CN100503600C - 杂环类农药 - Google Patents

杂环类农药 Download PDF

Info

Publication number
CN100503600C
CN100503600C CNB038123436A CN03812343A CN100503600C CN 100503600 C CN100503600 C CN 100503600C CN B038123436 A CNB038123436 A CN B038123436A CN 03812343 A CN03812343 A CN 03812343A CN 100503600 C CN100503600 C CN 100503600C
Authority
CN
China
Prior art keywords
och
chr
alkyl
hydrogen
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB038123436A
Other languages
English (en)
Other versions
CN1692108A (zh
Inventor
J·A·迪克森
Z·M·艾尔士纳维
H·R·温德特
S·西杰尔
R·H·亨里二世
D·M·劳世
P·丁
J·W·利加
S·F·多诺万
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience SA
Original Assignee
Bayer CropScience SA
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 Bayer CropScience SA filed Critical Bayer CropScience SA
Publication of CN1692108A publication Critical patent/CN1692108A/zh
Application granted granted Critical
Publication of CN100503600C publication Critical patent/CN100503600C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/88—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with three ring hetero atoms
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P7/00—Drugs for disorders of the blood or the extracellular fluid
    • A61P7/04—Antihaemorrhagics; Procoagulants; Haemostatic agents; Antifibrinolytic agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/70—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D211/74—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C07D233/08—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms
    • C07D233/10—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D233/22—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D233/24—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D233/26—Radicals substituted by carbon atoms having three bonds to hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D263/14—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
    • C07D273/02—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and only one oxygen atom
    • C07D273/04—Six-membered rings
    • 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
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D277/14—Oxygen 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
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon 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
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen 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
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no 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
    • C07D307/20—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/18—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member containing only hydrogen and carbon atoms in addition to the ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/20—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hydrogen atoms and substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/20—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hydrogen atoms and substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D309/22—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D309/30—Oxygen atoms, e.g. delta-lactones
    • 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
    • C07D333/06—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/08—Hydrogen atoms or radicals containing only hydrogen and 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
    • C07D333/06—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen 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
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/32—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C07D405/02—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
    • C07D405/04—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 directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6503—Five-membered rings
    • C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07F9/6533—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Diabetes (AREA)
  • Public Health (AREA)
  • Hematology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Animal Behavior & Ethology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Veterinary Medicine (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Pyrrole Compounds (AREA)

Abstract

现已发现一些新的杂环衍生物有意外的杀虫活性。这些化合物如通式(I)所示：这些化合物用通式(I)代表R优选的通式(I)化合物，其中R2和R3连接成＝NCH(R6)CH(R7)N(R8)，＝NC(R6)＝C(R7)N(R8)-或＝CHN＝C(R7)N(R8)-，及其互变异构体，其中R4和R5连接成＝CR11＝C(R12)C(R13)＝C(R14)112-，其中R，R，R6，R7，R8，R11，RR13，R14和X已述及。另外，也披露了组合物，这包含至少杀虫有效量的一种通式(I)化合物，且可任选包含至少一种有效量的第二化合物，同时包含至少一种适于杀虫剂的载体；同时公布了防治昆虫的方法，包括将所述组合物施应用至昆虫出没或预期会出没的所在地域。

Description

杂环类农药
发明的领域
本发明一般来说是有关农药化合物及其用于防治虫害。特别是它适于用作杀虫和杀螨的杂环衍生物及其农业上适用的盐，这些农药的组合物及其它们用于防治虫害的方法。
发明的背景
众所周知如昆虫和螨类那样的病虫害，对农业作物的生长可造成重大的危害，对于有关的作物而言可造成数百万美元价值的损失。
虽然昆虫的许多种类可造成重要作物的危害，例如同翅亚目昆虫就较显著。同翅亚目例如包括，蚜虫、叶蝉、蝉、粉虱科及粉蚧等几种。同翅目有剌入/吸吮口器，使用它们就可从维管植物吃到体液。同翅目昆虫的危害表现有几种不同的方式，与直接进食的危害不同。例如许多种排泄甘露、粘性髒物会粘附在昆虫进食及生活的植物上。光是甘露就对作物造成外观损伤。烟霉常会生长在甘露上，造成粮食产物或观赏植物看起来无吸引力。因此会降低美观性及经济价值。有些同翅目昆虫在进食时会有有毒的唾液注入植物。唾液能造成植物经毁形而损伤有时造成作物死亡去。同翅目昆虫也可传播引起疾病的病原。不同于直接的危害，并不需要大量传播疾病的昆虫就能对作物造成很大的危害。
螨类，例如棉红蜘蛛与豆叶螨对许多植物作物色括蕃茄、豆类及葫芦会造成严重的病虫害。这些螨类也和其它螨料一样也会对全世界广范围多种其它蔬菜、水果及观赏植物造成危害。叶螨科咬食茎叶对蔬菜作物会造成严重的经济损害，其作用为减少光合作用、蒸腾作用、叶子的叶绿素含量及叶氮降低和增加蒸腾作用。
螨类的咬食会减少芽的生成及使果实变小，最终也会造成低劣果实及严重变色。
因此就不断要求人们用新的杀虫剂以防治例如同翅目及其它目的昆虫；也包括新的杀螨剂，要求它们更安全、更有效、及价格更低廉，以用于上述作物，也为了应用于小麦、玉米、大豆、马铃薯及棉花等。为了保护作物，能够防治昆虫及蜱螨，对杀虫剂及杀螨剂的期望是对作物没有药害，以及对哺乳动物和其它活的生物体没有毒害。
由“陶氏农业科学”在美国化学会2000年第220次会议上以“芳烷基咪唑杀虫剂的限定类似物设计战略”为题，揭示了对棉蚜有杀虫活性的下列结构为例的一类咪唑化合物：
Figure C03812343D00071
在Journal of Medicinal Chemistry 1986年，29，463～467刊登了下列结构的一类咪唑衍生物对α1和α2肾上腺素能受体有生物活性：
Figure C03812343D00072
其中X为羟基或甲氧基而n为0～3。但没有揭示或提出那些肾上腺素受体化合物有杀虫活性。
发明概述
按照本发明，已发现某些新的杂环衍生物及其适用于农业的盐类，可用作杀虫剂组合物的有效成份和可用于本发明的方法。这些化合物如下列通式I所列：
其中R，R1、R2、R3、R4、R5及X的意义详述如下。其中优选的化合物为那些其中R2和R3相连成五元或六元环，即＝NCH(R6)CH(R7)N(R8)-，＝NC(R6)＝C(R7)N(R8)-，以及＝CHN＝(R7)N(R8)-；R4和R5相连成稠环，即C(R11)＝C(R12)C(R13)＝C(R14)-，而X选自-CHR17-，-CH2CHR17-，-OCH2-，以及-SCH2-；其中R6，R7，R8，R11，R12，R13，R14及R17详述如后文。
本发明也涉及含有杀虫有效量的至少一种通式I化合物，以及任选地有效量的至少一种第二化合物与至少一种与杀虫剂相容的载体的组合物。
本发明也涉及在需要控制的地方控制昆虫的方法，该方法包括将杀虫有效量的上述组合物施用在作物区或其它出现昆虫或预期会有昆虫出现的地方。
本发明的详细说明
本发明一个方面涉及某些新的和有用的化合物，及其农业上适用的盐类；
即如通式I所表示的某些新的杂环衍生物：
Figure C03812343D00081
其中R与R1分别选自H和烷基；
-R2和R3相连构成选自以下的五元或六元环：
＝NCH(R6)CH(R7)N(R8)-，＝NC(R6)＝C(R7)N(R8)-，＝CHC(R6)＝C(R7)N(R8)-，＝CHN＝C(R7)N(R8)-，＝N(CH2)3N(R8)-，＝NCH(R6)CH(R7)S-，＝NCH(R6)CH(R7)O-，＝CHCH＝CHCH＝N-，＝NN＝CHN(R8)-，＝NN＝NN(R8)-，-OCH(R6)CH(R7)N(R8)N＝及其互变异构体；其中
R6和R7各选自氢和烷基；
R8选自氢、烷基、氨基、硝基、氰基、甲酰基、-CH2R9-、-CH2OR9、-C(O)R9、-C(O)OR9、-CH2OC(O)R9、-C(O)N(R9)(R10)、-S(O)nR9-、S(O)nN(R9)(R10)，其中n是0、1或2，-Si(R9)3、-CH＝N(R9)、-P(O)(OR9)(OR10)，-P(O)(NR9R10)以及Y，其中Y代表i)上述五元或六元环的N-氧化物，或(ii)形成ORa键的形式，其中Ra选自氢和烷基；
R9和R10各选自氢、烷基、烷基羰基、烷氧基羰基芳基、芳烷基和杂芳基，其中芳基任选被一个或多个取代基取代，取代基各选自卤素、烷基或卤烷基；
-R4和R5连接成稠环，稠环选自-C(R11)＝C(R12)C(R13)＝(R14)、-SC(R15)＝C(R16)-、-C(R15)＝C(R16)S-以及-CH＝C(R15)N＝CH-
其中
R11和R14各选自氢、卤素及甲基；
R12选自氢、卤素、氨基、(C1-C2)烷基、甲氧基、卤代甲氧基、(C2-C3)链烯基及(C2-C3)炔基；
R13选自氢、卤素、氰基、(C1-C2)烷基、羟基、甲氧基、卤代甲基及(C2-C3)炔基；
R15和R16各选自氢、卤素、氰基、氨基、(C1-C2)烷基、(C2-C3)链烯基、(C2-C3)炔基、卤代甲基、羟基、甲氧基及卤代甲氧基；
-X选自-CHR17-、-CH2CHR17-、-C3H6-、-C4H8-、-O-、-OCH2-、-OC2H4-、-OC3H6-、-CH2O-、-CH2OCH2-、-CH2OC2H4-、-S-、-SCH2-、-CH2S(O)-、-CH2S(O)2-、-N(R17)CH2-；以及-CH2N(R17)-；
其中R17选自氢及烷基；
条件是，R和R1为氢；R2和R3连接成＝CHN＝C(R7)N(R8)-，其中R7和R8为氢；R4和R5连接成-C(R11)＝C(R12)C(R13)＝C(R14)-；而X为-CHR17，其中R17为氢；而R11、R12、R13或R14中至少有一个不是氢；
进一步的条件是，当R和R1是H；R2和R3连接成＝NCH(R6)CH(R7)N(R8)-；其中R6、R7和R8为H；R4和R5连接成-C(R11)＝C(R12)C(R13)C(R14)-，而X为-CHR17，其中R17为H时；则i)当R11、R13和R14为H时，则R12不是甲基；ii)当R11是H，R13是甲基以及R14是溴时，则R12不是H；iii)当R11和R14是H，且R12为甲氧基时，则R13就不是甲氧基；iv)当X是-CH2CH17-，或-OCH2-；R17为H；R11和R14为H，R12为甲氧基，而R13为甲基时，则R8不是-S-(O)nR9，其中n为2，而R9为甲基。
上述条件述及的化合物外，优选的是那些式I的化合物为，其中R2和R3连接成＝NCH(R6)CH(R7)N(R8)-，＝NC(R6)＝C(R7)N(R8)-，或＝CHN＝C(R7)N(R8)，及其互变异构体，其中R8选自H、氰基、-S(O)nN(R9)(R10)，以及-P(O)(OR9)(OR10)，其中n为2，R9和R10分别选自H和烷基；R4和R5连接成稠环，其中R4和R5连接成-C(R11)＝C(R12)C(R13)＝C(R14)，其中R11是氢，R12选自卤素和甲氧基，以及R13选自卤素和(C1-C2)烷基；而X选自-CHR17-，-CH2CHR17-，-OCH2-以及-SCH2-。特别优选的化合物是那些，其中R9和R10都是甲基；R12选自氯和甲氧基；R13选自氯和甲基；而R14选自H、氯和甲基；X选自-CH2CHR17-以及-OCH2-，其中R17为H。
此外，在某些情况下，本发明化合物具有不对称中心，就会产生光学对映体和非对映体。化合物可存在二种或多种形式，即多构型体，它们在物理和化学性质上是明显不同的。本发明化合物也存在互变异构体，其中氢原子在分子中的移位产生二种或多种结构而达平衡，例如本发明化合物256-278。本发明化合物也可具有酸性或碱性部分，从而可以形成适于农业上的盐类或农业上合适的金属配合物。
本发明包括这些化合物的对映体、多构型体、互变异构体、盐类及金属配合物的应用。农业上适用的盐和金属配合物所包括，例如铵盐、有机和无机酸的盐，诸如盐酸、磺酸、乙磺酸、三氟醋酸、甲基苯磺酸、磷酸、葡糖酸、扑姆酸、及其它酸所成的盐，以及碱金属及碱土金属碱配合物，例如钠、钾、锂、镁、钙及其它金属。
本发明的另一方面涉及组合物，其含有杀虫有效量的至少一种通式I化合物并含至少一种与杀虫剂相容的载体。
本发明另一方面涉及组合物，其含有至少一种杀虫有效量的通式I化合物及至少一种有效量的第二化合物，并含有至少一种与杀虫剂相容的载体。
在本发明的另一方面涉及防治昆虫的方法，通过将杀虫有效量的上述组合物施用到作物地区，作物(不受限制)例如为谷类、棉花、蔬菜及水果，或施用到其它有昆虫出没或预期有昆虫出没的区域。
本发明也包括所述化合物及组合物在防治非农业昆虫，例如干木白蚁、家白蚁中的应用；以及作用药剂及其组合物的应用。
如本说明书所用的，除非另有注明，取代基术语“烷基”和“烷氧基”，单独使用或作为大基团的部分，包括至少一个或二个碳原子的直链或支链，作为取代基优选多达12个碳原子，而以至多10个碳原子较优，最好至7个碳原子。术语“链烯基”和“炔基”单独使用或作为大基团的部分，包括直链或支链，至少有二个碳原子，含有至少一个碳-碳双键或三键，优选高至12个碳原子，而以多达10个碳原子为优，最好为多达7个碳原子。术语“芳基”指芳环结构，包括稠环、有4至10个碳原子，例如苯基或萘基。术语“杂芳基”指的是芳环结构，包括稠环，原子中至少有一个原子不是碳，例如为硫、氧或氮等，但不加限制。术语“GC分析”指的是例如反应混合物的气相色谱分析。术语“DMF”指的是N，N-二甲基甲酰胺。术语“THF”指的是四氢呋喃。术语“卤素”或“halo”指的是氟、溴、碘或氯。术语“超活性”或“昆虫超活性”指的是昆虫的异常身体状况，例如棉蚜过多地从植株上爬走消失。术语“环境温度”或“室温”通常缩写为“RT”，例如就化学反应混合物温度而言，指温度范围为20℃至30℃。术语“农药上”或“农药”指的是本发明化合物，无论是单独或至少与一种第二化合物，或与至少一种相容的载体相混合，对昆虫或螨类的活动、或对昆虫或螨类造成破坏或抑制。
通式I的杂环衍生物可用各自已知的工艺自可商购得到的中间体化合物合成。如下图I说明合成通式I杂环衍生物的一般步骤，尤其作为特定的例子，R和R1是氢；R2和R3连接成＝NCH(R6)CH(R7)N(R8)-；R4和R5相联成-C(R11)＝C(R12)C(R13)＝C(R14)-；而X是-CHR17-，CH2CHR17-，-OCH2-或-SCH2-，其中R6、R7、R8及R17是氢：
图I
Figure C03812343D00121
当X是-CHR 17 时，按照步骤a至步骤f：
a)n-BuL；/THF/DMF-60℃至-70℃(转化A＝-Br至-CHO)；b)2.2-二甲基-1、3-二噁烷-4、6-二酮/HCOOH/HCOOH/Et3N/-5℃至95℃(转化-CHO至中间体(i)；c)Eaton’s试剂/39℃(转化中间体(i)至中间体ii)；d)N＝CP(O)(OC2H5)2/LiCN/THF；/d)BF3-O(C2H5)2/甲苯/45℃(d和1d转化中间体(ii)至中间体(iii)；e)H2/10％ Pd-C/10％Pt-C/EfOAC(转化中间体iii)至中间体(iv)；f)p-CH3C6H4SO3-NH3 +CH2CH2NH2/140℃至160℃(转化中间体(iv)直至通式(I)化合物)。
当X是-CH 2 CHR 17 时，按照步骤a’至步骤f’：
a’)HC＝CCH2CH2OH/[(C6H5)3P]2PdCl2/90℃(转化A＝-Br至-C＝CCH2(H2OH))；b’)H2/10％Pd-C/CH3OH(转化-C＝C(CH2CH2OH至-CH2CH2CH2CH2OH)；c’)琼斯试剂/丙酮/0℃至室温(转化-CH2CH2CH2CH2OH至中间体(i))；d’)Eaton’s试剂/室温(转化中间体(i)至中间体(ii))；e’)(CH3)3Si CH/AlCl3/甲苯/70℃(转化中间体(iii)至硅杂乙氧基中间体))；le’)(CH3)3SiCl/NaI/CH3CN/H2O/室温(转化氰基-甲硅烷基中间体至中间体(iii)和中间体(iv)混合物)；2e’)H2/10％Pd-C/10％Pt-C/EtOAC(转化中间体(iii)和中间体(iv)混合物至中间体(iv))；f’)P-CH3C6H4SO3-NH3 +CH2CH2NH2/140℃-180℃(转化中间体iv至通式(I)化合物)。
当X是-OCH 2 -时，按照步骤a”至步骤e”：
a”)ClCH2CH2CH2OH/10％NaOH水溶液/回流(转化A＝-OH至OCH2CH2CH2OH)；或CH2＝CH2CN/
Figure C03812343D0013162055QIETU
B/回流(转化A＝OH至OCH2CH2CN)；b”)琼斯试剂/丙酮/5℃至10℃(转化OCH2CH2CH2OH至中间体(i))，或浓盐酸/回流(转化OCH2CH2CN至中间体(i))；c”)草酰氯/AlCl3/DMF/CH2Cl2/5℃至室温(转化中间体(i)至中间体(ii))；d”)(CH3)3SiCN/AlCl3/甲苯/70℃(转化中间体(ii)至硅杂乙氧基中间体))；1d”)(CH3)3SiCl/NaI/CH3CN/H2O/室温(转化氰基-甲硅烷工中间体至中间体(iv))；e”)P-CH3C6H4SO3-NH3 +CH2CH2NH2/140℃(转化中间体(iv)至通式(I)化合物))。
当X是-SCH 2 -时，按照步骤a”’至步骤e”’
a”’)BrCH2CH2CO2CH3/DMF(转化A＝-SH至-SCH2CH2CO2CH3))；b”’)10％KOH水溶液/CH3OH(转化-SCH2CH2CO2CH3至中间体(i))；c”’)草酰氯/AlCl3/DMF/CH2Cl2/5℃至室温(将中间体(i)转化为中间体(ii))；d”’)1-(CH3)3SiCN/AlCl3/甲苯/70℃，2-/(CH3)3SiCl/NaI/CH3CN/H2O/室温(将中间体(ii)转化为中间体(iv))；e”’)p-CH3C6H4SO3-NH3 +CH2CH2NH2/140℃(将中间体(iv)转化为通式(I)化合物))。
Figure C03812343D00132
当R2和R3相联成＝NCH(R6)CH(R7)N(R8)时，如图I所示，杂环代表一种互变异构体形式，其中该部份可以存在。
在前面图I的第一个步骤中，制备了合适的羧酸(中间体(i))，羧酸(i)的合成路线依赖于X部分是什么。例如，其中X为-CHR17-时，适当取代的溴化苯，如5-溴-2-甲氧基甲苯，在低温下锂化，然后在合适的溶剂中用DMF处理，得到相应的醛衍生物。将醛衍生物在升温下与2.2-二甲基-1，3-二噁烷-4，6-二酮缩合，之后脱羧并用三乙胺-甲酸盐还原，生成相应的羧酸(i)。当X是-CH2CHR17-时，将合适取代的溴化苯在升温下与合适的炔醇，如3-丁炔基-1-醇、碘化亚铜、三乙胺，在催化剂存在下，在合适的溶剂中反应，可得相应的苯基取代的炔基醇。将此炔基醇在10％钯-炭催化剂存在下，在合适的溶剂中氢化，可得相应的苯基取代的烷基醇，后者再用琼斯试剂处理，可得相应的羧酸(i)。当X为-OCH2-或-SCH2-时，可用合适取代的酚或硫酚，例如3-甲基苯酚或3-甲基苯硫酚与卤代烷基醇或卤代烷基酯在碱性条件下反应，则可得相应的苯氧基烷基醇或苯硫基烷基酯。然后，将苯氧基烷基醇用琼斯试剂处理和将苯硫基烷基酯用强碱处理，可得相应的羧酸(i)。另一个方法是，当X为-OCH2-时，用恰当取代的苯酚，例如3-甲基-4-甲氧基苯酚，在碱存在下与丙烯腈反应，可得相应的丙腈，例如3-(4-甲氧基-3-甲基苯氧基)丙腈。将此丙腈用浓盐酸处理可得相应的羧酸(i)。
在图I所示的第二步中，当X是-CHR17或-CH2CHR17-时，将羧酸(i)转化为环酮(中间体(ii))，办法是用Eaton’s试剂处理，例如可得6-甲氧基-5-甲基-二氢茚-1-酮(X是-CHR17-)或7-甲氧基-6-甲基-2，3，4-三氢萘-1-酮(X是-CH2CHR17-)，当X是-OCH2-时，羧酸(i)在低温、在合适的溶剂中先转化为相应的酰氯，之后用氯化铝处理，即得相应的环酮(ii)，例如7-甲基-苯并二氢吡喃-4-酮。
在图I所示的第三步，将环酮(ii)a)直接转化为不饱和腈(中间体(iii))，b)直接转化为饱和腈(中间体(iv))，或c)转化为(iii)和(iv)的混合物。当X是-CHR17时，将环酮(ii)例如6-甲氧基-5-甲基二氢茚-1-酮与氰化锂和氰基膦酸二乙酯在升温下反应，然后用三氟化硼乙醚配合物在合适溶剂中处理，可得相应的不饱和腈(iii)，例如5-甲氧基-6-甲基-茚-3-甲腈。当X是-CH2CHR17-时，则采用另一种方法，将环酮(ii)，例如7-甲氧基-6-甲基-2，3，4-三氢萘-1-酮，在催化量的三氯化铝存在下在升温下用三甲基氰基甲硅烷处理，可得硅杂乙氧基中间体。之后将此中间体用碘化钠、三甲基氯化甲硅烷和水在合适溶剂中反应，可得相应的不饱和腈(iii)和饱和腈(iv)的混合物；例如分别为7-甲氧基-6-甲基-3，4-二氢萘甲腈和7-甲氧基-6-甲基-1，2，3，4-四氢萘甲腈的混合物。当X是-OCH2-或-SCH2-时，环酮(ii)例如7-甲基苯并二氢吡喃-4-酮或7-甲基-2H，3H-苯并[e]噻喃-4-酮，也可与三甲基氰化甲硅烷，在催化量的三氯化铝存在下发生反应，然后用碘化钠、三甲基氯化甲硅烷和水在合适的溶剂中处理，直接可得相应的饱和腈(iv)；例如7-甲基苯并二氢吡喃-4-甲腈或7-甲基-2H，3H-苯并[e]噻喃-4-甲腈。
图I所示的第四步反应，是将上述所制得的不饱和腈(iii)及不饱和腈(iii)与饱和腈(iv)的混合物，在至少一种催化剂诸如10％铂-炭和/或10％钯-炭存在下，在合适的溶剂中氢化而转化为饱和腈(iv)。
如图I所示的第五步反应，当其中R2和R3相联成＝NCH(R6)CH(R7)N(R8)-时，通过饱和腈与对甲苯磺酸乙二胺盐在升温下反应，而将饱和腈(iv)转化为通式(I)的化合物。后面的实施例1-3，5和6将详述图I中的这些合成路线。
下面图II是对通式(I)其它杂环衍生物的合成作一般说明，其中特别列举，R和R1是氢；R2和R3连接成＝CHN＝C(R7)N(R8)-；R4和R5连接成-(R11)＝C(R12)C(R13)＝C(R14)-；而X是-CHR17-，-CH2CHR17-，-OCH2-或-SCH2-其中R7、R8、R17是H：
图II
Figure C03812343D00161
当X是-CHR 17 -时：
a)I2/2NNaOH水溶液/CH2Cl2/10℃；b)Na2SO3/H2O/EtOH/回流；c)(Ph)3CCl/Et3N/DMF/室温；d)中间体(ii)/EtMgBr/CH2Cl2/21℃；e)盐酸/CH3OH；f)H2/10％Pd-C/PtO2水合物/EtOH/室温。
如图II所列，先合成杂环(其中R2和R3连接成＝CHN＝C(R7)N(R8)-)，然后与环酮(ii)反应，得到相应的得通式(I)化合物的倒数第二个中间体(viii)。杂环(其中R2和R3连接成＝CHN＝C(R7)N(R8)-)，如图II所示，代表一种互变异构体形式，其中存在这一部分。
如图II所示，在低温碱性条件下，在合适溶剂中，咪唑与碘反应可得碘代咪唑混合物(v)，例如2，4，5-三碘咪唑和2，5-二碘咪唑的混合物。之后将碘代咪唑衍生物(v)混合物，用亚硫酸氢钠的水溶液，在合适溶剂中，升温处理，则可得单碘代衍生物(vi)，例如5-碘咪唑。在碱性条件下，合适溶剂中，用三苯基甲基氯化物反应而保护碘代咪唑(vi)的1-位的游离胺，可得相应的1-(三苯基甲基)-4-碘咪唑(vii)。该碘代咪唑(vii)在合适溶剂中，用乙基溴化镁处理，然后与适当的环酮(ii)例如6-甲氧基-5-甲基-二氢茚-1-酮(X是-CHR17-)反应，可得相应的1，2-不饱和杂环衍生物(viii)，例如3-(咪唑-5-基)-5-甲氧基-6-甲基茚。然后在前述条件下使杂环衍生物(viii)氢化，可得相应的通式(I)化合物，例如1-(咪唑-5-基)-6-甲氧基-5-甲基二氢茚。后述实施例4将详述图II所列的合成路线。
图III是对通式I其它杂环衍生物的合成作一般说明，其中特别列举：R和R1是H；R2和R3连接成＝CHN(R8)C(R7)＝N-；R4和R5连接成-C(R11)＝C(R12)C(R13)＝C(R14)-；而X是-CHR17-，-CH2CHR17-，-OCH2-或-SCH2-其中R7和R17是H，而R8是H以外的取代基：
图II
Figure C03812343D00181
当X是-OCH 2 -时：
a)C 2 H 5 MgBr/CH 2 Cl 2 ；b)CF 3 CO 2 H；c)5％铂/碳/10％钯/碳/CH 3 OH
如图III所示，碘代杂环同系物(其中，R2和R3连接成＝CHN(R8)C(R7)＝N-，R7是H而R8例如为-SO2N(CH3)2)可用市售品。杂环(其中R2和R3相联而成＝CHN(R8)C(R7)＝N-)如图III所示，代表可存在该部分的互变异构体形式。碘代杂环可与上述的中间体反应而制得通式(I)的另外化合物。
如图III所示，前述中间体(ii)，例如6-甲氧基-7-甲基-苯并二氢吡喃-4-酮，与格氏试剂反应(该格氏试剂由将杂环的碘同系物如[(4-碘代咪唑)磺酰基]二甲胺与乙基溴化镁反应而制得)，得到相应的4-羟基中间体(viii)，例如{[4-(4-羟基-6-甲氧基-7-甲基苯并二氢吡喃-4-基)-咪唑基]磺酰基}二甲胺。该羟基中间体(viii)，然后用脱水剂例如用三氟醋酸脱水可得相应的不饱和中间体(ix)，例如{[4-(6-甲氧基-7-甲基(2H-苯并吡喃-4-基)-咪唑基)磺酰基]二甲胺。最后，在合适的催化剂如10％Pd-C和5％Pt-C存在下，在合适溶剂中，用氢气还原中间体(ix)，可得通式(I)化合物例如{[4-(6-甲氧基-7-甲基苯并二氢吡喃-4-基)-咪唑基]磺酰基}二甲胺。后述实施例7将详述图III的合成路线。
图IV是对通式I其它杂环衍生物的合成作一般说明，其中特别列举：R和R1是H；R2和R2相联成＝NC(R6)＝C(R7)N(R8)；R4和R5相联成-C(R11)＝C(R12)C(R13)＝C(R14)-；而X是-CHR17-，-CH2CHR17-，-OCH2-或-SCH2-，其中R6、R7、R8及R17是H：
图IV
Figure C03812343D00201
当X是-CH 2 CR 17 -时：
a)LHMDS/(CF3SO2)2NC6H5/THF；b)60％NaH/ClCH2OCH2CH2Si(CH3)3/THF/0-5℃；
c)1-(xi)/n-BuLi/THF，2-ZnCl2/(C2H5)2O/-78℃，3-(x)/Pd[PPh3]4/-78℃至60℃；d)浓盐酸；e)H2/PtO/10％Pd-C/C2H5OH
e)H 2 /PtO/10％Pd/C/C 2 H 5 OH
如图IV所示，杂环(其中R2和R3连接成＝NC(R6)＝C(R7)N(R8)-)与例如环酮(ii)的三氟甲基甲磺酰氧基衍生物(ii)(其中R8位用离去基团如CH2OCH2CH2Si(CH3)3保护)偶联，可以多步反应得到通式(I)的化合物。
如图IV所示，前述中间体(ii)，例如7-甲氧基-6-甲基-2，3，4-三氢萘-1-酮，可用六甲基二硅氮烷锂处理，然后在适当溶剂中与N-苯基三氟甲磺酰亚胺反应，可得三氟甲磺酰氧基中间体(x)，例如7-甲氧基-6-甲基-3，4-二氢萘基(三氟甲基)磺酸酯。作为另一个反应，中间体(其中R2和R3相联成＝NC(R6)＝C(R7)N(R8)-如咪唑)，例如偶联用氢化钠处理，然后在合适的溶剂中与2-(三甲基甲硅烷基)乙氧甲基氯化物反应而得相应的硅杂丁烷中间体(xi)，其中R8已受保护。中间体(xi)，例如1-(咪唑基甲氧基)-3，3-二甲基-3-硅杂丁烷，然后在适当溶剂中，用下述试剂处理：1)正丁基锂，2)氯化锌；然后加入中间体(x)，及催化剂，如四(三苯膦)钯(O)一起作用，可得合适的硅杂丁烷中间体(xii)，例如1-{[2-(7-甲氧基-6-甲基(3，4-二氢萘)咪唑基)甲氧基]-3，3-二甲基-3-硅杂丁烷。然后例如用浓盐酸将中间体(xii)R8位脱去保护，可得相应的R8为氢的中间体(xiii)，例如4-咪唑-2-基-6-甲氧基-7-甲基-1，2-二氢萘。在合适的催化剂例如10％Pd-C和氧化铂存在下在适宜的溶剂中，将中间体(xiii)用氢气还原，可得通式(I)的化合物，例如1-咪唑2-基-7-甲氧基-6-甲基-1，2，3，4-四氢萘。后面实施例8对图IV的合成路线有详述。
本发明的通式(I)化合物，可进一步反应而得通式I的其它化合物。例如R8为H的通式I化合物，可与合适取代的卤化物，在碱性条件下，在适当溶剂中反应，而得R8为取代基的通式(I)化合物。在一个方法中，例如将通式(I)化合物与溴化氰或N.N-二甲氨基磺酰氯或氯磷酸二甲酯和N，N-二异丙胺，在合适的溶剂中反应，可得通式(I)的化合物，其中R8分别为氰基、-SO2N(CH3)2，或-P(O)(OCH3)2。这些合成路线在实施例9-11有详述。
本发明还涉及杀虫剂组合物，所述组合物将杀虫有效量的活性化合物与本领域常用的，以促进活性成份分散的助剂和载体混合在一起用于具体所需的应用。本发明的杀虫剂组合物包括至少一种杀虫有效量的通式I化合物及至少一种与杀虫剂相容的载体，
其中通式I化合物的结构为：
Figure C03812343D00221
其中
-R和R1分别选自H和烷基；
-R2和R3相联而成五元或六元环，选自
＝NCH(R6)CH(R7)N(R8)-、＝NC(R6)＝C(R7)N(R8)-、
＝CHC(R6)＝C(R7)N(R8)-、＝CHN＝C(R7)N(R8)-、
＝N(CH2)3N(R8)-、＝NCH(R6)CH(R7)S-、
＝NCH(R6)CH(R7)O-，＝CHCH＝CH＝N-、＝NN＝CHN(R8)-、
＝NN＝NN(R8)-、-OCH(R6)CH(R7)N(R8)N＝及其互变异构体；
其中
R6和R7分别选自H和烷基；
R8选自H、烷基、氨基、硝基、氰基、甲酰基、-CH2R9-、-CH2OR9、-C(O)R9，-C(O)OR9、-CH2OC(O)R9、-C(O)N(R9)(R10)、-S(O)nR9-，-S(O)nN(R9)(R10)，这里n为0、1或2，Si(R9)3、-CH＝N(R9)、-P(O)(OR9)(OR10)、-P(O)(NR9R10)(NR9R10)、以及Y，其中Y代表i)上述五元或六元环的N-氧化物，或ii)形成OR3键，其中R3选自H和烷基；
R9和R10分别选自H、烷基、烷基羰基、烷氧基羰基芳基、芳烷基及杂芳基，其中芳基任选有一个或二个取代基，取代基选自卤素、烷基或卤烷基；-R4和R5连接成稠环，选自-(CR11)＝(C(R12)C(R13)＝C(R14)-，-SC(R15)＝C(R16)-，-C(R15)＝C(R16)S-以及CH＝C(R15)N＝CH-，
其中
R11和R14分别选自H、卤素及甲基；
R12选自H、卤素、氨基、(C1-C2)烷基、甲氧基、卤代甲氧基、(C2-C3)链烯基和(C2-C3)炔基；
R13选自H、卤素、氰基、(C1-C2)烷基、羟基、甲氧基、卤代甲基以及(C2-C3)炔基；
而R15和R16分别选自H、卤素、氰基、氨基，(C1-C2)烷基，(C2-C3)链烯基、(C2-C3)炔基、卤代甲基、羟基、甲氧基以及卤代甲氧基；
-X选自-CHR17-、-CH2CHR17-、-C3H6-、-C4H8-、-O-、-OCH2-、-OC2H4-、-OC3H6-、-CH2O-、-CH2OCH2-、-CH2OC2H4-、-S-、-SCH2-、-CH2S-、-CH3S(O)-、-CH2S(O)2-、-N(R17)CH2-以及-CH2N(R17)-；
其中R17选自H和烷基；
及其农业上适用的盐类；
条件是，当R和R1为氢；R2和R3连接成＝CHN＝C(R7)N(R8)，其中R7和R8为H；R4和R5连接成-C(R11)＝C(R12)C(R13)＝C(R14)；而X是-CHR17，其中R17为H；则R11、R12、R13或R14中至少有一个不是H；更进一步的附加条件是当R和R1为H；R2和R3连接成＝NCH(R6)CH(R7)N(R8)-，其中R6、R7和R8氢；R4和R5连接成-C(R11)＝C(R12)C(R13)＝C(R14)-，X是-CHR17，其中R17为H；则i)当R11、R13和R14为氢时，则R12就不是甲基；ii)当R11是氢，R13为甲基、且R14是溴时，则R12就不是氢；iii)当R11和R14是H，且R12是甲氧基时，则R13就不是甲氧基；iv)当X是-CH2CHR17-或-OCH2-；R17是H；R11和R14是氢、R12是甲氧基、且R13是甲基时；则R8就不是-S(O)nR9，其中n是2，且R9是甲基。
除了上述条件中所述的那些化合物组合物之外，较好的杀虫剂组合物中的通式I化合物的是下面这些：其中R2和R3连接成＝NCH(R6)CH(R7)N(R8)-、＝NC(R6)＝CR7N(R8)-或＝CHN＝C(R7)N(R8)-及其互变异构体，其中R8选自H、氰基，-S(O)nN(R9)(R10)以及-P(O)(OR9)(OR10)，其中n是2，而R9和R10分别选自H和烷基；R4和R5连接成稠环，其中R4和R5合并成-C(R11)＝C(R12)C(R13)＝C(R14)，其中R11是H，R12选自卤素和甲氧基，而R13选自卤素和(C1-C2)烷基；以及X选自-CHR17-，-CH2CHR17-、-OCH2-和-SCH2-。特别好的杀虫剂组合物化合物是这些：其中R9和R10均为甲基；R12选自氯和甲氧基；R13选自氯和甲基，而R14选自H、氯和甲基；X选自-CH2CHR17-和-OCH2-，其中R17是H。
本领域技术人员当然会认识到，剂型和毒剂的应用方式会在给定的应用中影响农药的活性。因此，为了农业应用，本发明杀虫剂化合物可配成粒径比较大的粒子(例如8/16或4/8美国筛目)，配成水可溶或水可分散性的颗粒，配成粉末化的粉剂、配成可湿性粉剂、可转化的浓缩物、水乳剂、溶液，或者任何其它已知的农业上适用的剂型，可按所需应用方式而定。应该知道在说明书中指定的量，只是大致量，在指定量之前面加上“大约”二字。
这些杀虫剂组合物既可用水稀释后喷洒，也可用粉剂或颗粒剂施用到需要杀灭昆虫的地方。这些配方含量少则可用0.1％、0.2％或0.5％，多则可用95％或更多，均以活性成份重量计算。
粉剂是活性成份与细分的固体的自由流动的混合物，这些固体如滑石、天然粘土、硅藻土、多种材料粉末诸如核桃壳粉、棉子粉及其它有机和无机固体，作为是为做农药的分散剂和载体。这些磨细的固体的平均细度为小于约50微米。本发明典型的粉剂为含有1份或少于一份的杀虫剂化合物和99.0份滑石粉。
可湿性粉剂也是杀虫剂的常用剂型，以很细的粒子使快速分散于水中或其它分散剂中。可湿性粉剂以干粉或作为乳化于水或其它液体的形式最终施用于需要防治昆虫的地区。典型的用于可湿性粉剂的载体包括漂白土、高岭土、二氧化硅以及其它强吸附剂，快速吸湿的无机稀释剂。可湿性粉剂通常制成含约5～80％活性成分，这取决于载体的吸附性，通常还含少量的润湿剂、分散剂或乳化剂以促进分散。例如实用的可湿性粉剂含有80.0份杀虫剂化合物，17.9份矮棕榈粘土和1.0份木素磺酸钠，以及0.3份磺化的脂族聚酯作为润湿剂。常将可湿性剂和/或油追加至储槽混合物中以促进在植物叶子上的分散。
其它使用的杀虫剂剂型是可乳化的浓缩剂(ECs)，它是均匀的液体组合物，可分散至水或其它分散剂中，可全部由杀虫剂化合物和液体或固体乳化剂组成，或可含液体载体，诸如二甲苯、重芳烃、异佛尔酮，或其它不挥发的有机溶剂。作为这些浓缩的杀虫剂的应用，可分散至水中或其它液体载体中，常用于田间喷洒。主要活性成分的重量百分比，可按所用的组合物的施用方式而酌情改变，但以杀虫剂组合物重量计，活性成份按占0.5～95％。
可流动剂类似于ECs，除了活性成分悬浮于液体载体(一般是水)之外。流动剂与ECs相同，可包含少量表面活性剂，典型的活性成分含量按组合物重量计范围在0.5～95％，常用为10～50％。应用时可将流动剂用水或其它液体媒介物稀释，常用作喷洒剂处理农田。
典型的用于农业使用剂型中的润湿剂、分散剂或乳化剂包括，但不限于，烷基和烷芳基磺酸盐及硫酸盐和它们的钠盐；烷基芳基聚醚醇；硫酸化的高碳醇；聚环氧乙烷；磺化的动物和植物油；磺化的石油润滑油；多羟基醇脂肪酸酯和这种酯的环氧乙烷的加成产物；以及长链硫醇和环氧乙烷的加成产物。许多其它类型可可用的表面活性剂是可购得的。当用表面活性剂时，一般在组合物中的组成为1～15％(按重量计)。
其它有用的剂型包括活性成份在相对不挥发的溶剂中的悬浮剂，这些溶剂如水、玉米油、煤油、丙二醇、或其它合适的溶剂。
用作杀虫剂的其它有用的剂型还包括活性成份在溶剂中的简单溶液，溶液应溶解成所需的浓度，可用的溶剂诸如丙酮，烷基化的萘类、二甲苯或其它有机溶剂。颗粒剂为将杀虫剂支载于相对粗的粒子上，特别可用于飞机散播或用于穿透植物冠丛复盖层。也可用加压喷洒剂，典型的气溶胶剂，其中将活性成分以细分的形式分散，以低沸点分散溶剂载体造成汽化的结果。水可溶或水可分散的颗粒剂是自由流动的，非粉状的，水中可快速溶解或可混的。农民在田间使用时，颗粒剂、可乳化的浓缩剂、可流动浓缩剂、乳化水剂、溶液等，可用水稀释，所得活性成分的浓度为0.1或0.2％至1.5％或2％，
本发明杀虫剂活性化合物可与一种或多种第二化合物做成剂型和/或施用。第二化合物包括(但不限于)：其它杀虫剂、植物生长调节剂、肥料、土壤调节剂或其它农业化学品。在应用本发明活性化合物中，不管是单独配方，或是与其它农业化学品共用，当然要用所述活性化合物的有效量，和活性化合物的有效浓度。用量范围可有变化，即约为0.01至约为3千克/公顷，更好为约0.03至约1千克/公顷。在田间应用时，杀虫剂会有损失，可用较高的应用比例(即上述提出的四倍比例)。
当本发明杀虫活性化合物与一种或多种第二化合物如其它农药诸如除草剂组合施用时，这些除草剂包括(但不限于)，例如N-(膦酰基甲基)甘氨酸(草甘膦)；芳氧基链烷酸类，诸如(2，4-二氯苯氧)乙酸(2，4-滴)，(4-氯-2-甲基苯氧基)乙酸(2甲4氯)，(+/-)-2-(4-氯-2-甲基苯氧基)丙酸(2甲4氯丙酸)；脲类，诸如，N，N-二甲基-N’-[4-(1-甲基乙基)苯基]脲(＂isoproturon＂)；咪唑啉酮类诸如2-[4，5-二氢-4-甲基-4-(1-甲基乙基)-5-氧代-1H-咪唑-2-基]-3-吡啶羧酸(灭草烟)；一个反应产物，组成是(+/-)-2-[4，5二氢-4-甲基-4-(1-甲基乙基)-5-氧代-1H-咪唑-2-基]-4-甲基苯甲酸和(+/-)2-[4，5-二氢-4-甲基-4-(1-甲基乙基)-5-氧代-1H-咪唑-2-基]-5-甲基苯甲酸(咪草酯)；(+/-)2-[4，5-二氢-4-甲基-4-(1-甲基乙基)-5-氧代-1H-咪唑-2-基]5-乙基-3-吡啶羧酸(咪草烟)，和(+/-)-2-[4，5二氢-4-甲基-4-(1-甲基乙基)-5-氧代-1H-咪唑-2-基]-3-喹啉羧酸(灭草喹)；二苯醚类，诸如5-[2-氯-4-三氟三甲苯氧基]-2-硝基苯甲酸(二氟羧草醚)，5-(2，4-二氯苯氧基)-2-硝基苯甲酸甲酯(甲羧除草醚)，以及5-[2-氯-4-(三氟甲基)苯氧基]-N-(甲基磺酰基)-2-硝基苯甲酰胺(氟黄胺苯醚)；羟基苄腈类，诸如4-羟基-3，5-二碘苄腈(磺苄腈)和3，5-二溴-4-羟基苄腈(溴苄腈)；磺酰脲类，诸如2-[[[[(4-氯-6-甲氧基-2-嘧啶基)氨基]羰基]氨基]磺酰基]苯甲酸(苄嘧黄隆)，2-氯-N-[[(4-甲氧基-6-甲基-1，3，5-三嗪-2-基)氨基]羰基]苯磺酰胺(achlorsulfuron)，2-[[[[[(4，6-二甲氧基-2-嘧啶基)氨基]羰基]氨基]磺酰基]苯甲酸(＂bensulfuron＂)，2-[[[[(4，6-二甲氧基-2-嘧啶基)氨基]羰基]氨基]磺酰基]-1-甲基-1H-吡唑-4-羧酸(吡嘧黄隆)，3-[[[[(4-甲氧基-6-甲基-1，3，5-三嗪-2-基)氨基]羰基]氨基]磺酰基]-2-噻吩羧酸(噻黄隆)和2-(2-氯乙氧基)-N[[(4-甲氧基-6-甲基-1，3，5-三嗪-2-基)氨基]羰基]苯磺酰胺(醚苯黄隆)；2-(4-芳氧基苯氧基)链烷酸类，诸如(+/-)-2[4-[(6-氯-2-苯并噁唑基)氧]苯氧基]丙酸(噁唑禾草灵)，(+/-)-2-[4[[5-(三氟甲基)-2-吡啶基]氧]苯氧基]丙酸(吡氟禾草灵)，(+/-)2-[4-(6-氯-2-喹喔啉)氧]苯氧基]丙酸(喹禾灵)以及(+/-)-2-[(2，4-二氯苯氧基)苯氧基]丙酸(禾草灵)；苯并噻二嗪酮类，诸如3-(1-甲基乙基)-1H-1，2，3-苯并噻二嗪-4-(3H)-酮-2，2-二氧化物(灭草松)；2-氯乙酰苯胺类，诸如N-(丁氧基甲基)-2-氯-N-(2，6-二乙基苯基)乙酰胺(丁草胺)，2-氯-N-(2-乙基-6-甲基苯基)-N-(2-甲氧基-1-甲基乙基)-乙酰胺(异丙甲草胺)，2-氯-N-(乙氧基甲基)-N-(2-乙基-6-甲基苯基)乙酰胺(乙草胺)，以及(RS)-2-氯-N-(2，4-二甲基-3-噻吩基)-N-(2-甲氧基-1-甲基乙基)乙酰胺(二甲吩草胺)；芳烃羧酸类，诸如3，6-二氯-2-甲氧基苯甲酸(麦草畏)；吡啶氧乙酸类，诸如[(4-氨基-3，5-二氯-6-氟-2-吡啶基)氧]乙酸(氟草烟)及其它除草剂。
当本发明杀虫活性化合物与一种或多种第二化合物如其它农药，诸如其它杀虫剂并用时，这些其它杀虫剂包括，例如有机磷杀虫剂：如毒死蜱、地亚农、乐果、马拉硫磷、甲基一六O五、以及trebufus；拟除虫菊酯杀虫剂诸如：杀灭菊酯(氰戊菊酯)、溴氰菊酯、甲氰菊酯、氟氰戊菊酯、α-氯氰菊酯、联苯菊酯、可溶性氯氟氰菊酯、醚菊酯、S-氰戊菊酯、四溴菊酯、七氟菊酯、乙氰菊酯、β-氟氯氰菊酯、以及氟丙菊酯；氨基甲酸酯类杀虫剂，诸如：涕灭威、甲萘威、克百威以及灭多威；有机氯杀虫剂诸如硫丹、异狄氏剂、七氯以及林丹；苯甲酰脲类杀虫剂诸如：除虫脲、杀虫隆、伏虫隆、定虫隆、flucycloxurn、氟铃脲、氟虫脲、以及虱螨脲；以及其它杀虫剂，诸如：双虫脒、四虫螨、唑螨酯、噻螨酮、多休养霉毒、以及吡虫啉。
当本发明杀虫活性化合物与其它农药，诸如杀菌剂合用，即与一种或多种第二化合物并用时，这些杀菌剂包括：例如苯并咪唑类杀菌剂：苯菌灵、多菌灵、噻菌灵、甲基硫菌灵、1，2，4-三唑类杀菌剂，例如：氟环唑、环菌唑、氟硅唑、粉唑醇、丙环唑，戊唑醇、三唑酮以及三唑醇；取代酰苯胺杀菌剂，例如：甲霜灵、恶霜灵、腐霉利、以及乙烯菌核利；有机磷杀菌剂，诸如：三乙膦酸铝(乙磷铝)、异稻瘟净、吡嘧磷、敌瘟磷、以及甲基立枯磷；吗啉类杀菌剂，诸如：丁苯吗啉、十三吗啉以及十二环吗啉；其它内吸性杀菌剂例如：氯苯嘧啶醇、抑霉唑、咪鲜胺、三环唑以及嗪氨灵；二硫代氨基甲酸酯类杀菌剂，诸如：代森锰锌、代森锰、丙森锌、代森锌、以及福美锌；非内吸收类杀菌剂诸如：百菌清、苯氟磺胺、二嗪农、异菌脲、克菌丹、二硝巴豆酸酯、多果定、氟啶胺、gluazatine，五氯硝基苯、tricylamide以及井冈霉素。无机杀菌剂，例如铜和硫的化合物产品，以及其它杀菌剂。
当本发明杀虫活性化合物与其它农药，诸如其它一种或多种第二化合物例如杀线虫剂并用时，这些杀线虫剂包括，诸如：克百威、丁硫克百威、tubufus、涕灭威、灭线磷、虫胺磷、杀线威、氯唑磷、硫线磷，以及其它杀线虫剂。
当本发明杀虫活性化合物与其它一种或多种第二化合物合用时，例如与植物生长调节剂共同，这些植物生长调节剂包括：例如：抑芽丹、矮壮素、乙烯利、赤霉素、甲哌嗡、脱叶灵、抗倒胺、抑芽唑、多效唑、烯效唑、氯酞酸、稠环酸、trinexapac-ethyl、以及其它植物生长调节剂。
实施例11-(2-咪唑-2-基)-6-甲氧基-5-甲基茚满(化合物6)的合成
步骤A中间体(4-甲氧基-3-甲基苯基)-甲醛的合成
将180ml(1.6摩尔正己烷溶液，0.29摩尔)正丁基锂与250ml四氢呋喃所成的溶液，搅拌下冷至-60℃以下，以保持-55℃以下的反应混合物的速度加入50克(0.26摩尔)5-溴-2-甲氧基甲苯(市售品)的溶液。加完后将反应混合物冷至约-60℃至-70℃，搅拌70分钟。在保持反应混合物的温度低于-50℃的情况下，加入80mlDMF(0.99摩尔)。加完后，将反应混合物倾注至稀氯化钠溶液中，然后用乙醚提取二次。合并提取物，用稀氯化钠溶液洗一次，用饱和氯化钠溶液洗一次，之后用硫酸钠干燥。过滤混合物，减压浓缩滤液，得35.7克油状残留物。将油状物用硅胶柱层析提纯，以正己烷与乙酸乙酯混合物为洗提液。所要的洗提液合并后减压浓缩，得23.2克所需化合物，NMR(核磁谱)与预定的结构相一致。
步骤B中间体3-(4-甲氧基-3-甲基苯基)-丙酸的合成
将甲酸40.3克(0.88摩尔)搅拌并冷却至5℃以下，以保持反应温度低于20℃的速度加入三乙胺36.9克(0.37摩尔)，加完后将22.0克(0.15摩尔)(4-甲氧基-3-甲基苯基)-甲醛加至反应混合物中，接着加22.2克(0.15摩尔)2，2-二甲基-1，3-二噁烷-4，6-二酮。加完后将反应混合物加热至60℃，搅拌约15分钟。移去热源，此时因放热反应在反应器中会放出气体。放热反应平息后再次加热反应混合物至75～95℃二小时。之后用冰水浴冷却反应混合物，加入200ml水，再加入100ml4N盐酸。然后用乙醚提取混合物二次。全并提取液用稀氯化钠溶液洗二次，再用饱和氯化钠溶液洗一次，用硫酸钠干燥。过滤混合物，减压浓缩滤液，得到残留的固体。将此固体溶于1N碳酸钾水溶液，并用乙醚洗二次。水层用浓盐酸酸化，再用乙醚提取二次，合并乙醚层用稀氯化钠水溶液洗一次，再用硫酸钠干燥。过滤混合物，减压浓缩，得26.3克所需化合物NMR(核磁谱)与预定的结构相一致。
步骤C中间体6-甲氧基-5-甲基茚满-1-酮的合成
在干燥氮气保护下，将5.0克(0.029摩尔)的3-(4-甲氧基-3-甲基苯基)-丙酸(i)在100mlEatons试剂中的溶液加热至39℃，此时会发生放热反应而升温至49℃，移去热源，让反应混合物的温度回至35℃。再置热源，反应混合物再热至39℃并搅拌8小时。然后将反应混合物倾注至冰与水中，用二氯甲烷提取混合物二次，合并提取物，用饱和碳酸氢钠水溶液洗三次，用硫酸钠干燥有机层并过滤，减压浓缩液，用硅胶柱层析提纯残留物，先用石油醚与二氯甲烷混合物后用纯二氯甲烷为洗提液，合并所需洗出液部分，减压浓缩，得到所需的化合物。NMR(核磁谱)与预定的结构相一致。重复该反应二次，得到二次反应所需化合物总量为10.7克。
步骤D中间体5-甲氧基-6-甲基茚-3-甲腈(iii)的合成
将10.7克(0.061摩尔)6-甲氧基-5-甲基茚满-1-酮(ii)、29.7克(0.182摩尔)氰基膦酸二乙酯及6.1克(0.182摩尔)氰化锂在无水THF250ml所成的溶液于室温搅拌5小时。对反应混合物的气相色谱分析表明反应未完全。将反应混合物加热至45℃并搅拌约16小时。此时于反应混合物中加水、分层，用乙醚提取。提取物的气相色谱分析表明反应己完成约10％。追加入0.182摩尔氰基膦酸二乙酯及氰化锂至反应混合物中，加热至45℃并继续8小时。然后将反应混合物倾注至约300ml饱和氯化钠的水溶液中，用2×300ml醋酸乙酯提取，合并提取液，之后用饱和氯化钠水溶液洗三次并用硫酸钠干燥。过滤混合物，将滤液减压浓缩得残留物，将残留物溶于甲苯，再减压浓缩得残留物。加入500ml甲苯及20.7克(0.182摩尔)三氟化硼乙醚溶液处理该残留物。加完后将反应混合物于室温搅拌6小时，处理反应混合物如前，得残留物。用硅胶柱层析提纯该残留物，以己烷与乙酸乙酯混合物为洗提液，合并所需洗提液部分后减压浓缩，得2.8克所需化合手，NMR(核磁谱)与预定的结构相一致。
步骤E中间体6-甲氧基-5-甲基二氢化茚甲腈(iv)的合成
在氮保护下，将0.1克(催化剂)10％钯炭及0.05克5％铂炭(催化剂)放至250ml帕尔(Parr)氢化瓶中，接着加入由2.5克(0.014摩尔)5-甲氧基-6-甲基茚-3-甲腈(iii)与100ml乙酸乙酯所成的溶液。将混合物在帕尔氢化器中氢化45分钟，此时反应中已有理论量的氢气吸收。将反应混合物经硅藻土填板用二氯甲烷洗涤，减压浓缩二氯甲烷得2.4克所需化合物，核磁谱与预定的结构相一致。
步骤F中间体对甲苯磺酸乙二胺盐的合成
将50克(0.263摩尔)水合对甲苯磺酸与30ml水在150克冰中的混合物进行搅拌，一次加入22.1克(0.368摩尔)乙二胺，加完后搅拌反应混合物90分钟，此后减压浓缩反应混合物以移去大部分水留存残余物。残余物用2-丙醇处理，再减压浓缩至存残留物，再重复操作二次自残留物蒸去2-丙醇，得61.2克所需化合物。核磁谱与预定的结构相一致。
步骤G化合物6的合成
将2.4克(0.013摩尔)6-甲氧基-5-甲基茚满甲腈(iv)与11.2克(0.045摩尔)对甲苯磺酸的乙二胺盐的混合物搅拌并加热至140～160℃。保持此温度约4.5小时。然后冷却此反应混合物至室温并溶于5％碳酸钾水溶液及二氯甲烷的混合物。分出有机层，水层用二氯甲烷提取二次。合并提取物，有机层用5％碳酸钾水溶液洗一次。有机层用硫酸钠干燥并过滤。减压浓缩滤液得固体残留物。将残留物用II级碱性氧化铝(含3％水)柱层析提纯，以二氯甲烷与甲醇的混合物为洗提液，合并所需洗提液部分，减压浓缩，得到约2.1克所需化合物。核磁谱与预定的结构相一致。
实施例21-(2-咪唑啉-2-基)-7-甲氧基-6-甲基-1，2，3，4-四氢萘(化合物50)的合成
步骤A中间体4-(4-甲氧基-3-甲基苯基)-丁炔-3-醇-1的合成
将4.6克(0.023摩尔)5-溴-2-甲氧基甲苯(市售品)，3ml(0.040摩尔)3-丁炔醇-1，0.30克(0.002摩尔)碘化亚铜，14ml(0.100摩尔)三乙胺以及0.25克(0.0004摩尔)二氯双(三苯基膦)合钯(II)在60mlDMF中的混合物，于90℃加热18小时。之后将反应混合物倾注至水中，用乙醚提取。乙醚提取物用硫酸钠干燥并过滤。将滤液减压浓缩得残留物，用硅胶柱层析提纯残留物，以已烷与乙酸乙酯为洗提液。合并所需分出的洗提物，减压浓缩得1.5克所需化合物。其核磁谱与预定的结构相一致。
步骤B中间体4-(4-甲氧基-3-甲基苯基)-丁醇的合成
该化合物的制备类似于实施例1的步骤E，系将1.4克(0.0074摩尔)4-(4-甲氧基-3-甲基苯基)-丁炔-3-醇-1，存在0.05克(催化剂)10％钯炭在150ml甲醇的混合物的情况下氢化。用硅胶柱层析提纯反应产物，以已浣与乙酸乙酯的混合物为洗提液。合并所需分出的洗提物，减压浓缩，减压浓缩得0.8克所需化合物。其核磁谱与预定的结构相一致。此反应可大规模重复。
步骤C4-(4-甲氧基-3-甲基苯基)-丁酸(i)中间体的合成
将1.7克(0.009摩尔)4-(4-甲氧基-3-甲基苯基)-丁醇-1在50ml丙酮中的溶液搅拌下冷至0～4℃，然后滴加约15至20ml(过量)琼斯(Jones)试剂。加完后，将反应混合物于0℃搅拌2小时。让其温热至室温并搅拌3小时。然后用异丙醇稀释并过滤。滤饼用丙酮洗涤，合并滤液及洗出液，减压浓缩至留下残留物。将残留物用二氯甲烷与水共溶而分层，分出有机层用水洗涤。用硫酸钠干燥有机层并过滤。减压浓缩滤液得残留物。真空干燥残留物，得1.1克所需化合物。核磁谱与预定的结构相一致。重复该反应可得又一份本化合物。
步骤D7-甲氧基-6-甲基-2，3，4-三氢萘酮-1(ii)中间体的合成
本化合物的制备类似于实施例1步骤C。将0.9克(0.0043摩尔)4-(4-甲氧基-3-甲基苯基)-丁酸(i)用30ml试剂(Eaton’sReagent)反应。对反应物用硅胶柱层析提纯，以已烷与乙酸乙酯为洗提液。合并所需的分出洗提物，减压浓缩，得0.6克所要的化合物，其核磁谱与预定的结构相一致。
步骤E中间体7-甲氧基-6-甲基-1，2，3，4-四氢萘甲腈的合成
将0.6克(0.0032摩尔)7-甲氧基-6-甲基-2，3，4-三氢萘-1-酮(ii)，2.2ml(0.0170摩尔)三甲基甲硅烷基氰与催化量的氯化铝于20毫升甲苯所成的溶液搅拌下加热至70℃，并保持此温18小时。然后用100ml已烷处理，经硅藻土过滤。将滤液减压浓至呈油状残留物，此即中间体产物，名为7-甲氧基-6-甲基-1-(1，1-二甲-1-硅杂乙氧基-1，2，3，4-四氢萘甲氰(氰甲硅烷中间体)。如此制备的1-硅杂乙氧基中间体用100毫升乙腈处理，与2.0克(0.013摩尔)碘化钠、1.8ml(0.014摩尔)三甲基甲硅烷基氯与0.1ml水，于室温搅拌约72小时。然后将反应混合物倾注至水中，用乙酸乙酯提取。提取物依次用稀偏亚硫酸氢钠水溶液，水洗涤，硫酸钠干燥。减压浓缩此混合物至残留物，此混合物含主题化合物和中间体产物名称为：7-甲氧基-6-甲基-3，4-二氢萘甲腈(中间体(iii))。以相似于实施例1的步骤E，将3，4-二氢萘甲腈中间体和主题化合物的混合物用帕尔氢化器，存在0.1克(催化剂)10％铂炭及0.1克(催化剂)10％钯炭，于100ml乙酸乙酯中氢化。经90分钟氢化后，将反应混合物经硅藻土过滤，用二氯甲烷洗滤饼，合并滤液减压浓缩至得残留物。残留物的核磁谱表明仍然为主题化合物与3，4-二氢萘甲腈中间体的混合物。将主题化合物与3，4-二氢萘甲腈中间体的混合物重做氢化7小时，对反应混合物后处理如前得约0.25克主题化合物。其核磁谱与预定的结构相一致。
步骤F合成化合物50
本化合物的制备类似于实施例1步骤G。将0.1克(0.0005摩尔)的7-甲氧基-6-甲基-1，2，3，4-四氢萘腈(iv)与1.2克(0.0048摩尔)的p-甲苯磺酸的乙二胺盐(按照实施例1步骤F制备)反应。反应产物通过硅胶柱层析提纯，以二氯甲烷和甲醇为洗提液。合并所需的分出洗提物，减压浓缩，得0.07克主题化合物，其核磁谱与预定的结构相一致。
实施例34-(2-咪唑啉-2-基)-7-甲基苯并二氢吡喃(化合物88)的合成
步骤A3-(3-甲基苯氧基)-丙醇-1中间体的合成
将25克(0.23摩尔)3-甲基苯酚与18.8克(0.20摩尔)3-氯丙醇-1在100ml10％氢氧化钠水溶液所成的溶液搅拌、回流加热约40分钟。之后将反应混合物冷至室温，用乙醚3×100ml提取。合并提取物，用稀氢氧化钠水溶液3×50ml洗，然后用硫酸钠干燥。过滤混合物，减压浓缩，得29克标题化合物。核磁共振谱与预定的结构相一致。
步骤B3-(3-甲基苯氧基丙酸(i)中间体的合成
该化合物的制备类似于实施例2的步骤C，由2.0克(0.012摩尔)的3-(3-甲基苯氧基)-丙醇-1与10ml琼斯试剂在30ml丙酮中反应。得到所需的化合物1.5克。核磁共振谱与预定的结构相一致。
步骤C7-甲基苯并二氢吡喃-4-酮(ii)中间体的合成
将5.0克(0.028摩尔)3-(3-甲基苯氧基)丙酸(i)与5.3克(0.042摩尔)草酰氯在100ml二氯甲烷的溶液搅拌下冷至-5℃，加入几滴DMF。加完后，将反应混合物让其温热至室温，搅拌约2小时。然后将反应混合物减压浓缩至剩下残留物：此即为3-(3-甲基丙氧基)-丙酰氯，该酰氯于氮气保护下放置约18小时，然后溶于50ml二氯甲烷中。搅拌此溶液冷至.4℃并一次加入4.1克(0.031摩尔)氯化铝而温度应保持5℃或更低。加完后反应混合物保持5℃约3小时，然后将反应混合物倾注至冰中。用3×100ml二氯甲烷提取，合并提取物，用2×50ml水洗，用硫酸钠干燥。将混合物过滤，减压浓缩滤液得残留物。用硅胶柱层析提纯残留物，洗提液为乙酸乙酯与已烷的混合物。合并所需的洗提部分，减压浓缩，得3.5克所需化合物。核磁共振谱与预定结构相一致。
步骤D7-甲基-苯并二氢吡喃-4-甲腈(iv)中间体的合成
该化合物的制备类似于实施例2步骤E，由1)将1.0克(0.006摩尔)7-甲基苯并二氢吡喃酮-4(ii)与1.8克(0.018摩尔)三甲基甲硅烷基氰与0.2克(催化剂)氯化铝于30ml甲苯中反应而得中间体，名为：7-甲基-4-(1，1-二甲基-1-硅杂乙氧基)-苯并二氢吡喃-4-甲腈(氰基甲硅烷中间体)，然后2)将1-硅杂乙氧基中间体与3ml(0.024摩尔)三甲基甲硅烷基氯、3.6克(0.024摩尔)碘化钠及0.2毫升水在30ml乙腈中反应，得0.8克标题化合物。与实施例2步骤E相反，不需氢化步骤即可得所需化合物。核磁共振谱与预定结构相一致。
步骤E化合物88的合成
该化合物的制备类似于实施例1的步骤G，由0.6克(0.003摩尔)7-甲基苯并二氢吡喃-4-甲腈(iv)与2克(0.008摩尔)对甲苯磺酸乙二胺盐(由例1步骤F制备)。将反应产物在II级碱性氧化铝(含3％水)色谱中提纯，用二氯甲烷与甲醇的混合物为洗提液。将所需洗出液合并并减压浓缩得标题化合物0.25克。核磁共振谱与预定的结构相一致。
实施例41-(咪唑-5-基)-6-甲氧基-5-甲基二氢化茚(化合物257)的合成
步骤A中间体2，4，5-三碘咪唑与2.5-二碘咪唑混合物的合成
将15.0克(0.220摩尔)咪唑(可市售)在110ml 2N氢氧化钠中的溶液搅拌冷至约10℃，另加入540ml2N氢氧化钠水溶液。将168克碘(0.661摩尔)加至至500ml二氯甲烷中，会有些碘不溶解。另加500ml二氯甲烷至碘混合物中但也不能溶解所有的碘。保持反应混合物约10℃、费1小时滴加溶有碘的溶液至咪唑水溶液中。加完后将未溶解的碘同样用另1小时分次加至咪唑溶液中。加完后让反应混合物温热至室温，搅拌约18小时。自反应混合物分出水层，用固体亚硫酸钠处理，以分解所有未反应的碘。用浓盐酸调节水层的pH约为5，而用乙酸乙酯提取混合物三次。合并提取液用硫酸钠干燥并过滤。将滤液减压浓缩至剩残留物。该残留物的薄板层析表明其为2，4，5-三碘咪唑与2，5-二碘咪唑的混合物。将残留物用少量乙酸乙酯研磨并过滤以收集得固体。将滤液减压浓缩得残留物干燥得约2，4，5-三碘咪唑。过滤收集得的固体经干燥约可得41.7克2，5-二碘咪唑。2，4，5-碘衍生物与2，5-二碘衍生物的核磁共振谱表明与预定的结构相一致。
步骤B 5-碘咪唑(vi)中间体的合成
将17.9(0.040摩尔)2，4，5-三碘咪唑与41.7克(0.130摩尔)2，5-二碘咪唑(v)及500ml乙醇所成混合物的溶液在1500ml水中搅拌，分次加入75克(0.595摩尔)亚硫酸钠，加完后将反应混合物加热至回流搅拌18小时。然后将反应混合物冷至室温，减压浓缩以移去乙醇。用2×700ml乙酸乙酯提取该浓缩水溶液，再用2×250ml正丁醇提取。合并提取物用硫酸钠干燥并过滤。将滤液减压浓缩得残留物，残留物在水中混成浆状，过滤而收得固体，干燥得约13.2克标题化合物。核磁共振谱与预定的结构相一致。
步骤C中间体1-(三苯基甲基)-4-碘咪唑(vii)的合成
将100mlDMF搅拌，加入13.2克(0.068摩尔)5-碘咪唑，接着加入18.9克(0.068摩尔)三苯基甲基氯化物及3.3克(0.033摩尔)三乙胺。加完后将反应混合物于室温搅拌18小时。然后将反应混合物倾注至碎冰中，继续搅拌至冰融化，过滤收集得固体，在乙醚中研成粉末，再过滤而得固体，用乙醚洗得标题化合物。将乙醚滤液减压浓缩得残留物，再用乙醚研磨得另一份标题化合物，得全部标题化合物约5.0克。核磁共振谱与预定结构相一致。
步骤D3-(咪唑-5-基)-5-甲氧基-6-甲基茚(viii)中间体的合成
将5.0克(0.012摩尔)1-(三苯基甲基)-4-碘咪唑(vii)于约200ml无水二氯甲烷所成的溶液搅拌下冷至约21℃，加入3.84ml(3.0摩尔浓度乙醚溶液：0.012摩尔)乙基溴化镁。加完后，将反应混合物于23℃搅拌约1小时，然后一次加入2.0克(0.012摩尔)6-甲氧基-5-甲基茚满-1-酮(ii)(制法类似于实施例1步骤D)在50ml二氯甲烷中的溶液。加完后将反应混合物于室温搅拌约18小时。然后将反应混合物倾注至内有饱和氯化铵水溶液的分液漏斗中，分出有机层，水层用二氯甲烷提取二次，合并提取液及有机层，用硫酸钠干燥，过滤。将滤液减压浓缩至成残留物。该残留物溶于甲醇，加入4N盐酸溶液，加完后将混合物于室温搅拌18小时。然后减压蒸去混合物中甲醇，余下水溶液残留物。用乙醚洗残留物三次，之后用固体碳酸钠调节残留物的pH约为8～9。将混合物用二氯甲烷提取，用硫酸钠干燥提取物。过滤混合物，将滤液减压浓缩至得残留物。将此残留物再用4N盐酸处理，用乙醚洗混合物，加入固体碳酸钠调节水层的pH约为8～9。将混合物用二氯甲烷提取，提取物用硫酸钠干燥，过滤混合物，减压浓缩滤液，得到约0.5克标题化合物。核磁共振谱与预定的结构相一致。
步骤E化合物257的合成
该化合物的制备类似于实施例1的步骤E，将0.5克(0.0022摩尔)3-(咪唑-5-基)-5-甲氧基-6-甲基茚(viii)与0.1克(催化剂)10％钯炭与0.1克(催化剂)氧化铂水合物在40ml乙醇中氢化。生成标题化合物0.42克，mp.68～70℃，核磁共振谱与预定的结构相一致。
实施例54-(2-咪唑啉-2-基)-6甲氧基-7-甲基-苯并二氢吡喃(化合物89)的合成
步骤A中间体3-(4-甲氧基-3-甲基苯氧基)-丙腈的合成
搅拌7.0克(0.050摩尔)3-甲基-4-甲氧苯酚(已知化合物)在20mL丙烯腈的溶液，加入0.4mL氢氧化苄基三甲基铵(
Figure C03812343D0034163211QIETU
B)。添加完毕，反应混合物加热至回流，同时搅拌21小时。然后，反应混合物冷却至室温，用100mL二乙醚稀释。该混合物先用三份各50mL的10％氢氧化钾水溶液洗涤，再用三份各50mL 4N盐酸水溶液洗涤。有机层用硫酸钠干燥，过滤混合物。滤液减压下浓缩，得6.0克标题化合物。核磁共振谱与预定结构相一致。
步骤B中间体3-(4-甲氢基-3-甲基苯氧基)丙酸(i)的合成
将4.0克(0.048摩尔)3-(4-甲氧基-3-甲基苯氧基)-丙腈于100ml浓盐酸所成的溶液加热回流6小时。之后反应混合物任其冷至室温再搅拌18小时。过滤收集固体，用水泥。然后将其溶于10％氢氧化钾水溶液，过滤此溶液，滤液用浓盐酸酸化，过滤得沉淀，用水洗，之后溶于乙酸乙酯，用硫酸钠干燥此溶液，并过滤混合物。减压浓缩滤液，得2.4克标题化合物。核磁共振谱与预定结构相一致。
步骤C中间体6-甲氧基-7-甲基-苯并二氢吡喃-4-酮(ii)的合成
该化合物的制备类似于实施例3的步骤C，将0.1克(0.00056摩尔)3-(4-甲氧基-3-甲基苯氧基)-丙酸(i)，0.1克(0.00084摩尔)草酰氯，以及加有几滴DMF在10ml二氯甲烷中的混合物于约5℃反应。得到相应的丙酰氯.然于约0℃，将此酰氯与0.08克(0.00061摩尔)氯化铝在10ml二氯甲烷中反应，得0.09克标题化合物。该核磁共振谱与预定的结构相一致。该反应可以较大规模重复。
步骤D中间体6-甲氧基-7-甲基苯并二氢吡喃-4-甲腈的合成
该化合物的制备类似于实施例2步骤E，由1)将0.9克(0.0046摩尔)6-甲氧基-7-甲基苯并二氢哟喃-4-酮在30ml甲苯中，与0.1克三氯人铝(催化剂)与1.40克(0.0138摩尔)三甲基甲硅烷基氰化物反应，所得中间体产物名称为：6-甲氧基-7-甲基-4-(1.1-二甲基-1-硅杂乙氧基)-苯并二氢吡喃-4-甲腈(氰-甲硅烷基中间体)，然后2)将1-硅杂乙氧基中间体在30ml乙腈中与2.8克(0.0184摩尔)碘化钠及0.12ml水反应，得0.6克标题化合物。与例2步骤E不同，不需氢化即可得标题化合物。核磁共振谱与预定结构相一致。
步骤E化合物89的合成
该化合物的合成类似于实施例1的步骤G，由0.5克(0.002摩尔)7-甲基-6-甲氧基苯并二氢吡喃-4-甲腈(iv)与2克(0.008摩尔)对甲苯磺酸乙二胺盐(见实施例1步骤F制备)。反应产物由II级碱性氧化铝(含3％水)柱层析提纯，以99∶1的二氯甲烷与甲醇之比为洗脱液，合并所需洗脱液，减压浓缩，得0.30克标题化合物，核磁共振谱与预定的结构相一致。
实施例64-(2-咪唑啉-2-基)-7-甲基-2H，3H，4H-苯并[e]噻喃(化合物141)的合成
步骤A中间体3-(3-甲基苯硫基)丙酸甲酸的合成
将0.8克(0.009摩尔)三乙胺加至1.0克(0.008摩尔)3-甲基苯硫醇与1.4克(0.009摩尔)3-溴丙酸甲酯于10mlDMF所成的溶液中。加完后将反应混合物升温至约30℃。用机械振摇器振摇反应混合物1小时。之后由气相层析分析表明反应混合物的反应已完全。核磁共振分析反应混合物知已得标题化合物。
所做的重复反应为：将15.7克(0.126摩尔)3-甲基苯硫醇与23.3克(0.139摩尔)3-溴丙酸甲酯于约140mlDMF所成的溶液先用冰水溶冷却，加入14.1克(0.139摩尔)三乙胺。加完后将反应混合物让其温热至室温，搅拌反应18小时。之后将反应混合物倾注至200ml水中，用乙酸乙酯3×200ml提取混合物。合并提取液，用水洗涤，再用饱和氯化钠水溶液3×50ml洗。用硫酸钠干燥有机层，过滤混合物。减压液缩滤液得残留物。制得标题化合物23.5克。核磁共振谱与预定结构相一致。
步骤B中间体3-(3-甲基苯硫基)-丙酸的合成
将22.0克(0.105摩尔)3-(3-甲基苯硫基)-丙酸甲酯于200ml甲醇中的溶液搅拌，加入10％氢氧化钾水溶液，加完后将反应混合物于室温搅拌18小时。气相层析分析反应混合物表明反应未完全。另加30ml10％氢氧化钾水溶液，将反应混合物再搅拌3小时。然后将100ml水加至反应混合物中，减压蒸去甲醇，用乙醚3×50ml洗残留物。将冷却的残留物用10％盐酸酸化，用100ml乙醚提取，用硫酸钠干燥提取物并过滤，减压浓缩滤液至得油状残留物，将残留物与己烷搅拌并冷却，结果生成固体物，过滤得固体物并干燥，得17.0克标题化合物。核磁共振谱与预定的结构相一致。
步骤C7-甲基-2H，3H-苯并[e]噻喃-4-酮(ii)中间体的合成
该化合物的制备类似于实施例3步骤C，将15克(0.077摩尔)3-(3-甲基苯硫基)-丙酸(i)，14.5克(0.116摩尔)草酰氯与几滴DMF在200ml二氯甲烷中，于5℃反应，得到相应的丙酰氯化合物，将此酰氯化物用11.3克(0.085摩尔)氯化铝在200ml二氯甲烷约在0℃反应，反应产物用硅胶柱层析提纯，用乙酸乙酯与己烷为洗脱液，合并所需洗脱液，减压浓缩，得7.0克标题化合物，核磁共振谱与预定的结构相一致。
步骤D7-甲基-2H，3H，4H-苯并[e]噻喃-4-甲腈(iv)中间体的合成
该化合物的制备类似于实施例2步骤E，由1)将3.5克(0.0196摩尔)7-甲-2H，3H-苯并[e]噻喃-4-酮(ii)与11.2克(0.0588摩尔)三甲基甲硅烷基氰，存在0.3克(催化剂)氯化铝在约100ml甲苯中反应，可得中间体氰基-硅烷基产物然后2)将氰基硅烷基产物与8.5克(0.0784摩尔)三甲基甲硅烷基氯化物，11.8克(0.0784摩尔)碘化钠及0.52ml水在100ml乙腈中反应，得3.3克标题化合物，与例2步骤E不同不需做氢化步骤即可得标题化合物。核磁共振谱与预定结构相一致。
步骤E化合物141的合成
此化合物的合成类似于实施例1步骤G，由3.5克(0.0196摩尔)7-甲基-2H，3H-苯并[e]噻喃-4-甲腈(iv)与对甲苯磺酸乙二胺盐(例1步骤F制得)反应而得。由II级氧化铝(碱性一3％水)柱层析提纯反应产物以二氯甲烷与甲醇99:1的混合物为洗脱液，合并所需洗脱液部分，减压浓缩可得1.2克标题化合物。核磁共振谱与预定结构相一致。
实施例7{[4-(6-甲氧基-7-甲基苯并二氢吡喃-4基)-咪唑基]碘酰基}二甲胺(化合物278)的合成
步骤A中间体{[4-(4-羟基-6-甲氧基-7-甲基苯并二氢吡喃-4-基)-咪唑基]磺酰基}二甲胺(iii)的合成
将4.6克(0.016摩尔)[(4-碘咪唑基)-磺酰基]二甲胺(可用市售品)于10ml无水二氯甲烷中的溶液，加入5.7ml(0.018摩尔)乙基溴化镁(乙醚中3M溶液)。加完后，将反应混合物搅拌2.5小时。之后加入3.0克(0.016摩尔)6-甲氧基-7-甲基苯并二氢吡喃-4-酮(ii)(由例5步骤(制得)，再将反应混合物搅拌18小时。然后将反应混合物倾注至100ml氯化铵水溶液中，用3×100ml二氯甲烷提取。合并提取液用50ml水洗，再用硫酸钠干燥。过滤混合物，减压浓缩滤液得残留物，用II级碱性氧化铝(含3％水)柱层析提纯此残留物，用99:1二氯甲烷：甲醇作为洗脱液。合并所需洗脱液，减压浓缩，得3.3克标题化合物，核磁共振谱与预定的结构相一致。
步骤B{[4-(6-甲氧基-7-甲基(2H-苯并二氢吡喃-4-基)-咪唑基]磺酰基}二甲胺(ix)中间体的合成
将0.1克(0.00027摩尔){[4-(4-羟基-6-甲氧基-7-甲基苯并二氢吡喃-4-基)-咪唑基]磺酰基}二甲胺(ix)于10ml二氯甲烷所成的溶液在冰水浴中冷却，之后加入0.2ml三氟醋酸。加完后让反应混合物温热至室温，再搅拌1小时。然后将反应混合物倾注至20ml碳酸氢钠水溶液中，用3×30ml二氯甲烷提取混合物，合并提取物，用硫酸钠干燥并过滤，减压浓缩滤液得残留物，该残留物的核磁共振谱与预定的结构相一致。该反应可以较大规模重复，用1.5克(0.0041摩尔){[4-(4-羟基-6-氧基-7-甲基苯并二氢吡喃-4-基)-咪唑基]磺酰基}二甲胺(ix)可得1.3克标题化合物。其核磁共振谱与预定结构相一致。
步骤C化合物278的合成
将0.1克(0.0004摩尔){[4-(6-甲氧基-7-甲基(2H-苯并吡喃-4-基)-咪唑基)磺酰基]二甲胺(ix)，0.01克(催化剂)10％钯炭及0.005克(催化剂)5％铂炭在75ml甲醇中的混合物，用帕尔氢化器氢化2小时。洗脱液减压浓缩得残留物。残留物的核磁共振谱与预定的结构相一致。此反应以较大规模重复，即用1.1克(0.0044摩尔){[4-(6-甲氧基-7-甲基(2H-苯并吡喃-4-基)咪唑基)磺酰基]二甲胺。将反应产物在II级氧化铝(碱性含3％水)柱层析提纯，分别用二氯甲烷及二氯甲烷与甲醇之比为99.5:0.5的混合物为洗脱剂，将所需洗脱液部分合并，并减压浓缩得0.38克标题化合物，mp.138～139℃。核磁共振谱与预定结构相一致。
实施例8 1-咪唑-2-基7-甲氧基-6-甲基-1，2，3，4-四氢萘(化合物215)的合成
步骤A 1-(咪唑基甲氧基)-3，3-二甲基-3-硅杂丁烷中间体的合成
将1.2克60％氢化钠(0.03摩尔矿物油混合物)在25ml THF的悬浮液搅拌下冷至0℃～5℃，滴加由2.0克(0.03摩尔)咪唑在30ml四氢呋喃所成的溶液。加完后将反应混合物于0℃搅拌15分钟。然后滴加4.7克(0.03摩尔)2-(三甲基甲硅烷基)乙氧基甲基氯化物在10ml四氢呋喃中的溶液。将反应混合物任其回至室温，搅拌18小时。然后将反应混合物与水50ml搅拌，用乙酸乙酯提取混合物。提取液用饱和氯化钠水溶液洗，然后用硫酸镁干燥。过滤混合物，减压浓缩滤液至得残留物。将残留物减压蒸溜，得3.8克标题化合物；bp71℃/0.1乇，核磁共振谱与预定结构相一致。
步骤B 7-甲氧基-6-甲基-3，4-二氢萘基(三氟甲基)磺酸盐(x)中间体的合成
该化合物按照类似于Pal(Synthesis 1995，1485)所述，通过使4.2克(0.022摩尔)7-甲氧基-6-甲基-2，3，4-三氢萘-1-酮(ii)、22mL(0.022摩尔)六甲基二硅氮烷锂(1M溶液)和7.8克(0.022摩尔)N-苯基三氟甲烷磺酰亚胺在30mLTHF中反应制备。得0.41克标题化合物。核磁共振谱与预定结构相一致。
步骤C1-{[2-(7-甲氧基-6-甲基(3，4-二氢萘基)咪唑基)甲氧基]-3，3-二甲基-3-硅杂-丁烷中间体(xii)的合成
将1。7克(0.009摩尔)1-(咪唑基甲氧基)-3，3-二甲基-3-硅杂丁烷(xi)在20ml四氢呋喃中的溶液冷至-78℃，加入正丁基锂(己烷的1。6M溶液)5.63ml(0.009摩尔)。加完后将反应混合物于-70℃搅拌1小时，然后加入氯化锌(1.0摩尔乙醚溶液)25ml(0.025摩尔)，反应混合物于-78℃搅拌15分钟，然后任其回至室温搅拌1小时。加入2.6克(0.009摩尔)7-甲氧基-6-甲基-3，4-二氢萘基(三氟甲基)磺酸酯(x)，再加入0.05克(催化剂)四(三苯膦)合钯(O)。加完后，将反应混合物加热至60℃搅拌2小时，冷却反应混合物，减压浓缩至得残留物，在硅胶柱上柱层析，以97:3二氯甲烷与甲醇的比例为洗脱剂，合并所需洗脱剂并减压浓缩得3.4克标题化合物。核磁共振谱与预定结构相一致。
步骤D中间体4-咪唑-2-基-6-甲氧基-7-甲基-1，2-二氢萘(xiii)的合成
将3.0克(0.0081摩尔)1-{[2-(7-甲基-(3，4-二氢萘基)-)咪唑基]甲氧基}-3，3-二甲基-3-硅杂丁酸(xii)，5ml 3N盐酸溶液，以及25ml(0.025摩尔)四丁基氟化铵(1.0摩尔四氢呋喃溶液)搅拌下加热至50℃，再搅拌约2小时。然后将反应混合物作薄板层析分析表明反应并未完全，将反应混合物减压浓缩至剩残留物，加入15ml浓盐酸，加完后于室温搅拌反应混合物18小时，之后将反应混合物倾注至50％NaOH水溶液与冰的混合物中，搅拌混合物至冰融化，过滤得固体，用乙酸乙酯洗固体并干燥，得1.2克标题化合物，mp197～199℃。核磁共振谱与预定化合物相一致。
步骤E化合物215的合成
该化合物的制备类似于实施例7的步骤C，将0.7克(0.003摩尔)4-咪唑-2基-6-甲氧基-7-甲基-1，2-二氢萘(xiii)用帕尔氢化器，存在0.1克氧化铂(催化剂)和0.1克10％钯炭(催化剂)在50ml乙醇中氢化。得标题化合物0.34克mp168～169℃，核磁共振谱与预定结构相一致。
实施例92-(7-甲氧基-6-甲基-1，2，3，4-四氢萘基)-2-咪唑啉甲腈(化合物201)的合成
在9.5英钱(9.5×3.887克)螺旋盖小瓶中，放入0.20克(0.008摩尔)化合物50(在实施例5已有制取的记述)与0.16克(0.00081摩尔)N，N-二异丙基乙基胺在10ml二氯甲烷中的溶液，在冰水浴中冷却10分钟，然后放入由1ml溴化氰在30ml二氯甲烷中所成的储备溶液2.4ml(0.0008摩尔)。用机械搅拌器将反应混合物温和搅拌18小时，然后将反应混合物倾注至分液漏斗中的冰水中，将混合物用二氯甲烷提取三次，合并提取液用硫酸钠干燥并过滤。减压浓缩滤液至剩残留油，将残留油用II级氧化铝(碱性-含3％水)柱层析用二氯甲烷为洗脱液，提纯残留物，合并所需的洗脱液部分，减压浓缩得0.19克化合物201。核磁共振谱与预定的结构相一致。
实施例10 4{[2-(6-甲氧基-7-甲基并苯并二氢吡喃-4-基)(2-咪唑啉基)]磺酰基}二甲胺(化合物203)的合成
将0.2克(0.00081摩尔)化合物89(实施例5已述有制法)与0.16克(0.00081摩尔)N，N-二异丙基乙胺在10ml二氯甲烷的溶液在冰水溶中搅拌泠却10分钟，然后加入由1ml N，N-二甲基磺酰氯于30ml二氯甲烷所成的储备溶液，加完后将反应混合物让其温热至室温并搅拌18小时。然后将反应混合物倾注至分液漏斗中，再加入氯化铵饱和水溶液和二氯甲烷。振摇混合物分出有机层，用饱和氯化铵洗三次，用硫酸钠干燥，过滤混合物。减压浓缩滤液得残留物，将残留物溶于二氯甲烷后放在二级碱性氧化铝(含3％水)柱中提纯，用二氯甲烷洗脱，将所需洗脱部分合并，减压浓缩得0.16克化合物203，其核磁共振谱与预定的结构相一致。
实施例11二甲氧基[2-(6-甲氧基-7-甲基苯并二氢吡喃-4-基)-(2-咪唑啉基)-膦基-1-酮(化合物204)的合成
该化合物的制备类似于实施例10。将0.2克(0.00081摩尔)化合物89(制备如实施例5所述)，2.63ml(0.00081摩尔)备用溶液(由1ml氯磷酸二甲酯与30ml二氯甲烷配成)以及0.16克(0.00081摩尔)N，N-二异丙基乙胺在10ml二氯甲烷所成的溶液)反应。粗产物用II级碱性氧化铝(含3％水)柱层析提纯，采用二氯甲烷与甲醇之比99.5∶0.5为洗脱液，合并所需部分并减压浓缩，得约0.19克化合的204，核磁共振谱与预定结构相一致。
下表列出本发明其余化合物的例子。
表1
农药杂环化合物
其中R，R1与R8为氢；R2与R3结合为基团＝NCH(R6)CH(R7)N(R8)-；R4与R5结合为基团-C(R11)＝C(R12)C(R13)＝C(R14)-：
Figure C03812343D00411
化合物     X        R17     R6     R7     R11     R12       R13     R14
序号
1          -CHR17-  H       H      H      H       H         CH3     H
2          -CHR17-  H       H      H      H       H         CH3     H
HCl盐
3          -CHR17-  H       H      H      H       F         CH3     H
4          -CHR17-  H       H      H      H       OCH3      Cl      H
5          -CHR17-  H       H      H      H       OCH3      I       H
6          -CHR17-  H       H      H      H       OCH3      CH3     H
7          -CHR17-  H       H      H      H       OCH3      CH3     H
HCl盐
8          -CHR17-  H       H      H      H       H         H       Cl
9          -CHR17-  H       H      H      H       H         Cl      H
10         -CHR17-  H       H      H      H       Cl        H       H
HCl盐
11         -CHR17-  H       H      H      H       Cl        Cl      H
12         -CHR17-  H       H      H      H       H         H       CH3
HCl盐
13         -CHR17-  H       H      H      H       H         CH3     H
HCl盐
14         -CHR17-  H       H      H      H       H         CH3     H
15         -CHR17-  H       H      H      CH3     H         H       H
HCl盐
16         -CHR17-  H       H      H      H       H         CH3     H
HCl盐
17         -CHR17-  H       H      H      H       H         F       H
HCl盐
18         -CHR17-  H       H      H      H       H         OH      H
HCl盐
19         -CHR17-  H       H      H      H       OCH3      Cl      H
20         -CHR17-  H       H      H      H       OCH3      CH3     H
21         -CHR17-    H       H      H      H       I         CH3     H
22         -CHR17-    H       H      H      H       Cl        Cl      H
23         -CHR17-    H       H      H      H       H         CH3     Cl
24         -CHR17-    H       H      H      H       OCHF2     CH3     H
25         -CHR17-    H       H      H      H       OCF3      CH3     H
26         -CHR17-    H       H      H      H       NH2       CH3     H
27         -CHR17-    H       H      H      H       CH＝CH2   CH3     H
28         -CHR17-    H       H      H      H       CH＝CHCH3 CH3    H
29         -CHR17-    H       H      H      H       C＝CH     CH3     H
30         -CHR17-    H       H      H      H       C＝CCH3   CH3     H
31         -CHR17-    CH3     H      H      H       OCH3      CH3     H
32         -CHR17-    H       H      H      H       OCH3      CH3     H
33         -CHR17-    H       CH3    CH3    H       OCH3      CH3     H
34         -CHR17-    H       H      CH3    H       OCH3      CH3     H
35         -CHR17-    H       CH3    H      H       C2H5      CH3     H
36         -CHR17-    H       H      H      H       OCH3      CH3     Cl
37         -CHR17-    H       H      H      H       CH3       CH3     H
38         -CHR17-    H       H      H      H       F         CH3     H
39         -CHR17-    H       H      H      H       OCH3      F       H
40         -CHR17-    H       H      H      H       OCH3      CH3     CH3
41         -CHR17-    H       H      H      H       H         H       H
42         -CH2CHR17- H       H      H      H       Cl        H       H
43         -CH2CHR17- H       H      H      H       H         Cl      H
44         -CH2CHR17- H       H      H      H       H         H       Cl
45         -CH2CHR17- H       H      H      H       OCH3      H       H
46         -CH2CHR17- H       H      H      H       H         CH3     H
47         -CH2CHR17- H       H      H      H       H         CH3     H
HCl盐
48         -CH2CHR17- H       H      H      H       H         H       CH3
49         -CH2CHR17- H       H      H      H       OCH3      Cl      H
50         -CH2CHR17- H       H      H      H       OCH3      CH3     H
51         -CH2CHR17- H       H      H      H       OCH3      C2H5    H
52         -CH2CHR17- H       H      H      H       OCH3      CF3     H
53         -CH2CHR17- H       H      H      H       OCHF2     CH3     H
54         -CH2CHR17- H       H      H      H       OCF3      CH3     H
55         -CH2CHR17- H       H      H      H       OCH3      CN      H
56         -CH2CHR17- H       H      H      H       NH2       CH3     H
57         -CH2CHR17- H       H      H      H       CH＝CH2   CH3     H
58         -CH2CHR17- H       H      H      H       CH＝CHCH3 CH3    H
59           -CH2CHR17-     H       H      H      H       OCH3       C＝CH    H
60           -CH2CHR17-     H       H      H      H       C＝CCH3    CH3      H
61           -CH2CHR17-     CH3     H      H      H       OCH3       CH3      H
62           -CH2CHR17-     H       CH3    H      H       OCH3       CH3      H
63           -CH2CHR17-     H       H      CH3    H       OCH3       CH3      H
64           -CH2CHR17-     H       CH3    CH3    H       OCH3       CH3      H
65           -CH2CHR17-     H       H      H      H       Cl         H        Cl
66           -CH2CHR17-     H       H      H      H       Cl         Cl       H
67           -CH2CHR17-     H       H      H      H       H          Cl       Cl
68           -CH2CHR17-     H       H      H      H       H          H        H
69           -CH2CHR17-     H       H      H      H       CH3        Br       H
70           -CH2CHR17-     H       H      H      Cl      H          H        H
71           -CH2CHR17-     H       H      H      H       OCH3       CH3      Cl
72           -O-            ----    H      H      H       H          H        H
73           -O-            ----    H      H      H       OCH3       Cl       H
74           -O-            ----    H      H      H       H          CH3      H
75           -O-            ----    H      H      H       OCH3       CH3      H
76           -O-            ----    H      H      H       OCH3       C2H5     H
77           -O-            ----    H      H      H       OCH3       CN       H
78           -O-            ----    H      H      H       NH2        CH3      H
79           -O-            ----    H      H      H       CH＝CH2    CH3      H
80           -O-            ----    H      H      H       CH＝CHCH3  CH3     H
81           -O-            ----    H      H      H       C＝CH      CH3      H
82           -O-            ----    H      H      H       C＝CCH3    CH3      H
83           -O-            ----    CH3    H      H       OCH3       CH3      H
84           -O-            ----    H      CH3    H       OCH3       CH3      H
85           -O-            ----    CH3    CH3    H       OCH3       CH3      H
86           -OCH2-         ----    H      H      H       H          H        H
87           -OCH2-         ----    H      H      H       OCH3       Cl       H
88           -OCH2-         ----    H      H      H       H          CH3      H
89           -OCH2-         ----    H      H      H       OCH3       CH3      H
90           -OCH2-         ----    H      H      H       OCH3       C2H5     H
91           -OCH2-         ----    H      H      H       OCHF2      CH3      H
92           -OCH2-         ----    H      H      H       OCF3       CH3      H
93           -OCH2-         ----    H      H      H       NH2        CH3      H
94           -OCH2-         ----    H      H      H       CH＝CH2    CH3      H
95           -OCH2-         ----    H      H      H       CH＝CHCH3  CH3     H
96           -OCH2-         ----    H      H      H       C＝CH      CH3      H
97           -OCH2-         ----    H      H      H       C＝CCH3    CH3      H
98        -OCH2-       ----       CH3       H       H      OCH3      CH3      H
99        -OCH2-       ----       H         CH3     H      OCH3      CH3      H
100       -OCH2-       ----       CH3       CH3     H      OCH3      CH3      H
101       -C3H6-       ----       H         H       H      OCH3      Cl       H
102       -C3H6-       ----       H         H       H      OCH3      CH3      H
103       -C3H6-       ----       H         H       H      OCH3      C2H5     H
104       -C4H8-       ----       H         H       H      OCH3      Cl       H
105       -C4H8-       ----       H         H       H      OCH3      CH3      H
106       -C4H8-       ----       H         H       H      OCH3      C2H5     H
107       -OC2H4-      ----       H         H       H      OCH3      Cl       H
108       -OC2H4-      ----       H         H       H      OCH3      CH3      H
109       -OC2H4-      ----       H         H       H      OCH3      C2H5     H
110       -OC3H6-      ----       H         H       H      OCH3      Cl       H
111       -OC3H6-      ----       H         H       H      OCH3      CH3      H
112       -OC3H6-      ----       H         H       H      OCH3      C2H5     H
113       -CH2O-       ----       H         H       H      OCH3      Cl       H
114       -CH2O-       ----       H         H       H      OCH3      CH3      H
115       -CH2O-       ----       H         H       H      OCH3      C2H5     H
116       -CH2OCH2-    ----       H         H       H      OCH3      Cl       H
117       -CH2OCH2-    ----       H         H       H      OCH3      CH3      H
118       -CH2OCH2-    ----       H         H       H      OCH3      C2H5     H
119       -CH2OC2H4-   ----       H         H       H      OCH3      Cl       H
120       -CH2OC2H4-   ----       H         H       H      OCH3      CH3      H
121       -CH2OC2H4-   ----       H         H       H      OCH3      C2H5     H
122       -S-          ----       H         H       H      H         H        H
123       -S-          ----       H         H       H      OCH3      Cl       H
124       -S-          ----       H         H       H      H         CH3      H
125       -S-          ----       H         H       H      OCH3      CH3      H
126       -S-          ----       H         H       H      OCH3      C2H5     H
127       -S-          ----       H         H       H      CF3       CH3      H
128       -S-          ----       H         H       H      OCHF2     CH3      H
129       -S-          ----       H         H       H      OCF3      CH3      H
130       -S-          ----       H         H       H      NH2       CH3      H
131       -S-          ----       H         H       H      CH＝CH2   CH3      H
132       -S-          ----       H         H       H      CH＝CHCH3 CH3      H
133       -S-          ----       H         H       H      C＝CH     CH3      H
134       -S-          ----       H         H       H      C＝CCH3   CH3      H
135       -S-          ----       CH3       H       H      OCH3      CH3      H
136       -S-          ----       H         CH3     H      OCH3      CH3      H
137        -S-          ----      CH3      CH3      HOCH3      CH3      H
138        -SCH2-       ----      H        H        HOCH3      Cl       H
139        -SCH2-       ----      H        H        HOCH3      CH3      H
140        -SCH2-       ----      H        H        HOCH3      C2H5     H
141        -SCH2-       ----      H        H        HH         CH3      H
142        -CH2S-       ----      H        H        HOCH3      Cl       H
143        -CH2S-       ----      H        H        HOCH3      CH3      H
144        -CH2S-       ----      H        H        HOCH3      C2H5     H
145        -CH2S(O)-    ----      H        H        HOCH3      Cl       H
146        -CH2S(O)-    ----      H        H        HOCH3      CH3      H
147        -CH2S(O)-    ----      H        H        HOCH3      C2H5     H
148        -CH2S(O)2-   ----      H        H        HOCH3      Cl       H
149        -CH2S(O)2-   ----      H        H        HOCH3      CH3      H
150        -CH2S(O)2-   ----      H        H        HOCH3      C2H5     H
151        -N(R21)CH2-  H         H        H        HOCH3      Cl       H
152        -N(R21)CH2-  H         H        H        HOCH3      CH3      H
153        -N(R21)CH2-  H         H        H        HOCH3      C2H5     H
154        -N(R21)CH2-  H         H        H        HOCH3      n-C3H7   H
155        -N(R21)CH2-  H         H        H        HOCH3      Iso-C3H7 H
156        -N(R21)CH2-  CH3       H        H        HOCH3      CH3      H
157        -CH2N(R21)-  H         H        H        HOCH3      Cl       H
158        -CH2N(R21)-  H         H        H        HOCH3      CH3      H
159        -CH2N(R21)-  H         H        H        HOCH3      C2H5     H
160        -CH2N(R21)-  H         H        H        HOCH3      n-C3H7   H
161        -CH2N(R21)-  H         H        H        HOCH3      Iso-C3H7 H
162        -CH2N(R21)-  CH3       H        H        HOCH3      CH3      H
X为-CHR17-；而R6，R7，R8，R11，R14，R17为H，而R12为OCH3：
化合物序号       R            R1        R13
163              H            CH3       Cl
164              H            CH3       CH3
165              H            CH3       C2H5
166              CH3          CH3       Cl
167              CH3          CH3       CH3
168              CH3          CH3       C2H5
169              C2H5         C2H5      Cl
170              C2H5         C2H5      CH3
171              C2H5         C2H5      C2H5
R，R1，R6，R7，R11，R14而R17为H，而R12为OCH3：
化合物         X          R8               n        R9         R10         R13
序号
172            -CH2R17-   CH3              ----     ----       ----        Cl
173            -CH2R17-   CH3              ----     ----       ----        CH3
174            -CH2R17-   C(O)R9           ----     CH3        ----        Cl
175            -CH2R17-   C(O)R9           ----     CH3        ----        CH3
176            -CH2R17-   C(O)R9           ----     PhCH2      ----        Cl
177            -CH2R17-   C(O)R9           ----     PhCH2      ----        CH3
178            -CH2R17-   C(O)OR9          ----     CH3        ----        CH3
179            -CH2R17-   C(O)OR9          ----     PhCH2      ----        CH3
180            -CH2R17-   S(O)nR9          0        CH3        ----        CH3
181            -CH2R17-   S(O)nR9          0        PhCH2      ----        CH3
182            -CH2R17-   S(O)nR9          1        CH3        ----        CH3
183            -CH2R17-   S(O)nR9          1        PhCH2      ----        CH3
184            -CH2R17-   S(O)nR9          2        CH3        ----        CH3
185            -CH2R17-   S(O)nR9          2        PhCH2      ----        CH3
186            -CH2R17-   C(O)N(R9)(R10)   ----     H          H           CH3
187            -CH2R17-   C(O)N(R9)(R10)   ----     H          CH3         CH3
188            -CH2R17-   C(O)N(R9)(R10)   ----     CH3        CH3         CH3
189            -CH2R17-   C(O)N(R9)(R10)   ----     PhCH2      H           CH3
190            -CH2R17-   C(O)N(R9)(R10)   ----     PhCH2      CH3         CH3
191            -CH2R17-   C(O)N(R9)(R10)   0        H          CH3         CH3
192            -CH2R17-   C(O)N(R9)(R10)   0        CH3        CH3         CH3
193            -CH2R17-   C(O)N(R9)(R10)   0        PhCH2      H           CH3
194            -CH2R17-   C(O)N(R9)(R10)   1        H          CH3         CH3
195            -CH2R17-   C(O)N(R9)(R10)   1        CH3        CH3         CH3
196            -CH2R17-   C(O)N(R9)(R10)   1        PhCH2      H           CH3
197            -CH2R17-   C(O)N(R9)(R10)   2        H          CH3         CH3
198            -CH2R17-   C(O)N(R9)(R10)   2        CH3        CH3         CH3
199            -CH2R17-   C(O)N(R9)(R10)   2        PhCH2      H           CH3
200            -CH2R17-   P(O)(OR9)(OR10)  ----     C2H5       C2H5        CH3
201            -CH2CHR17- CN               ----     ----       ----        CH3
202            -OCH2-C    (O)R9            ----     CH3        ----        CH3
203            -OCH2-     S(O)nN(R9)(R10)  2        CH3        CH3         CH3
204            -OCH2-     P(O)(OR9)(OR10)  ----     CH3        CH3         CH3
205            -OCH2-     CN               ----     ----       ----        CH3
206            -OCH2-     CH3              ----     ----       ----        CH3
其中
R与R1为4；R2与R3结合为基团＝NC(R6)＝C(R7)N(R8)-；R4与R5结合为基团-C(R11)＝C(R12)C(R13)＝C(R14)-，其中R11与R14为H：
Figure C03812343D00471
化合物      X            R17        R6        R7         R8      R12      R13
序号
207         -CHR17-      H          H         H          H       OCH3     Cl
208         -CHR17-      H          H         H          H       OCH3     CH3
209         -CHR17-      H          H         H          H       OCH3     C2H5
210         -CHR17-      H          CH3       H          H       OCH3     CH3
211         -CHR17-      H          H         CH3        H       OCH3     CH3
212         -CHR17-      H          CH3       CH3        CH3     OCH3     CH3
213         -CHR17-      CH3        H         H          H       OCH3     CH3
214         -CH2CHR17-   H          H         H          H       OCH3     Cl
215         -CH2CHR17-   H          H         H          H       OCH3     CH3
216         -CH2CHR17-   H          H         H          H       OCH3C    C2H5
217         -CH2CHR17-   H          CH3       H          H       OCH3     CH3
218         -CH2CHR17-   H          H         CH3        H       OCH3     CH3
219         -CH2CHR17-   H          CH3       CH3        CH3     OCH3     CH3
220         -CH2CHR17-   CH3        H         H          H       OCH3     CH3
221         -CH2CHR17-   H          H         H          PhCH2   OCH3     CH3
222         -CH2CHR17-   H          H         H          C2H5    OCH3     CH3
223         -CH2CHR17-   H          H         H          CH3     OCH3     CH3
224         -OCH2-       ----       H         H          H       OCH3     Cl
225         -OCH2-       ----       H         H          H       H        CH3
226         -OCH2-       ----       H         H          H       OCH3     CH3
227         -OCH2-       ----       H         H          H       OCH3     C2H5
228         -OCH2-       ----       CH3       H          H       OCH3     CH3
229         -OCH2-       ----       H         CH3        H       OCH3     CH3
230         -OCH2-       ----       CH3       CH3        CH3     OCH3     CH3
其中
R，R1，R6，R7，R11，R14和R17为H，R12为OCH3，R为CH3：
化合物序号    X             R8                n      R9         R10
231           -CH2CHR17-    CH2OR9            ----   CH3        ----
232           -CH2CHR17-    CH2OC(O)R9        ----   C(CH3)3    ----
233           -CH2CHR17-    S(O)nN(R9)(R10)   2      CH3        CH3
234           -OCH2-        S(O)nN(R9)(R10)   2      CH3        CH3
其中
R和R1为H；R2和R3结合为基团＝CH(R6)＝C(R7)N(R8)-；R4和R5结合为基团-C(R11)＝C(R12)C(R13)＝C(R14)-，其中R11和R14为H：
Figure C03812343D00481
化合物    X          R21      R6        R7       R8        R12        R13
序号
235       -CHR17-    H        H         H        H         OCH3       Cl
236       -CHR17-    H        H         H        H         OCH3       CH3
237       -CHR17-    H        H         H        H         OCH3       C2H5
238       -CHR17-    H        CH3       H        H         OCH3       CH3
239       -CHR17-    H        H         CH3      H         OCH3       CH3
240       -CHR17-    H        CH3       CH3      CH3       OCH3       CH3
241       -CHR17-    CH3      H         H        H         OCH3       CH3
242       -CH2CHR17- H        H         H        H         OCH3       Cl
243       -CH2CHR17- H        H         H        H         OCH3       CH3
244       -CH2CHR17- H        H         H        H         OCH3       C2H5
245       -CH2CHR17- H        H         H        H         OCH3       CH3
246       -CH2CHR17- H        CH3       H        H         OCH3       CH3
247       -CH2CHR17- H        CH3       CH3      CH3       OCH3       CH3
248       -CH2CHR17- CH3      H         H        H         OCH3       CH3
249       -OCH2-     ----     H         HH                 OCH3       Cl
250           -OCH2-      ----        H      H        H         H     CH3
251           -OCH2-      ----        H      H        H         OCH3  CH3
252           -OCH2-      ----        H      H        H         OCH3  C2H5
253           -OCH2-      ----        CH3    H        H         OCH3  CH3
254           -OCH2-      ----        H      CH3      H         OCH3  CH3
255           -OCH2-      ----        CH3    CH3      CH3       OCH3  CH3
其中
R和R1为H；R2和R3结合为基团＝CHN＝C(R7)N(R8)-(互变异构体A)，或其＝CHN(R8)C(R7)＝N-(互变异构体B)；R4和R5结合为基团-C(R11)＝C(R13)＝C(R14)-，其中R11和R14为H；
            化合物A                          化合物B
化合物序号  互变异   X            R17       R7        R8       R12        R13
            构体
256         A        -CHR17-      H         H         H        OCH3       Cl
257         A        -CHR17-      H         H         H        OCH3       CH3
258         A        -CHR17-      H         H         H        OCH3       C2H5
259         A        -CHR17-      H         CH3       H        OCH3       CH3
260         A        -CHR17-      H                   CH3      OCH3       CH3
261         A        -CHR17-      H         CH3       CH3      OCH3       CH3
262         A        -CHR17-      CH3       H         H        OCH3       CH3
263         A        -CH2CHR17-   H         H         H        OCH3       Cl
264         A        -CH2CHR17-   H         H         H        OCH3       CH3
265         A        -CH2CHR17-   H         H         H        OCH3       C2H5
266         A        -CH2CHR17-   H         CH3       H        OCH3       CH3
267         A        -CH2CHR17-   H                   CH3      OCH3       CH3
268         A        -CH2CHR17-   H         CH3       CH3      OCH3       CH3
269         A        -CH2CHR17-   CH3       H         H        OCH3       CH3
270         A        -OCH2-       ----      H         H        OCH3       Cl
271        A        -OCH2-     ----      H          H         H        CH3
272        A        -OCH2-     ----      H          H         OCH3     CH3
273        A        -OCH2-     ----      H          H         OCH3     C2H5
274        A        -OCH2-     ----      CH3        H         OCH3     CH3
275        A        -OCH2-     ----                 CH3       OCH3     CH3
276        A        -OCH2-     ----      CH3        CH3       OCH3     CH3
化合物    互变     X      R7    R8              n    R9     R10    R12      R13
序号      异构体
277       B        -OCH2- H     CN              ---  ---    ----   OCH3     CH3
278       B        -OCH2- H     S(O)nN(R9)(R10) 2    CH3    CH3    OCH3     CH3
其中
R和R1为H；R2和R3结合为基团＝N(CH2)3N(R8)-；R4和R5结合为基团-C(R11)＝C(R13)＝C(R14)-，其中R11和R14为H：
Figure C03812343D00501
化合物序号  X            R17       R8        R12          R13
279         -CHR17-      H         H         OCH3         Cl
280         -CHR17-      H         H         OCH3         CH3
281         -CHR17-      H         H         OCH3         C2H5
282         -CHR17-      H         CH3       OCH3         CH3
283         -CHR17-      CH3       H         OCH3         CH3
284         -CHR17-      CH3       CH3       OCH3         CH3
285         -CH2CHR17-   H         H         OCH3         Cl
286         -CH2CHR17-   H         H         OCH3         CH3
287         -CH2CHR17-   H         H         OCH3         C2H5
288         -CH2CHR17-   H         CH3       OCH3         CH3
289         -CH2CHR17-   CH3       H         OCH3         CH3
290         -CH2CHR17-   CH3       CH3       OCH3         CH3
291         -OCH2-       ----      H         OCH3         Cl
292         -OCH2-       ----      H         H            CH3
293      -OCH2-    ----     H      OCH3          CH3
294      -OCH2-    ----     H      OCH3          C2H5
295      -OCH2-    ----     CH3    OCH3          CH3
其中
R和R1为H；R2和R3结合为基团＝NCH(R6)CH(R7)S-；R4和R5结合为基团-(R11)＝C(R12)C(R13)＝C(R14)-，其中R11和R14为H；
Figure C03812343D00511
化合物   X            R17         R6       R7       R12         R13
序号
296      -CHR17-      H           H        H        OCH3        Cl
297      -CHR17-      H           H        H        OCH3        CH3
298      -CHR17-      H           H        H        OCH3        C2H5
299      -CHR17-      H           CH3      H        OCH3        CH3
300      -CHR17-      H           H        CH3      OCH3        CH3
301      -CHR17-      H           CH3      CH3      OCH3        CH3
302      -CHR17-      CH3         H        H        OCH3        CH3
303      -CH2CHR17-   H           H        H        OCH3        Cl
304      -CH2CHR17-   H           H        H        OCH3        CH3
305      -CH2CHR17-   H           H        H        OCH3        C2H5
306      -CH2CHR17-   H           CH3      H        OCH3        CH3
307      -CH2CHR17-   H           H        CH3      OCH3        CH3
308      -CH2CHR17-   H           CH3      CH3      OCH3        CH3
309      -CH2CHR17-   CH3         H        H        OCH3        CH3
310      -OCH2-       ----        H        H        OCH3        Cl
311      -OCH2-       ----        H        H        H           CH3
312      -OCH2-       ----        H        H        OCH3        CH3
313      -OCH2-       -----       H        H        OCH3        C2H5
314      -OCH2-       ----        CH3      H        OCH3        CH3
315      -OCH2-       ----        H        CH3      OCH3        CH3
316      -OCH2-       ----        CH3      CH3      OCH3        CH3
其中
R和R1为H；R2和R3结合为基团＝NCH(R6)CH(R7)O-；R4和R5结合为基团-C(R11)C(R13)＝C(R14)-，其中R11和R14为H：
Figure C03812343D00521
化合物   X              R17          R6          R7       R12         R13
序号
317      -CHR17-        H            H           H        OCH3        Cl
318      -CHR17-        H            H           H        OCH3        CH3
319      -CHR17-        H            H           H        OCH3        C2H5
320      -CHR17-        H            CH3         H        OCH3        CH3
321      -CHR17-        H            H           CH3      OCH3        CH3
322      -CHR17-        H            CH3         CH3      OCH3        CH3
323      -CHR17-        CH3          H           H        OCH3        CH3
324      -CH2CHR17-     H            H           H        OCH3        Cl
325      -CH2CHR17-     H            H           H        OCH3        CH3
326      -CH2CHR17-     H            H           H        OCH3        C2H5
327      -CH2CHR17-     H            CH3         H        OCH3        CH3
328      -CH2CHR17-     H            H           CH3      OCH3        CH3
329      -CH2CHR17-     H            CH3         CH3      OCH3        CH3
330      -CH2CHR17-     CH3          H           H        OCH3        CH3
331      -OCH2-         ----         H           H        OCH3        Cl
332      -OCH2-         ----         H           H        H           CH3
333      -OCH2-         ----         H           H        OCH3        CH3
334      -OCH2-         ----         H           H        OCH3        C2H5
335      -OCH2-         ----         CH3         H        OCH3        CH3
336      -OCH2-         ----         HH          CH3      OCH3        CH3
337      -OCH2-         ----         CH3         CH3      OCH3        CH3
其中
R和R1为H；R2和R3结合为基团＝NCH(R6)CH(R7)N(R8)-；R4和R5结合为基团-SC(R15)＝C(R16)-：
Figure C03812343D00531
化合物   X            R17       R6       R7         R8         R15       R16
序号
338      -CHR17-      H         H        H          H          H         H
339      -CHR17-      H         H        CH3        H          Cl        Cl
340      -CHR17-      H         CH3      H          H          CH3       OCH3
341      -CHR17-      H         H        CH3        H          C2H5      Cl
342      -CHR17-      H         CH3      CH3        H          OCH3      CH3
343      -CHR17-      H         CH3      CH3        CH3        OCH3      CH3
344      -CHR17-      CH3        H        H          H          OCH3      CH3
345      -CH2CHR17-   H         H        H          H          H         H
346      -CH2CHR17-   H         H        CH3        H          Cl        Cl
347      -CH2CHR17-   H         CH3      H          H          CH3       OCH3
348      -CH2CHR17-   H         H        CH3        H          C2H5      Cl
349      -CH2CHR17-   H         CH3      CH3        H          OCH3      CH3
350      -CH2CHR17-   H         CH3      CH3        CH3        OCH3      CH3
351      -CH2CHR17-   CH3       H        H          H          OCH3      CH3
352      -OCH2-       ----      H        H          H          H         H
353      -OCH2-       ----      H        CH3        H          Cl        Cl
354      -OCH2-       ----      CH3      H          H          CH3       OCH3
355      -OCH2-       ----      CH3      CH3        H          C2H5      Cl
356      -OCH2-       ----      CH3        CH3        CH3        OCH3      CH3
其中
R和R1为H；R2和R3结合为基团＝NCH(R6)CH(R7)N(R8)-；R4和R5结合为基团-C(R15)＝C(R16)S-：
Figure C03812343D00541
化合物序   X            R17         R6        R7       R8        R15       R16
号
357        -CHR17-      H           H         H        H         H         H
358        -CHR17-      H           H         H        H         Cl        Cl
359        -CHR17-      H           H         H        H         CH3       OCH3
360        -CHR17-      H           H         H        H         C2H5      CH3
361        -CHR17-      H           H         H        H         OCH3      CH3
362        -CHR17-      H           CH3       H        H         OCH3      CH3
363        -CHR17-      H           H         CH3      H         OCH3      CH3
364        -CHR17-      H           CH3       CH3      H         OCH3      CH3
365        -CHR17-      H           CH3       CH3      CH3       OCH3      CH3
366        -CHR17-      CH3         H         H        H         OCH3      CH3
367        -CH2CHR17-   H           H         H        H         H         H
368        -CH2CHR17-   H           H         H        H         Cl        Cl
369        -CH2CHR17-   H           H         H        H         CH3       OCH3
370        -CH2CHR17-   H           H         H        H         C2H5      Cl
371        -CH2CHR17-   H           H         H        H         OCH3      CH3
372        -CH2CHR17-   H           CH3       H        H         OCH3      CH3
373        -CH2CHR17-   H           H         CH3      H         OCH3      CH3
374        -CH2CHR17-   H           CH3       CH3      H         OCH3      CH3
375        -CH2CHR17-   H           CH3       CH3      CH3       OCH3      CH3
376        -CH2CHR17-   CH3         H         H        H         OCH3      CH3
377        -OCH2-       ----        H         H        H         H         H
378        -OCH2-       ----        H         H        H         Cl        Cl
379        -OCH2-       ----        H         H        H         CH3       OCH3
380        -OCH2-       ----        H         H        H         C2H5      Cl
381        -OCH2-       ----        H         H        H         OCH3      CH3
382        -OCH2-       ----        CH3       H        H         OCH3      CH3
383        -OCH2-       ----        H         CH3      H         OCH3      CH3
384        -OCH2-       ----        CH3       CH3      H         OCH3      CH3
385        -OCH2-       ----        CH3       CH3      CH3       OCH3      CH3
其中
R和R1为H；R2和R3结合为基团＝NCH(R6)CH(R7)N(R8)-；R4和R5结合为基团-CH＝C(R15)N＝CH-：
Figure C03812343D00551
化合物序   X           R17       R6         R7        R8        R15
号
386        -CHR17-     H         H          H         H         H
387        -CHR17-     H         H          H         H         Cl
388        -CHR17     H         H          H         H         CH3
389        -CHR17-     H         H          H         H         C2H5
390        -CHR17-     H         H          H         H         OCH3
391        -CHR17-     H         CH3        H         H         OCH3
392        -CHR17-     H         H          CH3       H         OCH3
393        -CHR17-     H         CH3        CH3       H         OCH3
394        -CHR17-     H         CH3        CH3       CH3       OCH3
395        -CHR17-     CH3       H          H         H         OCH3
396        -CH2CHR17-  H         H          H         H         H
397        -CH2CHR17-  H         H          H         H         Cl
398        -CH2CHR17-  H         H          H         H         CH3
399        -CH2CHR17-  H         H          H         H         C2H5
400        -CH2CHR17-  H         H          H         H         OCH3
401        -CH2CHR17-  H         CH3        H         H         OCH3
402        -CH2CHR17-  H         H          CH3       H         OCH3
403        -CH2CHR17-  H         CH3        CH3       H         OCH3
404        -CH2CHR17-  H         CH3        CH3       CH3       OCH3
405        -CH2CHR17-  CH3       H          H         H         OCH3
406        -OCH2-      ----      H          H         H         H
407        -OCH2-      ----      H          H         H         Cl
408        -OCH2-      ----      H          H         H         CH3
409        -OCH2-      ----      H          H         H         C2H5
410        -OCH2-      ----      H          H         H         OCH3
411    -OCH2-    ----     CH3       H      H       OCH3
412    -OCH2-    ----     H         CH3    H       OCH3
413    -OCH2-    ----     CH3       CH3    H       OCH3
414    -OCH2-    ----     CH3       CH3    CH3     OCH3
其中
R和R1为H；R2和R3结合为基团-OCH(R6)CH(R7)N(R8)N＝；R4和R5结合为基团-C(R11)＝C(R12)C(R13)＝C(R14)-，其中R6，R7，R11和R14为H，R12为OCH3，而R13为CH3：
化合物   X                   R17           R8                    N         R9         R10
序号
415      -CH2-CHR17-         H             H                     ----      ----       ----
416      -CH2-CHR17-         H             C(O)R9                ----      NH2        ----
417      -CH2-CHR17-         H             CN                    ----      ----       ----
418      -CH2-CHR17-         H             S(O)nN(R9)(R10)       2         CH3        CH3
419      -CH2-CHR17-         H             P(O)N(OR9)(OR10)      ----      CH3        CH3
420      -CH2-CHR17-         H             P(O)(NR9R10)(NR9R10)   ----     CH3        CH3
421      -CH2-CHR17-         H             CHO                   ----     ----       ----
422      -OCH2-              ----          H                     ----     ----       ----
423      -OCH2-              ----          C(O)R9                ----     NH2        ----
424      -OCH2-              ----          CN                    ----     ----       ----
425      -OCH2-              ----          S(O)nN(R9)(R10)       2        CH3        CH3
426      -OCH2-              ----          P(O)N(OR9)(OR10)      ----     CH3        CH3
427      -OCH2-              ----          P(O)(NR9R10)(NR9R10)   ----     CH3        CH3
428      -OCH2-              ----          CHO                   ----     ----       ----
其中
R2和R3结合为基团＝NCH(R6)CH(R7)N(R8)-；R4和R5结合为基团-C(R11)＝C(R12)C(R13)＝C(R14)-，其中R，R1，R6，R7，R11，R14，和R17为H，R12为CH3，而R13为CH3：
Figure C03812343D00571
化合物序号  X            R8         n            R9
429         -CH2R17-     NH2        ----         ----
430         -CH2R17-     CH2R9      ----         Ph
431         -CH2R17-     S(O)nR9    1            CH3
432         -CH2R17-     Si(R9)3    ----         CH3
433         -CH2R17-     CH＝N(R9)  ----         CH3
434         -CH2CHR17-   NH2        ----         ----
435         -CH2CHR17-   CH2R9      ----         Ph
436         -CH2CHR17-   Si(R9)3    ----         CH3
437         -CH2CHR17-   CH＝N(R9)  ----         CH3
438         -OCH2-       NH2        ----         ----
439         -OCH2-C      H2R9       ----         Ph
440         -OCH2-       Si(R9)3    ----         CH3
441         -OCH2-       CH＝N(R9)  ----         CH3
化合物序号  X            R8         Y            Ra
442         -CH2R17-     Y          N-oxide      ----
443         -CH2R17-     ORa        ----         H
444         -CH2R17-     ORa        ----         CH3
445         -CH2CHR17-   Y          N-oxide      ----
446         -CH2CHR17-   ORa        ----         H
447         -CH2CHR17-   ORa        ----         CH3
448         -OCH2-       Y          N-oxide      ----
449         -OCH2-       ORa        ----         H
450         -OCH2-       ORa        ----         CH3
表2
农药杂环化合物
特性数据
化合物  实验式         物理状态          化合物     实验式        物理状态
序号                                     序号
1       C13H16N2       固体              47         C14H18N2HCl   固体
2       C13H16N2HCI    固体              48         C14H18N2      固体
3       C13H15FN2      固体              50C        15H20N2O      固体
4       C13H15CIN2O    固体              51         C16H22N2O     固体
5       C13H15IN2O     固体              52         C15H17F3N2O   固体
6       C14H18N2O      固体              55         C15H17N3O     固体
7       C14H18N2OHCl   固体              59         C16H18N2O     油
8       C12H13CIN2     固体              65         C13H14Cl2N2   固体
9       C12H13CIN2     固体mp122-130℃   66         C13H14Cl2N2   固体
10      C12H14CIN2HCl   固体mp250-254℃   67         C13H14Cl2N2   液体
11      C12H12Cl2N2    固体              68         C13H16N2      固体
12      C13H16N2HCl    固体              69         C14H17BrN2O   固体
13      C13H16N2HCl    固体              70C        13H15CIN2     固体
14      C13H16N2       固体              71         C15H19CIN2O   固体
15      C13H16N2HCl    固体              88         C13H16N2O2    固体
16      C14H18N2HCl    固体              89         C14H18N2O2    固体
17      C12H13FN2HCl   固体              139        C14H18N2OS    固体
18      C12H14N2OHBr   固体              141        C13H16N2S     固体
19      C13H15CIN2O    固体              152        C14H19N3O     固体
22      C12H12Cl2N2    固体              201        C16H19N3O     油
23      C13H15ClN2     固体              202        C16H20N2O3    固体
24      C14H16F2N2O    固体              203        C16H23N2O4S   油
26      C13H17N3       固体              204        C16H23N2O5P   油
27      C15H17N2       固体              205        C15H17N3O2    固体
29      C15H16N2       固体              206        C15H20N2O2    油
31      C15H2N2O       固体              215        C15H18N2O     固体197-229℃
35      C15H20N2       固体              221        C22H24N2O     油
36      C14H17ClN2O    固体              222        C17H22N2O     油
37      C14H18N2       固体              223        C16H20N2O     油
38      C13H15FN2      固体              226        C14H16N2O     固体
39      C13H15FN2O     固体              231        C17H22N2O2    油
40      C15H20N2O       固体              232        C21H28N2O2    油
42      C13H15ClN2HCl  固体              233        C16H20N2O     油
43    C13H15ClN2       固体             234      C16H21N3O4S       油
44    C13H16ClN2HCl    固体mp195-199℃  257      C14H16N2O         固体mp68-70℃
45    C14H19N2HCl      固体             264      C15H18N2O         固体
46    C14H18N2         固体             272      C14H16N2O2        固体
                                        278      C16H21N3O4S       固体mp138-139℃
作为评价化合物，例如本发明的通式I化合物的杀虫活性的方法之一，可比较处理区和未处理区的开始时已知的的虫口密度和经过一个时期后的虫口密度。例如棉蚜由于在其活动区与用试验化合物处理过的宿主植物而发生接触而逃逸。一旦棉蚜离开已处理的宿主植物，一般会因为得不到由取食宿主植物的营养而死亡。因此，本发明化合物在试验杀虫活性时，可观察到与未处理植物的棉蚜虫口密度相比，由于试验化合物在处理棉花植物上的高活性，棉蚜的虫口密度会减少。这些试验做法如下：
对于每个试验化合物的应用比率，选用二盆7至10天龄的大陆棉苗(Gossypiumhirsutium)生长于7.6cm直径的花盆以供试验之用。每株试验植物寄生有约120只棉蚜成虫，这些棉蚜源自棉花植物上长大的棉蚜寄生处，放至每片试验植物剪下的叶上。感染后，试验植物保持约12小时，让棉蚜完全易位至试验植物上。将每个试验化合物3mg溶于1ml丙酮配成300ppm溶液。每个溶液用9ml由0.03ml聚氧乙烯(10)异辛基苯醚在100ml水中的溶液稀释。每种试验化合物约需2.5ml喷洒至试验植物，每次试验均一式二份喷洒(对每个试验化合物总量为5ml)。如果需要，将上述300ppm的试验化合物用10％丙酮和300ppm聚氧乙烯(10)异辛基苯基醚在水中的溶液作系列稀释，以提供较低剂量配比之用，例如100ppm，10ppm，或3ppm。将试验化合物的溶液对每个试验植物一式二份喷洒，直至在叶子的上表面和下表面都喷到。对所有试验植物的喷洒均用Devilbus AtomizeR152型(Sunrise Medical，Carsbad，CA)型器械，以约0.63-0.74kg/cm2的压力，对试验植物的距离约30.5cm进行。为作对照之用，配成标准溶液，诸如(amitraz)或(demethylchlordimeform、DCDM)，以类似上述方法配制，也用10％丙酮和聚氧乙烯(10)异辛基苯醚在水中的300ppm溶液而不含试验化合物，也同样喷洒在试验植物上。将试验化合物的溶液、标准溶液以及不含试验化合物的溶液喷完后，让植物晾干。干燥完全后，将试验植物放至含2.5cm高度水的浅盘中，置培养室中至少24小时。然后，评估每株植物由试验化合物的高活性引起的蚜虫虫口密度的减少，与不用试验化合物的蚜虫密度比较。如果用化合物在植物上喷洒后棉蚜的虫口密度至少减少50％，则认为该化合物具有杀虫活性(SA)。如果试验植物上减少棉蚜虫口密度配制至少75％，则认为该化合物有较高的杀虫活性(A)。如果棉蚜很少或没有离开植物，则认为该试验化合物无活性(I)
所选的施用率的杀虫活性的结果列于表3。通式I的试验化合物用与表1中相应的序号表示
表3
杂环类农药对棉蚜的杀虫活性试验对棉蚜的药效
化合物序号         SA              A
1                                  X
2                  X
3                  X
4                                  X
5                  X
6                                  X
7                                  X
8                                  X
9                                  X
10                 X
11                 X
12                                 X
13                 X
14                 X
15                 X
16                                 X
17                                 X
18                                 X
19                                 X
22                                 X
23                 X
241                X
261                X
27                                 X
29                 X
311                                X
35                 X
361                                X
37                               X
38                               X
393                              X
40                               X
42            X
43                               X
44                               X
45                               X
46                               X
47                               X
48                               X
50                               X
511                              X
521                              X
552                              X
591           X
651                              X
661                              X
671                              X
68                               X
691           X
701           X
711                              X
88                               X
891                              X
139                              X
141                              X
1521          X
2011                             X
2021                             X
2032                             X
2042                             X
2051                             X
2061          X
2151                             X
2211                             X
2221          X
2232                             X
2261                             X
2311                     X
2321                     X
2331                     X
2341                     X
257                      X
2641                     X
2721                     X
2781                     X
除注明之外，昆虫接触植物为24小时(接触时期24小时)，该植物用300ppm试验化合物的浓度处理。
1、昆虫接触处理过的植物48小时(接触时期48小时)。
2、昆虫接触处理过的植物72小时(接触时期72小时)。
3、昆虫接触处理过的植物72小时(接触时期72小时)，用1000ppm浓度试验化合物处理植物。
在前述表中，表3所列的通式I化合物的大多数至少可使棉蚜虫口密度减少75％，而其余通式I化合物则至少可使棉蚜虫口密度减少50％。
虽然本发明的表述更着眼于优选实施方案的介绍，但本领域中的一般技术人员可理解，可以使用优选实施方案的各种变体，并且将本发明用于实践而不只在此详述。因此，本发明包括所有的变体均未脱离如下列权利要求书所限定的实质和范围。

Claims (20)

1.通式I化合物，或其农业上可接受的盐类；
其中：
-R和R1分别选自氢和C1-C12-烷基；
-R2和R3一起代表＝NC(R6)＝C(R7)N(R8)-，＝NCH(R6)CH(R7)N(R8)-，或其互变异构体，形成五元环；
其中
R6和R7分别选自氢和C1-C12-烷基；
R8选自氢，C1-C12-烷基，氨基，硝基，氰基，甲酰基，-CH2R9，-CH2OR9，-C(O)R9，-C(O)OR9，-CH2OC(O)R9，-C(O)N(R9)(R10)，-S(O)nR9，-S(O)nN(R9)(R10)，其中n为0，1或2，-Si(R9)3，-CH＝N(R9)，-P(O)(OR9)(OR10)，-P(O)(NR9R10)(NR9R10)和Y，在此Y表示i)所述五元环的N-氧化物，或ii)形成ORa键，其中Ra选自氢和C1-C12-烷基；和
R9和R10各自独立地选自氢，C1-C12-烷基，C1-C12-烷羰基，C1-C12-烷氧羰基，苯基，萘基，苯基-C1-C12-烷基，萘基-C1-C12-烷基和杂芳基，其中苯基和萘基任选地被一个或多个分别选自卤素、C1-C12-烷基或卤代-C1-C12-烷基的取代基所取代；
-R4和R5一起代表-C(R11)＝C(R12)C(R13)＝C(R14)-，形成稠环，
其中
R11和R14各自独立地选自氢、卤素和甲基；
R12选自氢，卤素，氨基，C1-C2-烷基，甲氧基，卤代甲氧基，C2-C3-链烯基和C2-C3-炔基；
R13选自氢、卤素、氰基，C1-C2-烷基，羟基，甲氧基，卤代甲基以及C2-C3-炔基；
-X选自-CHR17-和-CH2CHR17-，
其中
R17选自氢和C1-C12-烷基。
2.权利要求1所述的化合物，其特征在于，R2和R3一起形成＝NCH(R6)CH(R7)N(R8)-，或其互变异构体，其中R8选自氢，氰基，-S(O)nN(R9)(R10)和-P(O)(OR9)(OR10)，其中n为2，R9和R10各自独立地选自氢和C1-C12-烷基；R11为氢，R12选自卤素和甲氧基，R13选自卤素和C1-C2-烷基。
3.权利要求2所述的化合物，其特征在于，R9和R10分别为甲基；R12选自氯和甲氧基；R13选自氯和甲基；且R14选自氢，氯和甲基；而X选自-CH2CHR17-，其中R17是氢。
4.权利要求3所述的化合物，其特征在于，R2和R3一起形成＝NCH(R6)CH(R7)N(R8)-。
5.一种杀虫剂组合物，包含至少一种杀虫有效量的通式I的化合物或其农业上可接受的盐类和至少一种与其杀虫剂相容的载体，
其中通式I的化合物为：
Figure C03812343C00031
其中
-R和R1各自选自氢和C1-C12-烷基；
-R2和R3一起形成五元环，其选自＝NC(R6)＝C(R7)N(R8)-，＝NCH(R6)CH(R7)N(R8)-，或其互变异构体；其中
R6和R7各自独立地选自氢和C1-C12-烷基；
R8选自氢，C1-C12-烷基，氨基，硝基，氰基，甲酰基，-CH2R9，-CH2OR9，-C(O)R9，-C(O)OR9，-CH2OC(O)R9，-C(O)N(R9)(R10)，-S(O)nR9，-S(O)nN(R9)(R10)，其中n为0，1，或2，-Si(R9)3，-CH＝N(R9)，-P(O)(OR9)(OR10)，-P(O)(NR9R10)(NR9R10)和Y，其中Y代表i)所述五元环的N-氧化物，或ii)形成一个ORa键，其中Ra选自氢和C1-C12-烷基；和
R9和R10各自选自氢，C1-C12-烷基，C1-C12-烷羰基，C1-C12-烷氧羰基，苯基，萘基，苯基-C1-C12-烷基，萘基-C1-C12-烷基和杂芳基，其中苯基和萘基任选被一个或多个独立地选自卤素、C1-C12-烷基或卤代-C1-C12-烷基的取代基取代；
-R4和R5一起代表-C(R11)＝C(R12)C(R13)＝C(R14)-，形成稠环，
其中
R11和R14分别选自氢、卤素和甲基；
R12选自氢，卤素，氨基，C1-C2-烷基，甲氧基，卤代甲氧基，C2-C3-链烯基和C2-C3-炔基；
R13选自氢，卤素，氰基，C1-C2-烷基，羟基，甲氧基，卤代甲基和C2-C3-炔基；和
-X选自-CHR17-和-CH2CHR17-，
其中
R17选自氢和C1-C12-烷基。
6.权利要求5所述的杀虫剂组合物，其特征在于，R2和R3一起形成＝NCH(R6)CH(R7)N(R8)-或其互变异构体，其中R9选自氢，氰基，-S(O)nN(R9)(R10)和-P(O)(OR9)(OR10)，其中n是2，而R9和R10分别选自氢和C1-C12-烷基；R11是氢，R12选自卤素和甲氧基，而R13选自卤素和C1-C2-烷基。
7.权利要求6所述的杀虫剂组合物，其特征在于，R9和R10分别是甲基；R12选自氯和甲氧基；R13选自氯和甲基；而R14选自氢，氯和甲基；X选自-CH2CHR17-，其中R17是氢。
8.权利要求7所述的杀虫剂组合物，其特征在于，R2和R3一起形成＝NCH(R6)CH(R7)N(R8)-。
9.权利要求5所述的杀虫剂组合物，所述组合物进一步包含一种或多种选自除草剂、杀虫剂、杀菌剂、杀线虫剂、植物生长调节剂、土壤调节剂和肥料的第二化合物。
10.权利要求6所述的杀虫剂组合物，所述组合物进一步包含一种或多种选自除草剂、杀虫剂、杀菌剂、杀线虫剂、植物生长调节剂、土壤调节剂和肥料的第二化合物。
11.权利要求7所述的杀虫剂组合物，所述组合物进一步包含一种或多种选自除草剂、杀虫剂、杀菌剂、杀线虫剂、植物生长调节剂、土壤调节剂和肥料的第二化合物。
12.权利要求8所述的杀虫剂组合物，所述组合物进一步包含一种或多种选自除草剂、杀虫剂、杀菌剂、杀线虫剂、植物生长调节剂、土壤调节剂和肥料的第二化合物。
13.防治昆虫的方法，包括将杀虫有效量的权利要求5的组合物施用至有昆虫出没或预期有昆虫出没的地方。
14.防治昆虫的方法，包括将杀虫有效量的权利要求6的组合物施用至有昆虫出没或预期有昆虫出没的地方。
15.防治昆虫的方法，包括将杀虫有效量的权利要求7的组合物施用至有昆虫出没或预期有昆虫出没的地方。
16.防治昆虫的方法，包括将杀虫有效量的权利要求8的组合物施用至有昆虫出没或预期有昆虫出没的地方。
17.防治昆虫的方法，包括将杀虫有效量的权利要求9的组合物施用至有昆虫出没或预期有昆虫出没的地方。
18.防治昆虫的方法，包括将杀虫有效量的权利要求10的组合物施用至有昆虫出没或预期有昆虫出没的地方。
19.防治昆虫的方法，包括将杀虫有效量的权利要求11的组合物施用至有昆虫出没或预期有昆虫出没的地方。
20.防治昆虫的方法，包括将杀虫有效量的权利要求12的组合物施用至有昆虫出没或预期有昆虫出没的地方。
CNB038123436A 2002-04-29 2003-04-28 杂环类农药 Expired - Fee Related CN100503600C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US37636302P 2002-04-29 2002-04-29
US60/376,363 2002-04-29

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CNA2007101098100A Division CN101070317A (zh) 2002-04-29 2003-04-28 杂环衍生物,含它的组合物和防治昆虫的方法

Publications (2)

Publication Number Publication Date
CN1692108A CN1692108A (zh) 2005-11-02
CN100503600C true CN100503600C (zh) 2009-06-24

Family

ID=29401336

Family Applications (2)

Application Number Title Priority Date Filing Date
CNB038123436A Expired - Fee Related CN100503600C (zh) 2002-04-29 2003-04-28 杂环类农药
CNA2007101098100A Pending CN101070317A (zh) 2002-04-29 2003-04-28 杂环衍生物,含它的组合物和防治昆虫的方法

Family Applications After (1)

Application Number Title Priority Date Filing Date
CNA2007101098100A Pending CN101070317A (zh) 2002-04-29 2003-04-28 杂环衍生物,含它的组合物和防治昆虫的方法

Country Status (13)

Country Link
US (2) US7417057B2 (zh)
EP (1) EP1499609A4 (zh)
JP (1) JP2005523925A (zh)
KR (1) KR20040102148A (zh)
CN (2) CN100503600C (zh)
AR (1) AR039331A1 (zh)
AU (1) AU2003225189B2 (zh)
BR (1) BR0309448A (zh)
IL (1) IL164621A0 (zh)
MX (1) MXPA04010804A (zh)
TW (2) TW200930291A (zh)
WO (1) WO2003092374A2 (zh)
ZA (1) ZA200408030B (zh)

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007085558A1 (en) * 2006-01-27 2007-08-02 F. Hoffmann-La Roche Ag Use of 2-imidazoles for the treatment of cns disorders
US7592362B2 (en) 2006-01-19 2009-09-22 Pfizer Limited Substituted imidazoles
AU2007214826A1 (en) 2006-02-15 2007-08-23 Bayer Cropscience Ag Insecticidal substituted amino heterocyclic and heteroaryl derivatives
CN101528710B (zh) 2006-10-19 2012-11-07 弗·哈夫曼-拉罗切有限公司 氨基甲基-4-咪唑类
WO2008052907A1 (en) 2006-11-02 2008-05-08 F. Hoffmann-La Roche Ag Substituted 2-imidazoles as modulators of the trace amine associated receptors
JP2010510184A (ja) 2006-11-16 2010-04-02 エフ．ホフマン−ラ ロシュ アーゲー 置換４−イミダゾール類
CN101557810B (zh) 2006-12-13 2012-11-21 弗·哈夫曼-拉罗切有限公司 作为痕量胺相关受体（taar）的配体的新的2-咪唑类
US20080146523A1 (en) 2006-12-18 2008-06-19 Guido Galley Imidazole derivatives
KR101174191B1 (ko) 2007-02-02 2012-08-14 에프. 호프만-라 로슈 아게 중추 신경계 장애의 치료용 ｔａａｒ1 리간드로서 2-아미노옥사졸린
WO2008098857A1 (en) 2007-02-15 2008-08-21 F. Hoffmann-La Roche Ag 2-aminooxazolines as taar1 ligands
EP2014168A1 (de) * 2007-06-19 2009-01-14 Bayer CropScience AG Insektizide heterocyclische Verbindungen
EP2173720A2 (en) 2007-07-02 2010-04-14 F. Hoffmann-Roche AG 2-imidazolines having a good affinity to the trace amine associated receptors (taars)
CA2691704A1 (en) 2007-07-03 2009-01-08 F. Hoffmann-La Roche Ag 4-imidazolines and their use as antidepressants
KR101133862B1 (ko) 2007-07-27 2012-04-06 에프. 호프만-라 로슈 아게 Ｔａａｒ 리간드로서의 2-아제티딘메테인아민 및 2-피롤리딘메테인아민
WO2009019149A1 (en) 2007-08-03 2009-02-12 F. Hoffmann-La Roche Ag Pyridinecarboxamide and benzamide derivatives as taar1 ligands
US8242153B2 (en) 2008-07-24 2012-08-14 Hoffmann-La Roche Inc. 4,5-dihydro-oxazol-2YL derivatives
US8354441B2 (en) 2009-11-11 2013-01-15 Hoffmann-La Roche Inc. Oxazoline derivatives
KR101855471B1 (ko) * 2009-12-04 2018-05-09 선오비온 파마슈티컬스 인코포레이티드 다환형 화합물 및 이의 사용 방법
US9452980B2 (en) 2009-12-22 2016-09-27 Hoffmann-La Roche Inc. Substituted benzamides
CA2822357A1 (en) 2010-12-22 2012-06-28 Abbvie Inc. Hepatitis c inhibitors and uses thereof
CA2855954C (en) * 2011-11-17 2020-09-01 Merial Limited Compositions comprising an aryl pyrazole and a substituted imidazole, methods and uses thereof.
CN103224468A (zh) * 2013-05-10 2013-07-31 范强 四氢唑林的合成方法
WO2015152196A1 (ja) * 2014-03-31 2015-10-08 東レ株式会社 イミダゾリン誘導体及びその医薬用途
EP3288928B1 (en) * 2015-04-27 2021-10-13 FMC Corporation Butyrolactones as herbicides
WO2017157873A1 (en) 2016-03-17 2017-09-21 F. Hoffmann-La Roche Ag 5-ethyl-4-methyl-pyrazole-3-carboxamide derivative having activity as agonist of taar
SG11201900687VA (en) 2016-07-29 2019-02-27 Sunovion Pharmaceuticals Inc Compounds and compositions and uses thereof
UA125519C2 (uk) 2016-07-29 2022-04-13 Суновіон Фармасьютікалз Інк. Сполуки і композиції і їх застосування
CN106674121A (zh) * 2016-11-22 2017-05-17 杭州励德生物科技有限公司 一种4‑卤素‑1h‑咪唑的制备方法
JP7146782B2 (ja) 2017-02-16 2022-10-04 サノビオン ファーマシューティカルズ インク 統合失調症を処置する方法
CA3070993A1 (en) 2017-08-02 2019-02-07 Sunovion Pharmaceuticals Inc. Isochroman compounds and uses thereof
SG11202007823PA (en) 2018-02-16 2020-09-29 Sunovion Pharmaceuticals Inc Salts, crystal forms, and production methods thereof
AU2020236225A1 (en) 2019-03-14 2021-09-16 Sunovion Pharmaceuticals Inc. Salts of a isochromanyl compound and crystalline forms, processes for preparing, therapeutic uses, and pharmaceutical compositions thereof
IL297248A (en) 2020-04-14 2022-12-01 Sunovion Pharmaceuticals Inc (s)-(5,4-dihydro-7h-thiano[3,2-c]pyran-7-yl)-n-methylmethanamine for the treatment of neurological and psychiatric disorders

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2731471A (en) * 1956-01-17 Nxg hi
US2948724A (en) * 1958-04-21 1960-08-09 Sahyun Halogenated derivatives of tetrahydro-1-naphthyl cyclic amidines
US3485917A (en) 1966-04-14 1969-12-23 Janssen Pharmaceutica Nv Composition and method for combating fungus with imidazole carboxylates
CH619701A5 (zh) * 1975-08-07 1980-10-15 Bayer Ag
US4634705A (en) 1984-06-06 1987-01-06 Abbott Laboratories Adrenergic amidines
JPS63183579A (ja) * 1987-01-23 1988-07-28 Ss Pharmaceut Co Ltd 新規な２ｈ−１−ベンゾピラン誘導体
JP3061063B2 (ja) * 1990-11-14 2000-07-10 サントリー株式会社 イミダゾリル基を有する縮合７員環系化合物
GB2256135B (en) 1991-05-31 1995-01-18 Orion Yhtymae Oy Transdermal administration of 4-substituted imidazoles
GB9425211D0 (en) * 1994-12-14 1995-02-15 Ucb Sa Substituted 1H-imidazoles
GB9520150D0 (en) * 1995-10-03 1995-12-06 Orion Yhtymae Oy New imidazole derivatives
US6313309B1 (en) * 1999-04-05 2001-11-06 Ortho-Mcneil Pharmaceutical, Inc. 4-thionaphthyl—1H—imidazoles which are usefulα22-adrenoceptoR agonists/ antagonists
FI20000073A0 (fi) * 2000-01-14 2000-01-14 Orion Yhtymae Oy Uusia imidatsolijohdannaisia
FR2810979B1 (fr) * 2000-06-29 2002-08-23 Adir Nouveaux derives de diphenyluree, leur procede de preparation et les compositions pharmaceutiques qui les contiennent

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHARGE TRANSFER COMPLEXES OF DRUGS WITH IODINE INVESTIGATIONBY UV/VISIBLE SPECTROSCOPY. A.C.JAMBUT-ABSIL ET AL.INTERNATIONAL JOURNAL OF PHARMACEUTICS,Vol.35 . 1987 *
ETUDES PHOTOCHIMIQUES-XIII REACTIONS DE PHOTOADDITION DUBENZO[b]THIOPHENE ACEC DES AMINES ET AVEC LE PYRROLE. P.GRANDCLAUDON ET AL.TETRAHEDRON,Vol.29 . 1973 *
Medetomidine analogs as alpha-2 adrenergic ligands. ZHANG ET AL.Journal of medicinal chemistry, american chemical society,Vol.40 . 1997 *

Also Published As

Publication number Publication date
US7767667B2 (en) 2010-08-03
TW200306783A (en) 2003-12-01
IL164621A0 (en) 2005-12-18
WO2003092374A3 (en) 2004-08-12
US20050143418A1 (en) 2005-06-30
JP2005523925A (ja) 2005-08-11
EP1499609A2 (en) 2005-01-26
EP1499609A4 (en) 2005-09-14
AR039331A1 (es) 2005-02-16
KR20040102148A (ko) 2004-12-03
AU2003225189B2 (en) 2009-10-01
US7417057B2 (en) 2008-08-26
CN1692108A (zh) 2005-11-02
TW200930291A (en) 2009-07-16
ZA200408030B (en) 2005-10-19
BR0309448A (pt) 2005-02-09
AU2003225189A1 (en) 2003-11-17
US20090012070A1 (en) 2009-01-08
MXPA04010804A (es) 2005-03-07
CN101070317A (zh) 2007-11-14
WO2003092374A2 (en) 2003-11-13

Similar Documents

Publication Publication Date Title
CN100503600C (zh) 杂环类农药
BRPI0610195A2 (pt) derivados inseticidas de aminoalquil heterociclila e heteroarila substituìdas
JP2008545744A (ja) フェニルアルキル置換ヘテロアリール誘導体
JP2006525338A (ja) 殺虫性（ジハロプロペニル）フェニルアルキル置換ベンゾジオキソラン及びベンゾジオキソール誘導体
TW200418383A (en) Insecticidal tricyclic derivatives
AU5977596A (en) Herbicidal substituted 3-aryl-pyrazoles
WO2006138148A1 (en) Pesticidal 5-bis(methoxymethyl)aminopyrazole derivatives
JPS61130275A (ja) ピリダジノン誘導体，その製造法および殺虫・殺ダニ・殺菌剤
CN101094843A (zh) 杀虫的3－(二卤代烯基)苯基衍生物
CN1980903A (zh) 取代的环状脲衍生物
JP2008518929A (ja) 殺昆虫性ｎ，ｎ−ジ（ヘテロアリールアルキル）アミン誘導体
WO1991001978A1 (en) Triazine derivatives
JPS61243078A (ja) ピリダジノン誘導体，その製造法および殺虫・殺ダニ・殺線虫・殺菌剤
JPS58157771A (ja) △２−１，２，４−トリアゾリン−５−オン誘導体及びその製法並びにその用途
JPH0649041A (ja) カルバモイルトリアゾール誘導体、それを有効成分とする除草剤およびその製造方法
JP2007513166A (ja) 殺虫効果を有するｎ−（ヘテロアリールアルキル）アルカンジアミン誘導体
US20040157892A1 (en) Pesticidal fluoroethyl pyrazoles
CN115536586A (zh) 吡唑酰胺类化合物及其制备方法和应用
CN113512002A (zh) 含有偶氮结构的吡唑酰胺类化合物及其制备和应用
GB2185742A (en) Plant growth regulating triazoles
JPS62207262A (ja) ピリダジノン誘導体、その製法および殺虫、殺ダニ、殺線虫、殺菌剤
JPH0465805B2 (zh)
JPS6016974A (ja) ピラゾ−ル誘導体，その製造方法および選択性除草剤
MX2007004631A (en) Insecticidal 3-(dihaloalkenyl) phenyl derivatives

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
ASS Succession or assignment of patent right

Owner name: BAYER CROPSCIENCE AG

Free format text: FORMER OWNER: FMC CORP.

Effective date: 20071207

C41 Transfer of patent application or patent right or utility model
TA01 Transfer of patent application right

Effective date of registration: 20071207

Address after: The German Rhine Monheim

Applicant after: Bayer Cropscience SA

Address before: American Pennsylvania

Applicant before: FMC Corp.

C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20090624

Termination date: 20100428