CN1043500A

CN1043500A - Pyrrole insecticides

Info

Publication number: CN1043500A
Application number: CN89108985A
Authority: CN
Inventors: 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
Original assignee: Rhone Poulenc Agrochimie SA
Current assignee: Bayer CropScience SA
Priority date: 1988-12-09
Filing date: 1989-12-09
Publication date: 1990-07-04
Anticipated expiration: 2004-12-09
Also published as: PL162669B1; OA09248A; CN1028475C; NO174344B; FI95462C; EG19169A; TR25800A; BG60842B1; UA37172C2; DK620389A; MX18585A; PT92521B; IL92507A0; FI95462B; IL92507A; DK620389D0; CZ689989A3; SK278926B6; RU2063688C1; DK175618B1

Abstract

A kind of replacement of following structural formula-the 1-aryl-pyrrole compound:

Description

Pyrrole insecticides

The present invention relates to the new 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 sterilant, 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 sterilants.Also some to comprise pyrrole group (structure that contains a nitrogen-atoms) also be known sterilant.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 organophosphorus group.The simple pyrrole derivative that replaces is is recorded and narrated to agrochemicals, such as English Patent 2,189,242, but is to be used for as mycocide.

Novel azole compounds of the present invention has the structure formula I

In the formula:

X can be a halogen atom, or cyano group, cyanato-, the sulfo-cyanato-, haloalkyl, alkoxyl group, halogenated alkoxy, alkylthio, alkyl sulphinyl, alkyl sulphonyl, halogenated alkylthio, haloalkyl sulfinyl, halogenated alkyl sulfonyl, sulfo-thiazolinyl, thiazolinyl sulfinyl, the thiazolinyl alkylsulfonyl, haloalkene sulfenyl, haloalkenyl group sulfinyl, the haloalkenyl group alkylsulfonyl, 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 alkylsulfonyl; 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 heteroatoms 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 group 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 group, the alkoxyimino alkylidene group, 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 benzylidene imino-, alkylideneimino, alkoxyl group alkylideneimino, the dialkyl amido alkylideneimino, two (alkylthio) methyl, two (aryl sulfo-) methyl, alkylthio alkylideneimino, alkoxycarbonyl amino, halo alkoxy carbonyl 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 nitrogen heteroatom are monocyclic 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 group and halogenated alkoxy be straight chain or side chain, and generally have and be less than 10 carbonatoms, preferably for being less than 5 carbon atoms;

Y can be halogen atom or cyano group, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, alkyl sulphinyl, alkyl sulphonyl, alkylthio, halogenated alkylthio, haloalkyl sulfinyl, halogenated alkyl sulfonyl, alkyl-carbonyl, halogenated alkyl carbonyl, alkenyl (particularly allyl group), 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 group 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 group, halogenated alkoxy, alkylthio, alkyl sulphinyl, alkyl sulphonyl, halogenosulfanes base, haloalkyl sulfinyl, the haloalkane alkylsulfonyl, halogenated alkyl carbonyl, haloalkyl thio carbonyl, thiophenyl, phenyl sulfinyl, phenyl sulfonyl, sulfo-hetero-aromatic ring base, hetero-aromatic ring sulfinyl, or hetero-aromatic ring alkylsulfonyl; Wherein phenyl is selectively to be replaced by halogen, cyano group or haloalkyl, and the hetero-aromatic ring base is heteroatoms bonded 5 or the 6 yuan of monocycle bases and be selectively to be replaced by halogen, nitro, cyano group or haloalkyl by any way that comprise or two such as oxygen, sulphur or nitrogen; And in all above-mentioned groups, halo is single replaces or until full replacement, alkyl, haloalkyl, alkoxyl group 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 group, alkoxyimino alkylidene group, azido-, amino, alkylamino, 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 benzylidene imino-, alkylideneimino, the alkoxyl group alkylideneimino, the dialkyl amido alkylideneimino, selectively by the phenyl of halogen, cyano group or haloalkyl replacement, and comprising one or two identical or different heteroatomic 5 yuan or 6 yuan of monocyclic heteroaryls 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 group 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 group, halogenated alkoxy, alkyl sulphinyl, alkyl sulphonyl, alkylthio, halogenated alkylthio, the haloalkyl sulfinyl, halogenated alkyl sulfonyl, alkyl-carbonyl, halogenated alkyl carbonyl, alkenyl (particularly allyl group), 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 group, 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 formula I compound as sterilant and acaricidal general preferably formula I compound, in the formula:

X is halogen atom or R ⁵S(O) n group, wherein n is 0,1 or 2, R ⁵Be alkyl, haloalkyl, alkenyl or haloalkenyl group;

R ¹Be hydrogen atom, halogen atom or alkylthio; 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 formula 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 group, and C _1-3Alkylthio.

Preferably and other compounds of useful especially general formula I are following compounds:

A) have the high insect active that kills, general formula II compound,

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 alkylsulfonyl) pyrroles;

1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-chloro-3-cyano group-4-(one chlorodifluoramethyl-alkylsulfonyl) 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 alkylsulfonyl) 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-alkylsulfonyl) pyrroles;

1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-bromo-3-cyano group-4-(difluoro one methyl fluoride alkylsulfonyl)-5-bromine pyrroles;

1-(2,6-two chloro-4-Trifluoromethoxyphen-ls)-2-chloro-3-cyano group-4-(dichloro one methyl fluoride sulfinyl) pyrroles;

1-(2,6-two chloro-4-Trifluoromethoxyphen-ls)-2-ammonia-3-cyano group-4-(dichloro one methyl fluoride alkylsulfonyl) pyrroles;

1-(2-chloro-4-trifluoromethyl)-and 2-chloro-3-cyano group-4-(dichloro one methyl fluoride alkylsulfonyl) 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 alkylsulfonyl) 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 are 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 is 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 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-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-cyanogen-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)-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

C) have the compound of the general formula 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, CF ₂Cl or CF ₂Br), alkenyl, or haloalkenyl group;

R ¹And R ³It respectively is hydrogen atom;

R ²For being 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 group, and C _1-3Alkylthio, 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-(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 alkylsulfonyl) 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-(trichloromethylthio) pyrroles;

1-(2,4 ,-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-alkylsulfonyl) 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-alkylsulfonyl) 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) compound of other general preferably formula I is the compound with general formula 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 are 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 sterilant 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 formula I can prepare by use or revise currently known methods (exhausted or the method described promptly) in chemical literature: follow needs change substituting group after usually forming pyrrole ring.Also should be appreciated that: in the description of processing method 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 formula I compound can also change into other compounds of general formula I by currently known methods.

In the description of following processing method, 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 sheets.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 formula I of the present invention.

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 formula II, wherein R ¹And R ²For hydrogen former

According to characteristics of the present invention, the compound of general formula 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 formula 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 reagents reaction, this alkaline reagents is the alkaline reagents such as tertiary amine or alkali metal hydroxide or alkaline 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, halon, ether, ketone is such as the amine of N-Methyl pyrrolidone, perhaps water.

Method 2

According to another characteristics of the present invention, general formula IV compound can prepare by an alkali metal salt reaction with formyl succinonitrile or formyl succinonitrile from the anils 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 an alkali metal salt, an alkali metal salt can be according to K.Gewald, Z.Chem.1961, reaction by succinonitrile in the presence of alkaline reagents and formic acid lower alkyl ester described in 1,349 obtains.

Method 3

The compound of general formula 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, SULPHURYL CHLORIDE, N-neoprene imide, 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 methylene dichloride 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 formula 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 anhydride, cyanuryl chloride or P from X ₂O ₅Deng reagent dehydration reaction and prepare.Use some such dewatering 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 oxyamine 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 nitrous acid ester processing for being presented at following general formula VI midbody compound, then according to E.Fujita, K.lchikawa and K.Fuji, Tetrahedron Letters 1978,3561 is hydrolyzed.With the reaction of alkyl nitrous acid ester 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 formula I as defined above, can be by general formula III compound and three (alkylthio) methane or three (aryl sulfo-) methane at Lewis acid, be to react down and get preferably such as the existence of the sulfonium salt of Tetrafluoroboric acid dimethyl sulfuration sulfonium salt.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 formula 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 phase (pyridine) (hexamethyl phosphoric triamide) (Mo OPH), according to N.J.Lewis etc. at J.Org.hem.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 ⁴Have with Y that the formula I compound can be hydroxyl, R from corresponding X as the definition described in the general definition of the present invention 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 in the presence of alkali; handle and get with halogen cyan; utilization and D.Martin and M.Bauer to Org.Synth.61, the similar methods described in 35 is carried out deprotection reaction if desired again.

C) X is an alkoxyl group, R ¹Be amino, R ²Be cyano group, R ³Be hydrogen atom and X ¹, X ², X ³, X ⁴The general formula 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 analogue are handled and are got, and carry out protective reaction if desired again.

D) X is a halogenated alkoxy, R ¹Be amino, R ²Be cyano group, R ³Be hydrogen atom and X ¹, X ², X ³, X ⁴The general formula 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 hydrogen 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 Knunyants; I.L. and Yakobson; G.G. the haloalkyl method preparation described in the 263-269 page or leaf of " the Synthese of Fluoroorganic 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 ⁴The general formula I compound that has with definition identical in the general definition of the present invention with Y can be a formyl radical from corresponding X, carboxylic acid functional 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 diethylin sulphur trifluoride, X is provided is the compound of difluoromethyl and other substituting groups general formula I as defined above.Using the oxygenant oxidation X in sulfuric acid such as chromium trioxide is the above-mentioned general formula I midbody compound of formyl, obtains above-mentioned general formula 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 sulfonamide derivatives; 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 carboxylic acid functional 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 ⁴The general formula I compound that has in 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 formula I compound of other substituting groups, by with D.J.Burton and D.M.Wiemers at J.Am.Chem.Soc.1986, simulated condition described in 108,832 reacts with trifluoromethyl copper down and prepares.

Method 7

X is brooethyl or chloromethyl, R ¹Be amino, R ²Be cyano group, R ³Be hydrogen atom and X ¹, X ², X ³, X ⁴With Y have the general formula I compound of the meaning shown in the general definition of the present invention can by with N-bromo-succinimide or N-neoprene imide such as being in the solvent of tetracol phenixin; 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 the aforesaid general formula I midbody compound of formyl radical and other substituting groups passes 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 sodium borohydride 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 formula 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 amino continuously is selectively protected general formula 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.A.Olah, Chem.Soc.1989,111,393 preparations and the trimethylammonium trifluoromethyl silicomethane that uses.Other haloalkyl metal derivatives can be reference with the document also.Use trimethylammonium trifluoromethyl silane,

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 the general formula I compound shown in the general definition of the present invention with Y, by with [2, two (the 4-p-methoxy-phenyls)-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 formula I by using such as the halogenating agent of thionyl chloride or hydrogen bromide etc.Wherein X represents α-alkylhalide group α-monochloromethyl.Amido functional group protection is become such as the trifluoroacetyl sulfonamide derivatives to prevent that pyrrole ring from being useful by halogenation in this halogenation process.

Method 10

A) 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 with Y can be by being that alkali-metal MSCN handles general formula III compound and makes with M in the presence of bromine in such as methanol solvent at the general formula I compound of the meaning shown in the general definition of the present invention.

B) general formula I compound, wherein X is an alkylthio, 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 formula 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 methylene dichloride, 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.Cevasco, 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 formula 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 alkylogen or dialkylsulfates at the general formula 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 are 1 or 2, R ⁵Defined as the front.Operable oxygenant comprises hydrogen peroxide, peroxidation acetate, trifluoro peroxidation acetate and m-chloro peroxide acid are in the solvent such as methylene dichloride, acetate or trifluoroacetic acid, temperature is 0 ℃ to 25 ℃ at-40 ℃ to 80 ℃ preferably.Appropriate reaction conditions, promptly the length in temperature, reaction times and oxygenant consumption can change on request so that sulfinyl (n=1) or alkylsulfonyl (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 sulfonamide derivatives such as trifluoromethylthio.If, such as, trifluoro peroxidation acetate is chosen as oxygenant, described method can be represented with following formula:

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 the general formula I compound of the described meaning of general definition of the present invention under the simulated condition described in method 3 ¹Be amino, R ²Be oxygen base, R ³Be hydrogen and X ¹, X ², X ³, X ⁴Have general formula 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:

Method 14

R ³Be two (alkylthio) 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 the general formula 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 a tetrafluoro borate 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 formula 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 handle under the condition similar to method 4C or hydrolysis general expression (X III) compound system preparation by utilizing the alkyl nitrous acid ester, described method generally is expressed as follows:

Method 16

R ³Be oximino alkylidene group or alkoxyimino alkylidene group, 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 formula I of the meaning described in the general definition of the present invention ³Be alkyl-carbonyl or formyl radical R ¹Be amino, R ²Be cyano group and X, X ¹, X ², X ³, X ⁴Have at the general formula I compound of the meaning shown in the general expression of the present invention definition and azanol or at the general formula I compound of the meaning of general expression of the present invention shown in defining and azanol or O-alkyl azanol or the condensation in of its sour additive salt with Y and to form such as the alcoholic acid solvent.R is that the above-claimed cpd of alkyl-carbonyl is with final use 1,1, and 1-three (alkylthio or aryl sulfo-) alkane is as the preparation of the same way as of the compound (X IV) of parent material.

Method 17

Useful general formula 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 described in the general definition of the present invention with Y,, can reduce corresponding R by using in the presence of such as the precious 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 with X, R and R in the general formula I compound 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 ⁴The general formula 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 alkylamino, 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 the general formula 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 alkylogen 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 conditions.Selectively, require the monoalkylamine product, can use additive method, such as, amino is changed into (alkoxyl group alkylene imine base) by handling with alkyl orthoester, then restore.If the R that requires final 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 the aforesaid general formula I compound of protected amino and other substituting groups suitably, 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 ⁴The general formula I compound that has in the meaning described in the general definition of the present invention with Y can prepare by then carrying out deprotection base step again with the ammonia processing with phosgene (carbonyl chloride) 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, X ¹, X ², X ³, X ⁴Having in the meaning described in the general definition of the present invention with Y is that general formula I compound 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 first time definition of formula 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 the general formula I compound of the meaning shown in the general definition of the present invention and alkyl or halogenated alkyl sulfonyl halogenide or sulfonic anhydride with Y reacts under suitable condition and goes protection to prepare again.Suitable amido protecting group comprises alkoxyl group alkylene imine group in this class reaction, and this group can be by handling aminocompound with the alkyl ortho-formiate.The protection of going of described group typically comprises aqueous hydrolysis.

E) R ³Be alkyl amino-carbonyl amino or aromatic yl aminocarbonyl amino, R ¹Be amino, R ²Be cyano group and X, X ¹, X ², X ³, X ⁴Having with Y can be by the aminocompound suitably protect by general expression (X V) and alkyl or aryl isocyanic ester (wherein alkyl or aryl as described in defining the first time of the present invention) reaction at the general formula 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 again according to removing to protect alkoxyl group alkylene imine group as previously mentioned.

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 aminocompound and alkyl chloride manthanoate or the reaction of haloalkyl chloro-formic ester of the general expression (X V) of protection at the general formula 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 benzylidene 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) aminocompound 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 the general formula I compound of the meaning described in the general definition of the present invention, then goes to protect again and prepares.To the conditions suitable that forms Schiff's base can be described at the pointed reference of the 1165th page of ibid and the document by J.March be the selected condition of condensation 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 reference.

H) R ³Be alkoxyl group alkylene imine base, R ¹Be amino, R ²Be cyano group and X, X ¹, X ², X ³, X ⁴With Y have the general formula I compound of the meaning described in the general definition of the present invention can by the suitably protected aminocompound 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 223rd 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 ⁴The general formula 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.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 formula 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 Tetrafluoroboric 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 ⁴The general formula 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-tolylsulfonyl 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 diazonium salt, handle providing triazo-compound again with nitrous acid, carry out protective reaction then.

Method 19

The useful as intermediates compound of general formula 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 diazonium salt 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 reference.

B) selectively, the midbody compound of general formula 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 conditions reaction and prepare, as described in M.Swainbury ibid.

C) selectively, the midbody compound of general formula 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 Tetrahedron Lefter 1988,29,2135 and its reference with V.Snieckus etc. and making.

Method 20

R ³Be cyano group, 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 the general formula I compound of the meaning described in the general definition of the present invention ³For the general formula I compound of hydroxyl imido grpup methyl or alkoxyl group imido grpup methyne prepares by carrying out dehydration reaction according to the described method of method 4A.

Method 21

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 the general formula 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 the general formula 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 ⁴The general formula 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 react of Green that comes by alkylogen 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 the aforesaid general formula I compound of methyl and other substituting groups 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, 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 the general formula 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:

R represents the general expression X VI compound of alkyl can also be by R ³For thiocyano and other replace as defined in the X VI formula the formula I compound by being prepared from the similar methods described in the method 11 with alkylogen or analogue.

Method 24

R ³Be alkyl sulphinyl, alkyl sulphonyl, thiazolinyl sulfinyl, thiazolinyl alkylsulfonyl, haloalkyl sulfinyl, halogenated alkyl sulfonyl, haloalkenyl group sulfinyl, haloalkenyl group alkylsulfonyl, 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 the general formula I compound that constitutes and/or replace as described herein, 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 ³For having on the general formula I compound of the meaning described in general description the of the present invention, hydrogen and other substituting groups carry out the sulfenylation of amine according to aforesaid method; 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 group or halogenated alkoxy, R ¹Be amino, R ²Be cyano group and X, X ¹, X ², X ³, X ⁴The general formula I compound that has in the described meaning of 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 formula 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 formula 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 diazotization, use alkyl nitrous acid ester in such as the inert solvent of tetrahydrofuran (THF) or acetonitrile, to carry out diazotization preferably such as the tert-butyl nitrous acid ester, 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 formula 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 nitrous acid ester, such as the tert-butyl nitrous acid ester, carry out diazotization in the presence of such as the halogen atom donor of bromofom, tetracol phenixin, anhydrous cupric chloride or iodine and prepare.

C) R ¹Be thiocyano, alkylthio, 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 formula 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 being that the disulphide (wherein R is aforesaid alkyl, haloalkyl, thiazolinyl, haloalkenyl group, phenyl or heteroaryl) of RSSR is handled and prepared at (SCN) or general expression with alkyl nitride.Described reaction is typically finished with 1 to 5 normal alkyl nitrous acid ester and 2 to 5 normal disulphide in 0 ℃ in such as the solvent of chloroform.

Whole technological 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 formula I compound, wherein R ¹Be alkyl sulphinyl, alkyl sulphonyl, thiazolinyl sulfinyl, thiazolinyl alkylsulfonyl, haloalkyl sulfinyl, halogenated alkyl sulfonyl, haloalkenyl group sulfinyl, haloalkenyl group alkylsulfonyl, phenyl sulfinyl, phenyl sulfonyl, heteroaryl sulfinyl, R ²Be cyano group and R ³, X, X ¹, X ², X ³, X ⁴Having at the definition described in the general definition of the present invention and described phenyl and heteroaryl with Y is formation described here and/or replacement, can forms 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 similar stupid described in the method 24 that desired compound slightly is provided.

Method 29

General formula I compound, wherein R ¹Be alkylamino, 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, benzylidene imido grpup, alkoxyl group 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 78 by general expression (XI X) compound.

Method 30

A) R ¹Be formyl radical, R ²Be cyano group and R ³, X, X ¹, X ², X ³, X ⁴With Y have the general formula I compound of the meaning described in the general definition of the present invention can by general expression (XI X) compound by with Sodium Nitrite, HC=NOH, copper sulfate 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 thioacetalization 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 the general formula 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 group or alkoxyl group imido grpup alkylidene group, R ²Be cyano group and R ³, X, X ¹, X ², X ³, X ⁴With Y have the general formula 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 be that alkyl-carbonyl or formyl radical and the foregoing general formula I compound of other substituting groups form by R.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 lipid acid acyl chlorides or anhydride reaction or selectively reoxidize, prepare and get with the alkanoic condensation.R selectively ¹For the compound of alkyl-carbonyl can be the compound of formyl by corresponding R, by with the reaction of alkyl Grignard reagent, 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 the general formula I compound of the meaning described in the general definition of the present invention ¹For the compound of hydroxyl imide base methyne or alkoxyl group imido grpup methyne by with the similarity method preparation described in the method 4A.

D) R ¹Be halogenated alkyl carbonyl or haloalkane 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 the general formula I compound of the meaning described in the general definition of the present invention ¹For formyl radical and the aforesaid general formula I compound of other substituting groups 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 the general formula I compound of the meaning described in the general definition of the present invention ¹Handle under the condition similar for formyl radical or halogen and the general as defined above formula I compound of other substituting groups and to 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 the general formula I compound of the meaning described in the general definition of the present invention ¹For halogen and the aforesaid general formula I compound of other substituting groups by preparing with the similar methods described in method 19B and the 19C.

Method 32

R ¹Be cyanato-, alkoxyl group or halogenated alkoxy, R ²Be cyano group and R ³, X, X ¹, X ², X ³, X ⁴The general formula 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 is a formyl, R ¹, R ², X, X ¹, X ², X ³, X ⁴Having general formula 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 formula 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 reductive agent, be that diisobutyl lithium hydride is in solvent preferably, be 1: 1 the toluene and the mixed solution 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:

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 the useful general formula 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 formula I compound, wherein R ²Be hydroxyl imide base alkyl alkylidene, alkoxyl group imido grpup alkylidene, halogenated alkyl carbonyl, haloalkyl thio carbonyl, alkyl, two (alkyl 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 formula I compound of other substituting groups (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 formula 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 bases in the presence of, in alcoholic 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 formula I compound, wherein R ²Be alkylamino, 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, benzylidene imido grpup, alkoxyl group 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, 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 the general formula 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 the general formula I compound of the meaning described in the general definition of the present invention.

Method 39

General formula I compound, wherein R ²Be alkyl sulphinyl, alkyl sulphonyl, thiazolinyl sulfinyl, thiazolinyl alkylsulfonyl, haloalkyl sulfinyl, halogenated alkyl sulfonyl, haloalkenyl group sulfinyl, haloalkenyl group alkylsulfonyl, 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 the general formula I compound of oxidation, wherein R ²Be alkylthio, 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 formula 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 formula I compound of other substituting groups by with the similarity method preparation described in method 19B and the 19C.

Method 41

R ²Be cyanato-, alkoxyl group or halogenated alkoxy, R ¹, R ³, X, X ¹, X ², X ³,

R ²Be cyanato-, alkoxyl group or halogenated alkoxy, R ¹, R ³, X, X ¹, X ², X ³, X ⁴The general formula I compound that has in the meaning described in the general definition of the present invention with Y can be that the foregoing general formula I compound of halogen and other substituting groups is by preparing with the similarity method described in the method 5 by R.

With comprehensive form, present 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, alkyl sulphinyl, alkyl sulphonyl, halogenated alkylthio, haloalkyl sulfinyl, halogenated alkyl sulfonyl, alkenylthio group, haloalkene sulfenyl generation, haloalkenyl group sulfinyl, haloalkenyl group alkylsulfonyl, 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 nitrous acid ester reaction then, then thing contacts with oxyamine, uses 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 a basic 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 alkylogen 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, carry out to obtain general expression (I compound a) that X is alkylthio, halogenated alkylthio, alkenylthio group, haloalkene sulfenyl, thiophenyl or heteroarylthio, then selectively in a known way oxidation gained compound (I is compound a) to obtain general expression, wherein X is RS(O) n, n depends on that reaction conditions 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 group, halogenated alkoxy

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 group; 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 ⁴Have with the same meaning described in the method 1 with Y, 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

Amino and cyano group if desired can be suitably protected in the formula:

(a) with such as the fluorizating 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 fluorizating 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 sodium borohydride 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 imide again in suitable solvent is that (I is compound a) for the general expression of brooethyl 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

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; formyl radical; two (alkylthio or arylthio) methyl; haloalkyl; alkyl; selectively phenyl of Qu Daiing or heteroaryl; thiocyano; alkylthio; halogenated alkylthio; alkenylthio group; the haloalkene sulfenyl; thiophenyl; heteroarylthio; alkyl sulphinyl; alkyl sulphonyl; the thiazolinyl sulfinyl; the thiazolinyl alkylsulfonyl; the haloalkyl sulfinyl; halogenated alkyl sulfonyl; the haloalkenyl group sulfinyl; the haloalkenyl group alkylsulfonyl; 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 halogenide 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 ³For 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 formyl radical;

(c) react in a known way with the phenyl or the heteroaryl diazonium salt 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, 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 alkylsulfonyl; the haloalkyl sulfinyl; halogenated alkyl sulfonyl; the haloalkenyl group sulfinyl; the haloalkenyl group alkylsulfonyl; 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 currently known methods with lithium alkylide; then be according to method P1(c.d) carry out aqueous solution quenching and sulfation, be the thiocyano alkylthio 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 group, alkoxyl group imido grpup alkylidene group, cyano group, halogenated alkyl carbonyl or haloalkyl thio carbonyl or alkyl is characterized in following formula: compound

R in the formula ³For formyl radical or alkyl-carbonyl and X, cyano group and amino are protected by rights if desired:

(a) with azanol or O-alkyl azanol or its additive salt in such as alcoholic acid flux with it condensation to obtain R ³Be general expression (I b) compound of hydroxyl imide alkylidene group or alkoxyl group imines alkylidene group, and work as R ³During for hydroxyl imide base methyne or alkoxyl group imido grpup methyne, 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 formyl radical, according to method P3(a, b, c, d) react, obtain R ³General expression (I b) compound for methyl or haloalkyl or haloalkane carbonyl or haloalkyl thio carbonyl; Perhaps

(c) work as R ³During for formyl radical, use from alkylogen or lithium alkylide and derive and the Grignard reagent that comes reacts 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

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, alkylamino, 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, benzylidene imido grpup, alkoxyl group imido grpup, dialkyl amido alkylene imine base, alkylthio alkylene imine base or azido-, be characterized in following formula: compound

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 ratio or reaction conditions or dibasic amino or by restoring through the conversion of amino to alkoxyl group alkylene imine base obtain R ³General expression (XXX IV) compound for alkylamino, 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 chloride of acid 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 in known manner with the alkyl or aryl isocyanic ester, obtain R ³Compound for the general expression (XXX IV) of (alkylamino or arylamino) carbonylamino;

(f) react in known manner with alkyl chloroformate or chloro-formic ester 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 benzylidene imido grpup;

(h) with the alkyl orthoester reaction, obtain R ³General expression (XXX IV) compound for alkoxyl group 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 group nitrine or restore into hydrazine and handle with nitrous acid then and provide R by changing into diazonium salt 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 group or halogenated alkoxy is characterized in following formula: compound

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 group or halogenated alkoxy.

Method P8

A kind of method for preparing following formula: compound

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 alkylsulfonyl; the haloalkyl sulfinyl; halogenated alkyl sulfonyl; the haloalkenyl group sulfinyl; the haloalkenyl group alkylsulfonyl; the phenyl sulfinyl; phenyl sulfonyl; assorted fragrant sulfinyl; heteroarylsulfonyl; selectively phenyl of Qu Daiing or assorted virtue; alkyl-carbonyl; alkylamino; 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 benzylidene imino-; alkoxyl group alkylene imine base; dialkyl amido alkylene imine base; alkylthio alkylene imine base; azido-; two (alkylthio or aryl sulfo-) methyl; the formyl radical halogenated alkyl carbonyl; the haloalkyl thiocarbonyl group; haloalkyl or alkyl are characterized in following formula: compound

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 inert 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 reaction obtain R ¹Be general expression (I c) compound of halogen,, then change into R with lipid 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 nitrous acid ester, at (SCN) ₂Or under the existence of disulphide in such as the solvent of chloroform reaction obtain the general formula I compound that R is thiocyano, alkylthio, halogenated alkylthio, alkenylthio group, haloalkene sulfenyl, thiophenyl or heteroarylthio, then selectively according to method P1(d) oxidation obtains R ¹General expression (I c) compound for alkyl sulfinyl, alkyl sulphonyl, thiazolinyl sulfinyl, thiazolinyl alkylsulfonyl, haloalkyl sulfinyl, halogenated alkyl sulfonyl, haloalkenyl group sulfinyl, haloalkenyl group alkylsulfonyl, phenyl sulfinyl, phenyl sulfonyl, heteroaryl sulfinyl or heteroarylsulfonyl;

(d) according to method P6(a-k) react to obtain R ¹Be alkylamino, 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 benzylidene imido grpup, alkoxyl group 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 Sodium Nitrite and formoxime, copper sulfate 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 group, alkoxyl group imido grpup alkylidene group 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 formyl radical changes into R in a known way ¹General expression (I c) compound for two (alkylthio or arylthio) methyl.

Method P9

A kind of preparation X, R ³, X ¹, X ², X ³, X ⁴With Y have with the same meaning described in the method 1 and R ¹Method for general expression (I c) compound of cyanato-, alkoxyl group or halo oxygen base is characterized in following formula: compound

X, cyano group or R in the formula ³Be selectively protected, according to method P2(a, b, c with currently known methods) react, obtain R ¹Be general expression (I c) compound of cyanato-, alkoxyl group or halogenated alkoxy, then selectively carry 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 reductive agent, reacts in solvent, obtains R ²Be the compound of CHO, selectively the described compound of oxidation in a known way obtains corresponding general expression (XXX V) compound

Method P11

A kind of preparation 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 ²General formula I compound for hydroxyl imide base alkylidene group, alkoxyl group imido grpup alkylidene group, halogenated alkyl carbonyl, haloalkyl thio carbonyl, alkyl, haloalkyl, two (alkylthio or aryl sulfo-) methyl or cyano group is characterized in R ²For the general formula 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 formula 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; alkylamino; 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 benzylidene imido grpup; alkoxyl group alkylene imine base; dialkyl amido alkylene imine base; alkylthio alkylene imine base; azido-; hydrogen; halogen; thiocyano; alkylthio; halogenated alkylthio; alkenylthio group; the haloalkene sulfenyl; thiophenyl; heteroarylthio; alkyl sulphinyl; alkyl sulphonyl; the thiazolinyl sulfinyl; the thiazolinyl alkylsulfonyl; the haloalkyl sulfinyl; halogenated alkyl sulfonyl; the haloalkenyl group sulfinyl; the haloalkenyl group alkylsulfonyl; 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 bases 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 group or halogenated alkoxy is characterized in following formula: compound

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) halogenated compound 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:

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

React with alkaline agent.

Method P16

The invention still further relates to general formula 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 formula I compound.

Additive method:

X additionally produces disulphide and promotes the reductive method to prepare with free radical at last by chlorosulfonylation, reduction for the general formula I compound of crossing halogenated alkylthio.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 formula 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 chlorsulfonic acid or in such as the organic solvent of chloroform, methylene dichloride, tetracol phenixin or dimethyl formamide with the chlorsulfonic acid reaction, react and prepare in 0 ℃ to 150 ℃ temperature of reaction.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 chlorsulfonic 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 chlorosulphonation that is used for aromatics 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 formula I (with reference to hereinafter) can be by R ³For general expression (XXX IX) compound of hydrogen prepares by reacting under-70 ℃ to 25 ℃ temperature of reaction in such as the solvent of diethyl ether, acetonitrile or methylene dichloride with halogenating agent such as chlorine, N-neoprene imide or sulfuryl chloride.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 sulfuryl chloride processing in-40 ℃ in diethyl ether ¹Be amino, alkylamino or haloalkyl amino, R ²General expression (X L) compound for cyano group.

B) R ¹, R ², X ¹, X ², X ³, X ⁴With Y be that defined general expression in the general formula I (X L I) compound (with reference to hereinafter) can be by general expression (XXX IX) compound by using the reductive agent such as triphenyl phosphine, in the presence of organic solvent, handle and prepare in 0 ℃ to 110 ℃ temperature of reaction such as tetrahydrofuran (THF), toluene or methylene dichloride.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 tetrahydrofuran (THF), handling with triphenyl phosphine 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 formula I compound, wherein R ¹, R ², X ¹, X ², X ³, X ⁴Identical with the definition in the above-mentioned general formula I with Y, X was haloalkyl thio group, R ⁶S(is R wherein ⁶Be CFR ⁷R ⁸, and R ⁷Be F, Cl or Br, R ⁶Be 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 ⁸General expression (X L II) compound, i.e. ZCFR for F, Cl, Br or mistake fluoroalkyl ⁷R ⁸, the reaction and prepare, described reaction reductive agent, described reductive agent 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 hyposulfite or hydroxymethanesulfinate.The metal hyposulfite are such as basic metal or alkaline-earth metal hyposulfite, 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 hyposulfite that use general expression (X L III) or hydroxymethanesulfinate, need add alkali, such as, be selected from alkali metal hydroxide, alkaline earth metal hydroxides, ammonia, triethyl benzyl amine, or such as the salt of weak acid of Di-Sodium Phosphate, sodium metabisulfite, sodium bisulfite or Sodium Tetraborate.Described reaction generally (can make hyposulfite or hydroxymethanesulfinate and compound (X L II), ZCFR like this in the solvent such as acetonitrile, methane amide, dimethyl formamide, N,N-DIMETHYLACETAMIDE, hexamethylphosphoramide, N-Methyl pyrrolidone, 61 dimethyl sulfoxide (DMSO) or tetramethylene sulfone ⁷R ⁸Dissolving), in 20 ℃ to 85 ℃ temperature, react.The saturated solution that the basic metal hyposulfite can be used as in the water or in the methane amide is added in the reaction mixture, also can be used as solid and adds.When being when using gas-operated, this gas just is dissolved in the reaction solvent rarely, just requires to increase reaction pressure, such as being by 1 to 50 normal atmosphere.A specific example is, by general expression (X L I) compound, wherein R ¹Be hydrogen, amino, alkyl-carbonyl amido or halogenated alkyl carbonyl amide group, 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 l, R ⁷Be F, Cl, Br and R ⁸Be F, Cl, Br or perfluoroalkyl; React with V-Brite B and Di-Sodium Phosphate in dimethyl formamide at 25 ℃, prepare general formula I compound, wherein R 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.

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 formula 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 formula 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).

Table 2

Other typical azole compounds (RPC) of chemistry 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 chemistry 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 chemistry 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 chemistry 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 chemistry 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 chemistry 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 ₃The specific embodiment that compound is synthetic

Following examples 1 to 22 further specify the physical properties of synthetic method of the present invention and pesticide compound (and their chemical intermediates).

Embodiment 1

1-(2 with 910 milligrams (2.07 mmoles), 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 (trichloromethane) mmole), stirred at ambient temperature 1.5 hours, being heated to then refluxes spends the night.Add additional 45 milligrams (0.21 mmoles) between-chloro-peroxy benzoic acid, and continued reflux 1 hour.Stop heating then, and use the methylene dichloride diluted reaction mixture, clean with the first sodium bicarbonate aqueous solution again.This organic layer is through anhydrous Mg SO 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 methylene dichloride-hexane wash-out.Early effusive part 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.Recrystallization from hexane-ethyl acetate can obtain the colourless acicular crystal of 240 milligrams of sulfones, 198 ℃ of fusing points.

Embodiment 2

Continue to do the stratography effluent liquid at embodiment 1 rear portion, effusive from chromatography 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.Recrystallization from toluene-hexane can obtain the colourless powder of 390 milligrams of sulfoxides, and 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 parent 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 mmole), 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 nitrous acid tert-butyl ester ester of 3.9 milliliters (3.4 grams, 33 mmoles).After 30 minutes, this reaction mixture is heated to about 1 hour of backflow, under reduced pressure concentrates to obtain the solid residues of 3.69 grams then.Repeat this method to obtain 4.07 solid residue altogether, it is made chromatograph on silica gel separate, then with 1: 1v/v methylene dichloride-hexane 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.Recrystallization from hexane-ethyl acetate obtains the 1.87 colourless powder products that restrain, and fusing point is about 137 ℃.

Embodiment 5

With 0.94 milliliter (820 milligrams, 7.92 nitrous acid tert-butyl ester ester mmole) joins the 1-(2 of 2.4 grams (5.28 mmole), 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 (methenyl bromide) and in the dopant mixture under the inert gas atmosphere.After stirring 15 minutes at ambient temperature, answer mixture under reduced pressure to concentrate this 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 parent materials.Crude product is made chromatograph separate on silica gel, and with 4: 1v/v hexane one methylene dichloride 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-chloro pyrroles (embodiment 5), recrystallization from hexane obtains 780 milligrams colorless solid product, and fusing point is about 92 ℃.

Embodiment 6

1.91 the 1-(2 of gram (4.21 mmole), 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 mmoles) 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 mmoles).Reaction 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 mmole) this moment again.After reaction times amounted to 24 hours, reaction mixture was with the methylene dichloride dilution and concentrate it.Residue HCl solution washing, water cleans subsequently, recrystallization from hexane-ethyl acetate, obtain the 1-(2 of 860 milligrams (37%), 6-dichlor-4-trifluoromethyl phenyl)-and the 2-[(trifluoromethyl) carbonylamino]-3-trifluorothio-4-cyano group-5-chloro pyrroles (embodiment 6), it is the light green solid, and fusing point is about 190 ℃.

Embodiment 7

1.50 the 1-(2 of gram (3.3 mmole), 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), (mixture of the Acetyl Chloride 98Min. of the pyridine of 0.32 gram, 4.1 mmoles 0,0.31 milliliter (0.34 gram, 4.3 mmoles) and 10 milliliters acetonitrile stirred 4 days down at 20 ℃, and reflux 1 day for the 4-dimethylaminopyridine of 0.1 gram, 0.33 milliliter.Add additional 0.03 milliliter Acetyl Chloride 98Min. then, when the reaction cooling, continued reflux again one day, separate one by one with saturated sodium bicarbonate aqueous solution with the methylene dichloride 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.Follow recrystallization from alcohol-water, obtain the 1-(2 of 480 milligrams (29%), 6-dichlor-4-trifluoromethyl phenyl)-and 2-methyl carbonylamino-3-trifluoromethyl sulphur-4-cyano group-5-chloro pyrroles's (embodiment 7) colourless needle-like Jingjing body, fusing point is about 216 ℃.

Embodiment 8

1.50 the 1-(2 of gram (3.57 mmole), 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 sulfuryl chloride in 15 milliliters of anhydrous diethyl ethers of 0.29 milliliter (0.48 gram, 3.6 mmoles) in the mode of splashing under inert atmosphere.Then this reaction mixture is warmed to 20 ℃, and stirred 2.5 days, add the sulfuryl chloride of additional 0.03 milliliter (0.4 mmole) this moment again, and continue to stir one day again.The sulfuryl chloride 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 waterbearing stratum, collect then and merge this ether layer, water cleans, by anhydrous magnesium sulfate drying and concentrate to obtain the brown solids of 1.56 grams.This crude product is made chromatograph on silica gel separate, with 2: 1v/v methylene dichloride one hexane elutriant 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, recrystallize from hexanaphthene, obtain the product of 810 milligrams of canescence needle-like 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 final 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 final product is 1-(2,6-dichlor-4-trifluoromethyl phenyl)-2-amino-3-dichlorofluoromethyl sulfo--4-cyano group-5-chloro pyrroles (embodiment 10), and 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 trifluoromethane 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 mmole) is joined the 1-(2 of 1.53 grams (3.60 mmole), 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, reaction 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 mmoles)-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.Recrystallization from hexane/ethyl acetate, the product of 910 milligrams of colourless needle crystals of acquisition, fusing point is about 160 ℃.

Embodiment 13

2.00 the 1-(2 of gram (6.25 mmole), 6-dichlor-4-trifluoromethyl phenyl)-solution that has stirred of the methylene dichloride (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 mmoles) trifluoromethane sulfenyl chlorine in slowly inflow mode.0 ℃ stir 2 hours after, with flow through reaction mixture 1 hour of nitrogen gas 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 methylene dichloride-hexane 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 mmole), 6-dichlor-4-trifluoromethyl phenyl) amino]-2,3-dicyano propylene and 2.02 milliliters of (1.47 grams, 14.5 the solution reflux of triethylamine mmole) in 30 milliliters of benzene spends the night, and concentrates in a vacuum then.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.Recrystallization from alcohol-water, the 1-(2 of acquisition 2.79 grams (60%), 6-dichlor-4-trifluoromethyl phenyl)-2-amino-4-cyanpyrrole, fusing point is about 176 ℃.

Parent material 1-virtue is amino-2, and 3-dicyano propylene makes as follows: the sylvite sample dissolution of the formyl radical succinonitrile of 20.5 grams (0.140 mole) and is used the concentrated hydrochloric acid acidifying in about 30 milliliters water.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 mmole), in the solution of right-toluenesulphonic acids-hydrate in 50 milliliters of benzene of 6-dichlor-4-trifluoromethyl aniline and 40 milligrams.This heterogenetic reaction mixture is heated to reflux and spends the night, with water sepn.Then with this reaction 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 grinding of hexane) amino-2, the yellow solid of 3-dicyan propylene.Recrystallization from ethanol/water obtains sample, and its fusing point is about 101 ℃.

Embodiment 14A and 14B

With 0.19 milliliter (0.59,3.7 the solution of bromine mmole) in 5 milliliters of chloroforms joins the 1-(4-trifluoromethyl of 1.17 grams (3.30 mmole))-triethylamine of 2-amino-3-trifluoromethyl sulfo--4-cyanpyrrole and 0.46 milliliter (0.34 gram, 3.3 mmoles) is in 20 milliliters of suspension that are cooled in-20 ℃ the chloroform.Reaction 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 mmole), the additional stirring after 15 minutes use the methylene dichloride 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 mmole))-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 methylene dichloride-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.Recrystallization from hexane-ethyl acetate obtains light yellow laminar product, and 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)-2-amino-3-trifluoromethyl sulfo--4-cyano group-5-bromine pyrroles (embodiment 15B), 157 ℃ of fusing points make by the method for embodiment 14.

Embodiment 16A and 16B

The 1-(2 that makes by embodiment 13,6-dichlor-4-trifluoromethyl phenyl)-2-amino-4-cyanpyrrole, should example use the method for (CFSCl) to handle by embodiment 13(with CFCl-SCl, obtain 1-(2,6-two chloro-4-trimethylsilyl trifluoroacetamide phenyl)-and 2-amino-3-dichlorofluoromethyl sulfo--4-cyanpyrrole (embodiment 16A), its fusing point is about 202 ℃.

This compound is handled with the nitrous acid tert-butyl ester 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 sulfinyl) 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 alkylsulfonyl) pyrroles (embodiment 18), fusing point is 179 ℃.

Embodiment 19

Method by embodiment 4 is come the initial compound of Processing Example 16 with the nitrous acid tert-butyl ester 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 sulfinyl) 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-dichlor-4-trifluoromethyl-phenyl)-pyrroles and 2-chloro-3-cyano group-4-dichlorofluoromethyl sulfenyl-1-(2 ', 6 '-two chloro-4 '-trifluoromethyl)-(0.101 mole of pyrroles's mixture 47.77 gram, 1.0 equivalent) be 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 stir 9 hour down at 0 ℃ inferior morning, 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, reaction 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 (40.77 grams, 0.848 mole 1.0 equivalents) be dissolved in 0 ℃ the trifluoroacetic acid (188 milliliters), add 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 reaction 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 throw out of two secondary responses is combined and is dissolved in 500 milliliters of methylene dichloride, use 500 ml waters, 500 milliliter of 10% NaHSO again ₃The aqueous solution and 500 milliliters of saturated NaCl solution clean it.Organic phase 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 methylene dichloride (2: 1), add 20 milliliters of methylene dichloride 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).With this thing recrystallization from 103 milliliters of Virahols, obtain 3.97 grams, fusing point 187-188.5 ℃ then.

2-chloro-4-chlorine sulphonyl-3-cyano group-1-(2 ', 6 '-two chloro-4 '-trifluoromethyl)-pyrroles (3.97 gram, 9.06 mmoles, 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 mmoles, 1.06 equivalents) again, and this reaction is at room temperature stirred spend the night.Throw out generates, and adds 3 milliliters of THF, uses saturated NaCl solution washing reaction mixture twice then, and strips.Organic phase 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.Recrystallization from 140 milliliters of Virahols then, obtain two [2-chloro-3-cyano group-1-(2 ' of 2.54 grams (74.9%), 6 '-two chloro-4 '-trifluoromethyl)-pyrryl-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)-pyrryl-4-yl]-disulphide (0.80 gram, 1.08 mmoles, 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 mmoles, 3.0 equivalents) are dissolved in 5 ml waters, are added to then in the DMF solution.After forming throw out, add 15 milliliters of DMF and 10 ml waters.With solid Na ₂S ₂O ₄(0.564 gram, 3.24 mmoles, 3.0 equivalents) add, and this reactant transfers to faint yellow.Dibromodifluoromethane (0.65 gram, 3.1 mmoles, 2.87 equivalents) is added in the cold phial of weighing in advance, is transferred to then in the reactant, this reaction 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 ℃, reaction mixture is added in 200 ml waters and with 150 milliliters of extracted with diethyl ether 4 times.Organic phase 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 phase is by Mg SO 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 (ultimate production 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 fusing points are listed in table 3(ASE-numbering 1-91: the compound of chemical formula (1): this place, X and X are hydrogen, other substituents as the regulation) and table 4 in (ASE-numbers 92-195: the compound of chemical formula (1): X of this place and X are hydrogen, X and X are chlorine, Y is a trifluoromethyl, and other substituents are as regulation).

Table 4

The additional synthetic example (ASE) of chemistry formula I azole compounds

Wherein, X ²And X ³=H; X ¹And X ⁴=Cl and Y=CF ₃

Substituted radical

ASE R ¹X R ²R ³M.P.（℃）

NO.

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

The additional synthetic example (ASE) of chemistry formula I azole compounds

Wherein, X ²And X ³=H; X ¹And X ⁴=Cl and Y=CF ₃

Substituted radical

ASE R ¹X R ²R ³M.P.（℃）

NO.

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

The additional synthetic example (ASE) of chemistry formula I azole compounds

Wherein, X ²And X ³=H; X ¹And X ⁴=Cl and Y=CF ₃

Substituted radical

ASE R ¹X R ²R ³M.P.（℃）

NO.

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

The additional synthetic example (ASE) of chemistry formula I azole compounds

Wherein, X ²And X ³=H; X ¹And X ⁴=Cl and Y=CF ₃

Substituted radical

ASE R ¹X R ²R ³M.P.（℃）

NO.

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

The additional synthetic example (ASE) of chemistry formula I azole compounds

Wherein, X ²And X ³=H; X ¹And X ⁴=Cl and Y=CF ₃

Substituted radical

ASE R ¹X R ²R ³M.P.（℃）

NO.

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

The additional synthetic example (ASE) of chemistry formula I azole compounds

Wherein, X ²And X ³=H; X ¹And X ⁴=Cl and Y=CF

Substituted radical

ASE R ¹X R ²R ³M.P.（℃）

NO.

192. H CF ₃SO CH ₃OH ^＊149-151

193. Br CF ₃S CH ₃Br (oil) oil

194. Br Br H CF ₃S (oil) oil

195. H CF ₃S CN I 107-109

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 significant quantity is administered this area's method of pouring and administration (for example by), in logical formula I, each symbol is as afore mentioned rules.

Elsewhere, 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 Thysanura insect, Lepisma sacchatian 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 Thysanoptera, for example Hercinothrips femoralis and Thrips tabaci, by Hemiptera, 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.Hylotrupes bajulus.Agelastica alni.Leprinotarsa decemlineata.Phaedon cochleariae.Diabrotica spp.Psylliodes chrysoephala.Epilachna varivesris Atomaria spp.Orvyzaephilus surinamensis.Anthonomus spp.Sitophilus spp.Otiorrhynchus sulcatus.Cosmoplites sordidus.Ceuthorr-hynchus assimilis.Hypera postica.Dermesres spp.Trogoderma spp.Attagenus spp.Lyctus spp.Malige-thesaenaus.Ptinus spp.Niptus hololeucrus.Gibbium psylloides.Trobolim spp.Tenenrio molitor.Agrioes spp.Conoderus spp.Melolontha melolontha.Amphimallon solst it ialis and Costelytra zealandica. are by Hymenoptera, for example Diprion spp.Hoplocampa spp.Lasius spp.Monomorium phara-onis 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.Pegomyiahyoscyia.Cerat it is capitata.Dacus oleae and Tipula paludosa. are by Siphonaptera, for example Xenopsylla cheopis and Ceratophyllus spp. are by Araneida, for example Scorpio maurs and Latrodectus mactans. are by Hemiptera, Aleurodes brassicae.Bemisia tabaci.Trialeurodes yaporariorum.Aphis gossypii.Brevicoryna brassicae.Cryptomyzus ribis.Doralis fabae for example, Doralis pomi.Eriosoma lanigerus 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 lepidopteran, for example Pectinophora gossypiella.Bupalus piniarius.Cheimatobia brumata.Lithhocollet is blancardella.Hyponomeuta padel Plutella maculipennis.Malacosoma neustria.Euprocyis chrysorrhoea.Lymantria spp.Bucculatrix thurberiella.Phyllocnist is citrella.Agrot is spp.Euxoa spp.Earias insulana.Hheliothis spp.Laphygma exigua.Mamestra brassicae.Panolis flammea.Prodenia l itura.Spodoptera spp.Trichoplusiani.Carpocapsa pomondlla.Pieris spp.Chilo spp.Pyrausta nubilalis.Ephestiakuehniella.Galleria mellonella.Tineola bisselliella.Tinea pellionella.Hofmannophila pseudosretella.Cacoecia podana.Capua reticulana.Choriatoeura.Clysia ambiguells.Homona magnanime 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 active 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 active compounds place processed to per hectare, preferably be 0.02 kilogram/hectare to 2 kilograms/hectare ratio.Under the ideal 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 to 1 kilogram/hectare ratio.Best ratio depends on the type of the disease of desire control, growth phase and the channel space and the application process of infection plant.

When insect is confined to grow in the soil, the active 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 active compound can be by going into the whole area 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 disc 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 liquid 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 in the protection field; feed; the Botanical gardens; 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) and the earth crop (such as: potato; the sugar dish; Semen arachidis hypogaeae; soybean; coleseed); sugar-cane; grass field and feed (such as: corn; Chinese sorghum; clover); crop (such as: tealeaves; coffee; cocoa; banana; oil palm; coconut; rubber; spices); orchard and hurst are (such as: drupe with the fruit of kernel; lily of the valley fruit tree; both citrus; Chinese goosebeery; avocado; mango; olive and walnut); at greenhouse; the vineyard in garden or park; decorate crop; flowers and vegetables and shrub, forest (fallen leaves or evergreen both); crop and nurse-tree are valuable especially.

Simultaneously they tackle sawfly (that is: Urocerus) or beetle (as: ambrosia beetle, pig-hole borer worm, powder moth, grow moth, longicorn, death watch beetle) or termite at protection timber (stacking, cut generation, transhipment, storage or structure); for example: Reticulitermes spp.; Heterotermes 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 being levigated or combination finished product) is tackling the harm of moth, beetle and cereal weevil (Sitophilus granarius).Keep simultaneously the livestock 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 protozoon 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 financial 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 being 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 serious infectious result significantly descends their marketable value.

The administration of a small amount of of the compound of structure 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 coverture 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 structure formula I comprises:

To arthropods, nematode or protozoon invade and harass or the humans and animals that infects by non-enteron aisle, oral or topical 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, sprays, solvent, preserved material, shower agent, propellant, pulvis, finish (greases), hair washing agent, cream, wax coating agent 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 coating agent, lacquer, particle and bait to be to splash into water channel, well, water reservoir and other mobile or immobilized water; To the poultry in raising with control growing fly larvae 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 suspensoid of the segmentation of the compound of structure formula I and capsular compound; Handle with liquid slurry and pulvis, with coating as seed.

The compound of structure formula I can be used to control arthropods, nematode or protozoon with the composition of any kind of known technology, be suitable for vertebrates inside or outside dispenser or be used to be controlled at any house or indoor, outer geographic arthropods, which comprises at least compound and one or more required compatible thinner or conditioning agents that are used of a kind of structure formula I.All these based compositions can prepare with any known technology.

The composition that is suitable for vertebrates or people comprise preparation be suitable for oral, non-enteron aisle, through skin, that is: pour into or the medicament of topical application.

The composition of oral medicine comprises one or more compounds of structure formula I in conjunction with pharmaceutically acceptable carrier or tectum, 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 microcapsule maybe can wrap to be suitable for the coating in acidity or the alkalescence or to be used in the upward acceptable intestines of other medicines spy with in the dressing.Comprise edible thing that the premixed feed of The compounds of this invention and enriched material can be used for preparing medicine, tap water or other and can be used for the material that consumed by animal.

The composition of administered parenterally 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 in whole long period.

Comprise spray agent, pulvis, bath agent, preserved material, shower agent, propellant, finish, hair washing agent, ointment, wax coating agent 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 this 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 substances 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 inert and useful carrier and useful tensio-active agent.These compositions also are portion-forms of the present invention.

All kinds that these compositions also can comprise other composition such as protective colloid, binding agent, thickening material, thixotropic compound, permeate agent, sprinkling finish (when especially using), stablizer, sanitas (especially mould sanitas), sequestrant or like that as miticide.The known activeconstituents that simultaneously has (the especially sterilant or the sterilant) 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 fluid 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 activeconstituentss of the present invention, one or more carriers of about 1 to 95% and optionally, one or more tensio-active agents 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 promoting 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 activeconstituents to make and is easy to be applied to plant, seed or soil.So this carrier normally inert must be on the agricultural with it, and is especially acceptable to handled plant.This carrier can be solid (potter's clay, natural or synthetic silicate, silicon-dioxide, resin, wax, solid fertilizer, as an example, as ammonium salt and levigated natural crystal, such as; Kaolin, potter's clay, talcum, gypsum, attapulgite, montmorillonite, bentonite or diatomite and levigated synthetic mineral, such as: silicon oxide, aluminum oxide, silicate is aluminium or magnesium silicate especially.As the particulate solid carrier is suitable, for example: pulverizing and fractionated natural rock are such as calcite, marble, float stone, sepiolite and rhombspar, synthetic particle inorganic or organic powder also is suitable simultaneously, an and material of organic materials such as sawdust, Exocarpium cocois (Cocos nucifera L), corn cob and tobacco stem, diatomite, hoja, tricalcium phosphate, pulverous cork, the carbon black of adsorptivity and water miscible polymkeric substance, resin, wax, solid fertilizer and this class solids composition can contain one or more compatible wetting agent dispersion agents if desired, emulsifying agent or tinting material, 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, pimelinketone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and isophorone, petroleum cuts naphthalane hydrocarbon or aromatic carbon hydrogen compound, especially dimethyl benzene or alkylnaphthalene, petroleum cuts, Dormant oils or vegetables oil; Chlorinated aliphatic hydrocarbon, especially trichloroethane or methylene dichloride or chlorination aromatic hydrocarbon, especially Benzene Chloride; Water-soluble or strong polar solvent such as dimethyl formamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone and water; Liquefied gas and the like, with and composition thereof.

This tensio-active agent can be a kind of negatively charged ion or nonionic type emulsifying agent, dispersion agent or wetting agent, or this class surfactant mixtures.Here can mention; polyacrylate; sulfonated lignin, benzene sulfonate or naphthalenesulfonate; the polycondensate of ethylene oxide and Fatty Alcohol(C12-C14 and C12-C18) or lipid acid or fatty ester or aliphatic amide; the phenol (especially alkylphenol or aryl phenol class) that replaces; sulfosuccinate ester, taurine derivatives (especially alkyl tauride); the ester class of the ester of the alcohol of phosphoric acid or ethylene oxide and phenol, lipid acid and many alcohol, and the phosphoric acid salt functional deriv of vitriol, sulfonate and above-claimed cpd.Usually when only water-soluble slightly or the water insoluble and carrier of activeconstituents and/or inert support when being applied to water, have a kind of tensio-active agent at least.

Combination of the present invention can comprise different additives such as binding agent and tinting material further.Binding agent such as carboxymethyl cellulose and natural or synthetic polymkeric substance; be powdery, particle or latex form; such as: gum arabic, polyvinyl alcohol and Vinyl Acetate Copolymer, and natural phosphide, such as: Phosphotidyl ethanolamine and lecithin and synthetic phosphide can be used in the prescription.Further, additive can be Dormant oils and vegetables oil.Adoptable tinting material is a mineral dye, for example: ferric oxide, titanium oxide and Prussian orchid, and organic dye such as alizarine dyestuff, the salt of azoic dyestuff 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 compound or sesoxane) simultaneously, stable material, other sterilant, miticide, the plant nematocide agent, acarus-killing, the worm agent of killing, mycocide (be suitable on the agricultural or vertebrate as: F-1991, the dichlorophenyl first and second basic dioxy imidazolidine carbonyl acid amides) bactericide, arthropods or have the attractive substance of the animal of backbone, expellent, information is lured element, change flavor agent (reodorants) spices, dyestuff and auxiliary curative effect agent: trace elements.When needs, can be designed to improve the worm spectrum of its ability, stability, security, 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: Ortho 12420, Chlorpyrifos 94, demeton_S_methyl, thiodemeton, ethoprop (ethoprofos), fenitrothion 95, the Malathion, monocrotophos, parathion, zolone, pirimiphosmethyl, triazophos, Cyfluthin, Cypermethrin, deltamethrin, fenpropathrin, fenvalerate, permethrin, the aldicarb miticide, Carbosulfan, methomyl, oxamyl, Aphox Evil worm prestige, teflubenzuron, kelthane, 5a,6,9,9a-hexahydro-6,9-methano-2,4, lindane (lindane), benzoximate, cartap (Padan), cyhexatin, tetradifon, Avermectins, ivermectin, Milbex (milbemycins) thiophanate, Trichlorphon, SD-1750, diareridine and dimetri adazole.

As using on their agricultural, usually the compound of structure formula I is used with the composition forms that is various solids or liquid.Liquid 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 immobilized or mobile water.

Comprise the solid homogeneous phase of compound of one or more structure formula I or heterogeneous composition, for example: particle, pill, briquetting or capsule glue can be used for processing static or mobile water in the whole cycle.The enriched material 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 powdered powder (can contain the amount until the compound of 80% structure formula I) or wettable powder or particle, and especially those are by particulate vector extruding, closely knit, dipping or begin the medicament that obtains through granulating from powder (content of the compound of structure formula I is between 0.5 and 80% these wettable powder or particle).

Solution, especially emulsifiable concentrate, emulsification, flowable powder, aerosol, wettable powder (or the powder that is used to spray) but, exsiccant 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 enriched material usually also comprises 5 to 80% activeconstituents, and the situation of emulsification of using easily or solution is to contain 0.01 to 20% activeconstituents.Except solvent, this emulsifiable concentrate can comprise 2 to 50% suitable additive (time) if desired, such as: stablizer, tensio-active agent, permeate agent, corrosion inhibitor, tinting material or binding agent.

Any concentration that emulsion is required can obtain by these enriched materials of dilute with water, and it is particularly suitable for being applied to plant.

Spissated suspension, it can be used by sprinkling, so it is prepared into not sedimentary (fine grainding) stable product and contains active ingredient from 10 to 75% usually, tensio-active agent 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, stablizer, permeate agent, binding agent and as carrier, some organic solid or inorganic salt may be dissolved in and help in the carrier to prevent to deposit or as the antifreezing agent 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%, dispersion agent from 3 to 10% and if desired, one or more stablizers from 0 to 80% and/or other additive such as permeate agent, binding agent or anti-caking agent, tinting material or like that.

In order to obtain these wettable powders, active ingredient or all compositions are mixed in suitable blender with the material that can be immersed in the interpolation of porousness weighting agent, perhaps adopt pulverizing mill or other suitable shredder to mix.The wettable powder that produces, its wetting properties 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 wettable powder basically.They can pass through the illustrated granule preparation of wettable powder; also can be by wet method (with the activeconstituents and the inertia stopping composition 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 emulsification, for example:, be included in the general range of the composition of the present invention that can adopt according to wettable powder of the present invention or the emulsifiable concentrate composition that obtains by dilute with water.Emulsification 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 emulsifying agent 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 sterilant spray is irrigated or as system's sterilant or sub-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 protozoon 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, synergistic agent, trace elements or stablizer) 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 liquid 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 liquid composition through skin comprises usually from 0.1 to 90%(weight animal) one or more compounds of structure formula I.The feed of medicine comprises usually from 0.001% to 3%(weight) one or more compounds of structural formula.Be used for containing from 5% to 90% usually with feed blended enriched material or additive and being preferably 5% to 50%(weight) one or more compounds of structure formula I.Usually mineral salt contains on a small quantity from 0.1% to 10%(weight) one or more compounds of structure formula I.

Be used for 0.0001% to the 15%(weight that domestic animal, people, article, house (office) or outdoor geographic powder and liquid composition can comprise the compound of one or more structure formula I), more specifically be 0.005% to 2.0%(weight to reaching).Suitable concentration is between 0.0001ppm and 20ppm in the water of handling, and more specifically for the compound of the general structure of 0.001ppm to 5.0ppm (I) and also can be used for the medicinal of fish pond with suitable exposure duration.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 healthy state 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 some 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 structure formula I as activeconstituents, 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 weight percentage) of total component of example that is used in embodiment 23 to 28 is for as follows:

Ethylan BCP: nonylphenol ethylene oxide condenses

Soprohor BSU: the condenses of triphenylethylene phenol and ethylene oxide

The solution of Arylan CA:70%w/v calcium salt of dodecylbenzene sulfonate

Solvesso 150: light C-aromatic solvent

Arylan S: pelopon A

Darvan: sodium lignosulfonate

Celite PE: synthetic magnesium silicate carrier

Sopropon T36: poly carboxylic acid sodium salt

Rhodigel 23: the polysaccharide tragacanth gum

Bentone 38: the organic derivative that covers de-magging stone

7lerosil: the silicon-dioxide 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 EthylanBCP, add active ingredient up to dissolving in heating with under stirring then.By adding remaining solvent until the solution of quantitatively making generation.

Embodiment 24

A kind of emulsifiable concentrate 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 Solvessol50 then to quantitative.

Embodiment 25

A kind of wettable powder is by following preparation:

Active ingredient 40%

Arylan S 2%

Darvan No.2 5%

Celite PF 53%

Pulverize by mixed composition with in beater grinder, 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%

EthylanBCP 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 shredder.

Embodiment 27

A kind of emulsible suspending concentrate is by following preparation:

Active ingredient: 30.5%

Ethylan BCP 10.0%

Bentone 35 0.5%

Solvesso150 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 fluid energy (fluid-energy) pulverizer 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 refuse tip, 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 blower, 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 prepare by thorough mixing:

Active ingredient 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%

Pyrrole derivative 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, use through the intracutaneous infusion, perhaps, to per 100 kilograms the weight of animals, inject through non-enteron aisle with 1.2 to 12 milliliters solution by after poly tetrafluoroethylene (the 0.22 micron hole dimension) filter-sterilized.

Embodiment 32

A kind of wettable powder can be by being prepared as follows:

Active ingredient 50%

Ethylan BCP(9 mole oxide compound 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 beater grinder, obtain wettable powder, described powder dilutable water becomes the active compound 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 protozoon domestic animals harm or risk of infection, or oral with control arthropods, worm or protozoon by being placed in the tap 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 ruminant domestic animal and be stranded in and slowly discharge azole compounds in netted-cud continuously with the harm to ruminant domestic animal of control arthropods, nematode or protozoon 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 active compound and suitable softening agent, mix as two dioctyl phthalate (DOP)s, and carry out melt extruded or this homogeneous composition 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 depth of soil.

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 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% mortality ratio.

Embodiment 36

Activity to the mite class

Employing is tested at embodiment 35 identical prescriptions.Yet, train in light green beans strain at the acarid (tetranychus telarius Urtica) of the two spots of 150-200 bar and to grow.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 mortality ratio.

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 mortality ratio after five days: 100% mortality ratio is provided and provides 80% mortality ratio 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 adopting as implementing your the identical prescription in 35 carries out, it comprises following component in this case:

2.5 milligram active ingredient

0.05 gram dimethyl formamide

9.9228 gram acetone

0.0247 gram tensio-active agent (as in embodiment 35)

90 gram water

The compound of embodiment 4 obtains 100% mortality ratio 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 tensio-active agent (as in the embodiment 35)

90 gram water

Obtain mortality ratio 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 tensio-active agent (as in the embodiment 35)

89.988 gram water

Mexico Macroptilium beetle (Epilachna Varivestis, grow on about 15 centimetres high Sieva leguminous plants by second instar larvae training muls).Then, the mortality ratio that calculates after five days: the compound at embodiment 13 obtains 100% mortality ratio under 125ppm.

41: adopt as outside identical prescription carries out in embodiment 38, comprise that also the compound of embodiment 8 obtains 100% the mortality ratio 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 100% the mortality ratio to 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 tensio-active agent (as in the embodiment 35)

90 gram water

Then calculate the dead percentage ratio that Mexico Macroptilium beetle is obtained: obtain 80% mortality ratio and obtain 100% mortality ratio 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 toxic chemical agent 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

Tensio-active agent is (as implementing 2.15 24.3 14.25

In the example 35) (milligram)

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 ratio of fly, for as follows:

With embodiment 44: is 100% by embodiment 1,2,3B, 4,6,8,9,16C, 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 mortality ratio.

With embodiment 45: the compound by embodiment 12 is 100% in the 100ppm mortality ratio.

With embodiment 46: the compound by embodiment 1,2 and 5 is 100% in the 12.5ppm mortality ratio.

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 starting point 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/).

Contain the 200ppm test compounds prescription that 60 gram gizzards add five equilibrium in argillous jar (as the concentration of the test compound of suitable final soil), 3.2 ml waters and 5 corn seeds that germinate in advance at one.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 touchstone 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.

Claims

1, a kind of compound of following structural formula:

It is characterized in that:

X comprises halogen for being selected from, cyano group, the cyanic acid base, thiocyano, haloalkyl, alkoxyl group, halogenated alkoxy, alkylthio, alkyl sulphinyl, alkyl sulphonyl, halogenated alkylthio, the haloalkyl sulfinyl, halogenated alkyl sulfonyl, halogenated alkyl carbonyl, alkenyl thio, the alkenyl sulfinyl, the alkenyl alkylsulfonyl, the halogenated alkenyl sulfenyl, the halogenated alkenyl sulfinyl, halo alkene alkylsulfonyl, the haloalkyl thiocarbonyl group, thiophenyl, benzenesulfinyl, benzenesulfonyl, the heteroaryl sulfenyl, heteroaryl sulfinyl and assorted arylsulfonyl, phenyl in the formula is for optionally using halogen, cyano group or alkylhalide group replace and heteroaryl groups is to contain 1 or 2 identical or different oxygen, sulphur or cyanogen heteroatomic five yuan or single six-membered rings, and described heteroaryl groups is for optionally using halogen, nitro, cyano group or alkylhalide group replace; And described alkyl, alkylhalide group, alkenyl, halogenated alkenyl, alkoxyl group and halogenated alkoxy are the straight or branched that is less than 10 carbon atoms, and comprise one or more halogen atoms at the halo of all these groups, be identical or different groups from single halogen atom that replaces until full replacement;

R ¹, R ²And R ³Comprise following group for being selected from separately: be same as the listed a kind of substituting group illustrated as above-mentioned X; Hydrogen atom; Alkyl; And R ¹, R ²And R ³No more than a kind of substituting group is selected from and comprises formyl radical, hydroxyl imido alkyl, the Alkoximino alkylidene group, azido-, amino, alkoxyl group, dialkylamino, arylalkylamino, an amino carbonylamino, the alkane carboxyamino, halogenated alkyl carbonyl amino, aryl-amino-carbonyl, alkyl sulfonyl amino, the haloalkyl sulfonamido, alkyl amino-carbonyl amino, aromatic aminocarbonyl amino, the benzal imino-, alkylideneimino, the alkoxyl group alkylideneimino, the dialkylamino alkylideneimino, two (alkylthio) methyl, two (arylthio) methyl, the alkylthio alkylideneimino, alkoxycarbonyl amido, the haloalkoxy carbonylamino, optionally use halogen, nitro, the phenyl that cyano group or haloalkyl replace and contain 1 or 2 identical or different oxygen, the heteroaryl group of sulphur or nitrogen heteroatom five yuan or six-ring and described heteroaryl group use halogen, nitro, cyano group or alkyl halide group replace;

And described alkyl, haloalkyl, alkenyl, halogenated alkenyl, halogenated alkoxy and alkoxyl group are the chain that is less than the straight or branched of 10 carbon atoms, and comprise 1 or more than 1 halogen atom at the halo of all these groups, be identical or different group from single halogen atom that replaces up to full replacement;

Y comprises for being selected from: halogen, cyano group, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, alkyl sulphinyl, alkyl sulphonyl, alkylthio, halogenated alkylthio, haloalkyl sulfinyl, halogenated alkyl sulfonyl, alkyl-carbonyl, halogenated alkyl carbonyl, alkenyl, halogenated alkenyl, halo alkynyl group and alkynyl group; And described alkyl, alkoxyl group, alkylhalide group, halogenated alkoxy, alkenyl, halogenated alkenyl, halo alkynyl group and alkynyl group, for being less than the straight or branched of 10 carbon atoms, and comprise 1 or a plurality of halogen atom at the halo of all these groups, be identical or different group from single halogen atom that replaces until full replacement;

Perhaps Y is that hydrogen atom is worked as:

X is halogen atom or R ⁵N is 0,1 or 2 and R in S (O) the n group ⁵Be alkyl, haloalkyl, alkenyl or halogenated alkenyl; And the carbochain of this alkyl and alkenyl and halogen replace as above defined;

R ¹And R ³Each be hydrogen atom and

R ²Be cyano group;

X ¹, X ², X ³And X ⁴Being selected from the listed identical substituting group that illustrates as above-mentioned Y separately or being hydrogen atom, is condition: R with following still ¹, R ²And R ³At least a listed identical substituting group that is selected from as above-mentioned X explanation;

If X ⁴And X ¹Be H; And after X was hydrogen or cyanogen, R was different with X,

If X ⁴And X ¹Be H, and after Y was methyl, X not a bromine.

2, the compound of structure formula I as claimed in claim 1 is characterized in that:

X is for being selected from halogen atom, or cyano group, the cyanic acid base, thiocyano, haloalkyl, alkoxyl group, halogenated alkoxy, alkylthio, alkyl sulphinyl, alkyl sulphonyl, halogenated alkylthio, the haloalkyl sulfinyl, halogenated alkyl sulfonyl, halogenated alkyl carbonyl, the haloalkane thiocarbonyl group, thiophenyl, the phenyl sulfinyl, phenyl sulfonyl, heteroarylthio, the group of assorted fragrant sulfinyl and assorted arylsulfonyl, the phenyl in the formula is for optionally using halogen, cyano group or alkylhalide group replace and heteroaryl groups is to contain 1 or 2 oxygen identical or inequality, five yuan or single six-membered rings of sulphur or nitrogen heteroatom; And the alkyl in the formula, alkylhalide group, alkoxyl group and halogenated alkoxy be the straight or branched that is less than 10 carbon atoms, and be single replace or until full replacement at the halo of all these groups;

R ¹, R ²And R ³For being selected from separately: the identical substituting group illustrated as X; Hydrogen atom, alkyl; And R ¹, R ²And R ³No more than one substituting group comprise formyl radical for being selected from, the oximino alkylidene group, the Alkoximino alkylidene group, azido-, amino, alkylamino, dialkylamino, arylalkylamino, amino carbonyl amino, alkyl carbonyl amino, the alkylhalide group carbonylamino, aromatic carbonyl amino, alkyl sulphonyl, the haloalkyl sulfonamido, alkyl amino-carbonyl amino, aromatic aminocarbonyl amino, the benzylidene imino-, alkylideneimino, alkoxyl group alkylideneimino and dialkyl amido alkylideneimino, optionally use halogen, nitro, the phenyl that cyano group or haloalkyl replace and contain 1 or 2 identical or different oxygen, the heteroaryl group of heteroatomic five yuan or the single six-membered rings of sulphur or nitrogen, described heteroaryl group is for optionally using halogen, nitro, cyano group or alkyl halide group replace; And described alkyl, haloalkyl, halogenated alkoxy and alkoxyl group be the straight or branched that is less than 10 carbon atoms, and be single the replacement until full replacement at the halo of all these groups;

Y is for being selected from halogen atom or cyano group, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, alkyl sulphinyl, alkyl sulphonyl, alkylthio, halogenated alkylthio, haloalkyl sulfinyl, halogenated alkane base alkylsulfonyl, alkyl-carbonyl, halogenated alkyl carbonyl, alkenyl, halogenated alkenyl, halo alkynyl group and alkynyl group; And described alkyl, alkoxyl group, haloalkyl, halogenated alkoxy, halo alkynyl and alkynyl group be the straight or branched that is less than 10 carbon atoms, and be single replace or until full replacement at the halo of all these groups; And

X ¹, X ², X ³And X ⁴For as illustrated in the claim 1.

3, the compound of structure formula I as claimed in claim 1 or 2 is characterized in that by X, X ¹, X ², X ³, X ⁴, R ¹, R ², R ³With the substituent part of the alkyl of Y defined, alkenyl, alkynyl group, alkoxyl group for being less than 5 carbon atoms.

4, the compound of structure formula I as claimed in claim 3 is characterized in that:

X is halogen atom or R ⁵S(O) n group, n is 0,1 or 2 and R in formula ⁵Be alkyl, alkylhalide group, alkynyl group or halo alkynyl group;

R ¹Be hydrogen atom, halogen atom or alkylthio;

R ²Be the hydrogen base;

R ³Be hydrogen atom or halogen atom;

Y is hydrogen atom, halogen atom, alkylhalide group or halogenated alkoxy, and condition is to be hydrogen atom as the Y at claim 1 defined; And

X ¹, X ², X ³And X ⁴Comprise hydrogen atom, halogen atom, C for being selected from separately _1-3Alkyl, C _1-3Alkoxyl group and C _1-3The group of alkylthio.

5, compound as claimed in claim 4 has following structure formula II

It is characterized in that:

X is R ⁵S(O) n, n is 1 or 2 and R in the formula ⁵Be CH, CF ₃, CH ₂Cl, CFCl ₂, CF ₂Br, CHF ₂, CFCl 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, compound as claimed in claim 5 is characterized in that described compound 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 alkylsulfonyl) pyrroles;

1-(2,6-two chloro-4-fluoroform phenyl)-2-chloro-3-cyano group-4-(chlorodifluoramethyl-alkylsulfonyl) 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 methylthio group) 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 alkylsulfonyl) 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-chloro-3-cyano group-4-(dichlorofluoromethyl alkylsulfonyl-5-bromine) pyrroles;

1-(2,6-two chloro-4-trifluoromethoxy benzaldehyde bases)-2-bromo-3-cyano group-4-(chlorodifluoramethyl-alkylsulfonyl) 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 alkylsulfonyl) pyrroles;

1-(2-chloro-4-fluoroform phenyl)-and 2-chloro-3-cyano group-4-(dichlorofluoromethyl alkylsulfonyl) pyrroles;

1-(2-chloro-4-fluoroform phenyl)-and 2-chloro-3-cyano group-4-(dichlorofluoromethyl sulfinyl) pyrroles;

1-(2-chloro-4-fluoroform phenyl)-and 2-bromo-3-cyano group-4-(dichlorofluoromethyl alkylsulfonyl) 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 alkylsulfonyl) 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, the compound of structure formula I as claimed in claim 4 is characterized in that:

X is halogen atom or R ⁵S(O) n group, n is 0,1 or 2 and R in the formula ⁵Be alkyl, alkylhalide group, alkynyl group or halo alkynyl group;

R ¹And R ³Each is a hydrogen atom;

R ²Be cyano group;

Y is hydrogen atom or halogen atom; And

X ¹, X ², X ³And X ⁴Comprise for being selected from separately: hydrogen, halogen, C _1-3Alkyl, C _1-3Alkoxyl group and C _1-3The group of alkyl sulfide.

8, compound as claimed in claim 7 is characterized in that R ⁵For alkyl is 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 compounds, it is characterized in that R ⁵Be CF ₃, CCl ₃, CF ₂Cl, CFCl ₂Or CF ₂Br.

10, compound as claimed in claim 7 is characterized in that described compound 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-(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 alkylsulfonyl) pyrroles;

1-(2,4, the 6-trichlorophenyl)-3-cyano group-4-(trifluoromethyl sulfenyl) 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-alkylsulfonyl) pyrroles;

1-(2, the 6-trichlorophenyl)-3-cyano group-4-(dichlorofluoromethyl sulfenyl) 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-alkylsulfonyl) 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, as claim 1 to 4,7, the compound of 8 and 9 each described structure formula I, when it is characterized in that the Y substituting group is defined as alkenyl and halogenated alkenyl, be respectively allyl group and halogenated allyl, and when any Y substituting group is defined as alkynyl group and halo alkynyl group, be respectively propargyl and acetylenic halide propyl group.

12, as the compound of claim 1,2 or 3 described structure formula I, it is characterized in that

R ¹Be hydrogen atom or halogen atom;

R ²Be cyano group;

X is the n group of alkylhalide group-S(O), and n is 0,1 or 2 in the formula;

X ¹And X ⁴For except that hydrogen atom;

X ²And X ³Be hydrogen atom.

13, compound as claimed in claim 12 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.

14, compound as claimed in claim 2 has following structure formula II:

It is characterized in that:

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.

15, compound as claimed in claim 2 is characterized in that described compound is:

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-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-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)-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-Trifluoromethoxyphen-ls)-2-chloro-3-cyano group-4-(trifluoromethyl sulfonyl) pyrroles.

16, structural formula as claimed in claim 1 (III compound a):

It is characterized in that Y is H, Cl, Br, CF ₃Or OCF ₃And X ¹And X ⁴H, Cl, F, CH respectively do for oneself ₃Or SCH ₃, condition is: if X ¹And X ⁴Each is H, and Y is not H or Cl then.

17, compound as claimed in claim 1 is characterized in that X is that H or Cl and Y are CF ₃Or CF ₃O.

18, a kind of method that is prepared as follows the compound of structural formula:

X in the formula ¹, X ², X ³, X ⁴Has meaning identical in the claim 1 with Y; X is halogen, trifluoromethyl, cyano group, thiocyano, alkylthio, alkyl sulphinyl, alkyl sulphonyl, halogenated alkylthio, haloalkyl sulfinyl, halogenated alkyl sulfonyl, alkenyl thio, halo alkenyl thio, halogenated alkenyl sulfinyl, halogenated alkenyl alkylsulfonyl, thiophenyl, benzenesulfinyl, benzenesulfonyl, heteroarylthio, assorted fragrant sulfinyl or assorted arylsulfonyl, it is characterized in that the structural formula of compound is:

Various symbols in the formula are optionally protected with R amino as defined in claim 1:

(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:

X optionally the reacting that be two (alkyl sulfide) methyl or two (aryl sulphur) methyl and other symbol in the formula as defined in claim 1 with the alkyl nitrous acid ester, then by hydrolysis, to obtain the compound of the structural formula that X is a formyl radical (XI), then described compound is being contacted with azanol then 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 basic 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 an alkyl sulfide (I compound a); Perhaps

(d) with the sulfenyl halide reaction of formula R SHal, in the formula R be alkyl, alkylhalide group, phenyl or heteroaryl groups 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 alkyl sulfide, haloalkyl sulphur, alkenyl sulphur, halogenated alkenyl sulphur, phenyl sulphur or heteroaryl sulphur, with the optionally oxidation of known method, being RS(O then to obtain X) n is 1 or 2 structural formula (I compound a) in the n formula.

19, structural formula as claimed in claim 18 (preparation method of I compound a), X in the formula ¹, X ², X ³, X ⁴Have as identical meaning in claim 1 with Y, and X is cyanic acid base, alkoxyl group or halogenated alkoxy, it is characterized in that the compound of structural formula (XX VIII) is:

In the formula various symbols as defined in claim 1 and if desired, amino and cyano group is suitably protected:

(a) in the presence of acid acceptor, obtain the structural formula that X is the cyanic acid base (I compound a) with the halogen cyan reaction;

(b) optionally in the presence of alkali, obtain the structural formula that X is an alkoxyl group (I compound a) with alkylation reactions; Perhaps

(c) carry out haloalkylation with known method and obtain the structural formula that X is a halogenated alkoxy (I compound a).

20, the preparation method of compound as claimed in claim 18, X in the formula ¹, X ², X ³, X ⁴Have as identical meaning in claim 1 with Y, X is alkylhalide group, alkylhalide group carbonyl or alkylhalide group thiocarbonyl group, it is characterized in that the compound of structure formula VI is:

Various symbols are as defined in claim 1 in the formula, and amino and cyano group if desired can be suitably protected:

(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 brooethyl or chloromethyl; Perhaps

(d) then be transformed into alkylhalide group methyl alcohol and then obtain the structural formula that X is the alkylhalide group carbonyl (I compound a) with the currently known methods oxidation with alkylhalide group metal derivative or trimethylsilyl trifluoroacetamide base silicomethane reaction general-CHO; then optionally (ⅰ) described compound and LawessonShi reagent react; obtain the structural formula that X is alkylhalide group (thiocarbonyl group) (I compound a); perhaps (ⅱ) is that the compound of alkylhalide group methyl alcohol and halogenating agent reaction are to obtain the structural formula that X is α-alkylhalide group-α-monochloromethyl (I compound a) with X; if desired, all preceding back of step that get are then by deprotection base step.

21, the method for the compound of a kind of preparation structural formula (I b),

In the formula various symbols as defined in claim 1 and R ³Be halogen; formyl radical; two (alkyl sulfide or aryl sulphur) methyl; alkylhalide group; alkyl; optionally phenyl of Qu Daiing or heteroaryl; thiocyano; alkylthio; halogenated alkylthio; alkenyl thio; the halo alkenyl thio; thiophenyl; heteroarylthio; alkyl sulphinyl; alkyl sulphonyl; the alkenyl sulfinyl; the alkenyl alkylsulfonyl; the haloalkyl sulfinyl; halogenated alkyl sulfonyl; the halogenated alkenyl sulfinyl; the halogenated alkenyl alkylsulfonyl; benzenesulfinyl; benzenesulfonyl; heteroaryl sulfinyl or heteroarylsulfonyl; it is characterized in that (X in I compound a) is cyano group and amino to structural formula; if desired, optionally protected:

(a) by claim (18a) reaction, obtain R ³For halogen the compound of structural formula (I b), described then compound (ⅰ) optionally in the presence of copper with the heteroaryl of currently known methods and replacement or the reaction of phenyl halides, perhaps (ⅱ) with currently known methods and the phenyl or the heteroaryl acid reaction that optionally replace, obtains R in the presence of palladium ³For the compound of the structural formula (I b) of the phenyl that optionally replaces or heteroaryl groups, perhaps according to claim 18(a) reaction, obtain the compound of the structural formula that R is a trifluoromethyl (I b);

(b) according to claim 18(b) reaction, at first obtain the compound of R for the structural formula (I b) of two (alkyl sulfide) methyl or two (aryl sulphur) methyl, and then optionally, R ³Compound for the structural formula (I b) of formyl radical;

(c) optionally react with currently known methods, obtain R with phenyl that replaces or heteroaryl diazonium salt ³Be the compound of the structural formula (I b) of the phenyl that optionally replaces or heteroaryl, perhaps

(d) according to claim 18(c.d) reaction, obtain R ³For the compound of the structural formula (I b) of thiocyano, alkyl sulfide, haloalkyl sulphur, alkenyl sulphur, halo chain sulphur thiazolinyl, thiophenyl or heteroarylthio, then according to claim 18(d) optionally oxidation to be to obtain R ³Be the compound of the structural formula (I b) of alkyl sulphinyl, alkyl sulphonyl, alkenyl sulfinyl, alkenyl alkylsulfonyl, haloalkyl sulfinyl, halogenated alkyl sulfonyl, halogenated alkenyl sulfinyl, halogenated alkenyl alkylsulfonyl, benzenesulfinyl, benzenesulfonyl, assorted fragrant sulfinyl or assorted arylsulfonyl, 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 currently known methods with the alkyl lithium salts) sulfation to be to obtain the compound that X is the structural formula (I b) of alkyl sulfide, haloalkyl sulphur, alkenyl sulphur, halo alkenyl thio, thiophenyl or heteroarylthio.

22, the method for the compound of a kind of preparation structural formula (I b), X, X in the formula ¹, X ², X ³, X ⁴Having as identical meaning and R in claim 1 with Y is oxyimino alkylidene group, Alkoximino alkylidene group, cyano group, alkyl halide carbonyl or alkyl halide thiocarbonyl group or alkyl, it is characterized in that the structural formula of compound is:

R in the formula ³Be formyl radical or alkyl-carbonyl, other symbol is as defined in claim 1, and X, cyano group and amino if desired can be protected:

(a) with the salt of azanol or O-alkyl azanol or their addition in solvent condensation to obtain R ³Be the compound of the structural formula (I b) of oximino alkylidene group or Alkoximino alkylidene group, and work as R ³During for oximino alkylidene group or Alkoximino alkylidene group, transform described R and become cyano group, and obtain R ³Compound for the structural formula (I b) of cyano group;

(b) work as R ³During for formyl radical, according to claim 20(a.b.c or d) react to obtain R ³Compound for the structural formula (I b) of methyl, alkylhalide group, alkylhalide group carbonyl or alkyl halide sulfenyl carbonyl; Perhaps

(c) work as R ³During for formyl radical, use from the Grignard reagent reaction of haloalkyl derivative or with the lithium alkylide reaction and obtain methanol-based, then obtain R by dehydrating step ³Be alkenyl, subsequent by reducing to obtain R ³Compound for the structural formula (I b) of alkyl; Again by sloughing the protecting group step.

23, a kind of method that is prepared as follows the compound of structural formula,

Be used as midbody compound, X, X in the formula ¹, X ², X ³, X ⁴With Y be as in claim 1 defined and R ³Be amino, alkylamino, 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 amido, alkylideneimino, benzylidene imino-, alkoxyl group alkylideneimino, dialkyl amido alkylideneimino, alkyl sulfide alkylideneimino or azido-, it is characterized in that the compound of structural formula (XXX) is:

Various symbols are as defined in claim 1 in the formula, and amino protected with suitable method, in order to obtain R ³For the compound of the structural formula (XXX IV) of amino reduces, described compound with:

(a) alkylating agent reacts in organic solvent to obtain single or disubstituted amino or to transform this amino fully becoming the alkoxyl group alkylideneimino, following by reduction to obtain R ³Compound for the structural formula (XXX IV) of alkylamino, dialkyl amido or aryl alkyl amino;

(b) photoreactive gas is handled then and ammonia react obtains R ³Compound for the structural formula (XXX IV) of amino carbonyl amino;

(c) and alkyl acyl chloride or haloalkyl acyl chlorides or aryl acyl chlorides or optionally reaction in solvent and/or in the presence of the organic acid receptor of acid anhydrides, to obtain R ³Compound for the structural formula (XXX IV) of alkyl-carbonyl-amino, halogenated alkyl carbonyl amino or aryl-amino-carbonyl;

(d) and alkyl or haloalkyl sulfonic acid halide or sulphonic acid anhydride under appropriate condition, react, to obtain R ³Compound for the structural formula (XXX IV) of alkyl sulfonyl-amino or haloalkyl sulfonamido;

(e) and the alkyl or aryl isocyanic ester with the reaction of known method to obtain R ³Compound for the structural formula (XXX IV) of (alkylamino or arylamino) carbonylamino;

(f) and alkyl chloroformate or chloroformic acid haloalkyl ester react with known method, obtain the compound of the structural formula that R is alkoxycarbonyl amino or haloalkoxy carbonylamino (XXX IV);

(g) and alkyl or aryl aldehyde react with currently known methods, obtain R ³Compound for the structural formula (XXX IV) of alkylideneimino or benzylidene imino-;

(h) and alkyl orthoester reaction to obtain R ³Compound for the structural formula (XXX IV) of alkoxyl group alkylideneimino;

(i) and N, reaction of N-dialkylformamide or the reaction of dialkyl group acetal derivatives obtain R ³Compound for the structural formula (XXX IV) of dialkyl amido alkylideneimino;

(j) and three (alkyl sulfide) methane in organic solvent, react and obtain R ³Compound for the structural formula (XXX IV) of alkyl sulfide alkylideneimino; Perhaps

(k) and the p-Xylol sulfuryl azide then then handle with currently known methods reaction or by changing into diazonium salt with nitrous acid by being reduced into diazanyl, obtain R ³Compound for the structural formula (XXX IV) of azido-; Then remove the protecting group step if desired.

24, the method for the compound of a kind of preparation structural formula as claimed in claim 21 (I b), X, X in the formula ¹, X ², X ³, X ⁴, Y has as claim 1 same meaning and R ³Be cyanic acid base, alkoxyl group or halogenated alkoxy, it is characterized in that the structural formula of compound is:

Amino in the formula, cyano group and X be according to claim 19(a, b or c) reaction selectively protected to obtain R ³Compound for the structural formula (I b) of cyanic acid base, alkoxyl group or halogenated alkoxy.

25, a kind of method that is prepared as follows the compound of structural formula:

X, R in the formula ³, X ¹, X ², X ³, X ⁴The same meaning and the R that have claim 1 with Y ¹Be hydrogen; halogen; thiocyano; alkylthio; halogenated alkylthio; alkenyl thio; the halo alkenyl thio; thiophenyl; heteroarylthio; alkyl sulphinyl; alkyl sulphonyl; the alkenyl sulfinyl; the alkene alkylsulfonyl; the haloalkyl sulfinyl; halo alkene alkylsulfonyl; benzenesulfinyl; benzenesulfonyl; the heteroaryl sulfinyl; heteroarylsulfonyl; phenyl or heteroaryl that selectivity replaces; alkyl-carbonyl; alkylamino; dialkyl amido; aryl alkyl amino; amino carbonyl amino; alkyl carbonyl amino; halogenated alkyl carbonyl amino; aryl-amino-carbonyl; alkyl sulfonyl-amino; the haloalkane phenylsulfonamido; alkyl amino-carbonyl amino; aromatic yl aminocarbonyl amino; alkoxycarbonyl amido; the haloalkoxy carbonylamino; alkylideneimino; the benzylidene imino-; the alkoxyl group alkylideneimino; the dialkyl amido alkylideneimino; the alkylthio alkylideneimino; azido-; two (alkylthio or aryl sulfo-) methyl; formyl radical; halogenated alkyl carbonyl; the haloalkyl thiocarbonyl group; haloalkyl or alkyl is characterized in that the structural formula of compound is:

If desired at protection X, R ³Or after the cyano group, again amino is removed blocking group

(a) in inert solvent with diazotization agent reaction and to 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 ¹For the compound of the structural formula (I c) of alkyl-carbonyl or described compound according to claim 21(e) reaction to be to obtain the compound of the structural formula that R is phenyl or heteroaryl (I c);

(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 thiocyano, alkyl sulfide, haloalkyl sulphur, alkenyl sulphur, halogenated alkenyl sulphur, phenyl sulphur or heteroaryl sulphur; Then according to claim 18(d) optionally oxidation to be to obtain R ¹Compound for the structural formula (I c) of alkyl sulphinyl, alkyl sulphonyl, alkenyl sulfinyl, alkene alkylsulfonyl, haloalkyl sulfinyl, halogenated alkyl sulfonyl, halo alkene sulfinyl, halo alkene alkylsulfonyl, benzenesulfinyl, benzenesulfonyl, heteroaryl sulfinyl or heteroarylsulfonyl;

(d) according to claim 23(a-k) react to obtain R ¹Be alkylamino, 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 amido, the haloalkoxy carbonylamino, alkylideneimino, the benzylidene imino-, the alcoxyl alkylideneimino, the dialkyl amido alkylideneimino, the compound of the structural formula of alkyl sulfide alkylideneimino or azido-(I c); Perhaps

(e) react to obtain the compound of the structural formula that R is a formyl radical (I c) with currently known methods and Sodium Nitrite, formoxime, copper sulfate and HCl, then optionally (ⅰ) reacts with the alkyl Grignard reagent and follows oxidation to obtain R ¹Compound for the structural formula (I c) of alkyl-carbonyl, (ⅱ) according to claim 22(a) reaction is to obtain the compound that R is the structural formula (I c) of oxyimino alkylidene group, Alkoximino alkylidene group or cyano group, perhaps (ⅲ) is according to claim 20(a-d) react to obtain R ¹Be the compound of the structural formula (I c) of halogenated alkyl carbonyl, haloalkyl thiocarbonyl group, alkylhalide group, perhaps with currently known methods with R ¹For the above-claimed cpd of formyl radical changes into R ¹Compound for the structural formula (I c) of two (alkyl sulfide or aryl sulphur) methyl.

26, the method for the compound of a kind of preparation structural formula (I c), X, R in the formula ³, X ¹, X ², X ³, X ⁴Have identical meaning as claimed in claim 1 and R with Y ¹Be cyanic acid base, alkoxyl group or halo, alkoxyl group, it is characterized in that the structural formula of compound is:

In the formula various symbols such as claim 1 defined and X cyano group or R ³After can be with currently known methods optionally protected,, b and c according to claim 19(a) reaction to be to obtain R ¹Be the compound of the line structure formula (I c) of cyanic acid base, alkoxyl group or halogenated alkoxy, then deprotection base step by selecting.

27, a kind of method for preparing the compound of structure formula I, X, R in the formula ¹, R ³, X ¹, X ², X ³, X ⁴Have identical meaning as claimed in claim 1 and R with Y ²Be CHO, it is characterized in that the compound of structural formula (I c) becomes the CHO group so that R to be provided the CN groups converted with the reductive agent processing in solvent ²Be the compound of CHO, described compound with known method optionally oxidation to obtain the compound of corresponding structure formula (XXX V):

28, a kind of method for preparing the compound of structure formula I, X, R in the formula ¹, R ³, X ¹, X ², X ³, X ⁴Has identical meaning as claimed in claim 1 with Y and R is oxyimino alkylidene group, alkoxyimino alkylidene group, cyano group, halogenated alkyl carbonyl, haloalkyl thiocarbonyl group, alkyl, haloalkyl or two (alkylthio or aryl sulfo-) methyl; it is characterized in that R 2 is the structure formula I of CHO; if desired according to claim 20(a, b, c and d), 22(a and b) or 25(e) after X, the R 1 of optionally protection or the reaction of R 2 methods if desired, follow by sloughing the protecting group step.

29, a kind of method for preparing the compound of structure formula I, X, R in the formula ¹, R ³, X ¹, X ², X ³, X ⁴Have identical meaning as claimed in claim 1 and R for amino with Y; alkylamino; 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; the haloalkoxy carbonylamino; alkylideneimino; the benzylidene imino-; the alkoxyl group alkylideneimino; the dialkyl amido alkylideneimino; the alkyl sulfide alkylideneimino; azido-; hydrogen; halogen; thiocyano; alkyl sulfide; halogenated alkylthio; alkenyl thio; the halo alkenyl thio; thiophenyl; heteroarylthio; alkyl sulphinyl; alkyl sulphonyl; the alkene sulfinyl; the alkene alkylsulfonyl; halo alkene sulfinyl; the halogenated alkenyl alkylsulfonyl; the haloalkyl sulfinyl; halogenated alkyl sulfonyl; benzenesulfinyl; benzenesulfonyl; the heteroaryl sulfinyl; heteroarylsulfonyl; optionally phenyl of Qu Daiing or heteroaryl or trifluoromethyl; the compound that it is characterized in that structural formula as claimed in claim 27 (XXX V); if desired, with the X of known formula selective protection; R ¹Or R ³Afterwards; if desired; carrying out ladder outstanding this (Curtius) in storehouse under reaction conditions resets; for example: by be converted into acyl chlorides then by and an alkali metal azide reaction or then can hydrolysis with carbamate in the generation in alcoholic solvent in the presence of organic bases with the diphenyl phosphoryl azide reaction, to obtain R ²Be the corresponding compounds of amino, then with described compound according to claim 23(a-k) or 25(a-c) optionally the reaction, work as R ²During for halogen, if desired, optionally according to claim 21(a) reaction, then by deprotection base step.

30, a kind of method for preparing the compound of structure formula I, X, R in the formula ¹, R ³, X ¹, X ², X ³, X ⁴Having as claim 1 identical meaning and R with Y is cyanic acid base, alkoxyl group or halogenated alkoxy, it is characterized in that the structural formula of compound is:

Various symbols are as defined in claim 1, the optionally protection X, the R that have if desired then in the formula ¹Or R ³According to claim 14 reaction, follow by going to protect step if desired after the group.

31, a kind of method for preparing the compound of structural formula (XX VIII), (XX XI) (XX XII) and (XXX V) as claim 19,24,28 or 30; it is characterized in that as claim 18(a), 21(a), 25(b) or 29 corresponding compounds; if exist after the protected group; be converted into Grignard reagent or lithium derivative; then with the reaction of trialkylboron hydrochlorate and with known method oxidation; if desired, then by sloughing the step of protecting group.

32, a kind of method that is prepared as follows the compound of structural formula,

X in the formula ¹, X ², X ³, X ⁴Have the meaning identical with Y, it is characterized in that the dicyano acryloyl derivative of following structural formula as claim 1:

React with alkali reagent.

33, a kind of method for preparing the compound of structure formula I, R in the formula ¹, R ², R ³, Y, X ¹, X ², X ³With X as defined in claim 1, and X is perhalogeno alkylthio group, it is characterized in that comprising:

A) with the compound of structural formula (XXX VIII):

X is a hydrogen in the formula, and other symbol is as defined in claim 1, in 0 ℃ to 150 ℃, in the presence of solvent optionally with chlorsulfonic acid (ClSO ₃H) reaction, to prepare the compound of structural formula (XXX IX):

Various symbols are as defined in claim 1 in the formula;

B) with the compound of structural formula (XXX IX) and reductive agent at 0 ℃ to 110 ℃, reaction is to form the disulfide of structural formula (X LI) in organic solvent:

Various symbols are as defined in claim 1 in the formula, and

C) with the compound and the structural formula (XL of structural formula (XLI) ₁₁) perhalogeno alkane, ZCFR ⁷R ⁸Z is Cl, Br or I in the formula, R is that F, Cl or Br and R are F, Cl, Br or perfluoroalkyl, radical promote reductive agent in the presence of and in the presence of alkali optionally, in a kind of solvent, also optionally under pressure, react in 20 ℃ to 85 ℃, with the compound of preparation structure formula I, X is whole haloalkyl sulfenyl group and other symbol as defined in claim 1 in the formula.

34,, it is characterized in that the compound that then obtains thus by conversion becomes the compound as the structure formula I of defined in the claim 1 as each described method of claim 18 to 32.

35, as each described method of claim 18 to 34, it is characterized in that foregoing basically.

36, the compound of structure formula I according to claim 1 is characterized in that by claim 18 to 22,24 to 30 and 32 to 34 each described methods preparations.

37, a kind of kill branch animal, plant nematocide, drive wriggle (intestines) worm or antiprotozoal composition, it is characterized in that comprising compound and one or more compatible diluent or carriers as the structure formula I of claim 1 to 17 and 36 each defineds.

38, a kind of medicine that is used for the animal doctor and penkeeping or keep the composition of public health is characterized in that comprising at least a as claim 1 to 17 and 36 each the active ingredients of compound.

39, a kind of parasiticidal, kill composition mite or nematocides, it is characterized in that comprising as claim 1 to 17 and 36 each effective quantity of structure formula I compound.

40, composition as claimed in claim 39 is characterized in that comprising: 0.05% and 95%(weight) between one or more described active ingredients, 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.

41,, it is characterized in that further comprising that one or more are selected from comprises that protective colloid, binding agent, thickening material, thixotropic compound, permeate agent, spraying murder the group of worm active ingredient with oil, stablizer, sanitas, anti-(mould) Fungicide, sequestrant and other as claim 39 or 40 described compositions.

42,, it is characterized in that described carrier is a liquid or solid as claim 39,40 or 41 each described compositions.

43, composition as claimed in claim 37 is characterized in that basically as previously described.

44, a kind of control joint branch animal, a Plant nematode, wriggle (intestines) worm or the on-site method of protozoon disease is characterized in that comprising being applied to a kind of each the effective quantity of compound of structure formula I as claim 1 to 17 and 36 in location.

45, annotate 44 veterinary drug and penkeeping as the right village or keep the described method of public health, it is characterized in that controlling and colonize in the inside and outside joint branch animal of warm-blooded vertebrate, wriggle (intestines) worm or protozoon disease.

46, save the method for branch animal or plant nematode as the control of claim 44, it is characterized in that comprising the compound of the structure formula I that is applied to growing plants or the effective quantity of its medium.

47, as the control joint branch animal of claim 44 or the method for nematodiasiss, it is characterized in that the compound of using is positioned at the place of joint branch animal or eelworm harm, the consumption per hectare of controlling processed place is 0.005 kilogram to 15 kilograms a quantity.

48, method as claimed in claim 47 is characterized in that the quantity of the compound that is applied is that per hectare is 0.02 kilogram to 2 kilograms.

49, method as claimed in claim 47 is characterized in that the quantity of the compound that is applied is that per hectare is 0.01 kilogram to 1 kilogram.

50,, it is characterized in that described compound is for as claim 7,8,9 or 10 each the compounds of structure formula I as each described method of claim 44 to 49.

51, method as claimed in claim 44 is characterized in that basically as above-mentioned illustrated.

52, structure formula III, (XX VIII) is characterized in that to the compound of (XXX IX) and (X LI) the various substituting groups of described compound have the identical meaning of aforementioned claim.