[go: up one dir, main page]

WO2001011968A2 - Composes spiro heterocycliques utilises comme pesticides - Google Patents

Composes spiro heterocycliques utilises comme pesticides Download PDF

Info

Publication number
WO2001011968A2
WO2001011968A2 PCT/EP2000/007851 EP0007851W WO0111968A2 WO 2001011968 A2 WO2001011968 A2 WO 2001011968A2 EP 0007851 W EP0007851 W EP 0007851W WO 0111968 A2 WO0111968 A2 WO 0111968A2
Authority
WO
WIPO (PCT)
Prior art keywords
formula
compound
compounds
spp
composition
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.)
Ceased
Application number
PCT/EP2000/007851
Other languages
English (en)
Other versions
WO2001011968A3 (fr
Inventor
Stephen Lindell
Ulrich Sanft
Maria-Theresia Thönessen
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.)
Bayer CropScience AG
Original Assignee
Aventis CropScience GmbH
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 Aventis CropScience GmbH filed Critical Aventis CropScience GmbH
Priority to AU75092/00A priority Critical patent/AU7509200A/en
Priority to KR1020027001876A priority patent/KR20020029101A/ko
Priority to EP00964011A priority patent/EP1209974A2/fr
Priority to JP2001516331A priority patent/JP2003506468A/ja
Priority to BR0013085-0A priority patent/BR0013085A/pt
Publication of WO2001011968A2 publication Critical patent/WO2001011968A2/fr
Publication of WO2001011968A3 publication Critical patent/WO2001011968A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D498/20—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/025—Preservatives, e.g. antimicrobial agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • Agrochemically acceptable derivates include acid addition salts, quaternary salts and derivates hydrolyzable in vivo (prodrugs), of the compounds of formula (I).
  • Agrochemically acceptable acid addition salts of the compounds of formula (I) include the salts of mineral acids, for example, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid or phosphoric acid, and organic acids for example monobasic acids such as acetic acid, formic acid, propionic acid, methanesulfonic and ethanesulfonic acid or toluene sulfonic acid, and polybasic acids such as oxalic acid, malonic acid, malic acid, tartaric acid, maleic acid, fumaric acid or succinic acid or salts with acidic amino acids, such as aspartic and glutamic acids. Salts may be readily formed from the compounds of formula (I) by mixing with the appropriate acid or by exchange with an other acid addition salt of the compound of formula (I).
  • Some of the compounds of formula (I) contain asymmetric carbon or double bond (depending on the type of substituent groups involved) and hence exist as a plurality of optical and geometric isomers.
  • This invention includes all of these isomers, individually and in any mixture of two or more thereof.
  • (CrC 6 )-alkyl is identical to "lower alkyl” and means, unless otherwise specified, a linear or branched carbon chain of 1 to 6 carbon atoms, which is optionally substituted by one or more fluorine atoms.
  • (CrC ⁇ J-alkyl groups) there may be mentioned methyl, trifluoromethyl, ethyl, 2,2,2-trifluoro-ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, 2-methylbutyl, 1 ,2- dimethylpropyl, hexyl, isohexyl,
  • (CrC6)-alkoxy groups may be mentioned methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy (amyloxy), isopentyloxy, tert- pentyioxy, neopentyloxy, 2-methyl butoxy, 1 ,2-dimethylpropoxy, 1-ethylpropoxy and hexyloxy.
  • (CrC 6 )-alkylthio groups correspond to above lower alkoxy groups in which oxygen is replaced by sulfur.
  • Illustrative examples include methylthio, ethylthio, propylthio, isopropylthio, butylthio, sec-butylthio, tert-butylthio, pentylthio, neopentylthio, 2-methylbutylthio, 1,2- dimethylpropylthio and 1-ethylpropylthio.
  • (CrC 6 )-alkoxycarbonyl groups are derivable by carboxyl group esterification with a linear or branched alcohol of 1 to 6 carbon atoms, e .g. methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentoxycarbonyl, isopentyloxycarbonyl, tert-pentyloxycarbonyl, neopentylcarbonyl and hexyloxycarbonyl.
  • a linear or branched alcohol of 1 to 6 carbon atoms e .g. methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentoxycarbonyl
  • (CrC 6 )-alkanoyl groups include e.g. formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl and hexanoyl.
  • (CrC 6 )-alkanoyl groups include formyloxy, acetyloxy, trifluoroacetyloxy, propionyloxy, butyryloxy, isobutyryloxy, valeryloxy, isovaleryloxy, pivaloyloxy and hexanoyloxy.
  • (CrC ⁇ J-alkanoylthio groups” correspond to above (CrC 6 )-alkanoyloxy groups in which the oxygen of the oxy radical is replaced by sulfur.
  • Illustrative examples include formylthio, acetylthio, propionylthio, butyrylthio, isobutyrylthio, varelythio, isovalylthio, pivaloylthio and hexanoylthio.
  • ⁇ is a bivalent radical, preferably of 1, 2 or 3 carbon atoms, in which at least one of the carbon atoms may optionally be substituted by a (C C 6 ) alkyl group as defined above
  • illustrative examples include methylene, methylmethylene, dimethylmethylene, ethylene, trimethylene, 1- or 2-methylethylene, 1- or 2-ethylethylene, 1- or
  • Halogen atom may be any one of fluorine, chlorine, bromine or iodine.
  • the optional lower alkanediyl bridging group in the N-A-C-B-ring is as defined for "Alk"; examples of such saturated bicyclo rings are:
  • Preferred compounds are those in which the N-A-C-B-ring represents quinuclidine, 2- azabicyclo[2.2.1]heptane, 1-azabicyclo[2.2.1]heptane or 8-azabicyclo[3.2.1]octane and especially preferred are compounds in which the N-A-C-B-ring is 1- azabicyclo[2.2.1 . heptane.
  • R 10 is (CrCe)-alkyl, especially methyl, ethyl or propyl, (C 2 -C 6 )-alkenyl, especially allyl or prenyl, or (C 2 -C 6 )-alkynoyl, especially propargyl.
  • R 1 is hydrogen or alkyl, especially methyl or 2,2,2- trifluoroethyl, or in the case where R 1 forms ring A, methylene.
  • Quaternary salts which may be mentioned include N + -(C- ⁇ -C 6 )-alkyl, preferably N + - methyl.
  • Derivates hydrolyzable in vivo which may be mentioned include (C ⁇ -C 6 )- alky xycarbonyl, benzyloxycarbonyl or (C ⁇ -C 6 )-alkanoyl.
  • X represents a sulfur atom and/or
  • R 1 represents COR' and/or
  • R 2 , R 4 , R 5 represent (C C 6 )-alkyl and/or 7
  • R 3 represents H, (d-C ⁇ J-alkyl, carboxy, (CrC 6 )-alkoxycarbonyl, (CrC 6 )-alkanoyl and/or
  • R 6 represents a halogen atom, (CrC 6 )-alkyl, carboxy, (CrC 6 )-alkoxy, (CrC 6 )- alkanoyloxy, (CrC 6 )-alkylthio; (CrC 6 )-alkanoylthio.
  • the compounds of formula (I) can be prepared through various synthetic routes adapted for the individual chemical structures. Synthetic routes for the preparation of formula (I) in which W represents CR 9 R 10 are disclosed in EP-A 0311 313:
  • ring A 1 is a piperidine ring in which the nitrogen atom may be substituted by (C Ce) alkyl, (C-i-C 6 ) alkanoyl, (CrC 6 ) alkoxycarbonyl or a protective group for amines and/or may 11 be connected to a ring carbon (other than the common carbon atom of the spiro structure) via a (C ⁇ -C 6 ) alkylene bridging group;
  • ring A 2 is a piperidine ring in which the nitrogen atom may be substituted by (C Ce) alkanoyl (C Ce) alkoxycarbonyl or a protective group for amines and/or may be connected to a ring carbon (other than the common structure atom ofthe spiro structure) via a (C C 6 )
  • Z 3 and Z 4 are the same or different and selected from oxygen and sulfur atoms;
  • R 11 and R 12 are the same or different (C- ⁇ -C 6 ) alkyls;
  • R 13 is a hydrogen atom or (CrC 6 ) alkyl;
  • R 14 is a hydrogen atom or (C Ce) alkyl;
  • R 15 is a hydrogen atom or (C ⁇ -C 6 ) alkyl, carbonyl or (C- ⁇ -C 6 ) alkoxycarbonyl;
  • R 16 is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms;
  • R 17 is (C C 6 ) alkyl,
  • R 20 is hydroxyl, mercapto, (C ⁇ -C 6 ) alkoxy or (C C 6 ) alkylthio;
  • Ph is phenyl;
  • R 18 and R 19 are the same or different and selected from a hydrogen atom and (C Ce) alkyls.
  • compound (II) and alkali metal salt of compound (III) are allowed to react, or compound (II) and compound (III) are allowed to react in the presence of 12 base; the two reactants are used in equimolar amounts or with one reactant in slight excess.
  • the reaction is preferably carried out in an inert organic solvent under cooling or at room temperature.
  • Suitable solvents are aprotic compounds, such as dimethyl sulfoxide, benzene, toluene, xylene, dichloromethane, tetrahydrofurane, N,N-dimethylformamide, dichloroethane, chloroform and carbon tetrachlorides.
  • the alkali metal salt of compound (III) can be obtained by reaction of compound (III) with base, such as sodium hydride, preferably under anhydrous conditions.
  • base such as sodium hydride
  • the same type of base may be used in the reaction of compound (II) and compound (III) in free form.
  • any type of protective group commonly employed for amino groups may be used in this invention. These include groups of urethane type (e.g., t-butoxycarbonyl), of acyl type (e.g., formyl, acetyl and propionyl), and of benzyl type (e.g., benzyl, benzhydryl and trityl). Removal of these protective groups may be effected by usual methods, in the presence of acid or base for those of urethane type, in the presence of base for those of acyl type, and by catalytic reduction for those of benzyl type. Hydrochloric acid, trifluoroacetic acid and hydrobromic acid/acetic acid may be mentioned as acid catalyst, and sodium hydrochloride and potassium hydroxide as the base catalysts.
  • urethane type e.g., t-butoxycarbonyl
  • acyl type e.g., formyl, acetyl and propionyl
  • Compounds (II) can be obtained by reaction of oxo-heterocyclic compound carrying protective group, lower alkyl, lower alkanoyl and lower alkoxycarbonyl with lower alkyl dialkylphosphonoacetate in an inert solvent (e.g. dimethoxyethane, dioxane and tetrahydrofuran) in the presence of base under cooling or at room temperature, or by the normal Wittig reaction, followed by removal of any protective group.
  • an inert solvent e.g. dimethoxyethane, dioxane and tetrahydrofuran
  • Spiro compounds of 3-iodo-heterocyclic type represented by formula (lb) can be prepared by iodination of alkenyl-substituted, heterocyclic alcohol (IV), followed by removal of any protective group as required. 13 The reaction is preferably carried out by dissolving compund (IV) in an inert organic solvent, adding an aqueous alkaline solution of iodine in a more than stoichiometric amount, and holding the resulitng mixture under cooling or at room temperature.
  • Suitable organis solvents are aprotic compounds, such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, benzene, toluene, xylene and dimethyl sulfoxide; and sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide may be mentioned as examples of the alkali.
  • Compounds (IV) (starting material) are compounds, which can be easily obtained, as shown in the reaction formula given below, by the action of Grignard reagent, prepared from alkenyl halide and magnesium by usual method, upon oxo-heterocyclic compound.
  • This cyclization is effected by the action of Lewis acid (such as tin tetrachloride, titanium tetrachloride and boron trifluoride(diethyl ether complex) upon compound (V) dissolved in an inert organic solvent, followed by addition of base.
  • Lewis acid such as tin tetrachloride, titanium tetrachloride and boron trifluoride(diethyl ether complex
  • Suitable organic solvents are aprotic compounds, such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, benzene, toluene, xylene and dimethyl sulfoxide.
  • the base may be any compound that can trap the hydrochloric acid and metal salt formed, illustrative examples being organic bases, such as triethylamine, trimethylamine, pyri ⁇ ine, picoline, lutidine and dimethylaniline; and inorganic bases, such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
  • the reaction is preferably carried out under cooling or at room temperature.
  • the decarboxylation reaction is effected by heating (preferably under reflux) in the presence of acid.
  • the substituent group is a lower alkoxyacarbonyl
  • a process may be adopted in which the starting material (Id) may be dissolved in inert organic solvent (e.g., dimethylformamide and dimethyl sulfoxide) and this solution heated in the presence of an equimolar or excess amount of sodium chloride.
  • inert organic solvent e.g., dimethylformamide and dimethyl sulfoxide
  • Method 1 reaction product need not be isolated, but may be heated in the form of an acidic aqueous solution for direct conversion to compound (Ie).
  • Method 5 15 Compounds according to the invention can be prepared by reduction, and various reduction processes may be adopted depending on the type of radical to be reduced.
  • Method 5 is a process for obtaining compounds (If) carrying hydroxyl as substituent at 3-positio ⁇ by reduction of corresponding compounds in which the 3-position is carbonyl.
  • the reaction is preferably carried out in an inert solvent (for example, alcohols, such as methanol, ethanol and isopropanol, tetrahydrofuran and dioxanes) at room temperature or at elevated temperature using reducing agent that can selectively reduce the carbonyl at 3-position (e.g. a boron hydride compound, such as sodium borohydride and sodium cyanoborohydride).
  • an inert solvent for example, alcohols, such as methanol, ethanol and isopropanol, tetrahydrofuran and dioxanes
  • reducing agent that can selectively reduce the carbonyl at 3-position
  • a boron hydride compound such as sodium borohydride and sodium cyanoborohydride
  • N-lower-alkyl compounds of formula (Ih) can also be synthesized by reduction of starting material (Ig) carrying a lower alkanoyl as the substituent group at N-position.
  • the reaction is preferably carried out in an organic solvent (e.g. ether, tetrahydrofurane or dioxane) using, as reducing agent, an aluminium hydride compound (such as lithium aluminium hydride) at room temperature or at an elevated temperature.
  • organic solvent e.g. ether, tetrahydrofurane or dioxane
  • an aluminium hydride compound such as lithium aluminium hydride
  • N-methyl compounds according to the invention of formula (li) can be synthesized by reduction of compound (III) carrying a urethane-type substituent at the N-position.
  • the reduction is preferably effected in an organic solvent (e.g., tetrahydrofurane, ether or dioxane) using, as reducing agent, aluminium hydride (prepared from lithium aluminium hydride and sulfuric acid) at room temperature or at elevated temperature, or under cooling.
  • organic solvent e.g., tetrahydrofurane, ether or dioxane
  • aluminium hydride prepared from lithium aluminium hydride and sulfuric acid
  • Cyclic ketals of formula (k) can be synthesized by methods commonly employed for the preparation of cyclic ketals. For example, corresponding carbonyl compound (Ij) is allowed to react with compound (VIII), such as a glycol, a hydroxyaikanethiol or an alkanedithiol, or with epoxy compound (IX), to form compound (Ik).
  • compound (VIII) such as a glycol, a hydroxyaikanethiol or an alkanedithiol
  • epoxy compound (IX) epoxy compound
  • the reaction is carried out by dissolving compound (Ij) and an equimolar or excess amount of compound (III) in an inert organic solvent (preferably a solvent adapted for azeotropic dehydration, such as benzene, toluene or xylene) and heating the solution under reflux in the presence of acid catalyst to effect dehydration (preferably using a Dean-Stark azeotropic dehydration apparatus).
  • an inert organic solvent preferably a solvent adapted for azeotropic dehydration, such as benzene, toluene or xylene
  • the acid catalyst may be adipic-acid, oxalic acid or pyridine hydrochloride, but p-toluenesulfonic acid is the most preferred.
  • reaction is carried out in an inert solvent, such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, ether, dioxane or tetrahydrofuran, in the presence of Lewis acid (e.g., boron trifluoride/diethylether or in tin tetrachloride), the desired product can be obtained without dehydration or heating.
  • Lewis acid e.g., boron trifluoride/diethylether or in tin tetrachloride
  • epoxy compound (IX) is used as starting material
  • the reaction is carried out in an inert solvent (e.g.
  • dichloromethane dichloroethane, chloroform or carbon tetrachloride
  • stannous chloride or boron trifluoride/ether complex at room temperature or at elevated temperature, or in the presence of tetraethylammonium bromide at 80 to 150°C in an autoclave.
  • This reaction is preferably carried out in an inert, aprotic organic solvent (such as dimethyl sulfoxid, dimethylformamide, tetrahydrofuran, ether, dioxane, benzene, toluene or xylene) under cooling or at elevated temperature using an equimolar or 17 excess amount of compound (X).
  • aprotic organic solvent such as dimethyl sulfoxid, dimethylformamide, tetrahydrofuran, ether, dioxane, benzene, toluene or xylene
  • the compound (X) can be prepared by reaction of corresponding alkyltriphenylphosphonium halide with an equimolar or excess amount of base in the same solvent as above under cooling or heating.
  • the base used is preferably sodium hydride or n-butylithium.
  • R 1 , R 10 , A and B are as defined above for formula (I), Y' represents O or S, and in addition R 1 may represent a protecting group, or
  • R 1 , A and B are as defined above for formula (I) and in addition, R 1 may represent a protecting group, or 18 c) preparing a compound of formula (I) in which Y' is S by thiation of a corresponding compound of formula (I) in which Y' is O, or
  • R 1 , A and B are as defined above for formula (I), R" represents a C C 6 - alkyl group and in addition, R 1 may represent a protecting group, with hydroxyurea, or
  • reaction of process (a) methods similar to those described by Miles, H. T., (J. Amer. Chem. Soc. 79, 2565-8 (1957)] may be used.
  • the reaction may be carried out in the absence of a solvent and at a temperature of, for example, from 100°C- 250°C.
  • suitable leaving groups that X' may represent include halide, for example bromide, and alkoxy, eg methoxy.
  • the hydrolysis may be carried out in the presence of an acid, for example, hydrochloric or sulfuric acid in a solvent.
  • Protic solvents are preferred, for example, methanol, ethanol or water or mixtures thereof and at a temperature of, for example, from 0°C-100°C.
  • the thiation reaction may be carried out by methods similar to those described by De Amici using, for example, 2,4-bis(4-methoxyphenyl)-1 ,3-dithia-2,4- diphosphetane-2,4-disulfide (Lawesson's Reagent) in an inert solvent, for example, toluene at a temperature of, for example, from 50°C-120°C.
  • Lawesson's Reagent 2,4-bis(4-methoxyphenyl)-1 ,3-dithia-2,4- diphosphetane-2,4-disulfide
  • suitable leaving groups that X' may represent include halide, for example, bromide.
  • Protecting groups which R 1 may represent include benzyloxycarbonyl or a borane complex.
  • the reaction may be earned out in an inert solvent, for example, nitromethane, and at temperature of, for example, from 0°C to 50°C. 20
  • suitable leaving groups that Z' may represent include halide, for example bromide.
  • the reaction may be carried out in the presence of a base, for example in alkali carbonate in which the alkali metal may be, for example, sodium or potassium.
  • the reaction may be conducted in an inert solvent, for example an aprotic solvent such as acetone, and at a temperature of, for example, from 0°- to 100°C.
  • suitable leaving groups which L may represent include, for example, halogen, preferably chlorine, bromine or iodine, or an alkyl- or aryl- sulfonate group, for example, mesylate ortosyiate.
  • the alkylation reaction may be earned out in aprotic solvent, for example, acetonitrile, in the presence of a base, for example, potassium carbonate, and at a temperature of, for example, from 0° -100°C.
  • urethane formation may be earned out under similar conditions as those used in process (f) above.
  • methylation is accomplished by heating the amine with formic acid and formaldehyde at a temperature of, for example, from 50°C-100°C.
  • ring formation is carried out with hydroxyurea in the presence of a base, for example, an alkali alkoxide such as sodium methoxide, in a protic solvent, for example, an alcohol such as methanol and at a temperature of, for example, from 0°C - 50°C.
  • a base for example, an alkali alkoxide such as sodium methoxide
  • a protic solvent for example, an alcohol such as methanol
  • protecting groups are represented by benzyloxycarbonyl, which may readily be removed by, for example, triflic acid, hydrogenolysis or hydrogen bromide in acetic acid.
  • Other groups which may be mentioned include borane, which may be removed by aqueous sodium carbonate and t-butyloxycarbonyl which may be removed by trifluoracetic acid. Further protecting 21 groups and methods for their removal are described in T.W. Greene, Protective Groups in Organic Synthesis, Wiley-lnterscience, 1981.
  • compounds of formula (I) may be prepared by heating a compound of formula (XIII) together with a hydroxylamine of formula R 10 NHOH.
  • the reaction can be performed neat, or in a suitable solvent (such as toluene, xylene or mesitylene), at temperatures typically between 80 and 165 C C.
  • Compounds of formula (XI) may be prepared by reacting the corresponding compound of formula (XII) with a compound of formula R 0 -Y'-H, in which R 10 and Y' are as defined above.
  • the reaction may be earned out by heating the compound of formula (XII) with the appropriate alcohol or thioalcohol in the presence of a base, for example, potassium carbonate.
  • a base for example, potassium carbonate.
  • the reaction may be carried out at a temperature of, for example, from 20°C-100°C.
  • R 1 , and B are as defined above for formula (I) and in addition, R 1 may represent a protecting group with a nitrile oxide of formula (XV),
  • the nitrile oxide of formula (XV) may be prepared in situ from a corresponding compound of formula (XVI), 22
  • X is a halide
  • the reaction may be carried out by methods similar to those described by Vyas, D. M. et al. (Tet. Letts. 25, 487-490 (1984)].
  • the reaction may be carried out in the presence of a base, for example, sodium or potassium bicarbonate or sodium acetate in a suitable solvent.
  • Suitable solvents include water or an aprotic solvent, for example, ethyl acetate or methylene chloride.
  • the reaction may also be earned out in the presence of silver nitrate and aqueous acetic acid.
  • the reaction may be earned out at a temperature of, for example, from -10°C - 30°C.
  • Compounds of formula (XII) in which X' is alkoxy, for example methoxy may be prepared by alcoholysis of the corresponding compound of formula (XII) in which X' is halogen by reaction with an alcohol, for example methanol, in the presence of a base, for example potassium carbonate, at a temperature of, for example, from 20°C-100°C.
  • a base for example potassium carbonate
  • the starting materials of formula (XIV) may be prepared by a number of methods, for example, by reacting the corresponding compound of formula (XVII),
  • R 1 , A and B are as defined above for formula (I) and in addition R 1 may represent a protecting group, with a Wittig reagent, for example, methyl triphenyl- phosphonium bromide in the usual manner.
  • a Wittig reagent for example, methyl triphenyl- phosphonium bromide in the usual manner.
  • reaction may be earned out in the presence of a base, for example, butyl lithium or sodamide, in an aprotic solvent, for example, THF or hexane or mixtures of solvents, at a temperature of, for example, from 0°C-50°C.
  • a base for example, butyl lithium or sodamide
  • an aprotic solvent for example, THF or hexane or mixtures of solvents
  • esters can be synthesized by reaction of corresponding carboxylic acid or reactive derivatives thereof with lower alcohol or reactive derivative thereof (e.g., lower alkyl halide) in the presence of condensation agent or base as required, or by other commonly used esterification techniques.
  • lower alcohol or reactive derivative thereof e.g., lower alkyl halide
  • condensation agent or base e.g., lower alkyl halide
  • compounds of this invention having free carboxyl group can be derived from corresponding esters by hydrolysis.
  • Thiocarboxylic acids and esters thereof can be similarly prepared.
  • Compounds carrying a lower alkyl as substituent group at the N-position can be derived from corresponding free-nitrogen compounds by the usual N-alkylation methods using lower alkyl halide or by the action of lower alkylaldehyde in the presence of reducing agent, such as sodium borohydride or sodium cyanoborohydride.
  • Compounds carrying a lower alkanoyl a substituent group at the N-position can be derived from corresponding free-nitrogen compound by the usual amidation methods using lower alkanoic acid or reactive derivative thereof in the presence of base as required.
  • Compounds according to the invention carrying a mercapto substituent group at the 3- position can be synthesized by sulfonating corresponding compounds carrying a 24 hydroxy substituent group at the 3-position (wich may optionally have a protective group), followed by the action of thiocarboxyiic acid (such as thioacetic acid, CH 3 CO- SH), hydrolysis and removal of the protective group as required; or by forming corresponding N-alkyl compound according to Method 6 or Method 7.
  • thiocarboxyiic acid such as thioacetic acid, CH 3 CO- SH
  • Compounds carrying a thioether substituent group at the 3-position can be derived from the mercapto compounds obtained above or alkali metal salts thereof by the action of lower alkyl halide or lower alkyl sulfonate (preferably p-toluenesulfonate) in the presence of base as required.
  • Compounds carrying an ether substituent at the 3-position can be derived from corresponding 3-hydroxy compounds by the action of lower alkyl halide (e.g., lower alkyl iodide) in the presence of base, followed by removal of the protective group as required; or by forming corresponding N-alkyl compounds according to Method 6 or Method 7.
  • lower alkyl halide e.g., lower alkyl iodide
  • Acid addition salts of compounds of formula (I) may be converted to the corresponding free base by the action of a stronger base.
  • the acid addition salts of the compound of formula (I) may be prepared by reaction of the free base with an appropriate acid.
  • Quaternary salts may be prepared from the corresponding secondary or tertiary amines by conventional methods, for example as described in J March, Advanced Organic Chemistry, 3r ED, Wiley-lnterscience, 1985.
  • the compounds according to the invention (I) thus prepared are isolated and purified in the free form or as salts (obtainable by common salt-forming reactions). 25 Isolation and purification can be effected by common chemical operations, such as liquid/liquid separation, extraction, concentration, crystallization, filtration, recrystallization, and various types of chromatography.
  • the compounds according to the invention may be obtained in different isomeric forms (such as geometric isomers, racemic compounds, optical isomers and diastereomers), either alone or as a mixture thereof.
  • Geometric isomers can be separated by appropriately selecting the starting material or by utilizing differences in the pyhsicochemical properties of the isomers.
  • Optical isomers and diastereomers can be separated by appropriately selecting the starting material, by general racemic separation techniques (for example, forming diastereomer salts with optically active acid, such as tartaric acid, followed by optical resolution), or by commonly used for diastereomer separation (for example, fractional crystallization ahd chromatography).
  • reaction steps described with no reference to protective groups may also be carried out with protective groups present.
  • Collections of compounds of the formula (I) which can be synthesized by the abovementioned Methods may also be prepared in a parallel manner, and this may be effected manually or in a semiautomated or fully automated manner.
  • this is to be understood as meaning a procedure as it is described, for example, by S.H. DeWitt in "Annual Reports in Combinatorial Chemistry and Molecular Diversity: Automated synthesis", Volume 1 , Verlag Escom 1997, pages 69 to 77.
  • the apparatuses mentioned lead to a modular procedure in which the individual process steps are automated, but manual operations must be performed between the process steps. This can be prevented by employing semi-integrated or fully integrated automation systems where the automation modules in question are operated by, for example, robots.
  • Such automation systems can be obtained, for example, from Zymark Co ⁇ oration, Zymark Center, Hopkinton, MA 01748, USA.
  • compounds of the formula (I) may be prepared in part or fully by solid-phase-supported methods.
  • solid-phase-supported synthesis methods are described extensively in the specialist literature, for example Barry A. Bunin in 'The Combinatorial Index", Academic Press, 1998.
  • the use of solid-phase-supported synthesis methods permits a series of protocols which are known from the literature and which, in turn, can be performed manually or in an automated manner.
  • the "tea-bag method” Houghten, US 4,631 ,211 ; Houghten et al., Proc. Natl. Acad.
  • the preparation ofthe processes described herein yields compounds ofthe formula (I) in the form of substance collections which are termed libraries.
  • the present invention also relates to libraries which comprise at least two compounds of the formula (I).
  • the compounds of the formula (I) are suitable for controlling animal pests, in particular arthropods, e.g. insects and arachnids, helminths and mollusks, very especially preferably for controlling insects and arachnids which are encountered in agriculture, in livestock breeding, in forests, in the protection of stored goods and materials, and in the hygiene sector, and have good plant tolerance and favorable toxicity to warm-blooded species. They are active against normally sensitive and resistant species and against all or individual developmental stages.
  • the abovementioned pests include: from the order ofthe Acarina, for example, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Eotetranychus spp., Oligonychus spp., Eutetranychus spp. From the order ofthe Isopoda, for example, Oniscus aselus, Armadium vulgare, Porcell
  • Chilopoda for example, Geophilus carpophagus, Scutigera spp.
  • Symphyla for example, Scutigerella immaculata.
  • Thysanura for example, Lepisma saccharina.
  • Collembola for example, Onychiurus armatus.
  • Orthoptera for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
  • Isoptera for example, Reticulitermes spp.
  • Anoplura for example, Phylloera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
  • Thysanoptera From the order ofthe Thysanoptera, for example, Hercinothrips femoraiis, Thrips tabaci.
  • Heteroptera for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
  • Homoptera for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, 28
  • Hymenoptera From the order ofthe Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Siphonaptera for example, Xenopsylla cheopsis, Ceratophyllus spp.
  • Arachnida for example, Scorpio maurus, Latrodectus mactans.
  • helminths for example, Haemonchus, Trichostrongulus, Ostertagia, Cooperia, Chabertia, Strongyloides, Oesophagostomum, Hyostrongulus, Ancyiostoma, Ascaris and Heterakis and also Fasciola.
  • Gastropoda for example, Deroceras spp., Arion spp., Lymnaea spp., Galba spp., Succinea spp., Biomphalaria spp., Bulinus spp., Oncomelania spp.
  • Bivalva for example, Dreissena spp.
  • the plant-parasitic nematodes which can be controlled in accordance with the invention include, for example, the root-parasitic soil-dwelling nematodes such as, for example, those ofthe genera Meloidogyne (root knot nematodes, such as Meloidogyne incognita, Meloidogyne hapla and Meloidogyne javanica), Heterodera and Globodera (cyst-forming nematodes, such as Globodera rostochiensis, Globodera pallida, Heterodera trifolii) and of the genera Radopholus, such as Radopholus similis, Pratylenchus such as Pratyienchus neglectus, Pratylenchus penetrans and Pratylenchus curvitatus;
  • the root-parasitic soil-dwelling nematodes such as, for example, those ofthe genera Meloidogyne (root knot nem
  • Tylenchulus such as Tylenchulus semipenetrans, Tylenchorhynchus, such as Tylenchorhynchus dubius and Tylenchorhynchus claytoni, Rotylenchus such as Rotylenchus robustus, Heliocotylenchus such as Haliocotylenchus multicinctus, Belonoaimus such as Belonoaimus longicaudatus, Longidorus such as Longidorus elongatus, Trichodorus such Trichodorus primitivus and Xiphinema such as Xiphinema index.
  • Ditylenchus stem parasites, such as Ditylenchus dipsaci and Ditylenchus destructor
  • Aphelenchoides foliar nematodes, such as Aphelenchoides ritzemabosi
  • Anguina seed nematodes, such as Anguina tritici
  • the invention also relates to compositions, for example crop protection compositions, preferably insecticidal, acaricidal, ixodicidal, nematicidal, or molluskicidal, especially preferably insecticidal and acaricidal, compositions which comprise one or more compounds of the formula (I) in addition to suitable formulation auxiliaries.
  • crop protection compositions preferably insecticidal, acaricidal, ixodicidal, nematicidal, or molluskicidal, especially preferably insecticidal and acaricidal, compositions which comprise one or more compounds of the formula (I) in addition to suitable formulation auxiliaries.
  • compositions according to the invention comprise an effective amount, usually 1 to 95% by weight of one or more ofthe active substances of the formula (I).
  • compositions according to the invention To prepare the compositions according to the invention, the active substance and the other additives are combined and brought into suitable use form.
  • WP Wettable powders
  • EC emulsifiable concentrates
  • SL aqueous solutions
  • SC oil- or water-based dispersions
  • SE suspoemulsions
  • SE dusts
  • DP seed-dressing products
  • granules in the form of microgranules spray granules, coated granules and abso ⁇ tion granules, water-dispersible granules (WG), ULV formulations, microcapsules, waxes or baits.
  • auxilairies such as inert materials, surfactants, solvents and other additives
  • inert materials such as inert materials, surfactants, solvents and other additives
  • solvents and other additives are also known and described, for example, in Watkins, “Handbook of Insecticide Dust Diluents and Garners", 2nd Ed., Darland Books, Caldwell N.J.; H. v. 31 Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y.; Marsden, “Solvents Guide”, 2nd Ed., Interscience, N.Y. 1950; McCutcheon's, “Detergents and Emulsifiers Annual", MC Publ.
  • Wettable powders are preparations which are uniformly dispersible in water which, besides the active substance, also comprise wetters, for example polyoxyethylated alkylphenols, polyoxyethyiated fatty alcohols, alkylsulfonates or alkylphenolsulfonates and dispersants, for example sodium lignosulfonate or sodium 2,2'- dinaphthylmethane-6,6'-disulfonate, in addition to a diluent or inert material.
  • wetters for example polyoxyethylated alkylphenols, polyoxyethyiated fatty alcohols, alkylsulfonates or alkylphenolsulfonates and dispersants, for example sodium lignosulfonate or sodium 2,2'- dinaphthylmethane-6,6'-disulfonate, in addition to a diluent or inert material.
  • Emulsifiable concentrates are prepared by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons, with addition of one or more emulsifiers.
  • organic solvent for example butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons.
  • emulsifiers the following can be used, for example: calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensates, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters.
  • calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensates, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid est
  • Dusts are obtained, for example, by grinding the active substance with finely divided solid materials, for example talc or natural clays, such as kaolin, bentonite, pyrophyllite or diatomaceous earth.
  • Granules can be prepared either by atomizing the active substance onto adsorptive, granulated inert material or by applying active substance concentrates onto the surface of carrier materials such as sand or kaolinites, or of granulated inert material, by means of adhesives, for example polyvinyl alcohol or 32 sodium polyacrylate, or else mineral oils.
  • Suitable active substances can also be granulated in the manner which is customary for the preparation of fertilizer granules, if desired as a mixture with fertilizers.
  • the active substance concentration in wettable powders is, for example, approximately 10 to 90% by weight, the remainder to 100% by weight is composed of customary formulation auxiliaries.
  • the active substance concentration may be approximately 5 to 80% by weight.
  • Formulations in the form of dusts usually comprise 5 to 20% by weight of active substance, sprayable solutions approximately 2 to 20% by weight.
  • the active substance content depends partly on whether the active compound is in liquid or solid form and on which granulation auxiliaries, fillers and the like are being used.
  • the abovementioned active substance formulations comprise, if appropriate, the tackifiers, wetters, dispersants, emulsifiers, penetrants, solvents, fillers or carriers which are conventional in each case.
  • the concentrates which are present in commercially available form, are, if desired, diluted in the customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and in some cases also microgranules using water. Preparations in the form of dusts and granules and sprayable solutions are usually not diluted any further with other inert substances prior to use.
  • the application rate required varies with the external conditions such as, inter alia, temperature and humidity. It may vary within wide limits, for example between 0.0005 and 10.0 kg/ha or more of active substance, but it is preferably between 0.001 and 5 kg/ha.
  • the active substances according to the invention in their commercially available formulations and in the use forms prepared from these formulations (see the abovementioned compositions) may be present in mixtures with other active 33 substances such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, molluskicides, growth regulatory substances or herbicides.
  • the pesticides include, for example, phosphoric esters, carbamates, carboxylic esters, formamidines, tin compounds and materials produced by microorganisms.
  • alanycarb (OK-135), aldicarb, 2-sec-butylphenyl methylcarbamate (BPMC), carbaryl, carbofuran, carbosulfan, cloethocarb, benfuracarb, ethiofencarb, furathiocarb, HCN- 801 , isoprocarb, methomyl, 5-methyl-m-cumenylbutyryl (methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, 1-methylthio(ethylideneamino)-N-methyl-N- (mo ⁇ holinothio)carbamate (UC 51717), triazamate;
  • the active substance content ofthe use forms prepared from the commercially available formulations may range from 0.00000001 up to 95% by weight of active substance, preferably between 0.00001 and 1% by weight. Application is effected in a customary manner adapted to suit the use forms.
  • the invention also relates to a method of controlling harmful insects, Acarina, mites, endo and ectoparasites, helminths, mollusks and/or nematodes in which an effective amount of a compound according to the invention or of a composition according to the invention is applied to these or to the plants, areas or substrates infested with them.
  • the active substances according to the invention are also suitable for use in the veterinary medicine sector, preferably for controlling endoparasites and ectoparasites, and in the field of animal keeping.
  • the active substances according to the invention may be applied in the known manner, such as by oral administration in the form of, for example, tablets, capsules, drinks or granules, by dermal application in the form of, for example, dipping, spraying, pouring on and spotting on, and dusting, and by parenteral administration in the form of, for example, an injection.
  • the compounds according to the invention are also suitable for use in technology, for example as wood preservative, as preservative in paints, in cooling lubricants for metalworking, or as preservative in drilling and cutting oils.
  • the compounds of the formula (I) can also be employed particularly advantageously in livestock keeping (for example cattle, sheep, pigs and poultry such as chickens, geese and the like).
  • livestock keeping for example cattle, sheep, pigs and poultry such as chickens, geese and the like.
  • the compounds if appropriate in suitable formulations (cf. above), are administered orally to the animals, if appropriate together with the drinking water or feed. Since excretion in the feces is highly efficient, the development of insects in the animals' feces can be prevented very easily in this manner.
  • the dosages and formulations which are suitable in each case depend, in particular, on the species and the developmental stage of the productive livestock and also on the risk of infestation and can be determined readily and established by customary methods.
  • the compounds can be employed in cattle at dosages of 0.01 to 1 mg/kg bodyweight.
  • Such fungicides are described e.g. in C.D.S. Tomlin, S.B. Walker, The Pesticide Manual, 11 th ed., British Crop Protection Council, Famham 1997.
  • the invention also relates to seed, treated or coated with an effective amount of a compound according to the invention or of a composition according to the invention. 37
  • the compounds of the formula (I) can also be employed for controlling animal pests in crops of known genetically engineered plants or genetically engineered plants yet to be developed.
  • the transgenic plants are distinguished by especially advantageous properties, for example by resistances to particular crop protection agents, resistances to plant diseases or pathogens of plant diseases, such as particular insects or microorganisms such as fungi, bacteria or viruses.
  • Other particular properties concern, for example, the harvested material with regard to quantity, quality, storage properties, composition and specific constituents.
  • cereals such as wheat, barley, rye, oats, millet, rice, cassava and maize or else crops of sugar beet, cotton, soya, oilseed rape, potatoes, tomatoes, peas and other types of vegetables.
  • the invention therefore also relates to the use of compounds of the formula (I) for controlling harmful organisms in transgenic crop plants.
  • Ethyl lactate (3.26 g, 27.6 mmol) was instilled into a stirred suspension of sodium hydride (95 % dry; 0.66 g, 27.6 mmol) in dry DMF (10 ml) at 5°C. The temperature was allowed to rise to room temperature (r.t.) and after 1.5 hr ( 3-ethoxycarbonylmethylene)- 1-azabicycio [2.2.1] heptane (1.0 g, 5.5 mmol; prepared as described in EP-A 0 363 085) was instilled into the yellow reaction solution. The mixture was stirred at r. t. under nitrogen for 23 hr, acidified with ethanolic HCL solution and then evaporated under reduced pressure.
  • a dust is obtained by mixing 10 parts by weight of active substance and 90 parts by weight of talc as inert material and comminuting the mixture in a hammer mill.
  • a wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of active substance, 65 parts by weight of kaolin-containing quartz as inert material, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurinate as wetter and dispersant and grinding the mixture in a pinned-disk mill.
  • a dispersion concentrate which is readily dispersible in water is prepared by mixing 40 parts by weight of active substance with 7 parts by weight of a sulfosuccinic monoester, 2 parts by weight of a sodium lignosulfonate and 51 parts by weight of water and grinding the mixture in a ball mill to a fineness of below 5 microns.
  • An emulsifiable concentrate can be prepared from 15 parts by weight of active substance, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol (10 EO) as emulsifier.
  • Granules can be prepared from 2 to 15 parts by weight of active substance and an inert granule carrier material such as attapulgite, pumice granules and/or quartz sand. It is expedient to use a suspension of the wettable powder of Example b) with a solids content of 30%, which is sprayed onto the surface of attapulgite granules, and these are dried and mixed intimately.
  • the wettable powder amounts to approx. 5% by weight and the inert carrier material to approx. 95% by weight of the finished granules. 51
  • Bean plants Phaseoius vulgaris which were severely infested with a complete population of spider mites (Tetranychus urticae) were dipped into an aqueous solution ofthe formulated preparation to be tested. After 6 days storage in a controlled- environment cabinet at approx. 25°C, the mortality of all mite stages was determined. At a concentration of 300 ppm (based on the active substance content) a 50 - 100 % mortality was caused by the preparations of examples 2, 4, 6 and 53.
  • Field beans (Vicia faba) which were densly populated with the black bean aphid (Aphis fabae) were dipped for 5 seconds into an aqueous solution ofthe formulated preparation to be tested. The mortality ofthe aphids was determined after 6 days. At a concentration of 300 ppm a 50 - 100 % mortality was shown by the preparation of example 4.
  • Filter paper sections containing approx. 30 24-hour-old eggs of the tobacco budworm (Heliothis virescens) were immersed for 5 seconds into an aqueous solution of the formulated preparation to be tested and subsequently placed in the Petri dish.
  • a further 200 ⁇ l of the aqueous solution were distributed over the nutrient medium.
  • the mortality of the preparation on the eggs and any larvae hatched from them was determined. At a concentration of 300 ppm a 50 - 100 % mortality was shown by the preparations of examples 6, 36, 80 and 81.
  • the leaves of 12 rice plants having a stem length of 8 cm are dipped for 5 seconds into an aqueous solution of the formulated preparation to be examined. After the solution has dripped off, the rice plants are placed in a Petri dish and populated with approximately 20 larvae (L3 stage) of the rice leaf hopper species Niiaparvata lugens. After 6 days' storage at approx. 25°C, the mortality among the leaf hopper larvae is determined. At a concentration of 300 ppm a 50 - 100 % mortality was shown by the preparations of examples 4 and 53.
  • Example 6 Germinated broad bean seeds (Vicia faba) with radicles are transferred into brown glass bottles filled with tap water. Four milliliters of an aqueous solution ofthe formulated preparation to be examined are pipetted into the brown glass bottle. The broad bean is subsequently heavily populated with approximately 100 black bean aphids (Aphis fabae). After 6 days' storage at approx. 25°C, the root-systemic activity ofthe preparation on the aphids is determined. At a concentration of of 30 ppm a mortality of 50-100% among the aphids by root-systemic action was shown by the preparation of examples 4 and 53. 53
  • A represents (CH 2 ) m optionally substituted by R 4 ;
  • B represents (CH 2 ) n optionally substituted by R 5 ;
  • W represents CR 9 R 10 or NR 0 ;
  • X represents an oxygen or sulfur atom
  • Y represents (CO) or C(S);
  • Z 1 ,Z 2 represent oxygen or sulfur;
  • m,n represent an integer from 1 to 3 inclusive;
  • Alk represents a (CrC ⁇ J-alkylene chain
  • R 1 represents H, (C C 6 )-alkyl, COR', COOR', in which R' represents H, (C C 6 )- alkyl or phenyl;
  • R 2 , R 4 , R 5 , R 7 , R 8 , R 9 represent H or (Ci-QO-alkyl;
  • R 3 represent H, (CrC 6 )-alkyl, carboxy, (C ⁇ -C 6 )-alkoxycarbonyl, (CrC 6 )-alkanoyl;
  • R 6 represents a halogen atom, (C C 6 )-alkyl, carboxy, (C ⁇ -C 6 )-alkoxy, (C C ⁇ )- alkylthio, (CrC 6 )-alkanoyloxy, (CrC 6 )-alkylthio; (C C 6 )-alkanoyloxy or (C-i-C ⁇ )- alkanoylthio;
  • R 10 represents hydrogen, (C- ⁇ -C 6 )-alkyl, (C 2 -C 6 )-alkenyl or (C 2 -C 6 )-alkynyl, provided that any two of R 1 , R 4 and R 5 may together form a (C ⁇ -C 3 )-alkylene chain

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Dentistry (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Dispersion Chemistry (AREA)
  • Toxicology (AREA)
  • Materials Engineering (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

L'invention porte sur des composés spiro hétérocycliques (ou leurs sels) de formule (I) dans laquelle les symboles ont la signification donnée dans la description, et qui s'avèrent utiles pour combattre les animaux parasites.
PCT/EP2000/007851 1999-08-13 2000-08-11 Composes spiro heterocycliques utilises comme pesticides Ceased WO2001011968A2 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AU75092/00A AU7509200A (en) 1999-08-13 2000-08-11 Heterocyclic spiro compounds as pesticides
KR1020027001876A KR20020029101A (ko) 1999-08-13 2000-08-11 농약으로서의 헤테로사이클릭 스피로 화합물
EP00964011A EP1209974A2 (fr) 1999-08-13 2000-08-11 Composes spiro heterocycliques utilises comme pesticides
JP2001516331A JP2003506468A (ja) 1999-08-13 2000-08-11 農薬としての複素環式スピロ化合物
BR0013085-0A BR0013085A (pt) 1999-08-13 2000-08-11 Compostos espiro heterocìclicos como pesticidas

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP99115966.6 1999-08-13
EP99115968.2 1999-08-13
EP99115966 1999-08-13
EP99115968 1999-08-13

Publications (2)

Publication Number Publication Date
WO2001011968A2 true WO2001011968A2 (fr) 2001-02-22
WO2001011968A3 WO2001011968A3 (fr) 2001-08-30

Family

ID=26153084

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/007851 Ceased WO2001011968A2 (fr) 1999-08-13 2000-08-11 Composes spiro heterocycliques utilises comme pesticides

Country Status (7)

Country Link
EP (1) EP1209974A2 (fr)
JP (1) JP2003506468A (fr)
KR (1) KR20020029101A (fr)
CN (1) CN1368848A (fr)
AU (1) AU7509200A (fr)
BR (1) BR0013085A (fr)
WO (1) WO2001011968A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9845301B2 (en) 2015-07-31 2017-12-19 Pfizer Inc. 1,1,1-trifluoro-3-hydroxypropan-2-yl carbamate derivatives and 1,1,1-trifluoro-4-hydroxybutan-2-yl carbamate derivatives as MAGL inhibitors
US10329308B2 (en) 2017-01-20 2019-06-25 Pfizer Inc. 1,1,1-trifluoro-3-hydroxypropan-2-yl carbamate derivatives as MAGL inhibitors
US10858373B2 (en) 2017-01-23 2020-12-08 Pfizer Inc. Heterocyclic spiro compounds as MAGL inhibitors

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0601402D0 (en) * 2006-01-24 2006-03-08 Syngenta Participations Ag Chemical Compounds
ITMI20061279A1 (it) * 2006-06-30 2008-01-01 Consiglio Nazionale Ricerche Agonisti nicotinici selettivi per il sottotipo recettoriale alfa7,procedimento per la loro preparazione e relative composizioni farmaceutiche

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RO86918B1 (ro) * 1981-12-21 1985-05-31 Institutul De Cercetari Pentru Pesticide Procedeu pentru prepararea unor derivati tri spiranici
EP0189370A3 (fr) * 1985-01-16 1988-01-27 Sandoz Ag Spiro-dioxolanes, -dithiolanes et -oxothiolanes
EP0311313B1 (fr) * 1987-10-05 1995-05-10 Yamanouchi Pharmaceutical Co. Ltd. Composés spiro hétérocycliques et leur préparation
US5073560A (en) * 1990-07-20 1991-12-17 Fisons Corporation Spiro-isoxazolidine derivatives as cholinergic agents
DE19540736A1 (de) * 1994-12-23 1996-06-27 Bayer Ag 3-Aryl-tetronsäure-Derivate

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9845301B2 (en) 2015-07-31 2017-12-19 Pfizer Inc. 1,1,1-trifluoro-3-hydroxypropan-2-yl carbamate derivatives and 1,1,1-trifluoro-4-hydroxybutan-2-yl carbamate derivatives as MAGL inhibitors
US10428034B2 (en) 2015-07-31 2019-10-01 Pfizer Inc. 1,1,1-trifluoro-3-hydroxypropan-2-yl carbamate derivatives and 1,1,1-trifluoro-4-hydroxybutan-2-yl carbamate derivatives as MAGL inhibitors
US10723711B2 (en) 2015-07-31 2020-07-28 Pfizer Inc. 1,1,1-trifluoro-3-hydroxypropan-2-yl carbamate derivatives and 1,1,1-trifluoro-4-hydroxybutan-2-yl carbamate derivatives as MAGL inhibitors
US10329308B2 (en) 2017-01-20 2019-06-25 Pfizer Inc. 1,1,1-trifluoro-3-hydroxypropan-2-yl carbamate derivatives as MAGL inhibitors
US10626125B2 (en) 2017-01-20 2020-04-21 Pfizer Inc. 1,1,1-trifluoro-3-hydroxypropan-2-yl carbamate derivatives as MAGL inhibitors
US10858373B2 (en) 2017-01-23 2020-12-08 Pfizer Inc. Heterocyclic spiro compounds as MAGL inhibitors

Also Published As

Publication number Publication date
EP1209974A2 (fr) 2002-06-05
BR0013085A (pt) 2002-04-23
WO2001011968A3 (fr) 2001-08-30
CN1368848A (zh) 2002-09-11
JP2003506468A (ja) 2003-02-18
KR20020029101A (ko) 2002-04-17
AU7509200A (en) 2001-03-13

Similar Documents

Publication Publication Date Title
US6265350B1 (en) 1,3-oxazoline and 1,3-thiazoline derivatives, their preparation, and their use as pesticides
JP4366518B2 (ja) 農薬としてのヘテロシクリルニコチンアミド及び類似のピリミジン誘導体
JP4238035B2 (ja) アリールイソオキサゾリン誘導体、その製造方法及び農薬としてのその使用
US6555501B1 (en) 4-trifluoromethyl-3-oxazolylpyridines, processes for their preparation, compositions comprising them and their use as pesticides
US6949551B2 (en) Dihalopropene compounds, processes for their preparation, compositions comprising them and their use as pesticides
US20020032328A1 (en) Heterocyclic acylsulfimides, processes for their preparation, compositions comprising them and their use as pesticides
EP1140922A1 (fr) Trifluoromethyl-4 oxadiazolyl-3 pyridines, leur procede de production, produits les contenant et leur utilisation comme produits de lutte contre les parasites
US20040010145A1 (en) Heterocyclylalkylazole derivatives and their use as pesticides
WO2001011968A2 (fr) Composes spiro heterocycliques utilises comme pesticides
DE10014006A1 (de) Heterocyclische Acylsulfimine, Verfahren zu ihrer Herstellung , sie enthalten Mittel und ihre Verwendung als Schädlingsbekämpfungsmittel
US20040009992A1 (en) Azolylalkylazole derivatives, their preparation, and their use as pesticides
WO2001015532A1 (fr) Composes azabicyclo et azacyclo oximes et amines utilises comme pesticides
AU2008202971B2 (en) Arylisoxazoline derviatives
EP1236727A1 (fr) Composés azabicylco comme pesticides
MXPA00012631A (en) 1,3-oxazoline and 1,3-thiazoline derivatives, method for producing the same and their use as pesticides

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AU AZ BA BB BG BR BY BZ CA CN CR CU CZ DM DZ EE GD GE HR HU ID IL IN IS JP KG KP KR KZ LC LK LR LT LV MA MD MG MK MN MX MZ NO NZ PL RO RU SG SI SK TJ TM TR TT UA UZ VN YU ZA

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
AK Designated states

Kind code of ref document: A3

Designated state(s): AE AG AL AM AU AZ BA BB BG BR BY BZ CA CN CR CU CZ DM DZ EE GD GE HR HU ID IL IN IS JP KG KP KR KZ LC LK LR LT LV MA MD MG MK MN MX MZ NO NZ PL RO RU SG SI SK TJ TM TR TT UA UZ VN YU ZA

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

WWE Wipo information: entry into national phase

Ref document number: 2000964011

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 008115133

Country of ref document: CN

Ref document number: 1020027001826

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 1020027001876

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 1020027001826

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 1020027001826

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 1020027001876

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2000964011

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 2000964011

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1020027001876

Country of ref document: KR