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WO2003004474A1 - Aminoacetonitriles a action pesticide - Google Patents

Aminoacetonitriles a action pesticide Download PDF

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Publication number
WO2003004474A1
WO2003004474A1 PCT/EP2002/007515 EP0207515W WO03004474A1 WO 2003004474 A1 WO2003004474 A1 WO 2003004474A1 EP 0207515 W EP0207515 W EP 0207515W WO 03004474 A1 WO03004474 A1 WO 03004474A1
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Prior art keywords
halo
phenyl
alkyl
trifluoromethyl
unsubstituted
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PCT/EP2002/007515
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English (en)
Inventor
Arthur Steiger
Martin Eberle
Peter Renold
Anthony Cornelius O'sullivan
Werner Zambach
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Syngenta Participations Ag
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Publication of WO2003004474A1 publication Critical patent/WO2003004474A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
    • C07D237/14—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/34—One oxygen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
    • C07D241/16—Halogen atoms; Nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
    • C07D241/18—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
    • C07D241/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom 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 to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/32—Oxygen atoms

Definitions

  • the present invention relates to (1) compounds of formula
  • a and A 2 are each independently of the other unsubstituted or mono- to penta-substituted aryl or unsubstituted or, depending upon the possibility of substitution at the ring, mono- to tetra-substituted heteroaryl bonded via a ring carbon atom; the substituents of Ai and A 2 being selected independently of one another from the group consisting of halogen, cyano, nitro, OH, SH, C C 8 alkyl, halo-C C 8 alkyl, C C 8 alkoxy, halo- CrC 6 alkoxy, C 2 -C 6 alkenyl, halo-C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyloxy, halo-C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C ⁇ -C 6 alkylthi
  • X and Y are each independently of the other a bond, CrCealkylene, C 2 -C 6 alkenylene,
  • C 2 -C 6 alkynylene, phenylene, -O-, -S-, -C( O) ⁇ or a bridge of formula and wherein C- ⁇ -C 6 alkylene, C 2 -C 6 alkenylene, C 2 -C 6 alkynylene and phenylene are unsubstituted or, depending upon the possibility of substitution, are mono- to tetra- substituted independently of one another by substituents selected from the group consisting of halogen, CrC 6 alkoxy, halo-d-C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, cyano, nitro and unsubstituted or mono- to tetra-substituted C 3 -C 6 cycloalkyl, the substituents of C -C 6 cycloalkyl being selected from the group consisting of halogen and C C 6 alkyl;
  • R 2 is C C 6 alkyl, halo-d-C 6 aIkyl, d-Cealkoxy-d-dalkyl, d-C 6 alkylthio-d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl; unsubstituted or substituted C 3 -C 8 cycloalkyl; the substituents being selected independently of one another from the group consisting of halogen and d-C 6 alkyl; or unsubstituted or substituted phenyl, the substituents being selected from the group consisting of halogen, nitro, cyano, CrC 6 alkyl, halo-d-C 6 alkyl, d-C 6 alkoxy, halo- d-C 6 alkoxy, C C 6 alkylthio, haIo-d-C 6 alkylthio, C C 6 alkylsulfinyl, halo-Cr
  • V is d-C 6 alkylene, C 2 -C 6 alkenylene or C 2 -C 6 alkynylene which are unsubstituted or substituted independently of one another by substituents selected from the group consisting of halogen, d-C 6 alkoxy, halo-d-C 6 alkoxy, C C 6 alkylthio, halo-d-C 6 alkylthio; unsubstituted or substituted C 3 -C 8 cycloalkyl; the substituents being selected from the group consisting of halogen and C C 6 alkyl; and unsubstituted or substituted phenyl, the substituents being selected independently of one another from the group consisting of halogen, nitro, cyano, C Cealkyl, halo-C C 6 alkyl, d-C 6 alkoxy, halo-d-C 6 alkoxy, d-C 6 alkylthio, halo-d-C 6 alkyl
  • W is O, S, -S(O)-, -S(O 2 )- or N(R 3 );
  • R 4 and R 5 are each independently of the other hydrogen, CrC 6 alkyl, halo-d-C 6 alkyl, unsubstituted or mono- or poly-substituted C 3 -C 6 cycloalkyl, the substituents being selected independently of one another from the group consisting of halogen and d-C 6 alkyl; or unsubstituted or mono- or poly-substituted phenyl, the substituents being selected independently of one another from the group consisting of halogen, nitro, cyano, d-C 6 alkyl, halo-CrC 6 alkyl, d-C 6 alkoxy, halo-d-C 6 alkoxy, C C 6 aIkylthio, halo-d-C 6 alkylthio, d-C 6 alkylsulfinyl, halo- d-C 6 alkylsulfinyl, d-C 6 a!kylsul
  • the prepared compounds are in the form of mixtures of isomers and of their tautomers, in free form or in salt form. Accordingly, any reference to the compounds of formula (I) hereinabove and hereinbelow is to be understood, where applicable, as including also corresponding isomers, tautomeric forms of the isomers and, where appropriate, the salts of the isomers and tautomers, even if the latter are not specifically mentioned in every case.
  • the compounds of formula (I) and, where applicable, their tautomers may form salts, e.g. acid addition salts.
  • Such salts are formed, for example, with strong inorganic acids, such as mineral acids, e.g. sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted or substituted, e.g. halo-substituted, C C 4 alkane- carboxylic acids, for example acetic acid, saturated or unsaturated dicarboxylic acids, e.g. oxalic, malonic, maleic, fumaric or phthalic acid, hydroxycarboxylic acids, e.g.
  • compounds of formula (I) having at least one acid group may form salts with bases.
  • Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, e.g.
  • sodium, potassium or magnesium salts or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrroli- dine, a mono-, di- or tri-lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propyl- amine, or a mono-, di- or tri-hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine. It may also be possible for corresponding internal salts to be formed. The free form is preferred. Among the salts of compounds of formula (I) preference is given to the agro- chemically advantageous salts.
  • carbon-containing groups and compounds each contain from 1 up to and including 6, preferably from 1 up to and including 4, especially 1 or 2, carbon atoms.
  • Aryl is phenyl or naphthyl.
  • Heteroaryl is especially pyridazinyl, pyrimidyl, pyrazinyl, s-triazinyl, 1 ,2,3-triazinyl, 1 ,2,4-tri- azinyl, tetrazinyl, thienyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, 1 ,2,3- triazolyl, 1 ,2,4-triazolyl, oxazolyl, isoxalyl, thiadiazolyl or oxadiazolyl.
  • Halogen - as a group perse and as a structural element of other groups and compounds, such as haloalkyl, haloalkoxy and haloalkylthio - is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine.
  • Alkyl - as a group perse and as a structural element of other groups and compounds, such as haloalkyl, alkoxy and alkylthio - is, in each case giving due consideration to the number of carbon atoms contained in the group or compound in question, either straight-chained, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, or branched, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
  • Cycloalkyl - as a group perse and as a structural element of other groups and compounds, such as halocycloalkyl, cycloalkoxy and cycloalkylthio - is, in each case giving due consideration to the number of carbon atoms contained in the group or compound in question, cyclo- propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • Alkenyl - as a group perse and as a structural element of other groups and compounds - is, in each case giving due consideration to the number of carbon atoms and conjugated or isolated double bonds contained in the group or compound in question, either straight- chained, e.g. allyl, 2-butenyl, 3-pentenyl, 1 -hexenyl, 1-heptenyl, 1 ,3-hexadienyl or 1 ,3-octa- dienyl, or branched, e.g. isopropenyl, isobutenyl, isoprenyl, tert-pentenyl, isohexenyl, iso- heptenyl or isooctenyl.
  • straight- chained e.g. allyl, 2-butenyl, 3-pentenyl, 1 -hexenyl, 1-heptenyl, 1 ,3-hexadienyl or 1
  • Alkynyl - as a group perse and as a structural element of other groups and compounds - is, in each case giving due consideration to the number of carbon atoms and conjugated or isolated double bonds contained in the group or compound in question, either straight- chained, e.g. propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl, 3-hexen-1 -ynyl or 1 ,5- heptadien-3-ynyl, or branched, e.g. 3-methylbut-1 -ynyl, 4-ethylpent-1 -ynyl, 4-methylhex-2- ynyl or 2-methylhept-3-ynyl.
  • straight- chained e.g. propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl, 3-hexen-1 -yny
  • Halo-substituted carbon-containing groups and compounds such as haloalkyl, haloalkoxy and haloalkylthio, may be partially halogenated or perhalogenated, the halogen substituents in the case of polyhalogenation being the same or different.
  • haloalkyl - as a group perse and as a structural element of other groups and compounds, such as halo- alkoxy and haloalkylthio - are methyl substituted from one to three times by fluorine, chlorine and/or bromine, such as CHF 2 or CF 3 ; ethyl substituted from one to five times by fluorine, chlorine and/or bromine, such as CH 2 CF 3 , CF 2 CF 3 , CF 2 CCI 3 , CF 2 CHCI 2 , CF 2 CHF 2 , CF 2 CFCI 2 , CF 2 CHBr 2 , CF 2 CHCIF, CF 2 CHBrF or CCIFCHCIF; propyl or isopropyl substituted from one to seven times by fluorine, chlorine and/or bromine, such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 , CH 2 CF 2 CF 3 or CH(CF 3 ) 2 ; butyl
  • A is an unsubstituted or substituted heterocyclic 5-membered ring; preferably a ring having from 1 to 3 nitrogen atoms or having 1 or 2 nitrogen atoms and an oxygen or sulfur atom; especially having two nitrogen atoms or a nitrogen atom and a sulfur atom;
  • a ⁇ is an unsubstituted or substituted heterocyclic 6-membered ring; preferably a ring having from 1 to 3 nitrogen atoms or having 1 or 2 nitrogen atoms and an oxygen or sulfur atom; especially having two nitrogen atoms or a nitrogen atom and a sulfur atom;
  • Ai is an unsubstituted or substituted heterocyclic 5-membered ring; preferably a ring having from 1 to 3 nitrogen atoms or having 1 or 2 nitrogen atoms and an oxygen or sulfur atom; especially having a sulfur atom or a nitrogen atom and a sulfur atom;
  • A is an unsubstituted or substituted heterocyclic 6-membered ring; preferably a ring having from 1 to 3 nitrogen atoms or having 1 or 2 nitrogen atoms and an oxygen or sulfur atom; especially having two nitrogen atoms or a nitrogen atom and a sulfur atom;
  • the invention relates also to a process for the preparation of the compounds of formula (I) wherein A ⁇ A 2 , X, Y, R 1 ( R 2 , R 3 , R 4 , R 5 , n and V are as defined above for formula (I), and W is O, S, -S(O 2 )- or N(R 3 ), in which process
  • A-X - Y- ⁇ (Ml), O which is known or can be prepared by methods known perse and in which Ai, X and Y are as defined for formula (I) and Q is a leaving group, especially chlorine;
  • the invention relates also to a process for the preparation of the compounds of formula (I) above and, where applicable, their tautomers, in each case in free form or in salt form, in which process
  • R 4 , R 5 , V, W, n and A 2 are as defined for formula (I);
  • R 3 , R 4 , R 5 , V, W, n and A 2 are as defined for formula (I);
  • R 1 ; R 2 , R , R 5 , V, W, n and A 2 are as defined for formula (I);
  • the invention relates also to a process for the preparation of the compounds of formula (I) above and, where applicable, their tautomers, in each case in free form or in salt form, in which process
  • R 5 which is known or can be prepared by methods known per se and in which R 4 , R 5 , n, A 2 and W are as defined for formula (I), to form a compound of formula (VIII) above; and that compound of formula (VIM) is reacted further analogously to process steps (e) and (f) above.
  • the reactions described hereinabove and hereinbelow are carried out in a manner known per se, for example in the absence or, customarily, in the presence of a suitable solvent or diluent or of a mixture thereof, the reactions being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range of approximately from -80°C to the boiling temperature of the reaction medium, preferably from approximately 0°C to approximately +150°C, and, if necessary, in a closed vessel, under pressure, under an inert gas atmosphere and/or under anhydrous conditions.
  • a suitable solvent or diluent or of a mixture thereof the reactions being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range of approximately from -80°C to the boiling temperature of the reaction medium, preferably from approximately 0°C to approximately +150°C, and, if necessary, in a closed vessel, under pressure, under an inert gas atmosphere and/or under anhydrous conditions.
  • reaction time is not critical; a reaction time of from about 0.1 to about 24 hours, especially from about 0.5 to about 10 hours, is preferred.
  • the product is isolated by customary methods, for example by means of filtration, crystallisation, distillation or chromatography, or any suitable combination of such methods.
  • Suitable leaving groups Q in the compounds of formula (III) are e.g. hydroxy, d-C 8 alkoxy, halo-d-C 8 alkoxy, C C 8 alkanoyloxy, mercapto, d-C 8 alkylthio, halo-C C 8 alkylthio, d-C 8 - alkanesulfonyloxy, haIo-d-C 8 alkanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen, preferably toluenesulfonyloxy, trifluoromethanesulfonyloxy and halogen, especially halogen; more especially chlorine.
  • solvents and diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene and tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran and diox
  • a base e.g. alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or alkylsilylamides; alkylamines, alkylenediammes, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and also carbo- cyclic amines.
  • a base e.g. alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or alkylsilylamides; alkylamines, alkylenediammes, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and also carbo- cyclic amines.
  • Examples include sodium hydroxide, hydride, amide, methanolate, acetate and carbonate, potassium tert-butanolate, hydroxide, carbonate and hydride, lithium diiso- propylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropyl- ethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyI-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methyl- morpholine, benzyltrimethylammonium hydroxide and 1 ,5-diazabicyclo[5.4.0]undec-5-ene (DBU).
  • DBU benzyltrimethylammonium hydroxide
  • the reactions are advantageously carried out in a temperature range of from about room temperature to the boiling point of the solvent used, preferably from room temperature to about +150°C.
  • Suitable solvents and diluents include those mentioned under process variant (a). Preference is given to amides, for example dimethylformamide and dimethylacetamide.
  • Suitable bases for facilitating the reaction include those mentioned under process variant a).
  • Suitable solvents and diluents include those mentioned under process variant a).
  • Ethers for example tetrahydrofuran or dioxane, are preferred.
  • the reaction is advantageously carried out in a temperature range of from about 0°C to about 100°C, preferably at room temperature.
  • Suitable bases for facilitating the reaction include those mentioned under process variant a). Special preference is given to trialkylamines and alcoholates.
  • Suitable solvents and diluents include those mentioned under process variant (a).
  • Halogenated hydrocarbons such as methylene chloride, are preferred.
  • the reaction is advantageously carried out in a temperature range of from about -70°C to about +20°C, preferably at from -60°C to room temperature.
  • Suitable oxidising agents are e.g. inorganic oxides, such as sodium perborate, potassium permanganate, chromium trioxide and K 2 Cr 2 O 7 ; or hydrogen peroxide, NaOCI in acetic acid, or organic peracids, such as perbenzoic acid or peracetic acid; mixtures of organic acids and hydrogen peroxide, e.g. acetic acid/hydrogen peroxide; or a mixture of dimethyl sulfoxide and oxalyl chloride.
  • inorganic oxides such as sodium perborate, potassium permanganate, chromium trioxide and K 2 Cr 2 O 7 ; or hydrogen peroxide, NaOCI in acetic acid, or organic peracids, such as perbenzoic acid or peracetic acid
  • mixtures of organic acids and hydrogen peroxide e.g. acetic acid/hydrogen peroxide
  • dimethyl sulfoxide and oxalyl chloride e.g. acetic
  • Suitable solvents and diluents include especially water-miscible solvents, more especially cyclic ethers, such as dioxane and tetrahydrofuran, and water. Preference is given to a procedure in which the corresponding required base of formula NHRi is used in the form of its aqueous solution.
  • alkali metal cyanides such as sodium or potassium cyanide, and also zinc or copper cyanide.
  • the reaction is advantageously carried out at from room temperature to +60°C.
  • Suitable solvents and diluents include those mentioned under process variant (a). Preference is given to ketones, e.g. acetone; or ethers, e.g. tetrahydrofuran; or amides, such as dimethylformamide.
  • Suitable bases include especially carbonates, such as potassium or sodium carbonate, or metal alcoholates, such as sodium methanolate or potassium tert-butanolate.
  • Suitable halides in the compounds of formula (X) include especially chlorine and bromine, preferably chlorine.
  • Iodide salts for example sodium iodide or potassium iodide, can be added to catalyse the reaction.
  • Salts of compounds of formula (I) can be prepared in a manner known perse. For example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchange reagent, and salts with bases are obtained by treatment with a suitable base or a suitable ion exchange reagent.
  • Salts of compounds of formula (I) can be converted into the free compounds of formula (I) in customary manner; acid addition salts, for example, by treatment with a suitable basic agent or a suitable ion exchange reagent, and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent.
  • Salts of compounds of formula (I) can be converted into different salts of compounds of formula (I) in a manner known perse; acid addition salts, for example, can be converted into different acid addition salts, for example by treating a salt of an inorganic acid, such as a hydrochloride, with a suitable metal salt, such as a sodium, barium or silver salt, of an acid, for example silver acetate, in a suitable solvent in which an inorganic salt that forms, for example silver chloride, is insoluble and therefore separates out of the reaction mixture.
  • a salt of an inorganic acid such as a hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • an acid for example silver acetate
  • the compounds of formula (I) having salt-forming properties can be obtained in free form or in the form of salts.
  • the compounds of formula (I) may be in the form of one of the possible isomers or in the form of a mixture thereof, in the form of pure isomers or in the form of an isomeric mixture, i.e. in the form of a racemic mixture; the invention relates both to the pure isomers and to the racemic mixtures and is to be interpreted accordingly hereinabove and hereinbelow, even if stereochemical details are not mentioned specifically in every case.
  • racemates can be resolved into the optical antipodes by known methods, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, for example high pressure liquid chromatography (HPLC) on acetylcellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilised enzymes, or via the formation of inclusion compounds, for example using chiral crown ethers, only one isomer being complexed.
  • HPLC high pressure liquid chromatography
  • pure optical isomers can be obtained according to the invention also by generally known methods of enantioselective synthesis; or by carrying out the process according to the invention using starting materials having correspondingly suitable stereochemistry.
  • the compounds of formula (I) may also be obtained in the form of their hydrates and/or may include other solvents, for example solvents which may have been used for the crystallisation of compounds in solid form.
  • the invention relates to all those embodiments of the process according to which a compound obtainable as starting material or intermediate at any stage of the process is used as starting material and some or all of the remaining steps are carried out or a starting material is used in the form of a derivative or salt and/or its racemates or antipodes or, especially, is formed under the reaction conditions.
  • the invention relates especially to the preparation process described in Examples P.1 to P.4.
  • the compounds of formula (I) according to the invention are active ingredients exhibiting valuable preventive and/or curative activity with a very advantageous biocidal spectrum and a very broad spectrum, even at low rates of concentration, while being well tolerated by warm-blooded animals, fish and plants. They are, surprisingly, equally suitable for controlling both plant pests and ecto- and endo-parasites in humans and more especially in productive livestock, domestic animals and pets. They are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and representatives of the order Acarina, nematodes, cest- odes and trematodes, while at the same time protecting useful organisms.
  • the insecticidal or acaricidal activity of the active ingredients according to the invention may manifest itself directly, i.e. in the mortality of the pests, which occurs immediately or only after some time, for example on moulting, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %.
  • Suitable additives include, for example, representatives of the following classes of active ingredient: organophosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations.
  • mixing partners include: azamethiphos; chlorfenvinphos; cypermethrin, cypermethrin high-cis; cyromazine; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; iodofenphos; kino- prene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; diofenolan; a substance obtainable from the Bacillus thuringiensis strain GC91 or from NCTC11821 ; pymetrozine; bromopropylate; methoprene; disulfuton; quinalphos; tau- fluvalinate; thiocyclam; thiometon; aldicarb; azinphos-methyl
  • the said animal pests include, for example, those mentioned in European Patent Application EP-A-736 252, page 5, line 55, to page 6, line 55.
  • the pests mentioned therein are therefore included by reference in the subject matter of the present invention.
  • pests of the class Nematoda include, for example, root knot nematodes, cyst-forming nematodes and also stem and leaf nematodes; especially of Heterodera spp., e.g. Heterodera schachtii, Heterodora avenae and Heterodora trifolii; Globodera spp., e.g. Globodera rostochiensis; Meloidogyne spp., e.g. Meloidogyne incognita and Meloidogyne javanica; Radopholus spp., e.g.
  • Pratylen- chus e.g. Pratylenchus neglectans and Pratylenchus penetrans
  • Tylenchulus e.g. Tylen- chulus semipenetrans
  • Meloidogyne e.g. Mel
  • An especially important aspect of the present invention is the use of the compounds of formula (I) according to the invention in the protection of plants against parasitic feeding pests.
  • the active ingredients according to the invention can be used to control, i.e. to inhibit or destroy, pests of the mentioned type occurring on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as the fruits, blossoms, leaves, stems, tubers or roots, while in some cases plant parts that grow later are still protected against those pests.
  • Target crops include especially cereals, such as wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, e.g. pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, e.g.
  • strawberries, raspberries and blackberries leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil, cocoa and groundnuts; cucurbitaceae, such as marrows, cucumbers and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruits, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocado, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas, natural rubber plants and ornamentals.
  • active ingredients according to the invention are the protection of stored goods and storerooms and the protection of raw materials, and also in the hygiene sector, especially the protection of domestic animals and productive livestock against pests of the mentioned type, more especially the protection of domestic animals, especially cats and dogs, from attack by fleas, ticks and nematodes.
  • the invention therefore relates also to pesticidal compositions, such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules and encapsulations of polymer substances, that comprise at least one of the active ingredients according to the invention, the choice of formulation being made in accordance with the intended objectives and the prevailing circumstances.
  • pesticidal compositions such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules and encapsulations of polymer substances, that comprise at least one of the active ingredients according to the invention, the choice of formulation being made in accordance with the intended objectives and the prevailing circumstances.
  • the active ingredient is used in those compositions in pure form, a solid active ingredient, for example, in a specific particle size, or preferably together with at least one of the adjuvants customary in formulation technology, such as extenders, e.g. solvents or solid carriers, or surface-active compounds (surfactants).
  • extenders e.g. solvents or solid carriers
  • surfactants surface-active compounds
  • formulation adjuvants there are used, for example, solid carriers, solvents, stabilisers, "slow release” adjuvants, colourings and optionally surface-active substances (surfactants).
  • Suitable carriers and adjuvants include all substances customarily used.
  • adjuvants such as solvents, solid carriers, surface-active compounds, non-ionic surfactants, cationic surfactants, anionic surfactants and further adjuvants in the compositions used according to the invention, there come into consideration, for example, those described in EP-A-736 252, page 7, line 51 to page 8, line 39.
  • Dusts active ingredient: 0.1 to 10%, preferably 0.1 to 1 % solid carrier: 99.9 to 90%, preferably 99.9 to 99%
  • Suspension concentrates active ingredient: 5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30%
  • Wettable powders active ingredient: 0.5 to 90%, preferably 1 to 80% surfactant: 0.5 to 20%, preferably 1 to 15% solid carrier: 5 to 99%, preferably 15 to 98%
  • Granules active ingredient: 0.5 to 30%, preferably 3 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%
  • compositions according to the invention may also comprise further solid or liquid adjuvants, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders and/or tackifiers as well as fertilisers or other active ingredients for obtaining special effects, e.g. acaricides, bactericides, fungicides, nema- ticides, molluscicides or selective herbicides.
  • stabilisers e.g. vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders and/or tackifiers as well as fertilisers or other active ingredients for obtaining special effects,
  • the crop protection products according to the invention are prepared in known manner, in the absence of adjuvants, e.g. by grinding, sieving and/or compressing a solid active ingredient or mixture of active ingredients, for example to a certain particle size, and in the presence of at least one adjuvant, for example by intimately mixing and/or grinding the active ingredient or mixture of active ingredients with the adjuvant(s).
  • the invention relates likewise to those processes for the preparation of the compositions according to the invention and to the use of the compounds of formula (I) in the preparation of those compositions.
  • the invention relates also to the methods of application of the crop protection products, i.e.
  • Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient.
  • the rates of application per hectare are generally from 1 to 2000 g of active ingredient per hectare, especially from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.
  • a preferred method of application in the area of crop protection is application to the foliage of the plants (foliar application), the frequency and the rate of application being dependent upon the risk of infestation by the pest in question.
  • the active ingredient can also penetrate the plants through the roots (systemic action) when the locus of the plants is impregnated with a liquid formulation or when the active ingredient is incorporated in solid form, e.g. in granular form, into the locus of the plants, for example into the soil (soil application).
  • granules may be applied in metered amounts to the flooded rice field.
  • the crop protection products according to the invention are also suitable for protecting plant propagation material, e.g. seed material, such as fruits, tubers or grains, or plant cuttings, against animal pests.
  • the propagation material can be treated with the composition before planting: seed, for example, can be dressed before being sown.
  • the active ingredients according to the invention can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation.
  • the composition can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing.
  • the invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
  • P.1 b) 185 mg of potassium tert-butanolate are added to a solution of 300 mg of N-(1-cyano- 2-hydroxy-1 -methyl-ethyl)-4-trifluoromethyl-benzamide in 1.5 ml of dimethylformamide and the mixture is stirred at room temperature for 45 minutes. Then 221 mg of 4-chloro-6- trifluoromethylpyrimidine are added and the mixture is stirred at room temperature for 20 hours. The reaction mixture is poured into water and extracted with ethyl acetate. After purification over silica gel, the title product having a melting point of 216-218°C is obtained.
  • N-[1 -Cyano-1 -methyl-2-(5-trif luoromethyl-thiophen-3-yloxy)-ethyl]-4-tri- fluoromethyl-benzamide are obtained after purification over silica gel. Melting point: 83-87°C.
  • Example P.5 In a manner analogous to that described in Examples P.1 to P.4 it is also possible to prepare the compounds of formula (I) listed in Tables 1 to 44.
  • A.1 1 4-fluoro-phenyl - CH 3 0
  • A.231 4-(4-chlorophenoxy)-phenyl CH 2 - CH 3 0
  • A.231 4-(3-chlorophenoxy)-phenyl -CH 2 - H 0
  • A.555 4-cyclopropyl-2-methyl-thiazol-5-yl - CH 3 0
  • A.557 4-cyclopropyl-2-methyl-thiazol-5-yl -CH 2 - H 0
  • A.558 4-cyclopropy!-2-methyl-thiazol-5-yl -CH 2 - H 1
  • A.559 4-cyclopropyl-2-methyl-thiazol-5-yl -CH 2 - CH 3 0
  • A.560 4-cyclopropyl-2-methyl-thiazol-5-yl -CH 2 - CH 3 1
  • A.566 4-methyl-2-trifluoromethyl-thiazol-5-yl -CH 2 - H 1
  • A.601 1-methyl-3-trifluoromethyl-pyrazol-4-yl - H 0
  • A.630 4-trifluoromethyl-thiadiazol-5-yl -CH 2 - H 1
  • A.631 4-trifluoromethyl-thiadiazol-5-yl -CH 2 - CH 3 0
  • A.632 4-trifluoromethyl-thiadiazol-5-yl -CH 2 - CH 3 1
  • Table 1 A compound of general formula (la) wherein A 2 is 3-chloro-pyridazin-6-yl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.1 to A.632 of Table A.
  • Table 2 A compound of general formula (la) wherein A 2 is 3-methyl-pyridazin-6-yl and the combination of meanings of A-i, X, Y, R 2 and n for each compound corresponds to a line A.1 to A.632 of Table A.
  • Table 3 A compound of general formula (la) wherein A 2 is 6-chloro-pyrazin-2-yl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.1 to A.632 of Table A.
  • Table 4 A compound of general formula (la) wherein A 2 is 4,6-dichloro-triazin-2-yl and the combination of meanings of A-,, X, Y, R 2 and n for each compound corresponds to a line A.1 to A.632 of Table A.
  • Table 5 A compound of general formula (la) wherein A 2 is 2-trifiuoromethyl-thiophen-4-yl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.1 to A.632 of Table A.
  • Table 6 A compound of general formula (la) wherein A 2 is pyrimidin-2-yl and the combination of meanings of A 1 ( X, Y, R 2 and n for each compound corresponds to a line A.1 to A.632 of Table A.
  • Table 7 A compound of general formula (la) wherein A 2 is 4,6-dichloro-pyrimidin-2-yl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.1 to A.632 of Table A.
  • Table 8 A compound of general formula (la) wherein A 2 is 2,6-dichloro-pyrimidin-4-y
  • Table 9 A compound of general formula (la) wherein A 2 is 4-chloro-pyrimidin-2-yl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.1 to A.632 of Table A.
  • Table 10 A compound of general formula (la) wherein A 2 is 2-chloro-pyrimidin-4-yl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.1 to A.632 of Table A.
  • Table 11 A compound of general formula (la) wherein A 2 is 6-chloro-2-trifluoromethyl- pyrimidin-4-yl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.1 to A.632 of Table A.
  • Table 12 A compound of general formula (la) wherein A 2 is 6-chloro-2-trichloromethyl- pyrimidin-4-yl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.1 to A.632 of Table A.
  • Table 13 A compound of general formula (la) wherein A 2 is 2-trifluoromethyl-pyrimidin-5-y! and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.1 to A.632 of Table A.
  • Table 14 A compound of general formula (la) wherein A 2 is 2-trif luoromethyl-pyrimidin-4-yl and the combination of meanings of A-i, X, Y, R 2 and n for each compound corresponds to a line A.1 to A.632 of Table A.
  • Table 15 A compound of general formula (la) wherein A 2 is 6-trif luoromethyl-pyrimidin-4-yl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.1 to A.632 of Table A.
  • Table 16 A compound of general formula (la) wherein A 2 is 4-chloro-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 17 A compound of general formula (la) wherein A 2 is 4-fluoro-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 18 A compound of general formula (la) wherein A 2 is 4-trifluoromethyl-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 19 A compound of general formula (la) wherein A 2 is 4-trifluoromethoxy-phenyl and the combination of meanings of A 1 ⁇ X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 20 A compound of general formula (la) wherein A 2 is 4-methoxy-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 21 A compound of general formula (la) wherein A 2 is 4-methyl-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 22 A compound of general formula (la) wherein A 2 is 4-cyano-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 23 A compound of general formula (la) wherein A 2 is 4-nitro-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 24 A compound of general formula (la) wherein A 2 is 4-tert-butyl-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 25 A compound of general formula (la) wherein A 2 is 3-chloro-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 26 A compound of general formula (la) wherein A 2 is 3-fluoro-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 27 A compound of general formula (la) wherein A 2 is 3-trifluoromethyl-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 28 A compound of general formula (la) wherein A 2 is 3-trifluoromethoxy-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 29 A compound of general formula (la) wherein A 2 is 3-methoxy-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 30 A compound of general formula (la) wherein A 2 is 3-methyl-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 31 A compound of general formula (la) wherein A 2 is 3-cyano-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 32 A compound of general formula (la) wherein A 2 is 3-nitro-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 33 A compound of general formula (la) wherein A 2 is 2-chloro-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 34 A compound of general formula (la) wherein A 2 is 2-fluoro-phenyl and the combination of meanings of A-i, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 35 A compound of general formula (la) wherein A 2 is 2-trifluoromethyl-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 36 A compound of general formula (la) wherein A 2 is 2-trifluoromethoxy-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 37 A compound of general formula (la) wherein A 2 is 2-cyano-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 38 A compound of general formula (la) wherein A 2 is 2-nitro-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 39 A compound of general formula (la) wherein A 2 is 3,4-dichloro-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 40 A compound of general formula (la) wherein A 2 is 2,4-dichloro-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 41 A compound of general formula (la) wherein A 2 is 3,5-dichloro-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 42 A compound of general formula (la) wherein A 2 is 2,6-dichloro-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 43 A compound of general formula (la) wherein A 2 is 3-fluoro-4-chloro-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Table 44 A compound of general formula (la) wherein A 2 is 2,4,6-trichloro-phenyl and the combination of meanings of Ai, X, Y, R 2 and n for each compound corresponds to a line A.241 to A.632 of Table A.
  • Example F1 Emulsifiable concentrates a) b) c) active ingredient 25% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol ether 5% - -
  • Example F2 Solutions a) b) c) d) active ingredient 80% 10% 5% 95% ethylene glycol monomethyl ether 20% - - - polyethylene glycol (MW 400) - 70% - -
  • N-methylpyrrolid-2-one 20% - - epoxidised coconut oil - - 1% 5% petroleum ethers (boiling range: 160-190°) _ _ 94% _
  • Example F3 Granules a) b) ) d) active ingredient 5% 10% 8% 21 % kaolin 94% - 79% 54% highly disperse silicic acid 1 % _ 13% 7% attapulgite - 90% - 18%
  • the active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier mixture and the solvent is evaporated off in vacuo.
  • Example F4 Wettable powders a) b) c) active ingredient 25% 50% 75% sodium lignosulfonate 5% 5% - sodium lauryl sulfate 3% - 5% sodium diisobutylnaphthalenesulfonate - 6% 10% octylphenol polyethylene glycol ether - 2% -
  • Example F5 Emulsifiable concentrate active ingredient 10% octylphenol polyethylene glycol ether 3%
  • Example F6 Extruder granules active ingredient 10% sodium lignosulfonate 2% carboxymethylcellulose 1% kaolin 87%
  • Active ingredient and additives are mixed together and the mixture is ground, moistened with water, extruded and granulated, and the granules are dried in a stream of air.
  • Example F7 Coated granules active ingredient 3% polyethylene glycol (MW 200) 3% kaolin 94%
  • Example F8 Suspension concentrate active ingredient 40% ethylene glycol 10% nonylphenol polyethylene glycol ether 6%
  • Example B1 Action against Aphis craccivora
  • Pea seedlings are infested with Aphis craccivora, subsequently sprayed with a spray mixture comprising 100 ppm of active ingredient and then incubated at 20°C. 3 and 6 days later the percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants.
  • the compounds of the Tables exhibit good activity in this test.
  • the compounds prepared in Examples P.1 to P.3 exhibit an activity of more than 80 %.
  • Maize seedlings are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of active ingredient and, after the spray-coating has dried, are populated with 10 Diabrotica balteata larvae in the second stage and then placed in a plastics container. 6 days later, the percentage reduction in population (% activity) is determined by comparing the number of dead larvae on the treated plants with that on untreated plants.
  • the compounds of the Tables exhibit good activity in this test. In particular, the compounds prepared in Examples P.1 to P.3 exhibit an activity of more than 80 %.
  • Example B3 Action against Heliothis virescens
  • Example B4 Action against Spodoptera littoralis
  • Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of active ingredient and, after the spray-coating has dried, are populated with 10 caterpillars of Spodoptera littoralis in the third stage and then placed in a plastics container. 3 days later, the percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
  • the compounds of the Tables exhibit good activity in this test. In particular, the compounds prepared in Examples P.1 to P.3 exhibit an activity of more than 80 %.
  • Example B5 Action against Nilaparvata lugens
  • Rice plants are treated with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After the spray-coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stages. The evaluation is carried out 21 days later. The percentage reduction in population (% activity) is determined by comparing the number of surviving cicadas on the treated plants with that on untreated plants The compounds of the Tables exhibit good activity in this test.
  • Example B6 Action against Tetranychus urticae
  • Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed 1 day later with an aqueous emulsion spray mixture comprising 100 ppm of active ingredient, incubated for 6 days at 25°C and then evaluated.
  • the percentage reduction in population is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on untreated plants.
  • the compounds of the Tables exhibit good activity in this test.
  • the compounds prepared in Examples P.1 to P.3 exhibit an activity of more than 80 %.

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Abstract

L'invention concerne des composés de formule (I). Dans ladite formule, A1 et A2 sont chacun indépendamment aryle non substitué ou bien mono ou pentasubstitué, ou bien encore, en fonction de la possibilité de substitution sur la chaîne, hétéroaryle mono ou tétrasubstitué lié via un atome de carbone sur la chaîne; X et Y sont chacun indépendamment une liaison, alkylène C1-C6, alcénylène C2-C6, alkynylène C2-C6, phénylène, -O-, -S- ou C(=O)-; R1 est, par exemple, hydrogène, alkyle C1-C6 ou haloalkyle C1-C6; R2 est, par exemple, alkyle C1-C6, haloalkyle C1-C6 ou alcoxy C1-C6-alkyle C1-C6; V est alkylène C1-C6, alcénylène C2-C6 ou alkynylène C2-C6; W est O, S, -S(O)-, -S(O)-, -S(O2)- ou N(R3); et R3 est hydrogène, alkyle C1-C6, -C(=O)-alkyle C1-C6 ou alkyle C1-C6 ou alkyle C1-C6-O-alkyle C1-C6; n vaut 0 ou 1; et, lorsque n vaut 1, R4 et R5 sont, par exemple, hydrogène, alkyle C1-C6 ou haloalkyle C1-C6; et, le cas échéant, l'invention englobe les diastéréoisomères, les isomères E/Z, les mélanges isomères E/Z et/ou les tautomères des composés considérés, dans chaque cas sous forme libre ou sous forme sel. L'invention concerne également un procédé pour l'élaboration des composés en question et de leurs tautomères, y compris leur utilisation. Elle concerne par ailleurs: des pesticides dans lesquels le principe actif est l'un des composés considérés, y compris leurs tautomères; un procédé pour l'élaboration des mêmes compositions et leur utilisation; des intermédiaires, sous forme libre ou sous forme sel, pour l'élaboration des composés décrits et, le cas échéant, leurs tautomères, sous forme libre ou sous forme sel.
PCT/EP2002/007515 2001-07-06 2002-07-05 Aminoacetonitriles a action pesticide WO2003004474A1 (fr)

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WO2002049641A3 (fr) * 2000-12-20 2003-12-04 Novartis Ag Composes organiques
WO2003080577A3 (fr) * 2002-03-21 2004-07-01 Novartis Ag Composes organiques
JP2008501761A (ja) * 2004-06-10 2008-01-24 ノバルティス アクチエンゲゼルシャフト アミノアセトニトリル誘導体及び温血動物上の寄生虫を駆除するためのこれらの使用
WO2009012998A1 (fr) * 2007-07-26 2009-01-29 Syngenta Participations Ag Nouveaux microbiocides
US7494956B2 (en) 2003-11-06 2009-02-24 Novartis Ag Amidoacetonitrile derivatives
WO2009127718A3 (fr) * 2008-04-18 2010-02-04 Syngenta Participations Ag Nouveaux microbiocides
WO2015000929A1 (fr) * 2013-07-01 2015-01-08 Universität Zürich Dérivés de n-(1-cyano-2-hydroxy-1-méthyl-éthyl)-4-(trifluorométhylsulfanyl) benzamide en vue d'une utilisation comme médicaments nématocides
US9126944B2 (en) 2013-02-28 2015-09-08 Bristol-Myers Squibb Company Phenylpyrazole derivatives as potent ROCK1 and ROCK2 inhibitors
WO2016137010A1 (fr) * 2015-02-24 2016-09-01 Nihon Nohyaku Co., Ltd. Agent anticancéreux comprenant un composé d'aminoacétonitrile en tant que principe actif
JP2016531841A (ja) * 2013-09-13 2016-10-13 日本農薬株式会社 アミノアセトニトリル化合物を有効成分として含有する抗癌剤
US9828345B2 (en) 2013-02-28 2017-11-28 Bristol-Myers Squibb Company Phenylpyrazole derivatives as potent ROCK1 and ROCK2 inhibitors
EP3612526A2 (fr) * 2017-04-20 2020-02-26 The Regents of the University of California Modulateurs de k-ras
US10647705B2 (en) 2017-11-14 2020-05-12 Merck Sharp & Dohme Corp. Substituted biaryl compounds as indoleamine 2,3-dioxygenase (IDO) inhibitors
US11498904B2 (en) 2017-11-14 2022-11-15 Merck Sharp & Dohme Llc Substituted biaryl compounds as indoleamine 2,3-dioxygenase (IDO) inhibitors
US11541044B2 (en) 2015-05-06 2023-01-03 The Regents Of The University Of California K-Ras modulators

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WO2002049641A2 (fr) * 2000-12-20 2002-06-27 Novartis Ag Composes organiques
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EP0953565A2 (fr) * 1998-05-01 1999-11-03 Nihon Nohyaku Co., Ltd. Dérivés d'acétonitrile, insecticides utilisables dans l'agriculture et l'horticulture les contenant et leur utilisation
WO2002049641A2 (fr) * 2000-12-20 2002-06-27 Novartis Ag Composes organiques
WO2002051822A2 (fr) * 2000-12-22 2002-07-04 Nihon Bayer Agrochem K.K. Isothiazolecarboxamides

Cited By (27)

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US7700656B2 (en) 2000-12-20 2010-04-20 Novartis Ag Organic compounds
WO2002049641A3 (fr) * 2000-12-20 2003-12-04 Novartis Ag Composes organiques
WO2003080577A3 (fr) * 2002-03-21 2004-07-01 Novartis Ag Composes organiques
US7494956B2 (en) 2003-11-06 2009-02-24 Novartis Ag Amidoacetonitrile derivatives
JP2008501761A (ja) * 2004-06-10 2008-01-24 ノバルティス アクチエンゲゼルシャフト アミノアセトニトリル誘導体及び温血動物上の寄生虫を駆除するためのこれらの使用
WO2009012998A1 (fr) * 2007-07-26 2009-01-29 Syngenta Participations Ag Nouveaux microbiocides
US8324263B2 (en) 2007-07-26 2012-12-04 Syngenta Crop Protection, Llc Microbiocidally active carboxamides
WO2009127718A3 (fr) * 2008-04-18 2010-02-04 Syngenta Participations Ag Nouveaux microbiocides
US9458110B2 (en) 2013-02-28 2016-10-04 Bristol-Myers Squibb Company Phenylpyrazole derivatives as potent ROCK1 and ROCK2 inhibitors
US9126944B2 (en) 2013-02-28 2015-09-08 Bristol-Myers Squibb Company Phenylpyrazole derivatives as potent ROCK1 and ROCK2 inhibitors
US9828345B2 (en) 2013-02-28 2017-11-28 Bristol-Myers Squibb Company Phenylpyrazole derivatives as potent ROCK1 and ROCK2 inhibitors
AU2014286221B2 (en) * 2013-07-01 2018-05-31 The University Of Melbourne N-(1-cyano-2-hydroxy-1-methyl-ethyl)-4-(trifluoromethylsulfanyl)benzamide derivatives for use as nematocidal drugs
WO2015000929A1 (fr) * 2013-07-01 2015-01-08 Universität Zürich Dérivés de n-(1-cyano-2-hydroxy-1-méthyl-éthyl)-4-(trifluorométhylsulfanyl) benzamide en vue d'une utilisation comme médicaments nématocides
JP2016523281A (ja) * 2013-07-01 2016-08-08 ウニヴェルズィテート チューリッヒ 殺線虫薬として使用されるｎ−（１−シアノ−２−ヒドロキシ−１−メチル）−４−（トリフルオロメチルスルファニル）ベンズアミド誘導体
CN105658056B (zh) * 2013-07-01 2018-03-06 苏黎世大学 用作杀线虫药物的n‑(1‑氰基‑2‑羟基‑1‑甲基‑乙基)‑4‑(三氟甲基巯基)苯甲酰胺衍生物
CN105658056A (zh) * 2013-07-01 2016-06-08 苏黎世大学 用作杀线虫药物的n-(1-氰基-2-羟基-1-甲基-乙基)-4-(三氟甲基巯基)苯甲酰胺衍生物
JP2016531841A (ja) * 2013-09-13 2016-10-13 日本農薬株式会社 アミノアセトニトリル化合物を有効成分として含有する抗癌剤
US9907778B2 (en) * 2013-09-13 2018-03-06 Pitney Pharmaceuticals Pty Limited Anticancer agent comprising aminoacetonitrile compound as active ingredient
US10292960B2 (en) 2013-09-13 2019-05-21 Pitney Pharmaceuticals Pty Limited Anticancer agent comprising aminoacetonitrile compound as active ingredient
AU2014319290B2 (en) * 2013-09-13 2019-07-18 Pitney Pharmaceuticals Pty Limited Anticancer agent comprising aminoacetonitrile compound as active ingredient
WO2016137010A1 (fr) * 2015-02-24 2016-09-01 Nihon Nohyaku Co., Ltd. Agent anticancéreux comprenant un composé d'aminoacétonitrile en tant que principe actif
US11541044B2 (en) 2015-05-06 2023-01-03 The Regents Of The University Of California K-Ras modulators
EP3612526A2 (fr) * 2017-04-20 2020-02-26 The Regents of the University of California Modulateurs de k-ras
US11358940B2 (en) 2017-04-20 2022-06-14 The Regents Of The University Of California K-Ras modulators
US10647705B2 (en) 2017-11-14 2020-05-12 Merck Sharp & Dohme Corp. Substituted biaryl compounds as indoleamine 2,3-dioxygenase (IDO) inhibitors
US10995085B2 (en) 2017-11-14 2021-05-04 Merck Sharp & Dohme Corp. Substituted biaryl compounds as indoleamine 2,3-dioxygenase (IDO) inhibitors
US11498904B2 (en) 2017-11-14 2022-11-15 Merck Sharp & Dohme Llc Substituted biaryl compounds as indoleamine 2,3-dioxygenase (IDO) inhibitors

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