EP1347952A4 - Aryl et heteroarylcyclopropyl oxime ethers et leur utilisation comme fongicides - Google Patents

Aryl et heteroarylcyclopropyl oxime ethers et leur utilisation comme fongicides

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Publication number
EP1347952A4
EP1347952A4 EP01990185A EP01990185A EP1347952A4 EP 1347952 A4 EP1347952 A4 EP 1347952A4 EP 01990185 A EP01990185 A EP 01990185A EP 01990185 A EP01990185 A EP 01990185A EP 1347952 A4 EP1347952 A4 EP 1347952A4
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EP
European Patent Office
Prior art keywords
halo
alkyl
cyclopropyl
methyl
phenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01990185A
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German (de)
English (en)
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EP1347952A1 (fr
Inventor
Ronald Ross Jr
Duyan Vuong Nguyen
Steven Howard Shaber
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Corteva Agriscience LLC
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Dow AgroSciences LLC
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Publication of EP1347952A1 publication Critical patent/EP1347952A1/fr
Publication of EP1347952A4 publication Critical patent/EP1347952A4/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/42—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a ring other than a six-membered aromatic ring
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen 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
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • the present invention relates to certain aryl cyclopropyl oxime ether compounds, compositions containing these compounds, and methods for controlling fungi by the use of a fungitoxic effective amount of these compounds.
  • cyclopropyloxime ethers of the present invention have the Formula (I)
  • A is hydrogen, halo, cyano, (C 1 -C 12 )alkyl, or (C j -C 12 )alkoxy;
  • R. is (C 1 -C 12 )alkyl or halo(C ⁇ -Ci2)alkyl
  • R 2 is hydrogen, (C 1 -C 12 )alkyl, halo(C 1 -C 12 )alkyl, (C 3 -C 7 )cycloalkyl, halo(C 3 - C 7 )cycloalkyl, (C 2 -C 8 )alkenyl, halo(C 2 -C 8 )alkenyl, (C 2 -C 8 )alkynyl, halo(C 2 - C 8 )alkynyl, or cyano;
  • R 3 is hydrogen
  • R 4 and R 5 are independently hydrogen, (C 1 -C 12 )alkyl, halo(C 1 -C 12 )alkyl, (C 3 - C 7 )cycloalkyl, halo(C 3 -C 7 )cycloalkyl, (C 2 -C 8 )alkenyl, halo(C 2 -C 8 )alkenyl, (C 2 - C 8 )alkynyl, halo(C 2 -C 8 )alkynyl, halo, cyano, or (C j -C ⁇ alkoxycarbonyl; and wherein:
  • R 7 is aryl, arylalkyl, heterocyclic or heterocyclic(C 1 -C 4 )alkyl wherein the aryl or heterocyclic ring is substituted with from 2 to 5 substituents and wherein the positions on the aryl or heterocyclic ring adjacent to the bond to the cyclopropyl ring are both substituted and R 6 is hydrogen, (C j -C ⁇ alkyl, halo(C j -C 12 )alkyl, (C 3 - C 7 )cycloalkyl, halo(C 3 -C 7 )cycloalkyl, (C 2 -C 8 )alkenyl, halo(C 2 -C 8 )alkenyl, (C 2 - C 8 )alkynyl, halo(C 2 -C 8 )alkynyl, halo, cyano, or (C j -C 4 )alkoxycarbonyl; or B) R 7
  • the aforementioned (C 1 -C 12 )alkyl, (C 2 -C 8 )alkenyl, (C 2 -C 8 )alkynyl and (C 3 - C 7 )cycloalkyl groups may be optionally and independently substituted with up to three substituents selected from nitro, halomethyl, (d-C )alkoxycarbonyl, and cyano.
  • alkyl includes both branched and straight chain alkyl groups from 1 to 12 carbon atoms.
  • Typical alkyl groups are methyl, ethyl, n-propyl, iso-propyl, n- butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, isooctyl, nonyl, decyl, undecyl, dodecyl and the like.
  • haloalkyl refers to an alkyl group substituted with from 1 to 3 halogens.
  • alkenyl refers to an ethylenically unsaturated hydrocarbon group, straight or branched, having a chain length of from 2 to 8 carbon atoms and 1 or 2 ethylenic bonds.
  • haloalkenyl refers to an alkenyl group substituted with from 1 to 3 halogen atoms.
  • alkynyl refers to an unsaturated hydrocarbon group, straight or branched, having a chain length of from 2 to 8 carbon atoms and 1 or 2 acetylenic bonds.
  • aryl includes phenyl and naphthyl which maybe substituted with up to five substituents independently selected from halogen, cyano, nitro, trihalomethyl, trihalomethoxy, phenyl, phenoxy, (C 1 -C 4 )alkyl, (C 3 -C 7 )cycloalkyl, (C 2 -C 8 )alkenyl, (C r C 4 )alkoxy, (C r C 4 )alkylthio, (C r C 4 )alkylsulfoxide, halo(C r C 4 )alkyl, halo(C r C 4 )alkoxy, halo(C 3 -C 7 )cycloalkyl, halo(C 2 -C 8 )alkenyl, or (C j -C 4 )alkoxycarbonyl.
  • Typical phenyl substituents wherein at least one of the positions on the phenyl ring adjacent to the bond to the cyclopropyl ring is substituted with hydrogen include but are not limited to 2-chloro, 3-chloro, 4-chloro, 2-fluoro, 3-fluoro, 4-fluoro, 2-bromo, 3-bromo, 4-bromo, 2-methyl, 3-methyl, 4-methyl, 2-trifluoromethyl, 3- trifluoromethyl, 4-trifluoromethyl, 2-methoxy, 3-methoxy, 4-methoxy, 2- trifluoromethoxy, 3-trifluoromethoxy, 4-trifluoromethoxy, 2-cyano, 3-cyano, 4-cyano, 2,3-dichloro, 2,3-difluoro, 2,3-dibromo, 2,3-dimethyl, 2,3-dimethoxy, 2,3- bis(trifluoromethyl), 2,3bis-(trifluoromethoxy), 2,4-difluoro, 2,4-dich
  • Typical phenyl substituents where both positions on the phenyl ring adjacent to the bond to the cyclopropyl ring are substituted include but are not limited to 2,6- dichloro, 2,3,6-trichloro, 2,4,6-trichloro, 2,6-difluoro, 2,3,6-trifluoro, 2,4,6-trifluoro, 2,6-dibromo, 2,3,6-tribromo, 2,4,6-tribromo 2,3,4,6-tetrachloro, 2,3,5,6-tetrachloro, 2,3,4,5,6-pentachloro, 2,3,4,6-tefrabromo, 2,3,5,6-tefrabromo, 2,3,4,5,6-pentabromo, 2,3,4,6-tetrafluoro, 2,3,5,6-tetrafluoro, 2,3,4,5,6-pentafluoro, 2,6-dimethyl, 2,3,6- trimethyl, 2,4,6-trimethyl, 2,6-d
  • heterocyclic refers to a substituted 6 membered unsaturated ring selected from 3- or 4-pyridinyl, 5-pyrimidinyl, 3-pyridazinyl or a 5 membered unsaturated ring selected from 3-thienyl, 3-furyl, 3-pyrrolyl, 4-isoxazolyl, 4- isothiazolyl or 4-pyrazolyl wherein both the positions on the heterocyclic ring adjacent to the bond to the cyclopropyl ring are substituted and the ring is substituted with from 2 to 4 substituents independently selected from (C t -C 4 ) alkyl, (C 3 -C 7 )cycloalkyl, trihalomethyl, trihalomethoxy, halogen, cyano, (C j -C 4 )alkoxycarbonyl, nitro, phenyl, and phenoxy.
  • heterocyclic also refers to a substituted or unsubstituted 6 membered unsaturated ring containing one, two or three heteroatoms, preferably one, two or three heteroatoms independently selected from oxygen, nitrogen, and sulfur or a 5 membered unsaturated ring containing one, two or three heteroatoms, preferably one or two heteroatoms independently selected from oxygen, nitrogen, and sulfur wherein the heterocyclic ring is unsubstituted or is substituted with from 1 to 3 substituents wherein at least one of the positions of the heterocyclic ring adjacent to the bond to the cyclopropyl ring is a hydrogen substituent.
  • heterocycles include but are not limited to 2-, 3- or 4-pyridinyl, pyrazinyl, 4-, or 5-pyrimidinyl, pyridazinyl, pyrazole, imidazolyl, 2 or 3-thienyl, 2 or 3-furyl, 3-pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, and thiadiazolyl.
  • These rings may be optionally substituted with up from 1 to 3 substituents independently selected from (C j -C 4 ) alkyl, (C 3 -C 7 )cycloalkyl, trihalomethyl, halogen, cyano, (C ⁇ - C 4 )alkoxycarbonyl, nitro, phenyl, and phenoxy.
  • arylalkyl is used to describe a group wherein the alkyl chain is from 1 to 10 carbon atoms and can be branched or straight chain, preferably a straight chain, with the aryl portion, as defined above, forming a terminal portion of the arylalkyl moiety.
  • Typical arylalkyl moieties are optionally substituted benzyl, phenethyl, phenpropyl, and phenbutyl moieties.
  • Typical benzyl moieties wherein at least one of the positions on the phenyl ring, adjacent to the methylene which is bonded to the cyclopropyl ring, is substituted with hydrogen include but are not limited to 2-chlorobenzyl, 3-chlorobenzyl, 4-chloro- benzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2-bromobenzyl, 3- bromobenzyl, 4-bromobenzyl, 2-trifluoromethylbenzyl, 3-trifluoromethylbenzyl, 4- trifluoromethylbenzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl 2,3- difluorobenzyl, 2,3-dichlorobenzyl, 2,3-dibromobenzyl, 2,3-dimethylbenzyl, 2,4- difluorobenzyl, 2,4-dichlorobenzyl, 2,4-dibromobenz
  • Typical benzyl moieties wherein both positions on the phenyl ring, adjacent to the methylene which is bonded to the cyclopropyl ring, are substituted include but are not limited to 2,6-dichlorobenzyl, 2,3,6-trichlorobenzyl, 2,4,6- trichlorobenzyl, 2,6-difluorobenzyl, 2,3,6-fluorobenzyl, 2,4,6-trifluorobenzyl, 2,6- bis(trifluoromethyl)benzyl, 2,3,6-tris(trifluoromethyl)benzyl, 2,4,6- tris(trifluoromethyl)benzyl, 2,3,4,6-tetrachlorobenzyl, 2,3,5,6-tetrachlorobenzyl, 2,3,4,5,6-pentachlorobenzyl, 2,3,4,6-tetrabromobenzyl, 2,3,5,6-tetrabromobenzyl, 2,3,4,5,6-pen
  • Typical phenethyl moieties wherein at least one of the positions on the phenyl ring, adjacent to the ethyl moiety which is bonded to the cyclopropyl ring, is substituted with hydrogen include but are not limited to 2-(2- chlorophenyl)ethyl, 2-(3-chlorophenyl)ethyl, 2-(4-chlorophenyl)ethyl, 2-(2- fluorophenyl)ethyl, 2-(3-fluorophenyl)ethyl, 2-(4-fluoro- phenyl)ethyl, 2-(2-methylphenyl)ethyl, 2-(3-methylphenyl)ethyl, 2-(4-methylphenyl)- ethyl, 2-(4-trifluoromethylphenyl)ethyl, 2-(2,4-dichlorophenyl)ethyl, and 2-(3,5- dimethoxyphenyl)eth
  • Typical phenethyl moieties wherein both positions on the phenyl ring, adjacent to the ethyl moiety which is bonded to the cyclopropyl ring, are substituted include but are not limited to 2-(2,6-dichlorophenyl)ethyl, 2-(2,3,6- trichlorophenyl)ethyl, 2-(2,4,6-trichlorophenyl)ethyl, 2-(2,6-difluorophenyl)ethyl, 2- (2,3 ,6-trifluorophenyl)ethyl, 2-(2,4,6-trifluorophenyl)ethyl, 2-(2,6-dimethylphenyl)- ethyl, 2-(2,3,6-trimethyl ⁇ henyl)ethyl, 2-(2,4,6-trimethylphenyl)ethyl, 2-(2,6-bis- (trifluoromethyl)phenyl)ethyl, 2-(2,
  • Typical phenpropyl moieties wherein at least one of the positions on the phenyl ring, adjacent to the propyl moiety which is bonded to the cyclopropyl ring, is substituted with hydrogen include but are not limited to 3-phenylpropyl, 3-(2-chlorophenyl)propyl, 3-(3-chlorophenyl)- propyl, 3-(4-chlorophenyl)propyl, 3-(2,4-dichlorophenyl)propyl, 3-(2-fluorophenyl)- propyl, 3-(3-fluorophenyl)propyl, 3-(4-fluorophenyl)propyl, 3-(2-methylphenyl)- propyl, 3-(3-methylphenyl)propyl, 3-(4-methylphenyl)propyl, 3-(4-trifluoromethyl- phenyl)propyl, 3-(2,4-dichlorophenyl)propyl, and 3-(
  • Typical phenpropyl moieties wherein both positions on the phenyl ring, adjacent to the propyl moiety which is bonded to the cyclopropyl ring, are substituted include but are not limited to 3-(2,6-dichlorophenyl)propyl, 3-(2,3,6-trichlorophenyl)propyl, 3-(2,4,6- trichlorophenyl)propyl, 3-(2,6-difluorophenyl)propyl, 3-(2,3 ,6-trifluorophenyl)propyl, 3-(2,4,6-trifluorophenyl)propyl, 3-(2,6-dimethylphenyl)propyl, 3-(2,3,6-trimethyl- phenyl)propyl, 3-(2,4,6-trimethylphenyl)propyl and 3-(2,6-bis(trifluoromethyl)phenyl) propyl.
  • Typical phenbutyl moieties wherein at least one of the positions on the phenyl ring, adjacent to the butyl moiety which is bonded to the cyclopropyl ring, is substituted with hydrogen include but are not limited to 4-phenylbutyl, 4-(2-chloro- phenyl)butyl, 4-(3-chlorophenyl)butyl, 4-(4-chlorophenyl)butyl, 4-(2-fluorophenyl)- butyl, 4-(3-fluorophenyl)butyl, 4-(4-fluorophenyl)butyl, 4-(2-methylphenyl)butyl, 4- (3-methylphenyl)butyl, 4-(4-methylphenyl)butyl and 4-(2,4-dichlorophenyl)butyl.
  • Typical phenbutyl moieties wherein both positions on the phenyl ring, adjacent to the butyl moiety which is bonded to the cyclopropyl ring, are substituted include but are not limited to 4-(2,6-di-chlorophenyl)butyl, 4-(2,3,6-trichlorophenyl)butyl, 4-(2,4,6- trichlorophenyl)butyl, 4-(2,6-difluorophenyl)butyl, 4-(2,3,6-trifluorophenyl)butyl, 4- (2,4,6-trifluorophenyl)-butyl, 4-(2,6-dimethylphenyl)butyl, 4-(2,3 ,6-trimethyl- phenyl)butyl, 4-(2,4,6-trimethylphenyl)butyl and 4-(2,6-bis(trifluoromethyl)- phenyl)butyl.
  • Halogen or halo includes iodo, fluoro, bromo and chloro.
  • the compounds of the general Formula I may be obtained in preparation as E/Z isomeric mixtures. These isomers can be separated into individual components by conventional means.
  • the substituted cyclopropanes of Formula I may be obtained in preparation as cis and trans isomeric mixtures which can be separated into individual components by conventional means. Both the individual isomeric compounds and mixtures thereof form subjects of the present invention and can be used as fungicides and insecticides.
  • One preferred embodiment of this invention is the compounds, enantiomorphs, salts and complexes of Formula I wherein A, R 4 , and R 5 are hydrogen; R j and R 2 are independently (C j -C 4 )alkyl; R 7 is phenyl, phenylalkyl, or heterocyclic such that the positions on the phenyl ring and heterocyclic ring adjacent to the bond to the cyclopropyl ring are substituted, and R 6 is selected from hydrogen, (C j -C j ⁇ alkyl, halo(C r C 12 )alkyl, (C 3 -C 7 )cycloalkyl, halo(C 3 -C 7 )cycloalkyl, (C 2 -C 8 )alkenyl, halo(C 2 - C 8 )alkenyl, (C 2 -C 8 )alkynyl, and halo(C 2 -C 8 )alkynyl.
  • a more preferred embodiment of this invention is the compounds, enantiomorphs, salts and complexes of Formula I wherein A, R 4 , and R 5 are hydrogen; R j and R 2 are independently (C j -C 4 )alkyl; R 6 is hydrogen or (C 1 -C 12 )alkyl; and R 7 is 2,6-disubstitutedphenyl, 2,3,6-trisubstitutedphenyl,or 2,4,6- trisubstitutedphenyl.
  • An even more preferred embodiment of this invention is the compounds, enantiomorphs, salts and complexes of Formula I wherein A, R 4 , and R 5 are hydrogen; R j and R 2 are CH 3 ; R 6 is hydrogen or (C 1 -C 4 )alkyl; and R 7 is 2,6-dihalophenyl, 2,3,6- trihalophenyl, or 2,4,6-trihalophenyl
  • a second preferred embodiment of this invention is the compounds, enantiomorphs, salts and complexes of in Formula I wherein A, R 4 , and R 5 are hydrogen; R j and R 2 are independently (C j -C ⁇ alkyl; R 7 is phenyl, phenylalkyl, or heterocyclic wherein at least one of the positions on the phenyl or heterocyclic ring adjacent to the bond to the cyclopropyl ring is a hydrogen substituent; and R 6 is hydrogen, (C j -C 12 )alkyl, halo(C 1 -C 12 )alkyl, (C 3 -C 7 )cycloalkyl, halo(C 3 -C 7 )cycloalkyl, (C 2 -C 8 )alkenyl, halo(C 2 -C 8 )alkenyl, (C 2 -C 8 )alkynyl, or halo(C 2 -C 8 )alkyn
  • a second more preferred embodiment of this invention is the compounds, enantiomorphs, salts and complexes of Formula I wherein; A, R 4 , and R 5 are hydrogen; R j and 1 ⁇ is CH 3 ; R 7 is phenyl, 2-substitutedphenyl, 3-substitutedphenyl, 4- substitutedphenyl, 2,3-disubstitutedphenyl 2,4-disubstitutedphenyl, 2,5- disubstitutedphenyl, 3,4-disubstitutedphenyl, 3,5-disubstituted, 2,3,4- trisubstitutedphenyl, 2,3,5-trisubstitutedphenyl, 2,4,5-trisubstitutedphenyl, 3,4,5- trisubstitutedphenyl, or 2,3,4,5-tetrasubstitutedphenyl; and R 6 is hydrogen, (C 1 (C 1 - C 4 )alkyl or halo(C r C
  • a second even more preferred embodiment of this invention is the compounds, enantiomorphs, salts and complexes of Formula I wherein A, R 4 , and R 5 are hydrogen; R j and j are CH 3 ; R 7 is phenyl, 2-halophenyl, 3-halophenyl, 4-halophenyl, 2,3- dihalophenyl 2,4-dihalophenyl, 2,5-dihalophenyl, 3,4-dihalophenyl, 3,5-dihalophenyl, 2,3,4-trihalophenyl, 2,3,5-trihalophenyl, 2,4,5-trihalophenyl, or 3,4,5-trihalophenyl, and R 6 is hydrogen or (C j -C 4 )alkyl.
  • a most preferred embodiment of this invention is the compounds, enantiomorphs, salts and complexes of Formula II wherein R 7 is 2,6-dichlorophenyl,
  • Another most preferred embodiment of this invention is the compounds, enantiomorphs, salts and complexes of Formula IF wherein R 7 is phenyl, 2- chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3 -fluorophenyl or 4- fluorophenyl and R 6 is CH 3 .
  • Typical compounds of Formula I encompassed by the present invention wherein A, R 4 and R 5 are hydrogen; and R j is methyl include those compounds presented in Table 1 of Formula III where R 2 , R 6 , and R 7 are as defined in Table 1
  • Typical compounds of Formula I encompassed by the present invention wherein A, R 4 and R 5 are hydrogen and R t is methyl include those compounds presented in Table 3 of Formula III 3
  • Typical compounds of Formula I encompassed by the present invention wherein A, R 4 and R 5 are hydrogen; X is CH and Z is O; and R j is methyl include those compounds presented in Table 4 of Formula III where ⁇ R 6 , and R 7 are defined in Table 4.
  • Ph is understood to be phenyl
  • Scheme A describes the preparation of compounds of the Formula (P) where A and R j to R 7 are as defined in Tables 1-4.
  • the cyclopropyl oximes (N) are reacted with the appropriately substituted benzyl derivatives (IN), where Z is a halogen, such as bromo, chloro or iodo, preferably a benzyl bromide.
  • a cyclopropyl substituted oxime represented by the general formula (V) is treated, at room temperature, with an appropriate base to form an anion, followed by the addition of the benzyl bromide (IN).
  • Typical bases employed are metal hydrides such as sodium hydride, alkoxides such as sodium methoxide and hydroxide bases such as sodium or potassium hydroxide and alkali bases such as sodium or potassium carbonate.
  • Typical solvents employed with hydride bases are ⁇ , ⁇ -dimethylformamide (DMF) and tetrahydrofuran (THF); with hydroxide bases DMF, THF, methyl ethyl ketone (MEK) and acetone and with alkali bases solvents such as DMF, acetone, and MEK. in the E
  • isomer A higher R f on thin layer chromatography
  • isomer B lower R f on thin layer chromatography
  • the determination of which isomer, A or B possesses the E or Z geometry can be made by such conventional techniques as X ray crystallography or by spectroscopic means such as nuclear magnetic resonance spectroscopy.
  • isomer A has been assigned the E iminoxy configuration and isomer B, the Z iminoxy configuration.
  • Methyl ⁇ -(2-bromomethylphenyl)- ⁇ -alkoxycarbamate and specifically methyl N-(2-bromomethylphenyl)-N-methoxycarbamate (IN, where Z is bromo), are prepared as described in US 5,650,434 in a 4 step sequence as shown in scheme B.
  • o-nitrotoluene is reacted with ammonium chloride in the presence of zinc to provide ⁇ -2- methylhydroxylamine (XI) as described in Organic Synthesis Collective Volume III, p.668..
  • the hydroxylamine is acylated with methyl chloroformate to provide the methyl N-hydroxycarbamate (XII) which is alkylated, for example with dimethylsulfate (R is methyl), to provide (XIII) which is brominated under standard conditions such as N-bromosuccinimide in carbontetrachloride in the presence of a catalyst such as benzoyl peroxide to afford the intermediate benzylbromide (XIV).
  • the oximes of the general formula (V) can be obtained, as shown in Scheme C, by reacting the corresponding cyclopropyl aldehyde or ketone (X) with hydroxylamine hydrochloride from room temperature to reflux, preferably at room temperature, in an appropriate solvent such as methanol or ethanol in the presence of an appropriate alkali such as sodium hydroxide, potassium carbonate or pyridine.
  • an appropriate solvent such as methanol or ethanol
  • an appropriate alkali such as sodium hydroxide, potassium carbonate or pyridine.
  • the oximes of the general formula (III) when obtained as a mixture of syn or anti oxime isomers can be separated into individual isomers and alkylated as described in scheme A and B.
  • the compounds of the formula VI, Nil and IX can be separated into their individual isomers by conventional chromatographic techniques.
  • the cyclopropyl aldehydes or ketones (X) are prepared by conventional techniques.
  • the unsaturated intermediate XI (Scheme D) is reacted with a sulfur ylide, prepared from a dimethylsulfoxonium salt in the presence of a base, resulting in the substituted acyl cyclopropanes, X, as shown in Scheme D.
  • the chemistry of sulfur ylides is described in Trost and Melvin, Sulfur Ylids , Academic Press, New York, NY 1975 and in Block, Reactions of Organosulfur Compounds, pp. 91-123, Academic Press, New York, NY 1978.
  • Typical reaction conditions for sulfur ylide formation from a dimethylsulfoxonium salt utilizes bases such as hydroxides, metal hydrides and alkoxides in solvents such as dimethoxyethane, dimethylsulfoxide and water depending on the base employed.
  • the reactions are conducted from 0 to 20°C preferably from 10-15°C and preferably with alkali metal hydroxides in dimethylsulfoxide.
  • dimethylsulfoxonium methylide is prepared from trimethylsulfoxonium iodide in dimethylsulfoxide in the presence of powdered sodium hydroxide at room temperature.
  • the unsaturated aldehydes or ketones (XI) are added dropwise to the ylide and stirred at room temperature.
  • the ⁇ , ⁇ -unsaturated aldehydes or ketones XI can be prepared by conventional condensation techniques. A extensive description of the synthesis of ⁇ , ⁇ -unsaturated aldehydes or ketones (enones) is described in March, Advanced Organic Chemistry. 4th Ed, pp. 937-955 and references therein. For example Organic Reactions, Volume 16 describes the general aldol condensation of ketones and aldehydes.
  • the ketones and aldehydes are R 7 COR 6 (XII) and R 2 COCH 2 R 3 (XIII) where R 2 , R 3 , R 6 , and R 7 are defined previously.
  • the aldehydes R 7 CHO are for example benzaldehydes (arylCHO) or heterocyclic aldehydes substituted with from 2 to 5 substituents wherein the positions on the aryl and heterocyclic ring adjacent to the bond to the cyclopropyl ring, in Formula I, are both substituted.
  • These substituted benzaldehyes or heterocyclic aldehydes are commerically available or prepared by conventional techniques.
  • the aldehydes R 7 CHO (XIN) are reacted with the ketones R 2 COCH 2 R 3 , XIII, (as shown in Scheme E) to provide the intermediates enones XV.
  • the ketone, R 2 COCH 2 R 3 is dissolved in a hydroxylic solvent, such as methanol or ethanol, to which is added dropwise the aldehyde R 7 CHO followed by the base or alternatively a solution of the aldehyde in an aqueous basic solution is added.
  • a hydroxylic solvent such as methanol or ethanol
  • the typical bases used can be alkali metal hydroxides, such as barium, potassium or sodium hydroxide and the dropwise addition is conducted from 0°C to 35°C preferably at ambient temperature.
  • the solvent can be acetone to which is added R 7 COR 6 followed by the aqueous hydroxide solution.
  • the aldehyde is dissolved in a solvent mixture of acetone:water (1 :5) to which is added the base while stirring at room temperature.
  • R 7 COR 6 are the ketones arylCOR 6 or heterocyclic ketones, substituted with from 2 to 5 substituents wherein the positions on the aryl and heterocyclic rings adjacent to the bond to the cyclopropyl ring, in Formula I, are both substituted or aryl or heterocyclic ring is unsubstituted or substituted from 1 to 4 substituents wherein at least one of the positions on the aryl or heterocyclic rings adjacent to the bond to the cyclopropyl ring, in Formula I, is a hydrogen.
  • the , ⁇ -unsaturated cyclopropyl ketones X can be prepared from cyclopropyl nitriles XIN which are prepared via cyclopropanation of the acrylonitriles XNIII as is described in Scheme G.
  • the acrylonitriles XNIII starting materials, shown in Scheme G can be prepared by conventional synthetic methods as described in March, Advanced Organic Chemistry, 4th Ed, pp. 937-955 and references therein .
  • the nitrile derivative R 3 CH 2 C ⁇ is condensed with the ketone or aldehyde R 7 COR 6 in the presence of a base to provide the acrylonitriles XIII.
  • a nitrile is dissolved in a solvent such as ethanol and water to which is added the aldehyde or ketone followed by a base.
  • Typical bases used can be alkali metal hydroxides, such as barium, potassium or sodium hydroxide and the mixture is stirred typically at ambient temperature.
  • the acrylonitrile XNIII is treated as is described in Scheme D with a sulfur ylide to provide the cyclopropyl nitriles XVII.
  • the cyclopropyl nitrile XVII is transformed to the cyclopropyl ketone by organometallic addition to the nitrile followed by hydrolysis.
  • organometallic addition to the nitrile followed by hydrolysis For example the standard Grignard reagents R 2 MgX or organolithium reagents, R 2 Li, add to the nitrile functionality to provide the ketone X.
  • the addition reaction to nitriles is described in March, Advanced Organic Chemistry, 4th Ed, pp.935-936 and references cited therein.
  • cyclopropyl nitrile XVII can be transformed to the cyclopropyl aldehyde X' (where R 2 is H) by standard reductive methods such as with diisobutylaluminum hydride (DiBAL).
  • DIBAL diisobutylaluminum hydride
  • a direct synthesis of compounds of the formula VII or IX is shown in Scheme H.
  • Compounds of the Formula VII or IX can be prepared directly from the functionalized cyclopropyl ketones or aldehydes, X, by condensation with the -iminoxy intermediate XIX.
  • the preparation of aminoxy intermediate XIX is described in US Patent Number 5,194,662.
  • the aminoxy intermediate XIX is prepared in a two step sequence by the alkylation of IV (where X is N) with N- hydroxyphthalimide which is treated with hydrazine to provide XIX.
  • the aminoxy intermediate XIX is condensed with ketones or aldehydes X to provide VII which are treated as shown in scheme B to provide IX.
  • the reaction was worked up after 45 min. by vacuum filtering the reaction mixture through celite, washing the wet cake with 50ml ethyl alcohol and removing the solvent at 30°C on the rotary evaporator to give orange oil.
  • To the oil was added 300ml ether and 200ml water.
  • the organic phase was separated and washed with 3 x 200ml water using NaCl to break up the emulsion, dried over MgSO -anhyd., and the ether was removed at 30°C on the rotary evaporator to give 16. lg product as an orange oil (62.3% yield) which was used directly in the next step.
  • the aqueous fraction was then acidified to pH 2 with 6 N aqueous HC1, and a yellow solid was formed which was collected by filtration, washed with water, hexane, and air dried. This solid was re-suspended in 500 mis of 6 N aqueous HC1, and warmed to 50 °C for one hour. Analysis of an aliquot by TLC and GC indicated no starting material remained, and one new product was formed. The aqueous mixture was cooled to room temperature, then poured into 500 mis of water and extracted with 3 x 200 ml of ethyl ether.
  • the ether extract was washed with 2 x 100 mis of water, 100 mis of brine, dried over anhydrous magnesium sulfate, filtered through 2" of silica gel, and stripped to afford 97 g of a thick pale yellow oil which was fractionally distilled at 0.2 mm Hg.
  • the purest fractions were combined to afford 74 g of a pale yellow liquid which was about 88% pure by GC analysis, with several minor impurities remaining.
  • This material was then chromatographed on silica gel with 90%hexane/10% ethyl acetate. The pure fractions were combined to afford 37g of trans- 1 -methyl- l-(4-fluorophenyl)-2-acetyl-cyclopropane as a clear colorless liquid., in a 42% isolated yield.
  • reaction was then stirred for 10 minutes at ambient temperature, then poured into 200 mis of ice water and extracted with 3 x 100 ml of ethyl ether.
  • the ether extract was washed with 2 x 100 mis of water, lOOmls of brine, dried over anhydrous MgSO4, filtered through 2" of silica gel, and concentrated in vacuuo on a rotary evaporator to afford 31.7 g of a thick pale yellow oil which was chromatographed on silica gel with 90% hexane, 10% ethyl acetate.
  • Numerous compounds of this invention were tested for fungicidal activity in vivo against the diseases described below.
  • the compounds were dissolved in a 1 :1 mixture of acetone and methanol and then diluted with a 2: 1 : 1 mixture of water, acetone and methanol (by volume) to achieve the appropriate concentration.
  • the solution was sprayed onto the plants and allowed to dry for two hours.
  • the plants were then inoculated with fungal spores.
  • Each test utilized control plants which were sprayed with the appropriate solvent and inoculated. For these protective tests, the plants were inoculated one day after treating the plants with the compounds of this invention.
  • Puccinia recondita was cultured on 7-day old wheat plants (cv. Fielder) over a 12-day period in the greenhouse. Spores were collected from the leaves by settling on aluminum foil. The spores were cleaned by sieving through a 250-micron opening screen and stored dry. The dried spores were used within one month.
  • a spore suspension was prepared from dry uredia by adding 20 mg (9.5 million spores) per ml of Soltrol oil. The suspension was dispensed into gelatin capsules (0.7 ml capacity) which attach to the oil atomizers. One capsule is used per flat of twenty 2-inch square pots of 7-day old plants, cultivar Fielder. After waiting for at least 15 minutes for the oil to evaporate from the wheat leaves, the plants were placed in a Dew Chamber for 24 hours. The plants were then placed in the greenhouse and evaluated after 12 days for disease.
  • Wheat Leaf Blotch SNW
  • Erysiphe graminis (f. sp. tritici) was cultured on wheat seedlings (cv. Fielder) in a controlled temperature room at 18°C. Mildew spores were shaken from the culture plants onto 7-day old wheat seedlings which had been previously sprayed with the fungicide compound. The inoculated seedlings were kept in a controlled temperature room at 18°C and subirrigated. The percent disease control was rated 7 days after the inoculation. Disease control values were recorded as percent control. Cucumber Powdery Mildew fCPM)
  • Tomato Late Blight Tomato Late Blight
  • the fungal pathogen Colletotrichum lagenarium was cultured on potato dextrose agar (PDA) in the dark at 22°C for a period of 8 to 14 days. Spores of C. lagenarium were removed from the PDA plates by flooding the plate surface with distilled water, amended with 0.5% v/w of yeast extract. The upper surface of the fungal colony was scraped with a blunt plastic instrument until most of the spores were released into the aqueous environment. The spore suspension was filtered though cheesecloth, and the spore count was adjusted by adding more water, containing the yeast extract, until 3.0 x 10 6 spores per ml of water was achieved. The chemically-treated cucumber plants were 15-days old (cv.
  • the plants were inoculated with freshly prepared spore suspension using a DeVilbiss atomizer.
  • the spore suspension was applied to the upper surface of the leaves.
  • the plants were placed in a Dew Chamber at 20°C for 24 hr to allow for infection.
  • the plants were then transferred to a growth chamber at 22°C and 80% humidity for three days.
  • Disease control values were recorded a percent control.
  • When tested against wheat leaf rust at 150 grams per hectare compounds 1.11 A exhibited 95% control and at 100 grams per hectare 1.1 IB, 1.14A, 1.58A and 3.16A exhibited 95% or better control.
  • the compounds of this invention are useful as agricultural fungicides and, as such, can be applied to various loci such as the seed, the soil or the foliage of plants to be protected.
  • the compounds of this invention can be applied as ftmgicidal sprays by methods commonly employed, such as conventional high- volume hydraulic sprays, low- volume sprays, air-blast spray, aerial sprays and dusts.
  • the dilution and rate of application will depend upon the type of equipment employed, the method of application, plants to be treated and diseases to be controlled.
  • the compounds of this invention will be applied in amount of from about 0.005 kilogram to about 50 kilograms per hectare and preferably from about 0.025 to about 25 kilograms per hectare of the active ingredient.
  • the amount of toxicant coated on the seed is usually at a dosage rate of from about 0.05 to about 20, preferably from about 0.05 to about 4, and more preferably from about 0.1 to about 1 grams per hundred kilograms of seed.
  • the chemical can be incorporated in the soil or applied to the surface usually at a rate of from about 0.02 to about 20, preferably from about 0.05 to about 10, and more preferably from about 0.1 to about 5 kilograms per hectare.
  • the toxicant is usually applied to growing plants at a rate of from about 0.01 to about 10, preferably from about 0.02 to 5, and more preferably from about 0.25 to about 1 kilograms per hectare.
  • fungicidal activity displays fungicidal activity
  • these compounds can be combined with other known fungicides to provide broad spectrum activity.
  • Suitable fungicides include, but are not limited to, those compounds listed in U.S. Patent Number 5,252,594 (see in particular columns 14 and 15).
  • fungicides which an be combined with the compounds of this invention are dimethomorph, cymoxanil, thifluzamide, furalaxyl, ofurace, benalaxyl, oxadixyl, propamocarb, cyprofuram, fenpiclonil, fludioxonil, pyrimethanil, cyprodinil, triticonazole, fluquinconazole, metconazole, spiroxamine, carpropamid, azoxystrobin, kresoxim-methyl, metominostrobin and trifloxystrobin.
  • the compounds of this invention can be advantageously employed in various ways. Since these compounds possess broad spectrum fungicidal activity, they can be employed in the storage of cereal grain. These compounds can also be employed as fungicides in cereals including wheat, barley and rye, in rice, peanuts, beans and grapes, on turf, in fruit, nut and vegetable orchards, and for golf course applications.
  • diseases against which the compounds of the invention are useful include helminthosporium of com and barley, wheat and barley powdery mildew, wheat leaf and stem rusts, barley stripe and leaf rust, tomato early blight, tomato late blight, peanut early leaf spot, grape powdery mildew, grape black rot, apple scab, apple powdery mildew, cucumber powdery mildew, brown rot of fruits, botrytis, bean powdery mildew, cucumber anthracnose, wheat septoria nodorum, rice sheath blight and rice blast
  • compositions and formulations according to the present invention may also include known pesticidal compounds. This expands the spectrum of activity of the preparation and may give rise to synergism.
  • Suitable insecticides known in the art include those listed in U.S. Patent 5,075,471, see in particular columns 14 and 15.
  • the compounds of the present invention can be used in the form of compositions or formulations.
  • Examples of the preparation of compositions and formulations can be found in the American Chemical Society publication “Pesticidal Formulation Research,” (1969), Advances in Chemistry Series No. 86, written by Wade Van Valkenburg; and the Marcel Dekker, Inc. publication “Pesticide Formulations”, (1973) edited by Wade Van Valkenburg.
  • the active substance is mixed with conventional inert agronomically acceptable (i.e., plant compatible and/or pesticidally inert) pesticide diluents or extenders such as solid carrier material or liquid carrier material, of the type usable in conventional pesticide compositions or formulations.
  • agronomically acceptable carrier any substance which can be used to dissolve, disperse of diffuse the active ingredient in the composition without impairing the active ingredient's effectiveness and which by itself has no significant detrimental effect on the soil, equipment, desirable plants, or agronomic environment.
  • adjuvants such as surfactants, stabilizers, antifoam agents and anti-drift agents may also be combined.
  • compositions and formulations according to the invention are aqueous solutions and dispersions, oily solutions and oil dispersions, pastes, dusting powders, wettable powders, emulsifiable concentrates, flowables, granules, baits, invert emulsions, aerosol compositions and fumigating candles.
  • Wettable powders, pastes, flowables and emulsifiable concentrates are concentrated preparations which are diluted with water before or during use. In such formulations, the compounds are extended with a liquid or solid carrier and, when desired, suitable surfactants are incorporated.
  • Baits are preparations generally comprising a food or other substance attractive to insects, that includes at least one compound of the instant invention.
  • adjuvants such as wetting agents, spreading agents, dispersing agents, stickers, adhesive and the like in accordance with agricultural practices.
  • adjuvants such as wetting agents, spreading agents, dispersing agents, stickers, adhesive and the like in accordance with agricultural practices.
  • a listing of such adjuvants commonly used in the art, and a discussion of adjuvants, can be found in many references, such as in the John W. McCutcheon, Inc. publication "Detergents and Emulsifiers, Annual.”
  • the active compounds of the present invention may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides, arthropodicides, nematicides, fungicides, bactericides, rodenticides, herbicides, fertilizers, growth-regulating agents, synergists.
  • plant protection agents such as other insecticides, arthropodicides, nematicides, fungicides, bactericides, rodenticides, herbicides, fertilizers, growth-regulating agents, synergists.
  • the active compound is present in an amount from 0.0001 percent to 99 percent by weight.
  • the amount of active ingredient is preferably between 0.5 and 90 percent by weight, and more preferably between 1 and 75 percent by weight of the mixture.
  • Compositions suitable for direct application or field application generally contain the active compound in an amount between 0.0001 and 95 percent, preferably between 0.0005 and 90 percent by weight, and more preferably between 0.001 and 75 percent by weight of the mixture.
  • the composition can also be stated as a ratio of the compound to the carrier. In the present invention the weight ratio of these materials (active compound/carrier) can vary from 99:1 to 1:4 and more preferably from 10:1 to 1 :3.
  • the compounds of this invention can be dissolved in certain solvents such as acetone, methanol, ethanol, dimethylformamide, pyridine or dimethyl sulfoxide and such solutions can be diluted with water.
  • concentrations of the solution can vary from 1%> to 90% with a preferred range being from 5% to 50%.
  • the compound can be dissolved in suitable organic solvents, or a mixture of solvents, together with an emulsifying agent to enhance dispersion of the compound in water.
  • concentration of the active ingredient in emulsifiable concentrates is usually from 10% to 90%, and in flowable emulsion concentrates, can be as high as 75%.
  • Wettable powders suitable for spraying can be prepared by admixing the compound with a finely divided solid, such as clay, inorganic silicate and carbonate, and silica and incorporating wetting agents, sticking agents, and/or dispersing agents in such mixtures.
  • concentration of active ingredients in such formulations is usually in the range of from 20% to 99%, preferably from 40%o to 75%.
  • a typical wettable powder is made by blending 50 parts of a compound of Formula 1, 45 parts of a synthetic precipitated hydrated silicon dioxide and 5 parts of sodium lignosulfonate.
  • a kaolin type (Barden) clay is used in place of the synthetic precipitated hydrated silicon dioxide in the above wettable powder, and in another such preparation 25% of the silicon dioxide is replaced with a synthetic sodium silicoaluminate.
  • Dusts are prepared by mixing the compound with finely divided inert solids which can be organic or inorganic in nature.
  • Materials useful for this purpose include botanical flours, silicas, silicates, carbonates and clays.
  • One convenient method of preparing a dust is to dilute a wettable powder with a finely divided carrier. Dust concentrates containing from 20%> to 80% of the active ingredient are commonly made and are subsequently diluted to from 1% to 10% use concentration.
  • the preparations according to the invention may also contain other substances commonly used in preparations of this kind.
  • a lubricant such as calcium stearate or magnesium stearate
  • a wettable powder or to a mixture to be granulated may be added to a wettable powder or to a mixture to be granulated.
  • adheresives such as polyvinylalcohol-cellulose derivatives or other colloidal materials, such as casein, to improve the adherence of the pesticide to the surface to be protected.

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

Abstract

L'invention concerne certains composés de cyclopropyl oxime éther à substituants aryle et hétérocycliques, des compositions contenant ces composés, et des procédés de lutte contre les champignons grâce à l'utilisation d'une quantité fongitoxique efficace de ces composés. Ces composés et compositions possèdent des propriétés fongicides à large spectre.
EP01990185A 2000-12-08 2001-12-07 Aryl et heteroarylcyclopropyl oxime ethers et leur utilisation comme fongicides Withdrawn EP1347952A4 (fr)

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EP2547653B1 (fr) * 2010-03-18 2015-01-28 Basf Se N-carbométhoxy-N-méthoxy-(2-chlorométhyl)-anilines, leur préparation et leur application en tant que précurseurs pour la préparation de 2-(pyrazol-3'-yloxyméthylène)-anilides
CN110845370A (zh) * 2019-11-29 2020-02-28 江苏宝灵化工股份有限公司 一种合成氯啶菌酯中间体的方法

Citations (2)

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US5824705A (en) * 1992-01-29 1998-10-20 Basf Aktiengesellschaft Carbamates and crop protection agents containing them
EP0924197A1 (fr) * 1997-12-11 1999-06-23 Rohm And Haas Company Cyclopropylphénoxyméthyl-phénylcarbamates substitués et leur utilisation comme fongicides

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US6191171B1 (en) * 1997-11-20 2001-02-20 Merck & Co., Inc. Para-aminomethylaryl carboxamide derivatives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5824705A (en) * 1992-01-29 1998-10-20 Basf Aktiengesellschaft Carbamates and crop protection agents containing them
EP0924197A1 (fr) * 1997-12-11 1999-06-23 Rohm And Haas Company Cyclopropylphénoxyméthyl-phénylcarbamates substitués et leur utilisation comme fongicides

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Title
See also references of WO0246142A1 *

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BR0116471A (pt) 2004-01-06
AU2002229049A1 (en) 2002-06-18
CN1479718A (zh) 2004-03-03
MXPA03005093A (es) 2004-06-25

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