WO1991004965A1 - Amine derivatives - Google Patents

Amine derivatives Download PDF

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Publication number
WO1991004965A1
WO1991004965A1 PCT/JP1990/001282 JP9001282W WO9104965A1 WO 1991004965 A1 WO1991004965 A1 WO 1991004965A1 JP 9001282 W JP9001282 W JP 9001282W WO 9104965 A1 WO9104965 A1 WO 9104965A1
Authority
WO
WIPO (PCT)
Prior art keywords
optionally substituted
compound
formula
alkyl
cycloalkyl
Prior art date
Application number
PCT/JP1990/001282
Other languages
French (fr)
Inventor
Keiichi Ishimitsu
Junji Suzuki
Haruhito Ohishi
Tomio Yamada
Renpei Hatano
Nobuo Takakusa
Jun Mitsui
Original Assignee
Nippon Soda Co., 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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27523307&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1991004965(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to DE69032882T priority Critical patent/DE69032882T2/en
Priority to BR909006961A priority patent/BR9006961A/en
Priority to EP90914758A priority patent/EP0456826B1/en
Priority to US07/700,165 priority patent/US5304566A/en
Priority to KR1019910700545A priority patent/KR930008631B1/en
Priority to DK90914758T priority patent/DK0456826T3/en
Priority to DE122006000027C priority patent/DE122006000027I2/en
Application filed by Nippon Soda Co., Ltd. filed Critical Nippon Soda Co., Ltd.
Priority to RO147641A priority patent/RO112865B1/en
Priority to HU9802249A priority patent/HU220083B/en
Publication of WO1991004965A1 publication Critical patent/WO1991004965A1/en
Priority to IL9801491A priority patent/IL98014A/en
Priority to SU914895590A priority patent/RU2038352C1/en
Priority to LVP-92-617A priority patent/LV10155B/en
Priority to NL350028C priority patent/NL350028I2/en

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    • 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N47/40—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • 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
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
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    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/57—Nitriles
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    • 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
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    • 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/643—2-Phenoxypyridines; Derivatives thereof
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    • 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
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    • C07D213/70—Sulfur atoms
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    • 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
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
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    • 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
    • C07D213/84—Nitriles
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    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
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    • 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
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    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/08—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/12—Halogen atoms or nitro radicals
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    • 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
    • C07D239/26—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07—ORGANIC CHEMISTRY
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    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
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    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/16—Halogen atoms; Nitro radicals
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    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
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    • C07D277/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
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    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
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    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to new amine derivatives, the processes for the production thereof and insecticides containing the said derivatives as effective compounds.
  • organophosphorus insecticides such as parathion and malathion and carbamate insecticides such as carbaryl and methomyl
  • organophosphorus insecticides such as parathion and malathion and carbamate insecticides
  • carbaryl and methomyl carbamate insecticides
  • these insecticedes have played a very great role for the improvement of agricultural production.
  • some of these insecticides are regulated on their use because of problems such as environmental pollution due to residue or accumulation, or cause infestitation of resistant insect pests as a result of long-term use. Therefore, it is demanded to develop new chemicals which have excellent insecticidal characteristics over various types of insect pests including these resistant insect pests and which can be used safely.
  • the following compound is known as the analogous compound of this invention, which has no insecticidal activity.
  • the compound however shows no insecticidal activity against lepidopterous insects and green rice leafhopper which are more serious pests on crops, though it shows the activity against cotton aphid.
  • the purpose of this invention is to provide agricultural chemicals which can be advantageously synthesized industrially, have certain effects and are applicable safely.
  • the compound of this invention has high insecticidal activity against both lepidopterous and hemipterous insects.
  • the present invention relates to a compound having the formula
  • R 1 represents an optionally substituted 5 - 6 membered aromatic hetero ring containing nitrogen atom, except a non- substituted 2-pyridyl;
  • X represents an optionally substituted C 1-3 alkylene or alkylidene
  • R 2 represents a hydrogen, a carbamoyl, a mono or di C 1-5 alkyl carbamoyl, a thiocarbamoyl, a mono or di C 1-5 alkylthiocarbamoyl, a sulfamoyl, a mono or di C 1-5 alkylsulfamoyl, an optionally substituted C 1-5 alkyl, an optionally substituted C 2-5 alkenyl, an optionally substituted C 2-5 alkynyl, an optionally substituted C 3-8 cycloalkyl, an optionally substituted C 3-8 cycloalkenyl, an optionally substituted aryl or -Y-R 5 ;
  • Y represents O, S(O) n , CO, CS or CO 2 ;
  • n 0,1 or 2 ;
  • R 5 represents a hydrogen, an optionally substituted C 1-5 alkyl, an optionally substituted C 2-5 alkenyl, an optionally substituted C 2-5 alkynyl, an optionally substituted C 3-8 cycloalkyl, an optionally substituted C 3-8 cycloalkenyl or an optionally substituted aryl;
  • R 3 represents a hydrogen, an optionally substituted C 1-5 alkyl, an optionally substituted C 2-5 alkenyl, an optionally substituted C 2-5 alkynyl, an optionally substituted C 3-8 cycloalkyl or an optionally substituted C 3-8 cycloalkenyl;
  • R 4 represents a cyano or a nitro
  • Z represents CH or N
  • r 1 and r 2 represent a C 1-5 alkyl
  • X are as defined above.
  • reaction is carried out in an inactive organic solvent, preferably in an aromatic hydrocarbon solvent such as xylene, toluene or benzene, in the presence of acidic catalyst such as p-toluenesulfonic acid, if necessary, under reflux.
  • aromatic hydrocarbon solvent such as xylene, toluene or benzene
  • acidic catalyst such as p-toluenesulfonic acid
  • r 3 represents a C 1-5 alkyl
  • Hal represents a halogen
  • R 1 , R 2 , R 3 and X are as defined above.
  • This reaction is carried out in an inactive organic solvent, preferably DMF, THF, benzene acetonitrile, acetone, methylethylketone, in the presence of acid accepter such as potassium carbonate, NaH, triethylamine, between room temparature and the boiling point of the used solvent.
  • an inactive organic solvent preferably DMF, THF, benzene acetonitrile, acetone, methylethylketone
  • R 1 , R 2 , R 3 and X are as defined above.
  • This reaction is carried out in an inactive organic solvent, preferably acetonitrile, carbon tetrachloride, dichloroethane, in the presence of nitration reagent such as nitronium tetrafluoroborate, between -20°C and the boiling point of the used solvent.
  • nitration reagent such as nitronium tetrafluoroborate
  • the ratio varies depending on e.g. conditions of instrumental analysis.
  • Example 1 2 - ( 2 -chloro-5-pyridylmethylamino ) - 1-nitro- 1-butene :
  • the compounds of this invention exhibit high insecticidal activities against various species of insect pests such as cutworms, diamondback moth, aphids, leafhoppers and planthoppers.
  • insect pests such as cutworms, diamondback moth, aphids, leafhoppers and planthoppers.
  • the decrease of the control effects of organophosphorus and carbamate insecticides, which is caused by the development of resistance to these insecticides has become serious problem. In such situations, the development of new insecticides which is effective on the resistant pests has been desired.
  • the compounds of this invention possess superior insecticidal activities against not only susceptible strains but also resistant ones.
  • the insecticides covered by this invention contain as active ingredients one or more types of the compounds as expressed by the general formula (1). These active ingredients, may be used asproduced but normally they are used in any of the forms which ordinary agricultural chemicals can take, namely wettable powder, dust, emulsifiable concentrate, suspension concentrates, smoking chemicals, fumigant, granule, or other formulations.
  • active ingredients may be used asproduced but normally they are used in any of the forms which ordinary agricultural chemicals can take, namely wettable powder, dust, emulsifiable concentrate, suspension concentrates, smoking chemicals, fumigant, granule, or other formulations.
  • liquid formulations are intended, then for solvents are used kerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, water, etc.
  • a surface active agent may, if necessary, be added in order to give a homogeneous and suitable formulation.
  • the wettable powders, emulsifiable concentrates, suspension concentrates, etc. thus obtained are diluted with water into suspensions or emulsions of a prescribed concentration, before they are actually sprayed on plants in the field. In the case of dusts or granules, they are directly applied without further processing.
  • the compound(s) of this invention is effective even alone, but it can be used by mixing with various types of insecticides, acaricides and fungicides.
  • acaricides and insecticides which can be used by mixing with the compounds of this invention are described below:
  • Acaricides (fungicides):
  • chlorobenzilate chloropropylate, proclonol, bromopropylate, dicofol, dinobuton, binapacryl, chlordimeform, amitraz, propargite, PPPS, benzoximate, hexythiazox, fenbutatin oxide, polynactine, chinomethionat, thioquinox, chlorfenson, tetradifon, phenproxide, avermectins, clofentezine, flubenzimine, fenazaquin, pyridaben, fenproximate, chlorfenethol, thiophanate-methyl, benomyl, thiram, iprobenfos, edifenfos, fthalide, probenazole, isoprothiolane, chorothalonil, captan, polyoxin-B, blasticidin-S, kasugamycin, validamycin, tricyclazole, pyr
  • Organophosphorus-type and carbamate-type insecticides (acaridides): fenthion, fenitrothion, diazinon, chlorpyrifos, oxydeprofos, vamidothion, phenthoate, dimethoate, formothion, malathion, trichlorfon, thiometon, phosmet, menazon, dichlorvos, acephate,
  • EPBP dialifos, parathion-methyl, oxydemeton-methyl, ethion, aldicarb, propoxur, methomyl, fenobucarb, BPMC, pyraclofos, monocrotophos, salithion, cartap, carbosulfan carbofuran, benfuracarb, metolcarb, carbaryl, pirimicarb, ethiofencarb, fenoxycarb,
  • permethrin cypermethrin, deltamethrin, fenvalerate, fenpropathrin, pyrethrins, allethrin, tetramethrin, resmethrin, parthrin, dimethrin, proparthrin, bifenthrin, prothrin, fluvalinate, cyfluthrin, cyhalothrin, flucythrinate, ethofenprox, cycloprothrin, tralomethrin, silaneophan.
  • Example 7 Emulsifiable concentrate
  • liquid mixture is water-diluted into an emulsion.
  • Example 8 Wettable powder
  • Comparative compound B Test 2 Efficacy for green rice leafhopper
  • Rice seedlings of 7 days old after germination were immersed in a chemical solution, which was prepared in the way that the emulsifiable concentrate described in Example 7 of the above example of insecticide was diluted with water to 125 ppm of compound concentration according to prescription, for 30 seconds. After dried in air, the treated seedlings were placed in test tubes and 10 insects of 3rd-instar larvae of green rice leafhopper resistant to the organophosphorus and carbamate insecticides were inoculated. The tubes were covered with gauze, and placed in a thermostatic room at temperature of 25 °C and humidity of 65%. The mortality was checked 5 days later.
  • test compounds were formulated into the wettable powder in the same manner as Example 8.
  • the compounds were diluted with water to 125 ppm.
  • a maize leaf was immersed in the chemical solution for 30 seconds. After air-dried, the treated leaf was placed in a petri dish and five 3rd-instar larvae of rice armyworm were inoculated.
  • the petri dishes were covered with glass lids, and placed in a thermostatic room at 25oC and 65% relative humidity. The mortality was checked 5 days later. Two replications were conducted in the each test. The results are shown in Table 4.

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Abstract

The present invention relates to a compound having formula (I) which has an excellent insecticidal activity, wherein R1 represents an optionally substituted 5-6 membered aromatic hetero ring containing nitrogen atom, except a non-substituted 2-pyridyl; X represents an optionally substituted C1-3 alkylene or alkylidene; R2 represents a hydrogen, a carbamoyl, a mono or di C1-5 alkyl carbamoyl, a thiocarbamoyl, a mono or di C1-5 alkylthiocarbamoyl, a sulfamoyl, a mono or di C1-5 alkylsulfamoyl, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl, an optionally substituted C3-8 cycloalkenyl, an optionally substituted aryl or -Y-R5; Y represents O, S(O)n, CO, CS or CO2; n represents 0, 1 or 2; R5 represents a hydrogen, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl, an optionally substituted C3-8 cycloalkenyl or an optionally substituted aryl; R3 represents a hydrogen, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl or an optionally substituted C3-8 cycloalkenyl; R4 represents a cyano or a nitro; and Z represents CH or N; or its salt.

Description

DESCRIPTION
Amine Derivatives
Technical Field:
The present invention relates to new amine derivatives, the processes for the production thereof and insecticides containing the said derivatives as effective compounds.
Background art:
A large number of chemicals, for example, organophosphorus insecticides such as parathion and malathion and carbamate insecticides such as carbaryl and methomyl, have been developed and put to practical use by research and development on insecticides over many years. These insecticedes have played a very great role for the improvement of agricultural production. However, in recent years some of these insecticides are regulated on their use because of problems such as environmental pollution due to residue or accumulation, or cause infestitation of resistant insect pests as a result of long-term use. Therefore, it is demanded to develop new chemicals which have excellent insecticidal characteristics over various types of insect pests including these resistant insect pests and which can be used safely.
The following compound is known as the analogous compound of this invention, which has no insecticidal activity.
Figure imgf000003_0001
(Boll. Chim. Farm., 1979 118(11)661-666) Further, the following compound is described in USP 4918088, which has insecticidal activities.
Figure imgf000004_0001
The compound however shows no insecticidal activity against lepidopterous insects and green rice leafhopper which are more serious pests on crops, though it shows the activity against cotton aphid.
The purpose of this invention is to provide agricultural chemicals which can be advantageously synthesized industrially, have certain effects and are applicable safely.
The compound of this invention has high insecticidal activity against both lepidopterous and hemipterous insects.
Disclosure of Invention:
The present invention relates to a compound having the formula
(I)
Figure imgf000004_0002
wherein R1 represents an optionally substituted 5 - 6 membered aromatic hetero ring containing nitrogen atom, except a non- substituted 2-pyridyl;
X represents an optionally substituted C1-3 alkylene or alkylidene;
R2 represents a hydrogen, a carbamoyl, a mono or di C1-5 alkyl carbamoyl, a thiocarbamoyl, a mono or di C1-5 alkylthiocarbamoyl, a sulfamoyl, a mono or di C1-5 alkylsulfamoyl, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl, an optionally substituted C3-8 cycloalkenyl, an optionally substituted aryl or -Y-R5;
Y represents O, S(O)n, CO, CS or CO2 ;
n represents 0,1 or 2 ;
R5 represents a hydrogen, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl, an optionally substituted C3-8 cycloalkenyl or an optionally substituted aryl;
R3 represents a hydrogen, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl or an optionally substituted C3-8 cycloalkenyl;
R4 represents a cyano or a nitro; and Z represents CH or N;
or its salt.
Best Mode for Carrying Out the Invention:
The compounds of this invention can be prepared in accordance with the following reaction schemes: (1) Preparation Method 1:
Figure imgf000006_0001
where r1 and r2 represent a C1-5 alkyl; and R1, R2, R3, R4 and
X are as defined above.
The reaction is carried out in an inactive organic solvent, preferably in an aromatic hydrocarbon solvent such as xylene, toluene or benzene, in the presence of acidic catalyst such as p-toluenesulfonic acid, if necessary, under reflux.
(2) Preparation method 2:
Figure imgf000006_0002
where r3 represents a C1-5 alkyl:
and R1, R2, R3 and X are as defined above. This reaction is carried out in an inactive organic solvent, preferably in an alcohol such as methanol, ethanol, between room temperature and the boiling point of the used solvent. (3) Preparation Method 3:
Figure imgf000007_0003
where Hal represents a halogen; and R1, R2 , R3 and X are as defined above.
This reaction is carried out in an inactive organic solvent, preferably DMF, THF, benzene acetonitrile, acetone, methylethylketone, in the presence of acid accepter such as potassium carbonate, NaH, triethylamine, between room temparature and the boiling point of the used solvent.
(4) Preparation Method 4:
Figure imgf000007_0001
where R1, R2, R3, X and Hal are as defined above. This reaction is carried out in the same manner as that of Preparation Method 3.
(5) Preparation Method 5:
Figure imgf000007_0002
where R1, R2, R3 and X are as defined above. This reaction is carried out in an inactive organic solvent, preferably acetonitrile, carbon tetrachloride, dichloroethane, in the presence of nitration reagent such as nitronium tetrafluoroborate, between -20°C and the boiling point of the used solvent.
After the reaction is completed, an usual after-treatment gives the intended compound. The structure of the compounds of this invention was determined by such means as IR, NMR, MASS, etc. When R2 is hydrogen in a compound of this invention, tautomers represented by
can exist.
The syn - aniti isomers, when Z represents N, and the cis-trans isomers, when Z represents CH, as represented by,
Figure imgf000008_0002
can also exist.
The ratio varies depending on e.g. conditions of instrumental analysis.
The following examples illuslrate the present invention. Example 1 : 2 - ( 2 -chloro-5-pyridylmethylamino ) - 1-nitro- 1-butene :
Figure imgf000009_0001
In 50ml of toluene, 4.2g of 2-chloro-5-pyridylmethylamine, 3.5g of 1-nitro-2-butanone and 0.1g of p-toluene sulfonic acid were mixed and the mixture was refluxed for 2 hours. The solvent was then distilled off and the residue was purified by column chromatography on silica gel to afford 4. lg of compound No. 368. m.p. 95-98°C Example 2 : 2-(2-chloro-5-pyridylmethylamino)-1-cyano-1-propene:
Figure imgf000009_0002
1.4g of 2-chloro-5-pyridylmethylamine and 0.8g of 1-cyano-2- propanone were mixed and the mixture was stirred at room temperature over night. The solvent was then distilled off and the residue was purified by column chromatography on silica gel to afford 1.7g of compound No. 528. m.p. 95-98°C
Example 3 :
N-cyano-N'-(2-chloro-5-pyridylmethyl)-N'-methylacetamidine:
Figure imgf000009_0003
In 20ml of ethanol, 1.6g of N-methyl-2-cloro-5-pyridylmethylamine and 1.2g of ethyl-N-cyanoacetamidine were mixed and the mixture was stirred at room temperature over night. The solvent was then distilled off and the residue was purified by column chromatography on silica gel to afford 1.8g of compound No. 22. m.p. 101-103°C Example 4 :
N-cyano-N'-(2-chloro-5-pyridylmethyl)-N'-ethylacetamidine:
NCN
Figure imgf000010_0001
2 5
0.7g of sodium hydride (purity 60%) was added to the solution of 3.0g of N-cyano-N'-(2-chloro-5-pyridylmethyl)acetamidine in 20ml of N.N-dimthylformamide at ice bath temperature. After stirring it at the same temperature for 1 hour, 2.7g of ethyl iodide was added to the mixture, followed by stirring for 5 hours at room temperature. The reaction mixture was then poured into ice-water, extracted with ethyl acetate, dried over anhydrous magnesium sulfate and concentrated under reduced pressre. The residue obtained was purified by column chromatography on silica gel to afford 1.6g of compound No. 51. m.p. 100-101°C
Example 5 :
N-cyano-N-(2-chloro-5-pyridylmethyl)-N'-methylacetamidine: NCN NCN
Figure imgf000010_0002
3
0.6g of sodium hydride (purity 60%) was added to the solution of
1.3g of N-cyano-N'-methylacetamidine in 20ml of N,N- dimethylformamide at ice bath temperature. After stirring it at the same temperature for 1 hour, 2.2g of 2-chloro-5- pyridylmethylchlride was added to the mixture, followed by stirring for 5 hours at room temperature. The reaction mixture was then poured into ice-water, extrated with ethyl acetate, dried over anhydrous magnesium sulfate and concentrated under reduced pressre. The residue obtained was purified by column chromatography on silica gel to afford 1.5g of compound No.22 m.p. 101-103ºC Reference Example :
N-(2-chloro-5-pyridylmethyl)-N-methylacetamidine hydrochloride :
Figure imgf000011_0001
X A 3 V k
To 40ml of ethanol was added 5.1g of N-(2-chloro-5-pyridylmethyl)- N-Methylamine and then, 4g of ethyl acetimidate hydrochloride at 0°C. After stirring for an hour, the reaction mixture was allowed to warm to room temperature and stirred over night. The solvent was then distilled off. The obtained white residue was washed with diethyl ether to afford 7.3g of the title compound m.p. 192-197°C Example 6 :
N-(2-chloro-5-pyridylmethyl)-N-methyl-N'-nitroacetamidine:
NH NNO2
Figure imgf000011_0002
3 3
To a suspension of 1g of N-(2-chloro-5-pyridylmethyl)-N- methylamidine hydrochloride in 10ml of dry acetonitrile was added dropwise 0.7g of DBU under nitrogen at room temperature. After stirring for 30 minutes, the solution was added dropwise to a suspension of 0.6g of nitronium tetrafluoroborate in 5ml of dry acetonitrile under nitrogen on cooling with ice-water and let stir for 4 hours. After which time, the mixture was poured into ice- water, then extracted several time with chloroform. The combined chloroform layer was dried over magnesium sulfate, filtered and distilled off. The crude oil was purified by column chromatgraphy on silica gel to afford 0,3g of compound No. 236.
ND 251.5808
Typical examples of this invention including those described above are listed in Table 1.
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
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
* 1
'H-NMR(CDCl3) δ;ppm 3.32 (s, 3H), 4.63 (s, 2H), 7.37 (d, 111), 7.62 (dd, 1H),
8.37 (d, 1H)
The compounds of this invention exhibit high insecticidal
Figure imgf000072_0001
activities against various species of insect pests such as cutworms, diamondback moth, aphids, leafhoppers and planthoppers. In recent years the decrease of the control effects of organophosphorus and carbamate insecticides, which is caused by the development of resistance to these insecticides, has become serious problem. In such situations, the development of new insecticides which is effective on the resistant pests has been desired. The compounds of this invention possess superior insecticidal activities against not only susceptible strains but also resistant ones.
The insecticides covered by this invention contain as active ingredients one or more types of the compounds as expressed by the general formula (1). These active ingredients, may be used asproduced but normally they are used in any of the forms which ordinary agricultural chemicals can take, namely wettable powder, dust, emulsifiable concentrate, suspension concentrates, smoking chemicals, fumigant, granule, or other formulations. For additives and carriers are used soybean flour, wheat flour or other vegetable flours, diatomaceous earth, apatite, gypsum, talc, pyrophyllite, clay or other fine mineral powders, when solid formulations are intended.
When liquid formulations are intended, then for solvents are used kerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, water, etc. A surface active agent may, if necessary, be added in order to give a homogeneous and suitable formulation. The wettable powders, emulsifiable concentrates, suspension concentrates, etc. thus obtained are diluted with water into suspensions or emulsions of a prescribed concentration, before they are actually sprayed on plants in the field. In the case of dusts or granules, they are directly applied without further processing.
It goes without saying that the compound(s) of this invention is effective even alone, but it can be used by mixing with various types of insecticides, acaricides and fungicides.
Typical examples of acaricides and insecticides which can be used by mixing with the compounds of this invention are described below:
Acaricides (fungicides):
chlorobenzilate, chloropropylate, proclonol, bromopropylate, dicofol, dinobuton, binapacryl, chlordimeform, amitraz, propargite, PPPS, benzoximate, hexythiazox, fenbutatin oxide, polynactine, chinomethionat, thioquinox, chlorfenson, tetradifon, phenproxide, avermectins, clofentezine, flubenzimine, fenazaquin, pyridaben, fenproximate, chlorfenethol, thiophanate-methyl, benomyl, thiram, iprobenfos, edifenfos, fthalide, probenazole, isoprothiolane, chorothalonil, captan, polyoxin-B, blasticidin-S, kasugamycin, validamycin, tricyclazole, pyroquilon, phenazine oxide, mepronil, flutolanil, pencycuron, iprodione, hymexazole, metalaxyl, triflumizole, diclomezine, tecloftalam, vinclozolin, procymidone, bitertanol, triadimefon, prochloraz, pyrifenox, fenarimal, fenpropimorph, triforine, metalaxyl, oxycarboxin, pefrazoate, diclomedine, fluazinam, oxadixyl, ethoquinolac, TPTH, propamocarb, fosetyl, dihydrostreptomycin, anilazine, dithianon, diethofencarb. Organophosphorus-type and carbamate-type insecticides (acaridides): fenthion, fenitrothion, diazinon, chlorpyrifos, oxydeprofos, vamidothion, phenthoate, dimethoate, formothion, malathion, trichlorfon, thiometon, phosmet, menazon, dichlorvos, acephate,
EPBP, dialifos, parathion-methyl, oxydemeton-methyl, ethion, aldicarb, propoxur, methomyl, fenobucarb, BPMC, pyraclofos, monocrotophos, salithion, cartap, carbosulfan carbofuran, benfuracarb, metolcarb, carbaryl, pirimicarb, ethiofencarb, fenoxycarb,
Pyrethroide-type insecticides (acaricides):
permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropathrin, pyrethrins, allethrin, tetramethrin, resmethrin, parthrin, dimethrin, proparthrin, bifenthrin, prothrin, fluvalinate, cyfluthrin, cyhalothrin, flucythrinate, ethofenprox, cycloprothrin, tralomethrin, silaneophan.
Benzoylphenylurea-type and other types insecticides:
diflubenzuron, chlorfluazuron, triflumuron, teflubenzuron, buprofezin, pyriproxyfen, flufenoxuron, Machine oil.
Same examples of the formulations are given below. The carriers, surface-active agents, etc. that are added, however, are not limited to these Examples.
Example 7 : Emulsifiable concentrate
The compound of this invention 10 parts
Alkylphenyl polyoxyethylene 5 parts
Dimethyl formamide 50 parts
Xylene 35 parts
These components are mixed and dissolved and, for use in spraying, the liquid mixture is water-diluted into an emulsion.
Example 8 : Wettable powder
The compound of this invention 20 parts
Higher alcohol sulfuric ester 5 parts
Diatomaceous earth 70 parts
Silica 5 parts
These components are mixed and ground to fine powder, which for use in spraying, are water-diluted into a suspension.
Example 9 : Dust
The compound of this invention 5 parts
Talc 94.7 parts
Silica 0.3 parts
These are mixed and ground and used as-ground in spraying.
Example 10 : Granule
The compound of this invention 5 parts
Clay 73 parts
Bentonite 20 parats
Sodium dioctylsulfosuccinate 1 part
Sodium phosphate 1 part
The above compounds are granulated, and applied as it is when used. Industrial applicability:
The tests below show the insecticidal activity of the compounds of this invention.
Test 1 Efficacy for cotton aphid
30 to 50 insects of cotton aphid per plot were inoculated using a small brush on cucumber leaves which were seeded in pots, 10cm in diameter, and 10 days old after germination. A day later, wounded insect pests were removed, and a chemical solution, which was prepared in the way that the emulsifiable concentrate described in Example 7 of the above example of insecticide was diluted with water to 125 ppm of compound concentration according to the prescription, was sprayed. The pots were placed in a thermostatic room at temperature of 25°C and humidity of 65%. The number of survival pests was counted 7 days later and the control efficacy was calculated by comparing with that of untreated plot. The results are shown in Table 2.
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0003
Comparative compound A:
Figure imgf000079_0001
Comparative compound B:
Figure imgf000079_0002
Test 2 Efficacy for green rice leafhopper
Rice seedlings of 7 days old after germination were immersed in a chemical solution, which was prepared in the way that the emulsifiable concentrate described in Example 7 of the above example of insecticide was diluted with water to 125 ppm of compound concentration according to prescription, for 30 seconds. After dried in air, the treated seedlings were placed in test tubes and 10 insects of 3rd-instar larvae of green rice leafhopper resistant to the organophosphorus and carbamate insecticides were inoculated. The tubes were covered with gauze, and placed in a thermostatic room at temperature of 25 °C and humidity of 65%. The mortality was checked 5 days later.
The results are shown in Table 3.
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0002
Comparative compound A and B: The same as test 1
Compound C:
Figure imgf000083_0001
(malathion)
Test 3 Efficacy for rice armyworm
The test compounds were formulated into the wettable powder in the same manner as Example 8. The compounds were diluted with water to 125 ppm. A maize leaf was immersed in the chemical solution for 30 seconds. After air-dried, the treated leaf was placed in a petri dish and five 3rd-instar larvae of rice armyworm were inoculated. The petri dishes were covered with glass lids, and placed in a thermostatic room at 25ºC and 65% relative humidity. The mortality was checked 5 days later. Two replications were conducted in the each test. The results are shown in Table 4.
Figure imgf000085_0002
Comparative compound A and B: The same as Test 1
Compound D:
l- 3)2
3
Figure imgf000085_0001
(chlordimeform)

Claims

Claims
1. A compound having the formula
Figure imgf000086_0001
wherein R1 represents an optionally substituted 5 - 6 membered aromatic hetero ring containing nitrogen atom, except a non- substituted 2-pyridyl;
X represents an optionally substituted C1-3 alkylene or alkylidene;
R2 represents a hydrogen, a carbamoyl, a mono or di C1-5 alkyl carbamoyl, a thiocarbamoyl, a mono or di C1-5 alkylthiocarbamoyl, a sulfamoyl, a mono or di C1-5 alkylsulfamoyl, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl, an optionally substituted C3-8 cycloalkenyl, an optionally substituted aryl or -Y-R5;
Y represents O, S(O)n, CO, CS or CO2;
n represents 0,1 or 2;
R5 represents a hydrogen, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl, an optionally substituted C3-8 cycloalkenyl or an optionally substituted aryl;
R3 represents a hydrogen, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-8 cycloalkyl or an optionally substituted C3-8 cycloalkenyl;
R4 represents a cyano or a nitro; and Z represents CH or N ;
or its salt.
2. A compound according to claim 1,
wherein R1 represents a pyridyl, a pyrazyl, a pyrazolyl, a pyridazyl or a thiazolyl, which may be substituted by a C1-5 alkyl, a C1-5 haloalkyl, a C1-5 alkoxy, a C1-5 alkylthio, a C1-5 alkylsulfonyl, a cyano, a halogen or a di C1-5 alkylamino, respectively, except a non-substituted 2-pyridyl;
R2 represents a hydrogen, a mono or di C1-5 alkylcarbamoyl, an optionally substituted C1-5 alkyl, an optionally substituted C2-5 alkenyl, an optionally substituted C2-5 alkynyl, an optionally substituted C3-6 cycloalkyl, an optionally substituted aryl or -Y-R5;
Y represents 0, CO, CO2 or SO2;
R5 represents an optionally substituted C1-5 alkyl, or an optionally substituted aryl;
R3 represents a hydrogen, an optionally substituted C1-5 alkyl or an optionally substituted C3-6 cycloalkyl;
Z represents N;
3. An insecticidal composition comprising a compound according to claim 1 as an active ingredient.
4. An insecticidal composition comprising a compound according to claim 2 as an active ingredient.
5. A process for the preparation of a compound having the formula
Figure imgf000088_0001
2
which comprises reacting a compound having the formula
Figure imgf000088_0002
with a compound having the formula
Figure imgf000088_0003
wherein r1 and r2 are a C1-5 alkyl, respectively; and R1, R2 ,
R3 , R4 and X are as defined above.
6. A process for the preparation of a compound having the formula
Figure imgf000088_0004
which comprises reacting a compound having the formula
Figure imgf000088_0005
with a compound having the formula
Figure imgf000088_0006
wherein r3 represents a C1-5 alkyl; and R1, R2, R3 and X are as defined above.
7. A process for the preparation of a compound having the formula
Figure imgf000089_0001
which comprises reacting a compound having the formula
Figure imgf000089_0002
with a compound having the formula
R2-Hal
wherein Hal represents a halogen atom; and R1, R2, R3 and X are as defined above.
8. A process for the preparation of a compound having the formula
Figure imgf000089_0003
which comprises reacting a compound having the formula
Figure imgf000089_0004
with a compound having the formula
R1-X-Hal
wherein R1, R2, R3, X and Hal are as defind above.
9. A process for the preparation of a compound having the formula
Figure imgf000090_0001
which comprises reacting a compound having the formula
Figure imgf000090_0002
with nitration reagent,
wherein R1, R2, R3 and X are as defined above.
PCT/JP1990/001282 1989-10-06 1990-10-04 Amine derivatives WO1991004965A1 (en)

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HU9802249A HU220083B (en) 1989-10-06 1990-10-04 Insecticidal amine derivatives
DE122006000027C DE122006000027I2 (en) 1989-10-06 1990-10-04 AMIN DERIVATIVES
EP90914758A EP0456826B1 (en) 1989-10-06 1990-10-04 Amine derivatives
US07/700,165 US5304566A (en) 1989-10-06 1990-10-04 Pyridine compounds which have useful insecticidal utility
KR1019910700545A KR930008631B1 (en) 1989-10-06 1990-10-04 Amine derivatives
DK90914758T DK0456826T3 (en) 1989-10-06 1990-10-04 amine Derivatives
RO147641A RO112865B1 (en) 1989-10-06 1990-10-04 Amine derivatives, processes for preparation and insecticides containing said derivatives
DE69032882T DE69032882T2 (en) 1989-10-06 1990-10-04 AMINE DERIVATIVES
BR909006961A BR9006961A (en) 1989-10-06 1990-10-04 INSECTICIDE COMPOUND, INSECTICIDE COMPOSITION AND PROCESS TO PREPARE INSECTICIDE COMPOUND
IL9801491A IL98014A (en) 1990-05-02 1991-05-01 Amine derivatives their preparation and insecticidal compositions containing them
SU914895590A RU2038352C1 (en) 1989-10-06 1991-06-05 Amine derivatives or their salts and insecticide composition on their base
LVP-92-617A LV10155B (en) 1989-10-06 1992-12-30 Amine derivatives, process for its production and insekticidal composition containing the same
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CN1050714A (en) 1991-04-17
DE69032882D1 (en) 1999-02-18
AU633991B2 (en) 1993-02-11
DE69032882T2 (en) 1999-06-10
RO112865B1 (en) 1998-01-30
BR9006961A (en) 1991-12-17
JP2926954B2 (en) 1999-07-28
NL350028I2 (en) 2006-11-01
NL350028I1 (en) 2006-07-03
HUT57191A (en) 1991-11-28
AU6511790A (en) 1991-04-28
HU907896D0 (en) 1991-08-28
DE122006000027I2 (en) 2010-10-21
DK0456826T3 (en) 1999-08-30
HU214992B (en) 1998-12-28
ES2127718T3 (en) 1999-05-01
EP0456826A1 (en) 1991-11-21
ATE175405T1 (en) 1999-01-15
JPH04154741A (en) 1992-05-27
CA2041670C (en) 1997-03-18
EP0456826B1 (en) 1999-01-07
CN1056958C (en) 2000-10-04
CA2041670A1 (en) 1991-04-07

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