-yl, tetrahydropyrrole-2-yl, tetrahydropyrrole-3-yl, 2,3-dihydrofuran-2-yl, 2,3- Dihydrofuran-3-yl, 2.5-dihydrofuran-2-yl, 2.5-dihydrofuran-3-yl, 4.5-dihydrofuran-2-yl, 4.5-dihydrofuran-3-yl, 2-3 Dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,5-dihydrothiene-2-1,2,5-dihydrothiene-3,1,4,5-dihydrothien-2-yl, 4,5- Dihydrothien-3-yl, 2,3-dihydro-lH
  • 4- ⁇ 3 -thiadiazolin-2-yl 1.3, 4 —Thiadiazoline — 2, 1, 2 — dioxathiolane, 4, yl, 1,2, 3, ⁇ 2, triazoline, 4, yl, 3, ⁇ 2, triazoline, 5, yl, 1,2, 4 2 -Triazolin-3-yl,.
  • 1,4-dihydropyrimidine-4-yl 1,4-dihydropyrimidine-5-yl, 1,4-dihydropyrimidine-6-yl, 3,4-dihydropyrimidine-2-yl, 3,4-dihydropyrimidine-4-yl, 3,4-dihydropyrimidine-5-yl, 3,4-dihydropyrimidine-6-yl, pyridazine-3-yl, pyridazine-4-l, pyrimidine-2-yl, pyrimidine-4-yl, pyrimidine-5-yl, Pyrazine-2-yl, 1,3,5-triazine-2-1, 1,2,4-triazine-3-yl, 1,2,4-triazine-5-yl, 1,2,4-triazine 6-yl or 1,2,4,5-etra-tin-3-yl;
  • N-linked 5-membered rings such as:
  • Tetrahydropyrrole-1-yl 2,3-dihydro-IH-pyrrole-1-yl, 2,5-dihydro-IH-pyrrole-1-yl, pyrrole-1-yl, tetrahydropyrazole-1-yl, tetrahydroisoxazole-2- l, tetrahydroisothiazole-2-yl, tetrahydroimidazole-1-yl, tetrahydrooxazole-3-yl, tetrahydrothiazole-3-yl,
  • N-linked 6-membered rings such as:
  • N-linked cyclic imides such as:
  • Heterocyclylaminocarbonyl, N-alkyl-N-heterocyclylaminocarbonyl, heterocyclylsulfonyl or heterocyclyloxysulfonyl are, unless otherwise stated, preferably unsubstituted or carry one, two or three halogen atoms and / or a nitro group, a cyano radical and / or one or two methyl, trifluorom Methoxy or trifluoromethoxy substituents.
  • the variables A, R 1 to R 19 preferably have the following meanings, in each case individually or in combination:
  • R 6 is not hydrogen.
  • R 6 stands for C ⁇ -C 4 alkyl and very particularly preferably for methyl.
  • Another preferred class of compounds I are those in which A is S.
  • Ri halogen C ⁇ -C 4 alkyl, C ⁇ -C 4 alkoxy, especially methyl, methoxy or chlorine.
  • R 2 has the meanings mentioned, different from hydrogen, in particular
  • C ⁇ -C 4 -alkyl, C ⁇ -C 4 -haloalkyl, hydroxy, C ⁇ -C 4 -alkoxy, C ⁇ -C 4 -alkylsulfonyl, C ⁇ -C 4 -haloalkylsulfonyl, hydroxycarbonyl-C ⁇ -C -alkyl, C ( N-0 (-CC 4 -alkyl)) - (C ⁇ -C 4 -alkyl), NH 2 , C ⁇ -C 4 -alkylamino, di- (C ⁇ -C 4 -alkyl) amino, phenyl, phenylcarbonyl or benzyl, where the phenyl rings of the latter three substituents can be substituted by one or two halogen atoms, methoxy groups or methyl groups, cyano, C ⁇ -C-AlkyIcarbonyl,
  • C ⁇ -C 4 alkyl especially methyl
  • R 2 is Cx-C ß alkyl, or C3 -CG-alkenyl. Also particularly preferred are those compounds I in which R 2 is C 3 -C 6 -alkynyl, (1,3-dioxolan-2-yl) methyl, 2- (1, 3-dioxolan-2-yl) ethyl or Benzyl is in which the phenyl ring can be unsubstituted or can have 1 or 2 substituents selected from halogen, methyl or methoxy.
  • R 3 C ⁇ -C 4 alkyl, halogen and especially hydrogen.
  • A is 0 or S
  • Ri is methyl
  • R 3 is hydrogen
  • R 2 is a substituent other than hydrogen, in particular one of the substituents indicated above as preferred and especially C ⁇ -Cg-alkyl, C 3 -Cg-alkynyl, C 3 -C 6 -alkenyl, (1,3-dioxolan-2-yl) methyl, 2- (1,3-dioxolan-2-yl) ethyl or for benzyl, in which the phenyl ring may be unsubstituted or may have 1 or 2 substituents selected from halogen, methyl or methoxy.
  • R 7 , R 8 , R 9 , R i °, R 11 , R 12 and R 13 preferably have the following meanings:
  • N-linked heterocyclyl such as pyrrolidinyl, piperidinyl, morpholine, pyrazolinyl or imidazolidinyl, which can be partially or completely halogenated and / or one, two or three of the following radicals can wear: nitro, cyano, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy or C ⁇ -C 4 haloalkoxy; in particular
  • R i9 Hydroxy, 0R i4 , SR i4 , N (OR X8 ) R i9 ; particularly preferably hydroxy, C ⁇ -C 4 -alkyloxy, C ⁇ -C 4 -alkylamino, di- C ⁇ -C-alkylamino, N-C ⁇ -C 4 -alkoxy-C ⁇ -C -alkylamino, C ⁇ -C 4 -alkylthio, phenylthio, 0-CH 2 -phenyl, phenylcarbonyloxy, 2-, 3- or
  • R 8 , Ri 2 are hydrogen or C ⁇ -C 4 alkyl, such as methyl, ethyl or propyl; preferably hydrogen or methyl;
  • R 9 , R ü , R 13 are hydrogen or C ⁇ -C 4 alkyl, such as methyl, ethyl or propyl; preferably hydrogen or methyl;
  • R 9 and Rü or R U and R X3 together form a ⁇ bond or a C 3 -Cs alkyl chain which can carry up to three radicals from the following group: halogen, cyano, C ⁇ -C 4 alkyl, C ⁇ -C 4 -haloalkyl or C ⁇ -C 4 -alkoxycarbonyl, from;
  • R 9 and R i3 or R 8 and R 12 together form a C ⁇ -C 4 alkyl chain which can carry one to three radicals from the following group: halogen, cyano, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl or C ⁇ -C 4 alkoxy carbonyl, from;
  • Rio and R ü together form a -0- (CH 2 ) p -0-, -0- (CH 2 ) p -S- or -s- (CH 2 ) p -S chain, which consists of one to three residues can be substituted from the following group: halogen, cyano, C ⁇ -C 4 alkyl, C ⁇ -C haloalkyl or C ⁇ -C 4 alkoxycarbonyl; preferably R 10 and R 11 together form a -0- (CH 2 ) p -0-, -0- (CH 2 ) p -S- or -S- (CH 2 ) P -S chain, which is characterized by a to three of the radicals from the following group can be substituted: C ⁇ -C 4 haloalkyl or C ⁇ -C 4 alkoxycarbonyl;
  • the variable p preferably stands for 2 or 3 and the variable q preferably for 2, 3 or 4.
  • R X4 to R 19 are:
  • R X4 C ⁇ -C 6 alkyl, C 3 -Cg alkenyl, C 3 -Cg haloalkenyl,
  • C ⁇ -C 4 haloalkyl C ⁇ -C 4 alkoxy or C ⁇ -C 4 haloalkoxy; preferably C ⁇ -Cg-alkyl, C 3 -C 6 -alkenyl, C 3 -Cg-alkynyl, C ⁇ -Cg-alkylcarbonyl, C ⁇ -Cg-alkoxycarbonyl, C ⁇ -Cg-alkylaminocarbonyl or N, N-di (C ⁇ - Cg-alkyl) aminocarbonyl, where the alkyl or alkoxy radicals mentioned can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C ⁇ -C 4 alkoxy, C ⁇ -C 4 alkylthio or C ⁇ -C 4 -alkoxycarbonyl;
  • Phenyl or the heterocyclyl radical of the 10 last-mentioned substituents can be partially or completely halogenated or / and can carry one to three of the following radicals: nitro, cyano, C ⁇ -C-alkyl, C ⁇ -C 4 -haloalkyl, C ⁇ -C- Alkoxy or C ⁇ -C 4 haloalkoxy;
  • R15 C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 cycloalkyl, where the three radicals mentioned can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C ⁇ -C 4 alkoxy, C ⁇ -C-alkylthio, C ⁇ -C 4 -AlkyIcarbonyl or C ⁇ -C 4 -alkoxycarbonyl;
  • R 26 R i7 hydroxy, C ⁇ -Cg-alkyl, C ⁇ -C 6 -alkoxy, phenyl,
  • Phenyl-C ⁇ -C 4 alkyl or phenoxy where the three latter substituents can be partially or completely halogenated and / or can carry one to three of the following radicals: nitro, cyano, C ⁇ -C 4 alkyl, C ⁇ -C -Haloalkyl, C ⁇ -C 4 alkoxy, C ⁇ -C 4 haloalkoxy or C ⁇ -C 4 alkoxycarbonyl;
  • R i8 C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl,
  • Di- (C ⁇ -Cg-alkyl) amino where the alkyl, cycloalkyl or alkoxy radicals mentioned can be partially or completely halogenated and / or one to three of the following
  • Residues can carry: cyano, C ⁇ -C -alkoxycarbonyl, C ⁇ -C 4 alkylaminocarbonyl, di- (C ⁇ -C 4 alkyl) aminocarbonyl or C 3 -Cg cycloalkyl;
  • R 19 C ⁇ -Cg-alkyl or C 3 -Cg-alkenyl.
  • Preferred compounds of the general formula I are those in which hex represents a compound of the formula IIa or IIb ".
  • Examples of preferred radicals hex have the general formulas Ila-1 to IIa-8.
  • OH group in these radicals can also be replaced by one of the following groups: 0-CH 3 , N (CH 3 ) 2 , N (OCH 3 ) CH 3 , pyrididinyl, piperidinyl, morpholinyl, imidazolinyl, pyrazolinyl or S-phenyl.
  • a particularly preferred group of the compounds I has a radical Hex of the formula Ila-4.
  • Examples of preferred compounds of the general formula I are the benzazolonylcarbonylcyclohexenones I given in Tables 1 to 25 below, in which A, R 1 , R 2 and R 3 each have the meanings given in one row of the table.
  • the compound of the formula I in which R 7 is hydroxyl is prepared by reacting an activated carboxylic acid IVb or a carboxylic acid IVa, which is preferably activated in situ, with a cyclohexane-1,3-dione of the formula III2u and the acyl- product and subsequent relocation.
  • L i stands for a nucleophilically displaceable leaving group, such as halogen 2.
  • the activated carboxylic acid IVb can be used directly, as in the case of the Ben2oyl halides or generated in situ, e.g. B. with carbodiimides such as ethyl- (3'-dimethylaminopropy1) carbodiimide, dicyclohexylcarbodiimide, triphenylphosphine / azodicarboxylic acid ester, 2 — pyridine disulfide / triphenylphosphine, carbonyldiimidazole etc.
  • carbodiimides such as ethyl- (3'-dimethylaminopropy1) carbodiimide, dicyclohexylcarbodiimide, triphenylphosphine / azodicarboxylic acid ester, 2 — pyridine disulfide / triphenylphosphine, carbonyldiimidazole etc.
  • auxiliary base it may be advantageous to carry out the acylation reaction in the presence of a base.
  • the reactants and the auxiliary base are expediently used in equimolar amounts.
  • a small excess of the auxiliary base z. B. 1.2 to 1.5 molar equivalents, based on IVa b2w. IVb, may be beneficial.
  • Tertiary alkyl amines, pyridine or alkali metal carbonates are suitable as auxiliary bases.
  • a solvent for. B. chlorinated hydrocarbons, such as methylene chloride or 1,2-dichloroethane, aromatic hydrocarbons, such as toluene, xylene or chlorobenzene, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, polar aprotic solvents, such as acetonitrile, dimethylformamide or dimethyl sulfoxide or esters such as ethyl acetate or mixtures thereof.
  • chlorinated hydrocarbons such as methylene chloride or 1,2-dichloroethane
  • aromatic hydrocarbons such as toluene, xylene or chlorobenzene
  • ethers such as diethyl ether, methyl tert-butyl ether, tetrahydr
  • halides are used as the activated carboxylic acid component, it may be expedient to cool the reaction mixture to 0 ° C. to 10 ° C. when this reaction partner is added. The mixture is then stirred at 20 ° C. to 100 ° C., preferably at 25 ° C. to 50 ° C., until the reaction is complete.
  • the workup is carried out in the usual manner, for. B. the reaction mixture is poured onto water, the product of value extracted. Methylene chloride, diethyl ether and ethyl acetate are particularly suitable as solvents for this. After drying the organic phase and removing the solvent, the crude ester can be used for rearrangement without further purification.
  • the rearrangement of the esters to the compounds of the formula I is advantageously carried out at from 20 ° C. to 100 ° C. in a solvent and in the presence of a base and, if appropriate, using a cyano compound as a catalyst.
  • a solvent for example, acetonitrile, methylene chloride, 1,2-dichloroethane, dioxane, ethyl acetate, toluene or mixtures thereof can be used as solvents.
  • Preferred solvents are acetonitrile and dioxane.
  • Suitable bases are tertiary amines such as triethylamine, aromatic amines such as pyridine or alkali carbonates such as sodium carbonate or potassium carbonate, which are preferably used in an equimolar amount or up to a fourfold excess, based on the ester.
  • Triethylamine or alkali carbonate are preferably used, preferably in a double equimolar ratio in relation to the ester.
  • Inorganic cyanides such as sodium cyanide or potassium cyanide and organic cyano compounds such as acetone cyanohydrin or trimethylsilyl cyanide are suitable as cyano compounds. They are used in an amount of 1 to 50 mol percent, based on the ester. Acetone cyanohydrin or trimethylsilyl cyanide, e.g. in an amount of 5 to 15, preferably about 10 mole percent, based on the ester.
  • the reaction mixture is e.g. B. with dilute mineral acid, such as
  • 5% hydrochloric acid or sulfuric acid acidified, with an organic solvent, e.g. B. extracted methylene chloride or ethyl acetate.
  • the organic extract can be mixed with 5-10% alkali carbonate solution, e.g. B. sodium carbonate or potassium carbonate solution can be extracted.
  • the aqueous phase is acidified and the precipitate that forms is filtered off with suction and / or extracted with methylene chloride or ethyl acetate, dried and concentrated.
  • compound la stands for a compound of the general formula I, in which hex represents a radical of the general formula Ila and compound lb accordingly for a compound of the general formula I in which hex represents a radical Ilb.
  • halogenating agents examples include phosgene, diphosgene, triphosgene, thionyl chloride, oxalyl chloride, phosphorus oxychloride, phosphorus pentachloride, mesyl chloride, chloromethylene-N, N-dimethylammonium chloride, oxalyl bromide, phosphorus oxybromide etc.
  • L 2 stands for a nucleophilically displaceable leaving group, such as halogen, for example chlorine or bromine, hetaryl, for.
  • halogen for example chlorine or bromine
  • hetaryl for.
  • the compounds of formula V ⁇ , Vß, V ⁇ or v ⁇ can be used directly, such as. B. in the case of carboxylic acid halides or generated in situ, for. B. activated carboxylic acids (with carboxylic acid and dicyclohexylcarbodiimide etc.).
  • Vl ⁇ , Vl ⁇ or Vl ⁇ optionally in the presence of a base or with previous Sal2 formation.
  • HOR 4 Vl ⁇ or Ia and / or Ib (with
  • Suitable oxidizing agents are m-chloroperbenzoic acid, peroxyacetic acid, trifluoroperoxyacetic acid, hydrogen peroxide, if appropriate in the presence of a catalyst such as tungstate.
  • the starting compounds are usually used in an equimolar ratio. However, it can also be advantageous to use one or the other component in excess.
  • reactants and the base are expediently used in equimolar amounts.
  • Suitable bases are tertiary alkyl amines such as triethylamine, aromatic amines such as pyridine, alkali metal carbonates, e.g. As sodium carbonate or potassium carbonate, alkali metal hydrogen carbo- nates, such as sodium bicarbonate and potassium bicarbonate, alkali metal alcoholates such as sodium methoxide, sodium ethanolate, potassium tert. -butanolate or alkali metal hydrides, 2.B. Sodium hydride. Triethylamine or pyridine are preferred.
  • chlorinated hydrocarbons such as methylene chloride or 1,2-dichloroethane
  • aromatic hydrocarbons e.g. Toluene, xylene or chlorobenzene
  • ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane
  • polar aprotic solvents such as acetonitrile, dimethylformamide or dimethyl sulfoxide or esters such as ethyl acetate, or mixtures thereof.
  • reaction temperature is in the range from 0 ° C. to the boiling point of the reaction mixture.
  • the product can be worked up in a manner known per se.
  • compounds Ia, Ib or mixtures thereof can be formed in processes B to D.
  • the latter can be separated using classic separation methods such as e.g. B. crystallization, chromatography, etc., are separated.
  • cyclohexanediones of the formula III used as starting materials are known or can be prepared by processes known per se (e.g. EP-A 71 707, EP-A 142 741, EP-A 243 313, US 4,249,937, WO 92/13821).
  • alkylating agents V ⁇ , sulfonylating agents Vß, phosphonizing agents V ⁇ and V ⁇ , and the compounds Vl ⁇ , Vlß, Vl ⁇ , Vl ⁇ and Vl ⁇ are also known or can be prepared by known processes.
  • the carboxylic acids of the general formula IVa or their activated derivatives IVb are new and also a subject of the present invention.
  • Scheme 1 illustrates a general approach to the preparation of compounds of Formula IVa, wherein A is oxygen or NR 6 .
  • step a) the nitro compounds VIII are first brominated in the meta position to form the nitro group.
  • Common brominating agents for this purpose are bromine, N-bromosuccinimide,
  • N-bromohydantoin or pyridinium perbromide which are optionally used together with a Lewis acid such as FeBr 3 .
  • the bromination is usually carried out in an inert solvent.
  • Suitable solvents are aliphatic or cycloaliphatic hydrocarbons, for example n-hexane or cyclohexane, halogenated hydrocarbons, for example dichloromethane, trichloromethane, tetrachloromethane, trichloroethane, trichlorethylene, heteroaromates such as pyridine or anhydrous inorganic or organic acids, such as acetic acid.
  • Typical reaction temperatures are in the range from -15 ° C to 150 ° C, preferably in the range from -15 ° C to 100 ° C.
  • Processes for the bromination of nitro compounds are known, for. B. from Organikum, 16th ed., 1986, p. 315.
  • reducing agents are hydrazines, metal hydrides such as aluminum hydride and guided complex hydrides such as lithium aluminum hydride, diisobutyl aluminum hydride, or boranes, and nascent hydrogen, e.g. B. iron, zinc or tin in the presence of acids such as hydrochloric acid or carboxylic acids such as acetic acid.
  • Another suitable reducing agent is hydrogen in the presence of catalytic amounts of transition metals such as nickel, palladium, platinum, ruthenium or rhodium.
  • the transition metals can be used as such or in supported form, for example on activated carbon, in the form of activated metals, e.g. B. Raney nickel, or in the form of soluble complex compounds.
  • the reaction is preferably carried out in a solvent. Suitable solvents for the reduction depend on the solubility of the substrate to be hydrogenated and the chosen reducing agent, for example C 1 -C 4 alcohols, such as methanol, ethanol, n-propanol, isopropanol or n-butanol, halogenated C 1 -C 6 hydrocarbons, such as dichloromethane, Trichloromethane, trichloroethane, trichlorethylene, aromatic hydrocarbons, such as benzene, toluene, xylenes, chlorobenzene, aqueous solutions of inorganic acids, such as aqueous hydrochloric acid or organic acids and their mixtures with water.
  • C 1 -C 4 alcohols such as
  • the reduction is usually carried out at temperatures in the range from -15 ° C. to +100 ° C., preferably in the range from 0 ° C. to 40 ° C.
  • the reduction with hydrogen usually takes place at a hydrogen pressure in the range from 1 to 50 bar.
  • the catalytic hydrogenations are preferably carried out using hydrogen in the range from 1 to 10 bar.
  • the condensation of the 3-bromoaniline X to form the heterocycle in step c) is achieved by reacting the compound X with a carbonic acid equivalent, such as methyl chloroformate, phosgene or its synthesis equivalents such as diphosgene or triphosgene, under the conditions customary for phosgenation.
  • a carbonic acid equivalent such as methyl chloroformate, phosgene or its synthesis equivalents such as diphosgene or triphosgene
  • the cyclization is generally carried out under neutral to acidic reaction conditions at temperatures in the range from 0 ° C. to 150 ° C. and preferably in the range from 20 ° C. to 120 ° C.
  • the phosgenation is usually carried out in a solvent.
  • Particularly suitable solvents are aliphatic or cycloaliphatic hydrocarbons, such as n-hexane or cyclohexane, halogenated hydrocarbons, such as dichloromethane, trichloromethane, trichloroethane, trichlorethylene, aromatic hydrocarbons, such as benzene, aliphatic ethers, such as diethyl ether, methyl tert-butyl ether, or cyclic ones Ethers, such as tetrahydrofuran or dioxane.
  • Methods for phosgenation are known, see for example Justus Liebigs Ann. Chem., 1978, No. 2, 193-213; J. Med. Chem., 1987, 30, N 7, 1166-1176, J. Heterocycl. Chem. 1991, 28 (8), 1937-1939; J. Nat. Prod. 1995, 58 (3), 456-458.
  • step d) succeeds, for example, by reacting the 5-bromobenzazol-2-one XI obtained in step c) with R 2 -L or its precursor, where L stands for a nucleophilically displaceable leaving group.
  • Suitable leaving groups are, for example, halogen such as chlorine, bromine or iodine, carboxylate such as acetate or trifluoroacetate or sulfonates such as tosylate, mesylate or triflate.
  • the reaction is preferably carried out in the presence of an auxiliary base, e.g. B.
  • alkali or alkaline earth carbonates such as sodium, potassium, magnesium or calcium carbonate
  • alkali or alkaline earth hydrides for example sodium hydride
  • tertiary alkylamines for example triethylamine
  • aromatic amines for example pyridine, DMPU.
  • the reaction is usually carried out at temperatures in the range from -15 ° C to 150 ° C and preferably at 0 ° C to 100 ° C.
  • the reaction is usually carried out in a solvent.
  • Suitable solvents are, for example, the abovementioned inert hydrocarbons, the abovementioned halogenated hydrocarbons, aromatic hydrocarbons, such as benzene, toluene, xylene or chlorobenzene, the abovementioned acyclic or cyclic ethers, and also polar aprotic solvents such as dirnethylformamide, acetonitrile or dimethyl sulfoxide.
  • polar aprotic solvents such as dirnethylformamide, acetonitrile or dimethyl sulfoxide.
  • Typical reaction temperatures are in the range from -15 ° C to 150 ° C, preferably in the range from -15 ° C to 100 ° C.
  • Suitable solvents are anhydrous solvents, in particular the aforementioned inert cyclic or acylic hydrocarbons, the aforementioned aromatic hydrocarbons or the aforementioned acyclic or cyclic ethers.
  • Benzazolone-5-carboxylic acid IVa The carbon dioxide pressure is usually 1 to 6 bar.
  • XII can be converted into the carboxylic acid IVa by halogen-metal exchange with an alkali metal alkyl, for example a lithium alkyl such as methyl lithium, n-butyllithium or tert-butyllithium and subsequent reaction of the lithiation product with CO 2 become.
  • alkali metal alkyl for example a lithium alkyl such as methyl lithium, n-butyllithium or tert-butyllithium and subsequent reaction of the lithiation product with CO 2 become.
  • Usual reaction temperatures are in the range from -100 ° C to 0 ° C, preferably in the range from -78 ° C to -50 ° C.
  • Suitable solvents are anhydrous solvents, in particular the aforementioned inert hydrocarbons, the aforementioned aromatic hydrocarbons or the aforementioned acyclic or cyclic ethers.
  • Introducing dry carbon dioxide into the solution of the lithiation product of XII gives the
  • Reaction step e) in scheme 1 can also be carried out by reacting XII with carbon monoxide, a base and water under elevated pressure in the presence of a palladium, nickel, cobalt or rhodium catalyst.
  • the catalysts nickel, cobalt, rhodium and in particular palladium can be metallic or in the form of conventional salts such as in the form of halogen compounds, for example palladium (II) chloride, rhodium (III) chloride hydrate, acetates, for.
  • halogen compounds for example palladium (II) chloride, rhodium (III) chloride hydrate, acetates, for.
  • palladium (II) acetate, cyanides, etc. can be used in the known valence levels.
  • metal complexes with tertiary phosphines, metal alkylcarbonyls, metal carbonyls, eg. B. C0 2 (C0) 8 , Ni (CO) 4 metal carbonyl complexes with tertiary phosphines, for. B.
  • radicals R 24 to R 26 for low molecular weight alkyl for example Ci-Cg-alkyl, aryl, C ⁇ -C alkylaryl, z.
  • Aryl is 2.B. Naphthyl, anthryl and preferably substituted or unsubstituted phenyl, but only the inertness of the substituents in the carboxylation reaction has to be taken into account, otherwise they can be varied widely and include all inert C-organic radicals such as
  • C 1 -C 6 -alkyl radicals for example methyl, carboxyl radicals such as COOH, COOM (M is, for example, an alkali metal, alkaline earth metal or ammonium salt), or C-organic radicals bound via oxygen, such as C 1 -C 6 -alkoxy radicals.
  • A stands for a divalent organic radical, e.g. B. -C-C 4 alkyls, 1,2-cycloalkylene, ⁇ , ⁇ r -Ferrocendiyl, ⁇ , ⁇ -biphenyl or comparable bifunctional groups.
  • the preparation of the phosphine complexes can be carried out in a manner known per se, e.g. B. as described in the documents mentioned.
  • metal salts such as palladium (II) chloride or palladium (II) acetate
  • phosphine for example P (CgH 5 ) 3 , P (n-CHg) 3 , PCH 3 (C 6 H 5 ) 2 , l, 2-bis (diphenylphosphino) ethane.
  • the amount of phosphine, based on the transition metal is usually 0 to 20, in particular 0.1 to 10 molar equivalents, particularly preferably 1 to 5 molar equivalents.
  • the amount of transition metal is not critical. Of course, for reasons of cost, you will rather get a small amount, e.g. from 0.1 to 10 mol%, in particular 1 to 5 mol%, based on the starting material IVa.
  • the reaction is carried out with carbon monoxide and at least equimolar amounts of water, based on the bromide obtained in step d).
  • the reactant water can also serve as a solvent, i.e. H. the maximum amount is not critical.
  • Suitable inert solvents for carboxylation reactions are customary solvents such as hydrocarbons, for example toluene, xylene, hexane, pentane, cyclohexane, ether, for example methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted amides such as dimethylformamide, persubstituted ureas such as tetra-C ⁇ - C 4 alkylureas or nitriles such as benzonitrile or acetonitrile.
  • hydrocarbons for example toluene, xylene, hexane, pentane, cyclohexane, ether, for example methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted amides such as dimethylformamide, persubstituted urea
  • one of the reactants, in particular the base is used in excess, so that no additional solvent is required.
  • Bases suitable for the process are all inert bases which are able to bind the hydrogen iodide or hydrogen bromide released during the reaction.
  • tertiary amines such as tert-alkyl amines, e.g. B. trialkylamines such as triethylamine, cyclic amines such as N-methylpiperidine or N, N'-dimethylpiperazine, pyridine, alkali metal or hydrogen carbonates, or tetra- alkyl-substituted urea derivatives such as tetra -CC-alkyl urea, for. B. tetramethyl urea to name.
  • the amount of base is not critical. Usually 1 to 10, in particular 1 to 5 moles are used. If the base is simultaneously used as a solvent, the amount is generally such that the reactants are dissolved, unnecessarily high excesses being avoided for reasons of practicality in order to save costs, to be able to use small reaction vessels and to ensure maximum contact for the reactants.
  • the carbon monoxide pressure is adjusted so that there is always an excess of CO, based on the bromide.
  • the carbon monoxide pressure at room temperature is preferably 1 to 250 bar, in particular 5 to 150 bar CO.
  • the carbonylation is generally carried out continuously or batchwise at temperatures from 20 ° C. to 250 ° C., in particular at 30 ° C. to 150 ° C.
  • carbon monoxide is expediently pressed continuously onto the reaction mixture in order to maintain a constant pressure.
  • reaction step e) and then reaction step d) can also be carried out first.
  • the substituted acetophenone XIII can be prepared by Friedel-Crafts acylation in step f).
  • the acetyl group can be introduced in a known manner by reacting compound VIII with acetic acid or activated acetic acid, such as acetic anhydride or acetyl chloride, in the presence of a Lewis acid such as aluminum trichloride, boron trifluoride or trifluoroacetic acid under anhydrous conditions.
  • a Lewis acid such as aluminum trichloride, boron trifluoride or trifluoroacetic acid under anhydrous conditions.
  • Lewis acid such as aluminum trichloride, boron trifluoride or trifluoroacetic acid
  • this complex is hydrolytically cleaved.
  • Friedel-Crafts acylations are usually carried out in a solvent.
  • Suitable solvents are the aforementioned cyclic and acylic hydrocarbons, the aforementioned halogenated hydrocarbons, aromatic hydrocarbons such as nitrobenzene or the aforementioned ethers.
  • the reaction temperatures are generally in the range from 0 ° C. to 150 ° C. and preferably in the range from 20 ° C. to 120 ° C. Methods for introducing acyl groups are known, see, for example, Organikum, 16th ed. 1986, p. 325.
  • the substituted acetophenone XIII is then reduced to the amino compound XIV in step g).
  • the reduction is carried out in the manner described in step b) in scheme 1.
  • the aniline derivative XIV is then phosgenated in step h) in the manner described in step c) in Scheme 1.
  • the substituent R 2 can be introduced analogously to step d) in scheme 1 (step i) in scheme 2).
  • the conversion of the compound XVI obtained in step i) in Scheme 2 into the benzazolonecarboxylic acid IVa is achieved using the Halofor reaction.
  • a halogenating agent such as hypohalite, for example hypochlorite, or chlorine in an alkaline solution is allowed to act on the compound XVI.
  • a trihalomethylcarbonyl derivative is initially formed which, under the alkaline reaction conditions, forms the desired ones Benza2 ⁇ loncarbonkla IVa is hydrolytically cleaved.
  • Suitable bases are, in particular, alkali metal hydroxides, such as sodium or potassium hydroxide. The reaction is usually carried out in solution.
  • Particularly suitable solvents are water, mixtures of water and organic solvents, such as -C 4 alcohols, for example methanol, ethanol, propanol, butanol, or the aforementioned ethers.
  • Typical reaction temperatures are in the range from 0 ° C to 150 ° C, preferably in the range from 20 ° C to 120 ° C.
  • Typical reaction temperatures see, for example, Organikum, 16th ed. 1986, p. 375.
  • a in formula IVa is sulfur
  • the benzazolone carboxylic acid of the general formula IVa can also be prepared in the manner shown in scheme 3.
  • the transfer of the 2-aminobenzothia 20IS XVII in the 2-halobenzothiazole compound XVIII succeeds in a known manner under Sandmeyer conditions (step k)). In this way, further functionalities can be introduced in the 2-position of the ben2 thiazole ring.
  • Suitable solvents are in particular water or mixtures of water with organic solvents such as the abovementioned alcohols or ethers.
  • organic solvents such as the abovementioned alcohols or ethers.
  • the 2-halobenzothiazole compound XVIII can then be hydrolyzed in step 1) under acidic or alkaline conditions to give the benzothiazolone.
  • compound XVIII is mixed with a base, such as alkali or alkaline earth hydroxide, for example sodium, potassium or magnesium hydroxide, or alkali alcoholate, such as sodium or potassium methylate, or with an acid, such as hydrochloric acid.
  • a base such as alkali or alkaline earth hydroxide, for example sodium, potassium or magnesium hydroxide, or alkali alcoholate, such as sodium or potassium methylate
  • an acid such as hydrochloric acid.
  • the hydrolysis is usually carried out in a solvent.
  • Suitable solvents are, depending on the base used, polar aprotic solvents such as dimethyl formate, dimethyl sulfoxide, N-methylpyrrolidone or acetonitrile, ethers such as tetrahydrofuran or dioxane, water and mixtures of water with the abovementioned alcohols, ethers or polar aprotic solvents ,
  • polar aprotic solvents such as dimethyl formate, dimethyl sulfoxide, N-methylpyrrolidone or acetonitrile
  • ethers such as tetrahydrofuran or dioxane
  • water and mixtures of water with the abovementioned alcohols, ethers or polar aprotic solvents water and mixtures of water with the abovementioned alcohols, ethers or polar aprotic solvents
  • the hydrolysis is usually carried out at 0 ° C to 150 ° C and preferably at 20 ° C to 120 ° C.
  • step d) The introduction of the substituent R 2 into the compound XIX in step m) is carried out as described in step d) in scheme 1.
  • the benzazolone methyl ester XX obtained in step m) is set with alkali metal hydroxide, for. B. lithium, sodium or potassium hydroxide, with alkaline earth metal hydroxide such as magnesium hydroxide or with alkali iodides such as sodium iodide in a suitable solvent, preferably in the absence of oxygen.
  • Usual reaction temperatures are in the range from 0 ° C to 200 ° C and in particular in the range from 20 ° C to 180 ° C.
  • Suitable solvents are the aforementioned aliphatic or cycloaliphatic carbon Hydrogen, the halogenated hydrocarbons, the aromatic hydrocarbons, the aforementioned ethers and alcohols, aqueous, single-phase systems and pyridine.
  • saponification see, for example, Organikum, 16, Ed. 1986, p. 415, Mc Murry, Org. React. 1976, 24, 187; Taschner et al., Rocz. Chem. 1956, 30, 323; Houben-Weyl: "Methods of Organic Chemistry", Volume E 8 b 1994; P. 1010 f .; J. Chem. Soc.
  • the 2-chlorobenzothiazole compounds XXII can be prepared in a Sandmeyer reaction in step o).
  • the reaction conditions required for this correspond to those of step k) in scheme 3.
  • the 2-chlorobenzothiazole xxil can be brominated in an analogous manner to step a) in scheme 1, the bromine substituent selectively entering in the ortho position to R 1 (step p)) ,
  • the compound XXIII is then basic hydrolyzed under the conditions given for step 1) in scheme 3 (step q)).
  • the substituent R 2 can be introduced into XXIV under the conditions described for step d) in scheme 1.
  • the carboxy group (step s)) is introduced in accordance with the reaction conditions described in step e) in Scheme 1.
  • the o-chloronitrobenzenes of the general formula XXX known per se are first converted into the corresponding thioethers XXXI using alkali salts of benzyl mercaptan (step 1)).
  • the substitution is usually carried out in one of the abovementioned aliphatic or cycloaliphatic hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, ethers, dimethylformamine, NMP, sulfolane or diethyl sulfoxide.
  • Usual reaction temperatures are in the range from 0 ° C to 250 ° C and preferably in the range from 50 ° C to 175 ° C.
  • Methods for nucleophilic substitution are known, see also A. Bagno et al., J. Chem. Soc. Perkin Trans II, 1991 (5), 651-655; JR Beck et al., J. Org. Chem., 1978, 43, no. 10, 2048-2052.
  • step 2 The compound XXXI is then reduced in step 2) to the amino compound XXXII.
  • the reaction conditions required for this correspond to those for step b) in Scheme 1.
  • the amino compound XXXII is then cyclized under the reaction conditions described in step c) in Scheme 1 using carbonic acid equivalents to give the benzothiazolone XXXIII (step 3)).
  • the subsequent introduction of the substituent R 2 succeeds under the reaction conditions described in step d) in scheme 1 (step 4)).
  • Friedel-Crafts acylation of compound XXXIV enables the acetyl group to be introduced in the ortho position to the substituent R (step 5)).
  • the reaction conditions required for this correspond to those of step f) in Scheme 2.
  • Benzazolonecarboxylic acid IVa can be obtained from the compound XXXV by a haloform reaction (step 6)).
  • the reaction conditions required for this correspond to those in step j) in Scheme 2.
  • o-chloronitrobenzenes of the general formula XXX can be converted with alkali salts of alcoholates into the corresponding o-nitroethers XXXVI (step 7)).
  • This nucleophilic substitution on aromatics is usually carried out with the exclusion of water and is usually carried out in a solvent.
  • Suitable solvents are, in particular, the aforementioned aliphatic or cycloaliphatic hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, ethers, DMF, NMP, sulfolane or dimethyl sulfoxide.
  • the required reaction temperatures are in the range from 0 ° C to 250 ° C and preferably at 50 ° C to 175 ° C.
  • the hydroxyl group is then released by ether cleavage in step 9) under acidic reaction conditions in the presence of a Lewis acid, such as aluminum trichloride, aluminum tribromide or hydrohalic acids, such as hydroiodic acid or hydrobromic acid, to give 4-bromo-2-nitrophenols of the formula IX.
  • a Lewis acid such as aluminum trichloride, aluminum tribromide or hydrohalic acids, such as hydroiodic acid or hydrobromic acid
  • the ether cleavage is usually carried out in a solvent. Suitable solvents are the aforementioned acylic and cyclic hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons or acids, such as acetic acid.
  • the ether cleavage takes place at temperatures in the range from -15 ° C. to 150 ° C., preferably in the range from 0 ° C. to 100 ° C.
  • Organikum 16th ed. 1986, p. 192.
  • the compounds I of Examples 4 to 40 were prepared by analogously reacting the respective carboxylic acid IV with the corresponding cyclohexane-1,3-dione, the triketone initially obtained being successively used to prepare the compounds I of Examples 20, 21 and 28 Reaction with oxalyl chloride followed by pyrazole was derivatized.
  • the compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides.
  • the herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. This effect occurs especially at low application rates.
  • the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants.
  • the following crops are considered, for example:
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • the compounds I or the compositions comprising them can be sprayed, for example in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprays or granules. Misting, dusting, scattering, watering or treating the seed or mixing with the seed can be used.
  • the application forms depend on the use purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • the herbicidal compositions comprise a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I and auxiliaries customary for the formulation of crop protection agents.
  • Kerosene or diesel oil also coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol,
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • emulsions, pastes or oil dispersions the compounds of the formula I, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • the surface-active substances are the alkali metal, alkaline earth metal, ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa- , Hepta- and octadecanols and of fatty alcohol glycol ether, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenyl, alylphenol, , Tributy
  • Granules e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are mineral soils such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products such as corn flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range.
  • the formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • the compounds I according to the invention can be formulated, for example, as follows:
  • V 3 parts by weight of the active ingredient of the general formula I are mixed with 97 parts by weight of finely divided kaolin. In this way, a dust is obtained which contains 3% by weight of the active ingredient.
  • VI 20 parts by weight of the active ingredient of the general formula I are intimately mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
  • Emulsifier based on ethoxylated castor oil A stable emulsion concentrate is obtained.
  • the herbicidal compositions or the active compounds can be applied pre- or post-emergence or together with the seeds of a crop. There is also the possibility of applying the herbicidal compositions or active ingredients. ren that seed of a crop plant pretreated with the herbicidal compositions or active ingredients is applied. If the active ingredients are less compatible for certain crop plants, application techniques can be used in which the herbicides are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not struck wherever possible, while the active ingredients grow on the leaves below them unwanted plants or the uncovered floor area (post-directed, lay-by).
  • the application rates of active ingredient I are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a.s.), depending on the control target, the season, the target plants and the growth stage.
  • the compounds of the general formula I according to the invention can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
  • 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphorous acid and their derivatives, aminotriazoles, anilides, (het) -aryloxyalkanoic acid and their derivatives, benzoic acid and their derivatives come as mixing partners , Benzothiadiazinone, 2-Aroyl-l, 3-cyclohexanedione, 2-Hetaroyl-1, 3-cyclohexanedione, Hetaryl-Aryl-Ketone, Benzylisoxazolidinone, Meta-CF3-PhenyIderivate, Carbamate, Quinolinecarboxylic Acid and its Derivatives, Chloroacetanilide Cyclohexenone oxime ether derivatives, diazines
  • Plastic pots with loamy sand with about 3.0% humus as substrate served as culture vessels.
  • the seeds of the test plants were sown separately according to species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles.
  • the tubes were lightly sprinkled to promote germination and growth, and then covered with transparent plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.
  • test plants were first grown to a height of 3 to 15 cm and then treated with the active ingredients suspended or emulsified in water.
  • the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
  • the application rate for the post-emergence treatment was 250, 125, 62.5, 31.3 and / or 15.6 g / ha of active substance (see also).
  • the plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species.
  • the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated.
  • Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth. At least 95% damage corresponds to a very good herbicidal action.
  • the plants used in the greenhouse experiments are composed of the following types:
  • the compound I-la.1129 from Example 1 showed a very good herbicidal action against CHEAL, LAMAM, MATIN and SINAL in the post-emergence.
  • the compound I-lc.1129 from Example 2 showed a very good herbicidal action against CHEAL, ECHCG, PHBPU and POLPE in the post-emergence.
  • the compound I-Id.1129 from Example 3 showed a very good herbicidal action against CHEAL, PHBPU and POLPE, a good to very good herbicidal action against ECHCG and at application rates of 16.5 g / ha as a very good herbicidal activity against PHBPU and POLPE and a good to very good herbicidal activity against CHEAL and ECHCG.
  • the compound I-lc.1131 from Example 16 showed a very good herbicidal action against CHEAL, ECHCG, SETFA and POLPE in post-emergence.
  • the compound I-lx.1131 from Example 17 showed a very good post-emergence bicidal activity against BRAPL, CHEAL, ECHCG, SETFA and POLPE.
  • the compound I-la.1131 from Example 18 showed a very good herbicidal action against ABUTH, CHEAL, ECHCG and POLPE in the post-emergence.
  • the compound I-Id.1131 from Example 19 showed a very good herbicidal action against ABUTH, AMARE, CHEAL, ECHCG and SETFA in post-emergence.
  • the compound I-lx.1134 from Example 14 showed a very good herbicidal action against ABUTH, CHEAL, ECHCG and SETFA in post-emergence.
  • the compound I-Id.1134 from Example 15 showed a very good herbicidal action against ABUTH, AMARE, ECHCG and POLPE in post-emergence.
  • compound I-la.6 from example 9 showed a very good herbicidal action against AMARE, CHEAL, ECHCG and POLPE in the post-emergence.
  • the compound I-la.29 from Example 11 showed a very good herbicidal action against AMARE, CHEAL, ECHCG and POLPE in the post-emergence.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)

Abstract

L'invention concerne des dérivés cyclohexénone de benzazolones de la formule générale (I) dans laquelle R<1>, R<2>, R<3>, A et Hex ont la signification donnée dans la première revendication, ainsi que les sels desdits composés, et leur utilisation pour la lutte contre les plantes nuisibles.
EP01985385A 2000-12-11 2001-12-10 Benzazolonylcarbonyl cyclohexenones et utilisation en tant qu'herbicides Withdrawn EP1341776A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10061551 2000-12-11
DE10061551 2000-12-11
PCT/EP2001/014475 WO2002048121A1 (fr) 2000-12-11 2001-12-10 Benzazolonylcarbonyl cyclohexenones et utilisation en tant qu'herbicides

Publications (1)

Publication Number Publication Date
EP1341776A1 true EP1341776A1 (fr) 2003-09-10

Family

ID=7666612

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01985385A Withdrawn EP1341776A1 (fr) 2000-12-11 2001-12-10 Benzazolonylcarbonyl cyclohexenones et utilisation en tant qu'herbicides

Country Status (7)

Country Link
US (1) US6908884B2 (fr)
EP (1) EP1341776A1 (fr)
JP (1) JP2004526679A (fr)
AR (1) AR032779A1 (fr)
AU (1) AU2002234560A1 (fr)
CA (1) CA2431267A1 (fr)
WO (1) WO2002048121A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6480510B1 (en) * 1998-07-28 2002-11-12 Serconet Ltd. Local area network of serial intelligent cells
AR032779A1 (es) * 2000-12-11 2003-11-26 Basf Ag Derivados de ciclohexenona de benzazolonas, acidos benzazolonacarboxilicos, agentes que contienen por lo menos un derivado de ciclohexenona, procedimiento para combatir el crecimiento indeseado de plantas y uso de dichos derivados como herbicidas
CA2853340A1 (fr) 2011-11-16 2013-05-23 Basf Se Composes 1,2,5-oxadiazole substitues et leur utilisation comme herbicides agissant au niveau du photosysteme ii
CN104395304A (zh) 2012-04-27 2015-03-04 巴斯夫欧洲公司 取代的n-(四唑-5-基)-和n-(三唑-5-基)芳基羧酰胺化合物及其作为除草剂的用途
WO2014184019A1 (fr) 2013-05-15 2014-11-20 Basf Se Composés de n-(1,2,5-oxadiazol-3-yl)carboxamide et leur utilisation en tant qu'herbicides
CN115960086B (zh) * 2021-10-09 2024-05-28 山东先达农化股份有限公司 一种吡唑-苯并咪唑酮类化合物及其制备方法和应用、一种杀草剂

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1340284C (fr) 1987-03-19 1998-12-22 Zeneca Inc. Diones cycliques avec substitution, herbicides
DE4403670A1 (de) * 1994-02-07 1995-09-07 Basf Ag 2-Aroylcyclohexandione, Verfahren zu ihrer Herstellung sowie ihre Verwendung als Herbizide oder das Pflanzenwachstum regulierende Mittel
DE4427995A1 (de) 1994-08-08 1996-02-15 Basf Ag Saccharinderivate
ATE185139T1 (de) * 1995-02-24 1999-10-15 Basf Ag Herbizide benzoylderivate
DE19532311A1 (de) 1995-09-01 1997-03-06 Basf Ag Benzoylderivate
DE19638484A1 (de) * 1996-09-20 1998-03-26 Basf Ag Hetaroylderivate
US6165944A (en) * 1997-01-17 2000-12-26 Basf Aktiengesellschaft 4-(3-heterocyclyl-1-benzoyl) pyrazoles and their use as herbicides
US6140272A (en) * 1997-05-07 2000-10-31 Basf Aktiengesellschaft Substituted 4-benzoyl-pyrazoles
CN1326452A (zh) 1998-10-06 2001-12-12 出光兴产株式会社 三酮衍生物与除草剂
BR9915949A (pt) * 1998-12-04 2001-08-21 Basf Ag Derivado de 3-(heterociclila) benzoilpirazol, uso do memso, processo para prepará-lo, composição, e, proceso para prepará-la
US6500750B1 (en) * 1999-04-05 2002-12-31 Motorola, Inc. Semiconductor device and method of formation
EP1177179A1 (fr) 1999-05-07 2002-02-06 Basf Aktiengesellschaft Benzohetero cyclylcyclo hexenones et leur utilisation comme herbicides
ATE273965T1 (de) * 2000-05-18 2004-09-15 Basf Ag 3-(4,5-dihydroisoxazol-5-yl)benzoylcyclohexenon und ihre verwendung als herbizide
AR032779A1 (es) * 2000-12-11 2003-11-26 Basf Ag Derivados de ciclohexenona de benzazolonas, acidos benzazolonacarboxilicos, agentes que contienen por lo menos un derivado de ciclohexenona, procedimiento para combatir el crecimiento indeseado de plantas y uso de dichos derivados como herbicidas

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0248121A1 *

Also Published As

Publication number Publication date
AU2002234560A1 (en) 2002-06-24
US6908884B2 (en) 2005-06-21
JP2004526679A (ja) 2004-09-02
WO2002048121A1 (fr) 2002-06-20
CA2431267A1 (fr) 2002-06-20
AR032779A1 (es) 2003-11-26
US20040063584A1 (en) 2004-04-01

Similar Documents

Publication Publication Date Title
EP1177194B1 (fr) 4-(3&#39;,4&#39;-heterocyclyl benzoyl) pyrazoles en tant qu&#39;herbicides
US6589915B1 (en) Benzohetero cyclylcyclo hexenones and their use as herbicides
EP1341776A1 (fr) Benzazolonylcarbonyl cyclohexenones et utilisation en tant qu&#39;herbicides
EP1163240B1 (fr) Derives de benzoylpyrazol tricycliques s&#39;utilisant comme herbicides
EP1347969B1 (fr) 5- (pyrazol-4-yl)carbonyl]benzazolones en tant qu&#39;herbicides
EP1284969B1 (fr) 3-(4,5-dihydroisoxazol-5-yl)benzoylcyclohexenones et leur utilisation comme herbicides
EP1112256B1 (fr) Utilisation de derives de cyclohexenonchinolinoyl comme herbicides
EP1181295B1 (fr) Derives tricycliques de benzoylcyclohexanediones
EP1080089A1 (fr) Derives du type pyrazolyldioxothiochromanoyle
WO1999057111A9 (fr) Derives de cyclohexenonedioxothiochromanoyle
WO2001000584A2 (fr) Derives pyrazolyle d&#39;acides benzoiques bicycliques
EP1242393A1 (fr) Derives herbicides de benzoyl cyclohexenone substitues 3-(4,5-dihydroisoxazol-3-yl)
EP1135385A1 (fr) Derives de thiochromanoylpyrazolone
WO2001000607A1 (fr) Derives cyclohexenone d&#39;acide benzoique en tant qu&#39;herbicides
WO2001040199A1 (fr) 3-(4,5-dihydroisoxazol-3-yl)-benzoyl-cyclohexenones substituees par un halogenalkyle et a action herbicide
EP1144401A3 (fr) Derives de cyclohexenone de thiochromanoyl
WO2000059910A2 (fr) Derives tricycliques de pyrazolone
WO2000059911A2 (fr) Derives tricycliques de dione de cyclohexane

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030610

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LANGEMANN, KLAUS

Inventor name: LANDES, ANDREAS

Inventor name: ZAGAR, CYRILL

Inventor name: WITSCHEL, MATTHIAS

Inventor name: VOLK, THORSTEN

Inventor name: HOFMANN, MICHAEL

Inventor name: KUDIS, STEFFEN

Inventor name: VON DEYN, WOLFGANG

Inventor name: BAUMANN, ERNST

Inventor name: MISSLITZ, ULF

Inventor name: MAYER, GUIDO

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20060701