WO2001032609A1 - Composes possedant un groupe cyano, insecticides et acaricides les contenant - Google Patents

Composes possedant un groupe cyano, insecticides et acaricides les contenant Download PDF

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WO2001032609A1
WO2001032609A1 PCT/JP2000/007551 JP0007551W WO0132609A1 WO 2001032609 A1 WO2001032609 A1 WO 2001032609A1 JP 0007551 W JP0007551 W JP 0007551W WO 0132609 A1 WO0132609 A1 WO 0132609A1
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group
alkyl
optionally substituted
substituted
alkyl group
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PCT/JP2000/007551
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English (en)
Japanese (ja)
Inventor
Yasushi Shibata
Tomio Yagihara
Isamu Kasahara
Renpei Hatano
Takehiko Nakamura
Satoru Makita
Shigemi Suga
Jun Iwata
Fumihisa Suzuki
Jun Takahashi
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Nippon Soda Co., Ltd.
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Priority to BR0015158-0A priority Critical patent/BR0015158A/pt
Priority to JP2001534762A priority patent/JP4679781B2/ja
Priority to KR1020027005361A priority patent/KR20020059648A/ko
Priority to AU79604/00A priority patent/AU7960400A/en
Publication of WO2001032609A1 publication Critical patent/WO2001032609A1/fr

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    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/38—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/40—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by doubly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C07C329/02—Monothiocarbonic acids; Derivatives thereof
    • C07C329/04—Esters of monothiocarbonic acids
    • C07C329/06—Esters of monothiocarbonic acids having sulfur atoms of thiocarbonic groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

Definitions

  • the present invention relates to a novel compound, a method for producing the same, and an insecticide and acaricide.
  • Examples of the acrylonitrile compound similar to the compound of the present invention include EP.18969, WO97 / 40909, W098Z426683, and W098 / 359. It is described in Publication No. 35 and Publication No. W099Z44 993.
  • An object of the present invention is to provide a novel compound which can be industrially advantageously synthesized, has a certain effect, and can be used safely as an insecticide and acaricide.
  • the present invention is a.
  • A is represented by the following formulas Al, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11 and A12 Represents one selected from the group consisting of groups.
  • Xi x 2 , x 3 and x 4 each independently represent a hydrogen atom, a halogen atom, a c! S alkyl group or a c 6 haloalkyl group,
  • x 5 is hydrogen atom, - 6 alkyl group, c 2 s alkenyl group, ⁇ 2 - ⁇ Haroaruke represents a double group or an optionally substituted phenyl c _ 6 alkyl group!
  • chi 6, chi 7 are each independently a ⁇ 1 -6 alkyl group, also, chi beta and chi 7 may form a 5-8 membered ring together.
  • ⁇ is Shiano group, - s alkyl, C 3 - s cycloalkyl group, in optionally substituted Hue sulfonyl (1 - 6 alkyl group, a phenyl group which may be substituted with G t, in substituted which may phenoxy group, G may phenoxy CJ be substituted with t '6 alkyl group, in optionally substituted phenylene group, a heteroarylthio group, in optionally substituted phenylene thioether C i 6 alkyl group, in which substituted which may Hue Nils sulfinyl group which may be substituted by G t Fuenirusurufu Iniru C ⁇ 6 alkyl group, in optionally substituted phenylalanine alkylsulfonyl be group, an optionally substituted phenylalanine sulfonyl with Gi (!
  • _ 6 alkyl group in optionally substituted Anirino group, in optionally substituted Anirino C i 6 alkyl group, in an optionally substituted thienyl group, in optionally substituted thienyl C 6 alkyl group, substituted by G t Piri Le based on And optionally pyridyl C! It represents one group selected from the group consisting of _ 6 alkyl group.
  • Z represents an oxygen atom, a sulfur atom or, even in properly hydrogen atom - 6 alkyl group represents a nitrogen atom that substitute.
  • ⁇ ⁇ Rukiruami Roh group a di - 6 alkylamino amino group, door Li - 6 alkylsilyl, C ⁇ 6 ⁇ alkoxy 0 1 - 6 alkyl group, - 6 alkylthio C - 6 alkyl group, - 6 alkyl Rusurufiniru. 1-6 alkyl group, c 6 alkylsulfonyl 0 i 6 alkyl group, C
  • G 2 is - 6 alkyl group, a halogen atom, C i 6 haloalkyl group or a C i Roh represents a Roarukokishi group.
  • G 3 represents a C i 6 alkyl group or a halogen atom.
  • G 4 are nitro group, Shiano group, a halogen atom, - 6 alkyl group, C 6 Haroaruki group, - 6 alkoxy group, - 6 haloalkoxy group, an alkylthio group,
  • B represents a phenyl group substituted with W or a heterocyclic group substituted with W.
  • W is a nitro group, Shiano group, a halogen atom, C i-e alkyl group, C 3 _ 8 cyclo alkyl group, - 6 haloalkyl group, - 6 alkoxy group, - 6 Haroarukoki sheet group, C!
  • G 5 is a nitro group, Shiano group, a halogen atom, C -! Alkyl, C i-e Haroaruki group, - 6 alkoxy group, - 6 haloalkoxy group, C i-e alkylthio group, ( ⁇ _ 6 alkyl sulfinyl group, C i_ 6 alkylsulfonyl group, - 6 alkylamino Bruno It represents 6 alkoxy force Lupo two group, - group, di 0 1 - 6 alkylamino group, c 6 alkylcarbonyl group,
  • the heterocyclic group substituted with w is a triazolyl group, a thiazolyl group, an oxazolyl group, an isoxazolyl group, an isothiazolyl group, a pyrazolyl group, an imidazolyl group, a tetrazolyl group, an oxaziazolyl group, a thiadiazolyl group, a chenyl group, a furyl group, or a pyrrolyl group.
  • R is a hydrogen atom, C i_ 6 alkyl group, a group represented by the formula CO Ri, a group represented by the formula CS Ri, a group represented by S 0 2 R 2, - 6 alkylcarbonyl O alkoxy C i- 6 alkyl group, C 3
  • B is a pyridyl group substituted with a phenyl group or a W substituted with W
  • R is a hydrogen atom
  • C i 6 alkyl group, a group represented by the formula CO Ri is represented by the formula CSI ⁇
  • A is not a benzyl group substituted by A compound represented by the formula:
  • A represents any of the groups represented by the above formulas A 1 to A 12.
  • X 1 X 2 , X 3 and X 4 are each independently a hydrogen atom
  • Halogen atoms such as fluorine, chlorine, bromine and iodine
  • X 5 is a hydrogen atom
  • Ethenyl 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-12-propenyl, 1-pentenyl, Two —Pentyl, 3 —pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-to C 2 such cyclohexenyl - 6 alkenyl group,
  • X 6 and X 7 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isoptyl, t-butyl, pentyl and its isomers, hexyl and its isomers Represents a Ci- 6 alkyl group.
  • X 6 and X 7 may be taken together to form a ring having 5 to 8 carbon atoms.
  • Examples of such a ring having 5 to 8 carbon atoms may have a substituent (cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl).
  • Y is a cyano group
  • Cyclobutyl pill 1-methylcyclopropyl, 2,2,3,3-tetramethylcyclopentyl, cyclobutyl, cyclopentyl, 1-methylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, 4-methylcyclohexyl, etc. an optionally substituted C 3 - 8 consequent opening alkyl group,
  • phenyl C — 6 alkyl group G! A phenyl group optionally substituted with, a phenoxy group optionally substituted with, a phenoxyalkyl group optionally substituted with, a phenylthio group optionally substituted with, a phenylthio group optionally substituted with C!
  • _ 6 alkyl group in which may be substituted Hue Nils Luffy El group, in which may be substituted Hue Nils sulfinyl ⁇ , an alkyl group, in which may be substituted Fuenirusuru Honiru group, in which may be substituted good phenylalanine alkylsulfonyl C i _ 6 alkyl group, in unsubstituted or Yoi Anirino group, in optionally substituted Anirino CL- 6 alkyl group, in which may be substituted 2 - also is properly Choi two Le group 3 - thienyl group, in optionally substituted thienyl C _ 6 alkyl group, in which may be substituted 2 - pyridyl, 3 - pyridyl is properly 4 one Represent an Pyridyl C i _ 6 alkyl group optionally substituted by a pyridyl or G t.
  • Halogen atoms such as fluorine, chlorine, bromine and iodine
  • Ci- 6 haloalkyl groups such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, tolufluoroethyl, and pentafluoroethyl;
  • 6- alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, t-butoxy,
  • C such as chloromethoxy, dichloromethoxy, trichloromethoxy, trifluoromethoxy, 1-fluoroethoxy, 1,1 difluoroethoxy, 2,2,2—trifluoroethoxy, pentafluoroethoxy, etc.
  • _ 6 haloalkoxy group
  • C 2 _ 6 alkynyloxy groups such as 2 —propinyloxy, 2 —butynyloxy, 1 —methyl-2-propynyloxy,
  • Ci- 6 alkylthio groups methylsulfiel, ethylsulfinyl, propylsulfinyl, butylsulfinyl Alkylsulfinyl group such as
  • Ci-e alkylamino such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isoptylamino, sec-butylamino, t-butylamino, 1-methylbutylamino, n-pentylamino, etc.
  • Tri-C i- 6 alkylsilyl groups such as trimethylsilyl
  • C 1-6 alkoxy C i- 6 alkyl group such as methoxymethyl, methoxethyl, ethoxymethyl, propoxymethyl, butoxymethyl,
  • Ci- 6 alkylthio- 6 alkyl groups such as methylthiomethyl, methylthioethyl, ethylthioethyl, ethylthiomethyl, propylthiomethyl, and butylthiomethyl;
  • alkylsulfonyl - - 6 alkyl group methylsulfonylmethyl, C methylsulfonyl E chill, E chill sulfonyl E chill, Echiru sulfonyl methyl, propyl sulfonyl methyl, heptyl sulfonyl methyl and the like
  • C such as methylcarbonyl, ethylcarbonyl, propylcarbonyl, butylcarbon
  • a C x _ 6 alkoxy group, a phenyl group optionally substituted with G 3 , a pyridyl group optionally substituted with G 2 , a pyridyloxy group optionally substituted with G 2 , a phenyl group optionally substituted with G 4 Represents a phenyl group which may be substituted by a diyl group or G 4 .
  • G 2 is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec C-e alkyl groups such as monobutyl, isobutyl, t-butyl, n-pentyl and its isomers, n-hexyl and its isomers,
  • Halogen atoms such as fluorine, chlorine, bromine and iodine
  • Ci-6 haloalkyl groups such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluorofluoryl, pentafluoroethyl, etc .; Is
  • G 3 is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isoptyl, t-butyl, n-pentyl and its isomers, n-hexyl and its isomers, and the like. 6- alkyl group, or
  • G 4 is a nitro group, a cyano group
  • Halogen atoms such as fluorine, chlorine, bromine and iodine
  • C t-e alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, t-butoxy,
  • Ci- 6 haloalkoxy groups such as chloromethoxy, dichloromethoxy, trichloromethoxy, trifluoromethoxy, 1-fluoroethoxy, 1,1-difluoroethoxy, methylthio, ethylthioethyl, n-propylthio, isopropylthio, n-butylthio , Isobutylthio, sec-butylthio, t-butylthio and other Ci- 6 alkylthio groups, methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, n-butylsulfinyl and other 6- alkylsulfinyl groups,
  • alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, n-butylsulfonyl,
  • Di-C-alkylamino groups such as dimethylamino, getylamino, dipropylamino, dibutylamino, ethylisopropyl pyramino, and methylpropylamino;
  • a C-ealkylcarbonyl group such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, n-butylcarbonyl, or
  • Ci-alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, and t-butoxycarbonyl.
  • Z is an oxygen atom, a sulfur atom, or a hydrogen atom or a C ⁇ -alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isoptyl, t-butyl, etc. Represents a nitrogen atom.
  • B represents a phenyl group substituted with W or a heterocyclic group substituted with W.
  • W is a nitro group, a cyano group
  • Halogen atoms such as fluorine, chlorine, bromine and iodine
  • 6- alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, t-butoxy,
  • C- 6- nitroalkoxy groups such as chloromethoxy, dichloromethoxy, trichloromethoxy, trifluoromethoxy, 1-fluoroethoxy, 1,1-difluoroethoxy, methylthio, ethylthio, n-propylthio, isopropyl building thio, n- Puchiruchio, I Sobuchiruchio, sec- Puchiruchio, C alkylthio group such as t one Puchiruchio, methylsulfinyl, E chill sulfinyl, propyl sulfinyl, Puchirusurufi two Le etc. - 6 alkylsulfinyl group,
  • 6- alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, n-butylsulfonyl, Ci-e alkylamino groups such as methylamino, n-propylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec-butylamino, t-butylamino, 1-methylbutylamino, n-bentylamino, etc.
  • 6- alkylcarbonyl groups such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, n-butylcarbonyl, etc.
  • G 5 is a nitro group, a cyano group
  • Halogen atoms such as fluorine, chlorine, bromine and iodine
  • 6- alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, etc.
  • Ci-e haloalkyl groups such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoromethyl, pentafluoroethyl, etc .; butoxy, ethoxy, n- Purobokishi, Isopurobokishi, n - butoxy, sec - butoxy, isobutoxy, t one butoxy (: E - 6 alkoxy group,
  • Ci-s alkyls such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isoptylamino, sec-butylamino, t-butylamino, 1-methylbutylamino, n-bentylamino, etc.
  • Amino group methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isoptylamino, sec-butylamino, t-butylamino, 1-methylbutylamino, n-bentylamino, etc.
  • Amino group such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isoptylamino, sec-butylamino, t-butylamino
  • Dialkylamino groups such as dimethylamino, getylamino, pyruvamino dibu, dibutylamino, ethylisopropyl pyramino, methylpropylamino, methylbutylamino, etc.
  • heterocyclic group substituted by W a 5- or 6-membered heterocyclic group containing 1 to 4 nitrogen atoms, oxygen atoms or sulfur atoms is preferable, for example, 2-furyl, 3-furyl, 2-furyl.
  • R is a hydrogen atom
  • C alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and its isomers, represented by the formula CO Rt that group, a group ⁇ formula CS Ri, a group represented by S 0 2 R 2, ⁇ Se Tokishimechiru, Viva Roy Ruo carboxymethyl, hepta noisy Ruo carboxymethyl, ⁇ Se butoxy Echiru, hexyl or the like to ⁇ Se butoxy Alkyl carboxy ⁇ 3 t — 6 alkyl group, cyclopropyl carbonyl oxymethyl, cyclopentyl carbonyl oxymethyl, cyclohexyl carbonyl oxymethyl, cyclo propyl carbonyl oxethyl, cyclo propyl carbonyl oxy of cyclohex
  • Base may have a substituent emission zone I Ruo carboxymethyl represents phenylalanine carbonyl O carboxymethyl C! _ 6 alkyl groups such as 2- (Benzoiruokishi) Echiru.
  • Methylthio, Echiruchio, n - propylthio, isopropylthio, n - Puchiruchio, I Sobuchiruchio, sec - Puchiruchio, t - C i _ 6 alkylthio groups such Puchiruchio, Mechiruami Bruno, Echiruami Bruno, n- Puropiruami Roh, isopropyl ⁇ Mi Bruno, n—Butylamino, isobutylamino, sec—butylamino, t—butylamino, 1-methylbutylamino, n—pentylamino, and other CJ- 6 alkylamino groups,
  • Di-C-alkylamino groups such as dimethylamino, getylamino, dipropylamino, dibutylamino, ethylisobutyrylamino, methylpropylamino and methylbutylamino;
  • a phenyl c alkoxy group which may have a substituent, or
  • R 2 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isoptyl, sec-butyl, t-butyl, n-pentyl and its isomer, n-hexyl and its isomer, n-heptyl and its isomers, n - represents a nonyl and its isomers, C i "i 2 ⁇ alkyl group or an optionally substituted phenylene group, a n- dodecyl.
  • Examples of the substituent of the phenyl group which may have a substituent in R 1 or R 2 include halogen atoms such as fluorine, chlorine, bromine and iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. — Butyl, isobutyl, t-butyl, etc.
  • 6- alkyl groups chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trichloromethyl
  • Ci-haloalkyl groups such as fluoroethyl and pentafluorethyl; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and 6-alkoxy groups such as t-butoxy.
  • the substituent may have a Hue sulfonyl (- it is a 6 Hue sulfonyl (i-6 Al kill the alkyl group, benzyl, 1-Fueniruechiru, 2 - Fueniruechiru, 1 one-phenylene Rou 1-methylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl and the like, and the phenyl C i-e alkoxy group, which may have a substituent, phenyl C
  • ! _ 6 alkoxy groups include benzyloxy, 1-phenylethoxy, 2-phenyl Toxic, 1-phenyl 1-methylethoxy, 1-phenylpropoxy, 2-phenylpropoxy, 3-phenylpropoxy and the like.
  • the compound of the present invention can be produced, for example, by the following method.
  • a and B represent the same meaning as described above, and L represents a halogen atom, a C-e alkoxy group, a phenoxy group, a 1-imidazolyl group, a 1-pyrazolyl group, a p-toluenesulfonyloxy group
  • P -Re represents a leaving group such as a methylphenylsulfonyloxy group), a methanesulfonyloxy group (methylsulfonyloxy group), or a trifluoromethanesulfonyl group (trifluoromethylsulfonyloxy group).
  • the compound represented by the general formula (2) can be obtained.
  • Bases used in this reaction include metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, n-butyllithium, lithium diisopropylamide (LDA) And metal hydrides such as sodium hydride and potassium hydride, and organic bases such as triethylamine, diisopropylethylamine and pyridine.
  • metal hydroxides such as sodium hydroxide and potassium hydroxide
  • carbonates such as sodium carbonate and potassium carbonate
  • n-butyllithium lithium diisopropylamide (LDA)
  • LDA lithium diisopropylamide
  • metal hydrides such as sodium hydride and potassium hydride
  • organic bases such as triethylamine, diisopropylethylamine and pyridine.
  • Solvents that can be used include N, N-dimethylformamide (DMF), N, N-dimethylacetamide, dimethylsulfoxide (DMSO), and tetrahydrofuran.
  • reaction temperature is preferably in the range from 178 ° C to the boiling point of the solvent used.
  • L ' is a halogen atom, - 6 alkoxy group, phenoxy group, 1 one imidazolyl group, 1-pyrazolyl group, p- toluenesulfonyl O carboxymethyl
  • a leaving group such as a methanesulfonyloxy group, a trimethanesulfonyl group, a phthalimid group, or a succinic imid group.
  • a compound such as a substituted alkyl halide, substituted benzyl halide, or substituted phenyl halide represented by the formula (6), or a halogenating agent is reacted with a cyanoacetyl compound (5) in the presence or absence of a base.
  • the compound represented by the general formula (2) can be easily produced.
  • Examples of the salt J2 used in this reaction include metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, n-butyllithium, and lithium diisopropylamide.
  • Organic metal such as (LDA); metal hydrides such as sodium hydride and potassium hydride; and organic bases such as triethylamine, diisopropylethylamine, pyridine and the like.
  • reaction temperature is preferably in the range from 178 TC to the boiling point of the solvent used.
  • the cyanoacetyl compound represented by the general formula (5) which is a starting compound of the method of the present invention, can be easily produced, for example, by the method shown in the following formula.
  • L ′ is a halogen atom
  • p-tol R 3 represents a leaving group such as an ensulfonyloxy group, a methanesulfonyloxy group, or a trifluoromethanesulfonyloxy group
  • R 3 represents a C alkyl group
  • a compound represented by the formula (8) is obtained by reacting a cyanoacetic acid ester represented by the formula (7) with a compound represented by the formula (6) in the presence of a base.
  • This reaction is carried out by using a base such as sodium hydride, potassium hydride, sodium carbonate in a solvent such as DMF, DMS O, THF, acetonitrile, HMPT, or 2 Phase transfer catalysts such as quaternary amine salts and metal water such as sodium hydroxide and potassium hydroxide in a two-layer solvent of benzene, toluene, dichloromethane, chloroform, and carbon tetrachloride and water.
  • a base such as an oxide in a temperature range from 178 to the boiling point of the solvent used.
  • This reaction is carried out in a solvent such as DMF, DMSO, THF, acetone, HMPT, benzene, toluene, dichloromethane, chloroform, carbon tetrachloride, etc. in a solvent such as sodium hydroxide and potassium hydroxide.
  • a solvent such as sodium hydroxide and potassium hydroxide.
  • LDA lithium diisopropylamide
  • the reaction is carried out in a temperature range from 178 to the boiling point of the solvent used.
  • This reaction is carried out in a solvent such as water, methanol, ethanol, dimethoxetane, dioxane, DMF, DM.SO, benzene, toluene, etc., acid such as sulfuric acid, hydrochloric acid, acetic acid, P-toluenesulfonic acid, sodium hydroxide, sodium hydroxide, etc.
  • a solvent such as water, methanol, ethanol, dimethoxetane, dioxane, DMF, DM.SO, benzene, toluene, etc.
  • acid such as sulfuric acid, hydrochloric acid, acetic acid, P-toluenesulfonic acid, sodium hydroxide, sodium hydroxide, etc.
  • the reaction is carried out in a temperature range from 178 ° C to the boiling point of the solvent used, using a base such as ummethoxide or triethylamine, or a metal halide such as
  • the compound represented by the general formula (2) exists as a keto-type and an enol-type tautomer. All of these isomers are included in the scope of the present invention.
  • L represents a halogen atom, an e- 6 alkoxy group, a phenoxy group, a 1-imidazolyl group, an 1-pyrazolyl group, a p-toluenesulfonyloxy group.
  • a leaving group such as a methanesulfonyloxy group or a trifluorosulfonyloxy group.
  • the compound represented by the general formula (1) can be obtained by reacting the compound represented by the general formula (2) with a compound represented by the formula (10) in a solvent in the presence of a base. it can.
  • the base used in this reaction includes alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, and organic compounds such as N-butyllithium and LDA.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • carbonates such as sodium carbonate and potassium carbonate
  • organic compounds such as N-butyllithium and LDA.
  • metals metal hydrides such as sodium hydride and hydrogenation hydride
  • organic bases such as triethylamine, diisopropylethylamine, and pyridine.
  • Examples of the solvent that can be used include DMF, DMSO, THF, acetonitril, HMPT, benzene, toluene, dichloromethane, chloroform, and carbon tetrachloride.
  • the reaction temperature is preferably in the range from 178 ° C to the boiling point of the solvent used.
  • the compound of the present invention represented by the general formula (1) has a stereoisomer represented by the formula (1 ′) as shown below, and depending on the reaction conditions and the purification method, either one of them is present. In some cases, and a mixture of isomers in some cases. All of these isomers are included in the scope of the present invention.
  • the desired product can be obtained by performing ordinary post-treatment.
  • the structure of the compound of the present invention was determined from IR, NMR, MS and the like.
  • BR Xn BR Xn BR Xn bl r6 one b3 r6 4-iPr b6 r6 4-CF3 bl r6 4-F b3 r6 4-tBu b6 r6 4-OCFg bl r6 4-C1 b4 r6-b6 r6 4-iPr bl r6 4-Br b4 r6 4-F b6 r6 4-tBu bl r6 2,4-F 2 b4 r6 4-C1 b7 r6 ⁇ bl r6 2,4-Cl 2 b4 r6 4-Br b7 r6 4-F bl r6 2 , 4-Br 2 b4 r6 2,4-F 2 b7 r6 4-C1 bl r6 2,6-F 2 b4 r6 2,4-Cl 2 b7 r6 4-Br bl r6 2,6-Cl 2
  • Table ⁇ ⁇ illustrates all combinations of ⁇ and R represented by the above formulas 2-1 to 2-58.
  • the compound of the present invention is useful as an active ingredient of a pesticide, particularly useful as an insecticide, an acaricide, a nematocide, a sanitary pest control agent, or a biofouling agent attached to water.
  • a pesticide particularly useful as an insecticide, an acaricide, a nematocide, a sanitary pest control agent, or a biofouling agent attached to water.
  • the composition containing the compound of the present invention can be preferably applied particularly as an insecticide and acaricide.
  • the compound of the present invention When the compound of the present invention is actually applied, it can be used in a pure form without adding other components, and can be used in a form peculiar to general pesticides for use as pesticides, for example, wettable powders, granules Preparations, powders, emulsions, aqueous solvents, suspensions, flowables and the like.
  • mineral powder such as soybean grains, vegetable powder such as flour, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay, etc.
  • Organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate are used.
  • petroleum fractions such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, methylisobutyl Ketone, mineral oil, vegetable oil, water, etc. can be used as the solvent.
  • a surfactant may be added if necessary.
  • the surfactant is not particularly limited. Examples of the surfactant include polyoxyethylene-added alkyl ether, polyoxyethylene-added higher fatty acid ester, polyoxyethylene-added sorbitan higher fatty acid ester, and polyoxyethylene.
  • Non-ionic surfactants such as added tristyryl ether, sulfates of alkylphenol added with polyoxetylene, alkyl naphthalene sulfonates, polycarboxylates, lignin sulfonates, alkyl naphthalene sulfones
  • examples include a formaldehyde condensate of an acid salt and a copolymer of isobutylene-maleic anhydride.
  • the amount of the active ingredient in the preparation is preferably from 0.01 to 90% by weight, particularly preferably from 0.05 to 85% by weight.
  • the wettable powder, emulsion, suspension, and flowable thus obtained is diluted with water to a predetermined concentration to form a suspension or emulsion, and the powder and granules are used as they are in plants or Applies to soil.
  • the compound of the present invention alone is sufficiently effective, but it can also be used in combination with one or more of various fungicides, insecticides and acaricides, or synergists.
  • various fungicides, insecticides, acaricides, and plant growth regulators that can be used by mixing with the compound of the present invention are shown below.
  • Benzoylurea and other insecticides Difluvenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, benzepin, diafentiuron, imidacloprid, Fipronil, nicotine sulfate, rotenone, metaaldehyde, machine oil, microbial pesticides such as BT and entomopathogenic viruses.
  • Plant growth regulator Plant growth regulator
  • Gibberellins eg, gibberellin A3, gibberellin A4, gibberellin A7, IAA, NAA and the like.
  • the compound of the present invention can be used for controlling agricultural pests, sanitary pests, storage pests, clothing pests, house pests, and the like, and has an insecticidal, nymphalidic, larvicidal, and ovicidal action.
  • the following are typical examples.
  • Lepidopteran pests for example, Hasmonyoto, Totoga, Tamanayaga, Aomushi, Tamanaginba, Konaga, Tyano Kokakumonhamaki, Chiyamamaki, Momoshingiga, Nashihimeshinkui, Mikanhamoguriga, Chinohogaga, Koganogama Biancon Borra, American Whitebird, Suzimada Lameiga, Heliotis, Helicobelpa, Agrotis, Iga, Kodlinga, Petakamimushi, etc.
  • Hemiptera pests for example, peach aphid, peter aphid, mosquito aphid, wheat viviparous beetle, scorpion beetle, stag beetle, anopheles mosquito, lycopodium cylindris, lycopodium lice, white lice, and white lice Coleoptera, Pterodactyla, Pterodactyla, Pterodactyla serrata, Coleoptera japonicus, etc., Coleoptera insects, for example, Cypridina beetle, Periphyll beetle, Colorado potato beetle, Rice porphyra, Kokuzumushi, Azukizomushi, Ogyukota, Oxalus Pine beetle, Sesame beetle, Sesame beetle, Agryotis,
  • Diptera pests for example, house flies, oak fly, sarcophagid flies, perilla flies, mandarin fruit flies, seed flies, rice leaf maggots, key flies, sand flies, and sand flies Cayer power, Anetaishima power, Shinahamadara power, etc.
  • Hymenoptera pests for example, southern thistle ⁇ ; Chrysanthemum thistle, etc., Hymenoptera, pests, for example, pygmy ant, yellow-horned wasp, force-bumblebee, etc.
  • Orthoptera pests for example, Tonosa-sama grasshopper, Chinese cockroach, Scarlet cockroach, Japanese black cockroach, etc.
  • Isoptera pests for example, house termites, mountain termites,
  • Lepidopteran pests such as rodents, louse Pests, such as rodents,
  • Mites for example, Namihadani, Nisenamihadani, Kanzahadani, Citrus spider mite, Lingo red mite, Citrus avidani, Lingo savidani, Chianohoko lidani, Brevipalpas spp.
  • Plant-parasitic nematodes for example, sweet potato nematode, negusarecentiyu, soybean cistocentiyu, rice singarecentiyu, matsunoza centiyu, and the like.
  • Pests that are preferably applied include lepidopteran pests, Hemiptera pests, Coleoptera pests, Pteridophytes pests, and two kinds of spiders, particularly preferably Lepidoptera pests, Hemiptera pests, two kinds of spiders It is.
  • the compound of the present invention is an agent having an excellent insecticidal and acaricidal effect against not only susceptible strains but also pests of organic phosphorus, carbamate, and pyrethroid-resistant strains, and mites of acaricide-resistant strains. .
  • the compound of the present invention has low phytotoxicity, low toxicity to fish and warm-blooded animals, and is a highly safe drug.
  • the compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to aquatic organisms such as ship bottoms and fish nets.
  • Example 16 granules
  • composition of the present invention obtained as described above is applied as a pest control agent.
  • Example 7 15 to 10 days after germination of the seeds sown in a three-dimensional bowl, 15 inoculated female adults of Nami-Nada two, which are resistant to organic phosphorus, were administered.
  • a chemical solution diluted with water was sprayed so that the compound concentration was 125 ppm. They were placed in a thermostatic chamber at a temperature of 25 t; and a humidity of 65%, and three days after spraying, the adulticidal rate was examined. The test is a .2 iteration.
  • chlordimeform was used as a control compound.
  • the insecticidal rate of the control compound (125 ppm) was 13%.
  • 6 one 4, 6—9.6-10, 6—1 16-1 2-16, 6-17, 6-18 1 19, 6-20, 6-21, 6- twenty four

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Health & Medical Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Pyrrole Compounds (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des composés représentés par la formule générale (1), un procédé de production de ces composés, ainsi que des insecticides et acaricides contenant ces composés et les sels de ceux-ci, en tant que principe actif. Dans cette formule, A représente un élément choisi dans les groupes représentés par A1 à A12; B représente phényle substitué par W ou un groupe hétérocyclique substitué par W et R représente hydrogène, alkyle C1-6, COR1, CSR1, SO2R2, alkylcarbonyloxy C1-6 (alkyle C1-6), cycloalkylcarbonyloxy C3-6 (alkyle C1-6), ou phénylcarbonyloxy (alkyle C1-6) éventuellement substitué.
PCT/JP2000/007551 1999-10-29 2000-10-27 Composes possedant un groupe cyano, insecticides et acaricides les contenant WO2001032609A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR0015158-0A BR0015158A (pt) 1999-10-29 2000-10-27 Compostos, processo para produzir os mesmos, e, inseticida e acaricida
JP2001534762A JP4679781B2 (ja) 1999-10-29 2000-10-27 シアノ基を有する新規な化合物および殺虫・殺ダニ剤
KR1020027005361A KR20020059648A (ko) 1999-10-29 2000-10-27 시아노기를 갖는 신규한 화합물 및 살충ㆍ살비제
AU79604/00A AU7960400A (en) 1999-10-29 2000-10-27 Novel compounds having cyano and insecticides and miticides

Applications Claiming Priority (8)

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JP30832399 1999-10-29
JP11/308323 1999-10-29
JP2000-122521 2000-04-24
JP2000122521 2000-04-24
JP2000-178334 2000-06-14
JP2000178334 2000-06-14
JP2000-221795 2000-07-24
JP2000221795 2000-07-24

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002081429A1 (fr) * 2001-04-04 2002-10-17 Nippon Soda Co., Ltd. Nouveau compose possedant un groupe oxime et insecticide/acaricide
WO2009005015A1 (fr) * 2007-06-29 2009-01-08 Nissan Chemical Industries, Ltd. Composé isoxazoline ou énone oxime substitué, et agent de lutte contre les nuisibles

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Publication number Priority date Publication date Assignee Title
CN110776463B (zh) * 2019-11-28 2021-08-03 南通大学 含3-三氟甲基吡唑的吡唑肟类衍生物的制备和应用
CN110746356B (zh) * 2019-11-28 2021-06-29 南通大学 含3-三氟甲基-5-氯吡唑结构的二氟甲基吡唑肟酯的制备方法和用途

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DE4330105A1 (de) * 1993-09-06 1995-03-09 Bayer Ag Verwendung von beta-Hetaryl-beta-oxopropionsäurenitrile als Schädlingsbekämpfungsmittel
WO1998035935A1 (fr) * 1997-02-14 1998-08-20 Ishihara Sangyo Kaisha Ltd. Composes d'acrylonitrile, leur procede de production et les pesticides les contenant

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4330105A1 (de) * 1993-09-06 1995-03-09 Bayer Ag Verwendung von beta-Hetaryl-beta-oxopropionsäurenitrile als Schädlingsbekämpfungsmittel
WO1998035935A1 (fr) * 1997-02-14 1998-08-20 Ishihara Sangyo Kaisha Ltd. Composes d'acrylonitrile, leur procede de production et les pesticides les contenant

Non-Patent Citations (1)

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Title
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002081429A1 (fr) * 2001-04-04 2002-10-17 Nippon Soda Co., Ltd. Nouveau compose possedant un groupe oxime et insecticide/acaricide
WO2009005015A1 (fr) * 2007-06-29 2009-01-08 Nissan Chemical Industries, Ltd. Composé isoxazoline ou énone oxime substitué, et agent de lutte contre les nuisibles
US8053452B2 (en) 2007-06-29 2011-11-08 Nissan Chemical Industries, Ltd. Substituted isoxazoline or enone oxime compound, and pest control agent
JP5316808B2 (ja) * 2007-06-29 2013-10-16 日産化学工業株式会社 置換イソキサゾリン又はエノンオキシム化合物および有害生物防除剤

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JP4679781B2 (ja) 2011-04-27
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BR0015158A (pt) 2002-10-29
KR20020059648A (ko) 2002-07-13

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