CN1028475C - Pyrrole insecticides - Google Patents

Pyrrole insecticides Download PDF

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CN1028475C
CN1028475C CN89108985A CN89108985A CN1028475C CN 1028475 C CN1028475 C CN 1028475C CN 89108985 A CN89108985 A CN 89108985A CN 89108985 A CN89108985 A CN 89108985A CN 1028475 C CN1028475 C CN 1028475C
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cyano group
pyrroles
chloro
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CN1043500A (en
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菲力普·梯蒙斯
罗西尔·奥托卡脱
苏姗·克拉姆泼
派脱里西·克威特考夫斯基
阿尼巴尔·罗比斯
戴维·西诺梯斯
派乌尔·凯因
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Bayer CropScience SA
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Rhone Poulenc Agrochimie SA
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms

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  • Life Sciences & Earth Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Pyrrole Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Substituted-1-arylpyrrole compounds of general formula below.

Description

Pyrrole insecticides
The present invention relates to the noval chemical compound of pyroles and prepare the intermediate product of these compounds, and the method for preparing these compounds and intermediate product thereof.The invention still further relates to the application of described compound in agricultural.Especially for arthropodan insecticide, be preferably as insecticide and miticide.The invention still further relates to control arthropods, particularly insect and spider guiding principle class animal, useful agrochemical composition.
Many pyrazoles materials (heterocycle structure that contains two nitrogen-atoms) are well-known insecticides.Also some to comprise pyrrole group (structure that contains a nitrogen-atoms) also be known insecticide.Yet they have also comprised another chemical group usually in its structural formula, and this group itself has insecticidal properties as everyone knows, such as the pyrethroid ester group, or amino cresols ester group or some organic phosphor group.The simple azole derivatives that replaces is is recorded and narrated to agrochemicals, such as BP 2,189,242, but is to be used for as fungicide.
Novel azole compounds of the present invention has structural formula (I)
Figure 891089853_IMG16
In the formula:
X can be a halogen atom, or cyano group, cyanato-, the sulfo-cyanato-, haloalkyl, alkoxyl, halogenated alkoxy, alkylthio group, alkyl sulphinyl, alkyl sulphonyl, halogenated alkylthio, haloalkyl sulfinyl, halogenated alkyl sulfonyl, sulfo-thiazolinyl, thiazolinyl sulfinyl, the thiazolinyl sulfonyl, haloalkene sulfenyl, haloalkenyl group sulfinyl, the haloalkenyl group sulfonyl, halogenated alkyl carbonyl, haloalkyl thio carbonyl, thiophenyl, the phenyl sulfinyl, phenyl sulfonyl, hetero-aromatic ring sulfenyl, hetero-aromatic ring base sulfinyl, or hetero-aromatic ring base sulfonyl; Wherein phenyl is optionally to be replaced by halogen, cyano group or haloalkyl, the hetero-aromatic ring base is 5 or 6 yuan a monocyclic groups, wherein contains one or two such as oxygen, sulphur or nitrogen with the hetero atom of any combining form and be optionally to be replaced by halogen, nitro, cyano group or haloalkyl; And in all above-mentioned groups that comprise one or more halogen atoms, halogen atom wherein can be identical or different, replace until replacing fully from single, alkyl, haloalkyl, alkenyl, haloalkenyl group, alkoxyl and halogenated alkoxy be straight chain type or branched chain type, and have and usually be less than 10 carbon atoms, be less than 5 carbon atoms preferably;
R 1, R 2And R 3Can be to be selected from: with as above to the described identical substituting group of X; Hydrogen atom; Alkyl; And has only one of them (R 1, R 2, R 3) substituting group can be selected from formyl, the oximido alkylidene, the alkoxyimino alkylidene, azido, amino, alkylamino, dialkylamino, arylalkylamino, amino carbonyl amino, alkyl-carbonyl-amino, halogenated alkyl carbonyl amino, aryl-amino-carbonyl, alkyl sulfonyl amino, the alkylhalide group sulfonamido, alkyl amino-carbonyl amino, aromatic yl aminocarbonyl amino, the benzal imino group, alkylideneimino, alkoxyl alkylideneimino, the dialkyl amido alkylideneimino, two (alkylthio) methyl, two (aryl sulfo-) methyl, alkylthio alkylideneimino, alkoxycarbonyl amino, the halogenated alkoxy hydroxyl amino is selectively by halogen, cyano group, or the phenyl that replaces of haloalkyl, and comprise one or two identical or different from oxygen, sulphur, or 5 or 6 yuan of monocycles of nitrogen heteroatom and selectively by halogen, nitro, the hetero-aromatic ring base that cyano group or haloalkyl replace; And in above-mentioned group, halo wherein comprises one or more halogen atoms, this replacement can be identical or different, replace until full replacement by single, and alkyl, haloalkyl, alkenyl, haloalkenyl group, alkoxyl and halogenated alkoxy be straight chain or side chain, and generally have and be less than 10 carbon number, preferably for being less than 5 carbon atoms;
Y can be halogen atom or cyano group, alkyl, haloalkyl, alkoxyl, halogenated alkoxy, alkyl sulphinyl, alkyl sulphonyl, alkylthio, halogenated alkylthio, haloalkyl sulfinyl, halogenated alkyl sulfonyl, alkyl-carbonyl, halogenated alkyl carbonyl, alkenyl (particularly pi-allyl), haloalkenyl group (particularly halogenated allyl), alkynyl (particularly propargyl) or halo alkynyl (particularly acetylenic halide propyl group); Comprise in the group of one or more halogen atoms at these, halo can be identical or different, replace until full replacement from single, and alkyl, haloalkyl, alkenyl, haloalkenyl group, alkynyl, halo alkynyl, alkoxyl and halogenated alkoxy are straight or branched, and being generally and being less than 10 carbon atoms, is 5 carbon atoms preferably; Perhaps, when X be halogen atom or radicals R 5S(O) n, wherein n is 0,1 or 2 and R 5Be alkyl, haloalkyl, alkenyl or haloalkenyl group; And alkyl and thiazolinyl carbochain and halo are as defined above; R 1And R 3Respectively be hydrogen atom R 2During for cyano group, Y is a hydrogen atom;
X 1, X 2, X 3And X 4Be selected from respectively with Y is recorded and narrated identical substituting group or hydrogen atom;
Collateral condition is: R 1, R 2And R 3In at least one is to be selected from to identical substituting group that X recorded and narrated; If X 4And X 1Be hydrogen, X is halogen or cyano group, then R 2Different with X; If X 4And X 1Be hydrogen, Y is a methyl, and then X is not a bromine.
General expression of the present invention is that other concrete compounds of I are as described below, in the formula:
X can be a halogen atom, or cyano group, cyanato-, sulfo-cyanato-, haloalkyl, alkoxyl, halogenated alkoxy, alkylthio group, alkyl sulphinyl, alkyl sulphonyl, halogenosulfanes base, haloalkyl sulfinyl, the alkyl halide sulfonyl, halogenated alkyl carbonyl, haloalkyl thio carbonyl, thiophenyl, phenyl sulfinyl, phenyl sulfonyl, sulfo-hetero-aromatic ring base, hetero-aromatic ring sulfinyl, or hetero-aromatic ring sulfonyl; Wherein phenyl is selectively to be replaced by halogen, cyano group or haloalkyl, the hetero-aromatic ring base be comprise one or two such as oxygen, sulphur or nitrogen hetero atom by any way combination 5 or 6 yuan of monocycle bases and be selectively to be replaced by halogen, nitro, cyano group or haloalkyl; And in all above-mentioned groups, halo is single replaces or until full replacement, alkyl, haloalkyl, alkoxyl and halogenated alkoxy be straight chain or side chain, and generally have and be less than 10 carbon atoms, preferably for being less than 5 carbon atoms.
R 1, R 2And R 3Can be selected from identical substituting group X recorded and narrated; Hydrogen atom; Alkyl; And R only 1, R 2, R 3In one substituting group can be to be selected from formyl, oximido alkylidene, alkoxyimino alkylidene, azido, amino, alkyl amino, dialkyl amido, arylamino, amino carbonyl amino, alkyl-carbonyl-amino, halogenated alkyl carbonyl amino.Aryl-amino-carbonyl, alkyl sulfonyl-amino, haloalkyl sulfonamido, alkyl amino-carbonyl amino, aromatic yl aminocarbonyl amino, the benzal imino group, alkylideneimino, the alkoxyl alkylideneimino, the dialkyl amido alkylideneimino, selectively by the phenyl of halogen, cyano group or haloalkyl replacement, and comprising one or two heteroaryls identical or different heteroatomic 5 yuan or 6 yuan monocycles such as oxygen, sulphur or nitrogen, this heteroaryl is selectively replaced by halogen, nitro, cyano group or haloalkyl; Halo in above-mentioned all groups is single replace or until replacing fully, and alkyl, haloalkyl, alkoxyl and halogenated alkoxy be straight or branched, and has and generally be less than 10 carbon atom, is less than 5 carbon atoms preferably.
Y can be halogen atom or cyano group, alkyl, haloalkyl, alkoxyl, halogenated alkoxy, alkyl sulphinyl, alkyl sulphonyl, alkylthio group, halogenated alkylthio, the haloalkyl sulfinyl, halogenated alkyl sulfonyl, alkyl-carbonyl, halogenated alkyl carbonyl, alkenyl (particularly pi-allyl), haloalkenyl group (particularly halogenated allyl), alkynyl (particularly propargyl) or halo alkynyl (particularly acetylenic halide propyl group); And to replace be single replace or until full replacement and alkyl to halogen in these groups, haloalkyl, alkoxyl, halogenated alkoxy, alkynyl and halo alkynyl be straight chain or side chain, and have and generally be less than 10 carbon atom, preferably for being less than 5 carbon atoms;
X 1, X 2, X 3And X 4As defined above, and be suitable for above-mentioned collateral condition.
Usually be following general expression (I) compound as insecticide and acaricidal general expression preferably (I) compound, in the formula:
X is halogen atom or R 5S(O) nGroup, wherein n is 0,1 or 2, R 5Be alkyl, haloalkyl, alkenyl or haloalkenyl group;
R 1Be hydrogen atom, halogen atom or alkylthio group; R 2Be cyano group R 3Be hydrogen atom or halogen atom;
Y is a hydrogen atom, halogen atom, and haloalkyl or halogenated alkoxy suppose that in general expression (I) Y is a hydrogen as defined above; And
X 1, X 2, X 3And X 4Select hydrogen atom respectively, halogen atom, C 1-3Alkyl, C 1-3Alkoxyl, and C 1-3Alkylthio group.
Preferably and other compounds of useful especially general expression (I) are following compounds:
A) have the high insect active that kills, general expression (II) compound,
Figure 891089853_IMG17
In the formula:
X is R 5S(O) n, wherein n is 0,1 or 2, R 5Be CH 3, CF 3, CF 2Cl, CFCl 2, CF 2Br, CHF 2, CHCl 2Or CHClF;
R 2Be cyano group;
R 1Be H, F, Cl or Br;
R 3Be H, F, Cl or Br;
X 1Be H or Cl; And
Y is CF 3Or CF 3O
In these compounds, compound is preferably:
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(trifluoromethyl sulfo-) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(trifluoromethyl sulfonyl) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(dichloro one methyl fluoride sulfo-) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(dichloro one methyl fluoride sulfinyl) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(dichloro one methyl fluoride sulfonyl) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(one chlorodifluoramethyl-sulfonyl) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(one chlorodifluoramethyl-sulfinyl) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(one chlorodifluoramethyl-sulfo-) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-bromo-3-cyano group-4-(trifluoromethyl sulphinyl base) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-bromo-3-cyano group-4-(trifluoromethyl sulfonyl) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-bromo-3-cyano group-4-(dichloro one methyl fluoride sulfo-) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-bromo-3-cyano group-4-(dichloro one methyl fluoride sulfonyl) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-and 2-bromo-3-is fluorine-based-4-(dichloro one methyl fluoride sulfinyl) and the pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-bromo-3-cyano group-4-(one chlorodifluoramethyl-sulfo-) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-bromo-3-cyano group-4-(one chlorodifluoramethyl-sulfinyl) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-bromo-3-cyano group-4-(one chlorodifluoramethyl-sulfonyl) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(difluoro one methyl fluoride sulfonyl)-5-bromine pyrroles;
1-(2,6-two chloro-4-Trifluoromethoxyphen-ls)-2-ammonia-3-cyano group-4-(dichloro one methyl fluoride sulfinyl) pyrroles;
1-(2,6-two chloro-4-Trifluoromethoxyphen-ls)-2-chloro-3-cyano group-4-(dichloro one methyl fluoride sulfonyl) pyrroles;
1-(2,6-two chloro-4-Trifluoromethoxyphen-ls)-2-ammonia-3-cyano group-4-(dichloro one methyl fluoride sulfonyl) pyrroles;
1-(2-chloro-4-trifluoromethyl)-and 2-chloro-3-cyano group-4-(dichloro one methyl fluoride sulfonyl) pyrroles;
1-(2-chloro-4-trifluoromethyl)-and 2-bromo-3-cyano group-4-(dichloro one methyl fluoride sulfinyl) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(dichloro one methyl fluoride sulfo-)-5-methyl sulfo-pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(one bromine difluoro methyl sulfo-) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(one bromine difluoro methyl sulfinyl) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(one bromine difluoro methyl sulfonyl) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(methylsulfinyl) pyrroles; Perhaps
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(methyl sulphonyl) pyrroles;
B) has the high compound that kills other general expressions of insect active for (II);
X is R 5S(O) n, n is 0,1 or 2, and R 5Be CH 3, CF 3, CF 2Cl or CFCl 2,
R 2Be cyano group;
R 1Be H, F, Cl, Br or NH 2;
R 3Be H, F, Cl, Br, CF 3Or CN;
X 1Be H or Cl; And
Y is CF 3Or CF 3O.
According to kill insect active preferably The compounds of this invention be:
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(trifluoromethyl sulfo group) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(trifluoromethyl sulphinyl base) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(trifluoromethyl sulphinyl base)-5-bromine pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(trifluoromethyl sulfonyl)-5-bromine pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(trifluoromethyl sulfo-) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-bromo-3-trifluoromethyl sulfo--4-cyano group-5-chlorine pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-the 2-[(trifluoromethyl) carbonylamino]-3-trifluoromethyl sulfo--4-cyano group-5-chlorine pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-(methyl carbonylamino)-3-trifluoromethyl sulfo--4-cyano group-5-chlorine pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-amino-3-trifluoromethyl sulfo--4-cyano group-5-chlorine pyrroles;
1-(2-chloro-4-trifluoromethyl)-2-amino-3-trifluoromethyl sulfo--4-cyano group-5-chlorine pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-amino-3-dichloro one methyl fluoride sulfo--4-cyano group-5-chlorine pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2, two (trifluoromethyl the sulfo-)-3-cyano group of 4--5-amino-pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-amino-3-trifluoromethyl sulfo--4-cyano group-5-bromination pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-amino-3-trifluoromethyl sulfo--4-cyanopyrrole;
The 1-(4-trifluoromethyl)-2-amino-3-trifluoromethyl sulfo--4-cyano group-5-bromine pyrroles;
1-(2-chloro-4-trifluoromethyl)-2-amino-3-trifluoromethyl sulfo--4-cyano group-5-bromine pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(dichloro one methyl fluoride sulfo-) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(dichloro one methyl fluoride sulfinyl) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(dichloro one methyl fluoride sulfonyl) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano group-4-(dichloro one methyl fluoride sulfo-) pyrroles;
1-(2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano group-4-(dichloro one methyl fluoride sulfinyl) pyrroles; Perhaps
1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(trifluoromethyl sulfonyl) pyrroles;
C) have the compound of the general expression (I) of high especially acaricidal activity, in the formula:
X is a halogen, or R 5S(O) n, wherein n is 0,1 or 2, R 5For alkyl, be C preferably 1-4Alkyl, is that (and preferably, wherein halogen is that F, Cl, Br maybe can have replacement concurrently to trihalomethyl group, such as CF preferably at haloalkyl 3, CCl 3, CF 2Cl, CFCl 2Or CF 2Br), alkenyl, or haloalkenyl group;
R 1And R 3It respectively is hydrogen atom;
R 2Be cyano group;
Y is hydrogen atom or halogen atom, is Cl or Br preferably;
And
X 1, X 2, X 3And X 4Be to be selected from hydrogen separately, halogen, C 1-3Alkyl, C 1-3Alkoxyl, and C 1-3Alkylthio group, and X preferably 1And X 4Be respectively do for oneself H, F, Cl, Br or CH 3And X 2And X 3The hydrogen of respectively doing for oneself.
In these compounds, some preferably compound be:
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(one chlorodifluoramethyl-sulfo-) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(trifluoromethyl sulfo-) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(one chlorodifluoramethyl-sulfo-) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(one chlorodifluoramethyl-sulfinyl) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(dichloro one methyl fluoride sulfo-) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(dichloro one methyl fluoride sulfinyl) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(dichloro one methyl fluoride sulfinyl) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(dichloro one methyl fluoride sulfo-) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(dichloro one methyl fluoride sulfinyl) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(dichloro one methyl fluoride sulfonyl) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(trifluoromethyl sulfo-) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(trifluoromethyl sulphinyl base) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(trifluoromethyl sulfonyl) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(trifluoromethyl sulfo-) pyrroles;
1-(2, the 4-dichlorophenyl)-3-cyano group-4-(dichloro one methyl fluoride sulfo-) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-chlorine pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(one chlorodifluoramethyl-sulfonyl) pyrroles;
1-(2, the 6-dichlorophenyl)-3-cyano group-4-(dichloro one methyl fluoride sulfo-) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(trifluoromethyl sulphinyl base) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(trifluoromethyl sulfonyl) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(one chlorodifluoramethyl-sulfinyl) pyrroles;
1-(4-bromo-2, the 6-3,5-dimethylphenyl)-3-cyano group-4-(trifluoromethyl sulphinyl base) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(one chlorodifluoramethyl-sulfonyl) pyrroles;
1-(4-bromo-2, the 6-3,5-dimethylphenyl)-3-cyano group-4-(trifluoromethyl sulfonyl) pyrroles;
Perhaps
1-(4-bromo-2, the 6-difluorophenyl)-3-cyano group-4-(dichloro one methyl fluoride sulfo-) pyrroles;
D) other preferably the compound of general expression (I) be compound with general expression (I), and in the formula
R 1Be hydrogen atom or halogen atom, such as chlorine or bromine;
R 2Be cyano group;
X is haloalkyl thio group or haloalkyl sulfinyl or halogenated alkyl sulfonyl, is CF preferably 3S(O) n, n is 0,1 or 2;
X 1And X 4Be the atom except hydrogen;
X 2And X 3The hydrogen of respectively doing for oneself is atom, and
Y is haloalkyl or halogenated alkoxy.
The midbody compound that an object of the present invention is to provide pyroles novel insecticide and miticide and prepare them.
Another object of the present invention provides active very strong compound and synthetic method and their application.These and other purpose of the present invention is obtained by compounds described below fully or partly.
Synthetic method or technology
The compound of general expression (I) can prepare by use or revise known method (method that used or that described promptly) in Chemistry Literature: follow needs change substituting group after usually forming pyrrole ring.Also should be appreciated that: in the description of process below, on pyrrole ring, introduce the order of various groups and can finish, and can require suitable blocking group, as well-known to those skilled in the art with order inequality.General expression (I) compound can also change into other compounds of general expression (I) by known method.
In the description of following process, the symbol that occurs in the molecular formula is definition especially not, can be regarded as " as previously mentioned ", according to the definition first time of each symbol in this specification.Term " protection " should comprise and changes into suitable not reactive group, and the not adding of reactive functional group is provided.In the definition of technology, except that explanation, the unsubstituted amino of amino expression.
Present invention includes specific midbody compound, these intermediates are useful to preparing compound of expecting here.This midbody compound preferably, preparation as described herein, (III is a) to have general expression
Y is H, Cl, Br, CF in the formula 3Or OCF 3, X 1And X 4Be respectively H, Cl, F, CH 3Or SCH 3, suppose X 1And X 4Respectively be H, then Y is the group outside H or the Cl.This compound by the hypothesis definition does not belong to the interest field that the present invention requires, but still is the useful as intermediates of the compound of preparation general expression of the present invention (I).
As the intermediate general expression (III a) compound preferably those Y be CF 3Or OCF 3, X 1Be H or Cl, X 4Compound for Cl
Method 1
According to characteristics of the present invention, the compound of general expression (II), wherein R 1And R 2For hydrogen atom, X are cyano group, R 3Be amino (NH 2) and X 1, X 2, X 3, X 4Have identical definition in the general definition of the present invention that coexists with Y, that is to say, general expression (III) compound can be the dicyano acryloyl derivative of IV from general expression
(in the formula each symbol as defined above), by preparing with the alkaline reagent reaction, this alkaline reagent is the alkaline reagent such as tertiary amine or alkali metal hydroxide or alkali carbonate preferably.Preferentially reaction between-80 to 150 ℃ of reaction is preferably at 40 to 100 ℃.Solvent can be used, such as liquid alcohol, and hydrocarbon, halogenated hydrocarbon, ether, ketone is such as the amine of N-Methyl pyrrolidone, perhaps water.
Method 2
According to another characteristics of the present invention, general expression (IV) compound can prepare by the alkali metal salt reaction with formyl succinonitrile or formyl succinonitrile from the anil of general expression (V)
X in the formula 1, X 2, X 3, X 4Have disclosed in the General Definition of the present invention that coexists identical with Y.Described reaction generally in organic solvent or in the water, is reacted under 10 to 120 ℃ temperature, reacts under reflux temperature preferably.
Formyl fourth two is nitrile known compounds, generally can prepare by the acidifying of its alkali metal salt, alkali metal salt can be according to K.Gewald, Z.Chem.1961, reaction by succinonitrile in the presence of alkaline reagent and formic acid lower alkyl ester described in 1,349 obtains.
Method 3
The compound of general expression (I), X is a halogen in formula, R 1Be amino, R 2Be cyano group and R 3For hydrogen and other substituting groups have when the meaning described in the general definition of the present invention, can prepare by handle general expression III compound with halogenating agent, described halogenating agent is, such as, sulfonic acid chloride, N-neoprene imidodicarbonic diamide, N-bromo-succinimide, N-iodine succimide, pyridine bromide, perbromide or fluorine, chlorine, bromine or iodine molecule, the appropriate organic solvent that is used for these conversions comprises carrene and acetonitrile.Described being reflected at-80 ℃ carried out between 80 ℃, carries out at-30 ℃ to 25 ℃ preferably.When handling with element fluorine, it is favourable that amido protecting is become the trifluoroacetamido derivative.
Method 4
A) general expression (I) compound, X is a cyano group in formula, R 1Be amino, R 2Be cyano group and R 3During for meaning described in having that the present invention is general and describing of hydrogen and other substituting groups, can be that the respective compound of C=NOH group is by using acetic acid bar, cyanuric chloride or P from X 2O 5Deng reagent dehydration and prepare.Use some such dehydrating agent, need with suitable blocking group protection amino.
B) the above-mentioned midbody compound when the X in the base is C=NOH can be that the respective compound condensation of formyl forms by hydroxylamine and X.
C) X is that formyl (can be by hydrolysis X for the respective compound of two (alkylthio) methyl or two (aryl sulfo-) methyl or with after the suitable alkyl nitrites processing for being presented at following general expression (VI) midbody compound, then according to E.Fujita, Klchikawa and K.Fuji, Tetrahedron Letters 1978,3561 is hydrolyzed.With the reaction of alkyl nitrites the time, may need to protect amido functional group with suitable blocking group.
D) X is the midbody compound of two (alkylthio) methyl or two (aryl sulfo-) methyl and other groups general expression as defined above (I), can pass through general expression (III) compound and three (alkylthio) methane or three (aryl sulfo-) methane at lewis acid, be such as the existence of the sulfonium salt of first fluoboric acid dimethyl sulfuration sulfonium salt reaction and getting down preferably.The general condition that is used for this conversion can find in Synthesis 1984,166.
Method 5
A) X is a hydroxyl, R 1Be protected amino optionally, R 2Be cyano group, R 3Be hydrogen atom and X 1, X 2, X 3, X 4With Y be that the useful as intermediates compound of the general expression (I) of the described definition of general definition of the present invention can be that the corresponding compounds of halogen is by changing into refined reagent of Green or lithium derivative with standard method from X, then with oxo diperoxy molybdenum (pyridine) (hexamethyl phosphoric triamide) (Mo OPH), according to N.J.Lewis etc. at J.Org.Chem.1977, similar approach described in 44,1479 prepares and gets.Before forming refined reagent of Green or lithium derivative, may need with X be cyano group in the above-claimed cpd of halogen change into suitably protected derivative (such as, cyano group has been hydrolyzed into the respective compound De oxazoline derivative of carboxylic acid.Selectively, refined reagent of above-mentioned Green or lithium derivative can react with the trialkylboron hydrochlorate, then use hydrogen peroxide oxidation, according to M.F.Hawthorne at J.Org.Chem.1957 22,1001 or R.W.Hoffman and K.Ditrich described in the Synthesis 1983,107 similarly method produce.
B) X is a cyanato-, R 1Be amino, R 2Be cyano group, R 3Be hydrogen atom and X 1, X 2, X 3, X 4General expression (I) compound that has the definition described in general definition of the present invention with Y can be hydroxyl, R from corresponding X 1Be the amino of selectively protecting, R 3Be hydrogen atom and X 1, X 2, X 3, X 4The compound that has with same meaning in the general definition of the present invention with Y passes through to get with the cyanogen halides processing in the presence of alkali; utilization and D.Martin and M.Bauer to Org.Synth.61; similar methods described in 35 is carried out deprotection reaction if desired again.
C) X is an alkoxyl, R 1Be amino, R 2Be cyano group, R 3Be hydrogen atom and X 1, X 2, X 3, X 4General expression (I) compound that has with the identical definition described in the general definition of the present invention with Y can be a hydroxyl from corresponding X, R 1Be protected amino selectively, R 3Be hydrogen atom and X 1, X 2, X 3, X 4Has compound with Y with the identical definition described in the general definition of the present invention; by in the presence of alkali; in solvent such as acetone or dimethyl formamide; at 25 ℃ to the scope between the reflux temperature of solvent; use alkyl halide; alkyl sulfonic ester, dialkyl carbonate and analog are handled and are got, and carry out protective reaction if desired again.
C) X is a halogenated alkoxy, R 1Be amino, R 2Be cyano group, R 3Be hydrogen atom and X 1, X 2, X 3, X 4General expression (I) compound that has with definition identical in the general definition of the present invention with Y can be a hydroxyl from corresponding X, R 1Be protected amino selectively, R 3Be chlorine atom and X 1, X 2, X 3, X 4The compound that has with definition identical in the general definition of the present invention with Y passes through various at Knuyants; I.L and Yakobson; G.G. the haloalkyl method preparation described in the 263-269 page or leaf of " the Synthese ofF luoroorganic Compounds " of editor's Springer-Verlag:Berlin 1985 publication can then be carried out protective reaction if desired.
Method 6
X is a haloalkyl, R 1Be amino, R 2Be cyano group, R 3Be hydrogen atom and X 1, X 2, X 3, X 4General expression (I) compound that has with definition identical in the general definition of the present invention with Y can be a formoxyl from corresponding X, hydroxy acid functional group or halogen and selectively the protection amino compound and get.For example, with W.J.Middleton at J.Org.Chem.1975, the mode described in 40 574, handling carbamoyl compound with lignocaine sulphur trifluoride, X is provided is the compound of difluoromethyl and other substituting groups general expression (I) as defined above.Using such as oxidant oxidation X in sulfuric acid of chromium trioxide is above-mentioned general expression (I) midbody compound of formyl, obtains above-mentioned general expression (I) midbody compound, and wherein X is a carboxylic acid functional, R 1Be amino, R 2Be cyano group, R 3Be hydrogen atom and X 1, X 2, X 3, X 4Have in the meaning shown in the general definition of the present invention with Y.The protection amido functional group is favourable in this kinds of oxidation reaction; such as the trifluoroacetyl amine derivative; as G.A.Boswell etc. at Org.React 1974; 21, the X described in the 1-124 is trifluoromethyl and the foregoing compound of other groups for the above-claimed cpd of hydroxy acid functional group and sulfur tetrafluoride reaction provide X.
Selectively, X is a trifluoromethyl, R 1Be amino, R 2Be cyano group, R 3Be hydrogen atom and X 1, X 2, X 3, X 4General expression (I) compound that has with the meaning shown in the general definition of the present invention with Y can be a halogen from X, be iodine preferably, and the foregoing general expression of other substituting groups (I) compound, by with D.J.Burton and D.M.Wiemers at J.Am.Chem.Soc.1986, condition of similarity described in 108,832 reacts with trifluoromethyl copper down and prepares.
Method 7
X is bromomethyl or chloromethyl, R 1Be amino, R 2Be cyano group, R 3Be hydrogen atom and X 1, X 2, X 3, X 4With Y have general expression (I) compound of the meaning shown in the general definition of the present invention can by with N-bromo-succinimide or N-neoprene imidodicarbonic diamide such as being in the solvent of carbon tetrachloride; in 0 ℃ to the scope between the solvent refluxing temperature, handling corresponding X is that methyl and amino are that selectively the protected intermediates compound obtains.X is that the above-claimed cpd of methyl can be that formoxyl and the aforesaid general expression of other substituting groups (I) midbody compound pass through according to J.Am.Chem.Soc.1971 from X; 93; similarity method described in 1793 is handled with P-toluene sulfonyl hydrazide and cyano group borohydride sodium successively and is obtained.
Method 8
A) X is a halogenated alkyl carbonyl, R 1Be amino, R 2Be cyano group, R 3Be hydrogen atom and X 1, X 2, X 3, X 4Has general expression (I) compound with Y in the meaning shown in the general definition of the present invention; it also is general expression (VIII) compound; can followingly obtain: handling corresponding base continuously is selectively protected general expression (VI) compound; providing X with the processing of haloalkyl metal derivative is general expression (VII) compound of haloalkyl methyl alcohol; then oxidation; according to R.J.Linderman and D.M.Graves at Tetrahedron Lett.1987; 28; method described in 459 is carried out protective reaction if desired again.Suitable haloalkyl metallic compound comprises, according to P.G.Gassman and N.J.O ' Reilly, J.Org.Chem.1987,52,2481-249.The perfluoroalkyl lithium derivative of preparation, perhaps according to J.Am such as G.Am.Olah, Chem.Soc.1989,111,393 preparations and the trimethyl trifluoromethyl monosilane that uses.Other haloalkyl metal derivatives can be reference with the document also.Use trimethyl trifluoromethyl silane, this method can be described below:
B) can to change into X be the haloalkyl thio carbonyl to general expression (VIII) compound, R 1Be amino, R 2Be cyano group, R 3Be hydrogen atom and X 1, X 2, X 3, X 4Have at general expression (I) compound shown in the general definition of the present invention with Y, by with [2, two (the 4-methoxyphenyls)-1 of 4-, 3-two thiophenes-2, the two phosphniline alkane (diphosphetane)-2 of 4-, 4-disulphide] (Lawesson phosphonate reagent) processing.
Method 9
General expression (VIII) compound can be handled other compounds that change into general expression (I) by using such as the halogenating agent of thionyl chloride or hydrogen bromide etc.Wherein X represents α-alkylhalide group α-halomethyl.Amido functional group protection is become such as the trifluoroacetyl amine derivative to prevent that pyrrole ring from being useful by halogenation in this halogenation process.
Method 10
A) the X sulfo-cyanato-that is, R 1Be amino, R 2Be cyano group, R 3Be hydrogen atom and X 1, X 2, X 3, X 4Having with Y can be by being that alkali-metal MSCN handles general expression (III) compound and makes with M in the presence of bromine in such as methanol solvent at general expression (I) compound of the meaning shown in the general definition of the present invention.
B) general expression (I) compound, wherein X is an alkylthio group, halogenated alkylthio, alkenylthio group, haloalkene sulfenyl, thiophenyl or heteroarylthio, R 1Be amino, R 2Be cyano group, R 3Be hydrogen atom and X 1, X 2, X 3, X 4Have in the meaning shown in the general definition of the present invention with Y, and phenyl and heteroaryl be constitute as described herein and/or replace, it is general expression (IX) compound (vide infra), can in liquid phase reaction medium, react by general expression (III) compound and sulfenyl halides R SHal and prepare, wherein R is aforesaid alkyl, haloalkyl, thiazolinyl, haloalkenyl group, phenyl or heteroaryl and Hal are halogen atoms.-100 ℃ to 100 ℃ temperature with an organic solvent, such as carrene, be-80 ℃ to 250 ℃ preferably preferably, this reaction can be selectively at the acid acceptor such as tertiary amine, such as carrying out under the existence of pyridine.Alkyl sulfenyl chlorine can be according to S.Thea and G.Ceavasco, Tetrahedron Letters, 1988,2865 described preparations.When using sulfenyl chlorine, described method can followingly be represented:
Method 11
X is the sulfo-cyanato-, R 1Be amino, R 2Be cyano group, R 3Be hydrogen atom and X 1, X 2, X 3, X 4Having general expression (I) compound in the meaning shown in the general definition of the present invention with Y, can further to change into X be alkylthio groups, R 1Be amino, R 2Be cyano group, R 3Be hydrogen atom and X 1, X 2, X 3, X 4Have compound with Y, form by in solvent, using such as sodium hydroxide and potassium hydroxide treatment in the presence of such as alkyl halide or dialkylsulfates at the general expression (I) of the meaning shown in the general definition of the present invention.
Method 12
General expression (IX) compound can be oxidized to general expression (X) compound, and wherein X(vide infra) be R 5S(O) n, n is 1 or 2, R 5Defined as the front.Operable oxidant comprises hydrogen peroxide, peroxidating acetate, and trifluoro peroxidating acetate and m-chloro peroxide acid, in the solvent such as carrene, acetate or trifluoroacetic acid, temperature is 0 ℃ to 25 ℃ at-40 ℃ to 80 ℃ preferably.Appropriate reaction conditions, promptly the length in temperature, reaction time and oxidant consumption can change on request so that sulfinyl (n=1) or sulfonyl (n=2) derivative to be provided.Can also be from sulfinyl compound sulfonyl compound, with regard to as being easily and seeing to those skilled in the art.With some haloalkyl thio group,, be useful to amido functional group being protected into the trifluoroacetyl amine derivative such as trifluoromethylthio.If, such as, trifluoro peroxidating acetate is chosen as oxidant, described method can be represented with following formula:
Figure 891089853_IMG23
Method 13
R 3Be halogen, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Having with Y can be by handling R with halogenating agent at general expression (I) compound of the described meaning of general definition of the present invention under the condition of similarity described in method 3 1Be amino, R 2Be oxygen base, R 3Be hydrogen and X 1, X 2, X 3, X 4Have general expression (I) compound with Y, also promptly be expressed as the compound of general expression (XI) in the back and prepare in the meaning described in the general definition of the present invention.Common conversion is as follows:
Figure 891089853_IMG24
Method 14
R 3Be two (alkylthio group) methyl or two (alkylthio) methyl, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Having with Y can be by in the presence of lewis acidic at general expression (I) compound of the meaning shown in the general definition of the present invention, be blunderbuss salt preferably, in solvent, in 0 ℃ to the scope of solvent refluxing temperature, selectively in the presence of such as the acid acceptor of pyridine, by general expression (XI) compound and three (alkylthio) methane or three (aryl sulfo-) methane (R aS) 3CH(is R wherein aBe aryl or alkyl) reaction make.One preferably method to be to use acetonitrile be solvent, 25 ℃ with three (methyl sulfo-) methane as three (alkylthio) methane and with dimethyl (methyl sulfo-) blunderbuss tetrafluoroborate as lewis acid and need not sour acid acceptor.Described method usually can be as described below:
Method 15
The midbody compound of useful general expression (I), wherein R 3Be formyl, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Have in the meaning described in the general definition of invention with Y, it also is the general expression shown in the back (X IV) compound, can be by utilizing the alkyl nitrites under the condition similar, to handle or hydrolysis general expression (X III) compound prepares to method 4C, described method generally is expressed as follows:
Figure 891089853_IMG26
Method 16
R 3Be oximino alkylidene or alkoxyimino alkylidene, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Have midbody compound with Y,, can cross R as useful as intermediates at the general expression (I) of the meaning described in the general definition of the present invention 3Be alkyl-carbonyl or formoxyl R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Have at general expression (I) compound of the meaning shown in the general definition of the present invention and azanol or O-alkyl azanol or the condensation in of its sour addition salts with Y and to form R such as the solvent of ethanol 3For the above-claimed cpd of alkyl-carbonyl is with final use 1,1,1-three (alkylthio or aryl sulfo-) alkane is as the same way as preparation of the compound (X IV) of starting material.
Method 17
Useful general expression (I) midbody compound, wherein R 3Be amino, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Have in the meaning shown in the general definition of the present invention with Y,, can reduce corresponding R by using in the presence of such as the noble metal of platinum or palladium such as hydrogen as useful as intermediates 3For the compound of nitro makes, perhaps come the nickel preparation with hydrazine and Ruan.Use R 2Substituent merging replaces R and R in general expression (I) compound with X 2Be amino simultaneously, just may have limited its stability, and then require with suitable blocking group to protect one of them amino.R 3Be nitro, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4General expression (I) compound that has in the meaning shown in the general definition of invention with Y can make by utilizing nitric acid or the nitrated general expression of other nitrating agents (XI) compound in nitric acid and sulfuric acid or the aceticanhydride.It is useful using such as the amido functional group in blocking group protection (XI) formula compound of acetyl or trifluoroacetyl in some nitrifying process.
Method 18
As useful as intermediates, the derivative of various general expressions (XII) compound can prepare as follows:
A) R 3Be alkyl amino, dialkylamino or virtue amino, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Having with Y can be from corresponding R at general expression (I) compound of the meaning described in the general definition of the present invention 3For amino and other substituting groups compound as defined above prepare by using alkyl halide or aryl halide or sulfonate to carry out alkylation in such as the organic solvent of ethanol, acetonitrile and toluene.
Generations single or two alkylates can be controlled by stoichiometry result's operation or reaction condition.Selectively, require the monoalkylamine product, can use additive method, such as, amino is changed into (alkoxyl alkylene imine base) by handling with alkyl orthoester, then restore.If the R that requires end product to comprise 1Be unsubstituted amino, just need be amino with suitable blocking group protection before described processing.In this class situation, R 3Be amino, R 1Be suitably protected amino and the aforesaid general expression of other substituting groups (I) compound, that is to say general expression (X V) compound, be made into and be used as reactant.Add before the nitroreduction step that blocking group in (X V) formula compound is generally discussed in method 17.Amino according to planning at R 3Conversion subsequently, can select various blocking groups by following embodiment.
B) R 3Be amino carbonyl amino, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Meaning general expression (I) compound that has institute's art in general definition of the present invention with Y can prepare by then carrying out deprotection base step again with the ammonia processing with phosgene (phosgene) processing from the compound of general expression (X V).
C) R 3Be alkyl-carbonyl-amino, halogenated alkyl carbonyl amino, or aryl-amino-carbonyl, R 1Be amino, R 2Be cyano group and X 1, X 2, X 3, X 4General expression (I) compound that has in the meaning described in the general definition of the present invention with Y can be R by general expression (X V) compound and general expression b(C=0) acyl chlorides of Cl or [R b(C=0)] 2The anhydride reaction of O then carries out deprotection reaction and gets, wherein R bBe alkyl, haloalkyl or aryl (as defined in the definition first time of general expression (I)).Can felicity condition use down such as the solvent of acetonitrile with such as the acid acceptor of pyridine.
D) similarly, R 3Be alkyl sulfonyl-amino or halogenated alkyl sulfonyl amino, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Having the compound of protection amino that can be by general expression (X V) at general expression (I) compound of the meaning shown in the general definition of the present invention and alkyl or halogenated alkyl sulfonyl halide or sulfonic anhydride with Y reacts under suitable condition and goes protection to prepare again.Suitable amido protecting group comprises alkoxyl alkylene imine group in this class reaction, and this group can be by handling amino compound with the alkyl orthoformate.The protection of going of described group typically comprises aqueous hydrolysis.
E) R 3Be the basic amino or the aromatic yl aminocarbonyl amino of alkyl amino carbonyl, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Having with Y can be by the amino compound suitably protect by general expression (X V) and alkyl or aryl isocyanates (wherein alkyl or aryl as described in defining the first time of the present invention) reaction at general expression (I) compound of the described meaning of general definition of the present invention, then goes to protect and prepares.Be used for felicity condition that the urea class forms and record and narrate at J.March, draw at this and be reference the 802nd page of " Advanced Organrc Chemistry " Mc Graw-Hill publishing company (1985).Suitable amido protecting group comprises in this class reaction, and protects the alkoxyl alkylene at imine group according to going as previously mentioned again.
F) R 3Be alkoxycarbonyl amino or halo alkoxy carbonyl amino, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Having with Y can be by by the suitably amino compound and alkyl chloride formic acid esters or the reaction of haloalkyl chloro-formate of the general expression (X V) of protection at general expression (I) compound of the meaning described in the general definition of the present invention, follows the deprotection base and prepares.
G) R 3Be alkylene imine base or benzal imido grpup, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Having with Y can be by general expression (X V) amino compound of suitably protection and the condensation of alkyl or aryl aldehyde (defined in alkyl wherein and aryl such as the definition first time of the present invention) at general expression (I) compound of the meaning described in the general definition of the present invention, then goes to protect again and prepares.To the appropraite condition that forms schiff bases can be described at the pointed list of references of the 1165th page of ibid and the document by J.March be the selected condition of comprehensive step, draw at this and be reference.Suitable amido protecting group comprises acetyl or trifluoroacetyl and goes to protect step to finish by highly basic hydrolysis or additive method, as T.W.Greene in the 254th page of " Protecfive Groups in Organic Syntbesrs " J.Wiley publishing company (1987) and in the document as described in the pointed list of references.
H) R 3Be alkoxyl alkylene imine base, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4With Y have general expression (I) compound of the meaning described in the general definition of the present invention can by the suitably protected amino compound of general expression (X V) by with alkyl orthoester condensation, then deprotection reaction and preparing.Suitable blocking group comprises acid amides or carbamate derivatives, as T.W.Greene described in ibid the 233rd and 249 pages.
I) R 3Be dialkyl amido alkylene imine base, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4General expression (I) compound that has in the meaning described in the general definition of the present invention with Y can pass through general expression (X V) compound and N; the dialkyl group acetyl derivative of N-dialkylformamide reacts described in the 275th page of the ibid as T.W.Greene, then goes to protect step and prepares.Selectively be formula (X V) compound and N, the N-dialkylformamide under the Vilsmeier condition such as the reaction in the presence of the reagent of phosphoryl chloride phosphorus oxychloride.Suitable blocking group comprises acid amides or carbamate derivatives.
J) R 3Be alkylthio alkylene imine, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4With Y have general expression (I) compound in the meaning described in the general definition of the present invention can pass through general expression (X V) compound and three (alkylthio) methane pyridine as solvent in, selectively in the presence of suitable catalyzer, such as tetrafluoro boric acid dimethyl (methyl sulfo-) sulfonate, the reaction and prepare.
K) R 3Be azido, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4General expression (I) compound that has in the meaning described in the general definition of the present invention with Y can react under as the 573rd page of described condition of J.March ibid by general expression (X V) compound and P-tosyl triazo-compound; then go to protect step and make; selectively, aforesaid R 3For the compound of azido can then be reduced into diazanyl from general expression (X V) compound by amino conversion to diazol, handle providing triazo-compound again with nitrous acid, carry out protective reaction then.
Method 19
The useful as intermediates compound of general expression (I), wherein R 3Be phenyl or heteroaryl (as what replace described in the general definition of the present invention), R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Have in the meaning described in the general definition of the present invention with Y; can by general expression (XI) compound (wherein amino is selectively with the protection of suitable blocking group) by with the phenyl that suitably replaces or heteroaryl diazol as M.Swainsbury at Tetrahedron 1980; 36; 3327-3359, and reaction and preparing under the condition of the reaction of the Gomberg Baehmann described in its list of references.
B) selectively, the midbody compound of general expression (I), wherein R 3Be phenyl or heteroaryl (as what replace described in the general definition of the present invention), R 1Be amino, R 2Be cyano group, and X, X 1, X 2, X 3, X 4Have in the meaning described in the general definition of the present invention with Y; can be by general expression (XII) compound (wherein amino is selectively to protect with suitable blocking group) by phenyl or heteroaryl with suitably replacement; be that bromide or iodide are in the presence of copper preferably; under the Ullmann reaction condition reaction and prepare, as described in M.Swainbury ibid.
C) selectively, the midbody compound of general expression (I), wherein R 3For the phenyl that as described in the general definition of the present invention, replaces or want aryl, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Have in the meaning described in the general definition of the present invention with Y, can be by general expression (XII) compound, be bromide or iodide preferably, by phenyl or heteroaryl boric acid with quiet local replacement, in the presence of palladium (O), reacting under those the similar conditions described in Tetahedron Lefter 1988,29,2135 and its list of references with V.Snieckus etc. and making.
Method 20
R 3Be the base of cyanogen, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Having with Y can be by the R that records and narrates in method 16 at general expression (I) compound of the meaning described in the general definition of the present invention 3For general expression (I) compound of hydroxyl imido grpup methyl or alkoxyl imido grpup methine prepares by carrying out dehydration according to the described method of method 4A.
Method 21
R 3Be halogenated alkyl carbonyl or haloalkyl thio carbonyl, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Having with Y can be by the selectively amino method reaction of general expression (XII) compound by discussing in the method 8 of protection at general expression (I) compound of the meaning described in the general definition of the present invention; if desired, go again to protect step and prepare.
Method 22
A) R 3Be haloalkyl, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4Have general expression (XII) or (X IV) compound that selectively to be protected by amino at general expression (I) compound of the meaning described in the general definition of the present invention with Y; method preparation by discussing in method 6,7 and 9 can add protective reaction if desired again.
B) R 3Be alkyl, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4General expression (I) compound that has in the meaning described in the general definition of the present invention with Y can be selectively protected general expression (X IV) compound by amino; by using the refined reagent reacting of Green that comes by alkyl halide or lithium alkylide derivative with output methyl alcohol compounds; then dehydration is the compound of thiazolinyl to produce R, restores and prepares.R 3Be that methyl and the aforesaid general expression of other substituting groups (I) compound can be prepared from by method described in the method 7 by general expression (X IV) compound.
Method 23
R 3Be the sulfo-cyanato-, alkylthio group, halogenated alkylthio, alkenylthio group, haloalkene sulfenyl, thio-phenyl or thio ceteroary, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4With Y have the described meaning of general definition of the present invention and phenyl and heteroaryl be general expression (I) compound that constitutes as described herein and/or replace, also be general expression (X VI) compound (with reference to following), can be by the preparation and getting under the similar condition in of general expression (XI) compound with method 10, whole process flow can be represented with following formula:
Figure 891089853_IMG27
R represents the general expression X VI compound of alkyl can also be by R 3For thiocyano-and other replace as defined general expression (I) compound in the X VI formula by being prepared from the similar methods described in the method 11 with alkyl halide or analog.
Method 24
R 3Be alkyl sulphinyl, alkyl sulphonyl, thiazolinyl sulfinyl, thiazolinyl sulfonyl, haloalkyl sulfinyl, halogenated alkyl sulfonyl, haloalkenyl group sulfinyl, haloalkenyl group sulfonyl, phenyl sulfinyl, phenyl sulfonyl, heteroaryl sulfinyl, heteroarylsulfonyl, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4With Y have the meaning described in the general definition of the present invention and phenyl and heteroaryl can make by oxidation general expression (X VI) compound for general expression (I) compound that constitutes as described herein and/or replace, according to the similar methods described in the method 12.At those X is in the RS examples of groups, can carry out the competitive oxidation of non-requirement, can be halogen at X, is bromine or iodine preferably, R 1Be amino, R 2Be cyano group, R 3Has the sulfenylation that on general expression (I) compound of the meaning described in general description the of the present invention, carries out according to the method described above for hydrogen and other substituting groups; carry out oxidation again; then with lithium alkylide according to C.Kruse etc. at Heterocycles 1989; 29; similar methods described in 79 is handled, and then aqueous solution quenching provides general expression (X VII) compound.Compound X VII can be provided general expression (X VIII) compound by sulfenylation again.Whole process can be as described below:
Method 25
R 3Be cyanato-, alkoxyl or halogenated alkoxy, R 1Be amino, R 2Be cyano group and X, X 1, X 2, X 3, X 4General expression (I) compound that has with the meaning described in the general definition of the present invention with Y can be selectively protected general expression (XII) compound by amino; by with method 5 described similar methods, deprotection base preparation and getting as requested again.
Method 26
R 1Be hydrogen, R 2Be cyano group and R 3, X, X 1, X 2, X 3, X 4Having general expression (I) compound in the meaning described in the general definition of the present invention with Y, also is general expression (XX) compound (with reference to hereinafter), can be by R 1Be amino, R 2Be cyano group and R 3, X, X 1, X 2, X 3, X 4Has general expression (I) compound with Y in the meaning described in the general definition of the present invention, also be general expression (XI X) compound (with reference to hereinafter), pass through diazotising, use alkyl nitrites in such as the atent solvent of oxolane or acetonitrile, to carry out diazotising preferably such as the tert-butyl nitrites, described being reflected at-80 ℃ carried out between the reflux temperature of solvent, carries out between 0 ℃ to 25 ℃ preferably.
B) R 1Be halogen, R 2Be cyano group and R 3, X, X 1, X 2, X 3, X 4Has general expression (I) compound with Y in the meaning described in the general definition of the present invention, also be general expression (X XI) compound (with reference to hereinafter), can be by general expression (XI X) compound by using the alkyl nitrites, such as the tert-butyl nitrites, carry out diazotising in the presence of such as the halogen atom donor of bromofom, carbon tetrachloride, anhydrous cupric chloride or iodine and prepare.
C) R 1Be thiocyano-, alkylthio group, halogenated alkylthio, alkenylthio group, haloalkene sulfenyl, thiophenyl or heteroarylthio, R 2Be cyano group and R 3, X, X 1, X 2, X 3, X 4Have in the meaning described in the general definition of the present invention with Y, and phenyl and heteroaryl general expression (I) compound for constituting and/or replace as described herein, also be general expression (X XII) compound (with reference to hereinafter), can be by general expression (X IX) compound by using alkyl nitride at (SCN) 2Or general expression is that the disulphide (wherein R is aforesaid alkyl, haloalkyl, thiazolinyl, haloalkenyl group, phenyl or heteroaryl) of RSSR is handled and prepared.Described reaction typically in such as the solvent of chloroform in 0 ℃ with the disulphide of the alkyl nitrites of 1 to 5 equivalent and 2 to 5 equivalents and finish.
Whole technical process can be expressed from the next:
Method 27
Selectively, many general expressions (X XII) compound can be by general expression (XX) compound (R wherein 3Be amino), by preparing with the similar methods described in the method 10.Then amino of the present invention being changed into other functional groups can be undertaken by in the foregoing method.
Method 28
General expression (I) compound, wherein R 1Be alkyl sulphinyl, alkyl sulphonyl, thiazolinyl sulfinyl, thiazolinyl sulfonyl, haloalkyl sulfinyl, halogenated alkyl sulfonyl, haloalkenyl group sulfinyl, haloalkenyl group sulfonyl, phenyl sulfinyl, phenyl sulfonyl, heteroaryl sulfinyl, R 2Be cyano group and R 3, X, X 1, X 2, X 3, X 4Have in the definition described in the general definition of the present invention with Y, and described phenyl and heteroaryl be formation described here and/or replacement, can form according to the oxidation of the method described in the method 24 by general expression (X XII) compound.If X or R 3Be the SR group that remains on the level of sulfide oxidation, then can adopt the similar strategy described in the method 24 that desired compound is provided.
Method 29
General expression (I) compound, wherein R 1Be alkyl amino, dialkyl amido, aryl alkyl amino, amino carbonyl amino, alkyl sulfonyl-amino, halogenated alkyl sulfonyl amino; alkyl amino-carbonyl amino, aromatic yl aminocarbonyl amino, alkoxycarbonyl amino, halo alkoxy carbonyl amino, alkylideneimino, benzal imido grpup, alkoxyl alkylene imine base, dialkyl amido alkylene imine base, alkylthio alkylene imine base or azido, R 2Be cyano group and R 3, X, X 1, X 2, X 3, X 4Have in the meaning described in the general definition of the present invention with Y, can by with the similarity method described in the method 18 by general expression (XII X) compound.
Method 30
A) R 1Be formoxyl, R 2Be cyano group and R 3, X, X 1, X 2, X 3, X 4With Y have general expression (I) compound of the meaning described in the general definition of the present invention can by general expression (XI X) compound by with natrium nitrosum, HC=NOH, copper sulphate and HCl with W.F.Beech at J.Chem.Soc.1954, the mode described in 1297 is handled and is prepared.R in (if XI X) formula compound 3Be amino, suitable protection is provided possibly.R 1For the above-claimed cpd of formyl can be according among the 130th page of the T.W.Greene ibid and its described method of document of quoting as proof, the standard method by mercaptalization changes into R 1Compound for two (alkylthio) methyl or two (aryl sulfo-) methyl.Selectively, R 1Be two (alkylthio) methyl or two (aryl sulfo-) methyl, R 2Be cyano group, R 3Be amino and X, X 1, X 2, X 3, X 4With Y have general expression (I) compound of the meaning described in the general definition of the present invention can by with the similarity method described in the method 14 by R 3For amino general expression (XX) compound gets.Two (alkylthio) methyl or two (aryl sulfo-) methyl to the conversion of formyl can realize by those modes described in the method 15.Amino official of the present invention rolls into a ball and can realize by preceding method to the conversion of other functional groups.
B) R 1Be hydroxyl imide base alkylidene or alkoxyl imido grpup alkylidene, R 2Be cyano group and R 3, X, X 1, X 2, X 3, X 4With Y have general expression (I) compound of the meaning described in the general definition of the present invention can by with the similarity method described in the method 16 by R 1For alkyl-carbonyl or formoxyl and the foregoing general expression of other substituting groups (I) compound form.R 1For the above-claimed cpd of alkyl-carbonyl can be by corresponding R 1For the compound of halogen by changing into refined reagent of Ge Shi or lithium derivative, described in method 5 with the protection of selectable cyano group, then with fatty acid acyl chlorides or anhydride reaction or selectively reoxidize, prepare and get with the fatty aldehyde condensation.R selectively 1For the compound of alkyl-carbonyl can be by corresponding R 1Be the compound of formyl, by with alkyl Grignard reagent reaction, go oxidation again and prepare.
C) R 1Be cyano group, R 2Be cyano group and R 3, X, X 1, X 2, X 3, X 4Having with Y can be by corresponding R at general expression (I) compound of the meaning described in the general definition of the present invention 1For the compound of hydroxyl imide base methine or alkoxyl imido grpup methine by with the similarity method preparation described in the method 4A.
D) R 1Be halogenated alkyl carbonyl or alkyl halide thiocarbonyl group, R 2Be cyano group and R 3, X, X 1, X 2, X 3, X 4Having with Y can be by R at general expression (I) compound of the meaning described in the general definition of the present invention 1For formoxyl and the aforesaid general expression of other substituting groups (I) compound by to the similar condition described in the method 8 under handle and get.
E) R 1Be haloalkyl or alkyl, R 2Be cyano group and R 3, X, X 1, X 2, X 3, X 4Having with Y can be by R at general expression (I) compound of the meaning described in the general definition of the present invention 1For formoxyl or halogen and other substituting groups as defined above general expression (I) compound under the condition similar, handle and prepare to method 22.
Method 31
R 1Be phenyl or the heteroaryl that as described in the general definition of the present invention, replaces, R 2Be cyano group and R 3, X, X 1, X 2, X 3, X 4Having with Y can be by R at general expression (I) compound of the meaning described in the general definition of the present invention 1For halogen and the aforesaid general expression of other substituting groups (I) compound by preparing with the similar methods described in method 19B and the 19C.
Method 32
R 1Be cyanato-, alkoxyl or halogenated alkoxy, R 2Be cyano group and R 3, X, X 1, X 2, X 3, X 4General expression (I) compound that has in the meaning described in the general definition of the present invention with Y can be by general expression (XX) compound by preparing with the similar methods described in the method 5.
Method 33
R 2Be formyl, R 1, R 3, X, X 1, X 2, X 3, X 4Having general expression (I) compound in the meaning described in the general definition of the present invention with Y, also is general expression (XX IV) compound (with reference to hereinafter), can be by R 2Be cyano group, R 1, R 3, X, X 1, X 2, X 3, X 4Has general expression (I) compound with Y in the meaning described in the general definition of the present invention, also be general expression (XX III) compound (with reference to hereinafter), by using reductant, be that diisobutyl lithium hydride is in solvent preferably, be 1: 1 the toluene and the mixed liquor of hexane preferably, with with S.Trofimenro at J.Org.Chem.1964, similar methods described in 29,3046 handle and whole process is as follows:
Figure 891089853_IMG30
Method 34
R 2Be carboxylic acid functional, R 1, R 3, X, X 1, X 2, X 3, X 4Has midbody compound with Y at useful general expression (I) compound of the meaning described in the general definition of the present invention, also be general expression (XX V) compound (with reference to hereinafter), can be by preparing with John's reagent oxidation general expression (XX IV) compound.Whole process is as follows:
Method 35
General expression (I) compound, wherein R 2Be hydroxyl imide base alkyl alkylidene, alkoxyl imido grpup alkylidene, halogenated alkyl carbonyl, haloalkyl thio carbonyl, alkyl, two (alkylthio) methyl, two (aryl sulfo-) methyl, haloalkyl, and R 1, R 3, X, X 1, X 2, X 3, X 4Have in the meaning described in the general definition of the present invention with Y, can be by general expression (XX IV) compound or R 2Be halogen and the aforesaid general expression of other substituting groups (I) compound (its preparation method is described by method 38), by with method 30A), B), D) and E) described in the preparation of such similar methods.
Method 36
R 2Be amino, R 1, R 3, X, X 1, X 2, X 3, X 4Has general expression (I) compound with Y in the meaning described in the general expression of the present invention definition, also be general expression (XX VII) compound (with reference to hereinafter), can be by general expression (XX V) compound, by using the diphenylphosphine acylazide, such as triethylamine exist organic base in the presence of, in alcohols solvent, handle the carbamate of production (XX VI) such as uncle-butanols, then hydrolysis, and prepare.Comprise that from the additive method that (XX V) produces (XX VII) changing into acyl chlorides handles with the azides ion reaction and with alcohol again by the Curtius rearrangement, as J.March " Aduanced Orgamic Chemistry " Mc Graw-Hill publishing company (1985), described in the 984th page.Whole process is as follows:
Method 37
General expression (I) compound, wherein R 2Be alkyl amino, dialkyl amido, aryl alkyl amino, amino carbonyl amino, alkyl-carbonyl-amino, halogenated alkyl carbonyl amino, aryl-amino-carbonyl, alkyl sulfonyl-amino, halogenated alkyl sulfonyl amino, alkyl amino-carbonyl amino, aromatic yl aminocarbonyl amino, alkoxycarbonyl amino, halo alkoxy carbonyl amino, alkylene imine, benzal imido grpup, alkoxyl alkylene imine base, dialkyl amido alkylene imine, alkylthio alkylene imine base or triazo-compound, R 1, R 3, X, X 1, X 2, X 3, X 4Have in the meaning described in the general definition of the present invention with Y, can be by general expression (XX VII) compound by preparing with the similarity method described in the method 18.
Method 38
R 2Be hydrogen, halogen, thiocyano-, alkylthio group, halogenated alkylthio, alkenylthio group, haloalkene sulfenyl, thiophenyl or heteroaryl sulfo-, R 1, R 3, X, X 1, X 2, X 3, X 4With Y have general expression (I) compound of the meaning described in the general definition of the present invention can by general expression (XX VII) compound by with method 26 in the similar methods preparation.Selectively, R 2Be hydrogen, R 1, R 3, X, X 1, X 2, X 3, X 4Having with Y can be by general expression (XX V) compound by preparing heating in reflux temperature or in such as the high boiling solvent of naphthalane or quinoline in the presence of the copper in glacial acetic acid with 48%HBr at general expression (I) compound of the meaning described in the general definition of the present invention.
Method 39
General expression (I) compound, wherein R 2Be alkyl sulphinyl, alkyl sulphonyl, thiazolinyl sulfinyl, thiazolinyl sulfonyl, haloalkyl sulfinyl, halogenated alkyl sulfonyl, haloalkenyl group sulfinyl, haloalkenyl group sulfonyl, phenyl sulfinyl, phenyl sulfonyl, heteroaryl sulfinyl, heteroarylsulfonyl, R 1, R 3, X, X 1, X 2, X 3, X 4Have in the meaning described in the general definition of the present invention with Y, can according to the similar such method described in the method 24, by oxidation general expression (I) compound, wherein R 2Be alkylthio group, halogenated alkylthio, alkenylthio group, haloalkene sulfenyl, thiophenyl or heteroarylthio, and prepare.
Method 40
R 2Be phenyl or the heteroaryl that as general definition of the present invention is described, constitutes and/or replace, R 1, R 3, X, X 1, X 2, X 3, X 4Have general expression (I) compound with Y in the meaning described in the general definition of the present invention, can be by R 2For halogen and the foregoing general expression of other substituting groups (I) compound by with the similarity method preparation described in method 19B and the 19C.
Method 41
R 2Be cyanato-, alkoxyl or halogenated alkoxy, R 1, R 3, X, X 1, X 2, X 3, X 4Having with Y can be by R at general expression (I) compound of the meaning described in the general definition of the present invention 2For halogen and the foregoing general expression of other substituting groups (I) compound by with the similarity method preparation described in the method 5.
With comprehensive form, this method invention can be as described below and define:
Method P1
A kind of method for preparing following formula: compound:
X in the formula 1, X 2, X 3, X 4With Y have with method 1 in identical meaning; X is halogen, trifluoromethyl, cyano group, thiocyano-, alkylthio group, alkyl sulphinyl, alkyl sulphonyl, halogenated alkylthio, haloalkyl sulfinyl, halogenated alkyl sulfonyl, alkenylthio group, haloalkene sulfenyl generation, haloalkenyl group sulfinyl, haloalkenyl group sulfonyl, thiophenyl, phenyl sulfinyl, phenyl sulfonyl, heteroarylthio, assorted fragrant sulfinyl, assorted arylsulfonyl, is characterized in a compound being
Amino is selectively protected in the formula.
(a) with the halogenating agent reaction, selectively in the presence of solvent, carry out, obtain the general expression that X is a halogen (I compound a), then, selectively reacting described compound in known manner with trifluoromethyl copper, to draw X be that (I is compound a) for the general expression of trifluoromethyl;
(b) react in the presence of lewis acid with three (alkylthio) methane or three (aryl sulfo-) methane, X with gained is general expression (XXX VI) compound of two (alkylthio) methyl or two (aryl sulfo-) methyl and suitable alkyl nitrites reaction then, then hydrolysis is to obtain the general expression that X is a formyl (XXX VII) compound, then described compound is contacted with hydroxylamine, use such as P in a known way thereupon 2O 5Suitable reagent to dewater to obtain X be that (I is compound a) for the general expression of cyano group;
(c) compound with molecular formula MSCN reacts, M is an alkali metal, the described bromine that is reflected at exists down, carrying out to obtain X in such as methanol solvent is that (I is compound a) for the general expression of thiocyano-, then with alkyl halide or dialkylsulfates in the presence of such as the alkali of NaOH or KOH in solvent the described compound of reaction, (I is compound a) to obtain X and be the general expression of alkylthio; Perhaps
(d) with molecular formula be the sulfenyl halides reaction of RSHal, wherein R is alkyl, haloalkyl, phenyl or heteroaryl free radical, Hal is a halogen atom, described being reflected in the organic liquid phase medium, selectively in the presence of such as the acid acceptor of tertiary amine, obtain general expression (I compound a) that X is alkylthio group, halogenated alkylthio, alkenylthio group, haloalkene sulfenyl, thiophenyl or heteroarylthio, then selectively in a known way oxidation gained compound to obtain general expression (I is compound a), and wherein X is RS(O) n, n depends on that reaction condition is 1 or 2.
Method P2
A kind of preparation X 1, X 2, X 3, X 4Have meaning described in method 1 with Y, X is that (I method a) is characterized in following general expression compound for the general expression of cyanato-, alkoxyl, halogenated alkoxy
Figure 891089853_IMG35
Amino and cyano group are suitably protected if desired in the formula:
(a) with halogeno-cyanogen in the existence of acid acceptor reaction, (I is compound a) to obtain X and be the general expression of cyanato-;
(b) with alkylating reagent reaction, selectively carry out in the presence of alkali, (I is compound a) to obtain X and be the general expression of alkoxyl; Perhaps
(c) carry out haloalkylization in a known way, according to " Syntheses of Fluoroorganic Compounds " Knunyants, I.L. and Yakobson, G.G. edit, Springer Verlag publishes, Berlin, 1985, the 263-269 page or leaf is described, obtains the general expression that X is a halogenated alkoxy (I compound a).
Method P3
A kind ofly prepare general expression (I is the method for compound a), wherein X 1, X 2, X 3, X 4- yHave with the same meaning described in the method 1, X is haloalkyl [CF 2H, CF 3, BrCH 2, ClCH 2], halogenated alkyl carbonyl, haloalkyl thio carbonyl or-alpha-halogen alkyl-alpha-halogen methyl, be characterized in the compound that general expression is following
Figure 891089853_IMG36
Amino and cyano group if desired can be suitably protected in the formula:
(a) with such as the fluorization agent of diethylamino sulphur trifluoride react in known manner, (I is compound a) to obtain X and be the general expression of difluoromethyl;
(b) Yu such as the suitable oxidizing agent of chromium trioxide in sulfuric acid, react to obtain the compound that X is the carboxylic acid group, make described compound be subjected to fluorization agent then in known manner, obtain the general expression that X is a trifluoromethyl (I compound a) such as sulfur tetrafluoride;
(c) under the Wolff-Kischer condition, react, or other variations, use the cyano group borohydride sodium then such as handling with the P-toluene sulfonyl hydrazide, obtain the compound that X is a methyl, making described compound be subjected to handling to obtain X such as N-bromo-succinimide or N-neoprene imidodicarbonic diamide again in suitable solvent is that (I is compound a) for the general expression of bromomethyl or chloromethyl; Perhaps
(d) be that (I is compound a) for the general expression of haloalkyl methyl alcohol with the reaction of haloalkyl metal derivative or trifluoromethyl trimethyl silyl so that X to be provided successively; then carrying out oxidation in known manner is that (I is compound a) for the general expression of halogenated alkyl carbonyl so that X to be provided; selectively make described compound accept Lawsson reagent then; provide the general expression that X is haloalkyl (thiocarbonyl) (I compound a); perhaps using compound reaction that halogenating agent and X such as thionyl chloride or hydrogen bromide be haloalkyl methyl alcohol is that (I is compound a) for the general expression of alpha-halogen alkyl-alpha-halogen methyl to provide X; if desired, above-mentioned institute is carried out deprotection reaction in steps again.
Method P4
A kind of method for preparing general expression (I b) compound
Figure 891089853_IMG37
X, X in the formula 1, X 2, X 3, X 4Have with the identical meaning described in the method 1, R with Y 3Be halogen; formoxyl; two (alkylthio group or arylthio) methyl; haloalkyl; alkyl; selectively phenyl of Qu Daiing or heteroaryl; thiocyano-; alkylthio group; halogenated alkylthio; alkenylthio group; the haloalkene sulfenyl; thiophenyl; heteroarylthio; alkyl sulphinyl; alkyl sulphonyl; the thiazolinyl sulfinyl; the thiazolinyl sulfonyl; the haloalkyl sulfinyl; halogenated alkyl sulfonyl; the haloalkenyl group sulfinyl; the haloalkenyl group sulfonyl; the phenyl sulfinyl; phenyl sulfonyl; heteroaryl sulfinyl or assorted arylsulfonyl; if desired; selectively the X of protection is that (I is compound a) with amino general expression for cyano group in a suitable manner
(a) according to method P1(a) reaction, provide R 3Be general expression (I b) compound of halogen, then with described compound selectively with the heteroaryl or the phenyl halide that selectively replace, be bromide or iodide preferably, in the presence of copper, react in known manner, perhaps then with R 3The described compound that is bromide or iodide preferably selectively reacts in the presence of palladium in a known way with the phenyl or the heteroaryl boric acid that selectively replace, obtains R 3For the phenyl of selectively replacement or general expression (I b) compound of heteroaryl, perhaps then according to method P1(a) reaction R 3For the general expression of halogen (I a) compound to obtain R 3General expression (I b) compound for trifluoromethyl;
(b) according to P1(b) method reacts, and at first obtains R for general expression (I b) compound of two (alkylthio) methyl or two (aryl sulfo-) methyl and selectively obtain R again 3General expression (I b) compound for formoxyl;
(c) react in a known way with the phenyl or the heteroaryl diazol that selectively replace, obtain R 3Be the phenyl of selectively replacement or general expression (I b) compound of heteroaryl; Perhaps
(d) according to method P1(c.d) react to obtain R 3For general expression (I b) compound of thiocyano-, alkylthio group, halogenated alkylthio, alkenylthio group, haloalkene sulfenyl, thiophenyl or heteroarylthio, then selectively according to method P1(d) carry out oxidation to obtain general expression (I b) compound, wherein R 3Be alkyl sulphinyl; alkyl sulphonyl; the thiazolinyl sulfinyl; the thiazolinyl sulfonyl; the haloalkyl sulfinyl; halogenated alkyl sulfonyl; the haloalkenyl group sulfinyl; the haloalkenyl group sulfonyl; the phenyl sulfinyl; phenyl sulfonyl; heteroaryl sulfinyl or heteroarylsulfonyl; suppose that X is not the RS group that may carry out undesirable oxidation; and X is a halogen; selectively handle with known method with lithium alkylide; then be according to method P1(c.d) carry out aqueous solution quenching and sulfation, be the thiocyano-alkylthio group to obtain X; halogenated alkylthio; alkenylthio group; the haloalkene sulfenyl; the general expression of thiophenyl or heteroarylthio (I b) compound.
Method P5
A kind of preparation X, X 1, X 2, X 3, X 4Have with meaning identical in the method 1, R with Y 3Method for general expression (I b) compound of hydroxyl imide base alkylidene, alkoxyl imido grpup alkylidene, cyano group, halogenated alkyl carbonyl or haloalkyl thio carbonyl or alkyl is characterized in following formula: compound
R in the formula 3For formoxyl or alkyl-carbonyl and X, cyano group and amino are protected by rights if desired:
(a) with azanol or O-alkyl azanol or its addition salts in such as the alkane agent of ethanol with it condensation to obtain R 3Be general expression (I b) compound of hydroxyl imide alkylidene or alkoxyl imines alkylidene, and work as R 3During for hydroxyl imide base methine or alkoxyl imido grpup methine, according to method P1(b) water or alcohol selectively can be eliminated, obtain R 3General expression (I b) compound for cyano group;
(b) work as R 3During for formoxyl, according to method P3(a, b, c, d) react, obtain R 3General expression (I b) compound for methyl or haloalkyl or alkyl halide carbonyl or haloalkyl thio carbonyl; Perhaps
(c) work as R 3During for formoxyl, use from alkyl halide or lithium alkylide and derive and the Grignard reagent of coming is reacted generation methyl alcohol, then dewatering produces R 3Be the compound of thiazolinyl, restore to obtain R 3General expression (I b) compound for alkyl selectively goes to protect step then.
Method P6
A kind of method for preparing following formula: compound
Figure 891089853_IMG39
Be the useful as intermediates compound, X, X in the formula 1, X 2, X 3, X 4With Y in the method 1 definition, R 3For amino, alkyl amino, dialkyl amido, aryl alkyl amino, amino carbonyl amino, alkyl-carbonyl-amino, halogenated alkyl carbonyl amino, aryl-amino-carbonyl, alkyl sulfonyl-amino, halogenated alkyl sulfonyl amino, alkyl amino-carbonyl amino, aromatic yl aminocarbonyl amino, alkoxy amino, halo alkoxy carbonyl amino, alkylene imine base, benzal imido grpup, alkoxyl imido grpup, dialkyl amido alkylene imine base, alkylthio alkylene imine base or azido, be characterized in following formula: compound
Figure 891089853_IMG40
Amino is protected in a suitable manner in the formula, and reduction is to obtain R 3Be general expression (XXX IV) compound of amino, described compound is following the reaction:
(a) with suitable alkylating reagent in organic solvent, the list that can obtain through amino according to stoichiometric proportion or reaction condition or dibasic amino or by restoring through the conversion of amino to alkoxyl alkylene imine base obtain R 3General expression (XXX IV) compound for alkyl amino, dialkyl amido or aryl alkyl amino;
(b) and phosgene reaction, then and ammonia gas react, obtain R 3Be the compound of the general expression (XXX IV) of amino carbonyl amino,
(c), selectively in the presence of solvent and/or organic acid acceptor, react and obtain R with alkyl acyl chlorine or haloalkyl acid chloride or aryl-acyl chlorine or its acid anhydrides 3General expression (XXX IV) compound for alkyl-carbonyl-amino, halogenated alkyl carbonyl amino or aryl-amino-carbonyl;
(d) react under suitable condition with alkyl or halogenated alkyl sulfonyl or its acid anhydrides, obtain R 3General expression (XXX IV) compound for alkyl sulfonyl amino or halogenated alkyl sulfonyl amino;
(e) react with known method with the alkyl or aryl isocyanates, obtain R 3Compound for the general expression (XXX IV) of (alkyl amino or arylamino) carbonylamino;
(f) react in known manner with alkyl chloroformate or chloro-formate haloalkyl ester, obtain R 3General expression (XXX IV) compound for alkoxycarbonyl amino or halo alkoxy carbonyl amino;
(g) react in known manner with alkyl or aryl aldehyde, obtain R 3General expression (XXX IV) compound for alkylene imine base or benzal imido grpup;
(h) with the alkyl orthoester reaction, obtain R 3General expression (XXX IV) compound for alkoxyl alkylene imine base;
(i) and N, N-dialkylformamide or the reaction of dialkyl group acetaldehyde derivatives obtain R 3General expression (XXX IV) compound for dialkyl amido alkylene imine base;
(j) react in organic solvent with three (alkylthio) methane, obtain R 3General expression (XXX IV) compound for alkylthio alkylene imine base; Perhaps
(k) react in a known way with p-tosyl nitrine or restore into hydrazine and handle with nitrous acid then and provide R by changing into diazol 3General expression (XXX IV) compound for the nitrogen base carries out the deprotection base if desired again.
Method P7
A kind of preparation X, X 1, X 2, X 3, X 4Have same meaning in the method for coexisting 1, R with Y 3General expression (I b) compound for cyanato-, alkoxyl or halogenated alkoxy is characterized in following formula: compound
Figure 891089853_IMG41
Amino in the formula, cyano group and X are selectively protected in a suitable manner, according to method P2(a), (b), (c) react, and obtains R 3General expression [I b] compound for cyanato-, alkoxyl or halogenated alkoxy.
Method P8
A kind of method for preparing following formula: compound
Figure 891089853_IMG42
X, R in the formula 3, X 1, X 2, X 3, X 4Have with the identical meaning described in the method 1, R with Y 1Be hydrogen; halogen; thiocyano-; halogenated alkylthio; alkenylthio group; the haloalkene sulfenyl; thiophenyl; heteroarylthio; alkyl sulphinyl; alkyl sulphonyl; the thiazolinyl sulfinyl; the thiazolinyl sulfonyl; the haloalkyl sulfinyl; halogenated alkyl sulfonyl; the haloalkenyl group sulfinyl; the haloalkenyl group sulfonyl; the phenyl sulfinyl; phenyl sulfonyl; assorted fragrant sulfinyl; heteroarylsulfonyl; selectively phenyl of Qu Daiing or assorted virtue; alkyl-carbonyl; alkyl amino; dialkyl amido; aryl alkyl amino; amino carbonyl amino; alkyl-carbonyl-amino; halogenated alkyl carbonyl amino; aryl-amino-carbonyl; alkyl sulfonyl-amino; halosulfonyl groups amino; alkyl amino-carbonyl amino; aromatic yl aminocarbonyl amino; alkoxycarbonyl amino; halo alkoxy carbonyl amino; alkylideneimino; the benzal imino group; alkoxyl alkylene imine base; dialkyl amido alkylene imine base; alkylthio alkylene imine base; azido; two (alkylthio or aryl sulfo-) methyl; the formoxyl halogenated alkyl carbonyl; the haloalkyl thiocarbonyl group; haloalkyl or alkyl are characterized in following formula: compound
Figure 891089853_IMG43
P4 to P7 prepares according to method, if desired, is protecting X, R 3Or cyano group is incited somebody to action wherein amino deprotection afterwards again.
(a) and diazotization agent, with alkyl nitride, in atent solvent, react preferably, obtain R 1General expression (I c) compound for H;
(b) and diazotization agent, preferably with alkyl nitride, halogen give body in the presence of react.Obtain R 1Be general expression (I c) compound of halogen,, then change into R with fatty acid acyl chlorides or its ester anhydride reactant then selectively with Grignard reagent or the described compound of lithium derivatives reaction 1For general expression (I c) compound of alkyl-carbonyl or according to P4(a) method reacts described compound to obtain the general expression that R is phenyl or heteroaryl (I c) compound;
(c) and diazotization agent, preferably with the alkyl nitrites, at (SCN) 2Or under the existence of disulphide in such as the solvent of chloroform reaction to obtain R be thiocyano-, alkylthio group, halogenated alkylthio, alkenylthio group, the haloalkene sulfenyl, the general expression of thiophenyl or heteroarylthio (I) compound is then selectively according to method P1(d) to obtain R ' be alkyl sulfinyl in oxidation, alkyl sulphonyl, the thiazolinyl sulfinyl, the thiazolinyl sulfonyl, the haloalkyl sulfinyl, halogenated alkyl sulfonyl, the haloalkenyl group sulfinyl, the haloalkenyl group sulfonyl, the phenyl sulfinyl, phenyl sulfonyl, the general expression of heteroaryl sulfinyl or heteroarylsulfonyl (I c) compound;
(d) according to method P6(a-k) to react to obtain R ' be alkyl amino, dialkyl amido, aryl alkyl amino, amino carbonyl amino, alkyl-carbonyl-amino, halogenated alkyl carbonyl amino, aryl-amino-carbonyl, alkyl sulfonyl-amino, halogenated alkyl sulfonyl amino, alkyl amino-carbonyl amino, the arylamino carbonyl amino, alkoxycarbonyl amino, halo alkoxy carbonyl amino, alkylene imine base benzal imido grpup, alkoxyl alkylene imine base, dialkyl amino alkyl amino asia, alkylthio alkylene imine base or diazo general expression (I c) compound; Perhaps
(e) react to obtain R with known method with natrium nitrosum and formaldoxime, copper sulphate and HCl 1Be general expression (I c) compound of formyl, then selectively the reaction of (ⅰ) and alkyl Grignard reagent then oxidation conversion become R 1Be general expression (I c) compound of alkyl-carbonyl, (ⅱ) react and obtain R according to method P5 1For general expression (I c) compound of hydroxyl imide base alkylidene, alkoxyl imido grpup alkylidene or cyano group or (ⅲ) according to method P3(a-d) react and obtain R 1For general expression [I c] compound of halogenated alkyl carbonyl, haloalkyl thio carbonyl, haloalkyl or alkyl, slough protecting group if desired again, or with R 1For the above-claimed cpd of formoxyl changes into R in a known way 1General expression (I c) compound for two (alkylthio group or arylthio) methyl.
Method P9
A kind of preparation X, X 3, X 1, X 2, X 3, X 4With Y have with the same meaning described in the method 1 and R 1Be the method for general expression (I c) compound of cyanato-, alkoxyl or halo oxygen base, be characterized in following formula: compound
Figure 891089853_IMG44
X, cyano group or R in the formula 3Be selectively protected, according to method P2(a, b, c with known method) react, obtain R 1General expression (I c) compound for cyanato-, alkoxyl or halogenated alkoxy then selectively carries out
Deprotection reaction.
Method P10
A kind of preparation X, R 1, R 3, X 1, X 2, X 3, X 4With Y have with method 1 in identical meaning, and R 2Method for general expression [I] compound of CHO is characterized in being the diisobutyl alanate preferably with general expression (I c) compound and reductant, reacts in solvent, obtains R 2Be the compound of CHO,, obtain corresponding general expression (XXX V) compound selectively with the described compound of known method oxidation
Method P11
A kind of preparation X, R 1, R 3, X 1, X 2, X 3, X 4Have and the identical meaning R described in the method 1 with Y 2General expression (I) compound for hydroxyl imide base alkylidene, alkoxyl imido grpup alkylidene, halogenated alkyl carbonyl, haloalkyl thio carbonyl, alkyl, haloalkyl, two (alkylthio or aryl sulfo-) methyl or cyano group is characterized in R 2For general expression (I) compound of CHO has selectively been protected X, R in a known way as required 1Or R 3Afterwards, according to method P3(a, b, c, d), P5(a, b) or P8(e) react, then be deprotection steps if desired.
Method P12
A kind of method for preparing general expression (I) compound, wherein X, R 1, R 3, X 1, X 2, X 3, X 4Have and identical meaning and the R described in the method 1 with Y 2Be amino; alkyl amino; dialkyl amido; aryl alkyl amino; amino carbonyl amino; alkyl-carbonyl-amino; halogenated alkyl carbonyl amino; aryl-amino-carbonyl; alkyl sulfonyl-amino; halogenated alkyl sulfonyl amino; alkyl amino-carbonyl amino; aromatic yl aminocarbonyl amino; alkoxycarbonyl amino; halo alkoxy carbonyl amino; the alkylene imine base; the benzal imido grpup; alkoxyl alkylene imine base; dialkyl amido alkylene imine base; alkylthio alkylene imine base; azido; hydrogen; halogen; thiocyano-; alkylthio group; halogenated alkylthio; alkenylthio group; the haloalkene sulfenyl; thiophenyl; heteroarylthio; alkyl sulphinyl; alkyl sulphonyl; the thiazolinyl sulfinyl; the thiazolinyl sulfonyl; the haloalkyl sulfinyl; halogenated alkyl sulfonyl; the haloalkenyl group sulfinyl; the haloalkenyl group sulfonyl; the phenyl sulfinyl; phenyl sulfonyl; the heteroaryl sulfinyl; heteroarylsulfonyl; selectively phenyl of Qu Daiing or heteroaryl or trifluoromethyl particularly will selectively protected X as required in a known way; R or R 3General expression afterwards (XXX V) compound reacts under the condition that Ku Ertisi (Curtius) resets, for example produce carbamate by in solvent, reacting in the presence of such as the organic base of triethylamine again with alkali metal azide or with the diphenylphosphine acylazide by changing into acyl chlorides, with its hydrolysis of relief, obtain corresponding R and be amino compound, then selectively according to method P6(a-k) or P8(a-c) react, R then worked as 2During for halogen, selectively according to method P4(a) react, then slough protecting group if desired again.
Method P13
A kind of preparation X, R 1, R 3, X 1, X 2, X 3, X 4Have and same meaning and the R described in the method 1 with Y 2Method for general expression [I] compound of cyanic acid base, alkoxyl or halogenated alkoxy is characterized in following formula: compound
Figure 891089853_IMG46
If desired, be selectively to have protected X, R 1Or R 3Group, P7 reacts according to method, sloughs protecting group more as required.
Method P14
A kind of method for preparing general expression (XXX VIII), (XX XI), (XXX VI), (XXX VII) compound according to method P2, P7, P10 or P13; being characterized in will be accordingly according to method P1(a), P4(a), P8(b) the compound of halogenation protecting amino (if present) afterwards; change into Grignard reagent or lithium derivative; with reaction of trialkylboron hydrochlorate and oxidation in known manner, carry out deprotection reaction subsequently as required again.
Method P15
A kind of preparation following formula: compound:
Figure 891089853_IMG47
X in the formula 1, X 2, X 3, X 4Have the method for the meaning identical with Y, be characterized in following formula dicyano propenyl derivatives with the general expression I
Figure 891089853_IMG48
React with alkaline agent.
Method P16
The invention still further relates to general expression (III) and (XX VIII) to (XXX VII) compound, wherein the meaning that has as hereinbefore of each substituting group is particularly related to the useful as intermediates compound that is used for preparing according to the method for method P1 to P15 general expression (I) compound.
Additive method:
X was that general expression (I) compound of halogenated alkylthio additionally produces disulphide and promotes the method for reduction to prepare with free radical at last by chlorosulfonylation, reduction.Described method is as follows:
A) R 1, R 2, R 3, X 1, X 2, X 3, X 4With Y be defined general expression in the general expression (I) (XXX IX) compound (with reference to hereinafter) can by X be halogen general expression (XXX VIII) compound (with reference to hereinafter) by single with chlorosulfonic acid or in such as the organic solvent of chloroform, carrene, carbon tetrachloride or dimethyl formamide with the chlorosulfonic acid reaction, react and prepare in 0 ℃ to 150 ℃ reaction temperature.A more specific example is from general expression (XXX VIII) compound, wherein R 1Be amino, alkyl-carbonyl-amino or halogenated alkyl carbonyl amino, R 2Be cyano group, R 3Be hydrogen,, prepare general expression (XXX IX) compound (with reference to hereinafter), wherein R by handling with chlorosulfonic acid 1Be amino, alkyl-carbonyl-amino or halogenated alkyl carbonyl amino, R 2Be cyano group, R 3X is a hydrogen for the hydrogen while.The exemplary process of chlorosulfonation that is used for aromatic compound is at J.March, " Advaneed Organic Chemistry " " Mc Grabu Hill publishing company (1968), provide in the 402nd page.
R 1, R 2, X 1, X 2, X 3, X 4With Y be that defined general expression (X L) compound in the general expression (I) (with reference to hereinafter) can be by R 3For general expression (XXX IX) compound of hydrogen prepares by reacting under-70 ℃ to 25 ℃ reaction temperature in such as the solvent of diethyl ether, acetonitrile or carrene with halogenating agent such as chlorine, N-neoprene imidodicarbonic diamide or chlorosulfuric acid.One more certain embodiments be by R 1Be amino, alkyl-carbonyl-amino or halogenated alkyl carbonyl amino and R 2Be cyano group, R 3General expression (XXX IX) compound for hydrogen prepares R with chlorosulfuric acid processing in-40 ℃ in diethyl ether 1Be amino, alkyl amino or haloalkyl amino, R 2General expression (X l) compound for cyano group.
Figure 891089853_IMG50
B) R 1, R 2, X 1, X 2, X 3, X 4With Y be that defined general expression in the general expression (I) (X L I) compound (with reference to hereinafter) can be by general expression (XXX IX) compound by using the reductant such as triphenyl phasphine, in the presence of organic solvent, handle and prepare in 0 ℃ to 110 ℃ reaction temperature such as tetrachloro furans, toluene or carrene.A more specific example is, by general expression (XXX IX) compound, wherein R 1Be hydrogen, amino, alkyl-carbonyl-amino or halogenated alkyl carbonyl amino, R 2Be cyano group and R 3Be hydrogen or chlorine,, prepare general expression (X L I) compound, wherein R by in oxolane, handling with triphenyl phasphine in 25 ℃ 1Be hydrogen amino, alkyl-carbonyl-amino or halogenated alkyl carbonyl amino, R 2Be cyano group and R 3Be hydrogen or chlorine.The exemplary process that is used for toluene is reduced into p-toluene disulphide is provided among the J.Org.Chem 1980,45,4792 of G.A.Olah etc.:
C) general expression (I) compound, wherein R 1, R 2, X 1, X 2, X 3, X 4With Y is that definition in the general expression (I) is identical, and X was haloalkyl thio group, R 6S(is R wherein 6Be CFR 7R 8, and R 7Be F, Cl or Br, R 8Be F, Cl, Br or perfluoro alkyl group), can be Cl, Br or I, R by general expression (X L I) compound and Z 7Be F, Cl or Br and R 8For F, Cl, Br or cross fluothane general expression (X L II) compound, i.e. ZCFR 7R 8, the reaction and prepare, described reaction reductant, described reductant can promote by ZCFR 7R 8Form free radical CFR 7R 8, be to be selected from preferably such as zinc, cadmium, aluminium, manganese or and thio-oxidizing compound, for example metallic compound of dithionite or hydroxymethanesulfinate.The metal dithionite are such as alkali metal or alkaline earth metal dithionite, corresponding to general expression (X L III), Mn(S 2O 4), wherein the valence mumber n according to metal M can be 1 or 2.When dithionite that use general expression (X L III) or hydroxymethanesulfinate, need add alkali, such as, be selected from alkali metal hydroxide, alkaline earth metal hydroxide, ammonia, triethyl group benzyl amine, or such as the salt of weak acid of disodium hydrogen phosphate, sodium metabisulfite, sodium hydrogensulfite or Boratex.Described reaction generally (can make dithionite or hydroxymethanesulfinate and compound (X L II), ZCFR like this in the solvent such as acetonitrile, formamide, dimethyl formamide, dimethylacetylamide, hexamethyl phosphoramide, N-Methyl pyrrolidone, 61 dimethyl sulfoxide (DMSO)s or tetramethylene sulfone 7R 8Dissolving), in 20 ℃ to 85 ℃ temperature, react.The saturated solution that the alkali metal dithionite can be used as in the water or in the formamide is added in the reactant mixture, also can be used as solid and adds.When being when using gas-operated, this gas just is dissolved in the reaction dissolvent rarely, just requires to increase reaction pressure, such as being by 1 to 50 atmospheric pressure.A specific example is, by general expression (X L I) compound, wherein R 1Be hydrogen, amino, alkyl-carbonyl amido or halogenated alkyl carbonyl amide groups, R 2Be cyano group and R 3Be hydrogen or chlorine, with general expression (X L II) compound, ZCFR 7R 8, wherein Z is Cl, Br or I, R 7Be F, Cl, Br and R 8Be F, Cl, Br or perfluoroalkyl; In dimethyl formamide, react preparation general expression (I) compound, wherein R with sodium dithionite and disodium hydrogen phosphate at 25 ℃ 1Be hydrogen, amino, alkyl-carbonyl-amino or halogenated alkyl carbonyl amino, R 2Be cyano group, R 3For hydrogen or Cl and X were halogenated alkylthio, R 6S(is R wherein 6Be CFR 7R 8, and R 7Be F, Cl or Br, R 8Be F, Cl, Br or mistake fluoroalkyl).Described reaction is expressed from the next.
Figure 891089853_IMG52
The intermediate disulphide of the intermediate chlorosulfonylation compound of general expression (XXX IX) and general expression (X L I) is extention of the present invention.
Representative compounds of the present invention
The specific representative azole compounds of being finished by the present invention (RPC) is general expression (I) compound, wherein R 2Be cyano group, other substituting groups are just like the described meaning of table 1 (RPC 1-389 number).
Other specific representative azole compounds (RPC) that are included in the scope of the invention are general expression (I) compound, wherein X 2And X 3Be hydrogen, X 1And X 4Be chlorine, Y is CF 3And X, R 1, R 2And R 3Has meaning as described in Table 2 (RPC-390-491 number).
The specific embodiment that compound is synthetic
Following examples 1 to 22 further specify the physical property of synthetic method of the present invention and pesticide compound (and their chemical intermediates).
Embodiment 1
1-(2 with 910 milligrams (2.07 mMs), 6-dichlor-4-trifluoromethyl phenyl)-(394 milligrams of the 80%-chlorination benzoyl hydroperoxides of 2-chloro-3-cyano group-4-trifluoromethyl sulfo-pyrroles (method of describing according to embodiment 4 makes) and 492 milligrams, 2.28 the solution in 25 milliliters of chloroforms (chloroform) mM), stirred at ambient temperature 1.5 hours, and be heated to the liquid that refluxed then.Between 45 milligrams (0.21 mMs) that adding is additional-chloro-peroxy benzoic acid, and continue the heating 1 hour that refluxes.Stop heating then, and use the carrene diluted reaction mixture, clean with the first sodium bicarbonate aqueous solution again.This organic layer is through anhydrous MgSO 4Dry and under reduced pressure concentrated to obtain the colorless solid residue.Repeat this method to obtain 950 milligrams product altogether, this product is made chromatograph separate on silica gel, with 2: 1v/v carrene-hexane wash-out.Early the part that flows out contains the 1-(2 of 310 milligrams (240%), 6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-trifluoromethyl sulphonyl pyrroles (embodiment 1), it is a colorless solid.From hexane-ethyl acetate, be recrystallized, can obtain the colourless acicular crystal of 240 milligrams of sulfones, 198 ℃ of fusing points.
Embodiment 2
Continue to do the chromatography outflow liquid at embodiment 1 rear portion, from chromatography flow out than the rear section, can obtain the 1-(2 of 600 milligrams (48%), 6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-trifluoromethyl sulphinyl pyrroles (embodiment 2), it is a colorless solid.Be recrystallized from toluene-hexane, can obtain the colourless powder of 390 milligrams of sulfoxides, fusing point is 152-154.5 ℃.
Embodiment 3A and 3B
Repeat embodiment 1 and 2, but use 1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-trifluoromethyl sulfo--5-bromo pyrroles is as starting material, and this material makes by the method for embodiment 5.The compound of embodiment 3A is 1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-trifluoromethyl sulphinyl base-5-bromo pyrroles.This adopts the melting point compound that makes with embodiment 2 same procedure to be about 123 ℃.The compound of embodiment 3B is 1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-trifluoromethyl sulfonyl-5-bromo pyrroles.The fusing point of the compound that this employing and embodiment 1 same procedure make is about 113 ℃.
Embodiment 4
1-(2 with 3 grams (6.6 mM), 6-dichlor-4-trifluoromethyl phenyl)-solution of 2-amino-3-trifluoromethyl sulfo--4-cyano group-5-chloro pyrroles (method by embodiment 8 descriptions makes) in 50 milliliters of dry tetrahydrofurans, under nitrogen atmosphere, stir it, and add the alpha..alpha.-dimethylethyl nitrite ester of 3.9 milliliters (3.4 grams, 33 mMs).After 30 minutes, this reactant mixture is heated to about 1 hour of backflow, depresses concentrated then at alkali to obtain the solid residues of 3.69 grams.Repeat this method to obtain 4.07 solid residue altogether, it is made chromatograph on silica gel separate, then with 1: 1v/v carrene-hexane eluant, eluent carries out wash-out, obtain the 1-(2 of 2.9 grams (91%), 6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-trifluoromethyl sulfo-pyrroles's (embodiment 4) colorless solid.Be recrystallized from hexane-ethyl acetate, obtain the colourless powder product of 1.87 grams, fusing point is about 137 ℃.
Embodiment 5
With 0.94 milliliter (820 milligrams, 7.92 alpha..alpha.-dimethylethyl nitrite ester mM) joins the 1-(2 of 2.4 grams (5.28 mM), 6-dichlor-4-trifluoromethyl phenyl)-2-amino-3-trifluoromethyl sulfo--4-cyano group-chloro pyrroles (method of describing by embodiment 8 makes) is in 40 milliliters of bromofoms (bromoform), and in the dopant mixture under the inert gas atmosphere.After stirring 15 minutes at ambient temperature, this mixture is under reduced pressure concentrated to obtain 3.9 gram residues.This residue combines with the product of making above-mentioned reaction gained by 300 milligrams of identical pyrroles's starting materials.Crude product is made chromatograph separate on silica gel, and with 4: 1v/v hexane-carrene wash-out.Isolate the 1-(2 of 1.72 grams (56%), 6-dichlor-4-trifluoromethyl phenyl)-2-bromo-3-trifluoromethyl sulfo--4-cyano group-5-cyanpyrrole (embodiment 5), from hexane, be recrystallized, obtain 780 milligrams colorless solid product, fusing point is about 92 ℃.
Embodiment 6
1.91 the 1-(2 of gram (4.21 mM), 6-dichlor-4-trifluoromethyl phenyl)-2-amino-3-trifluoromethyl sulfo--4-cyano group-5-chloro pyrroles (method of describing by embodiment 8 makes), the solution of the 4-dimethylaminopyridine of 77 milligrams (0.63 mMs) and 20 milliliters pyridine, under inert atmosphere, be cooled to 0 ℃, and add the trifluoroacetic anhydride of 1.01 milliliters (1.5 gram, 7.14 mMs).Reactant mixture was stirred 1 hour down and stirred 4 hours down at 20 ℃ at 0 ℃, add the trifluoroacetic anhydride of additional 0.3 milliliter (2.1 mM) this moment again.After reaction time amounted to 24 hours, reactant mixture was with the carrene dilution and concentrate it.Residue HCl solution washing, water cleans subsequently, from hexane-ethyl acetate, be recrystallized, obtain the 1-(2 of 860 milligrams (37%), 6-dichlor-4-trifluoromethyl phenyl)-and the 2-[(trifluoromethyl) carbonylamino]-3-sulfonium triflate generation-4-cyano group-5-chloro pyrroles (embodiment 6), it is the light green color solid, and fusing point is about 190 ℃.
Embodiment 7
1.50 the 1-(2 of gram (3.3 mM), 6-dichlor-4-trifluoromethyl phenyl)-2-amino-3-trifluoromethyl sulfo--4-cyano group-5-chloro pyrroles 9 makes by the method that embodiment 8 describes), the 4-dimethylaminopyridine of 0.1 gram, the pyridine of 0.33 milliliter (0.32 gram, 4.1 mMs), 0.31 milliliter (0.34 gram, 4.3 the mixture of the acetonitrile of chloroacetic chloride mM) and 10 milliliters stirred 4 days down at 20 ℃, and the heating 1 day that refluxes.Add 0.03 milliliter additional chloroacetic chloride then, when the reaction cooling, continue the heating one day that refluxes again, separate one by one with saturated sodium bicarbonate aqueous solution with the carrene dilution and with the 1NHCl aqueous solution then.Organic layer also evaporates to obtain the beige solids of 1.42 grams with anhydrous magnesium sulfate drying.On silica gel, make chromatograph and separate, with 4: 1v/v hexane-eluent ethyl acetate.Then from alcohol-water, be recrystallized, obtain the 1-(2 of 480 milligrams (29%), 6-dichlor-4-trifluoromethyl phenyl)-2-methyl carbonylamino-3-trifluoromethyl sulphur-4-cyano group-5-chloro pyrroles's (embodiment 7) colourless acicular crystal, fusing point is about 216 ℃.
Embodiment 8
1.50 the 1-(2 of gram (3.57 mM), 6-dichlor-4-trifluoromethyl phenyl)-solution that stirred of 2-amino-3-trifluoromethyl sulfo--4-cyanpyrrole (method of describing by embodiment 13 makes) in 15 milliliters of ether is cooled to-20 ℃, and adds the solution of chlorosulfuric acid in 15 milliliters of absolute ethers of 0.29 milliliter (0.48 gram, 3.6 mMs) in the mode of splashing under inert atmosphere.Then this reactant mixture is warmed to 20 ℃, and stirred 2.5 days, add the chlorosulfuric acid of additional 0.03 milliliter (0.4 mM) this moment again, and continue to stir one day again.The chlorosulfuric acid that adds 0.03 milliliter again, after one day, this reaction with 28 milliliters 10% wet chemical quenching it.Separate each phase, use the extracted with diethyl ether water-bearing layer, collect then and merge this ether layer, water cleans, by anhydrous magnesium sulfate drying and concentrate to obtain the sepia solids of 1.56 grams.This crude product is made chromatograph on silica gel separate, with 2: 1v/v carrene-hexane eluent wash-out, obtain the 1-(2 of 1.30 grams (80%), 6-dichlor-4-trifluoromethyl phenyl)-2-amino-3-trifluoromethyl sulphur-4-cyano group-5-chloro pyrroles (embodiment 8) it be shallow rose solid, crystallization again from cyclohexane, obtain the product of 810 milligrams of canescence acicular crystals, fusing point is about 176 ℃.
Embodiment 9
Adopt the method identical with embodiment 8, different is that reactant is with 1-(2-chloro-4-trifluoromethyl)-2-amino-3-trifluoromethyl sulfo--4-cyanpyrrole (169 ℃ of fusing points) substitutes, and this material is that the method by embodiment 13 descriptions makes.Its end product is a 1-(2-chloro-4-trifluoromethyl)-2-amino-3-trifluoromethyl sulfo--4-cyano group-5-chloro pyrroles (embodiment 9), fusing point is about 148 ℃.
Embodiment 10
Adopt the method identical with embodiment 8, different is reactant is with 1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-amino-3-dichlorofluoromethyl sulfo--4-cyanpyrrole (202 ℃ of molten points) substitutes, and this thing is that the method by embodiment 13 descriptions makes.Its end product is 1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-amino-3-dichlorofluoromethyl sulfo--4-cyano group-5-chloro pyrroles (embodiment 10), fusing point is about 207 ℃.
Embodiment 11
Compound 1-(2,6-dichlor-4-trifluoromethyl phenyl)-2, it is 161 ℃ that two (trifluoromethyl the sulfo-)-3-cyano group of 4--5-amino-pyrroles (embodiment 11) has fusing point, and uses excessive fluoroform sulfenyl chlorine according to first compound of embodiment 13() method and make.
Embodiment 12
Under inert atmosphere, the solution of 80% pyridinium bromide perbromide in 15 milliliters of pyridines of 1.46 grams (3.6 mM) is joined the 1-(2 of 1.53 grams (3.60 mM), 6-dichlor-4-trifluoromethyl phenyl)-2-amino-3-trifluoromethyl sulfo--4-cyanpyrrole (method of describing by embodiment 13 makes, and fusing point is about 182 ℃) cold (0 ℃) solution in 15 milliliters of pyridines in.After 30 minutes, reactant mixture is poured in cold (0 ℃) ether, and the precipitation that will generate is removed by filtration.Filtrate is cleaned with the HCl aqueous solution, the NaOH aqueous solution and water.This organic layer with anhydrous magnesium sulfate drying and evaporation, produce the brown solid of 1.34 grams.This material and 230 milligrams of 1-(2,6-dichlor-4-trifluoromethyl phenyl) by 300 milligrams (0.7 mMs)-product of the previous above-mentioned reaction gained of 80% pyridinium bromide perbromide of 2-amino-3-trifluoromethyl sulfo--4-cyanpyrrole and 0.29 gram combines.Should merge product and on silica gel, do the chromatograph separation, with 4: 1v/v hexane-eluent ethyl acetate, obtain the 1-(2 of 1.31 grams (73%), 6-dichlor-4-trifluoromethyl phenyl)-2-amino-3-trifluoromethyl sulfo--4-cyano group-5-bromo pyrroles (embodiment 12), it is a white solid.Be recrystallized from hexane/ethyl acetate, obtain the product of 910 milligrams of colourless acicular crystals, molten point is about 160 ℃.
Embodiment 13
2.00 the 1-(2 of gram (6.25 mM), 6-dichlor-4-trifluoromethyl phenyl)-solution that has stirred of the carrene (by the method that hereinafter show make) of 2-amino-4-cyanpyrrole in 60 milliliters is put in the ice bath and cools off, and add 10 milliliters of cold (78 ℃) dichloromethane solutions that contain 0.55 milliliter of (0.85 gram, 6.2 mMs) fluoroform sulfenyl chlorine in slowly inflow mode.0 ℃ stir 2 hours after, with flow through reactant mixture 1 hour of nitrogen stream.It is separated with water with saturated sodium bicarbonate aqueous solution,, obtain the filbert solid of 3.14 grams by anhydrous magnesium sulfate drying and concentrated in a vacuum.It is made chromatograph separate on silica gel, with 3: 2v/v carrene-hexane eluant, eluent wash-out, acquisition weight are two colorless solid samples of 900 milligrams and 950 milligrams.From chloroform, make their recrystallizations, the 1-(2 of obtain respectively to do for oneself 680 milligrams and 630 milligrams, 6-dichlor-4-trifluoromethyl phenyl)-2-amino-3-trifluoromethyl sulfo--4-cyanpyrrole (embodiment 13), fusing point is about 182 ℃.
Reactant used in this method makes as follows: with the 1-[(2 of 4.64 grams (14.5 mM), 6-dichlor-4-trifluoromethyl phenyl) amino]-2,3-dicyano propylene and 2.02 milliliters of (1.47 grams, 14.5 the solution backflow heated overnight of triethylamine mM) in 30 milliliters of benzene concentrates then in a vacuum.Residue is separated between ether and water, and ether layer is by anhydrous magnesium sulfate drying and concentrate the light brown solids of acquisition 3.79 grams.From alcohol-water, be recrystallized, obtain the 1-(2 of 2.79 grams (60%), 6-dichlor-4-trifluoromethyl phenyl)-2-amino-4-cyanpyrrole, fusing point is about 176 ℃.
Starting material 1-virtue amino-2,3-dicyano propylene makes as follows: the sylvite samples of the formoxyl succinonitrile of 20.5 grams (0.140 mole) are dissolved in about 30 milliliters water, and use the concentrated hydrochloric acid acidifying.With ether it is extracted,, obtain the brown liquid of 3.87 grams with anhydrous magnesium sulfate dry and evaporation with the ether extract.This thing is incorporated in contains 2 of 5.04 grams (22 mM), in the solution of right-toluenesulfonic acid-hydrate in 50 milliliters of benzene of 6-dichlor-4-trifluoromethyl aniline and 40 milligrams.This heterogeneous reactant mixture is heated to reflux and spends the night, with moisture from.Then with this reactant mixture cooling and concentrated to obtain the yellow liquids of 7.66 grams.Owing to, be settled out the 1-[(2 of 6.68 grams (95%), 6-dichlor-4-trifluoromethyl phenyl with the abrasive action of hexane) amino-2, the yellow solid of 3-dicyan propylene.Be recrystallized from ethanol/water, obtain sample, its fusing point is about 101 ℃.
Embodiment 14A and 14B
With 0.19 milliliter (0.59,3.7 the solution of bromine mM) in 5 milliliters of chloroforms joins the 1-(4-trifluoromethyl of 1.17 grams (3.30 mM))-triethylamine of 2-amino-3-trifluoromethyl sulfo--4-cyanpyrrole and 0.46 milliliter (0.34 gram, 3.3 mMs) is in 20 milliliters of suspension that are cooled in-20 ℃ the chloroform.Reactant mixture stirred 1 hour down at-20 ℃, made then to be warmed to 0 ℃.And then adding the bromine of 0.04 milliliter (0.13 gram, 0.8 mM), the additional stirring after 15 minutes use the carrene diluted reaction mixture, and water separates with saturated sodium bicarbonate aqueous solution.This organic layer is by anhydrous magnesium sulfate drying and concentrated to obtain the brown solids of 1.11 grams.This material and 1-(4-trifluoromethyl by 1.00 grams (2.8 mM))-material of the previous reaction gained of the bromine of 2-amino-3-trifluoromethyl sulfo--4-cyanpyrrole and 0.15 milliliter combines.Make chromatograph and separate on silica gel, with 3: 1v/v carrene-hexane wash-out obtains the 1.40 1-(4-trifluoromethyls that restrain (52%))-2-amino-3-trifluoromethyl sulfo--4-cyano group-5-bromo pyrroles's (embodiment 14A) yellow solid.Be recrystallized from hexane-ethyl acetate, obtain light yellow laminar product, fusing point is about 175 ℃.
From the 1-[(4-trifluoromethyl) amino]-2,3-dicyan propylene can make the 1-(4-trifluoromethyl by the same procedure that embodiment 13 describes)-2-amino-3-trifluoromethyl sulfo--4-cyanpyrrole (embodiment 14B), fusing point is about 152 ℃.
Embodiment 15A and 15B
The same procedure of describing by embodiment 13 makes 1-[(2-chloro-4-trifluoromethyl) amino]-2,3-dicyan propylene, this dicyan-propylene is used to prepare 1-(2-chloro-4-trifluoromethyl)-2-amino-3-trifluoromethyl sulfo--4-cyanpyrrole (embodiment 15A), 169 ℃ of fusing points are produced by the same procedure that embodiment 13 describes.This pyrroles is used to prepare 1-(2-chloro-4-trifluoromethyl)-(embodiment 15B, 157 ℃ of fusing points make by the method for embodiment 14 2-amino-3-trifluoromethyl sulfo--4-cyano group-5-bromine pyrroles.
Embodiment 16A and 16B
By the 1-(2 that embodiment 13 makes, 6-dichlor-4-trifluoromethyl phenyl)-2-amino-4-cyanpyrrole, press embodiment 13(and should example use (CF 3SCl) method CFCl 2-SCl handles, and obtains 1-(2,6-two chloro-4-trimethylsilyl trifluoroacetamide phenyl)-2-amino-3-dichlorofluoromethyl sulfo--4-cyanpyrrole (embodiment 16A), its fusing point is about 202 ℃.
This compound is handled with the alpha..alpha.-dimethylethyl nitrite ester by the method for embodiment 4, obtains 1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(dichlorofluoromethyl sulfo-) pyrroles (embodiment 16B), its fusing point is about 158 ℃.
Embodiment 17
The final compound of embodiment 16 reacts by embodiment 1 method identical with 2, the hydrogen peroxide of employing in trifluoromethyl peracetic acid (substitute between-chloroperoxybenzoic acid), make 1-(2,6-dichlor-4-trifluoromethyl phenyl)-and 2-chloro-3-cyano group-4-(dichlorofluoromethyl sulfenyl pyrroles (embodiment 17), its fusing point is about 119 ℃.
Embodiment 18
Press the method for embodiment 17, use the hydrogen peroxide of qdx, the final compound of embodiment is changed into 1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(dichlorofluoromethyl sulfonyl) pyrroles (embodiment 18), fusing point is 179 ℃.
Embodiment 19
Method by embodiment 4 is come the initial compound of Processing Example 16 with the alpha..alpha.-dimethylethyl nitrite ester, obtains 1-(2,6-dichlor-4-trifluoromethyl phenyl)-3-cyano group-4-(dichlorofluoromethyl sulfo-) pyrroles (embodiment 19), fusing point is about 120 ℃.
Embodiment 20
Press the compound oxidation of the method for embodiment 17, obtain 1-(2,6-dichlor-4-trifluoromethyl phenyl embodiment 19)-3-cyano group-4-(dichlorofluoromethyl sulfenyl) pyrroles (embodiment 20), fusing point 150-152 ℃.
Embodiment 21A, 21B and 21C
Press the method for embodiment 13 final compounds, with 2,6-two chloro-4-trifluoro-methoxyanilines replace 2, and the 6-dichlor-4-trifluoromethyl aniline makes 1-[(2,6-two chloro-4-Trifluoromethoxyphen-ls) amino]-2,3-dicyano propylene.
Method by 13 second compounds of embodiment is converted into 1-(2 with above-claimed cpd, 6-two chloro-4-Trifluoromethoxyphen-ls)-2-amino-4-cyanpyrrole.
Press the method for embodiment 13 first compounds, change this compound into 1-(2,6-two chloro-4-Trifluoromethoxyphen-ls)-2-amino-3 trifluoromethyl sulfo--4-cyanpyrrole.
Press the method for embodiment 8, change this compound into 1-(2,6-two chloro-4-Trifluoromethoxyphen-ls)-2-amino-3-(trifluoromethyl sulfo-)-4-cyano group-5-chloro pyrroles (embodiment 21A), fusing point 196-197 ℃.
Press the method for embodiment 4, change this compound into 1-(2,6-two chloro-4-Trifluoromethoxyphen-ls)-2-chloro-3-cyano group-4-trifluoromethyl sulphur pyrroles (embodiment 21B), 172 ℃ of fusing points.
Press the method for embodiment 18, change this compound into 1-(2,6-two chloro-4-Trifluoromethoxyphen-ls)-2-chloro-3-cyano group-4-trifluoromethyl sulfonyl pyrroles (embodiment 21C), 187 ℃ of fusing points.
Embodiment 22A, 22B and 22C
2-chloro-4-chlorine sulfenyl-3-cyano group-1-(2 ', 6 '-two chloro-4 '-trifluoromethyl-phenyl)-pyrroles and 2-chloro-3-cyano group-4-dichlorofluoromethyl sulfenyl-1-(2 ', 6-two chloro-4 '-trifluoromethyl)-pyrroles's mixture 47.77 grams (0.101 mole, 1.0 equivalents) are dissolved in 0 ℃ the trifluoroacetic acid (190 milliliters).Add 30%H in the mode of splashing into 2O 2(10.8 milliliters, 0.106 mole, 1.05 equivalents).This is reflected at 0 ℃ and stirred 7 hours 15 minutes down, and putting into refrigerator (10 ℃) then spends the night, and adds 30%H inferior morning under 0 ℃ again 2O 2(10.8 milliliters, 0.106 mole, 1.05 equivalents), this is reflected at 0 ℃ and stirred 9 hours down, puts into refrigerator overnight then, adds 30%H inferior morning under 0 ℃ again 2O 2(10.8 milliliters 0.106 mole, 1.05 equivalents).3.5 after hour, reactant mixture is poured in 2 liters of frozen water, vigorous stirring is filtered then.
Equally, 2-chloro-4-chlorine sulfenyl-3-cyano group-1-(2 ', 6 '-two chloro-4 '-trifluoromethyl)-pyrroles and 2-chloro-3-cyano group-4-dichlorofluoromethyl sulfenyl-1-(2 ', 6 '-two chloro-4 '-trifluoromethyl)-pyrroles's mixture (0.848 mole of 1.0 equivalent of 40.77 grams) is dissolved in 0 ℃ the trifluoroacetic acid (188 milliliters), adds 30%H in the mode of splashing into 2O 2(17.7 milliliters, 0.173 mole, 2.05 equivalents).This is reflected at 0 ℃ and stirred 2 hours 45 minutes down, puts into refrigerator (10 ℃) then and spends the night.After 8 hours, this reactant mixture is put into refrigerator overnight once more 0 ℃ of stirring.Then this reactant is warmed to room temperature, and at room temperature stirs and spend the night.Add 0 ℃ 30%H inferior morning again 2O 2(9.05 milliliters, 0.0886 mole, 1.05 equivalents), and make reaction remain on 0 ℃ following 6 hours 40 minutes, be warmed to room temperature then and stirred weekend.Reactant is poured in 2 liters of frozen water, and vigorous stirring is filtered then.
The sediment of two secondary responses is combined and is dissolved in 500 milliliters of carrene, use 500 ml waters, 500 milliliters of 10%NaHSO again 3The aqueous solution and 500 milliliters of saturated NaCl solution clean it.Organic facies Na 2SO 4Drying is filtered, solvent evaporated, the solid of acquisition 74.96 grams (productive rate 79.9%).This material is from 690 milliliters of hexanes: recrystallization the carrene (2: 1), add 20 milliliters of carrene again, obtain the solid of 6.98 grams, be 2-chloro-4-chlorine sulphonyl-3-cyano group-1-(2 ' through differentiating, 6 '-two chloro-4 '-trifluoromethyl)-pyrroles (embodiment 22A).Then this thing is recrystallized from 103 milliliters of isopropyl alcohols, obtains 3.97 grams, fusing point 187-188.5 ℃.
2-chloro-4-chlorine sulphonyl-3-cyano group-1-(2 ', 6 '-two chloro-4 '-trifluoromethyl)-pyrroles (3.97 gram, 9.06 mMs, 1.0 equivalents) is dissolved in 0 ℃ THF(15.8 milliliter) in.Add solid triphenylphosphine (2.41 grams, 1.0 equivalents).Solution transfers yellow to.2.5 after hour, shift out ice bath, this reaction at room temperature stirred spend the night.Add triphenylphosphine (2.55 gram, 9.72 mMs, 1.06 equivalents) again, and this reaction is at room temperature stirred spend the night.Sediment generates, and adds 3 milliliters of THF, uses saturated NaCl solution washing reactant mixture twice then, and strips.Organic facies is passed through MgSO 4Drying is filtered, and evaporating solvent obtains 9.44 gram waxy solids in a vacuum.This thing is made chromatograph separate on silica gel, output 3.39 gram waxy solids.From 140 milliliters of isopropyl alcohols, be recrystallized then, obtain 2.54 grams (74.9%) two-[2-chloro-3-cyano group-1-(2 ', 6 '-two chloro-4 '-trifluoromethyl)-pyrrole radicals-4-yl]-disulphide (embodiment 22B), fusing point 218.8-220.3 ℃.
Will be two-[2-chloro-3-cyano group-1-(2 ', 6 '-two chloro-4 '-trifluoromethyl)-pyrrole radicals-4-yl]-disulphide (0.80 gram, 1.08 mMs, 1.0 equivalents) is dissolved in the DMF(10 milliliter) in, and be cooled to 0 ℃ with Na 2HPO 4(0.46 gram, 3.24 mMs, 3.0 equivalents) are dissolved in 5 ml waters, are added to then in the DMF solution.After forming sediment, add 15 milliliters of DMF and 10 ml waters.With solid Na 2S 2O 4(0.564 gram, 3.24 mMs, 3.0 equivalents) add, and this reactant transfers to faint yellow.Dibromodifluoromethane (0.65 gram, 3.1 mMs, 2.87 equivalents) is added in the cold phial of weighing in advance, is transferred to then in the reactant, this reactant mixture just becomes colorless and has white depositions.After 1 hour 50 minutes, add 10 milliliters of DMF, then add 0.93 gram CBr in addition 2F 2, closed reaction vessel at room temperature stirs and spends the night.After being cooled to 0 ℃, reactant mixture is added in 200 ml waters and with 150 milliliters of extracted with diethyl ether 4 times.Organic facies is with 100 milliliters of 5%HCl solution washings 2 times, with 100 milliliters of saturated NaHCO 3Solution washing 2 times is used 100 milliliters of saturated NaCl solution washings again.Organic facies is passed through MgSO 4Drying is filtered, and evaporating solvent obtains 80.7 milligrams of white solids in a vacuum.Then the initial water that contains is filtered out to collect a kind of white solid, it needs to spend the night through precipitation.It is dissolved in the two chloro-methane, and evaporating solvent, and drying in a vacuum to obtain 0.348 gram white solid (gross yield 0.429 gram, 40%).This material and above-mentioned 80.7 milligrams sample are combined, and on silica gel, make chromatograph and separate, obtain 0.362 gram white solid, identify and be 4-bromine difluoro methyl sulfenyl-2-chloro-3-cyano group-1-(2 ', 6 '-two chloro-4 '-trifluoromethyl)-pyrroles (embodiment 22C), fusing point 128.3-133.7 ℃.
Additional synthetic embodiment
The synthetic method of abideing by the compound of above-mentioned example 1 to 22, or synthetic methods of general description here can prepare the additional synthetic example (ASE) of many chemical formulas (1) azole compounds.The structure of these compounds and their corresponding molten points are listed in table 3(ASE-numbering 1-91: the compound of chemical formula (1): this place, X 2And X 3Be hydrogen, other substituents as the regulation) and table 4 in (ASE-numbers 92-195: the compound of chemical formula (1): this locates X 2And X 3Be hydrogen, X 1And X 4Be chlorine, Y is a trifluoromethyl, and other substituents are as regulation).
Utilization of pesticides method and composition thereof
According to characteristics of the present invention, a kind of method of controlling the arthropods in a certain place, particularly insects and spider animal, Plant nematode class and worm or protozoan pest can be provided, the compound that it comprises the chemical general formula (I) that uses effective dose is administered this area's method of pouring and administration (for example by), in general formula (I), each symbol is as afore mentioned rules.The compound of general formula (I) is particularly useful for veterinary medicine and livestock breeding field, and can be used for safeguarding the public health aspect, prevent to parasitize particularly for example people and family's letting animals feed such as ox of warm-blooded vertebrate of vertebrate, sheep, goat, horse, pig, poultry, body interior of dog and cat or outside arthropods, worm or protozoa, Acarina(Acarina for example), comprise tick class (as Ioxdes spp.Boophilus.spp. such as Boophilus microplus, Amblyomma spp.Hyalomma spp.Rhipicephalus spp. such as Rhipicephalus appendiculatus.Haemaphysalis spp.Dermacentor spp.Orntihodorus spp. such as Ornithodorus moubata) and moth class (as Damalinia spp.Dermahyssus gallinae.Sarcoptes spp. such as Sarcoptes scabici.Psoroptes spp.Chorioptes spp.Demodex spp.Eutrombicula spp.); Diptera(such as Aedes spp.Anopheles spp.Musca spp.Hypoderma spp.Gasterophilus spp.Simulium spp.); Hemiptera(such as Triatoma spp.); Phthirapter(such as Damalinia spp.Linognathus spp.); Siphonathus spp.); Siphonapters(such as Ctenocephalides spp.); Dictypotera(such as Periplaneta spp.Blatella spp.); Hymenoptera(such as Monomorium pharaonis); For example tackle the alimentary infection that causes by parasitic nematode, for example the member of this family has: Trichostrongylidae.Nippostrongylus brasiliensis.Trichinella spirslis.Haemonchus contortus.Trichostrongylus colubriformis.Nematodirus battus.Ostertsgis circumcincta.Trichostrongylus axci.Cooperiaspp. and Hymenolepis nana: in control with treat aspect the protozoic disease that it is caused by following insect, for example Eimeria spp. such as Eimeria tenella.Eimeria acervulina.Eimeria brunetti.Eimeria maxima and Eimeria necatrix.Trypanosoma cruzi.Leishamania spp.Plasmodium spp.Babesia spp.Trichomonadidae spp.Histomonas spp.Giardia spp.Toxoplasma spp.Entamoeba histolytica and Theileria spp. are aspect protection storage product, for example cereal comprises grain, flour, peanut, animal feed, timber and family expenses kinds of goods such as carpet and textile, tackle and be subjected to arthropodan attack, particularly coleoptera comprises stinkbug, moth moth worm and trombiculid, Ephestia spp.(flour moth for example) Anthrenus spp.(carpet beetle) .Triboloum spp.(flour beetle), Sitophilus spp.(paddy stinkbug) and Acarus spp.(trombiculid), the control cockroach, ant and termite and similar arthropod cutting apart the aspect and controlling the ditch to civilian and industrial house, well, the mosquito aspect of reservoir or other circulating waters or stagnant water; Be Ground Treatment, structure and soil, prevent the infringement aspect of termite to building, for example, Reticulitermes spp.Heterotermes spp.Copttermes spp, on agricultural, prevent the adult of lepidopterous insects, larva and ovum aspect (flying butterfly and moth) are for example, Heliothis spp. such as Heliothis vorescens(tobacco budworm) Heliothis armigera and Heliothis zea. Spodoptera such as Sexempta.S.littoralis(Egyptian cotton worm), S.eridania(south mythimna separata), Mamestra configurata(flower mythimna separata); Earias spp. is the Egyptian corn earworm of E.insulana(for example), Pectinophora spp. is Pectinophora gossypiella(China pink corn earworm for example) .Ostrinia spp. such as O.nubilalis(European corn snout moth's larva) Trichoplusiani(Chinese cabbage looper), Pieris spp.(cabbageworm), Laphygma spp.(mythimna separata) Agrotis and Amathes spp.(burglar moth), Wiseana spp.(is eaten into moth), Chilo spp.(rice bar snout moth's larva) Tryporyza spp. and Diatraea spp.(dried sugarcane borer of sugar and rice borer), Sparganothia pilleriana(grape berry moth), Cydia Pomonella(griggles moth), Archips spp.(fruit tree volume moth), Plutella xylostella(diamond-back moth), for example tackle coleopterous adult and larva (beetle), Hypothenemus hampei(coffee bean moth), Hylesinus spp.(small worm, Anthonomus grandis(cotton bollworm), Acalymma spp.(cucumber beetle), Lema spp.Psylliodes spp.Leptinotarsa decemlineata(Colorado potato beetle), Diabrotica spp.(corn root moth), Gonocephalim spp.(line simulator worm), Agriotes spp.(nematode), Dermolepida and the white grub of Heteronychus spp.() Phae don cochleariae(mustard beetle), Lissorhoptrus(rice water stinkbug), Meligethes spp.(pollen beetle), Ceutorhynchus spp.Rhychophorus and Cosmopolites spp.(root stinkbug), tackle half wing amount animal such as Psylla spp.Bemisia spp.Trialeurodes spp.Aphis spp.Myzus spp.Megoura viciae.Phylloxera sppAdelges spp.Phorodon humuli(phorodon aphid worm), Aeneilamia spp.Nephotettix spp.(rice leaf locust), the brown Aspidiotus of Empoasca spp.Nilaparvata spp.Perkinsiella spp.Pyrilla spp.Aonidiella spp.(), Coccus spp.Pseucoccus spp.Helopeltis spp.(mosquito), Lygus spp.Dysdercus spp.Oxycarenus spp.Nezara spp. Hymenoptera is Athalia spp. and Cephus spp.(sawfly for example), Atta spp.(leaf cutting ant), dipteral insect is Hylemyia spp.(root fly for example), Atherigona spp. and Chlorops spp.(penetrate fly), Phytomyza spp.(leaf bores worm), Ceratitis spp.(fruit bat), thrips such as Thrips tabaci, true wing order such as Locusta and Schistocerca spp.(locust) and cricket for example Sminthurus spp. and Onychhiurus spp.(springtail of Gryllus spp. and Acheta spp. Collembola for example) isoptera insect Odontotemes spp.(termite for example), lead for example Forficula spp.(earwig Sou of homopterous insect) and the segmental appendage class insect such as the acarian of other agriculture meaning aspects nibble trombiculid for example 3Tetranychus spp.Panonychus spp. and Bryobia spp.(spider mite), Eriophyes spp.(goitre mite) Polyphagotarsonemus spp.Blaniulus spp.(thousand-legger), Scutigerella spp.(wood wasp), Oniscus spp.(steals worm) and Triops spp.(Crustachia insect), these insects of nematode are in agricultural, on forest and the gardening main infringement plant and the insect of trees, they or directly the infringement, perhaps plant is scattered bacterium, mycoplasma or fungal disease, root nematode such as Meloidogyna spp.(be the travel incognito worm for example), Cyst nematode such as Globodera spp.(be Grostochiensisa for example), Heterodera spp.(is H.avenae for example), 3Radopholus spp.(is Rsimilis for example): infringement nematode such as Pratylenchus spp.(be P.pratensis for example), Belonolaimus spp.(is B.gracilis for example), Tylenchulus spp.(is T.semipenetrsns for example), Rotylenchulus spp.(is R.reniformis for example), Rotyenchus spp.(is R.robustus for example), Helicotylenchus spp.(is Hmulticinctus for example), Hemicycliophora spp.(is H.gracilis for example), Criconemoides spp.(is C.similis for example), Trichodorus spp.(is T.primitivus for example), sword shape nematode such as Xiphinema spp.(be X.diversicaudatum for example), Longidorus spp.(is L.elongatus for example), Hoplolaimus spp.(is H.coronatus for example), Apheienchoides spp.(is A.ritzema-besseyi for example), stem and bulb eelworm such as Ditylenchus spp.(be D.dipsaci for example).
In addition, can be used for the insect that The compounds of this invention controls comprises: the Isopoda insect, Oniseus asellus for example, Armadillidium vulgare and Porcellio scaber. wing Lian order insect (Diplopoda) for example Blaniulus guttulatus by centipede class (clam foot guiding principle) for example Geophilus carpophagus and Scutigera spex, by symphysis order insect Scutigerella immaculata for example, by the Thysanoptera insect, Lepisma sacchat ian for example, by collembolan, for example Onythiurus. is by straight wing amount, for example Blatta roientalis Periplaneta americana.Leucophaea maderae.Blatella germamica.Acheta domesticus.Gryllotalpa spp.Locusta migratotia migratotioides.Melanoplus differentialis and Schistocerca gregaria. are by careless homopterous insect, Forficula auricularia for example, by isoptera insect, for example Reticulitermes spp. is by Anoplura, for example Phylloxera vastatrix.Pemphigus spp.Pediculus humanus corporis.Haematopinus spp. and Linognathus spp. are by Mallophaga, for example Trichodectes spp. and 3 Damalinea spp. are by thrips, for example Hercinothrips femoralis and Thrips tabaci, by Semiptera, Eurygaster spp.Dysdercus intermedius.Piesmaaaquadrata for example, Cimex lectularius.Rhodnius prolixus and Triatoma spp. are by coleoptera, for example Anobium punctatum.Rhizopertha dominica.Bruchidius obtectus.Acanthoscelides obtectus.Hylotrupesbajulus.Agelastica alni.Leprinotarsa decemlineata.Phaedon cochleariae.Diabrotica spp.Psylliodes chrysoephala.Epilachna varivesris Atomaria spp.Orvyzaephilus surinamensis.Anthonomus spp.Sitophilus spp.Otiorrhynchus sulcatus.Cosmoplites sordidus.Ceuthorrhynchus assimilis.Hypera postica.Dermesres spp.Trogoderma spp.Attagenus spp.Lyctus spp.Maligethesaenaus.Ptinus spp.Niptus hololeucrus.Gibbium psylloides.Trobolim spp.Tenenrio molitor.Agrioes spp.Conoderus spp.Melolontha melolontha.Amphimallon solstitialis and Costelytra zealandica. are by Hymenoptera, for example Diprion spp.Hoplocampa spp.Lasius spp.Monomorium Pharaonis and Vespa spp. are by diptera, for example Aedes spp.Anopheles spp.Culsx spp.Drosophila melanogaster.Musca spp.3Fannia spp. Calliphora erythrocephala.Lusilia spp.Chrysomyia spp.Cuterenra spp.Gastrophilus spp.Hyppobosca spp.Stomoxvs spp.Osstrus spp.Hypoderma spp.Tannia spp.Bibio hortulanus.Oscinella frit.Phorbia spp.Pegomyia hyoscyia.Ceratitis capitata.Dacus oleae and Tiupla paludosa. are by Siphonaptera, for example Xenopsylla cheopis and Ceratophyllus spp. are by Araneida, for example Scorpio maurs and Latrodectus mactans. are by Semiptera, for example, Aleurodes brassicae.Bemisia tabaci.Trialeurodes yaporariorum.Aphis gossypii.Brevicoryna brassicae.Cryptomyzus ribis.Doralis fabae, Doralis pomi.Eriosoma lanigerum Hyalopterus aruninis.Macrosiphum avenae.Myxus spp.Phorodon humuli.hopalosiphum padi.Empoasca spp.Escelis bilbatus.Nephotetttx cincticeps.Lecanium corni.Saissetia oleae.Laodelphax striatellus.Nilaparvata ligens.Aonidiella aurantii.Aspidiotus hederae.Pseudococcus spp. and Psylls spp. be by Lepidoptera, for example Pectinophora gossypiella.Bupalus piniarius.Cheimatobia brumata.Lithhocollet is blancardella.Hyponomeuta padel Plutella maculipennis.Malacosoma neustria.Euprocyischrysorrhoea.Lymantria spp.Bucculatrix thurberiella.Phyllocnist is citrella.Agrot is spp.Euxoa spp.Earias insulana.Hheliothis spp.Laphygma cxigua.Mamestra brassicae.Panolis flammea.Prodenial itura.Spodoptera spp.Trichoplusiani.Carpocapsa pomondlla.Pieris spp.Chilo spp.Pyrausta nubilalis.Ephestiakuchniella.Galle ria mellonella.Tineola bisselliella.Tinea pellionella.Hofmannophila Pseudosretella.Cacoecia podana.Capua reticulana.Choriatoeura.Clysia ambiguells.Homona magnanimew and Tortix viridana.
The present invention provides a kind of method of controlling the disease of arthropods or Plant nematode simultaneously, and it comprises that effective quantity of the compound of using general structure (I) is in the medium of plant or their growths.
In order to control arthropods and nematode, normally this reactive compound is applied to the place that is positioned at arthropods or eelworm harm, be controlled at about 0.05 kilogram to about 15 kilograms of reactive compounds place processed to per hectare, preferably be 0.02 kilogram/hectare to 2 kilograms/hectare ratio.Under desirable condition,, can provide the protection of adaptation in lower ratio according to controlled disease.On the other hand, the resistance of disadvantageous weather condition, disease and other factors may need the active ingredient of higher proportion.When being applied to leafage, can use 0.01 kilogram of ratio to 1 kilogram of hectare.Best ratio depends on the type of the disease of desire control, vegetative stage and the channel space and the application process of infection plant.
When insect is confined to grow in the soil, the reactive compound that this prescription comprises is distributed in processed All Ranges equably with common any means.If desired, normally can be applied in the area of field or plant growth or approaching closely protected seed or the plant that is endangered.This reactive compound can be by going into the whole distract of soil with the water hydro-peening or can being stayed by the operation of nature of rainfall.If desired, during using or after using, if desired, this prescription can mechanically be broadcast into soil, for example by ploughing and weeding or use the disk harrow farming.Using can be before between planting season, when plantation or after the plantation, but will germinate take place before or after the germination.
The compound of general structure (I) can be to be used in the nematode that the there is lived in major control in the soil with solid or fluid composition, but, control the aerobic part (that is: above-mentioned listed Aphelenchoides spp. and Ditylenchas spp) of the plant of those nematode infringements also simultaneously to leaf.
The compound of general structure (I) may be indirect from the plant of application points feed-in part in the value of Pest Control, and for example: killing with the leaf by the compound that provides that is applied to root is the insect of foodstuff.
The compound of general structure (I) is protection field, feed, botanical garden, greenhouse, orchard and vineyard crop; to ornament and crop and forest-tree, for example: cereal (such as corn, wheat, rice, Chinese sorghum), cotton, tobacco, vegetables and living vegetables (such as: beans, cole crop, Hu Lu, lettuce, onion, tomato and pepper) the earth crop (such as: potato, sugar
Figure 891089853_IMG53
Dish, peanut, soybean, coleseed), sugar cane, careless field and feed (such as: corn, Chinese sorghum, clover), crop (such as: tealeaves, coffee, cocoa, banana, oil palm, coconut, rubber, spices), orchard and hurst (such as: drupe with fruit, lily of the valley fruit tree, both citrus, kiwi fruit, avocado, mango, olive and the walnut of kernel), in the vineyard in greenhouse, garden or park, decorate crop, flowers and vegetables and shrub, forest (fallen leaves or evergreen both), crop and nurse-tree are valuable especially.
They tackle sawfly (that is: Urocerus) or beetle (as: ambrosia beetle, pig-hole borer worm, powder moth, long moth, longicorn, death watch beetle) or termite at protection timber (stacking, felling, transhipment, storage or structure) simultaneously; for example: Reticulitermes spp.; Heterot ermes spp., Coptotermes spp is valuable.
It has been used in storage product such as cereal, fruit, drupe, spices and tobacco, and the maintenance of (no matter be levigate or combination finished product) is tackling the harm of moth, beetle and cereal weevil (Sitophilus granarius).Keep simultaneously the animal product stored such as: the form natural or that it has been processed (as: carpet or fabric) of fur, hair, wool and leather is to tackle the harm of moth and beetle; While also keeps meat, the fish of storage to avoid the attack of mite class or fly.
The compound of general structure (I) may or be valuable especially to the disease media of people and domestic animal in control arthropods, nematode or protozoic injury or propagation on, mention in front as an example, and be valuable especially especially control tick class, mite class, louse, flea class, buffalo gnat and thorn chela fly, little fly and maggot fly.To colonize in animal inside or wash with watercolours life be useful especially at animal skin or the arthropods, nematode or the protozoa that inhale animal blood to the compound of general structure (I) being controlled at, for this purpose, they can be with oral, parenteral, through subcutaneous or dispenser partly.Coccidiosis is to infect the disease cause by protozoan parasite Eimeia, is the important potential cause of domestic animal and birds economic loss, especially those raisings or remains on situation under the intensive conditions.As an example, ox, sheep, pig and rabbit are influenced by this may, but this disease is even more important in chicken in poultry especially.
Poultry disease is picked up on the refuse that infectious agent is spread in pollution by birds or or the route infection by food drinking-water usually on every side.This disease disease condition be hemorrhage, under (Ceca) caecum extravasated blood, the drop of blood that flows through, cause weak and digestive disorders.This disease finally usually causes animal dead, and bird is subjected to the serious result who infects significantly descends their market value.
The administration of a small amount of of the compound of structural formula (I) preferably by combining with poultry feed, may effectively prevent or reduce the influence of coccidia.These compounds tackle fowl caecum form (being caused by E.tenella) and intestines form (mainly being caused by E.acervulina, E.bruneti, E.maxima and E.necatris), and both are effective.
The compound of general structure (I) also can play a role on the inhibition egg capsule, by significantly reducing the generation of its quantity and/or those spores.
Produce and area that the combination system of following description architecture formula (I) is used for the humans and animals epidermis and protects storage product, domestic articles, general environment, in addition, the covering of the cereal that is generally used for growing and the place of corn growing and seed.The suitable application process of the compound of structural formula (I) comprising:
To arthropods, nematode or protozoa invade and harass or the humans and animals that infects by non-enteron aisle, oral or local application can show at once and/or at whole girth long term with antagonism arthropods, nematode or protozoic composition, as an example, by with the feed of feed or the medicine prescription of suitable absorption that can be oral, edible bait, salt electuary, food, irritate agent prescription, spray, solvent, preserved material, shower agent, propellant, pulvis, finish (greases), hair washing agent, cream, wax smears and poultry self-handling system and cooperate; At common environment or the privileged site that particularly may hide to insect, comprise product, timber, domestic articles and family and the industrial occupancy of hiding storage, with sprinkling, spraying, pulvis, cigarette smoke, wax smears, lacquer, particle and bait to be to splash into water channel, well, cistern and other mobile or static water; To the poultry in raising with control growing screwworm in excrement; Cereal to growth is sprinkled upon pulvis, particle, spraying and bubble jet on the leaf.Smoke with foam by liquid immersion liquid, pulvis, particle, cigarette simultaneously and handle as soil and root for the compound of the suspended substance of the segmentation of the compound of structural formula (I) and capsule; Handle with liquid slurry and pulvis, with coating as seed.
The compound of structural formula (I) can be used to control arthropods, nematode or protozoa with the composition of any kind of known technology, be suitable for vertebrate inside or outside dispenser or be used to be controlled at any house or arthropods indoor, outer area, which comprises at least compound and one or more required compatible thinner or conditioning agents that are used of a kind of structural formula (I).All these based compositions can prepare with any known technology.
The composition that is suitable for vertebrate or people comprise preparation be suitable for oral, non-enteron aisle, through skin, that is: pour into or the medicament of local application.
The composition of oral medicine comprises one or more compounds of structural formula (I) in conjunction with pharmaceutically acceptable carrier or cover layer, and for example comprises: recipe fill-in, slowly-releasing agglomerate or other slowly-releasing measure of tablet, pill, capsule, paste, glue, filling agent, pharmaceutical feed, medicine drinking-water, doctor's thing remain in the intestines and stomach with prolongation.Active substance can be wrapped into microcapsules maybe can wrap to be suitable for the coating in acidity or the alkalescence or to be used on the other drug acceptable intestines with in the dressing.Comprise edible thing that the premixed feed of The compounds of this invention and concentrate can be used for preparing medicine, drinking water or other and can be used for the material that consumed by animal.
The composition of parenteral comprises that solution, emulsion or suspension are at suitable arbitrarily pharmaceutically acceptable carrier and solid or semisolid hypodermic implant or be designed to discharge the pill of active ingredient and can and make aseptic with any suitable known technology preparation at whole long period.
Comprise spray agent, pulvis, bath agent, preserved material, shower agent, propellant, finish, hair washing agent, ointment, wax smears or pour into preparation and measure (for example: be attached to animal ear outside and provide locality and general ground to arthropodan control) as composition with the method through skin and local dispenser.
Be suitable for controlling compound and carrier or thinner that arthropodan solid or liquid bait comprise one or more general structures (I), it can comprise food substance or some other material of luring arthropods to consume.In fact the compound of the present invention that is used for agricultural adopts seldom separately.Most of with the part of these compounds as composition.These composition useful as pesticides, it comprises compound of the present invention, such as: earlier the explanation as active ingredient in conjunction with acceptable solid or liquid support and agricultural on the agricultural also acceptable surfactant.Especially, can adopt inertia with useful carrier and useful surfactant.These compositions also are portion-forms of the present invention.
All kinds that these compositions also can comprise other composition such as protecting colloid, binding agent, thickener, thixotropic compound, bleeding agent, sprinkling finish (when especially using), stabilizing agent, preservative (especially mould preservative), chelating agent or like that as miticide.The known active component that simultaneously has (the especially insecticide or the bactericide) of insecticidal properties with other or have a coordinate plant growth performance combines.More generally, the composition that adopts in the present invention can be in conjunction with in all solids or the extremely corresponding useful technology prescription of liquid additive.
Limit in the scope that the dosage of the compound of Cai Yonging can be wide in the present invention, depend on that especially person's character of the insect that will eliminate and the general degree of cereal being invaded and harassed owing to these insects decide.
Usually, contain 0.05 to the 95%(weight of having an appointment usually according to composition of the present invention) one or more active components of the present invention, one or more carriers of about 1 to 95% and optionally, one or more surfactants of about 0.1 to 50%.
Illustrated that the compound that adopts in the present invention is normally in conjunction with carrier and mating surface activating agent optionally.
Natural or the synthetic composition of a kind of organic or inorganic of this term of this external declaration " carrier " expression, it combines with active component to make and is easy to be applied to plant, seed or soil.So this carrier normally inertia must be on the agricultural with it, especially acceptable to handled plant.This carrier can be solid (potter's clay, natural or synthetic silicate, silica, resin, wax, solid fertilizer, as an example, as ammonium salt and levigate natural crystal, such as; Kaolin, potter's clay, talcum, gypsum, Attagel, montmorillonite, bentonite or diatomite and levigate synthetic mineral, such as: silica, aluminium oxide, silicate is aluminium or magnesium silicate especially.Solid carrier as particle is suitable, for example: the natural rock of pulverizing and classification is such as calcite, marble, float stone, sepiolite and dolomite, synthetic particle inorganic simultaneously or organic powder also is suitable, and the particle of organic material such as sawdust, cocoa husk, corncob and tobacco stem, diatomite, hoja, tricalcium phosphate, pulverous cork, the carbon black of adsorptivity and water miscible polymer, resin, wax, solid fertilizer and this class solid composite can contain one or more compatible wetting agent dispersants if desired, emulsifier or colouring agent, if solid can be used as the thinner time spent, this carrier also can be liquid: ethanol, especially butanols or ethylene glycol, and their ether or ester class, especially ethylene glycol acetate methyl esters, ketone, especially acetone, cyclohexanone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and isophorone, petroleum cuts naphthalane hydrocarbon or aromatic carbon hydrogen compound, especially dimethyl benzene or Fluhyzon, petroleum cuts, Dormant oils or vegetable oil; Chlorinated aliphatic hydrocarbon, especially trichloroethanes or carrene or chlorination aromatic hydrocarbon, especially Benzene Chloride; The solvent of water-soluble or strong polarity such as dimethyl formamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone and water; Liquefied gas and the like, with and composition thereof.
This surfactant can be a kind of anion or nonionic type emulsifier, dispersant or wetting agent, or this class surfactant mixtures.Here can mention; polyacrylate; lignosulfonates, benzene sulfonate or naphthalene sulfonate; the condensation polymer of ethylene oxide and fatty alcohol or fatty acid or fatty ester or fatty amine; the phenol (especially alkylphenol or aryl phenol class) that replaces; sulfosuccinate ester, taurine derivatives (especially alkyltaurate); the ester class of the ester of the alcohol of phosphoric acid or ethylene oxide and phenol, fatty acid and many alcohol, and the phosphate functional deriv of sulphate, sulfonate and above-claimed cpd.Usually when only water-soluble slightly or the water insoluble and carrier of active component and/or inert carrier when being applied to water, have a kind of surfactant at least.
Combination of the present invention can comprise different additives such as binding agent and colouring agent further.Binding agent such as carboxymethyl cellulose and natural or synthetic polymer; be powdery, particle or latex form; such as: gum Arabic, polyvinyl alcohol and polyvinyl acetate, and natural phosphide, such as: kephalin and lecithin and synthetic phosphide can be used in the prescription.Further, additive can be Dormant oils and vegetable oil.Adoptable colouring agent is an inorganic pigment, for example: iron oxide, titanium oxide and Prussian blue, and organic dyestuff such as alizarin dyes, the salt of azo dyes and metal phthalocyanine dyestuff and a spot of natural iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The compound compositions that comprises general structure (I) can be used for controlling arthropods, Plant nematode, acarid or protozoic disease also can comprise synergy agent (as: piperonyl fourth oxide or sesoxane) simultaneously, stable material, other insecticide, miticide, the plant nematocide agent, acarus-killing, the worm agent of killing, fungicide (be suitable on the agricultural or vertebrate as: benomyl, the dichlorophenyl first and second basic dioxy imidazolidine carbonyl acid amides) bactericide, arthropods or have the attractant of the animal of backbone, expellent, information is lured element, change flavor agent (reodorants) spices, dyestuff and auxiliary curative effect agent: trace element.When needs, can be designed to improve the worm spectrum of its ability, stability, safety, controlled insect or can carry out other useful function at the composition in the zone of same animal or processing.
Can comprise in conjunction with the example that is used in the compound of other insecticidal activity in the composition of the present invention and be: orthen, chlopyrifos, demeton-methyl, disulfoton, ethoprop (ethoprofos), sumithion, the malathion, nuvacron, parathion, zolone, Actellic, Hostathion, Cyfluthin, Cypermethrin, deltamethrin, fenpropathrin, fenvalerate, permethrin, the aldicarb miticide, Carbosulfan, methomyl, oxamoyl, anti-bud prestige Evil worm prestige, teflubenzuron, dicofol, 5a,6,9,9a-hexahydro-6,9-methano-2,4, lindane (lindane), benzoximate, cartap (Padan), cyhexatin, tetradifon, Avermectins, ivermectin, Milbex (milbemycins) topsin, chlorophos, dichlorvos, diareridine and dimetri adazole.
As using on their agricultural, usually the compound of structural formula (I) is used with the composition forms that is various solids or liquid.Fluid composition can be used for treated substance or places by arthropods endangering the zone that the place that maybe may endanger comprises house, outdoor or indoor stock or work, the place of container or equipment and water static or that flow.
Comprise solid homogeneous phase of compound of one or more structural formulas (I) or heterogeneous composition, for example: particle, pill, briquetting or capsule glue can be used for processing to static or mobile water in the whole cycle.The concentrate that adopts drip or adopt feed-in intermittently can be dispersed in the water also can reach similar effects in this explanation.
Be aerosol form and water-soluble or non-aqueous solution or suitably the composition of discrete form also can be used as sprinkling, spraying and sprinkling low or ultralow amount.
The solid form of composition can be mentioned powder (amount that can contain the compound of the structural formula (I) until 80%) or the wettable powder or the particle of powdery, especially the medicament that obtains through granulating from powder (content of the compound of structural formula these wettable powder or particle (I) is between 0.5 and 80%) of those particulate vectors or begin by extruding, closely knit, dipping.
Solution, especially emulsible concentrate, emulsion, flowable powder, aerosol, wettable powder (or the powder that is used to spray) but, dry fluid or slurry, the composition that this place can be mentioned can be liquid or making forms of liquid compositions when using.
Emulsible or soluble concentrate usually also comprises 5 to 80% active component, and the situation of emulsion of using easily or solution is to contain 0.01 to 20% active component.Except solvent, this emulsifiable concentrate can comprise 2 to 50% suitable additive (time) if desired, such as: stabilizing agent, surfactant, bleeding agent, corrosion inhibitor, colouring agent or binding agent.
Any concentration that emulsion is required can obtain by these concentrates of dilute with water, and it is particularly suitable for being applied to plant.
The suspension that concentrates, it can be used by sprinkling, so it is prepared into (fine lapping) that do not deposit stable product and contains active ingredient from 10 to 75% usually, surfactant from 0.5 to 30%, the thixotropic agent from 0.1 to 10% (thixotropic compound), the suitable additive from 0 to 30% such as: defoamer, corrosion inhibitor, stabilizing agent, bleeding agent, binding agent and as carrier, some organic solid or mineral salt may be dissolved in and help in the carrier to prevent to deposit or as the antifreeze of water when indissoluble or water insoluble or organic liquid therein.
This wettable powder (or the pulvis that is used to spray) is prepared into usually and contains 10 to 80% active ingredients, and they are generally comprised within the solid carrier, wetting agent from 0 to 5%, dispersant from 3 to 10% and if desired, one or more stabilizing agents from 0 to 80% and/or other additive such as bleeding agent, binding agent or anti-caking agent, colouring agent or like that.
In order to obtain these wetting powders, active ingredient or all compositions are mixed in suitable mixer with the material that can be immersed in the interpolation of porous filler, perhaps adopt flour mill or other suitable grinder to mix.The wetting powder that produces, its wettable and suspension are superior: they can be suspended in the water especially can be applied to plant leaf easily to obtain any required concentration and this suspension.
This " water dispersible granules " (WG) (is dispersed in the particle in the water easily) and has the composition that approaches wetting powder basically.They can pass through the illustrated granule preparation of wettable Fen agent; also can be by wet method (with the active component and the inertia inserts of segmentation with go into a spot of water promptly 1 to 20%; perhaps with aqueous dispersant or binding agent; then drying and screening), perhaps by dry method (comprise and compressing) then by grinding and sieving.
As illustrating, this liquid dispersion and emulsion, for example: by the composition that dilute with water obtains, be included in the composition general range of the present invention that can adopt according to wetting powder of the present invention or emulsible concentrate.Emulsion can be that Water-In-Oil or oil-in-water type and they can have a kind of thick toughness.
All these fluid dispersion or emulsifier or spraying mixture can be applied to crop, in any suitable method, mainly are to spray, and spray with the ratio of 100 to 12,00 liter spraying mixtures to per hectare usually.
Usually be applied to vegetation and particularly root and leaf had the effect of eliminating insect according to product of the present invention and composition.
Other method of using according to compound of the present invention or composition is by synergism, and the prescription that is about to contain active ingredient joins in the irrigation water.This irrigation can be used as that leaf insecticide spray is irrigated or as system's insecticide or subsurface irrigation on the ground.0.1 and 10 kilogram/hectare between, preferably 0.5 and 4 kilogram/hectare between, particularly can with the character of the method used and compositions for use decide usually by ratio and concentration for the dosage of active ingredient.
Generally speaking, the composition that is used to control arthropods, Plant nematode, worm or protozoa disease contains usually from 0.00001% to 95%(weight), more specifically, for from 0.0005% to 50%(weight) the compound of one or more general structures (I) or total active ingredient (that is: the compound of general structure (I) and other toxicant, vermicide, acarus-killing, synergist, trace element or stabilizing agent) to arthropods and Plant nematode.The composition and their ratio of using of the reality that adopts will be by the required effect selection that reaches of farmer, Livestock Production person, medicine or animal doctor professional, Pest management operator or other person skilled in the art.Typically, being used for the product of animal, trees, storage or the solid and the fluid composition of household goods contains usually from 0.00005% to 90%(weight), more specifically from 0.001% to 10%(weight) one or more compounds of general structure (I).Be used for oral or parenterai administration, comprise that solid or the fluid composition through skin comprises usually from 0.1 to 90%(weight animal) one or more compounds of structural formula (I).The feed of medicine comprises usually from 0.001% to 3%(weight) one or more compounds of structural formula.Being used for the concentrate that mixes with feed or additive contains from 5% to 90% usually and is preferably 5% to 50%(weight) one or more compounds of structural formula (I).Usually mineral salt contains on a small quantity from 0.1% to 10%(weight) one or more compounds of structural formula (I).
0.0001% to the 15%(weight that is used for the powder and the compound that fluid composition can comprise one or more structural formulas (I) in domestic animal, people, article, house (office) or outdoor area), more specifically be 0.005% to 2.0%(weight to reaching).Suitable concentration be between 0.0001ppm and 20ppm in the water of handling, and more body ground be 0.001ppm to 5.0ppm general structure (I) compound and also can be used for the medicinal of fish pond with suitable open-assembly time.Edible bait can contain from 0.01% to 5%(weight) and be preferably 0.01% to 1.0(weight) one or more compounds of general structure (I).
When giving vertebrate parenteral administration, oral or during through skin or other administration, the dosage of the compound of general structure (I) will depend on vertebrate kind, age and health status and character and its practical extent or potential invasion by arthropods, nematode or protozoan pest.Single dose be 0.1 to 100 milligram, preferably 2.0 to 20.0 milligrams/heavy animal kg body weight or every day 0.01 to 20 milligram of/kilogram the weight of animals and preferably be 0.1 to 5.0 milligram to per kilogram the weight of animals every day, as generally being suitable by oral or parenterai administration continued treatment.Be used for continuing the prescription or the device of release, can merge single administration in animal at the cycle of several months aequum.
Following special embodiment explanation contains compound of the present invention and farmingization composition, and the character of insecticide in view of the above and miticide and certain this compound, and the use embodiment of set of applications compound (prescription).
Following composition embodiment 23 to 28 explanation compositions are used to resist arthropods, especially to insects, Araneae, Plant nematode and worm or protozoan pest, its feature comprises the compound of structural formula (I) as active component, especially such as at those compositions embodiment 1 to 22 preparation and explanation in table 3 and 4.At the composition of embodiment 23 to 28 explanations, each can be diluted in the concentration that obtains being suitable for using the composition that sprays down on the farm in the water.The chemical descriptor (being percetage by weight) of total component of example that is used in embodiment 23 to 28 is for as follows:
Ethylan BCP: nonyl phenol ethylene oxide condensation product
Soprohor BSU: the condensation product of triphenylethylene phenol and ethylene oxide
The solution of Arylan CA:70%w/v calcium salt of dodecylbenzene sulfonate
Solvesso 150: light C 10-aromatic solvent
Arylan S: pelopon A
Darvan: sodium lignin sulfonate
Celite PE: synthetic magnesium silicate carrier
Sopropon T36: polycarboxylic acid sodium salt
Rhodigel 23: the yellow work of polysaccharide glue
Bentone 38: the organic derivative that covers de-magging stone
7lerosil: the silica of fine particle size
Embodiment 23
A kind of water-soluble concentrate is by following preparation:
Active ingredient 7%
Ethylan BCP 10%
N-Methyl pyrrolidone 83%
Be dissolved in N-Methyl pyrrolidone partly by Ethylan BCP, add active ingredient until dissolving in heating with under stirring then.By adding remaining solvent until the solution of quantitatively making generation.
Embodiment 24
A kind of emulsible concentrate is by following preparation:
Active ingredient 7%
Sopraphor BSU 4%
Arylan CA 4%
N-Methyl pyrrolidone 50%
Solvesso 150 35%
Be dissolved in the N-Methyl pyrrolidone by Soprophor BSU, Arylan CA and active ingredient, and add Solvesso150 then to quantitative.
Embodiment 25
A kind of wettable powder is by following preparation:
Active component 40%
Arylan S 2%
Darvan No.2 5%
Celite PF 53%
Pulverize by mixed composition with in hammer mill, until sized particles less than 50 microns.
Embodiment 26
A kind of liquid flow prescription is by being prepared as follows;
Active ingredient 40.00%
Ethylan BCP 1.00%
Sopropon T36 0.20%
Ethylene glycol 5.00%
Rhodige123 0.15%
Water 53.65%
Component is through mixing fully and grinding until average particle size less than 3 microns with husky grinder.
Embodiment 27
A kind of emulsible suspending concentrate is by following preparation:
Active ingredient: 30.5%
Ethylan BCP 10.0%
Bentone 35 0.5%
Solvesso 150 59.5%
Grind until average particle size particle size less than 3 microns by mixed composition with in sand mill.
Embodiment 28
But a kind of discrete particles is by being prepared as follows:
Active ingredient 30%
Darvan No.2 15%
Arylan S 8%
Celite PF 47%
By mixed composition and in liquid energy (fluid-energy) cracker micronization, and be sprayed into sufficient water (until 10%W/v) then, fine powder is made pill rolling into the ball machine.The particle that produces is dry to remove excessive water in moving-bed dryer.
Embodiment 29
But following component can be passed through directly to mix in a kind of dusting end:
Active constituent 1 to 10%
Superfine talcum powder 99 to 90%
This powder can be applied to the place of arthropods harm, for example: tip or soot, the place of storage article or domestic articles or animal harassing and wrecking, or in the suction of the local through port of arthropods invasion and attack harm with the control arthropods.To comprise the measure of mechanical hair-dryer, manual duster and livestock self-handling with the device of the appropriate action of dusting in arthropods harm place.
Embodiment 30
A kind of edible bait can be by fully being mixed with:
Active component 0.1 to 10%
Wheat flour 80%
(giving up) molasses 19.9 to 19.0%
This edible bait can be executed the house that is sowed at family and industry, i.e. kitchen, hospital or storeroom, or outdoor area, and through port absorbs for example ant, locust, the arthropodan harm of cockroach and fly (flies) of control arthropods.
Embodiment 31
A kind of solution can prepare by following composition:
Active ingredient 15%
Dimethyl sulfoxide (DMSO) 85%
Azole derivatives is dissolved in a part of dimethyl sulfoxide (DMSO) and adds required quantitative dimethyl sulfoxide (DMSO) then.This solution can be applied to the domestic animals that is subjected to arthropods harm, uses through the intracutaneous infusion, perhaps by after poly tetrafluoroethylene (the 0.22 micron hole dimension) filter-sterilized,, injects through non-enteron aisle per 100 kilograms the weight of animals with 10 to 12 milliliters solution.
Embodiment 32
A kind of wettable powder can be by being prepared as follows:
Active ingredient 50%
Ethylan BCP(9 mole oxide is to 1 moles of phenol) 5%
Aersosil 5%
Celite PF 40%
Be adsorbed on the Aersosil by Ethylan BCP, mix with other composition, this mixture grinds in hammer mill, obtain wettable powder, described powder dilutable water becomes the compound of the activity of 0.001% to 2%m/v concentration, and be applied to the place of arthropods harm, as an example as: the Nuscidae or the Plant nematode that are sprayed on dipteron, or it is be sprayed on or dipping is being subjected to arthropods, worm or protozoa domestic animals harm or risk of infection, or oral with control arthropods, worm or protozoa by being placed in the drinking water.
Embodiment 33
A kind of agglomerate of slow release can by comprise pile up agent, binding agent, agent for slow releasing and as the active ingredient for preparing of embodiment 27 form with the particle of the composition of percentage.Can form by compressing this mixture that to have proportion be 2 or greater than 2 agglomerate and can orally be administered to anti-domestic animal and be stranded in and slowly discharge azole compounds in netted-cud continuously with the harm to anti-domestic animal of control arthropods, nematode or protozoa in the time of whole prolongation.
Embodiment 34
A kind of composition of slow release can be by being prepared as follows:
Active ingredient 0.5 to 50%
Polyvinyl chloride-based 75 to 99.5%
By with polyvinyl chloride-based and reactive compound and suitable plasticizer, mix as two dioctyl phthalates, and the composition that carries out melt extruded or this homogeneous phase of molding becomes suitable shape, as: particle, ball, fritter or long tape, as an example, suitably conduct is added in the immobilising water, or under the situation of long tape, be assembled into ring or ear-tagger with annex as domestic animal, by slow release of active compounds with control insect disease.
The active ingredient that similar compositions can adopt any other suitable quantity of compound of general structure (I) to replace in the example composition prepares.
The Application Example of disinsection method:
Following Application Example 35 to 47 is to adopt the compound of the various concentration of the present invention.Contain 1 part of compound concentrations in each 1,000,000 parts of testing liquid that used 1ppm(adopts) be applied to solution on the leaf or suspension or emulsion and quite be similar to the active ingredient of using 1 gram/hectare, with the quantity (the abundant discharging) that approaches 1000 liter/hectares.So will be equivalent to 6-500 gram/hectare in following sprinkling of using from 6.25 to 500ppm, as soil application, the concentration of the soil of 1ppm is equivalent to using near 1000 gram/hectares sowing field on the basis of about 7.5 centimetres of soil depth.
Embodiment 35
Activity to aphid:
A kind of mixture prepares with following composition:
0.01 gram active ingredient
0.16 gram dimethyl formamide
0.838 gram acetone
0.002 gram surfactant mixture (comprise alkylaryl-Aethoxy Sklerol and have the poly-alkyl-aryl ether alcohol of sulfonic acid group at aryl moiety)
98.99 gram water
This dilute aqueous be sprayed onto have on it grow and the potted plant short garden nasturtium plant of hyperfunction sandlwood aphid (aphid Nasturtium) on, train and grow.The aphid number of every basin be 100-150.The volume of spraying liquid mixture is for being enough to wetting this plant to trickling.After the sprinkling, with basin in 20 ℃ of storages one day, the aphid that calculate to live then.Embodiment 1,2,3A, 4,5,16C, 17,18,19 and 20 and ASENo.12,24,23,33,34,38,39,42,44,45,54,57,60,62,98 to 100,102,104,125,130,131,135,137,141,142,144,157,158,162,166 and 174 compound under the concentration of 100ppm, draw 100% lethality.
Embodiment 36
Activity to the mite class
Employing is tested at embodiment 35 identical prescriptions.Yet, in light green beans strain, breed at the acarid (tetranychus telarius Urtica) of the two spots of 150-200 bar.After the sprinkling, this plant remained on 30 ℃, 5 days.Use embodiment 2,3A, 16C, 17 and 18 and ASENo.9,20,25,41,44,46,52,53,58,59,63,64,70,74,77 to 81,83,90,98,99,120,124 and 141 compound under the concentration of 100ppm, obtain 100% acarid lethality.
Embodiment 37-39
Activity to southern armyworm
37: adopt as the same recipe in embodiment 35, the propagation of southern in this case armyworm (Spodoptera eridania) second instar larvae is on about 15 centimetres high Steva beans plant.Then calculate lethality after five days: 100% lethality is provided and provides 80% lethality in 500ppm in 100ppm at the compound of embodiment 13 at embodiment 3A, 3B, 5,6,7,8,9,11,12,15B, 16C, 17,18,20,21B, 21C and ASENo.42,44,60,62,64,98 to 100,102,103,121,124,125,131,141,142,144,162,166 and 174 compound.
38: except employing was carried out as the identical prescription in embodiment 35, it comprised following component in this case:
2.5 milligram active ingredient
0.05 gram dimethyl formamide
9.9228 gram acetone
0.0247 gram surfactant (as in embodiment 35)
90 gram water
The compound of embodiment 4 obtains 100% lethality in 25ppm.
39: it comprises following component in this case except employing is carried out as the same recipe in embodiment 38:
0.625 milligram active ingredient
12.5 milligram dimethyl formamide
9.9621 gram acetone
0.0247 gram surfactant (as in the embodiment 35)
90 gram water
Obtain lethality at the compound of embodiment 1 and 2 in 6.25ppm to southern armyworm 100%.
Embodiment 40 to 43
Activity to Mexico Macroptilium beetle
Except adopting as identical prescription carries out in embodiment 37, it comprises following component in this case:
12.5 milligram active ingredient
0.25 gram dimethyl formamide
9.726 gram acetone
24.1 milligram surfactant (as in the embodiment 35)
89.988 gram water
Mexico Macroptilium beetle (Epilachna Varivest is, grow on about 15 centimetres high Sieva leguminous plant by second instar larvae training muls).Then, the lethality that calculates after five days: the compound at embodiment 13 obtains 100% lethality under 125ppm.
41: adopt as outside identical prescription carries out in embodiment 38, comprise that also the compound of embodiment 8 obtains 100% the lethality to Mexico Macroptilium beetle in 25ppm as active ingredient.
42: adopt as outside identical prescription carries out in embodiment 35, comprise that also the compound of the non-bromo of embodiment 15A obtains the lethality of 100% pair of Mexico Macroptilium beetle in 100ppm as active ingredient.
43: except adopting as the same recipe of embodiment 40 is carried out, it comprises following component in this case:
10 milligrams of active constituents
0.2 gram dimethyl formamide
9.7657 gram acetone
0.0243 gram surfactant (as in the embodiment 35)
90 gram water
Then calculate the dead percentage that Mexico Macroptilium beetle is obtained: obtain 80% lethality and obtain 100% lethality in 100ppm in 100ppm at embodiment 1,2,9,17,18 and ASENo.42,44,60,62,64,98,99,124,125,141,142 and 144 compound at the compound of embodiment 15A and 15B.
Embodiment 44-46
Activity to housefly:
This toxic agent is similar to the method prescription of embodiment 35, and with the form (comprising the sugar of 10w/w and the gas of 100ppm) of 10 milliliters of sugar aqueous solutions, serial dilution is made on demand further.Below be the preparation of three kinds of different test recipes:
Embodiment
44 45 46
Active ingredient (milligram) 10 10 1.25
Dimethyl formamide (milligram) 160 200 25
Surfactant (as among the embodiment 35) (milligram) 2.15 24.3 14.25
Acetone (gram) 8.42 9.766 5.73
Water (gram) 88.99 81 84.38
Sugar (gram) 10 9 9.84
With 25 budding flies (Musscadomesica) with carbon dioxide narcosis and be transferred to then and comprise the luring in the collection cup of poisonous substance prescription.After 27 ℃/day, calculate the dead percentage of fly, for as follows:
With embodiment 44: is 100% by embodiment 1,2,3, B, 4,6,8,9,16, C, 17,20,21B and 21C and ASENo.42,44,60,62,64,98,99,100,102,103,121,124,125,131,141,142,144,162,166 and 174 compound in the 100ppm lethality.
With embodiment 45: the compound by embodiment 12 is 100% in the 100ppm lethality.
With embodiment 46: the compound by embodiment 1,2 and 5 is 100% in the 12.5ppm lethality.
Embodiment 47
Activity to southern corn root beetle:
Except adopting the prescription that similarly method prepares in embodiment 35, only with 48.99 gram water, the initial concentration that test compound is provided is 200ppm in this case.According to following process of the test directly according to required concentration, this prescription can adopt be divided into ppm(1,000,000/).
200ppm test compound prescription (as the concentration of the test compound of suitable final soil), 3.2 ml waters and 5 corn seeds that germinate in advance of in a jar that contains 60 gram gizzard earth, adding five equilibrium.Should fully rock to obtain test recipe and distribute uniformly by jar.Then 20 southern corn root beetle ovum are put into the hole, it is made by soil.With vermiculite (1 milliliter) and water 107(milliliter) add in this hole.With similar method, preparation does not contain water-acetone, DMF, the emulsion of test compound, and a kind of liquid of its similar the application is as untreated contrast.In addition, a kind of compound formulas of commercial technology as the contrast of handling, is used as test standard with identical method.After 7 days, calculate the root mealworm number of living with known " Berlese " funnel extracting process.The 3B of following examples, 4 and 17 to 19 and ASENo.98,99,101,105,113,119,121,124,125,130 and 173 compound, in soil concentration be 1.45,0.72 and 0.36ppm be 100% of reference examples.
Figure 891089853_IMG54
Figure 891089853_IMG55
Figure 891089853_IMG57
Figure 891089853_IMG58
Figure 891089853_IMG59
Figure 891089853_IMG60
Figure 891089853_IMG64
Figure 891089853_IMG65
Figure 891089853_IMG66
Figure 891089853_IMG67
Figure 891089853_IMG68
Figure 891089853_IMG69
Figure 891089853_IMG70
Figure 891089853_IMG71
Figure 891089853_IMG73
Figure 891089853_IMG74
Figure 891089853_IMG75
Figure 891089853_IMG76
Figure 891089853_IMG78
Figure 891089853_IMG79
Figure 891089853_IMG81
Table 2
Other typical azole compounds (RPC) of chemical formula (I):
X wherein 2And X 3=H; X 1And X 4=Cl; And Y=CF 3
Substituted radical
RPC-No. R 1X R 3R 2
390. H SCF 3Cl H
391. H SOCF 3Cl H
392. H SO 2CF 3Cl H
393. H SCF 3F H
394. H SOCF 3F H
395. H SO 2CF 3F H
396. H SCF 3CN H
397. H SOCF 3CN H
398. H SO 2CF 3CN H
399. H SCF 3CF 3H
400. H SOCF 3CF 3H
401. H SO 2CF 3CF 3H
402. H SCF 3SO 2CF 3H
403. H SOCF 3SO 2CF 3H
404. H SO 2CF 3SO 2CF 3H
405. Cl SCF 3Cl H
406. Cl SOCF 3Cl H
407. Cl SO 2CF 3Cl H
408. Cl SCF 3F H
409. Cl SOCF 3F H
Table 2
Other typical azole compounds (RPC) of chemical formula (I):
X wherein 2And X 3=H; X 1And X 4=Cl; And Y=CF 3
Substituted radical
RPC-No. R 1X R 3R 2
410. Cl SCF 3CN H
411. Cl SOCF 3CN H
412. Cl SO 2CF 3CN H
413. CN SCF 3Cl H
414. CN SOCF 3Cl H
415. CN SO 2CF 3Cl H
416. CN SCF 3F H
417. CN SOCF 3F H
418. CN SO 2CF 3F H
419. CN SCF 3CF 3H
420. CN SOCF 3CF 3H
421. CN SO 2CF 3CF 3H
422. F SCF 3Cl H
423. F SOCF 3Cl H
424. F SO 2CF 3Cl H
425. H SCF 3Cl Cl
426. H SOCF 3Cl Cl
427. H SO 2CF 3Cl Cl
428. H SCF 3F Cl
429. H SOCF 3F Cl
Table 2
Other typical azole compounds (RPC) of chemical formula (I):
X wherein 2And X 3=H; X 1And X 4=Cl; And Y=CF 3
Substituted radical
RPC-No. R 1X R 3R 2
430. H SO 2CF 3F Cl
431. H SCF 3CN Cl
432. H SOCF 3CN Cl
433. H SO 2CF 3CN Cl
434. H SCF 3CF 3Cl
435. H SOCF 3CF 3Cl
436. H SO 2CF 3CF 3Cl
437. Cl SCF 3Cl Cl
438. Cl SOCF 3Cl Cl
439. Cl SO 2CF 3Cl Cl
440. Cl SCF 3F Cl
441. Cl SOCF 3F Cl
442. Cl SO 2CF 3F Cl
443. Cl SCF 3CN Cl
444. Cl SOCF 3CN Cl
445. Cl SO 2CF 3CN Cl
446. Cl SCF 3CF 3Cl
447. Cl SOCF 3CF 3Cl
448. Cl SO 2CF 3CF 3Cl
449. CN SCF 3Cl Cl
Table 2
Other typical azole compounds (RPC) of chemical formula (I):
X wherein 2And X 3=H; X 1And X 4=Cl; And Y=CF 3
Substituted radical
RPC-No. R 1X R 3R 2
450. CN SOCF 3Cl Cl
451. CN SO 2CF 3Cl Cl
452. CN SCF 3F Cl
453. CN SOCF 3F Cl
454. CN SO 2CF 3F Cl
455. CN SCF 3CN Cl
456. CN SOCF 3CN Cl
457. CN SO 2CF 3CN Cl
458. CN SCF 3CF 3Cl
459. Cl SO 2CF 3F H
460. CN SOCF 3CF 3Cl
461. CN SO 2CF 3CF 3Cl
462. H SCF 3Cl CF 3
463. H SCF 3F CF 3
464. H SOCF 3F CF 3
465. H SO 2CF 3F CF 3
466. H SCF 3CN CF 3
467. H SOCF 3CN CF 3
468. H SO 2CF 3CN CF 3
469. H SCF 3Cl CF 3
Table 2
Other typical azole compounds (RPC) of chemical formula (I):
X wherein 2And X 3=H; X 1And X 4=Cl; And Y=CF 3
Substituted radical
RPC-No. R 1X R 3R 2
470. H SOCF 3Cl CF 3
471. H SO 2CF 3Cl CF 3
472. H SCF 3Cl CH 3
473. H SOCF 3Cl CH 3
474. H SO 2CF 3Cl CH 3
475. H SCF 3F CH 3
476. H SOCF 3F CH 3
477. H SO 2CF 3F CH 3
478. H SCHF 2Cl CN
479. H SOCHF 2Cl CN
480. H SO 2CHF 2Cl CN
481. H SCHF 2H CN
482. H SOCHF 2H CN
483. H SO 2CHF 2H CN
484. H SO 2CHCl 2Cl CN
485. H SOCHCl 2Cl CN
486. H SOCHClF Cl CN
487. H SO 2CHClF Cl CN
488. H SCHF 2Cl Cl
489. H SO 2CHF 2Cl Cl
Table 2
Other typical azole compounds (RPC) of chemical formula (I):
X wherein 2And X 3=H; X 1And X 4=Cl; And Y=CF 3
Substituted radical
RPC-No. R 1X R 3R 2
490. H SOCHF 2Br CH 3
491. Cl SO 2CHF 2Cl CF 3
Figure 891089853_IMG83
Figure 891089853_IMG85
Figure 891089853_IMG88
Table 4
Chemical formula (I) is coughed up the additional synthetic example (ASE) of compound
Wherein, X 2And X 3-H; X 1And X 4-Cl and Y=CF 3
Substituted radical
ASE R 1X R 2R 3Fusing point (℃)
Numbering
92. NH 2CF 2ClS CN H 160.5-175
93. H CF 3SO 2CN H 199.5-201
94. H CF 2ClS CN H 104.9-106.8
95. H CF 2ClS CN CF 2ClS 114.5-117
96. NH 2CF 2ClS CN Cl 178-181
97. H CF 2ClSO 2CN H 199.8-202
98. H CF 2ClSO 2CN Cl 193.1-195.8
99. H CF 2ClSO CN Cl 145.2-147.5
100. H CF 2ClS CN Cl 139.0-143.1
101. H CF 3S CN Br 137-138
102. H CF 3SO CN Br 164-165.5
103. H CF 3SO 2CN Br 197-198
104. H CF 2ClSO CN H 126.8-129.6
105. H CF 3S CN H 152-153
106. NH 2CFCl 2CF 2S CN H 183-190
107. NH 2CCl 3S CN H 189-193
108. H CFCl 2CF 2S CN H 118.8-123.8
109. H CFCl 2CF 2SO 2CN H 157.5-161.9
110. H CFCl 2CF 2SO CN H 182.5-183.9
111. NH 2CFCl 2CF 2S CN Cl 186.5-188
Table 4
Chemical formula (I) is coughed up the additional synthetic example (ASE) of compound
Wherein, X 2And X 3=H; X 1And X 4=Cl and Y=CF 3
Substituted radical
ASE R 1X R 2R 3Fusing point (℃)
Numbering
112. H CFCl 2CF 2SO CN Cl 149.5-151
113. Br CF 3S CN H 163-164
114. H CFCl 2CF 2S CN Cl 113.5-116.5
115. H CCl 3S CN Cl 177-182
116. H CFCl 2CF 2SO 2CN Cl 147-150.5
117. H CCl 3SO 2CN Cl 200-202
118. H CCl 3SO CN Cl 152.2-153.5
119. Cl CF 3SO CN H 161.5-162.5
120. NH 2CH 3S CN H 150-151
121. H CFCl 2S CN Br 117-142
122. NH 2CFCl 2S CN Br 195.5-197
123. Br CF 3SO CN H 170-172
124. H CFCl 2SO 2CN Br 176-178.5
125. H CFCl 2SO CN Br 116.5-135.5
126. H SCN CN H 173-173.5
127. Br CF 3SO 2CN H 179-180.5
128. H CH 3S CN H 107-108.5
129. NH 2CF 2ClS CN Br 174.5-178
130. Br CF 2ClS CN Cl 129.5-133.5
131. H CF 2ClS CN Br 133.5-137.1
Table 4
Chemical formula (I) is coughed up the additional synthetic example (ASE) of compound
Wherein, X 2And X 3=H; X 1And X 4=Cl and Y=CF 3
Substituted radical
ASE R 1X R 2R 3Fusing point (℃)
Numbering
132. NH 2Cl CN H 159.5-160
133. NH 2CF 3S CN SCN 169-171
134. H CF 3S CN SCN 105-106.5
135. Br CF 2ClSO CN Cl 157.5-159
136. H Cl CN H 105.5-106.5
137. H CH 3SO CN H 144.5-145.5
138. H CH 3SO 2CN H 173-173.5
139. NH 2CF 3S CN SCH 3146-148
140. H CF 3S CN SOCH 3143-145
141. H CF 2ClSO CN Br 143-146.5
142. Br CFCl 2SO 2CN Cl 117.8-122.5
143. CF 3CONH CF 3S CN H 187-188.5
144. H CF 2ClSO 2CN Br 182-185
145. H CF 3S CN CH 3S 89-91
146. H CF 3S CN CH 3SO 2136-138
147. H CF 3SO CN CH 3SO 2161-163
148. NH 2CF 3CCl 2S CN H 200-220
149. NH 2CF 3CCl 2S CN Cl 223.5-232.5
150. H CF 3CCl 2S CN Cl 170-172.5
151. H CF 3CCl 2SO 2CN Cl 195.6-197.2
Table 4
Chemical formula (I) is coughed up the additional synthetic example (ASE) of compound
Wherein, X 2And X 3=H; X 1And X 4=Cl and Y=CF 3
Substituted radical
ASE R 1X R 2R 3Fusing point (℃)
Numbering
152. H CF 3CCl 2SO CN Cl 161-161.5
153. H CF 3S CN CF 3S 95-96
154. NH 2CH 3SO CN H 130-132
155. NH 2CH 3SO 2CN H 248-248.5
156. H CF 3SO CN CF 3S 145-148
157. H CH 3S CN Cl 128-129
158. NH 2CF 3S CN SOCH 3139-141
159. CH 3S CF 3S CN Cl 73-74
160. NH 2CFCl 2SO CN H 156.4-195
161. H CF 3SO 2CN CF 3S 156-157
162. H CH 3SO CN Cl 130-131
163. NH 2CF 3S CN F 164-164.5
164. H Cl CN Cl 129-129.5
165. CH 3SO CF 3S CN Cl 133-135
166. CH 3S CFCl 2S CN Cl 112.2-124.8
167. NH 2CFCl 2SO CN Cl 163-169.5
168. CF 3CONH CF 3SO CN H 195-197.5
169. H CF 3S CN F 116-117
170. CH 3SO 2CFCl 2S CN Cl 164.5-170.5
171. CH 3SO CFCl 2S CN Cl 193-195.7
Table 4
Chemical formula (I) is coughed up the additional synthetic example (ASE) of compound
Wherein, X 2And X 3=H; X 1And X 4=Cl and Y=CF 3
Substituted radical
ASE R 1X R 2R 3Fusing point (℃)
Numbering
172. NH 2CF 3SO CN H dec.above 175
173. H CF 3S CF 2H H 54-56
174. H CH 3SO 2CN Cl 165-166
175. H Br CN Br 127.5-128
176. H Br CN H 120-121
177. NH 2CFCl 2SO 2CN Cl 203-214.5
178. H CF 3SO CN F 129-130
179. Br Cl CN H 121-123
180. NH 2CF 3SO 2CN H 258-260
181. CH 3SO CF 3SO CN Cl 238-239
182. H CF 2BrS CN Cl 128.3-133.7
183. H CF 2BrSO CN Cl 117-119
184. H CF 2BrSO 2CN Cl 172-181
185. H CF 3S CH 3H oil
186. H CF 3SO CH 3Br 106-107
187. H CF 3SO 2CH 3Br 76-77
188. NH 2CF 3S CN CH（SCH 3） 2159-161
189. CH 3SCH＝N CF 3S CN CH（SCH 3） 2124.5-125.5
190. H CF 3S （CH 3） 3COCONH Br 113-114
191. H CF 3S Br Br oil
Table 4
Chemical formula (I) is coughed up the additional synthetic example (ASE) of compound
Wherein, X 2And X 3=H; X 1And X 4=Cl and Y=CF
Substituted radical
ASE R 1X R 2R 3Fusing point (℃)
Numbering
192. H CF 3SO CH 3OH ＊149-151
＊May exist as the keto tautomer
193. Br CF 3S CH 3Br oil
194. Br Br H CF 3S oil
195. H CF 3S CN I 107-109

Claims (23)

1, a kind of kill the joint branch animal, plant nematocide, drive antiprotozoal composition of (intestines) worm that wriggles, comprise active ingredient and one or more compatible diluent or carriers of effective dose, it is characterized in that described active ingredient comprises a kind of compound of following structural formula:
Figure 891089853_IMG2
Group in the described structural formula (I):
X=halogen, cyano group, thiocyanogen, junior alkyl halides, lower alkylthio, low alkyl group sulfinyl, lower alkyl sulfonyl, halogenated lower alkylthio, junior alkyl halides sulfinyl, junior alkyl halides sulfonyl and comprise that at the halo of all these groups the single of one or more identical or different halogen atoms replaces until full replacement;
R 1=hydrogen, low alkyl group, junior alkyl halides, amino, halogen, lower alkylcarbonyl amino, junior alkyl halides carbonylamino, lower alkylthio, low alkyl group sulfinyl or low alkyl group sulfonyl or low alkyl group sulfo-alkylideneimino;
R 2=hydrogen, low alkyl group cyano group, formoxyl, junior alkyl halides or lower alkylcarbonyl amino;
R 3=hydrogen, hydroxyl, halogen, halogenated lower alkylthio, thiocyano, lower alkylthio, low alkyl group sulfinyl, low alkyl group sulfonyl, junior alkyl halides, cyano group or the low alkyl group that replaces by one or more lower alkylthios;
Y=halogen, junior alkyl halides, lower alkoxycarbonyl, halogenated lower alkoxy, and comprise that at the halo of all these groups the single of halogen atom that one or more are identical or different replaces until full replacement; Perhaps, when (1) X be halogen atom or R 5N=0 in S (O) the n formula, 1 or 2 and R 5Be low alkyl group or junior alkyl halides (2) R 1And R 3Each is a hydrogen atom, and (3) R 2During for cyano group, Y can further represent hydrogen atom;
X 1=hydrogen, halogen, low alkyl group;
X 2=hydrogen, halogen;
X 3=hydrogen, halogen;
X 4=hydrogen, halogen or low alkyl group;
But condition is: R 1, R 2And R 3In at least one be to be selected from the illustrated identical substituting group of above X,
If X 1And X 4Be hydrogen, and X is halogen or cyano group, and R 2For being different from X.
2, composition as claimed in claim 1 is characterized in that in the structural formula (I) of the compound of described active ingredient by X, X 1, X 4, R 1, R 2, R 3With the low alkyl group of Y defined be the straight or branched low alkyl group that is less than 6 carbon atoms.
3, composition as claimed in claim 2 is characterized in that, in the structural formula of the compound of described active ingredient (I) by X, X 1, X 4, R 1, R 2, R 3With the low alkyl group of Y defined be the straight or branched low alkyl group that is less than 5 carbon atoms.
4, composition as claimed in claim 3 is characterized in that in the structural formula of compound (I) on the described active ingredient:
X is halogen atom or R 5S(O) n group, n is 0,1 or 2 and R in formula 5Be low alkyl group, junior alkyl halides;
R 1Be hydrogen atom, halogen atom or lower alkylthio;
R 2Be cyano group;
R 3Be hydrogen atom or halogen atom;
Y is hydrogen atom, halogen atom, alkylhalide group or halogenated lower alkoxy, and condition is to be hydrogen atom as the Y at claim 1 defined; And
X 1And X 4For being selected from hydrogen atom, halogen atom, C separately 1-3Alkyl.
5, composition as claimed in claim 4 is characterized in that the compound of described active ingredient has following structural formula (II)
Figure 891089853_IMG3
X is R 5S(O) n, n is 0,1 or 2 and R in the formula 5Be CH 3, CF 3, CF 2Cl, CFCl 2, CF 2Br, CHF 2, CHCl 2Or CHClF;
R 1Be H, F, Cl or Br;
R 3Be H, F, Cl; And
X is H or Cl; And
Y is CF 3Or CF 3O
6, composition as claimed in claim 5 is characterized in that the compound of described active ingredient is:
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(trifluoromethyl sulfenyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(trifluoromethyl sulfonyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(dichlorofluoromethyl sulfenyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(dichlorofluoromethyl sulfinyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(dichlorofluoromethyl sulfonyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(chlorodifluoramethyl-sulfonyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(chlorodifluoramethyl-sulfinyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(chlorine difluoro methyl mercapto) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-bromo-3-cyano group-4-(trifluoromethyl sulphinyl sulfenyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-bromo-3-cyano group-4-(trifluoromethyl sulfonyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-bromo-3-cyano group-4-(dichlorofluoromethyl sulfenyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-bromo-3-cyano group-4-(dichlorofluoromethyl sulfonyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-bromo-3-cyano group-4-(dichlorofluoromethyl sulfonyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-bromo-3-cyano group-4-(chlorodifluoramethyl-sulfenyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-bromo-3-cyano group-4-(chlorodifluoramethyl-sulfinyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-bromo-3-cyano group-4-(dichlorofluoromethyl sulfonyl) pyrroles;
1-(2,6-two chloro-4-trifluoromethoxy benzaldehyde bases)-2-bromo-3-cyano group-4-(chlorodifluoramethyl-sulfonyl) pyrroles;
1-(2,6-two chloro-4-trifluoromethoxy benzaldehyde bases)-2-chloro-3-cyano group-4-(dichlorofluoromethyl sulfinyl) pyrroles;
1-(2,6-chloro-4-trifluoromethoxy benzaldehyde base)-2-chloro-3-cyano group-4-(dichlorofluoromethyl sulfonyl) pyrroles;
1-(2-chloro-4-fluoroform phenyl)-and 2-chloro-3-cyano group-4-(dichlorofluoromethyl sulfonyl) pyrroles;
1-(2-chloro-4-fluoroform phenyl)-and 2-chloro-3-cyano group-4-(dichlorofluoromethyl sulfinyl) pyrroles;
1-(2-two chloro-4-fluoroform phenyl)-and 2-bromo-3-cyano group-4-(dichlorofluoromethyl sulfonyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-bromo-3-cyano group-4-(dichlorofluoromethyl sulfenyl)-5-methyl sulphur pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(bromine difluoro methyl sulfenyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(bromine difluoro methyl sulfinyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(bromine difluoro methyl sulfonyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(methylsulfinyl) pyrroles; Or
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(methyl sulphonyl) pyrroles;
7, composition as claimed in claim 4 is characterized in that in the compound of described active ingredient:
X is halogen atom or R 5S(O) n group, n is 0,1 or 2 and R in the formula 5Be low alkyl group, junior alkyl halides
R 1And R 3Each is a hydrogen atom;
R 2Be cyano group;
Y is hydrogen atom or halogen atom; And
X 1And X 4For being selected from hydrogen, halogen, C separately 1-3Alkyl.
8, composition as claimed in claim 7 is characterized in that R in the compound of active ingredient 5Be C 1-4Alkyl, and haloalkyl is a trihalomethyl group; The Y halogen is Cl or Br and X 1And X 4Each represents H, F, Cl, Br or CH 3And X 2And X 3Each is a hydrogen.
9, as claim 7 or 8 described compositions, it is characterized in that R 5Be CF 3, CCl 3, CF 2Cl, CFCl 2Or CF 2Br.
10, composition as claimed in claim 7 is characterized in that the compound of described active ingredient is:
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(chlorodifluoramethyl-sulfenyl) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(trifluoromethyl sulfenyl) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(chlorodifluoramethyl-sulfenyl) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(chlorodifluoramethyl-sulfinyl) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(dichlorofluoromethyl sulfenyl) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(dichlorofluoromethyl sulfinyl) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(dichlorofluoromethyl sulfinyl) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(dichlorofluoromethyl iodoxy) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(dichlorofluoromethyl sulfinyl) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(dichlorofluoromethyl sulfonyl) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(trifluoromethyl sulfenyl) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(trifluoromethyl sulphinyl base) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(trifluoromethyl sulfonyl) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(trichloromethyl sulfenyl) pyrroles;
1-(2,4 ,-dichlorophenyl)-3-cyano group-4-(dichlorofluoromethyl sulfenyl) pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-chlorine pyrroles;
1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(chlorodifluoramethyl-sulfonyl) pyrroles;
1-(2, the 6-trichlorophenyl)-3-cyano group-4-(dichlorofluoromethyl sulfenyl) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(trifluoromethyl sulphinyl base) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(chlorodifluoramethyl-sulfinyl) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(chlorodifluoramethyl-sulfonyl) pyrroles;
1-(4-bromo-2, the 6-dichlorophenyl)-3-cyano group-4-(chlorodifluoramethyl-sulfonyl) pyrroles;
1-(4-bromo-2, the 6-xylyl)-3-cyano group-4-(trifluoromethyl sulphinyl base) pyrroles;
1-(4-bromo-2, the 6-xylyl)-3-cyano group-4-(trifluoromethyl sulfonyl) pyrroles; Or
1-(4-bromo-2, the 6-difluorophenyl)-3-cyano group-4-(dichlorofluoromethyl sulfenyl) pyrroles.
11, composition as claimed in claim 3 is characterized in that in the compound of structural formula (I) of described active ingredient:
R 1Be hydrogen atom or halogen atom;
R 2Be cyano group;
X is the n group of rudimentary alkylhalide group-S(O), and n is 0,1 or 2 in the formula;
X 1And X 4Be halogen atom or C 1-3Alkyl;
X 2And X 3Be hydrogen atom.
12, composition as claimed in claim 11 is characterized in that: work as R 1When being defined as halogen atom, be chlorine or bromine; And when X is defined as the n group of alkylhalide group-S(O), be trifluoromethyl sulfenyl, trifluoromethyl sulphinyl base or trifluoromethyl sulfonyl group.
13, composition as claimed in claim 2 is characterized in that described active ingredient has the compound of following structural formula (II):
Figure 891089853_IMG4
X is R 5(S(O) n, n is 0,1 or 2 and R in the formula 5Be CH 3, CF 3, CF 2Cl or CFCl 2;
R 2Be cyano group;
R 1Be H, F, Cl, Br or NH 2;
R 3Be H, F, Cl, Br, CF 3Or CN;
X 1Be H or Cl; And
Y is CF 3Or CF 3O.
14, composition as claimed in claim 2 is characterized in that 1 compound of described active ingredient is:
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(trifluoromethyl sulfonyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(trifluoromethyl sulphinyl base) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-trifluoromethyl sulphinyl base-5-bromine pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-trifluoromethyl sulfonyl-5-bromine pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(trifluoromethyl sulfenyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-bromo-3-trifluoromethyl sulfenyl-4-cyano group-5-chlorine pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-the 2-[(trifluoromethyl) carbonylamino]-3-trifluoromethyl sulfenyl-4-cyano group-5-chlorine pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-(methyl carbonylamino)-3-trifluoromethyl sulfenyl-4-cyano group-5-chlorine pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-amino-3-trifluoromethyl sulfenyl-4-cyano group-5-chlorine pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-amino-3-trifluoromethyl sulfenyl-4-cyano group-5-chlorine pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-amino-3-dichlorofluoromethyl sulfenyl-4-cyano group-5-chlorine pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2, two (trifluoromethyl the sulfenyl)-3-cyano group of 4--5-amino-pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-amino-3-trifluoromethyl sulfenyl-4-cyano group-5-bromine pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-amino-3-trifluoromethyl sulfenyl-4-cyanopyrrole;
1-(4-fluoroform phenyl)-2-amino-3-trifluoromethyl sulfenyl-4-cyano group-5-bromine pyrroles;
1-(2-chloro-4-fluoroform phenyl)-2-amino-3-trifluoromethyl sulfenyl-4-cyano group-5-bromine pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(dichlorofluoromethyl sulfenyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(dichlorofluoromethyl sulfinyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(dichlorofluoromethyl sulfonyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-3-cyano group-4-(dichlorofluoromethyl sulfenyl) pyrroles;
1-(2,6-two chloro-4-fluoroform phenyl)-3-cyano group-4-(dichlorofluoromethyl sulfinyl) pyrroles; Or
1-(2,6-two chloro-4-trifluoromethoxy oxygen phenyl)-2-chloro-3-cyano group-4-(trifluoromethyl sulfonyl) pyrroles.
15, such as claim 1 composition, it is characterized in that active ingredient be have the following structures formula (III compound a):
Figure 891089853_IMG5
It is characterized in that Y is H, Cl, Br, CF 3Or OCF 3And X 1And X 4H, Cl, F or CH respectively do for oneself 3, condition is: if X 1And X 4Each is H, and Y is not H or Cl then.
16, composition as claimed in claim 1 is characterized in that the compound in the active ingredient structural formula (I): X is that H or Cl and Y are CF 3Or CF 3O.
17, antiprotozoal method for compositions that the joint branch is animal, plant nematocide, drive (intestines) worm that wriggles is killed in a kind of preparation, comprises compound and one or more compatible diluent or carriers of mixing a kind of following structural formula:
Group in the described structural formula (I):
The inferior acyl group of X=halogen, cyano group, thiocyanogen, junior alkyl halides, lower alkylthio, low alkyl group sulfinyl, lower alkyl sulfonyl, halogenated lower alkylthio, junior alkyl halides, junior alkyl halides sulfonyl and comprise that at the halo of all these groups one or more identical or different halogen atoms replace until full replacement from single;
R 1=hydrogen, low alkyl group, junior alkyl halides, amino, halogen, lower alkylcarbonyl amino, junior alkyl halides carbonylamino, lower alkylthio, low alkyl group sulfinyl or low alkyl group sulfonyl or low alkyl group sulfo-alkylideneimino;
R 2=hydrogen, low alkyl group, cyano group, formoxyl, junior alkyl halides or lower alkylcarbonyl amino;
R 3=hydrogen, hydroxyl, halogen, halogenated lower alkylthio, thiocyano, lower alkylthio, low alkyl group sulfinyl, low alkyl group sulfonyl, junior alkyl halides, cyano group or the low alkyl group that replaces by one or more lower alkylthios;
Y=halogen, junior alkyl halides, lower alkoxycarbonyl, halogenated lower alkoxy, and comprise that at the halo of all these groups one or more identical or different halogen atoms replace until full replacement from single; Perhaps, when (1) X be halogen atom or R 5S(O) n=0 in the n formula, 1 or 2 and R 5Be low alkyl group or junior alkyl halides, (2) R 1And R 3Each is a hydrogen atom, and (3) R 2During for cyano group, Y can further represent hydrogen atom;
X 1=hydrogen, halogen, low alkyl group;
X 2=hydrogen, halogen;
X 3=hydrogen, halogen;
X 4=hydrogen, halogen or low alkyl group;
But condition is: R 1, R 2And R 3In at least one be to be selected from the illustrated identical substituting group of above X,
If X 1And X 4Be hydrogen, and when X be halogen or cyano group, and R 2For being different from X.
18, preparation method as claimed in claim 17 is characterized in that comprising a kind of compound of following structural formula:
X, X in the formula 1, X 2, X 3, X 4Have meaning identical in the claim 17 with Y, it is synthetic as follows by the compound of following structural formula:
Figure 891089853_IMG8
(a) (I compound a) optionally reacts described compound and trifluoromethyl copper with known method then and obtains that X is structural formula (I compound a) of trifluoromethyl in the formula optionally to obtain the structural formula that X in the formula is a halogen with halogenating agent reaction in the presence of solvent;
(b) in the presence of lewis acid with three (alkyl sulfide) methane or three (aryl sulphur) methane reaction, obtain the compound of structural formula (XI) then:
Figure 891089853_IMG9
X meets as claim 1 defined for two (alkyl sulfide) methyl or two (aryl sulphur) methyl and other in the formula, and then optionally react with the alkyl nitrites, then by hydrolysis, to obtain the compound of the structural formula that X is a formoxyl (XI), then described compound is contacted with azanol, again in a known way by dehydration, to obtain the structural formula that X is a cyano group (I compound a);
(c) in the presence of bromine, compound with structural formula MSCN in a kind of solvent reacts, wherein M is a kind of alkali metal, with obtain the structural formula that X is a thiocyano-(I compound a), then optionally with described compound and alkyl halide or dialkylsulfates in the presence of alkali in the solvent reaction to obtain the structural formula that X is a low-grade alkyl sulphur (I compound a); Perhaps
(d) and formula R 5The sulfenyl halide reaction of SHal, R in the formula 5For low alkyl group, rudimentary alkylhalide group and Hal be halogen atom the liquid organic reactant reaction medium, optionally in the presence of acid acceptor reaction to obtain structural formula (I compound a) that X is low-grade alkyl sulphur, junior alkyl halides sulphur, with the optionally oxidation of known method, be R then to obtain X 5S(O) n is 1 or 2 structural formula (I compound a) in the n formula.
19, preparation of compositions method as claimed in claim 17 comprises compound and one or more compatible diluent or carriers of mixing a kind of following structural formula:
Figure 891089853_IMG10
X in the formula 1, X 2, X 3, X 4Have as identical meaning in claim 17 with Y, and X is cyanato-, lower alkoxy or halogenated lower alkoxy, it is characterized in that the compound of described structural formula I a, synthetic by the compound of structural formula (XX VIII):
Figure 891089853_IMG11
Various symbols are as defined in claim 17 in the formula, and if desired, and are amino and cyano group is suitably protected, comprising:
(a) in the presence of acid acceptor, obtain the structural formula that X is a cyanato-(I compound a) with the cyanogen halides reaction;
(b) optionally in the presence of alkali, obtain the structural formula that X is a lower alkoxy (I compound a) with alkylation reactions; Perhaps
(c) carrying out haloalkylation with known method obtains the structural formula that X is a halogenated lower alkoxy (I compound a) if desired, will be above-mentioned obtain behind the products therefrom deprotection in each step.
20, preparation of compositions method as claimed in claim 17, X in the formula 1, X 2, X 3, X 4Have as identical meaning in claim 1 with Y, X is rudimentary alkylhalide group, it is characterized in that comprising the compound of structural formula (VI):
Figure 891089853_IMG12
Various symbols are as defined in claim 1 in the formula, and amino and cyano group if desired can be suitably protected, and its legal method comprises:
(a) be structural formula (I compound a) of difluoromethyl with known method and fluorination reagent reaction to obtain;
(b) become hydroxy-acid group with oxidant reaction general-CHO groups converted, compound and the fluorination reagent that obtains reacted to obtain the structural formula that X is a trifluoromethyl (I compound a) with known method;
(c) with in the compound-the CHO group substitutes by methyl, then compound and the halogenating agent that obtains reacted in solvent to obtain the compound that X is bromomethyl or chloromethyl;
The back of if desired, all abovementioned steps is then by deprotection base step.
21, preparation of compositions method as claimed in claim 17, its feature comprises a kind of compound of following structural formula:
Figure 891089853_IMG13
Various symbols are as defined in claim 1 in the formula, and its synthetic method comprises:
(a) by claim (18a) reaction, obtain R 3For halogen the compound of structural formula (I b);
(b) according to claim 18(b) reaction, at first obtain R 3Be the compound of the structural formula (I b) of two (alkyl sulfide) methyl or two (aryl sulphur) methyl, and then optionally, R is the compound of the structural formula (I b) of formoxyl;
(c) according to claim 18(c.d) reaction, obtain R 3For the compound of the structural formula (I b) of thiocyano-, alkyl sulfide, haloalkyl sulphur, then according to claim 18(d) optionally oxidation to be to obtain R 3Be the compound of the structural formula (I b) of low alkyl group sulfinyl, low alkyl group sulfonyl, junior alkyl halides sulfinyl, junior alkyl halides sulfonyl, condition is that X can may suffer unwanted oxidation RS group; And when X be halogen, optionally handle to follow by water quenching and according to claim 18(c.d with known method with the alkyl lithium salts) sulfation to be to obtain the compound that X is the structural formula (I b) of low-grade alkyl sulphur, junior alkyl halides sulphur.
22, preparation of compositions method as claimed in claim 17, its feature comprises the compound of following structural formula:
X, R in the formula 3, X 1, X 2, X 3, X 4With the same meaning that Y has claim 17, it is synthetic by the compound of following structural formula:
Figure 891089853_IMG15
(a) in atent solvent with diazotization agent reaction and obtain R 1Compound for the structural formula (I c) of H;
(b) in the presence of halogenic donator, react to obtain R with diazotization agent 1Be the compound of the structural formula (I c) of halogen, then optionally with described compound and Grignard reagent or lithium derivatives reaction then by being converted into R with fatty acyl ammonia or anhydride reaction 1Compound for the structural formula (I c) of lower alkylcarbonyl;
(c) at (SCN) 2Or under the existence of disulfide, in solvent, react to obtain R with diazo reagent 1Compound for the structural formula (I c) of low-grade alkyl sulphur, junior alkyl halides sulphur; Then according to claim 18(d) optionally oxidation to be to obtain R 1Compound for the structural formula (I c) of low alkyl group sulfinyl, low alkyl group sulfonyl, junior alkyl halides sulfonyl;
(d) according to claim 20(a-d) react to obtain R 1Compound for the structural formula (I c) of junior alkyl halides; If desired, remove amido protecting group in the above-mentioned products therefrom.
23, a kind of desinsection, kill composition mite or nematocide, it is characterized in that comprising: 0.05% and 95%(weight) between one or more as each structural formula (I) compound of claim 1 to 17, and 1% and 95%(weight) between one or more agriculturals go up acceptable carriers; And 0.1 and 50%(weight) between one or more agriculturals go up acceptable surfactant.
CN89108985A 1988-12-09 1989-12-09 Pyrrole insecticides Expired - Lifetime CN1028475C (en)

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