+

WO1997003976A1 - Semicarbazone derivatives and pesticides - Google Patents

Semicarbazone derivatives and pesticides Download PDF

Info

Publication number
WO1997003976A1
WO1997003976A1 PCT/JP1996/002022 JP9602022W WO9703976A1 WO 1997003976 A1 WO1997003976 A1 WO 1997003976A1 JP 9602022 W JP9602022 W JP 9602022W WO 9703976 A1 WO9703976 A1 WO 9703976A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
substituted
alkyl
hydrogen atom
och
Prior art date
Application number
PCT/JP1996/002022
Other languages
French (fr)
Inventor
Kazuo Yagi
Tadashi Ohtsu
Atsushi Irimata
Tomoyuki Ogura
Takeshi Mita
Toshiro Miyake
Youichi Inoue
Norihiko Mimori
Shinji Takii
Original Assignee
Nissan Chemical Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Industries, Ltd. filed Critical Nissan Chemical Industries, Ltd.
Priority to AU64703/96A priority Critical patent/AU6470396A/en
Publication of WO1997003976A1 publication Critical patent/WO1997003976A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
    • 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
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • 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
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/86—Hydrazides; Thio or imino analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with 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
    • C07D231/38—Nitrogen atoms
    • C07D231/40—Acylated on said nitrogen atom
    • 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
    • C07D239/42—One nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D261/18—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or 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
    • C07D277/38—Nitrogen atoms
    • C07D277/44—Acylated amino or imino radicals
    • C07D277/46—Acylated amino or imino radicals by carboxylic acids, or sulfur or nitrogen analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or 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
    • C07D277/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/82—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or 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
    • 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
    • C07D333/38—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 novel semicarbazone derivatives and pesticides containing such derivatives as active ingredients.
  • the present inventors have conducted extensive researches on semicarbazone derivatives and as a result, have found that novel 5- or 6-membered hetero ring-substituted semicarbazone derivatives and their salts exhibit excellent pesticidal activities, particularly insecticidal activities at a low dose, and they are very useful compounds substantially free from adverse effects against mammals, fishes and beneficial insects.
  • the present invention has been accomplished on the basis of these discoveries.
  • the present invention provides a semicarbazone derivative of the formula (I) or its salt:
  • Q is any one of Q-1 to Q-37:
  • J is any one of J-1 to J-33, provided that when Q is and G is G-1, J is other than J-33;
  • G is any one of G-1 to G-8, provided that when Q is Q-37 and J is J-33, G is other than G-1;
  • W is an oxygen atom or a sulfur atom
  • each of X, Y and Z which are independent of one another, is a hydrogen atom, a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 1-6 haloalkyl group, a C 2-6 haloalkenyl group, a C 2-6
  • haloalkynyl group a C 3-6 cycloalkyl group, a C 3-6
  • halocycloalkyl group a C 4-7 cycloalkylalkyl group, -OR 10 , -CN, -N 3 , -SCN, -NO 2 , -SH, -S(O) r R 7 , -OCHO, -CHO, -C(O)R 7 , -C(O)OR 7 , -C(O)NR 7 R 8 , -S(O) 2 NR 7 R 8 , -NR 7 R 8 , -NR 8 CHO,
  • each of R 1 , R 2 and R 3 which are independent of one another, is a hydrogen atom, a C 1-6 alkyl group, a
  • -N CR 11 R 12 , -P(O)(OR 13 ) 2 , -P(S)(OR 13 ) 2 , -S(O) r R 7 ,
  • each of R 4 and R 5 which are independent of each other, is a hydrogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 1-6 haloalkyl group, a C 2-6 haloalkenyl group, a C 2-6 haloalkynyl group, a C 3-6 cycloalkyl group, a C 3-6 halocycloalkyl group, a C 4-7 cycloalkylalkyl group, a C 2-6 alkoxyalkyl group, a C 2-6 alkylthioalkyl group, a C 1-6 nitroalkyl group, a C 2-6 cyanoalkyl group, a C 3-8 alkoxycarbonylalkyl group, -CHO, -C(O)R 7 , -C(O)OR 7 , -C(O)NR 7 R 8 , or -S(O) 2
  • R 6 is a hydrogen atom, a halogen atom, a hydroxyl group, -CN, -NO 2 , a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 1-6 alkoxy group, a C 1-6 haloalkoxy group, a C 1- 6 alkylthio group, a C 1-6 haloalkylthio group, a C 1-6 alkylsufonyl group, a C 1-6 haloalkylsulfonyl group, a C 2-6 alkoxycarbonyl group, an amino group, or a di-C 1-6 alkylamino group;
  • R 7 is a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 1-6 haloalkyl group, a C 2-6 haloalkenyl group, a C 2-6 haloalkynyl group, a C 3-6 cycloalkyl group, a C 3-6 halocycloalkyl group, a C 4-7 cycloalkylalkyl group, a C 2-6 alkoxyalkyl group, a C 2-6 alkylthioalkyl group, a C 1-6 nitroalkyl group, a C 2-6 cyanoalkyl group, a C 3-8 alkoxycarbonylalkyl group, a phenyl group which may be substituted by (R 6 ) q , a benzyl group which may be
  • R 8 is a hydrogen atom, a C 1-4 alkyl group, a C 2-4 alkenyl group, or a C 2-4 alkynyl group;
  • R 7 and R 8 may together form -CH 2 CH 2 CH 2 CH 2 -,
  • R 9 is a C 1-3 alkoxy group, a C 1-3 haloalkoxy group, -CN, -NO 2 , -S(O) r R 7 , -P(O)(OR 13 ) 2 , -P(S) (OR 13 ) 2 , -C(O)R 7 , -C(O)OR 7 , or a phenyl group which may be substituted by
  • R 10 is a hydrogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 1-6 haloalkyl group, a C 2-6 haloalkenyl group, a C 2-6 haloalkynyl group.
  • R 11 is a hydrogen atom, a C 1-4 alkyl group, -C(O)R 7 , or -C(O)OR 7 ;
  • R 12 is a hydrogen atom, a C 1-4 alkyl group, a C 1-4 haloalkyl group, or a phenyl group which may be
  • R 11 and R 12 may together form
  • R 13 is a C 1-3 alkyl group, or a phenyl group which may be substituted by (R 6 ) q ;
  • R 14 is a C 1-4 alkyl group
  • R 15 is a C 1-18 alkyl group
  • R 16 and R 17 which are independent of each other is a C 1-4 alkyl group, or R 16 and R 17 may together form -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, or -CH 2 CH 2 OCH 2 CH 2 -; each of R 18 and R 19 which are independent of each other, is a C 1-4 alkyl group;
  • R 20 is a C 1-4 alkyl group, or a phenyl group which may be substituted by (R 6 ) q ;
  • k is an integer of from 0 to 5, provided that when k is from 2 to 5, the plurality of X may be the same or different;
  • n is an integer of from 0 to 5, provided that when m is from 2 to 5, the plurality of Y may be the same or different;
  • n is an integer of from 0 to 5, provided that when n is from 2 to 5, the plurality of Z may be the same or different;
  • p is an integer of from 1 to 3, provided that when p is 2 or 3, the plurality of R 9 may be the same or
  • q is an integer of from 0 to 4, provided that when q is from 2 or 4, the plurality of R 6 may be the same or different;
  • r is an integer of from 0 to 2.
  • the present invention also provides a pesticide which contains at least one such semicarbazone derivative or its salt as an active ingredient.
  • each substituent disclosed above may be linear, branched or cyclic.
  • n- means normal, i- means iso, sec- means secondary, t- means tertiary, and c- means cyclo.
  • the alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, an i-butyl group, a sec-butyl group, a t- butyl group, a n-pentyl group, a n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, or a 1-ethyl-1-butyl group.
  • the alkenyl group may, for example, be an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 2-methyl-2-propenyl group, a 2-butenyl group, a 3-methyl-2-butenyl group, a 3-butenyl group, a 4-pentenyl group, or a 2,3-dimethyl-2-butenyl group.
  • the alkynyl group may, for example, be an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, or a 4,4-dimethylpentynyl group.
  • the cycloalkyl group may, for example, be a c-propyl group, a c-butyl group, a c-pentyl group, a c-hexyl group or a 1-methyl-c-propyl group.
  • the pyridyl group may, for example, be a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group.
  • the alkoxy group may, for example, be a methoxy group, an ethoxy group, a n-propoxy group, an i-propoxy group, a n-butoxy group, an i-butoxy group, a sec-butoxy group or a t-butoxy group.
  • the alkylthio group may, for example, be a methylthio group, an ethylthio group, a n-propylthio group, an i-propylthio group, a n-butylthio group, an i-butylthio group, a sec-butylthio group or a t-butylthio group.
  • the halogen atom may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • W is an oxygen atom or a sulfur atom, preferably an oxygen atom.
  • Each of X, Y and Z which are independent of one another, may, for example, be a hydrogen atom, a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, C 1-6 haloalkyl group, a C 2-6 haloalkenyl group, a C 2-6 haloalkynyl group, a C 3-6 cycloalkyl group, a C 3-6 halocycloalkyl group, a C 4-7 cycloalkylalkyl group, a hydroxyl group, a C 1-6 alkoxy group, a C 2-6 alkenyloxy group, a C 2-6 alkynyloxy group, a C 1-6 haloalkoxy group, a C 2-6 haloalkenyloxy group, a C 2-6 haloalkynyloxy group, a C 3-6 cycloalkyloxy group,
  • alkylthioalkyloxy group a C 2-7 cyanoalkyloxy group, a C 3-8 alkoxycarbonylalkyloxy group, a C 2-7 alkylcarbonyloxy group, a C 3-7 alkenylcarbonyloxy group, a C 3-7
  • alkynylcarbonyloxy group a C 2-7 haloalkylcarbonyloxy group, a C 3-7 haloalkenylcarbonyloxy group, a C 3-7
  • alkoxyalkylcarbonyloxy group a C 3-7 alkylthioalkylcarbonyloxy group, a C 3-7
  • alkylthioalkylthio group a C 2-6 cyanoalkylthio group, a C 3-8 alkoxycarbonylalkylthio group, a phenylthio group which may be substituted by (R 6 ) q , a benzylthio group which may be substituted by (R 6 ) q , a pyridylthio group which may be substituted by (R 6 ) q , a C 1-6 alkylsulfinyl group, a C 2-6 alkenylsulfinyl group, a C 2-6
  • alkynylsulfinyl group a C 1-6 haloalkylsulfinyl group, a C 2-6 haloalkenylsulfinyl group, a C 2-6 haloalkynylsulfinyl group, a C 3-6 cycloalkylsulfinyl group, a C 3-6
  • cycloalkylalkylsulfinyl group a C 2-6 alkoxyalkylsulfinyl group, a C 2-6 alkylthioalkylsulfinyl group, a
  • phenylsulfinyl group which may be substituted by (R 6 ) q , a benzylsulfinyl group which may be substituted by (R 6 ) q , a pyridylsulfinyl group which may be substituted by (R 6 ) q , a C 1-6 alkylsulfonyl group, a C 2-6 alk ⁇ nylsulfonyl group, a C 2-6 alkynylsulfonyl group, a C 1-6 haloalkylsulfonyl group, a C 2-6 haloalkenylsulfonyl group, a C 2-6
  • haloalkynylsulfonyl group a C 3-6 cycloalkylsulfonyl group, a C 3-6 halocycloalkylsulfonyl group, a C 4-7 cycloalkylalkylsulfonyl group, a C 2-6 alkoxyalkylsulfonyl group, a C 2-6 alkylthioalkylsulfonyl group, a C 2-6 cyanoalkylsulfonyl group, a C 3-8
  • alkoxycarbonylalkylsulfonyl group a phenylsulfonyl group which may be substituted by (R 6 ) q , a benzylsulfonyl group which may be substituted by (R 6 ) q , a pyridylsulfonyl group which may be substituted by (R 6 ) q , -CHO, a C 2-7 alkylcarbonyl group, a C 3-7 alkenylcarbonyl group, a C 3-7 alkynylcarbonyl group, a C 2-7 haloalkylcarbonyl group, a C 4-7 cycloaklylcarbonyl group, a C 4-7
  • halocycloalkylcarbonyl group a C 3-7 alkoxyalkylcarbonyl group, a C 3-7 alkylthioalkylcarbonyl group, a C 3-7 cyanoalkylcarbonyl group, a benzoyl group which may be substituted by (R 6 ) q , a benzylcarbonyl group which may be substituted by (R 6 ) q , a pyridylcarbonyl group which may be substituted by (R 6 ) q , a C 2-7 alkoxycarbonyl group, a C 2-7 haloalkoxycarbonyl group, a C 4-7
  • pyridyloxycarbonyl group which may be substituted by (R 6 ) q , an N-C 1-6 alkyl-C 2-5 alkylcarbamoyl group, a C 2-7 mono-alkylaminocarbonyl group, an N-C 1-6 haloalkyl-C 2-5 alkylcarbamoyl group, a C 2-7 monohaloalkylaminocarbonyl group, a phenylaminocarbonyl group which may be
  • haloalkylcarbonylamino group an N-C 1-4 alkyl-C 4-7 cycloalkylcarbonylamino group, an N-C 1-4 alkyl-C 4-7 halocycloalkylcarbonylamino group, a phenylcarbonylamino group which may be substituted by (R 6 ) q , a
  • alkylsulfonylamino group an N-C 1-4 alkyl-C 1-6
  • haloalkylsulfonylamino group a C 1-6 alkylsulfonylamino group, a C 1-6 haloalkylsulfonylamino group, a
  • R 6 may, for example, be a hydrogen atom, a halogen atom, a hydroxyl group, -CN, -NO 2 , a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 1-6 alkoxy group, a C 1-6 haloalkoxy group, a C 1-6 alkylthio group, a C 1-6 haloalkylthio group, a C 1-6 alkylsulfonyl group, a C 1-6 haloalkylsulfonyl group, a C 2-6 alkoxycarbonyl group, an amino group, or a di-C 1-6 alkyl-amino group, and q is an integer of from 0 to 4.
  • X may preferably be, for example, a hydrogen atom, a halogen atom, a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 1-6 alkoxy group, a C 1-6 haloalkoxy group, a C 1-6 alkylthio group, a C 1-6 haloalkylthio group, a C 1-6 alkylsulfonyl group, or a C 1-6 haloalkylsulfonyl group.
  • k is an integer of from 0 to 5, preferably 0, 1 or 2.
  • the plurality of X may be the same or different.
  • Z may preferably be, for example, a halogen atom, a cyano group, a nitro group, a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 1-6 alkoxy group, a C 1-6 haloalkoxy group, a C 1-6 alkylthio group, a C 1-6 haloalkylthio group, a C 1-6 alkylsulfinyl group, a C 1-6 haloalkylsulfinyl group, a C 1-6 alkylsulfonyl group, a C 1-6
  • n is an integer of from 0 to 5, preferably 1 or 2.
  • the plurality of Z may be the same or different.
  • R 1 , R 2 and R 3 which are independent of one another, may, for example, be a hydrogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 1-6 haloalkyl group, a C 2-6 haloalkenyl group, a C 2-6 haloalkynyl group, a C 3-6 cycloalkyl group, a C 3-6 halocycloalkyl group, a C 4-7 cycloalkylalkyl group, -CHO, a C 2-7 alkylcarbonyl group, a C 3-7 alkenylcarbonyl group, a C 3-7 alkylcarbonyl group, a C 2-7 haloalkylcarbonyl group, a C 3-7 haloalkenylcarbonyl group, a C 3-7
  • haloalkynylcarbonyl group a C 4-7 cycloalkylcarbonyl group, a C 4-7 halocycloalkylcarbonyl group, a C 5-8 cycloalkylalkylcarbonyl group, a C 3-7 alkoxyalkylcarbonyl group, a C 3-7 alkylthioalkylcarbonyl group, a C 3-7 cyanoalkylcarbonyl group, a C 4-9
  • alkoxycarbonylalkylcarbonyl group a benzoyl group which may be substituted by (R 6 ) q , a benzylcarbonyl group which may be substituted by (R 6 ) q , a pyridylcarbonyl group which may be substituted by (R 6 ) q , a C 2-7 alkoxycarbonyl group, a C 3-7 alkenyloxycarbonyl group, a C 3-7
  • alkynyloxycarbonyl group a C 2-7 haloalkoxycarbonyl group, a C 3-7 haloalkenyloxycarbonyl group, a C 3-7 haloalkynyloxycarbonyl group, a C 4-7
  • alkoxyalkoxycarbonyl group a C 3-7
  • alkylthioalkoxycarbonyl group a C 3-7
  • pyridyloxycarbonyl group which may be substituted by (R 6 ) q , a C 2-7 alkyl-thiocarbonyl group, a C 2-7 haloalkyl- thiocarbonyl group, a C 2-7 alkylthio-carbonyl group, a C 2-7 haloalkylthio-carbonyl group, a C 2-7 alkylthio- thiocarbonyl group, a C 2-7 haloalkylthio-thiocarbonyl group, a C 3-8 alkoxycarbonylcarbonyl group, a C 3-8 haloalkoxycarbonylcarbonyl group, an amino group, a C 1-6 alkylamino group, an N-C 1-4 alkyl-C 1-6 alkylamino group, a C 2-7 alkylcarbonylamino group, a di-C 2-7 alkylcarbonylamino group, a C 2-7 alkoxycarbonylamino group
  • alkoxycarbonylalkylsulfonyl group an N-C 1-4 alkyl-C 2-19 alkoxycarbonylaminothio group, a di-C 1-4 alkyl-aminothio group, a 1-pyrrolidin ⁇ thio group, a 1-piperidinothio group, a 1-morpholinothio group, a phenyl group which may be substituted by (R 6 ) q , a C 2-9 alkoxyalkyl group, a C 2-9 haloalkoxyalkyl group, a C 2-7 cyanoalkyl group, a C 2-12 alkylthioalkyl group, a C 3-13 alkylcarbonylalkyl group, a C 3-13 alkoxycarbonylalkyl group, or a benzyl group which may be substituted by (R 6 ) q .
  • R 6 may, for example, be a hydrogen atom, a halogen atom, a hydroxyl group, -CN, -NO 2 , a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 1-6 alkoxy group, a C 1-6 haloalkoxy group, a C 1- 6 alkylthio group, a C 1-6 haloalkylthio group, a C 1-6 alkylsulfonyl group, a C 1-6 haloalkylsulfonyl group, a C 2-6 alkoxycarbonyl group, an amino group, or a di-C 1-6 alkyl-amino group, and q is preferably an integer of from 0 to 2.
  • R 1 may, for example, be preferably a hydrogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 1-6 haloalkyl group, a C 2-6 haloalkenyl group, a C 2-6 haloalkynyl group, a C 3-6 cycloalkyl group, a C 3-6 halocycloalkyl group, a C 4-7 cycloalkylalkyl group, a C 2-9 alkoxyalkyl group, a C 2-9 haloalkoxyalkyl group, a C 2-7 cyanoalkyl group, a C 2-12 alkylthioalkyl group, a C 2-12 alkylcarbonylalkyl group, a C 2-12 alkoxycarbonylalkyl group, or a benzyl group which may be substituted by (R 6 ) q .
  • R 6 may, for example, be a hydrogen atom, a halogen atom, a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 1-6 alkoxy group, or a C 1-6 haloalkoxy group, and q is preferably an integer of from 0 to 2.
  • R 2 may, for example, be preferably a hydrogen atom, a C 1-6 alkyl group, a C 2-9 alkoxyalkyl group, or a C 2-7 alkoxycarbonyl group.
  • R 3 may, for example, be preferably a hydrogen atom, a C 1-6 alkyl group, -CHO, a C 2-7 alkylcarbonyl group, a C 3-7 alkenylcarbonyl group, a C 3-7 alkynylcarbonyl group, a C 2-7 haloalkylcarbonyl group, a C 4-7 cycloalkylcarbonyl group, a C 4-7 halocycloalkylcarbonyl group, a C 3-7 alkoxyalkylcarbonyl group, a C 3-7 alkylthioalkylcarbonyl group, a C 3-7 cyanoalkylcarbonyl group, a benzoyl group which may be substituted by (R 6 ) q , a benzylcarbonyl group which may be substituted by (R 6 ) q , a pyridylcarbonyl group which may be substituted by (R 6 ) q , a C 2-7
  • alkoxycarbonyl group a C 2-7 haloalkoxycarbonyl group, a C 4-7 cycloalkyloxycarbonyl group, a C 4-7
  • R 6 may, for example, be a hydrogen atom, a halogen atom, a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 1-6 alkoxy group, or a C 1-6 haloalkoxy group, and q is preferably an integer of from 0 to 2.
  • X is a hydrogen atom, a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-5 alkynyl group, a C 1-6 haloalkyl group, a C 2-6 haloalkenyl group, a C 2-6
  • haloalkynyl group a C 3-6 cycloalkyl group, a C 3-6
  • halocycloalkyl group a C 4-7 cycloalkylalkyl group, -OR 10 , -CN, -NO 2 , -S(O) r R 7 , -OS(O) 2 R 7 , or -C(O)OR 7 ;
  • Y is a hydrogen atom, a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 1-6 haloalkyl group, a C 2-6 haloalkenyl group, a C 2-6
  • haloalkynyl group a C 3-6 cycloalkyl group, a C 3-6
  • R 1 is a hydrogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 1-6 haloalkyl group, a C 2-6 haloalkenyl group, a C 2-6 haloalkynyl group, a C 3-6 cycloalkyl group, a C 3-6 halocycloalkyl group, a C 4 - 7 cycloalkylalkyl group, -CHO, -C(O)R 7 , -C(O)OR 7 ,
  • R 2 is a hydrogen atom, a C 1-6 alkyl group, a C 1-6 alkyl group which may be substituted by (R 9 ) p , or
  • each of R 4 and R 5 which are independent of each other is a hydrogen atom, a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 3-6 cycloalkyl group, a C 2-6
  • alkoxyalkyl group a C 2-6 alkylthioalkyl group, -C(O)OR 7 , -C(O)NR 7 R 8 , or -S(O) 2 NR 7 R 8 ;
  • R 7 is a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 3-6 cycloalkyl group, or a phenyl group which may be substituted by (R 6 ) q ;
  • R 9 is a C 1-3 alkoxy group, -CN, or -C(O)OR 7 ;
  • R 10 is a hydrogen atom, a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 3-6 cycloalkyl group, a C 2-7
  • k is an integer of from 0 to 2, provided that when k is 2, two X may be the same or different;
  • n is an integer of from 0 to 3, provided that when m is 2 or 3, the plurality of Y may be the same or
  • n is an integer of from 1 to 3, provided that when n is 2 or 3, the plurality of Z may be the same or
  • Q is Q-1, Q-2, Q-3, Q-4, Q-5, Q-8, Q-9, Q-10, Q-14, Q-15, Q-16, Q-17, Q-18, Q-22, Q-25, Q-27, Q-28, Q-29, Q-30, Q-31, Q-32 or Q-37.
  • J is J-1, J-2, J-7, J-8, J-9, J-10, J-13, J-14, J-15, J-24, J-25, J-26, J-27, J-28, J-30 or J-33.
  • G is G-1.
  • J is J-1, J-2, J-7, J-8, J-9, J-10, J-13, J-14, J-15, J-24, J-25, J-26, J-27, J-28, J-30 or J-33;
  • G is G-1.
  • Q is Q-1 or Q-37;
  • n is an integer of 1 or 2, provided that when m is 2, two Y may be the same or different;
  • n is an integer of 1 or 2, provided that when n is 2, two Z may be the same or different, and the substituted position is the 3-position, the 4-position or the 3- and 4-positions.
  • n is an integer of 1 or 2, provided that when m is 2, two Y may be the same or different, and the substituted position is the 3-position, the 4-position or the 3- and 4-positions;
  • n is an integer of 1 or 2, provided that when n is 2, two Z may be the same or different, and the substituted position is the 3-position, the 4-position or the 3- and 4-positions.
  • W is an oxygen atom
  • X is a hydrogen atom, a halogen atom, a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 1-6 alkoxy group, a C 1-6 haloalkoxy group, a C 1-6 alkylthio group, a C 1-6
  • haloalkylthio group a C 1-6 alkylsulfonyl group, or a C 1-6 haloalkylsulfonyl group;
  • Y is a halogen atom, a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 1-6 alkoxy group, a C 1-6 haloalkoxy group, a C 1-6 alkylthio group, a C 1-6 haloalkylthio group, a C 1-6 alkylsulfonyl group, a C 1-6 haloalkylsulfonyl group, a C 1-6 alkylsulfonyloxy group, a C 1-6
  • Z is a halogen atom, a C 1-6 alkyl group, a C 1-6 haloalkyl group, a C 1-6 alkoxy group, a C 1-6 haloalkoxy group, a C 1-6 alkylthio group, a C 1-6 haloalkylthio group, a C 1-6 alkylsulfinyl group, a C 1-6 haloalkylsulfinyl group, a C 1-6 alkylsulfonyl group, a C 1-6
  • n is an integer of 1 or 2, provided that when m is 2, two Y may be the same or different;
  • n is an integer of 1 or 2, provided that when n is 2, two Z may be the same or different, and the substituted position is the 3-position, the 4-position or the 3- and 4-positions;
  • R 1 is a hydrogen atom, a C 1-6 alkyl group, a C 2-6 alkoxyalkyl group, or a C 2-6 alkylthioalkyl group;
  • R 2 is a hydrogen atom, a C 1-6 alkyl group, a C 2-6 alkoxyalkyl group, or a -C(O)O-C 1-6 alkyl group;
  • R 3 is a hydrogen atom, an amino group, a C 1-6 alkyl group, a -C (O) -C 1-6 alkyl group or a -C (O)O-C 1-6 alkyl group.
  • the compound of the present invention may have E-form and Z-form isomers.
  • the present invention covers such E-form and Z-form as well as a mixture containing such E-form and Z-form in an optional ratio.
  • the compound of the present invention has an asymmetric carbon atom, it includes R-form and S-form.
  • R 1 is a hydrogen atom
  • the compound of the present invention may be in the form of the following tautomers, and such structures are also covered by the present invention.
  • the pesticide means in particular, an agent for controlling insect pests.
  • the compound of the present invention exhibits pesticidal effects against various insect pests at an extremely low dose.
  • the insect pests include, for example, agricultural insect pests such as green rice leafhopper (Nephotettix cincticeps), brown rice
  • sanitary insect pests such as common gnat (Culex pipiens pallens), housefly, German cockroach
  • Formosan subterranean termite Coptotermes formosanus
  • animal pests such as mites, fleas and louses
  • indoor dust mites such as acarid mites (Acaridae), Dermatophaqoides farinae, and Chenyletus malaccensis
  • mollusks such as slugs (Philomycidae) and snails.
  • the compound of the present invention is capable of effectively
  • the compound of the present invention has been found to be an extremely useful compound which is substantially free from adverse effects against mammals, fishes, Crustacea and beneficial insects. On the basis of this discovery, the present invention has been accomplished.
  • the compounds of the present invention are novel semicarbazone
  • each of L 1 , L 2 , L 3 and L 4 is an excellent leaving group such as a chlorine atom, a bromine atom, an iodine atom, an alkylsulfonate group or an arylsulfonate group.
  • a compound of the formula (III) can be obtained by reacting a compound of the formula (II) with e.g.
  • a compound of the formula (I) of the present invention can be obtained by reacting the compound of the formula (V) of the present invention and a compound of the formula (VI) in the presence or absence of a base in an inert solvent.
  • the solvent to be used in Process 1 may, for example, be an aromatic hydrocarbon such as benzene or toluene, or a halogenated hydrocarbon such as carbon tetrachloride or 1,1,2-trichloroethane. It is preferred to employ from 1 to 3 equivalents of phosphorus pentachloride in toluene.
  • the reaction temperature can be set at an optional level within a range of from 0°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 60°C to the reflux temperature.
  • the base to be used in Process 2 may, for example, be an alkali metal alkoxide such as sodium ethoxide or potassium tert-butoxide, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate, an alkali metal hydride such as sodium hydride or potassium hydride, or an organic base such as triethylamine or pyridine.
  • the solvent to be used may be any solvent so long as it does not hinder the reaction.
  • a lower alcohol such as methanol or ethanol
  • an aromatic hydrocarbon such as benzene or toluene
  • an ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or 1,4-dioxane
  • an ester such as ethyl acetate
  • a halogenated hydrocarbon such as dichloromethane or 1,2-dichloroethane
  • an amide such as dimethylformamide or dimethylacetamide
  • inert solvents may be used alone or in combination as a mixture.
  • base usually, it is preferred to use as the base, from 1 to 2 equivalents of an organic base such as triethylamine or pyridine and as a solvent an aromatic hydrocarbon such as benzene or toluene, or an ether such as tetrahydrofuran or diethyl ether.
  • the reaction temperature may be set at an optional level within a range of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction within a range of from 0°C to reflux temperature of the reaction mixture.
  • the base to be used in Process 3 may, for example, be the same as used in Process 2.
  • the solvent to be used may be any solvent so long as it does not hinder the reaction.
  • it may be a lower alcohol such as methanol or ethanol, an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2- dimethoxyethane, tetrahydrofuran or 1,4-dioxane, an ester such as ethyl acetate, a ketone such as acetone or methyl ethyl ketone, a halogenated hydrocarbon such as
  • dichloromethane or 1,2-dichloroethane an amide such as dimethylformamide or dimethylacetamide, acetonitrile, dimethylsulfoxide, or water.
  • amide such as dimethylformamide or dimethylacetamide, acetonitrile, dimethylsulfoxide, or water.
  • inert solvents may be used alone or in combination as a mixture.
  • reaction temperature can be set at an optional level within a range of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 0°C to 90°C.
  • a compound of the formula (VIII) can be obtained by reacting a compound of the formula (VII) and diphosphorus pentasulfide in an inert solvent or without solvent, or by reacting a compound of the formula (VII) with a
  • the compound of the formula (X) and a compound of the formula (XI) are reacted in an inert solvent in the presence or absence of a base to obtain a compound of the formula (XII) (a compound of the formula (I) of the present invention wherein R 3 is a hydrogen atom).
  • the compound of the formula (X) can also be obtained by reacting the compound of the formula (IX) to the compound of the formula (III) obtained in Process 1 of Method A.
  • the solvent to be used in Process 1 may be any solvent so long as it does not hinder the reaction.
  • it may be an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2- dimethoxyethane, tetrahydrofuran or 1,4-dioxane, an ester such as ethyl acetate, a halogenated hydrocarbon such as dichloromethane or 1,2-dichloroethane, an amide such as dimethylformamide or dimethylacetamide, acetonitrile, pyridine, dimethylsulfoxide, or water.
  • aromatic hydrocarbon such as benzene or toluene
  • an ether such as diethyl ether, 1,2- dimethoxyethane, tetrahydrofuran or 1,4-dioxane
  • an ester such as ethyl acetate
  • a halogenated hydrocarbon such as dichloromethane or
  • reaction temperature can be set at an optional level within a range of from 0°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 60°C to the reflux temperature.
  • the solvent to be used for Process 2 may be any solvent so long as it does not hinder the reaction.
  • a lower alcohol such as methanol or ethanol
  • an aromatic hydrocarbon such as benzene or toluene
  • an ether such as diethyl ether, 1,2-dimethoxyethane
  • dichloromethane or 1,2-dichloroethane an amide such as dimethylformamide or dimethylacetamide, acetonitrile, pyridine, dimethylsulfoxide or water, may be mentioned.
  • amide such as dimethylformamide or dimethylacetamide, acetonitrile, pyridine, dimethylsulfoxide or water.
  • solvents may be used alone or in combination as a mixture of two or more of them.
  • a copper salt such as copper chloride may, for example, be mentioned.
  • the reaction temperature may be set at any optional level from 0°C to the reflux temperature of the reaction mixture. However, it is usually preferred to conduct the reaction, for example, at a temperature within a range of from 60°C to the reflux temperature in ethanol.
  • the base and the solvent to be used in Process 3 may be the same as used in Process 2 in Method A.
  • the reaction temperature can be set at an optional level within a range of from 0°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 0°C to 50°C.
  • a compound of the formula (XV) can be obtained by reacting a compound of the formula (XIII) (an
  • the base to be used in Process 1 may be the same as used in Process 2 in Method A.
  • the solvent to be used may be the same as used in Process 3 in Method A.
  • a base for example, from 1 to 3 equivalents, based on the substrate.
  • the reaction temperature may be set at any optional level from -60°C to the reflux temperature of the
  • reaction mixture it is preferred to conduct the reaction within a range of from 0°C to 90°C.
  • Processes 2 and 3 can be carried out in the same manner as in Method B.
  • a compound of the formula (XIX) can be obtained by reacting a compound of the formula (XVIII) with phosgene or a phosgene equivalent (phosgen dimer or triphosgene), if necessary in the presence of a suitable base.
  • the base to be used in Process 1, may be the same as used in Process 2 in Method A.
  • the solvent to be used may be any solvent so long as it does not hinder the reaction.
  • an organic solvent such as an organic solvent so long as it does not hinder the reaction.
  • an organic solvent such as an organic solvent so long as it does not hinder the reaction.
  • an organic solvent to be used such as an organic solvent so long as it does not hinder the reaction.
  • aromatic hydrocarbon such as benzene or toluene
  • an ether such as diethyl ether, 1,2-dimethoxyethane, ethylene glycol dimethyl ether, tetrahydrofuran or 1,4-dioxane
  • an ester such as ethyl acetate
  • a halogenated hydrocarbon such as dichloromethane or 1,2-dichloroethane
  • an amide such as dimethylformamide or dimethylacetamide
  • acetonitrile or pyridine
  • solvents may be used alone or in combination as a mixture of two or more of them.
  • the reaction temperature may be set at an optional level from 0°C to the reflux temperature of the reaction mixture. However, it is preferred to carry out the reaction within a range of from 0°C to 25°C.
  • the base to be used in Process 2 may be the same as used in Process 2 in Method A.
  • the solvent to be employed may be the same as used in Process 1 of this method.
  • the reaction temperature may be set at any optional level from 0°C to the reflux temperature of the reaction mixture. However, it is preferred to carry out the reaction within a range of from 0 to 25°C.
  • a compound of the formula (XII) of the present invention can be obtained by reacting a compound of the formula (XX) of the present invention and a compound of the formula (XXI) in the presence of a base in an inert solvent. Then, the compound of the formula (XII) of the present invention and a compound of the formula (XXII) are reacted in the presence of a base in an inert solvent to obtain a compound of the formula (I) of the present invention.
  • the base to be used in this reaction may, for example, be the same as used in Process 2 in Method A.
  • the solvent to be used may be any solvent so long as it does not hinder the reaction.
  • it may be the same as in Process 3 in Method A.
  • the reaction temperature can be set at an optional level within a range of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 0°C to 90°C.
  • a compound of the formula (I) of the present invention can be obtained without isolating the compound of the formula (XII) by using two equivalents of the compound of the formula (XXI) and two equivalents of a base.
  • the compound of the formula (XV) can be prepared from the compound of the formula (XXIII) or
  • the suitable solvent to be used for this reaction may, for example, be an ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or 1,4-dioxane, or a phosphoric amide such as hexamethylphosphoric triamide. These solvents may be used alone or in combination as a mixture of two or more of them.
  • the reaction temperature can be set at an optional level from -78°C to the reflux temperature of the
  • reaction mixture it is preferred to carry out the reaction within a range of from -78°C to 25°C.
  • the compound of the formula (XXIII) wherein Q is Q-5, Q-14, Q-18 or Q-22 may be reacted with a compound of the formula (XXV) in a solvent inert to the reaction, if necessary in the presence of a suitable base, to obtain a compound of the formula (XIII) wherein Q is Q-5, Q-14, Q-18 or Q-22.
  • the base to be used for this reaction may be the same as used in Process 2 in Method A.
  • the solvent to be used may be the same as used in Process 3 in Method A.
  • reaction in a solvent such as tetrahydrofuran or dichloromethane without using any base, or to carry out the reaction by firstly preparing an alkali metal salt by using as a base from 0.01 to 2 equivalents, based on the substrate, of an organic base such as triethylamine, or from 1 to 2 equivalents, based on the substrate, of sodium hydride or the like.
  • a solvent such as tetrahydrofuran or dichloromethane
  • organic base such as triethylamine
  • the reaction temperature may be set at an optional level from -20°C to the reflux temperature of the
  • the base to be used for this reaction may, for example, be an alkali metal carbonate such as sodium carbonate, potassium carbonate or sodium
  • an alkali metal hydride such as sodium hydride or potassium hydride
  • an organic base such as triethylamine or pyridine.
  • the solvent to be used may be any solvent so long as it does not hinder the reaction.
  • an organic solvent such as an organic solvent so long as it does not hinder the reaction.
  • an organic solvent such as an organic solvent so long as it does not hinder the reaction.
  • aromatic hydrocarbon such as benzene or toluene
  • an ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or 1,4-dioxane
  • an ester such as ethyl acetate
  • a halogenated hydrocarbon such as
  • dichloromethane or 1,2-dichloroethane an amide such as dimethylformamide, dimethylacetamide, acetone,
  • acetonitrile or water
  • solvents may be used alone or in combination as a mixture of two or more of them.
  • the base usually, it is preferred to employ as the base from 1 to 3 equivalents, based on the substrate, of an organic base such as triethylamine or pyridine in a solvent such as tetrahydrofuran, ethyl acetate, dichloromethane or benzene.
  • the reaction temperature may be set at any optional level from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to carry out the reaction within a range of from 0 to 120°C.
  • the compound of the formula (VII) wherein R 1 ⁇ H can be produced also by reacting a compound of the formula (II) which can be produced by reacting the compound of the formula (XXVI) and the compound of the formula (XXVIII) in the same manner, with a compound of the formula (VI), if necessary in the presence of a base in a solvent inert to the reaction.
  • the base to be used here may be the same as used in Process 2 in Method A.
  • the solvent to be used may be the same as used in Process 3 is Method A.
  • the base usually, it is preferred to use as the base from 1 to 3 equivalents, based on the substrate, of sodium hydride, potassium hydride, potassium tert-butoxide or potassium hydroxide in a polar solvent such as tetrahydrofuran or dimethylformamide, or to use as the base from 1 to 3 equivalents, based on the substrate, of potassium
  • the reaction temperature may be set at an optional level of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to carry out the reaction within a range of from 0 to 90°C.
  • the catalyst to be used in this reaction may, for example, be an organic base such as triethylenediamine or diazabicycloundecene.
  • the amount of the catalyst to be used can be set at an optional level within a range of from 0.001 wt% to 10 wt%, relative to the compound of the formula (XI).
  • the solvent may be any solvent so long as it does not hinder the reaction.
  • it may be an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or 1,4-dioxane, an ester such as ethyl acetate, a
  • halogenated hydrocarbon such as dichloromethane
  • the reaction temperature can be set at an optional level within a range of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 0°C to 50°C. In this reaction, the molar ratio of the reactants is not particularly limited. However, in order to obtain the compound of the formula (XXIX) in good yield, it is preferred to employ the compound of the formula (IX) in a slightly excess amount relative to the compound of the formula (XI).
  • a compound of the formula (XXXI) can be obtained by reacting a compound of the formula (XXX) and a compound of the formula (XI) in the presence or absence of a catalyst in an inert solvent.
  • the catalyst, the solvent and the reaction conditions such as the temperature to be used in this reaction may be similar to those in
  • the compound of the formula (XXIX) can be obtained in good yield by using equimolar amounts of the compound of the formula (XXX) and the compound of the formula (XI).
  • the acid to be used may, for example, be an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as
  • the solvent may be any solvent so long as it does not hinder the reaction.
  • it may be a lower alcohol such as methanol or ethanol, an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or 1,4-dioxane, an ester such as ethyl acetate, a halogenated hydrocarbon such as dichloromethane, carbon tetrachloride or 1,2-dichloroethane, an amide such as dimethylformamide or dimethylacetamide, acetonitrile, dimethylsulfoxide, acetic acid, or water.
  • These inert solvents may be used alone or in combination as a mixture. Usually, it is preferred to employ from 1 to 50 equivalents of
  • the reaction temperature can be set at an optional level within a range of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 0°C to the reflux temperature of the reaction mixture.
  • the molar ratios of the respective reactants are not particularly limited.
  • the compound of the present invention can be separated and purified by an optional purification method such as recrystallization, column chromatography or thin layer chromatography.
  • a suitable carrier for example, a solid carrier such as clay, pulp, bentonite, diatomaceous earth or fine silica powder, or a liquid carrier such as water, an alcohol (such as isopropanol, butanol, benzyl alcohol or furfuryl alcohol), an aromatic hydrocarbon (such as toluene or xylene), an ether (such as anisol), a ketone (such as cyclohexanone or isophorone), an ester (such as butyl acetate), an acid amide (such as N-methylpyrrolidone) or a halogenated hydrocarbon (such as chlorobenzene).
  • thickener an anti-freezing agent, an anti-solidification agent and/or a stabilizer may be added. It may be practically used in the form of an optional formulation such as a liquid formulation, an emulsifiable
  • the compound of the present invention may be mixed with various other herbicides, insecticides, miticides, nematocides, fungicides, plant growth regulating agents, synergists, fertilizers or soil improving agents, as the case requires.
  • the dose in application of the compound of the present invention varies depending upon the application site, the application season, the manner of application and the type of the crop plant. However, it is usually in an amount of from 0.005 to 50 kg/ha as the amount of active ingredient.
  • an antisolidification agent may, for example, be mentioned.
  • an antifreezing agent and a thickener may, for example, be mentioned.
  • the compounds of the present invention were prepared or can be prepared in accordance with the following
  • pentasulfide were added to 30 ml of pyridine, and the mixture was stirred for 2 hours under reflux under heating and then added to 300 ml of ice water.
  • the mixture was made alkaline by an addition of an aqueous sodium hydroxide solution and then extracted with 200 ml of ethyl acetate.
  • the organic layer was washed twice with dilute hydrochloric acid and dried over anhydrous sodium sulfate.
  • the solvent was distilled off under reduced pressure. The residue was washed with
  • isothiocyanate was dropwise added thereto.
  • the mixture was returned to room temperature, and then the stirring was further continued overnight.
  • 30 ml of 1N HCl was added to the reaction solution, and the mixture was extracted with 200 ml of ethyl acetate.
  • the organic layer was washed with water and dried over anhydrous sodium sulfate.
  • the solvent was distilled off under reduced pressure. The residue was washed with
  • Ethyl 2-aminothiazole-4-carboxylate was added to a mixture comprising 30 ml of concentrated hydrochloric acid and 10 ml of phosphoric acid, and the mixture was stirred under cooling with ice. Then, 10 ml of an aqueous solution containing 1.6 g of sodium nitrite was dropwise added thereto. After completion of the dropwise addition, stirring was further continued for 4 hours at room temperature. The mixture was dropwise added to 50 ml of chloroform having 1.90 g of copper chloride
  • 2-chlorothiazole-4-carboxylic acid was converted to 2-chlorothiazole-4-carboxylic acid chloride by means of thionyl chloride. Then, 10 ml of a dichloromethane solution thereof was dropwise added to 50 ml of a
  • tetrahydrofuran solution containing 1.5 g of pyrrole was dropwise added with stirring at room temperature. After completion of the dropwise addition, the mixture was stirred for one hour at room temperature. Then, 20 ml of a tetrahydrofuran solution containing 3.2 g of
  • hydrazine monohydrate was added to 5 ml of an ethanol solution containing 0.48 g of methyl N-(4-cyanophenyl)pyrrole-1-thioimidate, and the mixture was stirred for 1.5 hours at room temperature. Then, 5 ml of ethanol was further added thereto, and the mixture was stirred overnight. Then, 20 ml of ethyl acetate was added to the reaction mixture, and the mixture was washed with water and a saturated sodium chloride aqueous solution and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue was dissolved in 5 ml of tetrahydrofuran, and 0.5 g of 4-trifluoromethylphenyl isocyanate was added
  • the compounds of the present invention can be synthesized in accordance with the above described production methods and Examples. Specific examples of such compounds are shown in Tables 6 to 9. However, it should be understood that the present invention is by no means restricted to such specific Examples.
  • Compound of the present invention 50 parts Zeeklite PFP (tradename for Kaoline-type clay, manufactured by Zeeklite Mining Industries Co., Ltd.)
  • Sorpol 5050 (tradename for anionic surfactant, manufactured by Toho Chemicals Ind. Co., Ltd.)
  • Lunox 1000C (tradename for anionic surfactant, manufactured by Toho Chemicals Ind. Co., Ltd.)
  • Carplex #80 antioxidant (tradename for fine silica, manufactured by Shionogi & Co., Ltd.)
  • Sorpol 3005X (tradename for a mixture of a nonionic surfactant and an anionic surfactant, manufactured by Toho Chemicals Ind. Co., Ltd.)
  • Agrisol S-711 (tradename for a nonionic surfactant, manufactured by Kao Corporation)
  • Lunox 1000C (tradename for anionic surfactant, manufactured by Toho Chemicals Ind. Co., Ltd.)
  • Rodopol water (tradename for a thickener,
  • the above components are uniformly mixed to obtain a flowable.
  • Compound of the present invention 75 parts Isoban No. 1 (tradename for an anion surfactant, manufactured by Kuraray Isoprene Chemical K.K.)
  • Anilex N (tradename for anionic surfactant,
  • Carplex #80 (tradename for fine silica, manufactured by Shionogi & Co., Ltd.)
  • the above components are uniformly mixed and finely pulverized to obtain a dry flowable.
  • the above components are uniformly mixed and triturated. Then, a small amount of water is added thereto. The mixture is stirred, kneaded and then granulated by an extrusion-type granulator, followed by drying to obtain a granule.
  • Carplex #80 (tradename for fine silica, manufactured by Shionogi & Co., Ltd.)
  • the above wettable powder, emulsifiable concentrate, flowable or dry flowable is diluted from 50 to 20,000 times with water and applied so that the active ingredient will be from 0.05 to 50 kg/ha.
  • 5% emulsifiable concentrates of the compounds of the present invention (25% wettable powders in the case of certain compounds) were diluted with water containing a spreader to prepare the samples of liquid insecticides with a concentration of 1,000 ppm. Leaves of cabbage were immersed in the respective samples of liquid
  • insects per dish 10 insects per dish.
  • the dishes were closed with a perforated cover and kept in a 25°C thermostatic chamber.
  • the percentage of mortality of the insects after the lapse of 6 days was calculated by the following formula. The tests were conducted twice for each compound.
  • TEST EXAMPLE 2 Insecticidal test on twenty eight-spotted ladybird (Epilachna vigintioctopunctata)
  • 5% emulsifiable concentrates of the compounds of the present invention (25% wettable powders in the case of certain compounds) were diluted with water containing a spreader to prepare the samples of liquid insecticides with a concentration of 1,000 ppm. Leaves of tomato were immersed in the respective samples of liquid insecticides for about 10 seconds. Then, after air drying the leaves, they were placed in the Petri dishes and the second instar nymphae of twenty eight-spotted ladybird

Landscapes

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

Abstract

A semicarbazone derivative of formula (I) or its salt, and a pesticide containing it, are presented. In said formula (I) Q is Q-1, Q-2 or the like, J is J-1, J-2 and or like, G is G-1, G-2 and or like, W is an oxygen atom or a sulfur atom; each of X, Y and Z which are independent of one another, is a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group or the like, k is an integer of from 0 to 5, provided that when k is from 2 to 5, the plurality of X may be the same or different; m is an integer of from 0 to 5, provided that when m is from 2 to 5, the plurality of y may be the same or different; n is an integer of from 0 to 5, provided that when n is from 2 to 5, the plurality of z may be the same or different; each of R?1, R2 and R3¿ which are independent of one another, is a hydrogen atom, a C¿1-6? alkyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group.

Description

DESCRIPTION
SEMICARBAZONE DERIVATIVES AND PESTICIDES
TECHNICAL FIELD
The present invention relates to novel semicarbazone derivatives and pesticides containing such derivatives as active ingredients.
BACKGROUND ART
Heretofore, with respect to semicarbazone derivatives of benzamide, compounds of 4-RC6H4C=(NHC6H4R'-4)NNHCWNHR" (wherein R = H, MeO, Me, Cl, NO2; R' = H, MeO, Me, Cl; R" = Ph; W = O, S) have been known in Eur. J. Med. Chem., 26, 273 (1991). However, here, R" is limited to an unsubstituted phenyl group, and the corresponding
compounds wherein R" is a substituted phenyl group are novel. Further, 4-phenyl semicarbazone derivatives of 2-pyridinecarboxanilide are disclosed in Ann. Univ. Mariae Curie-Sklodowska, Sect. AA; Phys. Chem. 1980. Volume Date 1976-1977, 31-32, 277. However, these literatures disclose nothing about pesticidal activities although they indicate pharmaceutical activities.
In recent years, insect pests have acquired
resistance due to use of insecticides over many years, and it has become difficult to control them by
conventional insecticides. Further, some of insecticides have high toxicity, and some of them have residual toxicity, whereby the ecosystem tends to be disturbed. Accordingly, it is desired to develop a novel insecticide having a low toxicity and a low residual effect.
DISCLOSURE OF INVENTION
The present inventors have conducted extensive researches on semicarbazone derivatives and as a result, have found that novel 5- or 6-membered hetero ring-substituted semicarbazone derivatives and their salts exhibit excellent pesticidal activities, particularly insecticidal activities at a low dose, and they are very useful compounds substantially free from adverse effects against mammals, fishes and beneficial insects. The present invention has been accomplished on the basis of these discoveries.
The present invention provides a semicarbazone derivative of the formula (I) or its salt:
Figure imgf000004_0001
wherein Q is any one of Q-1 to Q-37:
Figure imgf000005_0001
Figure imgf000006_0001
J is any one of J-1 to J-33, provided that when Q is and G is G-1, J is other than J-33;
Figure imgf000007_0001
Figure imgf000008_0001
G is any one of G-1 to G-8, provided that when Q is Q-37 and J is J-33, G is other than G-1;
Figure imgf000008_0002
Figure imgf000008_0003
W is an oxygen atom or a sulfur atom;
each of X, Y and Z which are independent of one another, is a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6
haloalkynyl group, a C3-6 cycloalkyl group, a C3-6
halocycloalkyl group, a C4-7 cycloalkylalkyl group, -OR10, -CN, -N3, -SCN, -NO2, -SH, -S(O)rR7, -OCHO, -CHO, -C(O)R7, -C(O)OR7, -C(O)NR7R8, -S(O)2NR7R8, -NR7R8, -NR8CHO,
-NR8C(O)R7, -NR8C(O)NHR7, -NR8S(O)2R7, -SiR18R19R20, -SF5, a phenyl group which may be substituted by (R6)q, a pyridyl group which may be substituted by (R6)q, or a C1-6 alkyl group which may be substituted by (R9)p, provided that when k, m or n is 2, and two X, Y or Z are adjacent to each other, they may form -CH=CH-CH=CH-, -OCH2O-, -OCF2O-, -OCH2CH2O-, -OCH2C(CH3)2O-, -CF2CF2O- or
-OCF2CF2O-;
each of R1, R2 and R3 which are independent of one another, is a hydrogen atom, a C1-6 alkyl group, a
C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6 haloalkynyl group, a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C4-7 cycloalkylalkyl group, -CHO, -C(O)R7, -C(O)OR7, -C(O)SR7, -C(S)R7, -C(S)SR7, -C(O)C(O)OR7, -NR10R11,
-N=CR11R12, -P(O)(OR13)2, -P(S)(OR13)2, -S(O)rR7,
-S(O)2CH2C(O)OR7, -S(O)rN(R14)C(O)OR15, -S(O)rNR16R17, a phenyl group which may be substituted by (R6)q, or a C1-6 alkyl group which may be substituted by (R9)p;
each of R4 and R5 which are independent of each other, is a hydrogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6 haloalkynyl group, a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C4-7 cycloalkylalkyl group, a C2-6 alkoxyalkyl group, a C2-6 alkylthioalkyl group, a C1-6 nitroalkyl group, a C2-6 cyanoalkyl group, a C3-8 alkoxycarbonylalkyl group, -CHO, -C(O)R7, -C(O)OR7, -C(O)NR7R8, or -S(O)2NR7R8;
R6 is a hydrogen atom, a halogen atom, a hydroxyl group, -CN, -NO2, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a C1- 6 alkylthio group, a C1-6 haloalkylthio group, a C1-6 alkylsufonyl group, a C1-6 haloalkylsulfonyl group, a C2-6 alkoxycarbonyl group, an amino group, or a di-C1-6 alkylamino group;
R7 is a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6 haloalkynyl group, a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C4-7 cycloalkylalkyl group, a C2-6 alkoxyalkyl group, a C2-6 alkylthioalkyl group, a C1-6 nitroalkyl group, a C2-6 cyanoalkyl group, a C3-8 alkoxycarbonylalkyl group, a phenyl group which may be substituted by (R6)q, a benzyl group which may be
substituted by (R6)q, or a pyridyl group which may be substituted by (R6)q;
R8 is a hydrogen atom, a C1-4 alkyl group, a C2-4 alkenyl group, or a C2-4 alkynyl group;
provided that when R7 and R8 are bonded to the same atom, they may together form -CH2CH2CH2CH2-,
-CH2CH2CH2CH2CH2-, -CH2CH2OCH2CH2-;
R9 is a C1-3 alkoxy group, a C1-3 haloalkoxy group, -CN, -NO2, -S(O)rR7, -P(O)(OR13)2, -P(S) (OR13)2, -C(O)R7, -C(O)OR7, or a phenyl group which may be substituted by
(R6)q;
R10 is a hydrogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6 haloalkynyl group. a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C4-7 cycloalkylalkyl group, a C2-7 alkoxyalkyl group, a C2-7 haloalkoxyalkyl group, a C2-7 alkylthioalkyl group, a C2-7 cyanoalkyl group, a C3-8 alkoxycarbonylalkyl group, -C(O)R7, -C(O)OR7, -C(O)NR7R8, -S(O)2NR7R8, -S(O)2R7, a phenyl group which may be substituted by (R6)q, a benzyl group which may be substituted by (R6)q, or a pyridyl group which may be substituted by (R6)q;
R11 is a hydrogen atom, a C1-4 alkyl group, -C(O)R7, or -C(O)OR7;
R12 is a hydrogen atom, a C1-4 alkyl group, a C1-4 haloalkyl group, or a phenyl group which may be
substituted by (R6)q;
provided that R11 and R12 may together form
-CH2CH2CH2CH2-, or -CH2CH2CH2CH2CH2-;
R13 is a C1-3 alkyl group, or a phenyl group which may be substituted by (R6)q;
R14 is a C1-4 alkyl group;
R15 is a C1-18 alkyl group;
Each of R16 and R17 which are independent of each other, is a C1-4 alkyl group, or R16 and R17 may together form -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, or -CH2CH2OCH2CH2-; each of R18 and R19 which are independent of each other, is a C1-4 alkyl group;
R20 is a C1-4 alkyl group, or a phenyl group which may be substituted by (R6)q;
k is an integer of from 0 to 5, provided that when k is from 2 to 5, the plurality of X may be the same or different;
m is an integer of from 0 to 5, provided that when m is from 2 to 5, the plurality of Y may be the same or different;
n is an integer of from 0 to 5, provided that when n is from 2 to 5, the plurality of Z may be the same or different;
p is an integer of from 1 to 3, provided that when p is 2 or 3, the plurality of R9 may be the same or
different;
q is an integer of from 0 to 4, provided that when q is from 2 or 4, the plurality of R6 may be the same or different; and
r is an integer of from 0 to 2.
The present invention also provides a pesticide which contains at least one such semicarbazone derivative or its salt as an active ingredient.
Now, specific examples will be given for each substituent disclosed above. The carbon chain in each substituent may be linear, branched or cyclic. In the following description, n- means normal, i- means iso, sec- means secondary, t- means tertiary, and c- means cyclo.
The alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, an i-butyl group, a sec-butyl group, a t- butyl group, a n-pentyl group, a n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, or a 1-ethyl-1-butyl group.
The alkenyl group may, for example, be an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 2-methyl-2-propenyl group, a 2-butenyl group, a 3-methyl-2-butenyl group, a 3-butenyl group, a 4-pentenyl group, or a 2,3-dimethyl-2-butenyl group.
The alkynyl group may, for example, be an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, or a 4,4-dimethylpentynyl group.
The cycloalkyl group may, for example, be a c-propyl group, a c-butyl group, a c-pentyl group, a c-hexyl group or a 1-methyl-c-propyl group.
The pyridyl group may, for example, be a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group.
The alkoxy group may, for example, be a methoxy group, an ethoxy group, a n-propoxy group, an i-propoxy group, a n-butoxy group, an i-butoxy group, a sec-butoxy group or a t-butoxy group.
The alkylthio group may, for example, be a methylthio group, an ethylthio group, a n-propylthio group, an i-propylthio group, a n-butylthio group, an i-butylthio group, a sec-butylthio group or a t-butylthio group.
The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
W is an oxygen atom or a sulfur atom, preferably an oxygen atom.
Each of X, Y and Z which are independent of one another, may, for example, be a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6 haloalkynyl group, a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C4-7 cycloalkylalkyl group, a hydroxyl group, a C1-6 alkoxy group, a C2-6 alkenyloxy group, a C2-6 alkynyloxy group, a C1-6 haloalkoxy group, a C2-6 haloalkenyloxy group, a C2-6 haloalkynyloxy group, a C3-6 cycloalkyloxy group, a C3-6 halocycloalkyloxy group, a C4-7 cycloalkylalkyloxy group, a C2-7 alkoxyalkyloxy group, a C2-7 haloalkoxyalkoxy group, a C2-7
alkylthioalkyloxy group, a C2-7 cyanoalkyloxy group, a C3-8 alkoxycarbonylalkyloxy group, a C2-7 alkylcarbonyloxy group, a C3-7 alkenylcarbonyloxy group, a C3-7
alkynylcarbonyloxy group, a C2-7 haloalkylcarbonyloxy group, a C3-7 haloalkenylcarbonyloxy group, a C3-7
haloalkynylcarbonyloxy group, a C4-7
cycloalkylcarbonyloxy group, a C4-7
halocycloalkylcarbonyloxy group, a C5-8
cycloalkylalkylcarbonyloxy group, a C3-7
alkoxyalkylcarbonyloxy group, a C3-7 alkylthioalkylcarbonyloxy group, a C3-7
cyanoalkylcarbonyloxy group, a phenylcarbonyloxy group which may be substituted by (R6)q, a benzylcarbonyloxy group which may be substituted by (R6)q, a
pyridylcarbonyloxy group which may be substituted by
(R6)q, a C2-7 alkoxycarbonyloxy group, an N-C1-6 alkyl-C2-5 alkylcarbamoyloxy group, a C2-7 mono-alkylaminocarbonyloxy group, an N-C1-6 alkyl-C1-4
alkylsulfamoyloxy group, a
C1-6 alkylsulfonyloxy group, a C1-6 haloalkylsulfonyloxy group, a C3-6 cycloalkylsulfonyloxy group, a C3-6
halocycloalkylsulfonyloxy group, a C2-6
cyanoalkylsulfonyloxy group, a phenylsulfonyloxy group which may be substituted by (R6)q, a benzylsulfonyloxy group which may be substituted by (R6)q, a
pyridylsulfonyloxy group which may be substituted by (R6)q, a phenoxy group which may be substituted by (R6)q, a benzyloxy group which may be substituted by (R6)q, a pyridyloxy group which may be substituted by (R6)q,
-OCHO, -CN, -N3, -SCN, -NO2, -SH, a C1-6 alkylthio group, a C2-6 alkenylthio group, a C2-6 alkynylthio group, a C1-6 haloalkylthio group, a C2-6 haloalkenylthio group, a C2-6 haloalkynylthio group, a C3-6 cycloalkylthio group, a C3-6 halocycloalkylthio group, a C4-7 cycloalkylalkylthio group, a C2-6 alkoxyalkylthio group, a C2-6
alkylthioalkylthio group, a C2-6 cyanoalkylthio group, a C3-8 alkoxycarbonylalkylthio group, a phenylthio group which may be substituted by (R6)q, a benzylthio group which may be substituted by (R6)q, a pyridylthio group which may be substituted by (R6)q, a C1-6 alkylsulfinyl group, a C2-6 alkenylsulfinyl group, a C2-6
alkynylsulfinyl group, a C1-6 haloalkylsulfinyl group, a C2-6 haloalkenylsulfinyl group, a C2-6 haloalkynylsulfinyl group, a C3-6 cycloalkylsulfinyl group, a C3-6
halocycloalkylsulfinyl group, a C4-7
cycloalkylalkylsulfinyl group, a C2-6 alkoxyalkylsulfinyl group, a C2-6 alkylthioalkylsulfinyl group, a
phenylsulfinyl group which may be substituted by (R6)q, a benzylsulfinyl group which may be substituted by (R6)q, a pyridylsulfinyl group which may be substituted by (R6)q, a C1-6 alkylsulfonyl group, a C2-6 alkεnylsulfonyl group, a C2-6 alkynylsulfonyl group, a C1-6 haloalkylsulfonyl group, a C2-6 haloalkenylsulfonyl group, a C2-6
haloalkynylsulfonyl group, a C3-6 cycloalkylsulfonyl group, a C3-6 halocycloalkylsulfonyl group, a C4-7 cycloalkylalkylsulfonyl group, a C2-6 alkoxyalkylsulfonyl group, a C2-6 alkylthioalkylsulfonyl group, a C2-6 cyanoalkylsulfonyl group, a C3-8
alkoxycarbonylalkylsulfonyl group, a phenylsulfonyl group which may be substituted by (R6)q, a benzylsulfonyl group which may be substituted by (R6)q, a pyridylsulfonyl group which may be substituted by (R6)q, -CHO, a C2-7 alkylcarbonyl group, a C3-7 alkenylcarbonyl group, a C3-7 alkynylcarbonyl group, a C2-7 haloalkylcarbonyl group, a C4-7 cycloaklylcarbonyl group, a C4-7
halocycloalkylcarbonyl group, a C3-7 alkoxyalkylcarbonyl group, a C3-7 alkylthioalkylcarbonyl group, a C3-7 cyanoalkylcarbonyl group, a benzoyl group which may be substituted by (R6)q, a benzylcarbonyl group which may be substituted by (R6)q, a pyridylcarbonyl group which may be substituted by (R6)q, a C2-7 alkoxycarbonyl group, a C2-7 haloalkoxycarbonyl group, a C4-7
cycloalkyloxycarbonyl group, a C4-7
halocycloalkyloxycarbonyl group, a C3-7
cyanoalkyloxycarbonyl group, a phenoxycarbonyl group which may be substituted by (R6)q, a benzyloxycarbonyl group which may be substituted by (R6)q, a
pyridyloxycarbonyl group which may be substituted by (R6)q, an N-C1-6 alkyl-C2-5 alkylcarbamoyl group, a C2-7 mono-alkylaminocarbonyl group, an N-C1-6 haloalkyl-C2-5 alkylcarbamoyl group, a C2-7 monohaloalkylaminocarbonyl group, a phenylaminocarbonyl group which may be
substituted by (R6)q, a benzylaminocarbonyl group which may be substituted by (R6)q, a pyridylaminocarbonyl group which may be substituted by (R6)q, an N-C1-6 alkyl-C1-4 alkylsulfamoyl group, a C1-6 monoalkylsulfamoyl group, an N-C1-6 haloalkyl-C1-4 alkylsulfamoyl group, a C1-6
monohaloalkylsulfamoyl group, a phenylsulfamoyl group which may be substituted by (R6)q, a benzylsulfamoyl group which may be substituted by (R6)q, a
pyridylsulfamoyl group which may be substituted by (R6)q, an N-C1-6 alkyl-C1-4 alkylamino group, a C1-6
monoalkylamino group, an N-C1-6 haloalkyl-C1-4 alkylamino group, a C1-6 monohaloalkylamino group, a phenylamino group which may be substituted by (R6)q, a benzylamino group which may be substituted by (R6)q, a pyridylamino group which may be substituted by (R6)q, -NHCHO, an N-formyl-C1-4 alkylamino group, a C2-7 alkylcarbonylamino group, a C2-7 haloalkylcarbonylamino group, a C4-7 cycloalkylcarbonylamino group, a C4-7
halocycloalkylcarbonylamino group, an N-C1-4 alkyl-C2-7 alkylcarbonylamino group, an N-C1-4 alkyl-C2-7
haloalkylcarbonylamino group, an N-C1-4 alkyl-C4-7 cycloalkylcarbonylamino group, an N-C1-4 alkyl-C4-7 halocycloalkylcarbonylamino group, a phenylcarbonylamino group which may be substituted by (R6)q, a
benzylcarbonylamino group which may be substituted by (R6)q, a pyridylcarbonylamino group which may be
substituted by (R6)q, an N-C1-4 alkyl-C1-6
alkylsulfonylamino group, an N-C1-4 alkyl-C1-6
haloalkylsulfonylamino group, a C1-6 alkylsulfonylamino group, a C1-6 haloalkylsulfonylamino group, a
phenylsulfonylamino group which may be substituted by (R6)q, a benzylsulfonylamino group which may be
substituted by (R6)q, a pyridylsulfonylamino group which may be substituted by (R6)q, a trimethylsilyl group, a phenyldimethylsilyl group, a t-butyldimethylsilyl group, -SF5, a phenyl group which may be substituted by (R6)q, a pyridyl group which may be substituted by (R6)q, a C2-9 alkoxyalkyl group, a C2-9 haloalkoxyalkyl group, a C2-9 alkylthioalkyl group, a C2-7 cyanoalkyl group, a C3-13 alkoxycarbonylalkyl group, or a benzyl group which may be substituted by (R6)q. Further, when k, m or n is 2, and two X, Y or Z are adjacent to each other, they may form -CH=CH-CH=CH-, -OCH2O-, -OCF2O-, -OCH2CH2O-,
-OCH2C(CH3)2O-, -CF2CF2O- or -OCF2CF2O-. Here, the above R6 may, for example, be a hydrogen atom, a halogen atom, a hydroxyl group, -CN, -NO2, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a C1-6 alkylthio group, a C1-6 haloalkylthio group, a C1-6 alkylsulfonyl group, a C1-6 haloalkylsulfonyl group, a C2-6 alkoxycarbonyl group, an amino group, or a di-C1-6 alkyl-amino group, and q is an integer of from 0 to 4.
X may preferably be, for example, a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a C1-6 alkylthio group, a C1-6 haloalkylthio group, a C1-6 alkylsulfonyl group, or a C1-6 haloalkylsulfonyl group. Here, k is an integer of from 0 to 5, preferably 0, 1 or 2. When k is from 2 to 5, the plurality of X may be the same or different.
Y may preferably be, for example, a halogen atom, a cyano group, a nitro group, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C2-7 alkoxycarbonyl group, a C2-7 haloalkoxycarbonyl group, a C1-6 haloalkoxy group, a C1-6 alkylthio group, a C1-6 haloalkylthio group, a C1-6 alkylsulfonyl group, a C1-6 haloalkynylsulfonyl group, a C1-6 alkylsulfonyloxy group, a C1-6 haloalkylsulfonyloxy group, or -OCF2O-, -OCF2CF2O-, -CH=CH-CH=CH-, -OCH2O-, -OCH2CH2O-, -OCH2C(CH3)2O-, or -CF2CF2O- bridging the adjacent carbon atoms. Here, m is an integer of from 0 to 5, preferably 1 or 2. When m is from 2 to 5, the plurality of Y may be the same or different.
Z may preferably be, for example, a halogen atom, a cyano group, a nitro group, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a C1-6 alkylthio group, a C1-6 haloalkylthio group, a C1-6 alkylsulfinyl group, a C1-6 haloalkylsulfinyl group, a C1-6 alkylsulfonyl group, a C1-6
haloalkylsulfonyl group, a C1-6 alkylsulfonyloxy group, a C1-6 haloalkylsulfonyloxy group, a -SF5 group, or -OCF2O-, -OCF2CF2O-, -OCF2CF2-, -CH=CH-CH=CH-, -OCH2O-, -OCH2CH2O-, or -OCH2C(CH3)2O- bridging the adjacent carbon atoms.
Here, n is an integer of from 0 to 5, preferably 1 or 2. When n is from 2 to 5, the plurality of Z may be the same or different.
Each of R1, R2 and R3 which are independent of one another, may, for example, be a hydrogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6 haloalkynyl group, a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C4-7 cycloalkylalkyl group, -CHO, a C2-7 alkylcarbonyl group, a C3-7 alkenylcarbonyl group, a C3-7 alkylcarbonyl group, a C2-7 haloalkylcarbonyl group, a C3-7 haloalkenylcarbonyl group, a C3-7
haloalkynylcarbonyl group, a C4-7 cycloalkylcarbonyl group, a C4-7 halocycloalkylcarbonyl group, a C5-8 cycloalkylalkylcarbonyl group, a C3-7 alkoxyalkylcarbonyl group, a C3-7 alkylthioalkylcarbonyl group, a C3-7 cyanoalkylcarbonyl group, a C4-9
alkoxycarbonylalkylcarbonyl group, a benzoyl group which may be substituted by (R6)q, a benzylcarbonyl group which may be substituted by (R6)q, a pyridylcarbonyl group which may be substituted by (R6)q, a C2-7 alkoxycarbonyl group, a C3-7 alkenyloxycarbonyl group, a C3-7
alkynyloxycarbonyl group, a C2-7 haloalkoxycarbonyl group, a C3-7 haloalkenyloxycarbonyl group, a C3-7 haloalkynyloxycarbonyl group, a C4-7
cycloalkyloxycarbonyl group, a C4-7
halocycloalkyloxycarbonyl group, a C5-8
cycloalkylalkyloxycarbonyl group, a C3-7
alkoxyalkoxycarbonyl group, a C3-7
alkylthioalkoxycarbonyl group, a C3-7
cyanoalkyloxycarbonyl group, a phenoxycarbonyl group which may be substituted by (R6)q, a benzyloxycarbonyl group which may be substituted by (R6)q, a
pyridyloxycarbonyl group which may be substituted by (R6)q, a C2-7 alkyl-thiocarbonyl group, a C2-7 haloalkyl- thiocarbonyl group, a C2-7 alkylthio-carbonyl group, a C2-7 haloalkylthio-carbonyl group, a C2-7 alkylthio- thiocarbonyl group, a C2-7 haloalkylthio-thiocarbonyl group, a C3-8 alkoxycarbonylcarbonyl group, a C3-8 haloalkoxycarbonylcarbonyl group, an amino group, a C1-6 alkylamino group, an N-C1-4 alkyl-C1-6 alkylamino group, a C2-7 alkylcarbonylamino group, a di-C2-7 alkylcarbonylamino group, a C2-7 alkoxycarbonylamino group, a di-C2-7 alkoxycarbonyl-amino group, a C2-9 alkylideneamino group, a 1-phenyl-C1-6 alkylideneamino group, a di-C1-3 alkoxy-phosphonyl group, a di-phenoxy-phosphonyl group, a di-C1- 3 alkoxy-thiophosphonyl group, a di-phenoxy-thiophosphonyl group, a C1-6 alkylthio group, a C1-6 haloalkylthio group, a C1-6 alkylsulfinyl group, a C1-6 haloalkylsulfinyl group, a C1-6 alkylsulfonyl group, a C1-6 haloalkylsulfonyl group, a C3-8
alkoxycarbonylalkylsulfonyl group, an N-C1-4 alkyl-C2-19 alkoxycarbonylaminothio group, a di-C1-4 alkyl-aminothio group, a 1-pyrrolidinσthio group, a 1-piperidinothio group, a 1-morpholinothio group, a phenyl group which may be substituted by (R6)q, a C2-9 alkoxyalkyl group, a C2-9 haloalkoxyalkyl group, a C2-7 cyanoalkyl group, a C2-12 alkylthioalkyl group, a C3-13 alkylcarbonylalkyl group, a C3-13 alkoxycarbonylalkyl group, or a benzyl group which may be substituted by (R6)q. Here, the above R6 may, for example, be a hydrogen atom, a halogen atom, a hydroxyl group, -CN, -NO2, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a C1- 6 alkylthio group, a C1-6 haloalkylthio group, a C1-6 alkylsulfonyl group, a C1-6 haloalkylsulfonyl group, a C2-6 alkoxycarbonyl group, an amino group, or a di-C1-6 alkyl-amino group, and q is preferably an integer of from 0 to 2.
R1 may, for example, be preferably a hydrogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6 haloalkynyl group, a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C4-7 cycloalkylalkyl group, a C2-9 alkoxyalkyl group, a C2-9 haloalkoxyalkyl group, a C2-7 cyanoalkyl group, a C2-12 alkylthioalkyl group, a C2-12 alkylcarbonylalkyl group, a C2-12 alkoxycarbonylalkyl group, or a benzyl group which may be substituted by (R6)q. Here, R6 may, for example, be a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, or a C1-6 haloalkoxy group, and q is preferably an integer of from 0 to 2.
R2 may, for example, be preferably a hydrogen atom, a C1-6 alkyl group, a C2-9 alkoxyalkyl group, or a C2-7 alkoxycarbonyl group.
R3 may, for example, be preferably a hydrogen atom, a C1-6 alkyl group, -CHO, a C2-7 alkylcarbonyl group, a C3-7 alkenylcarbonyl group, a C3-7 alkynylcarbonyl group, a C2-7 haloalkylcarbonyl group, a C4-7 cycloalkylcarbonyl group, a C4-7 halocycloalkylcarbonyl group, a C3-7 alkoxyalkylcarbonyl group, a C3-7 alkylthioalkylcarbonyl group, a C3-7 cyanoalkylcarbonyl group, a benzoyl group which may be substituted by (R6)q, a benzylcarbonyl group which may be substituted by (R6)q, a pyridylcarbonyl group which may be substituted by (R6)q, a C2-7
alkoxycarbonyl group, a C2-7 haloalkoxycarbonyl group, a C4-7 cycloalkyloxycarbonyl group, a C4-7
halocycloalkyloxycarbonyl group, a C3-7
cyanoalkyloxycarbonyl group, a phenoxycarbonyl group which may be substituted by (R6)q, a benzyloxycarbonyl group which may be substituted by (R6)q, a
pyridyloxycarbonyl group which may be substituted by (R6)q, or an amino group. R6 may, for example, be a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, or a C1-6 haloalkoxy group, and q is preferably an integer of from 0 to 2.
The following compounds may be mentioned as preferred compounds of the present invention.
(1) A semicarbazone derivative of the formula (I) or its salt, wherein;
X is a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-5 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6
haloalkynyl group, a C3-6 cycloalkyl group, a C3-6
halocycloalkyl group, a C4-7 cycloalkylalkyl group, -OR10, -CN, -NO2, -S(O)rR7, -OS(O)2R7, or -C(O)OR7; Y is a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6
haloalkynyl group, a C3-6 cycloalkyl group, a C3-6
halocycloalkyl group, a C4-7 cycloalkylalkyl group, -OR10, -CN, -NO2, -S(O)rR7, -S(O)2NR7R8, -OS(O)2R7, or -C(O)OR7, provided that when m is 2, and two Y are adjacent to each other, they may form -CH=CH-CH=CH-, -OCH2O-, -OCF2O-, -OCH2CH2O-, -OCH2C(CH3)2O-, -CF2CF2O-, or -OCF2CF2O-;
Z is a halogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6 haloalkynyl group, a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C4-7 cycloalkylalkyl group, -OR10, -CN, -NO2, -S(O)rR7, -S(O)2NR7R8, -OS(O)2R7, -C(O)OR7, or -SF5, provided that when n is 2, and two Z are adjacent to each other, they may form -CH=CH-CH=CH-, -OCH2O-, -OCF2O-, -OCH2CH2O-, -OCH2C(CH3)2O-, -CF2CF2O-, or -OCF2CF2O-;
R1 is a hydrogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6 haloalkynyl group, a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C 4-7 cycloalkylalkyl group, -CHO, -C(O)R7, -C(O)OR7,
-S(O)rR7, -S(O)rN(R14)C(O)OR15, -S(O)rNR16R17, a phenyl group which may be substituted by (R6)q, or a C1-6 alkyl group which may be substituted by (R9)p;
R2 is a hydrogen atom, a C1-6 alkyl group, a C1-6 alkyl group which may be substituted by (R9)p, or
-C(O)OR7;
R3 is a hydrogen atom, a C1-6 alkyl group, -CHO, -C(O)R7, -C(O)OR7, -C(O)SR7, -NR10Rn, -N=CR11R12,
-S(O)2R7, -S(O)rN(R14)C(O)OR15, or -S(O)rNR16R17;
each of R4 and R5 which are independent of each other, is a hydrogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group, a C3-6 cycloalkyl group, a C2-6
alkoxyalkyl group, a C2-6 alkylthioalkyl group, -C(O)OR7, -C(O)NR7R8, or -S(O)2NR7R8;
R7 is a C1-6 alkyl group, a C1-6 haloalkyl group, a C3-6 cycloalkyl group, or a phenyl group which may be substituted by (R6)q;
R9 is a C1-3 alkoxy group, -CN, or -C(O)OR7;
R10 is a hydrogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group, a C3-6 cycloalkyl group, a C2-7
haloalkoxyalkyl group, or a C3-6 halocycloalkyl group; k is an integer of from 0 to 2, provided that when k is 2, two X may be the same or different;
m is an integer of from 0 to 3, provided that when m is 2 or 3, the plurality of Y may be the same or
different;
n is an integer of from 1 to 3, provided that when n is 2 or 3, the plurality of Z may be the same or
different; and
p is 1.
(2) A semicarbazone derivative of the above (1) or its salt, wherein:
Q is Q-1, Q-2, Q-3, Q-4, Q-5, Q-8, Q-9, Q-10, Q-14, Q-15, Q-16, Q-17, Q-18, Q-22, Q-25, Q-27, Q-28, Q-29, Q-30, Q-31, Q-32 or Q-37.
(3) A semicarbazone derivative of the above (1) or its salt, wherein:
J is J-1, J-2, J-7, J-8, J-9, J-10, J-13, J-14, J-15, J-24, J-25, J-26, J-27, J-28, J-30 or J-33.
(4) A semicarbazone derivative of the above (1) or its salt, wherein:
G is G-1.
(5) A semicarbazone derivative of the above (2) or its salt, wherein:
J is J-1, J-2, J-7, J-8, J-9, J-10, J-13, J-14, J-15, J-24, J-25, J-26, J-27, J-28, J-30 or J-33; and
G is G-1.
(6) A semicarbazone derivative of the above (4) or its salt, wherein:
Q is Q-1 or Q-37;
m is an integer of 1 or 2, provided that when m is 2, two Y may be the same or different;
n is an integer of 1 or 2, provided that when n is 2, two Z may be the same or different, and the substituted position is the 3-position, the 4-position or the 3- and 4-positions.
(7) A semicarbazone derivative of the above (4) or its salt, wherein: J is J-33 ;
m is an integer of 1 or 2, provided that when m is 2, two Y may be the same or different, and the substituted position is the 3-position, the 4-position or the 3- and 4-positions; and
n is an integer of 1 or 2, provided that when n is 2, two Z may be the same or different, and the substituted position is the 3-position, the 4-position or the 3- and 4-positions.
(8) A semicarbazone derivative of the above (5) or its salt, wherein:
W is an oxygen atom;
X is a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a C1-6 alkylthio group, a C1-6
haloalkylthio group, a C1-6 alkylsulfonyl group, or a C1-6 haloalkylsulfonyl group;
Y is a halogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a C1-6 alkylthio group, a C1-6 haloalkylthio group, a C1-6 alkylsulfonyl group, a C1-6 haloalkylsulfonyl group, a C1-6 alkylsulfonyloxy group, a C1-6
haloalkylsulfonyloxy group, a C2-7 alkoxycarbonyl group, a C2-7 haloalkoxycarbonyl group, -CN, -NO2, or when m is 2, adjacent two Y may form -CH=CH-CH=CH-, -OCH2O-,
-OCF2O-, -OCH2CH2O-, -OCH2C(CH3)2O-, -CF2CF-O-, or
-OCF2CF2O-; Z is a halogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a C1-6 alkylthio group, a C1-6 haloalkylthio group, a C1-6 alkylsulfinyl group, a C1-6 haloalkylsulfinyl group, a C1-6 alkylsulfonyl group, a C1-6
haloalkylsulfonyl group, a C1-6 alkylsulfonyloxy group, a C1-6 haloalkylsulfonyloxy group, -CN, -NO2, -SF5, or when n is 2, adjacent two Z may form -CH=CH-CH=CH-, -OCH2O-, -OCF2O-, -OCH2CH2O-, -OCH2C(CH3)2O-, -CF2CF2O-, or
-OCF2CF2O-;
m is an integer of 1 or 2, provided that when m is 2, two Y may be the same or different;
n is an integer of 1 or 2, provided that when n is 2, two Z may be the same or different, and the substituted position is the 3-position, the 4-position or the 3- and 4-positions;
R1 is a hydrogen atom, a C1-6 alkyl group, a C2-6 alkoxyalkyl group, or a C2-6 alkylthioalkyl group;
R2 is a hydrogen atom, a C1-6 alkyl group, a C2-6 alkoxyalkyl group, or a -C(O)O-C1-6 alkyl group; and
R3 is a hydrogen atom, an amino group, a C1-6 alkyl group, a -C (O) -C1-6 alkyl group or a -C (O)O-C1-6 alkyl group.
The compound of the present invention may have E-form and Z-form isomers. The present invention covers such E-form and Z-form as well as a mixture containing such E-form and Z-form in an optional ratio. Further, when the compound of the present invention has an asymmetric carbon atom, it includes R-form and S-form. Furthermore, when R1 is a hydrogen atom, the compound of the present invention may be in the form of the following tautomers, and such structures are also covered by the present invention.
Figure imgf000030_0001
Specific examples of the compound of the present invention include the compounds shown in Tables 1 to 5. However, the compounds in Tables 1 to 5 are merely illustrative, and the present invention is by no means limited to such specific examples.
Figure imgf000031_0002
In the Table 1, A1 to A7 represent the following substituents:
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0001
Figure imgf000106_0001
Figure imgf000107_0001
Figure imgf000108_0001
Figure imgf000109_0001
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
Figure imgf000119_0001
Figure imgf000120_0001
Figure imgf000121_0001
Figure imgf000122_0001
Figure imgf000123_0001
Figure imgf000124_0001
Figure imgf000125_0001
Figure imgf000126_0001
Figure imgf000127_0001
Figure imgf000128_0001
Figure imgf000129_0001
Figure imgf000130_0001
Figure imgf000131_0001
Figure imgf000132_0001
Figure imgf000133_0001
Figure imgf000134_0001
Figure imgf000135_0001
Figure imgf000136_0001
Figure imgf000137_0001
Figure imgf000138_0001
Figure imgf000139_0001
Figure imgf000140_0001
Figure imgf000141_0001
Figure imgf000142_0001
Figure imgf000143_0001
Figure imgf000144_0001
Figure imgf000145_0001
Figure imgf000146_0001
Figure imgf000147_0001
Figure imgf000148_0001
Figure imgf000149_0001
Figure imgf000150_0001
Figure imgf000151_0001
Figure imgf000152_0001
Figure imgf000153_0001
Figure imgf000154_0001
Figure imgf000155_0001
Figure imgf000156_0001
Figure imgf000157_0001
Figure imgf000158_0001
Figure imgf000159_0001
Figure imgf000160_0001
Figure imgf000161_0001
Figure imgf000162_0001
Figure imgf000163_0001
Figure imgf000164_0001
Figure imgf000165_0001
Figure imgf000166_0001
Figure imgf000167_0001
Figure imgf000168_0001
Figure imgf000169_0001
Figure imgf000170_0001
Figure imgf000171_0001
Figure imgf000172_0001
Figure imgf000173_0001
Figure imgf000174_0001
Figure imgf000175_0001
Figure imgf000176_0001
Figure imgf000177_0001
Figure imgf000178_0001
Figure imgf000179_0001
Figure imgf000180_0001
Figure imgf000181_0001
Figure imgf000182_0001
Figure imgf000183_0001
Figure imgf000184_0001
Figure imgf000185_0001
Figure imgf000186_0001
Figure imgf000187_0001
Figure imgf000188_0001
Figure imgf000189_0001
Figure imgf000190_0001
Figure imgf000191_0001
Figure imgf000192_0001
Figure imgf000193_0001
Figure imgf000194_0001
Figure imgf000195_0001
In the present invention, the pesticide means, in particular, an agent for controlling insect pests.
The compound of the present invention exhibits pesticidal effects against various insect pests at an extremely low dose. The insect pests include, for example, agricultural insect pests such as green rice leafhopper (Nephotettix cincticeps), brown rice
planthopper (Nilaparvata luqens), green peach aphid
(Myzus persicae), 28-spotted ladybird (Epilachna
vigintioctopunctata), tobacco budworm (Heliothis
virescensl, european corn borer (Ostrinia nubilalis), fall armyworm (Spodoptera fruqiperda), corn earworm
(Helicoverpa zea), cabbage armyworm (Mantestra brassicae), common cutworm (Spodoptera litura), common white (Pieris rapae crucivora), cabbage sawfly (Athalia rosae
ruficornis), smaller tea tortrix (Adoxofhyes sp.), oriental tea tortrix (Homona maqnanima), rice leafroller (Cnaphalocrocis medinalis), diamondback moth (Plutella xylostella), southern corn rootworm (Diabrotica
undecimpunctata howardi), northern corn rootworm (D.
longicornis barberi), western corn rootworm (D. virgifera virgifera., Colorado potato beetle (Leptinotarsa
decemlineata); sanitary insect pests such as common gnat (Culex pipiens pallens), housefly, German cockroach
(Blattela germanica), ants, fleas and louses; stored grain insect pests such as maize weevil (Sitophilus zeamais), red flour beetle (Tribolium castaneum) and almond moth (Cadra cautella); house pests such as
Formosan subterranean termite (Coptotermes formosanus); animal pests such as mites, fleas and louses; indoor dust mites such as acarid mites (Acaridae), Dermatophaqoides farinae, and Chenyletus malaccensis; and mollusks such as slugs (Philomycidae) and snails. Namely, the compound of the present invention is capable of effectively
controlling pests such as orthoptera, hemiptera,
lepidoptera, coleoptera, hymenoptera, diptera, isoptera and acarina at a low dose. On the other hand, the compound of the present invention has been found to be an extremely useful compound which is substantially free from adverse effects against mammals, fishes, Crustacea and beneficial insects. On the basis of this discovery, the present invention has been accomplished.
Now, methods for preparing the compounds of the present invention will be described. The compounds of the present invention are novel semicarbazone
derivatives, and representative methods for their
production will be described specifically.
In the respective methods, Q, J, G, W, X, Y, Z, R1, R2, and R3 are as defined above, and each of L1, L2, L3 and L4 is an excellent leaving group such as a chlorine atom, a bromine atom, an iodine atom, an alkylsulfonate group or an arylsulfonate group. Method A
Figure imgf000198_0001
Process 1
A compound of the formula (III) can be obtained by reacting a compound of the formula (II) with e.g.
phosphorus pentachloride, a mixture of phosphorus pentachloride and phosphorus oxychloride, or phosphorus oxychloride in an inert solvent or without any solvent, or by reacting a compound of the formula (II) with thionyl chloride in an inert solvent or without any solvent. In the case of the reaction with thionyl chloride, the reaction proceeds more efficiently if from 0.001 to 0.1 equivalents of dimethylformamide is added. Process 2
Then, the compound of the formula (III) and a compound of the formula (IV) are reacted in the presence or absence of a base in an inert solvent to obtain a compound of the formula (V) of the present invention (a compound of the formula (I) wherein R1 is a hydrogen atom).
Process 3
Further, a compound of the formula (I) of the present invention can be obtained by reacting the compound of the formula (V) of the present invention and a compound of the formula (VI) in the presence or absence of a base in an inert solvent.
The solvent to be used in Process 1 may, for example, be an aromatic hydrocarbon such as benzene or toluene, or a halogenated hydrocarbon such as carbon tetrachloride or 1,1,2-trichloroethane. It is preferred to employ from 1 to 3 equivalents of phosphorus pentachloride in toluene. The reaction temperature can be set at an optional level within a range of from 0°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 60°C to the reflux temperature.
The base to be used in Process 2 may, for example, be an alkali metal alkoxide such as sodium ethoxide or potassium tert-butoxide, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate, an alkali metal hydride such as sodium hydride or potassium hydride, or an organic base such as triethylamine or pyridine. The solvent to be used may be any solvent so long as it does not hinder the reaction. For example, a lower alcohol such as methanol or ethanol, an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or 1,4-dioxane, an ester such as ethyl acetate, a halogenated hydrocarbon such as dichloromethane or 1,2-dichloroethane, an amide such as dimethylformamide or dimethylacetamide,
acetonitrile, dimethylsulfoxide, or water, may be
mentioned. These inert solvents may be used alone or in combination as a mixture. Usually, it is preferred to use as the base, from 1 to 2 equivalents of an organic base such as triethylamine or pyridine and as a solvent an aromatic hydrocarbon such as benzene or toluene, or an ether such as tetrahydrofuran or diethyl ether. The reaction temperature may be set at an optional level within a range of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction within a range of from 0°C to reflux temperature of the reaction mixture.
The base to be used in Process 3 may, for example, be the same as used in Process 2. The solvent to be used may be any solvent so long as it does not hinder the reaction. For example, it may be a lower alcohol such as methanol or ethanol, an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2- dimethoxyethane, tetrahydrofuran or 1,4-dioxane, an ester such as ethyl acetate, a ketone such as acetone or methyl ethyl ketone, a halogenated hydrocarbon such as
dichloromethane or 1,2-dichloroethane, an amide such as dimethylformamide or dimethylacetamide, acetonitrile, dimethylsulfoxide, or water. Such inert solvents may be used alone or in combination as a mixture. Usually, it is preferred to employ as the base from 1 to 3
equivalents sodium hydride, potassium hydride, potassium tert-butoxide, or potassium hydroxide in a polar solvent such as tetrahydrofuran or dimethylformamide. The reaction temperature can be set at an optional level within a range of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 0°C to 90°C.
Method B
Figure imgf000201_0001
Process 1
A compound of the formula (VIII) can be obtained by reacting a compound of the formula (VII) and diphosphorus pentasulfide in an inert solvent or without solvent, or by reacting a compound of the formula (VII) with a
Lawesson's reagent in an inert solvent or without
solvent.
Process 2
Then, the compound of the formula (VIII) and the compound of the formula (IX) are reacted in the presence or absence of a desulfurization accelerator in an inert solvent or without solvent, to obtain a compound of the formula (X).
Process 3
Further, the compound of the formula (X) and a compound of the formula (XI) are reacted in an inert solvent in the presence or absence of a base to obtain a compound of the formula (XII) (a compound of the formula (I) of the present invention wherein R3 is a hydrogen atom). The compound of the formula (X) can also be obtained by reacting the compound of the formula (IX) to the compound of the formula (III) obtained in Process 1 of Method A.
The solvent to be used in Process 1 may be any solvent so long as it does not hinder the reaction. For example, it may be an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2- dimethoxyethane, tetrahydrofuran or 1,4-dioxane, an ester such as ethyl acetate, a halogenated hydrocarbon such as dichloromethane or 1,2-dichloroethane, an amide such as dimethylformamide or dimethylacetamide, acetonitrile, pyridine, dimethylsulfoxide, or water. These inert solvents may be used alone or in combination as a
mixture. Usually, it is preferred to employ from 0.5 to 1.5 mol times, based on the substrate, of diphosphorus sulfide in pyridine. The reaction temperature can be set at an optional level within a range of from 0°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 60°C to the reflux temperature.
The solvent to be used for Process 2, may be any solvent so long as it does not hinder the reaction. For example, a lower alcohol such as methanol or ethanol, an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2-dimethoxyethane,
tetrahydrofuran or 1,4-dioxane, an ester such as ethyl acetate, a halogenated hydrocarbon such as
dichloromethane or 1,2-dichloroethane, an amide such as dimethylformamide or dimethylacetamide, acetonitrile, pyridine, dimethylsulfoxide or water, may be mentioned. These solvents may be used alone or in combination as a mixture of two or more of them.
As a suitable desulfurization accelerator, a copper salt such as copper chloride may, for example, be mentioned.
The reaction temperature may be set at any optional level from 0°C to the reflux temperature of the reaction mixture. However, it is usually preferred to conduct the reaction, for example, at a temperature within a range of from 60°C to the reflux temperature in ethanol.
The base and the solvent to be used in Process 3, may be the same as used in Process 2 in Method A. Usually, it is preferred to employ as the base from 0.01 to 2 equivalents of an organic base such as triethylamine or pyridine and as the solvent a halogenated hydrocarbon such as dichloromethane or 1,2-dichloroethane. The reaction temperature can be set at an optional level within a range of from 0°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 0°C to 50°C.
Method C
Figure imgf000204_0001
Process 1
A compound of the formula (XV) can be obtained by reacting a compound of the formula (XIII) (an
intermediate of the formula (VIII) as described in Method B wherein R1 is a hydrogen atom) with a compound of the formula (XIV) in a solvent inert to the reaction, if necessary in the presence of a suitable base.
Process 2
Then, the compound of the formula (XV) and a compound of the formula (IX) are reacted in a solvent inert to the reaction or without any solvent, if necessary in the presence of a suitable base to obtain a compound of the formula (XVI) (an intermediate of the formula (X) as described in Method B wherein R1 is a hydrogen atom).
Process 3
Further, the compound of the formula (XVI) and a compound of the formula (XI) are reacted in a solvent inert to the reaction, if necessary in the presence of a suitable base, to obtain a compound of the formula (XVII) (a compound of the formula (I) of the present invention wherein R1=R3=H).
The base to be used in Process 1 may be the same as used in Process 2 in Method A.
The solvent to be used, may be the same as used in Process 3 in Method A.
Usually, it is preferred to employ as a base, for example, from 1 to 3 equivalents, based on the substrate. of sodium hydride, potassium hydride, potassium tert- butoxide, potassium carbonate or potassium hydroxide in a polar solvent such as tetrahydrofuran, dimethylformamide, acetonitrile or acetone.
The reaction temperature may be set at any optional level from -60°C to the reflux temperature of the
reaction mixture. However, it is preferred to conduct the reaction within a range of from 0°C to 90°C.
Processes 2 and 3 can be carried out in the same manner as in Method B.
Method D
Figure imgf000206_0001
Process 1
A compound of the formula (XIX) can be obtained by reacting a compound of the formula (XVIII) with phosgene or a phosgene equivalent (phosgen dimer or triphosgene), if necessary in the presence of a suitable base.
Process 2
Then, the compound of the formula (XIX) and a
compound of the formula (X) are reacted in a solvent inert to the reaction, if necessary in the presence of a suitable base, to obtain a compound of the formula (I) of the present invention wherein R3≠H.
The base to be used in Process 1, may be the same as used in Process 2 in Method A.
The solvent to be used may be any solvent so long as it does not hinder the reaction. For example, an
aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2-dimethoxyethane, ethylene glycol dimethyl ether, tetrahydrofuran or 1,4-dioxane, an ester such as ethyl acetate, a halogenated hydrocarbon such as dichloromethane or 1,2-dichloroethane, an amide such as dimethylformamide or dimethylacetamide,
acetonitrile, or pyridine, may be mentioned. These solvents may be used alone or in combination as a mixture of two or more of them.
Usually, it is preferred to react the compound with phosgene in e.g. a solvent mixture of
dichloromethane/ethylene glycol dimethyl ether in the presence of from 1 to 3 equivalents, based on the
substrate, of sodium hydride. The reaction temperature may be set at an optional level from 0°C to the reflux temperature of the reaction mixture. However, it is preferred to carry out the reaction within a range of from 0°C to 25°C.
The base to be used in Process 2, may be the same as used in Process 2 in Method A.
The solvent to be employed, may be the same as used in Process 1 of this method.
Usually, it is preferred to carry out the reaction in a solvent such as dichloromethane or tetrahydrofuran using as the base from 1 to 3 equivalents, based on the substrate, of an organic base such as triethylamine or pyridine.
The reaction temperature may be set at any optional level from 0°C to the reflux temperature of the reaction mixture. However, it is preferred to carry out the reaction within a range of from 0 to 25°C.
Method E
Figure imgf000208_0001
This method is a method of introducing R2 and R3 into a compound of the formula (XX) of the present invention wherein R3 = R4 = hydrogen atom. A compound of the formula (XII) of the present invention can be obtained by reacting a compound of the formula (XX) of the present invention and a compound of the formula (XXI) in the presence of a base in an inert solvent. Then, the compound of the formula (XII) of the present invention and a compound of the formula (XXII) are reacted in the presence of a base in an inert solvent to obtain a compound of the formula (I) of the present invention. The base to be used in this reaction may, for example, be the same as used in Process 2 in Method A. The solvent to be used may be any solvent so long as it does not hinder the reaction. For example, it may be the same as in Process 3 in Method A. Usually, it is preferred to employ as the base from 1 to 3 equivalents of sodium hydride, potassium hydride, potassium tert-butoxide or potassium hydroxide in a polar solvent such as
tetrahydrofuran or dimethylformamide. The reaction temperature can be set at an optional level within a range of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 0°C to 90°C. In this reaction, in the case where R2=R3, a compound of the formula (I) of the present invention can be obtained without isolating the compound of the formula (XII) by using two equivalents of the compound of the formula (XXI) and two equivalents of a base.
Preparation of starting materials and intermediates in Methods A to E
Figure imgf000209_0001
As another method for producing the intermediate of the formula (XIII) or (XV), a compound of the formula
(XXIII) or (XXIV) is treated with from 1 to 2 equivalents of a reactant such as n-butyl lithium or lithium
diisopropylamide in a solvent inert to the reaction and then reacted with a compound of the formula (XXV) to obtain a compound of the formula (XIII). The obtained compound of the formula (XIII) is reacted with a compound of the formula (XIV) in the same manner as in Process 1 in Method C to obtain a compound of the formula (XV).
Further, the compound of the formula (XV) can be prepared from the compound of the formula (XXIII) or
(XXIV) by one pot by adding the compound of the formula (XIV) to the reaction mixture without isolating the compound of the formula (XIII).
The suitable solvent to be used for this reaction, may, for example, be an ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or 1,4-dioxane, or a phosphoric amide such as hexamethylphosphoric triamide. These solvents may be used alone or in combination as a mixture of two or more of them.
The reaction temperature can be set at an optional level from -78°C to the reflux temperature of the
reaction mixture. However, it is preferred to carry out the reaction within a range of from -78°C to 25°C.
On the other hand, in this method, the compound of the formula (XXIII) wherein Q is Q-5, Q-14, Q-18 or Q-22, may be reacted with a compound of the formula (XXV) in a solvent inert to the reaction, if necessary in the presence of a suitable base, to obtain a compound of the formula (XIII) wherein Q is Q-5, Q-14, Q-18 or Q-22.
The base to be used for this reaction, may be the same as used in Process 2 in Method A.
The solvent to be used, may be the same as used in Process 3 in Method A.
Usually it is preferred to carry out the reaction in a solvent such as tetrahydrofuran or dichloromethane without using any base, or to carry out the reaction by firstly preparing an alkali metal salt by using as a base from 0.01 to 2 equivalents, based on the substrate, of an organic base such as triethylamine, or from 1 to 2 equivalents, based on the substrate, of sodium hydride or the like.
The reaction temperature may be set at an optional level from -20°C to the reflux temperature of the
reaction mixture. However, it is preferred to carry out the reaction within a range of from 0 to 25°C. The compound of the formula (XV) wherein Q is Q-5, Q-14, Q-18 or Q-22, can be obtained by reacting the obtained
compound of the formula (XIII) with a compound of the formula (XIV) in the same manner as in Process 1 in
Method C. Further, in a case where this reaction is carried out by firstly preparing an alkali metal salt by means of e.g. sodium hydride, it is possible to produce the compound of the formula (XV) by one pot from the compound of the formula (XXIII) by adding from 1 to 2 equivalents of the compound of the formula (XIV) to the reaction mixture.
Figure imgf000212_0001
(R1≠H) The compound of the formula (VII) to be used as a starting material in Method B, can be obtained by
reacting a compound of the formula (XXVI) and a compound of the formula (XXVII) in the presence of a base in a solvent inert to the reaction.
The base to be used for this reaction, may, for example, be an alkali metal carbonate such as sodium carbonate, potassium carbonate or sodium
hydrogencarbonate, an alkali metal hydride such as sodium hydride or potassium hydride, or an organic base such as triethylamine or pyridine.
The solvent to be used, may be any solvent so long as it does not hinder the reaction. For example, an
aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or 1,4-dioxane, an ester such as ethyl acetate, a halogenated hydrocarbon such as
dichloromethane or 1,2-dichloroethane, an amide such as dimethylformamide, dimethylacetamide, acetone,
acetonitrile, or water, may be mentioned. These solvents may be used alone or in combination as a mixture of two or more of them.
Usually, it is preferred to employ as the base from 1 to 3 equivalents, based on the substrate, of an organic base such as triethylamine or pyridine in a solvent such as tetrahydrofuran, ethyl acetate, dichloromethane or benzene. The reaction temperature may be set at any optional level from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to carry out the reaction within a range of from 0 to 120°C.
Further, the compound of the formula (VII) wherein R1≠H, can be produced also by reacting a compound of the formula (II) which can be produced by reacting the compound of the formula (XXVI) and the compound of the formula (XXVIII) in the same manner, with a compound of the formula (VI), if necessary in the presence of a base in a solvent inert to the reaction.
The base to be used here, may be the same as used in Process 2 in Method A.
The solvent to be used, may be the same as used in Process 3 is Method A.
Usually, it is preferred to use as the base from 1 to 3 equivalents, based on the substrate, of sodium hydride, potassium hydride, potassium tert-butoxide or potassium hydroxide in a polar solvent such as tetrahydrofuran or dimethylformamide, or to use as the base from 1 to 3 equivalents, based on the substrate, of potassium
carbonate in a polar solvent such as dimethylformamide, acetonitrile or acetone.
The reaction temperature may be set at an optional level of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to carry out the reaction within a range of from 0 to 90°C.
Figure imgf000214_0001
A compound of the formula (XXIX) (an intermediate of the formula (IV) in Method A wherein R3=H) can be
obtained by reacting a compound of the formula (XI) and a compound of the formula (IX) in the presence or absence of a catalyst in an inert solvent. The catalyst to be used in this reaction may, for example, be an organic base such as triethylenediamine or diazabicycloundecene. The amount of the catalyst to be used can be set at an optional level within a range of from 0.001 wt% to 10 wt%, relative to the compound of the formula (XI).
However, an amount of from 0.1wt% to 1 wt% is preferred. The solvent may be any solvent so long as it does not hinder the reaction. For example, it may be an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or 1,4-dioxane, an ester such as ethyl acetate, a
halogenated hydrocarbon such as dichloromethane,
chloroform or 1,2-dichloroethane, an amide such as dimethylformamide or dimethylacetamide, acetonitrile, dimethylsulfoxide, or water. These inert solvents may be used alone or in combination as a mixture. The reaction temperature can be set at an optional level within a range of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 0°C to 50°C. In this reaction, the molar ratio of the reactants is not particularly limited. However, in order to obtain the compound of the formula (XXIX) in good yield, it is preferred to employ the compound of the formula (IX) in a slightly excess amount relative to the compound of the formula (XI).
Figure imgf000215_0001
A compound of the formula (XXXI) can be obtained by reacting a compound of the formula (XXX) and a compound of the formula (XI) in the presence or absence of a catalyst in an inert solvent. The catalyst, the solvent and the reaction conditions such as the temperature to be used in this reaction may be similar to those in
synthesis of the compound of the formula (XXIX). It is a feature of this method that the compound of the formula (XXXI) can be obtained in good yield by using equimolar amounts of the compound of the formula (XXX) and the compound of the formula (XI). In Process 2, the compound of the formula (XXXI) is reacted in the presence of an acid in an inert solvent to obtain a compound of the formula (XXXII) (an intermediate of the formula (IV) in Method A wherein R2=R3=H). The acid to be used may, for example, be an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as
paratoluenesulfonic acid or trifluoroacetic acid. The solvent may be any solvent so long as it does not hinder the reaction. For example, it may be a lower alcohol such as methanol or ethanol, an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or 1,4-dioxane, an ester such as ethyl acetate, a halogenated hydrocarbon such as dichloromethane, carbon tetrachloride or 1,2-dichloroethane, an amide such as dimethylformamide or dimethylacetamide, acetonitrile, dimethylsulfoxide, acetic acid, or water. These inert solvents may be used alone or in combination as a mixture. Usually, it is preferred to employ from 1 to 50 equivalents of
hydrochloric acid in a lower alcohol such as methanol or ethanol. The reaction temperature can be set at an optional level within a range of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 0°C to the reflux temperature of the reaction mixture.
In the respective methods, the molar ratios of the respective reactants are not particularly limited.
However, it is advantageous to conduct the reactions in equimolar or close to equimolar amounts.
When it is necessary to purify the compound of the present invention, the compound can be separated and purified by an optional purification method such as recrystallization, column chromatography or thin layer chromatography.
When the compound of the present invention is to be used as a pesticide, it is usually applied as admixed with a suitable carrier, for example, a solid carrier such as clay, pulp, bentonite, diatomaceous earth or fine silica powder, or a liquid carrier such as water, an alcohol (such as isopropanol, butanol, benzyl alcohol or furfuryl alcohol), an aromatic hydrocarbon (such as toluene or xylene), an ether (such as anisol), a ketone (such as cyclohexanone or isophorone), an ester (such as butyl acetate), an acid amide (such as N-methylpyrrolidone) or a halogenated hydrocarbon (such as chlorobenzene). If desired, a surfactant, an emulsifier, a dispersant, a penetrating agent, an extender, a
thickener, an anti-freezing agent, an anti-solidification agent and/or a stabilizer may be added. It may be practically used in the form of an optional formulation such as a liquid formulation, an emulsifiable
concentrate, a wettable powder, a dry flowable, a
flowable, a dust or a granule.
Further, at the time of formulation or application, the compound of the present invention may be mixed with various other herbicides, insecticides, miticides, nematocides, fungicides, plant growth regulating agents, synergists, fertilizers or soil improving agents, as the case requires.
Particularly by mixing it with other agricultural chemicals or plant hormones, it can be expected to reduce the cost by a reduction of the dose in its application, to broaden the insecticidal spectrum due to synergistic effects of the mixed agents or to obtain higher
pesticidal effects. In such a case, it is possible to combine it with a plurality of known agricultural
chemicals. Compounds disclosed in 1994 Issue of Farm Chemicals Handbook may, for example, be mentioned as types of agricultural chemicals which can be used in admixture with the compound of the present invention. The dose in application of the compound of the present invention varies depending upon the application site, the application season, the manner of application and the type of the crop plant. However, it is usually in an amount of from 0.005 to 50 kg/ha as the amount of active ingredient.
Now, Formulation Examples will be given in which compounds of the present invention are used. However, it should be understood that the present invention is by no means restricted to such specific Formulation Examples.
In the following Formulation Examples, "parts" means
"parts by weight".
Wettable powder
Figure imgf000219_0001
As "others" an antisolidification agent may, for example, be mentioned.
Emulsifiable concentrate
Figure imgf000219_0002
Flowable
Figure imgf000219_0003
Figure imgf000220_0001
As "others" an antifreezing agent and a thickener may, for example, be mentioned.
Dry flowable
Figure imgf000220_0002
Granule
Figure imgf000220_0003
Dust
Figure imgf000220_0004
Now, the present invention will be described in further detail with reference to Examples (Preparation
Examples, Formulation Examples and Test Examples).
PREPARATION EXAMPLES
The compounds of the present invention were prepared or can be prepared in accordance with the following
Preparation Examples. However, it should be understood that the present invention is by no means restricted by such specific Preparation Examples.
PREPARATION EXAMPLE 1
N-(4-cyanophenyl)-2-thiophenecarboxamide 4-(4- trifluoromethoxyphenyl) semicarbazone (Compound No. 1-13 of the present invention)
Process 1: N-(4-cyanophenyl)-2-thiophenecarboxamide
25 mℓ of a benzene solution containing 8.04 g of 2-thenoyl chloride was dropwise added to 75 mℓ of a benzene solution containing 8.04 g of 4-aminobenzonitrile and 6.07 g of triethylamine at room temperature with
stirring. After completion of the dropwise addition, stirring was further continued overnight at room
temperature. The solvent was distilled off under reduced pressure, and then 300 mℓ of ethyl acetate was added. The mixture was washed twice with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was
recrystallized from diisopropyl ether to obtain 12.32 g of the desired compound.
Melting point: 205.0-206.0°C
1HNMR(CDCℓ3-DMSO-d6,Me4Si ,60MHz )S10.62 (s,1H,NH), 7.20-8.21(m,7H,Ar).
Process 2: N-(4-cyanophenyl)-2-thiophenecarboxamide 4-(4-trifluoromethoxyphenyl)semicarbazone
1.14 g of N-(4-cyanophenyl)-2-thiophenecarboxamide and 1.14 g of phosphorus pentachloride were added to 10 mℓ of toluene, and the mixture was stirred for 3 hours under reflux under heating. The solvent and the formed phosphorus oxychloride were distilled off under reduced pressure, and the residue was dissolved in 10 mℓ of benzene. Then, 0.50 g of triethylamine and 1.18 g of 4- (4-trifluoromethoxyphenyl)semicarbazide were added thereto, and the mixture was stirred for 2 hours under reflux under heating. Then, 150 mℓ of ethyl acetate was added thereto, and the mixture was washed with water and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue was washed with diisopropyl ether to obtain 0.70 g of the desired compound.
Melting point: 185.0-186.0°C
1HNMR(CDCℓ3-DMSO-d6,Me4Si ,60MHz)δ9.67 ( s,1H,NH),
8.83(s,1H,NH), 8.77(s,1H,NH), 6.53-7.73(m,11H,Ar).
PREPARATION EXAMPLE 2
N-(4-cyanophenyl)-N-methyl-2-thiophenecarboxamide 4-(4-trifluoromethoxyphenyl) semicarbazone (Compound No. 1-45 of the present invention)
Process 1: N-(4-cyanophenyl)-N-methyl-2-thiophenecarboxamide
1.63 g of sodium hydride (purity: 55%) was suspended in 30 mℓ of dimethylformamide, and 50 mℓ of a
dimethylformamide solution containing 7.80 g of N-(4- cyanophenyl)-2-thiophenecarboxamide prepared in Process 1 in Example 1, was dropwise added thereto with stirring under cooling with ice. After completion of the dropwise addition, stirring was continued for 30 minutes at room temperature. Then, 9.66 g of methyl iodide was added, and stirring was further continued overnight at room temperature. Then, the mixture was heated at 60°C for 30 minutes to complete the reaction. The solvent was distilled off under reduced pressure, and 200 mℓ of ethyl acetate was added to the residue. The mixture was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was triturated in the diisopropyl ether to obtain 6.47 g of the desired compound.
Melting point: 128.0-130.0°C
1HNMR(CDCℓ3,Me4Si,60MHz)57.71(s,1H,Ar), 7.62 (s,1H,Ar), 6.85-7.84(m,5H,Ar), 3.48(s,3H,CH3).
Process 2: N-(4-cyanophenyl)-N-methyl-2-thiophenecarbothioamide
6.47 g of N-(4-cyanophenyl)-N-methyl-2-thiophenecarboxamide and 6.23 g of diphosphorus
pentasulfide were added to 30 mℓ of pyridine, and the mixture was stirred for 2 hours under reflux under heating and then added to 300 mℓ of ice water. The mixture was made alkaline by an addition of an aqueous sodium hydroxide solution and then extracted with 200 mℓ of ethyl acetate. The organic layer was washed twice with dilute hydrochloric acid and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue was washed with
diisopropyl ether to obtain 6.00 g of the desired
compound.
Melting point: 95.0-96.0°C. Process 3: N-(4-cyanophenyl)-N-methyl-2- thiophenecarboxamide hydrazone
6.00 g of N-(4-cyanophenyl)-N-methyl-2- thiophenecarbothioamide and 4.67 g of hydrazine
monohydrate were added to 100 mℓ of ethanol, and the mixture was stirred for 2 hours under reflux under heating. The mixture was left to cool to room
temperature, and then 100 mℓ of water was added thereto. Then, ethanol was distilled off under reduced pressure. 200 mℓ of ethyl acetate was added to the residue, and the mixture was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from a solution of a mixture comprising diisopropyl ether, hexane and ethyl acetate to obtain 4.00 g of the desired compound.
Melting point: 101.0-102.0°C
1HNMR(CDCℓ3,Me4Si ,60MHz)δ6.72-7.52 (m,7H,Ar),
5.57(br,2H,NH2), 3.25(s,3H,CH3).
Process 4: N-4-(cyanophenyl)-N-methyl-2-thiophenecarboxamide 4-(4-trifluoromethoxyphenyl)-semicarbazone
0.26 g of N-(4-cyanophenyl)-N-methyl-2-thiophenecarboxamide hydrazone, 0.21 g of 4-trifluoromethoxyphenyl isocyanate and two drops of triethylamine were added to 5 mℓ of dichloromethane, and the mixture was stirred overnight at room temperature. After completion of the reaction, 50 mℓ of ethyl acetate was added thereto, and the mixture was washed with water and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue was washed with diisopropyl ether to obtain 0.40 g of the desired compound.
Melting point: 196.0-198.0°C
1HNMR(CDCℓ3-DMSO-d6,Me4Si,60MHz)510.11(s,1H,NH),
8.78(s,1H,NH), 6.72-7.73(m,11H,Ar), 3.28(s,3H,CH3).
PREPARATION EXAMPLE 3
N-4-(cyanophenyl)-4-methylthiazole-2-carboxamide 4-(4-trifluoromethoxyphenyl)semicarbazone (Compound No. 3-4 of the present invention)
Process 1: N-4-(cyanophenyl)-4-methylthiazole-2-thiocarboxamide
32 mℓ of n-BuLi (1.68N, hexane solution) was
dropwise added to 50 mℓ of a THF solution containing 5.00 g of 4-methylthioazole with stirring at -78°C. After completion of the dropwise addition, stirring was
continued for 30 minutes at -78°C, and then 50 mℓ of a THF solution containing 8.00 g of 4-cyanophenyl
isothiocyanate was dropwise added thereto. The mixture was returned to room temperature, and then the stirring was further continued overnight. Then, 30 mℓ of 1N HCℓ was added to the reaction solution, and the mixture was extracted with 200 mℓ of ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue was washed with
diisopropyl ether to obtain 1.20 g of the desired compound.
Melting point: 159.0-161.0°C
1HNMR(CDCℓ3-DMSO-d6,Me4Si ,60MHz )δ11.00 ( S,1H,NH),
8.32 (d, J=6.9Hz , 2H,Ar ) , 7.71 (d, J=6.9Hz , 2H, Ar ) ,
7.21 (s,1H,thiazole), 2.42 ( s , 3H,CH3).
Process 2: N-4-(cyanophenyl)-4-methylthiazole-2-carboxamide hydrazone
1.90 g of N-4-(cyanophenyl)-4-methylthiazole-2-thiocarboxamide and 0.64 g of potassium carbonate were added to 10 mℓ of acetonitrile, and 0.65 g of methyl iodide was dropwise added thereto at room temperature, followed by stirring for 3 hours. Then, potassium carbonate was filtered off, and 50 mℓ of ethyl acetate was added to the filtrate. The mixture was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 1.10 g of methyl N-(4-cyanophenyl)-4-methylthiazole-2-thioimidate.
0.80 g of hydrazine monohydrate was added to 30 mℓ of an ethanol solution containing 1.1 g of the obtained methyl N-(4-cyanophenyl)-4-methylthiazole-2-thioimidate, and the mixture was stirred at room temperature for 4 hours. Nitrogen gas was blown into the reaction solution for 10 minutes, and then 50 mℓ of ethyl acetate was added thereto. The mixture was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was washed with diisopropyl ether to obtain 0.83 g of the desired compound.
Melting point: 151.0-152.0°C
Process 3: N-(4-cyanophenyl)-4-methylthiazole-2-carboxamide 4-(4-trifluoromethoxyphenyl)semicarbazone
10 mℓ of a dichloromethane solution containing 0.41 g of 4-trifluoromethoxyphenyl isocyanate was dropwise added to 10 mℓ of a dichloromethane solution containing 0.51 g of N-(4-cyanophenyl)-4-methylthiazole-2-carboxamide hydrazone at room temperature, and stirring was further continued overnight at room temperature. The solvent was distilled off under reduced pressure, and the residue was washed with diisopropyl ether to obtain 0.90 g of the desired compound.
Melting point: 148.0-150.0°C
1HNMR(CDCℓ3-DMSO-d6,Me4Si,60MHz)δ9.67 (s,1H,NH),
9.15(s,1H,NH), 9.03 (s,1H,NH),7.80-6.62 (m,9H,Ar, thiazole), 2.37(s,3H,CH3).
PREPARATION EXAMPLE 4
N-(4-cyanophenyl)-2-chlorothiazole-4-carboxamide 4-(4-trifluoromethoxyphenyl)semicarbazone (Compound No. 3-5 of the present invention)
Process 1: ethyl 2-aminothiazole-4-carboxylate
22.0 g of ethyl bromoacetate and 10.0 g of thiourea were added to 100 mℓ of ethanol, and the mixture was stirred for 5 hours under reflux under heating. The mixture was returned to room temperature, and
precipitated solid was collected by filtration and dissolved in an aqueous alkaline solution and extracted by an addition of 200 mℓ of ethyl acetate and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 8.4 g of the desired compound as yellow oil.
1HNMR(CDCℓ3-DMSO-d6,Me4Si ,60MHz) δ7.33 (s ,1H,thiazole), 7.18(s,2H,NH2), 4.27(q,J=7.0Hz, 2H,CH2),
1.33(t,J=7.0Hz, 3H,CH3).
Process 2: ethyl 2-chlorothiazole-4-carboxylate
Ethyl 2-aminothiazole-4-carboxylate was added to a mixture comprising 30 mℓ of concentrated hydrochloric acid and 10 mℓ of phosphoric acid, and the mixture was stirred under cooling with ice. Then, 10 mℓ of an aqueous solution containing 1.6 g of sodium nitrite was dropwise added thereto. After completion of the dropwise addition, stirring was further continued for 4 hours at room temperature. The mixture was dropwise added to 50 mℓ of chloroform having 1.90 g of copper chloride
suspended therein, at room temperature, and stirring was further continued for 2 hours. Insoluble substances were removed by filtration, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 2.70 g of the desired compound.
1HNMR(CDCℓ3-DMSO-d6,Me4Si, 60MHz) δ8.12 (s,1H, thiazole), 4.39(q,J=7.0Hz, 2H,CH2), 1.37(t,J=7.0Hz,3H,CH3).
Process 3: 2-chlorothiazole-4-carboxylic acid
10 mℓ of concentrated sulfuric acid and 50 mℓ of water were added to ethyl 2-chlorothiazole-4-carboxylate, and the mixture was heated and stirred at 80°C for 3 hours. The mixture was returned to room temperature and extracted with 100 mℓ of ethyl acetate and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 1.90 g of the desired compound.
1HNMR(CDCℓ3-DMSO-d6,Me4Si ,60MHz) δ12.66 (s ,1H,COOH),
8.25 (s ,1H,thiazole)
Process 4: N-(4-cyanophenyl)-2-chlorothiazole-4-carboxamide
2-chlorothiazole-4-carboxylic acid was converted to 2-chlorothiazole-4-carboxylic acid chloride by means of thionyl chloride. Then, 10 mℓ of a dichloromethane solution thereof was dropwise added to 50 mℓ of a
dichloromethane solution containing 0.71 g of 4-aminobenzonitrile and 0.61 g of triethylamine with stirring at room temperature. After completion of the dropwise addition, stirring was further continued
overnight at room temperature. The solvent was distilled off under reduced pressure, and then 100 mℓ of ethyl acetate was added thereto. The mixture was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was washed with a 10:1 mixed solution of
diisopropyl ether/isopropanol to obtain 1.00 g of the desired compound.
Melting point: 156.0-158.0°C
1HNMR(CDCℓ3-DMSO-d6,Me4Si ,60MHz) δ10.07 (br,1H,NH), 8.39- 7.45(m,4H,Ar), 8.27 (s,1H, thiazole)
Process 5: N-(4-cyanophenyl)-2-chlorothiazole-4-carboxamide 4-(4-trifluoromethoxyphenyl)semicarbazone
1.00 g of N-(4-cyanophenyl)-2-chlorothiazole-4-carboxamide and 0.87 g of phosphorus pentachloride were added to 10 mℓ of toluene and stirred for 3 hours under reflux under heating. The solvent and the formed
phosphorus oxychloride were distilled off under reduced pressure, and the residue was dissolved in 10 mℓ of benzene. Then, 0.38 g of triethylamine and 0.89 g of 4-(4-trifluoromethoxyphenyl)semicarbazide were added thereto, and the mixture was stirred for 2 hours under reflux under heating. 150 mℓ of ethyl acetate were added thereto, and the mixture was washed with water and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue was washed with a 10:1 mixed solution of diisopropyl
ether/diisopropanol to obtain 0.10 g of the desired compound.
Melting point: 190.0-192.0°C 1HNMR(CDCℓ3-DMSO-d6,Me4Si ,60MHz) δ9.49 (s,1H,NH),
8.90(s,2H,NH), 8.08(s,1H,thiazole), 7.81-6.60 (m,8H,Ar). PREPARATION EXAMPLE 5
N-(4-cyanophenyl)pyrrole-1-carboxamide 4-(4-trifluoromethoxyphenyl)semicarbazone (Compound No. 3-1 of the present invention)
Process 1: methyl N-(4-cyanophenyl)pyrrole-1-thioimidate
1.1 g of sodium hydride (purity: 55%) was suspended in 30 mℓ of tetrahydrofuran, and 5 mℓ of a
tetrahydrofuran solution containing 1.5 g of pyrrole was dropwise added with stirring at room temperature. After completion of the dropwise addition, the mixture was stirred for one hour at room temperature. Then, 20 mℓ of a tetrahydrofuran solution containing 3.2 g of
isothiocyanate was added thereto, followed by stirring for 4 hours. Then, 4.7 g of methyl iodide was added to this mixture, and the mixture was further stirred
overnight at room temperature. The reaction solution was poured into water and extracted with 100 mℓ of ethyl acetate. The extract was washed with a saturated sodium chloride aqueous solution and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was washed with diisopropyl ether to obtain 4.20 g of the desired product.
1HNMR(CDCℓ3-DMSO-d6,Me4Si,60MHz) δ7.57 (d,J=8.2Hz, 2H,Ar), 7.26-7.06 (m,2H,pyrrole), 6.95 (d,J=8.2Hz,2H,Ar), 6.47-6.17 (m, 2H, pyr role ) , 2.27 ( s , 3H, CH3 ) . Process 2: N-(4-cyanophenyl)pyrrole-1-carboxamide 4-(4- trifluoromethoxyphenyl)semicarbazone
0.5 g of hydrazine monohydrate was added to 5 mℓ of an ethanol solution containing 0.48 g of methyl N-(4-cyanophenyl)pyrrole-1-thioimidate, and the mixture was stirred for 1.5 hours at room temperature. Then, 5 mℓ of ethanol was further added thereto, and the mixture was stirred overnight. Then, 20 mℓ of ethyl acetate was added to the reaction mixture, and the mixture was washed with water and a saturated sodium chloride aqueous solution and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue was dissolved in 5 mℓ of tetrahydrofuran, and 0.5 g of 4-trifluoromethylphenyl isocyanate was added
thereto. The mixture was stirred for 4 hours at room temperature. Hexane was added thereto, and precipitated crystals were collected by filtration and washed with diisopropyl ether to obtain 0.77 g of the desired
compound.
Melting point: 194.0-196.0°C
1HNMR(CDCℓ3-DMSO-d6,Me4Si, 60MHz)58.82 (br, 2H,NH),
8.15(br,1H,NH), 7.62-7.11(m,6H,Ar), 7.08-6.88 (m, 2H, pyrrole ) , 6.87-6.40 (m, 2H, Ar ) , 6.28- 6.11 (m, 2H, pyrrole ) .
PREPARATION EXAMPLE 6
N-(4-cyanophenyl)pyrazole-1-carboxamide 4-(4-trifluoromethoxyphenyl) semicarbazone (Compound No. 3-8 of the present invention)
Process 1: N-(4-cyanophenyl)pyrazole-1-thiocarboxamide
10 mℓ of a dichloromethane solution containing 2.1 g of pyrazole was dropwise added to 50 mℓ of a
dichloromethane solution containing 5 g of 4-cyanophenyl isothiocyanate, and the mixture was stirred overnight at room temperature. The solvent was distilled off under reduced pressure, and the residue was washed with
diisopropyl ether and recrystallized from a solvent mixture of hexane/ethyl acetate to obtain 5.2 g of the desired compound.
1HNMR(CDCℓ3-DMSO-d6,Me4Si, 60MHz )δ11.00 (br ,1H,NH),
8.75 (br,1H,pyrazole), 8.16-7.48 (m, 5H,Ar,pyrazole),
6.48 (br,1H,pyrazole).
Process 2: methyl N-(4-cyanophenyl-pyrazole-1-thioimidate
3.8 g of potassium carbonate was added to 30 mℓ of an acetonitrile solution of N-(4-cyanophenyl)pyrazole-1-thiocarboxamide, and the mixture was stirred for 30 minutes at room temperature. Then, 3.3 g of methyl iodide was dropwise added thereto, and the mixture was stirred overnight. Then, potassium carbonate was
filtered off, and 50 mℓ of ethyl acetate was added to the filtrate. The mixture was washed with water and a saturated sodium chloride aqueous solution and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was washed with diisopropyl ether to obtain 5.0 g of the desired compound.
1HNMR(CDCℓ3-DMSO-d6,Me4Si, 60MHz)δ7.84-7.47 (m,4H,Ar,pyrazole), 7.00 (d,J=8.0Hz, 2H,Ar),
6.39 (m,1H,pyrazole), 2.36(s,3H,CH3).
Process 3: 4-(4-cyanophenyl)pyrazole-1-carboxamide 4-(4-trifluoromethoxyphenyl)semicarbazone
4.1 g of hydrazine monohydrate was dropwise added to 30 mℓ of an ethanol solution containing 4.0 g of methyl N-(4-cyanophenyl)pyrazole-1-thioimidate, and the mixture was stirred for 2 hours at room temperature. 30 mℓ of water was added to the reaction solution, and the mixture was extracted with 100 mℓ of ethyl acetate. The organic layer was washed with a saturated sodium chloride aqueous solution and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 4.8 g of N-(4-cyanophenyl)pyrazole-1-carboxamide hydrazone as reddish brown oil.
0.8 g of 4-methoxyphenyl isocyanate was added to 5 mℓ of a tetrahydrofuran solution containing 0.75 g of the obtained N-(4-cyanophenyl)pyrazole-1-carboxamide
hydrazone at room temperature, and the mixture was stirred overnight. Precipitated solid was collected by filtration, and the residue was washed with diisopropyl ether and recrystallized from acetonitrile to obtain 0.50 g of the desired compound.
Melting point: 187.0-188.0°C
1HNMR(CDCℓ3-DMSO-d6,Me4Si, 60MHz) δ9.27 (s,1H,NH), 9.04 (s,1H,NH), 8.52 (s,1H,NH), 8.20 (br,1H,pyrazole), 7.72-6.98 (m,7H,Ar,pyrazole), 6.76-6.33 (m,3H,Ar,pyrazole), 2.96 (s,3H,CH3).
PREPARATION EXAMPLE 7
N-(5-chloropyrimidin-2-yl)-3-fluorobenzamide 4-(4-trifluoromethoxyphenyl) semicarbazone (Compound No. 4-14 of the present invention)
Process 1: N-(5-chloropyrimidin-2-yl)-3-fluorobenzamide
6.08 g of 3-fluorobenzoyl chloride was dropwise added to 40 mℓ of a pyridine solution containing 4.97 g of 2-amino-5-chloropyrimidine with stirring at room
temperature. After completion of the dropwise addition, the mixture was further stirred for one hour under reflux under heating. The reaction mixture was added to 400 mℓ of ice water, and precipitated solid was collected by filtration. The obtained crude product was dissolved in 400 mℓ of ethyl acetate and washed five times with 100 mℓ of dilute hydrochloric acid and further washed with 100 mℓ of a saturated sodium chloride aqueous solution, and then it was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from benzene to obtain 7.51 g of the desired compound.
Melting point: 149.1-150.3°C
1HNMR(CDCℓ3-DMSO-d6,Me4Si, 60MHz)δ11.20 (S, 1H,NH),
8.72(s,2H,Pyr.), 7.96-7.32(m, 4H,Ar).
Process 2: N-(5-chloropyrimidin-2-yl)-3-fluorobenzamide 4-(4-trifluoromethoxyphenyl)semicarbazone
0.63 g of N-(5-chloropyrimidin-2-yl)-3-fluorobenzamide and 0.57 g of phosphorus pentachloride were added to 5 mℓ of toluene, and the mixture was stirred for 4 hours under reflux under heating. The solvent and formed phosphorus oxychloride were distilled off under reduced pressure, and the residue was dissolved in 10 mℓ of tetrahydrofuran. Then, 0.30 g of
triethylamine and 0.59 g of 4-(4-trifluoromethoxyphenyl)semicarbazide were added thereto, and the mixture was stirred overnight at room
temperature. Then, 250 mℓ of ethyl acetate was added, and the mixture was washed twice with 50 mℓ of a
saturated sodium chloride aqueous solution and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue was washed with a mixed solution of diisopropyl ether/isopropanol to obtain 1.09 g of the desired compound.
Melting point: 201.2-202.0°C
1HNMR(DMSO-d6,Me4Si,400MHz)δ9.98 (s,1H,NH), 9.57 (s,1H,NH), 9.27 (s,1H,NH), 8.49 (d,J=1.6Hz,2H,Pyr.),
7.72 (d,J=8.2Hz,3H,Ar), 7.55 (d,J=7.7Hz,1H,Ar),
7.43 (q,J=7.7Hz,1H,Ar), 7.32 (d,J=8.4Hz,2H,Ar),
7.22 (t,J=8.4Hz,1H,Ar).
PREPARATION EXAMPLE 8
N-(5-nitropyridin-2-yl)-3-fluorobenzamide 4-(4-trifluoromethoxyphenyl)semicarbazone (Compound No. 4-13 of the present invention)
Process 1: N-(5-nitropyridin-2-yl)-3-fluorobenzamide
7.93 g of 3-fluorobenzoyl chloride was dropwise added to 50 mℓ of a pyridine solution containing 6.96 g of 2-amino-5-nitropyridine with stirring at room temperature. After completion of the dropwise addition, the mixture was further stirred for 15 minutes under reflux under heating. The reaction mixture was added to 50 mℓ of ice water, and precipitated solid was collected by
filtration. The obtained crude product was dissolved in 500 mℓ of ethyl acetate and washed five times with 100 mℓ of dilute hydrochloric acid and further washed with 100 mℓ of a saturated sodium chloride aqueous solution. It was then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was washed with diisopropyl ether to obtain 12.11 g of the desired compound.
Melting point: 172.9-174.2°C
1HNMR(CDCℓ3-DMSO-d6,Me4Si, 60MHz)δ11.34 (s, 1H,NH),
9.17 (t,J=1.6Hz,1H,Py.), 8.49 (m,2H,Py.) 7.80-7.31(m,4H,Ar).
process 2: N-(5-nitropyridin-2-yl)-3-fluorobenzamide 4-(4-trifluoromethoxyphenyl)semicarbazone
0.65 g of N-(5-nitropyridin-2-yl)-3-fluorobenzamide and 0.57 g of phosphorus pentachloride were added to 5 mℓ of toluene, and the mixture was stirred for 3 hours under reflux under heating. The solvent and formed phosphorus oxychloride were distilled off under reduced pressure, and the residue was dissolved in 10 mℓ of benzene. Then, 0.30 g of triethylamine and 0.59 g of 4-(4-trifluoromethoxyphenyl)semicarbazide were added thereto, and the mixture was stirred for one hour under reflux under heating. Then, 250 mℓ of ethyl acetate was added thereto, and the mixture was washed twice with 50 mℓ of a saturated sodium chloride aqueous solution and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue was washed with diisopropyl ether to obtain 0.97 g of the desired
compound.
Melting point: 189.9-191.8°C
1HNMR(DMSO-d6,Me4Si,400MHz)δ10.16 (bs,NH), 9.74 (bs,NH), 9.27 (s,NH), 8.88(s,NH), 8.37 (dq,J=9.2,1.3Hz,1H,Py.), 7.77-7.73 (m,3H,Ar), 7.52(d,J=7.7Hz,1H,Ar),
7.43 (q,J=7.0Hz,1H,Ar), 7.32(d,J=8.6Hz, 2H,Ar),
7.25 (q,J=7.1Hz,2H,Ar), 6.84 (d,J=9.3Hz,1H,Py.).
PREPARATION EXAMPLE 9
N-(4-trifluoromethylthiazol-2-yl)-3-fluorobenzamide 4-(4-trifluoromethoxyphenyl)semicarbazone (Compound No. 4-6 of the present invention)
Process 1: N-(4-trifluoromethylthiazol-2-yl)-3-fluorobenzamide
4.76 g of 3-fluorobenzoyl chloride was dropwise added to 30 mℓ of a pyridine solution containing 5.04 g of 2-amino-4-trifluoromethylthiazole with stirring at room temperature. After completion of the dropwise addition, the mixture was further stirred for 15 minutes under reflux under heating. The reaction mixture was added to 300 mℓ of ice water, and precipitated solid was collected by filtration. The obtained crude product was dissolved in 300 mℓ of ethyl acetate and washed five times with 100 mℓ of dilute hydrochloric acid and further washed with 100 mℓ of a saturated sodium chloride aqueous solution. Then, it was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was washed with hexane to obtain 7.36 g of the desired compound.
Melting point: 95.9-98.9°C
1HNMR ( CDCℓ3 , Me4Si , 60MHz ) δ10.44 ( s , 1H,NH) , 7.74-7.27(m,5H,Ar)
Process 2: N-(4-trifluoromethylthiazol-2-yl)-3-fluorobenzamide 4-(4-trifluoromethoxyphenyl)semicarbazone
0.73 g of N-(4-trifluoromethylthiazol-2-yl)-3-fluorobenzamide and 0.57 g of phosphorus pentachloride were added to 5 mℓ of toluene, and the mixture was stirred for 2 hours under reflux under heating. The solvent and formed phosphorus oxychloride were distilled off under reduced pressure, and the residue was dissolved in 10 mℓ of benzene. Then, 0.30 g of triethylamine and 0.59 g of 4-(4-trifluoromethoxyphenyl)semicarbazide were added thereto, and the mixture was stirred overnight at room temperature. Then, 250 mℓ of ethyl acetate was added thereto, and the mixture was washed twice with 50 mℓ of a saturated sodium chloride aqueous solution and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue was recrystallized from diisopropyl ether to obtain 0.22 g of the desired compound as a mixture of isomers A and B.
Melting point: 146.0-148.8°C
1HNMR(DMSO-d6,Me4Si,400MHz) isomer A: δ11.55(s,1H,NH), 9.05(s,1H,NH), 8.86(s,1H,NH), 7.85-7.27 (m,9H,Ar), isomer B: δ10.35 (s,1H,NH), 10.09 (s,1H,NH), 9.26 (s,1H,NH), 7.85-7.27(m,9H,Ar).
The compounds of the present invention can be synthesized in accordance with the above described production methods and Examples. Specific examples of such compounds are shown in Tables 6 to 9. However, it should be understood that the present invention is by no means restricted to such specific Examples.
Figure imgf000241_0001
Figure imgf000242_0001
Figure imgf000243_0001
Figure imgf000244_0001
Figure imgf000245_0001
FORMULATION EXAMPLES
Now, Formulation Examples will be given for
pesticides containing compounds of the present invention as active ingredients. However, it should be understood that the present invention is by no means restricted to such specific Examples. In the following Formulation Examples, "parts" means "parts by weight".
FORMULATION EXAMPLE 1: Wettable powder
Compound of the present invention 50 parts Zeeklite PFP (tradename for Kaoline-type clay, manufactured by Zeeklite Mining Industries Co., Ltd.)
43 parts Sorpol 5050 (tradename for anionic surfactant, manufactured by Toho Chemicals Ind. Co., Ltd.)
2 parts Lunox 1000C (tradename for anionic surfactant, manufactured by Toho Chemicals Ind. Co., Ltd.)
3 parts Carplex #80 (antisolidification agent) (tradename for fine silica, manufactured by Shionogi & Co., Ltd.)
2 parts
The above components are uniformly mixed and
triturated to obtain a wettable powder.
FORMULATION EXAMPLE 2: Emulsifiable concentrate
Compound of the present invention 3 parts
Xylene 76 parts
Isophorone 15 parts
Sorpol 3005X (tradename for a mixture of a nonionic surfactant and an anionic surfactant, manufactured by Toho Chemicals Ind. Co., Ltd.)
6 parts
The above components are uniformly mixed to obtain an emulsifiable concentrate. FORMULATION EXAMPLE 3: Flowable
Compound of the present invention 35 parts
Agrisol S-711 (tradename for a nonionic surfactant, manufactured by Kao Corporation)
8 parts Lunox 1000C (tradename for anionic surfactant, manufactured by Toho Chemicals Ind. Co., Ltd.)
0.5 part
1% Rodopol water (tradename for a thickener,
manufactured by Rhône-Poulenc)
20 parts
Ethylene glycol (antifreezing agent) 8 parts Water 28.5 parts
The above components are uniformly mixed to obtain a flowable.
FORMULATION EXAMPLE 4: Dry flowable
Compound of the present invention 75 parts Isoban No. 1 (tradename for an anion surfactant, manufactured by Kuraray Isoprene Chemical K.K.)
10 parts
Anilex N (tradename for anionic surfactant,
manufactured by Sanyo Kokusaku Pulp K.K.)
5 parts
Carplex #80 (tradename for fine silica, manufactured by Shionogi & Co., Ltd.)
10 parts
The above components are uniformly mixed and finely pulverized to obtain a dry flowable.
FORMULATION EXAMPLE 5: Granule
Compound of the present invention 0.1 part Bentonite 55.0 parts
Talc 44.9 parts
The above components are uniformly mixed and triturated. Then, a small amount of water is added thereto. The mixture is stirred, kneaded and then granulated by an extrusion-type granulator, followed by drying to obtain a granule.
FORMULATION EXAMPLE 6: Dust
Compound of the present invention 3.0 parts
Carplex #80 (tradename for fine silica, manufactured by Shionogi & Co., Ltd.)
0.5 part
Clay 95 parts Diisopropyl phosphate 1.5 parts
The above components are uniformly mixed and
triturated to obtain a dust.
In use, the above wettable powder, emulsifiable concentrate, flowable or dry flowable is diluted from 50 to 20,000 times with water and applied so that the active ingredient will be from 0.05 to 50 kg/ha.
TEST EXAMPLES
Now, usefulness of the compounds of the present invention as pesticides will be described in detail with reference to the following Test Examples.
TEST EXAMPLE 1: Insecticidal test on common cutworm
(Spodoptera litura)
5% emulsifiable concentrates of the compounds of the present invention (25% wettable powders in the case of certain compounds) were diluted with water containing a spreader to prepare the samples of liquid insecticides with a concentration of 1,000 ppm. Leaves of cabbage were immersed in the respective samples of liquid
insecticides for about 10 seconds. After air drying, the leaves were placed in the Petri dishes and the second instar nymphae of common cutworm (Spodoptera litura) were released in the said dishes (10 insects per dish). The dishes were closed with a perforated cover and kept in a 25°C thermostatic chamber. The percentage of mortality of the insects after the lapse of 6 days was calculated by the following formula. The tests were conducted twice for each compound.
Figure imgf000249_0001
In the test results, the following compounds of the present invention exhibited a mortality of 100%.
Compound Nos.: 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-10, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-24, 1-25, 1-26, 1-28, 1-29, 1-30, 1-31, 1-32, 1-34, 1-35, 1-36, 1-37, 1-38, 1-39, 1-40, 1-42, 1-45, 1-47, 1-48, 1-50, 2-1, 2-2, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 3-1, 3-2, 3-3, 3-4, 3-5, 3-8, 3-10, 3-15, 3-16, 3-17, 4-2, 4-4, 4-6, 4-8, 4-10, 4-14, 4-15.
TEST EXAMPLE 2: Insecticidal test on twenty eight-spotted ladybird (Epilachna vigintioctopunctata)
5% emulsifiable concentrates of the compounds of the present invention (25% wettable powders in the case of certain compounds) were diluted with water containing a spreader to prepare the samples of liquid insecticides with a concentration of 1,000 ppm. Leaves of tomato were immersed in the respective samples of liquid insecticides for about 10 seconds. Then, after air drying the leaves, they were placed in the Petri dishes and the second instar nymphae of twenty eight-spotted ladybird
(Epilachna viqintioctopunctata) were released in the respective dishes (10 insects per dish). After covered, the dishes were kept in a 25°C thermostatic chamber. The percentage of mortality after the lapse of 6 days was calculated by the following formula. The tests were conducted twice for each compound.
Figure imgf000250_0001
In the results, the following compounds of the present invention exhibited a mortality of 100%.
compounds Nos.: 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-10, 1-11, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-24, 1-25, 1-26, 1-28, 1-29, 1-30, 1-31, 1-32, 1-34, 1-35, 1-36, 1-37, 1-38, 1-39, 1-40, 1-42, 1-45, 1-46, 1-47, 1-48, 1-49, 1-50, 2-1, 2-2, 2-3, 2-5, 2-6, 2-7, 2-8, 2-9, 3-1, 3-3, 3-6, 3-8, 3-9, 3-13, 3-15, 3-16, 3-17, 4-3, 4-4, 4-5, 4-6, 4-7, 4-8, 4-10, 4-11, 4-13, 4-14, 4-15.

Claims

CLAIMS :
1. A semicarbazone derivative of the formula (I) or its salt:
Figure imgf000251_0001
wherein Q is any one of Q-1 to Q-37:
Figure imgf000252_0001
Figure imgf000253_0001
J is any one of J-1 to J-33, provided that when Q is37 and G is G-1, J is other than J-33;
Figure imgf000254_0001
Figure imgf000255_0002
G is any one of G-1 to G-8, provided that when Q is Q-37 and J is J-33, G is other than G-1;
Figure imgf000255_0001
W is an oxygen atom or a sulfur atom;
each of X, Y and Z which are independent of one another, is a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6
haloalkynyl group, a C3-6 cycloalkyl group, a C3-6
halocycloalkyl group, a C4-7 cycloalkylalkyl group, -OR10, -CN, -N3, -SCN, -NO2, -SH, -S(O)rR7, -OCHO, -CHO, -C(O)R7, -C(O)OR7, -C(O)NR7R8, -S(O)2NR7R8, -NR7R8, -NR8CHO,
-NR8C(O)R7, -NR8C(O)NHR7, -NR8S(O)2R7, -SiR18R19R20, -SF5, a phenyl group which may be substituted by (R6)q, a pyridyl group which may be substituted by (R6)q, or a C1-6 alkyl group which may be substituted by (R9)p, provided that when k, m or n is 2, and two X, Y or Z are adjacent to each other, they may form -CH=CH-CH=CH-, -OCH2O-, -OCF2O-, -OCH2CH2O-, -OCH2C(CH3)2O-, -CF2CF2O- or
-OCF2CF2O-;
each of R1, R2 and R3 which are independent of one another, is a hydrogen atom, a C1-6 alkyl group, a
C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6 haloalkynyl group, a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C4-7 cycloalkylalkyl group, -CHO, -C(O)R7, -C(O)OR7, -C(O)SR7, -C(S)R7, -C(S)SR7, -C(O)C(O)OR7, -NR10R11,
-N=CR11R12, -P(O) (OR13)2, -P(S)(OR13)2, -S(O)rR7,
-S(O)2CH2C(O)OR7, -S(O)rN(R14)C(O)OR15, -S(O)rNR16R17, a phenyl group which may be substituted by (R6)q, or a C1-6 alkyl group which may be substituted by (R9)p;
each of R4 and R5 which are independent of each other, is a hydrogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6 haloalkynyl group, a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C4-7 cycloalkylalkyl group, a C2-6 alkoxyalkyl group, a C2-6 alkylthioalkyl group, a C1-6 nitroalkyl group, a C2-6 cyanoalkyl group, a C3-8 alkoxycarbonylalkyl group, -CHO, -C(O)R7, -C(O)OR7, -C(O)NR7R8, or -S(O)2NR7R8;
R6 is a hydrogen atom, a halogen atom, a hydroxyl group, -CN, -NO2, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a C1- 6 alkylthio group, a C1-6 haloalkylthio group, a C1-6 alkylsufonyl group, a C1-6 haloalkylsulfonyl group, a C2-6 alkoxycarbonyl group, an amino group, or a di-C1-6 alkylamino group;
R7 is a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6 haloalkynyl group, a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C4-7 cycloalkylalkyl group, a C2-6 alkoxyalkyl group, a C2-6 alkylthioalkyl group, a C1-6 nitroalkyl group, a C2-6 cyanoalkyl group, a C3-8 alkoxycarbonylalkyl group, a phenyl group which may be substituted by (R6)q, a benzyl group which may be
substituted by (R6)q, or a pyridyl group which may be substituted by (R6)q;
R8 is a hydrogen atom, a C1-4 alkyl group, a C2-4 alkenyl group, or a C2-4 alkynyl group;
provided that when R7 and R8 are bonded to the same atom, they may together form -CH2CH2CH2CH2-,
-CH2CH2CH2CH2CH2-, -CH2CH2OCH2CH2-;
R9 is a C1-3 alkoxy group, a C1-3 haloalkoxy group, -CN, -NO2, -S(O)rR7, -P(O)(OR13)2, -P(S) (OR13)2, -C(O)R7, -C(O)OR7, or a phenyl group which may be substituted by
(R6)q;
R 10 is a hydrogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6 haloalkynyl group. a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C4-7 cycloalkylalkyl group, a C2-7 alkoxyalkyl group, a C2-7 haloalkoxyalkyl group, a C2-7 alkylthioalkyl group, a C2-7 cyanoalkyl group, a C3-8 alkoxycarbonylalkyl group, -C(O)R7, -C(O)OR7, -C(O)NR7R8, -S(O)2NR7R8, -S(O)2R7, a phenyl group which may be substituted by (R6)q, a benzyl group which may be substituted by (R6)q, or a pyridyl group which may be substituted by (R6)q;
R11 is a hydrogen atom, a C1-4 alkyl group, -C(O)R7, or -C(O)OR7;
R12 is a hydrogen atom, a C1-4 alkyl group, a C1-4 haloalkyl group, or a phenyl group which may be
substituted by (R6)q;
provided that R11 and R12 may together form
-CH2CH2CH2CH2-, or -CH2CH2CH2CH2CH2-;
R13 is a C1-3 alkyl group, or a phenyl group which may be substituted by (R6)q;
R14 is a C1-4 alkyl group;
R15 is a C1-18 alkyl group;
Each of R16 and R17 which are independent of each other, is a C1-4 alkyl group, or R16 and R17 may together form -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, or -CH2CH2OCH2CH2-; each of R18 and R19 which are independent of each other, is a C1-4 alkyl group;
R20 is a C1-4 alkyl group, or a phenyl group which may be substituted by (R6)q;
k is an integer of from 0 to 5, provided that when k is from 2 to 5, the plurality of X may be the same or different;
m is an integer of from 0 to 5, provided that when m is from 2 to 5, the plurality of Y may be the same or different;
n is an integer of from 0 to 5, provided that when n is from 2 to 5, the plurality of Z may be the same or different;
p is an integer of from 1 to 3, provided that when p is 2 or 3, the plurality of R9 may be the same or
different;
q is an integer of from 0 to 4, provided that when q is from 2 or 4, the plurality of R6 may be the same or different; and
r is an integer of from 0 to 2.
2. The semicarbazone derivative or its salt according to Claim 1, wherein:
X is a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6
haloalkynyl group, a C3-6 cycloalkyl group, a C3-6
halocycloalkyl group, a C4-7 cycloalkylalkyl group, -OR10, -CN, -NO2, -S(O)rR7, -OS(O)2R7, or -C(O)OR7;
Y is a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6
haloalkynyl group, a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C4-7 cycloalkylalkyl group, -OR10, -CN, -NO2, -S(O)rR7, -S(O)2NR7R8, -OS(O)2R7, or -C(O)OR7, provided that when m is 2, and two Y are adjacent to each other, they may form -CH=CH-CH=CH-, -OCH2O-, -OCF2O-, -OCH2CH2O-, -OCH2C(CH3)2O-, -CF2CF2O-, or -OCF2CF2O-;
Z is a halogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6 haloalkynyl group, a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C4-7 cycloalkylalkyl group, -OR10, -CN, -NO2, -S(O)rR7, -S(O)2NR7R8, -OS(O)2R7, -C(O)OR7, or -SF5, provided that when n is 2, and two Z are adjacent to each other, they may form -CH=CH-CH=CH-, -OCH2O-, -OCF2O-, -OCH2CH2O-, -OCH2C(CH3)2O-, -CF2CF2O-, or -OCF2CF2O-;
R1 is a hydrogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 haloalkyl group, a C2-6 haloalkenyl group, a C2-6 haloalkynyl group, a C3-6 cycloalkyl group, a C3-6 halocycloalkyl group, a C4-7 cycloalkylalkyl group, -CHO, -C(O)R7, -C(O)OR7,
-S(O)rR7, -S(O)rN(R14)C(O)OR15, -S(O)rNR16R17, a phenyl group which may be substituted by (R6)q, or a C1-6 alkyl group which may be substituted by (R9)p;
R2 is a hydrogen atom, a C1-6 alkyl group, a C1-6 alkyl group which may be substituted by (R9)p, or
-C(O)OR7;
R3 is a hydrogen atom, a C1-6 alkyl group, -CHO,
-C(O)R7, -C(O)OR7, -C(O)SR7, -NR10R11, -N=CR11R12, -S(O)2R7 , -S(O)rN(R14 ) C(O)OR15 , or -S(O)rNR16R17 ;
each of R4 and R5 which are independent of each other, is a hydrogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group, a C3-6 cycloalkyl group, a C2-6
alkoxyalkyl group, a C2-6 alkylthioalkyl group, -C(O)OR7, -C(O)NR7R8, or -S(O)2NR7R8;
R7 is a C1-6 alkyl group, a C1-6 haloalkyl group, a C3-6 cycloalkyl group, or a phenyl group which may be substituted by (R6)q;
R9 is a C1-3 alkoxy group, -CN, or -C(O)OR7;
R10 is a hydrogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group, a C3-6 cycloalkyl group, a C2-7
haloalkoxyalkyl group, or a C3-6 halocycloalkyl group; k is an integer of from 0 to 2, provided that when k is 2, two X may be the same or different;
m is an integer of from 0 to 3, provided that when m is 2 or 3, the plurality of Y may be the same or
different;
n is an integer of from 1 to 3, provided that when n is 2 or 3, the plurality of Z may be the same or
different; and
p is 1.
3. The semicarbazone derivative or its salt according to Claim 2, wherein Q is Q-l, Q-2, Q-3, Q-4, Q-5, Q-8, Q-9, Q-10, Q-14, Q-15, Q-16, Q-17, Q-18, Q-22, Q-25, Q-27, Q-28, Q-29, Q-30, Q-31, Q-32 or Q-37.
4. The semicarbazone derivative or its salt according to Claim 2, wherein J is J-1, J-2, J-7, J-8, J-9, J-10, J-13, J-14, J-15, J-24, J-25, J-26, J-27, J-28, J-30 or J-33.
5. The semicarbazone derivative or its salt according to Claim 2, wherein G is G-1.
6. The semicarbazone derivative or its salt according to Claim 3, wherein is J-1, J-2, J-7, J-8, J-9, J-10, J-13, J-14, J-15, J-24, J-25, J-26, J-27, J-28, J-30 or J-33, and G is G-1.
7. The semicarbazone derivative or its salt according to Claim 5, wherein Q is Q-1 or Q-37, m is an integer of 1 or 2, provided that when m is 2, two Y may be the same or different, and n is an integer of 1 or 2, provided that when n is 2, two Z may be the same or different, and the substituted position is the 3-position, the 4-position or the 3- and 4-positions.
8. The semicarbazone derivative or its salt according to Claim 5, wherein J is J-33, m is an integer of 1 or 2, provided that when m is 2, two Y may be the same or different, and the substituted position is the 3-position, the 4-position or the 3- and 4-positions, and n is an integer of 1 or 2, provided that when n is 2, two Z may be the same or different, and the substituted
position is the 3-position, the 4-position or the 3- and 4-positions.
9. The semicarbazone derivative or its salt according to Claim 6, wherein: W is an oxygen atom;
X is a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a C1-6 alkylthio group, a C1-6
haloalkylthio group, a C1-6 alkylsulfonyl group, or a C1-6 haloalkylsulfonyloxy group;
Y is a halogen atom, a cyano group, a nitro group, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C2-7 alkoxycarbonyl group, a C2-7
haloalkoxycarbonyl group, a C1-6 haloalkoxy group, a C1-6 alkylthio group, a C1-6 haloalkylthio group, a C1-6 alkylsulfonyl group, a C1-6 haloalkylsulfonyl group, a C1-6 alkylsulfonyloxy group, a C1-6 haloalkylsulfonyloxy group, or -CH=CH-CH=CH-, -OCH2O-, -OCH2CH2O-,
-OCH2C(CH3)2O-, -CF2CF2O-, -OCF2O- or -OCF2CF2O- bridging the adjacent carbon atoms;
Z is a halogen atom, a cyano group, a nitro group, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a C1-6 alkylthio group, a C1-6 haloalkylthio group, a C1-6 alkylsulfinyl group, a C1-6 haloaklylsulfinyl group, a C1-6 alkylsulfonyl group, a
C1-6 haloalkylsulfonyl group, a C1-6 alkylsulfonyloxy group, a C1-6 haloalkylsulfonyloxy group, a SF5 group, or -CH=CH-CH=CH-, -OCH2O-, -OCH2CH2O-, -OCH2C(CH3)2O-,
-OCF2O-, -OCF2CF2O- or -OCF2CF2- bridging the adjacent carbon atoms; m is an integer of 1 or 2, provided that when m is 2, two Y may be the same or different;
n is an integer of 1 or 2, provided that when n is 2, two Z may be the same or different, and the substituted position is the 3-position, the 4-position or the 3- and 4-positions;
R1 is a hydrogen atom, a C1-6 alkyl group, a C2-6 alkoxyalkyl group or a C2-6 alkylthioalkyl group;
R2 is a hydrogen atom, a C1-6 alkyl group, a C2-6 alkoxyalkyl group, or a -C (O)O-C1-6 alkyl group; and
R3 is a hydrogen atom, an amino group, a C1-6 alkyl group, a -C(O)-C1-6 alkyl group or a -C(O)O-C1-6 alkyl group.
10. A pesticide which contains at least one semicarbazone derivative of Claim 1 to 9 as an active ingredient.
11. An insecticide which contains at least one
semicarbazone derivative of Claim 1 to 9 as an active ingredient.
PCT/JP1996/002022 1995-07-21 1996-07-19 Semicarbazone derivatives and pesticides WO1997003976A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU64703/96A AU6470396A (en) 1995-07-21 1996-07-19 Semicarbazone derivatives and pesticides

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP18581495 1995-07-21
JP7/185814 1995-07-21
JP14837996 1996-05-17
JP8/148379 1996-05-17

Publications (1)

Publication Number Publication Date
WO1997003976A1 true WO1997003976A1 (en) 1997-02-06

Family

ID=26478602

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1996/002022 WO1997003976A1 (en) 1995-07-21 1996-07-19 Semicarbazone derivatives and pesticides

Country Status (2)

Country Link
AU (1) AU6470396A (en)
WO (1) WO1997003976A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7094807B2 (en) 2002-11-19 2006-08-22 Achillion Pharmaceuticals, Inc. Substituted aryl thioureas and related compounds; inhibitors of viral replication
US7767706B2 (en) 2004-05-18 2010-08-03 Achillion Pharmaceuticals, Inc. Substituted aryl acylthioureas and related compounds; inhibitors of viral replication
CN104163792A (en) * 2013-05-20 2014-11-26 湖南化工研究院 N-picolinamide compound, preparation method and application thereof
WO2014187297A1 (en) * 2013-05-20 2014-11-27 湖南化工研究院有限公司 N-pyridine(hetero)aromatic amide compound and preparation method and use thereof
US11884682B2 (en) * 2020-06-23 2024-01-30 Nanjing Immunophage Biotech Co., Ltd. Compounds and their uses as MIF inhibitors

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07165697A (en) * 1993-10-04 1995-06-27 Nissan Chem Ind Ltd Semiconductor compound and pest-controlling agent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07165697A (en) * 1993-10-04 1995-06-27 Nissan Chem Ind Ltd Semiconductor compound and pest-controlling agent
WO1996010560A1 (en) * 1994-10-04 1996-04-11 Nissan Chemical Industries, Ltd. Benzamide semicarbazone derivatives and their use as pesticides

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
ACTA. POL. PHARM., vol. 52, no. 4, 1995, pages 297 - 300 *
ANN. UNIV. MARIAE CURIE-SKLODOVSKA, SECT. AA: PHYS. CHEM., vol. 31-32, 1980, pages 277 - 283 *
CHEMICAL ABSTRACTS, vol. 117, no. 25, 1992, Columbus, Ohio, US; abstract no. 251312, L.S. SAMOILENKO ET AL.: "Synthesis of substituted 2-amino-4-methylpyrimidine based on the arylamides of alpha-phenylaminomethylidene-beta-ketothiobutyric acid" page 688; column 1; XP002016751 *
CHEMICAL ABSTRACTS, vol. 124, no. 7, 19 February 1996, Columbus, Ohio, US; abstract no. 86903, B. MODZELWSKA: "The reaction of N3-substituted amidrazones of 4-picoline with isothiocyanates" page 1304; column 1; XP002016750 *
CHEMICAL ABSTRACTS, vol. 95, no. 1, 1981, Columbus, Ohio, US; abstract no. 7159, T. BANY ET AL.: "Synthesis of some derivatives of 1,2,4-triazole and 1,3,4-thiadiazole using N3-substituted amidrazones as starting materials" page 678; column 1; XP002016752 *
DATABASE WPI Week 9535, Derwent World Patents Index; AN 95-265767, XP002016753 *
F. KURZER ET AL.: "Heterocyclic compounds from urea derivatives. Part XI. Synthesis of 1,2-diamino-3-phenylguanidine", JOURNAL OF THE CHEMICAL SOCIETY, SECTION C: ORGANIC CHEMISTRY, vol. 67, no. 8, 1967, LETCHWORTH GB, pages 742 - 746, XP002016749 *
UKR. KHIM. ZH. (RUSS. ED.), vol. 57, no. 4, 1991, pages 409 - 414 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7094807B2 (en) 2002-11-19 2006-08-22 Achillion Pharmaceuticals, Inc. Substituted aryl thioureas and related compounds; inhibitors of viral replication
US7476686B2 (en) 2002-11-19 2009-01-13 Achillion Pharmaceuticals, Inc. Substituted aryl thioureas and related compounds; inhibitors of viral replication
US7767706B2 (en) 2004-05-18 2010-08-03 Achillion Pharmaceuticals, Inc. Substituted aryl acylthioureas and related compounds; inhibitors of viral replication
CN104163792A (en) * 2013-05-20 2014-11-26 湖南化工研究院 N-picolinamide compound, preparation method and application thereof
WO2014187297A1 (en) * 2013-05-20 2014-11-27 湖南化工研究院有限公司 N-pyridine(hetero)aromatic amide compound and preparation method and use thereof
US11884682B2 (en) * 2020-06-23 2024-01-30 Nanjing Immunophage Biotech Co., Ltd. Compounds and their uses as MIF inhibitors

Also Published As

Publication number Publication date
AU6470396A (en) 1997-02-18

Similar Documents

Publication Publication Date Title
EP0438209B1 (en) Uracil derivatives and pesticides containing the same as active ingredient
EP1204642B1 (en) Fungicides
EP1204323B1 (en) Fungicides
US7964735B2 (en) Insecticidal 3-acylaminobenzanilides
JP2009286773A (en) Insecticidal condensed-ring aryl compounds
EP0944314A1 (en) Methyl substituted fungicides and arthropodicides
JP2010037311A (en) Novel insecticidal acylaminobenzamide derivative
EP0707000A1 (en) Aldoxime derivative and agrohorticultural bactericide
JPH013184A (en) Nitro-substituted heterocyclic compounds and pesticides
JP2019513785A (en) Pesticide
JP3023794B2 (en) Insecticidal nitro-substituted heterocyclic compounds
JP2946656B2 (en) Uracil derivative and herbicide
WO1999052882A1 (en) 1,2,3-thiadiazole derivative or salt thereof and pest control agent, and method of use thereof
WO2001000599A1 (en) Benzamide derivatives, insecticides for agricultural and horticultural use and usage thereof
WO2000029398A1 (en) Isothiazolecarboxylic acid derivatives
WO1997003976A1 (en) Semicarbazone derivatives and pesticides
JP2995726B2 (en) 4-Phenethylaminopyrimidine derivative, method for producing the same, and pesticide for agricultural and horticultural use
KR100349484B1 (en) Plant disease release agent
JP3596032B2 (en) Semicarbazone derivative
WO1996010560A1 (en) Benzamide semicarbazone derivatives and their use as pesticides
JPH01305088A (en) Triazoloazine
US4782074A (en) Fungicidal N,N-disubstituted-heterocyclic carboxamides
JP2000159610A (en) Agricultural and horticultural plant disease control agents and novel isoxazole carboxylic acid derivatives
JP3074658B2 (en) Aralkylaminopyrimidine derivatives, their preparation and pesticides
KR0149513B1 (en) Uracil derivatives and pesticides containing the same as active ingredient

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA CN KR LT LV MX NZ RU SI UA US VN

AL Designated countries for regional patents

Kind code of ref document: A1

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

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载