DD289920A5 - INSECTICIDES, ACARICIDES OR NEMOTOCIDES COMPOSITION - Google Patents

Abstract

The invention relates to insecticidal, acaricidal or nematocidal compositions which contain as active ingredients substituted 1-arylpyrrole compounds of the formula (I) and whose substituents have the following preferred meanings:

Description

(D,

in which mean

X is halogen, cyano, cyanato, thiocyanato, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, haloalkylcarbonyl, alkenylthio, alkenylsulfinyl, alkenylsulfonyl, haloalkenylthio, haloalkenylsulfinyl, haloalkenylsulfonyl, haloalkylthiocarbonyl, phenylthio, phenylsulfinyl, phenylsulfonyl, heteroarylthio Heteroarylsulfinyl or Hetenarylsulfonyl, wherein the phenyl groups are optionally substituted by halogen, cyano or haloalkyl groups, dio heteroaryl groups are five- or six-membered monocyclicu rings having one or two selected from oxygen, sulfur and nitrogen heteroatoms and agi. are substituted with halogen, nitro, cyano or haloalkyl groups, and the alkyl, haloalkyl, alkenyl, haloalkenyl, alkoxy and haloalkoxy groups listed above are straight-chain or branched and have 1 ', s 10 and preferably less than 5 carbon atoms, wherein the halogen substitution in all of the aforementioned groups is one or more identical or different halogen atoms and monosubstitution may be present until complete polysubstitution; R ', R ² and R ^{3 are} independently the same as defined above for X, and hydrogen or alkyl, wherein one of the substituents R ¹ , R ² and H ³ may be selected from formyl, hydroxyiminoalkylidenyl, alkoximinoalkylidenyl, azido, amino, alkylamino, dialkylamino, aralkylamines Aminocarbonylamino.Alkylcarbonylarnino, HalogenalkylcarbonylaminOiArylcarbonylamino.Alkylsulfonylamino, haloalkylsulfonylamino, Alkylaminocarbonylamino.Arylaminocarbonylamino, benzylideneimino, Alkylidonimino, alkoxyalkylideneimino, dialkylaminoalkylideneimino, bis (alkylthio) methyl, bis (arylthio) methyl, alkylthioalkylideneimino, alkoxycarbonylamino, haloalkoxycarbonylamino, phenyl which is optionally substituted with halogen, cyano or haloalkyl, and heteroaryl groups having a five- or six-membered monocyclic ring having one or more heteroatoms selected from oxygen, sulfur and nitrogen, and pgf. is substituted by halogen, nitro, cyano or haloalkyl groups,

wherein the abovementioned alkyl, haloalkyl, alkenyl, haloalkenyl, haloalkoxy and alkoxy groups are straight-chain or branched and have 1 to 10 and preferably less than 5 carbon atoms, the halogen substitution in all the abovementioned groups being composed of one or more identical or different Halogen atoms and monosubstitution may be present until complete polysubstitution; ^

Y is halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylsulfinyl, alkylsulonyl, alkylthio, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkenyl, in particular allyl, haloalkenyl, in particular haloallyl, alkynyl, in particular propargyl or haloalkynyl, in particular halopropargyl .

wherein said alkyl, alkoxy, haloalkyl and haloalkoxy groups are straight chain or branched and have from 1 to 10, preferably less than 5 carbon atoms and halogen replacement in all of these groups consists of one or more identical or different halogen atoms and mono-substitution is present until complete polysubstitution can be, or a hydrogen atom, if X is a halogen atom or a group R ⁵ S (O) _n ,

where η is 0.1 or 2 and

R ^{5 is} alkyl, haloalkyl, alkenyl or haloalkenyl and the alkyl and alkertyl carbon chains and the halogen substituent are as defined above,

R ¹ and R ³ jaweiis a hydrogen atom and

R ^{2 is} cyano, and X ¹ , X ² , X ³ and X ^{4 are} independently the same as defined above for Y or a hydrogen atom, the following conditions

present:

at least one of the substituents R ¹ , R ² and R ³ is selected from the meanings defined above for X;

if X ⁴ and X ¹ dog

X is halogen or cyano,

R ^{2 is} different from X, and

when X ⁴ and X ^{1 are} hydrogen and Y is methyl,

X does not mean bromine.

More specific orringungsgomäße pyroll compounds are compounds of formol I, in which mean

X is halogen, cyano, cyanato, thiocyanato, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, haloalkylcarbonyl, haloalkylthiocarbonyl, phonylthio, phenylsulfinyl, phenylsulfonyl, heteroarylthio, heteroarylsulfinyl or heteroarylsulfonyl, where the phenyl groups optionally with halogen , Cyano or haloalkyl groups and the heteroaryl moiety are five- or six-membered monocyclic rings and have one or two oxygen, sulfur and nitrogen-selected heteroatoms and optionally substituted with halogen, nitro, cyano or haloalkyl, wherein said alkyl, haloalkyl -, alkoxy and haloalkoxy groups are straight or branched and have 1 to 10, preferably less than 5 carbon atom!) And the halogen substitution in all these groups consists of one or more identical or different halogen atoms and Monosu bstitution to complete polysubstitution, R ', R ¹ and R ^{3 are} independently the same as defined above for X and hydrogen or alkyl, where one of the substituents R ¹ , R' and R ³ may be selected from formyl, hydroxyiminoalkylidenyl, alkoximinoalkylidenyl, Azido, amino, alkylamino, dialkylamino, aralkylamino, aminocarbonylamino, alkylcarbonylamino, haloalkylcarbonylamino, arylcarbonylamino, alkylsulfonylamino, haloalkylsulfonylamino, alkylaminocarbonylaminOfArylaminocarbonylamino, benzylidenimino, alkylidenimino, alkoxyalkylidonimino, dialkylaminoalkylidenimino, phenyl optionally substituted by halo, cyano or haloalkyl, and heteroaryl groups having one a five- or six-membered monocyclic ring which has one or two selected from oxygen, sulfur and nitrogen; And optionally substituted with halogen, nitro, cyano or haloalkyl groups, said alkyl, haloalkyl, haloalkoxy and alkoxy groups being straight or branched and having 1 to 10, preferably less than 5, carbon atoms and halogen substitution in all these groups consists of one or more identical or different halogen atoms and monosubstitution may be present until complete polysubstitution,

Y is halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylsulfinyl, alkylsulfonyl, alkylthio, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkenyl, in particular allyl, haloalkenyl, in particular haloallyl, alkynyl, in particular proparyl or halogonalkinyl, in particular halopropargyl,

wherein said alkyl, alkoxy, haloalkyl and haloalkoxy groups are straight-chain or branched and have from 1 to 10 carbon atoms and the halogen substitution in all of these groups consists of one or more identical or different halogen atoms and mono-substitution may be present until complete polysubstitution,

and X '. X ² , X ³ and X ^{4 are the} same as defined above,

where the same conditions apply as defined above.

Generally preferred compounds of the formula I which are of interest as insecticides and acaricides are compounds of the formula I in which X is a halogen atom or a group R ⁵ S (O) _n ,

where η is 0.1 or 2 and

R ^{6 is} alkyl, haloalkyl, alkenyl or haloalkenyl, R ^{1 is} a hydrogen atom, a halogen atom or alkylthio, R ^{2 is} cyano, R ^{3 is} a hydrogen atom or a halogen atom,

Y represents a hydrogen atom, a halogen atom, haloalkyl or haloalkoxy, with the proviso that Y denotes a hydrogen atom under the conditions defined above,

X ', X ² , X ³ and X ^{4 are} independently a hydrogen atom, a halogen atom, C _1-3 -alkyl, C |. ₃ -alkoxy cdei C _1-3 -alkylthio. More specific compounds of the general formula I, which are preferred and of particular interest, are the following compounds: (A) compounds of the formula II which have high insecticidal activity,

(II)

in which: R ⁵ S (O) _n ,

where η is 0.1 or 2

R ^{5 is} CH ₃ , CF ₃ , CF ₂ Cl, CFCl ₂ , CF ₂ Br, CHF ₂ , CHCl ₂ or CHCIF, R ^{1 is} H, F, Cl or Br, R ^{3 is} H, F, Cl or Br, X ¹ H or Cl

and Y is CF ₃ or CF ₃ O.

Of these compounds, the following compounds are preferred:

1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- {trifluoromethylthio) pyrrole; 1- (2,6-dichloro-4-trifluormnthylphonyl) -2-chloro-3-cyano-4- (trifluor8ulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4 - ((iichlorofluoromethylthio) -pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3 cyano-4- (dichlorofluoromethylsulfinyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylsulfonyl) -pyrrole; 1- (2, e-dichloro) -pyrrole; 4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (chlorodifluoromethylsulfonyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (chlorodifluoromethylsulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (chlorodifluoromethylthio) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3- cyano-4- (trifluoro-ethylsufinyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (trifluoromethylsulfonyl) -pyrrole; 1- (2,6-dichloro-4 -trifluoromethylphenyl) -2-bromo-3-cyano-4- (dichlorofluoromethylthio) -pyriol; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (dichloro (luoromethylsulforiyl) - pyrrole:

1- (2,6-dichloro-4-trifluorrnethylphenyl) -2-bromo-3-cyano-4- (dichlorfluormethylsulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (chlorodifluoromethylthio pyrrole!;

1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (chlordifluormethyisulfinyi) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorfluormethylsulfonyl) -5-bromopyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyanü-4- (chlordifluormethylsulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (dichlorfluormethylsulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (dichlorfluorniflthylsulfonyl) pyrrole; 1- (2-chloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorfluormethylsulfonyi) -pyrrcl; 1- (2-chloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylsulfinyl) pyrrole; 1- (2-chloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (dichlorfluormethylsulfony!) - pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylthio) -5-methylthiopyrroi; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (bromdifluormethylthio) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (bromdiiiuormethylsulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (bromdifluormethylsulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (methylsulfinyl) -pyrrole and 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3- cyano-4- (methylsulfonyl) pyrrole.

(B) Other compounds having high insecticidal activity are those compounds of the formula II in which: XR ⁶ S (O) _n ,

where η is 0.1 or 2 and

R ^{5 is} CH ₃ , CF ₃ , CF ₂ Cl or CFCl ₂ , R ^{1 is} H, F, Cl, Br or NH ₂ , R ^{2 is} cyano,

R ^{3 is} H, F, Cl, Br, CF ₃ or CN, X 'H or Cl

Y CF ₃ or CF ₃ O.

Of these compounds, the following are even more preferable: 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (trifluoromethylsulfonyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (trifluoromethylsulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfinyl-5-bromopyrrole; 1- (2,6-dichloro-4-trifluorrnethylphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfonyl-5-bromopyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylthio) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-trifluoromethylthio-4-cyano-5-chloropyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2 - [(trifluoromethyl) carbonylamino] -3-trifluoromethylthio-4-cyano-5-chloropyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2- (methylcarbonylamino) -3-trifluoromethylthio-4-cyano-5-chloropyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-chlOipyrrol; 1- (2-chloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5chlorpyrrol; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-dichlorofluoromethylthio-4-cyano-5-chloropyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2,4-bis (trifluoromethylthio) -3-cyano-5-aminopyrrole; 1- (2,8-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-bromopyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrro '; 1- (4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-bromopyrrole; 1- (2-chloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-bromopyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylthio) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorfluormethylsulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorfluormethylsulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluormothylphenyl) -3-cyano-4- (dichlorofluoromethylthio) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-cyano-4- (dichlorofluoromethylsulfinyl) -pyrrole and 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (trifluoromethylsulfonyl) pyrrole.

(C) Compounds having surprisingly high acaricidal activity are compounds of the formula I in which

X is a halogen atom or a group R ⁶ S (O) _n , where η is 0.1 or 2

and R ^{5 is} alkyl, preferably C ₁ -alkyl, haloalkyl, preferably trihalomethyl, wherein the halogen atoms are F, Cl, Br or

Combinations thereof are, for. B. CF ₃ , CCI ₃ , CF ₂ CI, CFCI ₂ or CF ₂ Br, alkenyl or haloalkenyl, R 'and R ^{3 are} each a hydrogen atom, R ² cyano,

Y is a hydrogen atom or a halogen atom, preferably Cl or Br and

X ¹ , X ² , X ³ and X ^{4 are} independently hydrogen, halogen, C 1-3 -alkyl, C 1 -alkoxy or C 1. _3- alkylthio, wherein X ¹ and X ^{4 are} preferably

independently H, F, Cl, Br or CH ₃ and X ² and X ^{3 are} each hydrogen. Of these compounds, the following are more preferable: iM-bromo ^ .e-dichlorophenyO-S-cyano ^ -chlorodifluoromethylthiol-pyrrole; iM-bromo ^ e-dichlorphonyll-S-cyano ^ -ltrifluormothylthioJ-pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chlorodifluoromethylthio) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chlorodifluoromethylsulfinyl) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichlorofluoromethylthio) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichlorfluormethylsulfinyi) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichlorfluormethylsulfonyl) pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (dichlorofluoromethylthio) pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (dichlorfluormethylsulfinyl) pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (dichlorfluormethylsulfonyl) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trifluoromethylthio) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trifluoromethylsulfinyl) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trifluoromethylsulfonyl) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trichloromethylthio) pyrrole; 1- (2,4-dichlorophenyl) -3-cyano-4- (dichlorofluoromethylthio) pyrrole; 1- (2,4,6-trichloro-1-yl-cyano-1-chloropyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chlorodifluoromethylsulfonyl) -pyrrole; 1- (2,6- Dichlorophenyl) -3-cyano-4- (dichlorofluoromethylthio) -pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (trifluoromethylsulfinyl) -pyirole; 1- (4-bromo-2, 6-dichlorophenyl) -3-cyano-4- (trifluoromethylsulfonyl) -pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (chlorodifluoromethylsulfinyl) -pyrrole; 1- (4-bromo 2,6-dichlorophenyl) -3-cyano-4- (chlorodifluoromethylsulfonyl) -pyrrole; 1- (4-bromo-2,6-dimethylphenyl) -3-cya.-io-4- (trifluoromethylsulfinyl) -pyrrole; 1- (4-Bromo-2,6-dimethylphenyl) -3-cyano-4- (trifluoromethylsulfonyl) -pyrrole and 1- (4-bromo-2,6-difluorophenyl) -3-cyano-4- (dichlorofluoromethylthio) -pyrrole.

(D) Further preferred compounds according to the invention are compounds of the formula I in which R 'is a hydrogen atom or a halogen atom, such as chlorine or bromine, R ^{2 is} cyano,

X is haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl, preferably CF ₃ S (O) _n , in which η is 0.1 or 2, X 'and X ^{4 are} each hydrogen substituent, X ² and X ^{3 are} each hydrogen

Y is haloalkyl or haloalkoxy.

The compounds of general formula I can be prepared by the application or adaptation of known methods as used in the prior art or described in the chemical literature; These methods are generally based on the fact that first the pyrrole ring is formed, followed, if necessary, subsequently replaced substituents. In this context, it should also be noted that in the following description of the procedures of the invention, the introduction of the various groups on the pyrrole ring can also be carried out in a different order, as well as that suitable protective groups may be required, as is familiar to the expert. Compounds of the general formula I can also be converted into other compounds of the general formula I by processes known per se. Furthermore, if substituent designations are not specifically defined in the following description of the methods of the invention, it will be understood that the first definition of the subject substituent given above is valid. Protection with protecting groups means the conversion to a corresponding non-reactive group from which, if desired, the protected group can be released again; furthermore, it also means the addition of groups, by means of which the corresponding functionality becomes nonreactive. Unless defined otherwise, the substituent definition amino refers to an unsubstituted amino group.

The invention also relates to specific intermediate compounds which are advantageously suitable for the preparation of certain end products. Such preferred intermediates, the preparation of which is explained below, have the formula IIIa.

-CT

NH ..

(IIIa)

in which: Y is H, Cl, Br, CF ₃ or CF ₃ O and X ¹ and X ^{4 are} independently H, Cl, F, CH ₃ or CH ₃ S, with the proviso that when X ¹ and X ^{4 are} each H mean Y does not represent H or Cl. The compounds which are excluded by the above disclalmors are not part of the subject of the invention, but are nevertheless well suited for the preparation of compounds according to the invention of formol I.

Particularly suitable intermediates are compounds of formol IIIa, in which Y is CF ₃ or CF ₃ O, X 'is H or Cl and X ^{4 is} Cl.

Method 1

The compounds of the formula I in which R 'and R ^{2 are} hydrogen, X is a cyarro group and R ^{3 is} an amino group (NH ₂ ) and X ¹ X ² , X ³ and X ⁴ and Y is the same as defined above for formula I in general , ie the precursors of formol III,

H Ii - ^CN

- _N

_X 2_ [1 JI _X 3

can be prepared from corresponding Dicyanopropinderivaten of formula IV,

NH-CH = C-CH ₂ -CN. ^ CN

X ³

(IV)

in which the corresponding substituents are as defined above, by reaction with a basic agent, preferably an alkaline agent such as a tertiary amine or an alkali metal hydroxide or carbonate. The reaction is advantageously carried out at a temperature between -80 and 15O ⁰ C and preferably at a temperature of 40 to 100 ⁰ C. In this case, solvents, such as liquid alcohols, Kohlenv asserstoffe, halogenated hydrocarbons, ethers, ketones, amides such as N-methylpyrrolidone or about water, have been used.

Method 2

The compounds of the formula IV can be prepared from an aniline derivative of the formula V,

in which X ¹ , X ² , X ³ , X ⁴ and Y have the same meaning as generally defined by reaction with formyl succinonitrile or an alkali metal salt of formyl succinonitrile. This reaction is generally carried out in an organic solvent or in water at a temperature between 10 and 120 ° C and preferably at the reflux temperature of the reaction system.

Formylsuccinonitrile is a known compound which can generally be prepared by acidification of its alkali metal salt, which in turn is obtained by reacting succinonitrile with a lower alkyl formate in the presence of an alkaline agent (see K.Gewald, Z. Chem.1 [1961] 349).

Method 3

The compounds of the general formula I in which X is halogen, R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} hydrogen, the other substituents corresponding to the above general definition can be prepared by treating compounds of the general formula III with halogenating agents, such as sulfuryl chloride, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, pyridinium bromide perbromide or molecular fluorine, bromine or iodine. Suitable organic solvents for these transformations are z. For example, dichloromethane and acetonitrile. The reactions are carried out at a temperature between -80 and + 8O ⁰ C and preferably between -30 and +25 ⁰ C. It may be advantageous to protect the amino groups during the treatment with elemental fluorine as trifluoroacetamide derivatives.

Method 4

A) The compounds of the general formula I in which X is cyano, R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} hydrogen and the other substituents correspond to the above general definition can be selected from the corresponding compounds in whose formula X is a group C = NOH is prepared by Wasserabspaitung with agents such as acetic anhydride, cyanuric chloride, P ₂ O ₆ and the like. When using certain such dehydrating agents, it may be necessary to protect the amino groups with a suitable protecting group.

B) The above intermediate membrane, in which formol X olno group C = NOH, may be obtained by condonation of hydroxylamine with the precursors of preconcone, in dorone Formol X Formyl-Buteutot.

C) vorο Intermediates in which formol X is a formyl group, d. H. the compounds dor Formol Vl, by hydrolysis of the corresponding compounds, in dorone formol X olno Dis (alkylthlo) nielhyl odor bis (arylthio) methyl group, or by treatment nilthyl alkyl nitrite and subsequent Hydrolyso horgostollt be (see E. Fujita, K. lchikiwa and K. Fuji, Tetrahedron Lottors 1978, 5661). Protection of the amino function with an ooror gooignone protecting group may be required in the reaction with alkyl nitrite.

D) The intermediate compounds of the general formula I, in which X is bis (alkylthio) -mothyl or bis (arylthio) -mothyl bodoutot, where the other groups correspond to the obigon definition, can be prepared by reversing oinor preconnection of formula III with oinom tris (alkylthio) -methane or tris (arylthio) -mothan in the presence of a Lowissäuro, preferably oinom SuKoniumsalz such as dimothyl (methylthio) -sulfoniumtetrafluorborat, hergostollt wordon. Allgomolno conditions for such transformations are described in the literature (Synthesis 1984, 166).

Method 5

A) Suitable Zwiechonvorbindungen of the general formula I, in which X is hydroxy, R 'is optionally protected amino group, R ^{J is} a cyano group and R ^{1 is} a hydrogen atom and X', X ² , X ³ , X * and Y of the above general DofiniOon from the corresponding compounds in which formula X denotes halogone, may be prepared by conversion into a Grignard reagent or a lithium derivative by standard method and subsequent treatments with oxodiperoxymolybdenum (pyridine) (hoxamethylphosphortriamide) (MoOPH) following preparations similar to those described in the literature (NJ Lewis et al., J. Org. Chem. 42 (1977) 1479). In this case, it may be necessary to convert the cyano group in the formula of the orthogonal compound into a corresponding protected derivative (for example an oxazoline derivative of the corresponding compound in which the cyano group has been hydrolyzed to a carboxyl group) before the generation of the Grignard Reagons odor of the lithium derivative is made. Alternatively, the Grignard reagent or lithium derivative described above may also be reacted with oxy-tri-alkyl borate, followed by nine oxidation with hydrogen peroxide following an ancestor analogous to procedures described in the literature (MF Hawthorne, J. Org. Chom [1957] 1001, and RW Hoffmann and K.Ditrich, Synthesis 1983, 107, respectively).

B) The Vorbindungen of the general formula I, in which X is cyanato, R 'amino, R ^{2 is} cyano and R ^{3 is} a hydrogen atom and X ¹ , X ² , X ³ , X ⁴ and Y correspond to the above general definition can, from the corresponding precursor, in which formula X is hydroxy, R 'oino may be protected amino and R ^{3 is} hydrogen and X ¹ , X ^J , X ³ , X ⁴ and Y are as defined above, by treatment with cyanogen halogonidone in the presence of oinor base be prepared by similar methods, as they are in the literature boschriebon (D. Martin and M. Bauor, Org. Synth. 61,35), followed, if necessary, followed by cleavage of protective groups.

C) The compounds of the general formula I in which X is alkoxy, R 'is amino, R' is cyano and R ^{3 is} hydrogen and X ', X ² , X ³ , X ⁴ and Y have the general definition given above can be obtained from corresponding compounds in which X is hydroxyl, R 'is an optionally protected amino group and R ^{3 is} a hydrogen atom and X', X ² , X ³ , X ⁴ and Y are as defined above, by treatment with an alkyl halide, alkylsulfonate, Dialkyl sulfate and the like., Optionally in the presence of a base in a solvent such as acetone or dimethylformamide at einor temperature between 25 ⁰ C and the reflux temperature of the solvent sowio if necessary downstream Schutzgrupponabspaltung be prepared.

D) The compounds of the general formula I in which X is halogenoalkoxy, R 'is amino, R ^{2 is} cyano and R ^{3 is} a hydrogen atom and X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, can be derived from corresponding compounds in which X is hydroxyl, R ^{1 is} a possibly protected amino group and R ^{3 is} a hydrogen atom and X ', X ² , X ³ , X ⁴ and Y are as defined above, prepared by various haloalkylation processes, as described in the literature (Syntheses of Fluoroorganic Compounds, ILKnunyants, and GG Yakobson, Eds .; Springer-Verlag, Berlin, 1985, pp. 263-269) followed, if necessary, by a deprotection step.

Method 6

The compounds of the general formula I in which X is a haloalkyl group, R 'is an amino group, R ^{2 is} a cyano group and R ^{3 is} a hydrogen atom and X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, can be selected from the corresponding compounds are prepared in the formula X is a formyl group, a carboxyl function or halogen, wherein the amino group is optionally protected. So z. B. The treatment of the formyl compounds with diethylaminosulphur trifluoride analogous to a method described in the literature (WJ Middleton, J. Org. Chem. 40, [1975], 574) compounds of general formula I in which X represents a difluoromethyl group, the remaining Substituents are as defined above. The oxidation of the above-mentioned intermediate compounds of the general formula I in which X is formyl with oxidizing agents such as chromium trioxide in sulfuric acid (Jones reagent) leads to intermediate compounds of the general formula I in which X is a carboxylic acid function, R 'is amino, R ^{2 is} cyano and R ^{3 represents} a hydrogen atom and X ¹ , X ² , X ³ , X ⁴ and Y are as defined above. It may be advantageous to protect the amino function during such oxidation reactions, for example as Trifliioracotamid derivative. Reaction of the above compounds, in which formula X represents a carboxyl group, with sulfur tetrafluoride as described in the literature (GA Boswell et al., Org. React. 21 (1974) 1-124) leads to compounds in whose formula X. a trifluoromethyl group, the remaining groups being as defined above. Alternatively, the compounds of general Fc ' ^! ir X is trifluoromethyl, R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} hydrogen and X ¹ , X ² , X ³ , X ⁴ and Y correspond to the above general definition, also from compounds of the general formula I in which X is halogen, preferably iodine, when jutet and the remaining substituents are as defined above, by reaction with trifluoromethyl copper under conditions similar to those described in the literature (DJ Burton and DM Wiemers, J. Am. Chem. Soc. 108 [1986] 832) become.

Methodo 7

Dio Vorbindungon dor allgomoinon Formol I, in which X Brommothyl or Chlorormothyl, R 'Amino, H ^! Cyano and R ¹ in the hydrogen atom and X ¹ , X ¹ , X ³ , X ⁴ and Y of the general definition above are available by treatment of the corresponding intermediate compound, in which formol X is Mothyl bodoutot and boi (ionone dio amino group) is protected , with N-bromosuccinimide or N-chlorosuccinimide in solvents, carbon tetrachloride boor tomporaturone between O ¹ C and the reflux tendency of the solvent accessible Dio obigon Vorbindungon, in doron Formol X Mothyl bodoutot, can be obtained from donwishon binding dor allgomoinon Formol I, Inor X. Formyl, wherein the other substituent ions are either dofiniorto, by nufoinandorfolgondo treatment with p-toluenesulphonylhydrazine and sodium cyanoborohydride similar to that in the literature boschriobunon Vorfnhron horgostollt wordon (J. Am. Chom. Soc., 93 (1971) 1793).

Method 8

A) Dio-preconcentration of nalcoinoinone of formula I, in which X is halo-nylcarbonyl, R * is amino, R ^{2 is} cynioio and R ³ is wossorsloffatom bodouton and X ¹ , X ² , X ³ , X ⁴ and Y is doroborn allgomoinone Dofinition ontsprechon, ie the precursor ion Formol VIII may be prepared by adding an analogous preparation of formol Vl, in which the amino group may be grafted with oinom halogonalkylmotalic dorivate to give precombinone formol VII, in which haloalkylcarbinol moiety is bottoutot, and subsequently oxidation to oinomide in boron boschriobonon ancestor (RJ Lindorman and DM Graves, Totrohodron Lottors 28 (1987) 4259) and orfordorlichonfolls anschlioßondo protective group cleavage horgostollt wordon. Gooignote Halogonalkylmetalldorivato are boisplolswoiso Porfluoralkyllithk'mdorivdto, according to PGGassman and NJO'Reilly, J. Org. Chom. 52 (1987) 2481-2490), or trimethyltrifluoromethylsilane prepared according to GA Olahot et al., J. Am. Chom. Soc. \ 11 (1989) 393 and oingosotzt. Litorature to further Halogonalkylmetalldorivaten is in diosor publication ebonfalls nngogobon. At Bolspiol, prewear of trimethyltrifluoromethylsilone can be explained by the ancestor wio follows wordon:

CN

(CHJ ₁ SlCF ₁

(VI) (Vila) (VIIIa)

B) The precursors of formol VIII can be converted to compounds of general formula I by treatment with 2,4-bis (4-mothoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawessons's reagent) in which X is haloalkylthiocarbonyl, R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} a hydrogen atom and X ¹ , X ² , X ³ , X ⁴ and Y are each generally in accordance with the general definition.

Method 9

The compounds of formula VIII can be converted to other compounds of allgomoinone formol I by treatment with halonating solvents such as thionyl chloride or hydrogen bromide, in which X represents a halo-alkyl-α-halomethyl group. In this case, it may be advantageous to protect the amino function, for example in the form of the corresponding trifluoroacetamide derivative, in order to prevent halogenation of the pyrrole ring as a result of such halogenation reaction.

Method 10

A) The compounds of the general formula I in which X is thiocyanato, R ^{1 is} amino, R ^{2 is} cyano and R ³ is hydrogen and X ', X ² , X ³ , X ⁴ and Y correspond to the above general definition, can be obtained by treatment .g of compounds of formula III with compounds of the formol MSCN, in which M oin alkali metal, are prepared in the presence of bromine in a solvent such as methanol.

B) Dir compounds of the general formula I, in which X is alkylthio, haloalkylthio, alkynylthio, haloalkonylthio, phonylthio or heteroarylthio, R ¹ , amino, R ^{2 is} cyano and R ^{3 is} a hydrogen atom and X ¹ , X ² , X ³ , X ⁴ and Y are as defined above and wherein the phenyl and heteroaryl groups are supported and substituted as described above, ie the compounds of formula IX can be prepared by reacting a compound of formula III with a sulfenyl halide of the formula RSHaI in which R is alkyl, Haloalkyl, alkenyl, haloalkenyl, phenyl or heteroaryl as defined above and Hal represents a halogen atom, are prepared in a liquid reaction medium.

Preferably, a organischos solvent, for example Dichlormothan, at a temperature in the range of -100 to + 100 ° C and preferably -80 to +25 ⁰ C is used. This reaction may optionally be carried out in the presence of an acid acceptor such as a tertiary amine, for example pyridine. The alkylsulfonyl chlorides can be prepared by a method known from the literature (S. Thea and G. Cosco, Tetrahedron Letters, 1988, 2865). If a sulfenyl chloride is used, the process can be illustrated by the following equation:

RSCl

(ΠΙ)

(IX)

methods

The compounds of the general formula I in which X is thiocynnato, R 'is amino, R'jCyano and R ^{3 is} a hydrogen atom and X', X ² , X ³ , X * and Y are as defined above, can furthermore be obtained by treatment with a base such as sodium hydroxide or potassium hydroxide in the presence of an alkyl halide, dialkyl sulfate or the like in a solvent has been converted into compounds of general formula I in which X is alkylthio, R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} a hydrogen atom bodouton and X ¹ , X ² , X ^J , X * and Y correspond to the above general definition.

Method 12

The compounds of formol IX may be oxidized to compounds of formol X in which X is a group RS (C) _n , where η is 1 or 2 and R is dofiniort as above. To the vulnerable oxidizing agents include hydrogen peroxide, Peroxyessigsäuro, trifluoroperoxyacetic acid and m-Poroxybonzoesäuro in solvents such as Dlchlormothan, acetic acid or Trifluoress'psäuro at temperatures between --40 and +80 ⁰ C and preferably 0 to 25 ° C. The respective roughening conditions used, ie temperature, reaction time and amount of the oxidizing agent, can be varied as desired to give the sulfinyl derivatives (n = 1) or the sulfonyl dorivato (n = 2). It is also possible to prepare the sulfonyl derivatives from the corresponding Sulfinylvorbindungen, as the Fachman η is familiar. In the case of certain Halogonalkylthiogrørror, for example, trifluoromethylthio, it may also be beneficial to protect the amino function, for example in the form of the corresponding trifluoroacotamide derivative. For example, when trifluoropor oxyacetic acid is selected as the oxidizing agent, the process can be illustrated by the following equation:

R-S

CF ₃ CO ₃ H -

CN

-X ⁴ X ³

(VII)

(X)

Method 13

The compounds of the general formula I wherein R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} halogen and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, can be prepared by treating compounds of the general formula Formula I wherein R 'is amino, R ^{1 is} cyano and R ^{3 is} hydrogen and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, ie compounds of formula XI, with malogenating agents among similar ones Conditions are prepared as described above under Method 3. The conversion taking place in this way can generally be represented as follows:

Hai = halogen

(XI)

(XII)

Method 14

The compounds of the general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} bis (alkylthio) methyl or bis (arylthio) methyl and X, X ¹ , X ² , X ³ , X ⁴ and Y are not general definition can, by reacting a compound of formula Xl with a tris (alkylthio) -methane or tris (arylthio) -mothan of the formula (RaS) ₃ CH in the presence of a Lewis acid, preferably a sulfonium salt, in a solvent at a Temperature between O ⁰ C and the reflux temperature of the solvent, if necessary, in the presence of an acid acceptor, such as pyridine, are prepared. According to one

More preferably, acetonitrile is used as solvent at 25 ¹ C together with tris (methylthio) -methane as tris (alkylthio) -methane and ülmethyKmethylthioJ-sulfonium tetrafluoroborate as Lewis acid without acid acceptor. The method generally illustrates Rieh as follows:

CN

(RaS) ₁ CH

X

CN

H ₂ NU. JL-CH (Ras),

(XIII)

MethodeiS

Suitable intermediate compounds of general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} formyl and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, ie compounds of formula XIV by hydrolysis of compounds of the formula XIII or by treatment with alkyl nitrites under similar reaction conditions as described above under Method 4 C). This procedure can be generally illustrated as follows:

(XIII)

Method 16

The intermediates of the general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} hydroxyiminoalkylidenyl or alkoxyiminoalkylidenyl and X, X ', X ² , X ³ , X ⁴ and Y are as defined above, which are advantageous intermediates, may represent by condensation of a compound of general formula ¹ 1, in which R 'is amino, R ^{2 is} cyano and R ^{3 is} alkylcarbonyl and X, X ¹ , X ² , X ³ , X ⁴ and Y of the general definition f above, with hydroxylamine or an O-alkylhydroxylamine or their acid addition salts in a solvent such as ethanol. The above compounds in which R ^{3 represents} alkylcarbonyl are prepared in the same manner as the compounds of formula XIV except that the starting material is 1,1,1-tris (alkylthio) alkane or 1,1, 1-Tris (arvlthio) -alkar) is used.

Method 17

The compounds of the formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} amino and X, X ', X ² , X ³ , X ⁴ and Y are as defined above, which are favorable intermediates, may be prepared by reduction the corresponding compounds in the formula R ^{3 is} nitro, for example, with hydrogen in the presence of a noble metal catalyst, such as platinum or palladium, oddr produced with hydrazine and Raney nickel. In the presence of certain combinations of substituents R ² and X, the compounds of formula I wherein R ¹ and R ^{2 are} both amino, have limited stability and require the protection of one of the amino groups with a suitable protecting group. The compounds of the general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} nitro and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, can in turn be prepared by nitration of Compounds of formula Xl can be prepared by the action of nitric acid and sulfuric acid or nitric acid in acetanhydrate or other nitrating agent. In addition, for certain nitration reactions it may be advantageous to protect the amino function of the compounds of formula XI with a suitable protecting group, such as acetyl or trifluoroacetyl.

Method 18

Various derivatives of compounds of the formula XV which are suitable as cheap intermediates

= Amino group suitably protected

(XV)

can be made as follows:

A) The compounds of the general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} alkylamino and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, can be prepared from the corresponding compounds in which formula λ ^{1 represents} amino, the remaining substituents being as defined above, by alkylation with alkyl or aralkyl halides or sulfonates in organic solvents such as ethanol, acetonitrile, toluene and the like. The formation of mono-odor dialkylated products can be controlled by appropriate choice of the stoichiometric ratios or the reaction conditions. Alternatively, when monoalkylamino products are desired, other methods such as the conversion of the amino group to an alkoxyalkylidene-imino group by treatment with an orthoester and subsequent reduction may also be employed. If the desired end products R 'are contained in the form of an unsubstituted amino group, it may be necessary to protect the amino group with such a suitable protective group before such treatment. In such cases, the compound of general formula I in which R ^{3 is} amino and R ^{1 is} a suitably protected amino group and the remaining substituents are as defined above, ie the compound of formula XV, prepared and used as a reactant. The protecting group is normally applied to the compounds of formula XI prior to reduction of the nitro groups (see Method 17). Depending on the subsequent desired conversion of the amino group in the position R ³ , various protective groups can be selected, as can be seen from the following examples.

B) The compounds of the general formula I, in which R 'is amino, R ^{2 is} cyano and R ^{3 is} aminocarbonylamino and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, can be prepared from compounds of the formula XV can be prepared by treatment with phosgene and then with ammonia and subsequent Schutzgruppeonspspaltung.

C) The compounds of general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} alkylcarbonylamino, haloalkylcarbonyl-amino or arylcarbonylamino and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above , can be prepared by reacting a compound of formula XV with acid chlorides of the formula R ^b (C =O) Cl or acid anhydrides of formula R ^b ((C =L)) J ₂ O, in which R ^{b is} an alkyl, haloalkyl or aryl group , as defined above for formula I in general meaning and downstream deprotection can be made. Thereby, solvents such as acetonitrile and acid acceptor such as pyridine can be used under suitable conditions.

D) Similarly, the compounds of the general formula I in which R ^{3 is} amino, R ^{2 is} cyano and R ^{3 is} alkylsulfonylamino or halosulfonylamino and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above , are prepared from compounds having a protected amino group of formol XV by reaction with alkyl or halosulfonyl halides or sulfonic anhydrides under suitable reaction conditions and subsequent deprotection. Suitable protecting groups useful in these reactions are, for example, alkoxyalkylidene-imino groups obtainable by treatment of the amino compound with a corresponding alkyl orthoformate. The deprotection procedures for such groups typically include aqueous hydrolysis.

E) The compounds of the general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} alkylaminocarbonylamino or arylaminocarbonylamino and X, X ', X ² , X ³ , X ⁴ and Y corresponds to the above general definition can be selected from a suitably amino protected compound of formula XV by reaction with an alkyl or aryl isocyanate in which the alkyl or aryl groups conform to the above general definition and subsequent deprotection. Suitable reaction conditions for forming corresponding urea compounds are described in the literature (J.March in Advanced Organic Chemistry, McGraw-Hill Publ. [1985), 802, with further references). Suitable amino protecting groups for such reactions include alkoxyalkylidenimino groups, their cleavage as described above.

F) The compounds of the general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} alkoxycarbonylamino or haloalkoxycarbonylamino and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, may be prepared from in suitably aminogo-protected compounds of formula XV by reaction with an alkyl chloroformate or haloalkyl chloroformate and subsequent Schutzgruppenabspaltung be annealed.

G) The compounds of the general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} alkylidenimino or ßenzylidenimino and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, can be obtained by condensation a suitably catalytically protected compound of formula XV having an alkyl aldehyde or an aryl aldehyde in which the alkyl or aryl groups conform to the above general definition and subsequent deprotection. Suitable reaction conditions for generating corresponding Schiff bases can be selected according to literature data for the condensation step (compare J. March, ibid., 1165, with further references). Examples of suitable amino protecting groups are acetyl and trifluoroacetyl; deprotection can be carried out by alkaline hydrolysis or other methods described in the literature (see TW Greene in Protective Groups in Organic Synthesis, J.Wiley Publ. 1981,254, with further references).

H) The compounds of general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} alkoxyalkylidenimino, and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, can be selected from a corresponding amino-protected compound of formula XV can be prepared by condensation with an alkyl orthooster and subsequent deprotection. Suitable protecting groups are, for example, the amide derivatives or carbamate derivatives (compare TWGreene, ibid., 223 and 249).

I) The compounds of general formula I in which R 'is amino, R ^{2 is} cyano and R ^{3 is} dialkylaminoalkylidenimino and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, can be prepared by reacting a compound of formula XV with a dialkyl acetal derivative of a Ν, Ν-dialkylformamide (see TWGreence, ibid., 275) and subsequent deprotection. Alternatively, the reaction of the compound of formula XV with an N, N-dialkylformamide in the presence of an agent such as phosphorus oxychloride under Vilsmeier conditions is possible. Suitable protecting groups for this are the amide derivatives and carbamate derivatives.

J) The compounds of the general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} alkylthioalkylidenimino and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, can be prepared by reacting a compound of formula XV with a tris (alkylthio) -methane in pyridine as solvent, optionally in the presence of a suitable catalyst, for example dimethylmethylthiosulfonium tetrafluoroborate.

K) Dio compounds of the general formula I in which R ^{1 is} amino, II 'cyano and R ^{3 is} azido and X ₁ X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, can be prepared by reacting a compound of formula XV with p-toluenesulfonylazicl under conditions described in the literature (J. March, ibid., 673, with further references) and subsequent deprotection. Alternatively, the compounds listed above, in whose formula R ^{3 is} azido, can also be prepared from compounds of the formula XV by conversion of the amino group into a diazonium salt and subsequent reduction to a hydrazlnogroup and subsequent treatment with nitrous acid. echonden AzId and deprotection can be produced.

Method 19

A) Compounds of the general formula I in which R ^{1 is} amino, H ^{2 is} cyano and R ^{3 is} substituted phenyl or heteroaryl according to the above general definition, and X, X ', X ² , X ³ , X ⁴ and Y of the above general According to definition, which are favorable intermediates, can be prepared from compounds of formula XI in which the amino group is optionally protected with a suitable protecting group by treatment with a suitably substituted phenyl or heteroaryldiazonium salt under the conditions of the Gomberg-Bachmann reaction (see M.Swainsbury, Tetrahedron 36 [1980] 3327-3359, with further references).

B) Alternatively, the intermediate compounds of the general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} substituted phenyl or homoaryro according to the above general definition and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, from compounds of formula XII whose amino group is optionally protected with a suitable protecting group, by treatment with an appropriately substituted phenyl or heteroaryl halide, preferably a bromide or iodide, in the presence of copper under the conditions of the Ullmann reaction (see M. Sainsbury, ibid.).

C) Alternatively, the intermediate compounds of the general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} substituted phenyl or heteroaryl according to the above general definition and X, X ¹ , X ² , X ³ , X ⁴ and Y conforming to the generally defined definition of compounds of formol XII, preferably a bromide or iodide, by treatment with a suitably substituted phenyl or heteroaryl boronic acid in the presence of metallic palladium under conditions similar to those described in the literature (cf. V. Snieckus et al., Tetrahedron Letters 29 [1988]) 2135, with further references).

Method 20

The compounds of the general formula I in which R ^{1 is} amino and R ² and R ^{3 are} cyano and X, X ¹ , X ', X ³ , X ⁴ and Y correspond to the above general definition can be prepared from the compounds of the general formula I in which R ^{3 is} hydroxyiminomethylidenyl or alkoximinomethylidenyl (see Method 16) by dehydration according to the methods described under Method 4 (A).

Method 21

The compounds of the general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} halo-enalkylcarbonyl or Hdlogenalkylthiocarbonyl and X, X ¹ , X ² , X ³ , X ⁴ and Y correspond to the above general definition may optionally from Amine-protected compounds of formula XIV are prepared according to the method described in Method 8 and, if necessary, subsequent deprotection.

Method 22

A) The compounds of the general formula I, in which R 'is amino, R ^{2 is} cyano and R ^{3 is} haloalkyl and X, X', X ² , X ³ , X ⁴ and Y are as defined above, can be prepared from compounds of the formula XII or XIV, in which the amino group is optionally protected, according to methods as described in the methods β, 7 and 8, and if necessary subsequent deprotection can be prepared.

B) The compounds of the general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} alkyl and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, can be prepared from compounds of the formula XIV, whose amino group gg / s. is protected by reaction with a derived from an alkyl halide Grignard reagent or an alkyllithium to give the corresponding carbinol and subsequent dehydration to a compound in the formula R ³ alkenyl, and final reduction are prepared. The compounds of the general formula i in which R ^{3 is} methyl, the remaining substituents being as defined above, can be prepared from compounds of the formula XIV by the method described under Method 7.

Method 23

The compounds of general formula I in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} thiocyanato, alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, phenylthio or heteroarylthio and X, X ¹ , X ² , X ³ , X ⁴ and Y of The above general definition corresponds to where constitution and / or substitution of the phenyl and heteroaryl groups likewise correspond to the above general definition, ie the compounds of the formula XVI can be prepared from compounds of the formula XI under conditions similar to those described in method 10. The overall process can be illustrated by the following equation:

(XI) (XVI)

The compounds of the formula XVI in which R is alkyl can likewise be prepared from compounds of the general formula I in which R ^{3 is} thiocyanate and the other substituents are as defined in formula XVI, by treatment with alkylhologenidone and the like. Like. Be prepared in a similar manner as described in Method 11.

Method 24

The compounds of general formula I ₁ in which R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, alkenylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenylsulfinyl, haloalkenylsulfonyl, phenylsulfinyl, phenylsulfonyl, heteroarylsulfinyl or heteroarylsulfonyl and X, X ¹ , X ² , X ³ , X ⁴ and Y correspond to the above general definition, wherein the constitution and / or substitution of the phenyl and heteroaryl groups also correspond to the above general definition, by oxidation of compounds of formula XVI in a similar manner as in Method 12 described were prepared. In cases where X represents a group RS which may undergo unwanted oxidation as a side reaction, the sulfenylation may be carried out according to the procedures given above on a compound of general formula I wherein X is halogen, preferably bromine or iodine, R ¹ Amino, R ^{2 is} cyano and R ^{3 is} hydrogen and the other substituents conform to the above general definition, followed by oxidation and treatment with an alkyllithium compound following a procedure similar to that described in the literature (see C. Kruse et al., Heterocycles 29 [1989] 79), followed by reaction with an aqueous stopping agent to give a compound of formula XVII. The compound of formula XVII can then be sulfenylated to yield compounds of formula XVIII. The Gestmtverfahren can be represented as follows:

^Hal ~]

^CN

shark

Ii I '* * _X 2_JI J_x3

HaI-H ₂ N-

"" Ν

JJ-S (O) _n R

H ₂ N-> L JJ-S (O) _n RN

(XVII)

(XVIII)

Method 25

The compounds of general formula I in which R 'is amino, R ^{2 is} cyano and R ^{3 is} cyanato, alkoxy or haloalkoxy and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, may be selected from compounds of the formula XII in which the amino group is optionally protected, in a similar manner as described in Method 5 and, if necessary, final deprotection can be prepared.

Method 26

A) The compounds of general formula I in which R ^{1 is} hydrogen and R ^{2 is} cyano and R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, ie the compounds of formula XX , from compounds of the general formula I in which R ^{1 is} amino and R ^{2 is} cyano and R ³ , X, X ', X ² , X ³ , X ⁴ and Y are as defined above, ie compounds of the formula XIX, by diazotization, preferably with an alkyl nitrite such as t-butyl nitrite in an inert solvent such as tetrahydrofuran or acetonitrile. This reaction may be at a temperature between -80 ⁰ C and the reflux temperature of the solvent are performed, preferably between O and 25 ° C.

B) The compounds of the general formula I in which R ^{1 is} halogen and R ^{2 is} cyano and R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, ie the compounds of the general invention Formula XXI can be prepared from compounds of formula XIX by diazotization with an alkyl nitrite, for example t-butyl nitrite, in the presence of a halogen atom donor such as bromoform, carbon tetrachloride, anhydrous copper di-chloride or iodine.

C) The compounds of the general formula I in which R ^{1 is} thiocyanate, alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, phenylthio or heteroarylthio and R ^{2 is} cyano and R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are the the constitution and / or substitution of the phenyl and heteroaryl groups likewise correspond to the above general definition, ie the precursors of the formula XXII can be prepared from compounds of the formula XIX by treatment with an alkyl nitrite in the presence of (SCN)] or a disulfide of the formula RSSR in which R represents alkyl, haloalkyl, alkenyl, haloalkenyl, phenyl or heteroaryl according to the above general definition. The reaction is typically carried out in a solvent such as chloroform at ⁰ ° C. with 1 to 5 equivalents of the alkylnitrite and 2 to 5 equivalents of the disulfide.

The overall procedure can be represented as follows:

(XX) RC = H

(XXI) RC = halogen

(XXII) RC = SR

Method 27

Alternatively, numerous compounds of formula XXII may be prepared from compounds of general formula XX in which R ^{3 is} amino by a method similar to that described in method 10. The conversion of the amino group into other functional groups according to the invention can then be carried out according to one of the methods described above.

Method 28

Compounds of the general formula I in which R 'is alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, alkenylsulfonyi, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenylsulfinyl, haloalkenylsulfonyl, phenylsulfinyl, phenylsulfonyl, heteroarylsulfinyl or heteroarylsulfonyl and R ^{2 is} cyano and R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y correspond to the above general definition, wherein constitution and / or substitution of the phenyl and heteroaryl groups also correspond to the above general definition, can be prepared by oxidation of compounds of formula XXII according to the method described in Method 24. If the groups X or R ³ also represent groups SR which are to be kept at the oxidation state of the sulfide can be proceeded in a similar manner as described in Method 24 to obtain the desired compounds.

Method 29

The compounds of the general formula I in which R ^{1 is} alkylamino, dialkylamino, aralkylamines), aminocarbonylamino, alkylcarbonylamino, haloalkylcarbonylamino, arylcarbonylarrino, alkylsulfonylamino, haloalkylsulfonylamino, alkylaminocarbonylamino, arylaminocarbonylamino, alkoxycarbonylamino, haloalkoxycarbonylamino, alkylidenimino, benzylidenimino, alkoxyalkylidenimino, dialkylaminoalkylidenimino, alkylthioalkylidenimino or azido and R ^{2 is} cyano and R ³ , X, X ', X ² , X ³ , X ⁴ and Y are as defined above, can be prepared from compounds of general formula XIX by methods similar to those described in Method 18.

Method 30

A) The compounds of the general formula I in which R ^{1 is} formyl and R ^? Cyano and R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y conform to the general definition above, may be prepared from compounds of general formula XIX by treatment with sodium nitrite, HC = NOH, copper sulfate and HCl analogous to that described in U.S. Pat Literature (see WF Beech, J. Chem. Soc. 1954, 1297). When R ^{3 is} an amino group in the compounds of formula XIX, a suitable protecting group may be provided. The above compounds, in which formula R ^{1 is} formyl, can be converted by standard methods of thioacetalization (see TWGreene, ibid., 130, as well as literatures therein) into corresponding compounds in whose formula R ^{1 is} bis (alkylthio) methyl or bis ( arylthio) -methyl. Alternatively, the compounds of general formula I wherein R ^{1 is} bis (alkylthio) methyl or bis (arylthio) methyl, R ^{2 is} cyano and R ^{3 is} amino and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, from compounds of general formula XX in which R ^{3 represents} amino, similar to the method described in Method 14 are prepared. The conversion of the bis (alkylthio) methyl or bis (arylthio) methyl group into a formyl group can be carried out analogously to the procedure described in Method 15. The conversion of the amino function into other functional groups according to the invention can be carried out according to one of the methods described above.

B) The compounds of the general formula I ₁ in which R ^{1 is} hydroxyiminoalkyldimethyl or alkoxyminoalkylidenyl and R ^{2 is} cyano and R ¹ , X, X ¹ , X ² , X ¹ , X ⁴ and Y are of the general general meaning, may be selected from compounds of general formula I in which R ^{1 is} alkylcarbonyl or formyl and the other substituents are as defined above, prepared by similar methods as described in Method 16. The above compounds, in which formula R 'represents alkylcarbonyl, may be protected from the corresponding compounds in which formula R ^{1 is} halogen by conversion to a Grignard reagent or a lithium derivative, the cyano group optionally being protected as explained under Method 5 and subsequent reaction with an aliphatic acid chloride or anhydride or alternatively by condensation with an aliphatic aldehyde and subsequent oxidation.

Alternatively, the compounds in which R ^{1 is} alkylcarbonyl may also be prepared from the corresponding compounds in which R 'is formyl by reaction with an alkyl Grignard reagent followed by oxidation.

C) The compounds of the general formula I in which R ¹ and R ^{2 are} cyano and R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, can be prepared from the corresponding compounds, In whose formula R ¹ represents Hydroxyimlnomethylidenyl or Alkoxlminomethylidenyl, in a similar procedure as described in Method 4A) are prepared.

D) The compounds of the general formula I in which R ^{1 is} haloalkylcarbonyl or haloalkylthiocarbonyl and R ^{2 is} cyano and R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, can be prepared from compounds of the formula general formula I wherein R * is formyl and the remaining substituents are as defined above, prepared by treatment under conditions similar to those described in Method 8.

E) The compounds of the general formula I in which R ^{1 is} haloalkyl or alkyl and R ^{2 is} cyano and R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above can be prepared from compounds of the formula general formula I in which R ^{1 is} formyl or halogen and the other substituents are as defined above, by treatment under similar conditions as described in Method 22 are prepared.

Method 31

The compounds of the general formula I in which R ^{1 is} substituted phenyl or heteroaryl according to the above general definition and R ^{2 is} cyano and R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y also correspond to the above general definition , can be prepared from compounds of the general formula I in which R 'is halogen and the remaining substituents are as defined above, by similar procedures as described in methods 19 B) and 19 C).

Method 32

The compounds of the general formula I in which R ^{1 is} cyanoato, alkoxy or haloalkoxy and R ^{2 is} cyano and R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, can be prepared from compounds of the formula Formula XXI are prepared by similar methods as described in Method 5.

Method 33

The compounds of the general formula I in which R ^{2 is} formyl and R ¹ , R ³ , X, X ¹ , X ² X ³ , X ⁴ and Y are as defined above, ie the compounds of the formula XXIV ₁ can be prepared from compounds of the formula I in which R ^{2 is} cyano and R ', R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, ie compounds of the formula XXIII, by treatment with a reducing agent, preferably diisobutylaluminum hydride in a solvent, preferably a 1: 1 mixture of toluene and hexane, similar to a method described in the literature are prepared (see S.Trofimenko, J. Org. Chem. 29 (1964) 3046)

 The overall process can be represented as follows:

X ⁴ X ³

(XXIII)

(XXIV)

Method 34

Suitable Zwisrhenverbindungen the general formula I, in which R ^{2 represents} a carboxylic acid function, and R ¹ , R ³ , X, X ', X ² , X ³ , X ⁴ and Y are as defined above, ie compounds of formula XXV, can by oxidation of compounds of formula XXIV with Jones reagent. The overall procedure is as follows:

CHO

CO ₁ H

(O (XXV)

Method 35

The compounds of the general formula I in which R ^{2 is} hydroxylmethylene, alkyloxyminoyl, haloalkylcarbonyl, haloalkylthiocarboyl, alkyl, bis (alkylthio) methyl, bis (arylthio) methyl or haloalkyl and R ¹ , R ³ , X, X ¹ , X ² , X ¹ , X ⁴ and Y correspond to the general definition above, can be prepared from compounds of formula XXIV or compounds of general formula I in which R ^{2 is} halogen and the remaining substituents are as defined above, their preparation under Method 38 is prepared in a similar manner as described in Method 30 A), B), D and E).

Method 36

The compounds of the general formula I in which R ^{2 is} amino and R ¹ , R ³ , X, X ', X ² , X ³ , X ⁴ and Y are as defined above, ie compounds of the formula XXVII, can be prepared from compounds of formula XXV by treatment with diphenylphosphoryl azide in the presence of an organic base such as triethylamine in an alcoholic solvent! such as t-butanol to give the corresponding carbamate of formula XXVI and subsequent hydrolysis are prepared. Other methods of preparing compounds of formula XXVII from compounds of formula XXV via a Curtius rearrangement include conversion of the acid chloride and subsequent reaction with azide ions and treatment with an alcohol (see J. March, "Advanced Organic Chemistry", McGraw -Hill Publ., 1985, 984). The overall procedure is as follows:

CO ₂ H

(XXV)

(XXVI)

(XXVII)

Method 37

The compounds of the general formula I in which R ^{2 is} alkylamino, dialkylamino, aralkylamino, aminocarbony'amino, alkylcarbonylamino, haloalkylcarbonylamino, arylcarbonylamino, alkylsulfonylamino, haloalkylsulfonylamino, alkylaminocarbonylamino, arylaminocarbonylamino, alkoxycarbonylamino, haloalkoxycarbonylamino, alkylidenimino, benzylidenimino, alkoxyalkylidenimino, dialkylaminoalkylidenimino, alkylthioalkylidenimino or azido and R ¹ , R ³ , X, X ', X ² , X ³ , X ⁴ and Y correspond to the above general definition can be prepared from the compounds of formula XXVII in a similar manner as described in Method 18.

Method 38

The compounds of the general formula I in which R ^{2 is} hydrogen, halogen, thiocyanato, alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, phenylthio or heteroarylthio and R ¹ , R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y of the general definition above can be prepared from the compounds of formula XXVII by methods similar to those described in Method 26.

Alternatively, the compounds of general formula I in which R ^{2 is} hydrogen and R ¹ , R ³ , X, X ', X ² , X ³ , X ⁴ and Y are as defined above, may also be compounds of formula XXV by heating with 48% HPr in glacial acetic acid or heating in a high boiling solvent such as decalin or quinoline in the presence of copper.

Method 39

The compounds of general formula I in which R ^{2 is} alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, alkenylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenylsulfinyl, haloalkenylsulfonyl, phenylsulfinyl, phenylsulfonyl, heteroarylsulfinyl or heteroarylsulfonyl and R ¹ , R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, may be prepared by oxidation of compounds of general formula I wherein R ^{2 is} alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, phenylthio or heteroarylthio, following procedures similar to those described in Method 24 getting produced.

Method 40

The compounds of general formula I in which R ^{2 is} substituted phenyl or heteroaryl according to the above general definition and R ¹ , R ³ , X, X ', X ² , X ³ , X ⁴ and Y are as defined above from compounds of the general formula I in which R ^{2 is} halogen and the remaining substituent is as defined above, prepared by similar methods as described in Method 19 B) and 19 C).

Method 41

The compounds of formula I in which R 'represents cyanato, alkoxy or haloalkoxy and R ¹ , R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, may be selected from compounds of general Formula I, in which R ^{2 is} halogen and the remaining substituents as defined above, are prepared in a similar manner as described in Method 5. Globally, the methods of the invention can be described as follows:

Method 1

The process for the preparation of the compounds of the formula Ia,

(La),

in which mean

X ¹ , X ² , X ³ , X ⁴ and Y are the same as in Method 1

and X is halogen, trifluoromethyl, cyano, thiocyanates, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkenylthio, haloalkylthio, halogonalkenylsulfinyl, haloalkenylsulfonyl, phenylthio, phenylsulfinyl, phenylsulfonyl, heteroaryithio, heteroarylsulfinyl or

Heteroarylsulfonyl, is characterized by reacting a compound of formula III,

(III)

in which X ¹ , X ² , X ³ , X ⁴ and Y have the above meaning and the amino group is optionally protected,

(A) with a halogenating agent, if appropriate in the presence of a solvent, to give a compound of the formula Ia, in which X is halogen, and, if appropriate, subsequent reaction of this compound with trifluoromethyl copper in a manner known per se to give compounds of the formula Ia in which X represents trifluoromethyl;

(b) with a tris (alkylthio) -methane or tris (arylthio) -methane in the presence of a Lewis acid and subsequent reaction of the resulting compound of formula Xl in which X is bis (alkylthio) methyl or bis (arylthio) methyl represents represents unte with a suitable alkyl nitrite followed by hydrolysis ^r obtain a compound of formula XXXVII in which X is formyl, and optionally, subsequent Inkontaktbringcn this compound with hydroxylamine and subsequent dehydration with suitable agents such as pJO ₆ in manner known per se to give a compound of the formula I a, in which X represents a cyano group;

(c) with a compound of the formula MSCN, wherein M is an alkali metal, in the presence of Brcm in a solvent such as methanol to give a compound of the formula Ia, in which X is a thiocyanato group, and optionally subsequently reacting this compound with an alkyl halide or a dialkyl sulfate in the presence of a base such as NaOH or KOH in a solvent to give a compound of formula Ia in which X is alkylthio,

(d) with a sulfenyl halide of the formula RSHaI in which R is alkyl, haloalkyl, phenyl or heteroaryl and Hal is a halogen atom, in an organic liquid reaction medium, optionally in the presence of an acid acceptor such as a tertiary amine, to give a compound of formula Ia in which X represents alkylthio, haloalkylthio, alkenylthio, haloalkylthio, phenylthio or heteroaryithio, and, if appropriate, subsequent oxidation of the compound obtained in a manner known per se to give a compound of the formula Ia in which X represents RS (O) _n , where η is each By the reaction condition, it means 1 or 2.

Method 2

The process for preparing the compounds of the formula I a, in which X ^1, X ^2, X ^3, X ⁴ and Y have the same meanings as in Method 1, and X is cyanato, alkoxy or haloalkoxy, is characterized by reacting a prebinding of Forme! XXVIII,

(XXVIII)

in which X ', X ² , X ³ , X ⁴ and Y have the meaning defined above and the amino group and the cyano group are optionally suitably protected,

(a) with a cyanogen halide in the presence of an acid acceptor to give a compound of formula I a wherein X is cyanato;

(b) with an alkylating agent, if appropriate in the presence of a base, to give compounds of the formula Ia in which X is alkoxy, or

(c) by halogen alkylation known per se (compare Syntheses of Fluoroorganic Compounds, I. L. Knunyants and

G. G. Yakobson, Eds., Springer-Ve; Berlin, 1985, 2663-269) to compounds of the formula Ia in which X is halogenoalkoxy.

Method 3

The process for the preparation of the compounds of the formula Ia in which X ¹ , X ² , X ³ , X ⁴ and Y are the same as in Method 1 and X is haloalkyl (CF ₂ H, CFa, BrCH !, CICH!), Haloalkylcarhonyl, haloalkylthiocarbonyl or a-haloalkyl-a-halomethyl, is characterized by reacting a compound of formula VI.

^OHC T ~ ir ^CN

ILJJ

(Vl),

_2 _ ±

in which X ^1, X ^2, X ^3, X ⁴ and Y have the above meanings and the amino group and the cyano group, if necessary. are suitably protected,

(A) with a fluorinating agent such as diethylaminosulfur trifluoride in known Welse to a compound of formula Ia, wherein X is a difluoromethyl group;

(b) with a suitable oxide '^; onsmittel such as chromium trioxide in sulfuric acid to compounds in the formula X represents a carboxyl group, and subsequent reaction of these compounds with a fluorinating agent such as sulfur tetrafluoride in a conventional manner to compounds of the forms! la, in which X is trifluoromethyl;

(c) under Wolff-Kishner conditions or a variant thereof, such as treatment with p-toluenesulfonyl hydrazide and then with sodium cyanoborohydride to give compounds of which formula X is a methyl group and then reacting this compound with a halogenating agent such as N-bromosuccinimide or N-chlorosuccinimide in a suitable solvent to give a compound of the formula Ia, in which X is bromomethyl or chloromethyl,

(d) successively reacting with a haloalkylmetal derivative or trifluorotrimethylsilane to give compounds of formula Ia in which X represents haloalkylcarbinol, then oxidation in a manner known per se to compounds of formula Ia in which X represents haloalkylcarbonyl and then reacting the resulting compounds with Lawesson's reagent to compounds of formula Ia, in which X represents haloalkylthiocarbonyl, or reaction of the compound in which X represents haloalkylcarbinol with halogenating agents, such as thionyl chloride or hydrogen bromide, to give compounds of formula Ia, in which X represents a-haloalkyl-α-halomethyl, wherein If necessary, a deprotection followed by all the above steps.

Method 4

The process for the preparation of the compounds of the formula I b,

(Ib)

in which mean

XX \ X ² , X \ X ^{4 and} Y1801 are the methods 1 and

R ^{} is} halogen, formyl, bis (alkylthio) methyl, Bie (arylthio) methyl, haloalkyl, alkyl, gpfs. substituted phonyl or hotoropryl, thiocyanato, alkylthio, haloalkylthio, alkenylthio, haloalkylyllithio, phenylthio, hotoioarylthio, alkylsulinyl, alkylaliphonyl, alkonylsulfinyl, alkenylsulfonyl, haloalkylsulfonyl, haloalkylsulfonyl, halogonalkenylsulfinyl, haloalkenylsulfonyl, phenylsultinyl, phenylsulfonyl, hoteroarylsulfinyl or hotoroarylsulfonyl,

is characterized by reacting a compound of the formula Ia in which X, cyano and amino are optionally protected in geoignetor Woiso,

(a) by method 1 (a) I b, in which R ³ represents halogen to compounds of the formula subsequent reaction with compounds diosor einom if necessary. substituierton Hotoroaryl- odor Phonylhalogenid, preferably a bromide or iodide in the presence of copper in a known per se Catfish, or subsequent conversion diosor Vorbindung in which R ^{3 is} preferably bromine or iodine, with a possibly substituted. Phenyl odor Hotoroaryldihydroxyborane (phonyl or Heteroarylboronsäuro) in the presence of palladium In bokannte Weisozu verbin ment of the formol Ib, in dor R ^{3 is} optionally substituted phenyl or heteroaryl group, It, or subsequent reaction of a compound of formol I a, in which R ^{3 is} halogen, according to ancestor 1 (a) to compounds dor formula Ib, in which R ³ trifluoromethyl bodoutet;

(b) according to process 1 (b) to give a compound of formula Ib in which R ^{3 is} bis (alkylthio) -mothyl or bis (arylthio) -methyl and then a compound of formol I b in which R ^{3 is} formyl bodoutot ;

(c) with an optionally substituted phenyl or Hoteroaryldiazoniumsalz in known per se to Vorbindungon dor Formol I (b), in the R ³ optionally substituted phenyl or Hotoroaryl means

(d) according to process 1 (c), (d) to compounds of formula Ib in which R ^{3 is} alkylthio, haloalkylthio, alkenylthio, halogonalkenylthio, phenylthio or heteroarylthio, optionally followed by oxidation according to process 1 (d) to compounds of the formula I b, in which R ^{3 is} alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, alkonylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, halogonalkenylsulfinyl, haloalkenylsulfonyl, phenylsulfinyl, phenylsulfonyl, hoteroarylsulfinyl or heteroarylsulfonyl, with the proviso that X is not a group RS, may be an undesirable oxidation followed by treatment, when X is a halogen, with an alkyllithium in a manner known per se followed by aqueous quenchboaction and sulfenylation according to process 1 (c), (d) to compounds of formol Ib in which X is alkylthio, haloalkylthio, alkenylthio, halogonalkenylthio , Phenylthio or heteroarylthio.

Ancestors 5

The process for the preparation of compounds of the formula Ib in which X, X ¹ , X ² , X ³ , X ⁴ and Y denote helium in method 1 and R ^{3 represents} hydroxyiminoalkylidenyl, alkoximinoalkylidenyl, cyano, haloalkylcarbonyl, haloalkylthiocarbonyl or alkyl, is characterized by reacting a precursor of the formula XXIX,

^CN

(XXIX)

in which R ^{3 is} kormyl or alkylcarbonyl and

X, Cyano and Amir are optionally protected in a suitable manner,

(a) by condensation with hydroxylamine or an O-alkylhydroxylamine or an addition salt of these compounds in a solvent, wi) ethanol to give a compound of formula Ib in which R ^{3 represents} hydroxyiminoalkylidenyl or alkoximinoalkylidenyl b, and if R ^{3 represents} hydroxyiminomethylidenyl or alkoximinomethylidenyl Separating the water or alcohol moieties according to process 1 (b) to obtain a compound of formula I b in which K ^{3 is} cyano;

(b) when R ^{3 is} formyl, according to process 3 (a), (b), (c), (d), to give a compound of formula Ib in which R ^{3 is} methyl, haloalkyl, haloalkylcarbonyl or haloalkylthiocarbonyl,

(c) when R ^{3 is} formyl, * a Grignard reagent derived from an alkyl halide or alkyllithium, to the corresponding carbinol, including dehydration to a precursor in which formula R ^{3 is} alkenyl, and subsequent reduction to corresponding compounds of formula Ib in which R ^{3 is} alkyl, and, if appropriate, subsequent deprotection.

Ancestors 6

The preparation for the preparation of the invention of formula XXXIV,

(XXXIV)

in the mean;

X, X ¹ , X ² , X ³ , X ⁴ and Ydasselbo wio above

and R ^{3 is} amino, alkylamino, dialkylamino, aralkylamino, aminocarbonylamino.alkylcarbonylamino, halogonalkylcarbonylamino, arylcarbonylamino.alkylsulfonylamino, haloalkylsulfonylamino.alkylamino-carbonylamino, arylaminocarbonylamino, alkoxycarbonylamino.alkylidonimino, bonzylidone-amino-alkoxyalkylideneimino, dialkylaminoalkylidone-imino,

Alkylthioalkylidene-amino or azido, as the Z "isonone-perchlorinone is characterized by reduction of a compound of formula XXX,

(XXX),

in which the amino group is suitably protected, to verbir.dungone of the formula XXXIV, in which R ^{3 is} amino, and reversal of these precursors

(A) with suitable Alkylierungsmittoln In organic solvents, depending on the stochiomotrischen conditions or Reaktionsbodingungen compounds with mono- or disubstituted amino group are obtained, or by conversion of Amincgruppo into a Alkoxyalkylideniminogruppe and subsequent reduction to compounds of formula XXXIV, in the R ³ alkylamino , Dialkylamino or aralkylamino represents;

(b) with phosgene and subsequently with ammonia to give compounds of formol XXXIV in which R ^{3 is} aminocarbonylamino;

(c) with alkyl acid chloride or haloalkyl chlorides or aryl acid chlorides or anhydrides thereof, optionally in the presence of a solvent and / or organic acid acceptors, to form a compound of formula XXXIV wherein R ^{3 is} alkylcarbonylamino, haloalkylcarbonylamino or arylcarbonylamino;

(d) with alkyl or haloalkylsulfonyl halides or anhydrides thereof under suitable reaction conditions to give compounds of formula XXXIV wherein R ^{3 is} alkylsulfonylamino or haloalkylsulfonylamino;

(e) with alkyl or aryl isocyanate groups in a manner known per se to give compounds of the formula XXXIV in which R ^{3 is} alkylaminocarbonylamino or arylaminocarbonylamino;

(0 with an alkyl chloroformate or a haloalkyl chloroformate in a conventional manner to compounds of the formula

XXXIV in which R ^{3 is} alkoxycarbonylamino or haloalkoxycarbonylamino; (g) with an alkylaldehyde or an arylaldohyde in a manner known per se to give compounds of the formula XXXIV, in which R ^{3 is} alkylidonimino dor-butylbenzyliminoimino;

(h) with an alkyl orthoester to give compounds of formula XXXIV wherein R ^{3 is} alkoxyalkylidenimino; (i) with a Ν, Ν-dialkylformamide or a dialkyl acetal derivative thereof to give precursors of the formula XXXIV, in which R ³

Dialkylaminoalkylidenimino means, (j) with a tris (alkylhio) -mothane in an organic solvent to give compounds of the formula XXXIV in which R ³

Alkylthioalkylidenimino, or (k) with p-toluenesulfonyl azide in a conventional manner or by reaction to a diazonium salt and subsequent reduction to the corresponding hydrazino compound and subsequent treatment with nitrous acid to a compound of formula XXXIV, in which R ^{3 is} an azido group, and if necessary, subsequent deprotection.

Method 7

The process for the preparation of the compounds of the formula Ib in which X, X ¹ , X ² , X ³ , X ⁴ and Y are the same as in Method 1 and R ^{3 is} cyanato, alkoxy or haloalkoxy is characterized by reacting a compound of the formula XXXI,

in which amino, cyano and X are optionally protected in geoigneter catfish, according to process 2 (α), (b), (c), wherein compounds of formula Ic are obtained in which R ^{3 is} cyanato, alkoxy or haloalkoxy.

Method 8

The process for the preparation of the compounds of formol Ic,

(Ic)

inderbedeuton:

X, X ', X', X ³ , X ⁴ , Y and R ^{3 are the} same as in Method 1 and

R 'is hydrogen, halogen, thiocyanato.alkylthio, haloalkylthio.alkenylthio, haloalkonylthio, phanylthio, heteroarylthio, alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, alkonylsulfonyl, halugonealkylsulfinyl !, haloalkylsulfonyl, halogonalkenylfulfinyl, haloalkylsulfonyl, phenylsulfinyl, phonylsulfonyl, heteroarylsulfinyl, hoteroaryl-sulfonyl, if necessary. substitute, tes phenyl odor Hoteroaryi, alkylcarbonyl, alkylamino, dialkylamino, aralkylamino, aminocarbonylamino, Alkylcarbonylamino.Halogonalkylcarbonylamino.Arylcarbonylami.io.Alkylsulfonylamino.Halogonalkylsulfon lamino, Alkylaminocarbon / bend left-mino.Arylaminocarbonylfimino.Alkoxycarbonylamino, Halogonalkoxycarbonylamino, Alkylidonimino, Benzylidenimir.o.Alkoxyalkylidenimino , Dialkylaminoalkylidenimino, alkylthioalkylidenimino, azido, bis (alkylthio) methyl, bis (arylthio) -mothyl, fornyl, haloalkylcarbonyl, haloalkylthiocarbonyl, haloalkyl or alkyl,

is characterized by reacting a compound of formol I b or XXXIV,

(Ib or XXXlV),

which is prepared according to one of the processes 4 to 7 and in which the aminogroup is freed from SchuU of the groups X, R ³ or cyano if necessary, from the protective group,

(a) with a diazotizing agent, preferably an acyl nitrite, in an inert solvent to give a compound of the formula Ic in which R is hydrogen;

(B) with a diazotizing agent, preferably aikylnitrit, in the presence of a halogen donor to a compound of formula Ic in which R ^{1 is} halogen, then reacting this compound with a Grignard reagent or a lithium derivative and subsequent reaction with an aliphatic acid chloride or a corresponding anhydride with conversion into a compound of the formula Ic, in which R ^{1 is} alkylcarbonyl 1, or reaction of this compound according to process 4 (a) to obtain compounds of the formula I c, in which R 'is phenyl or hoteroaryl;

(c) with a diacid agent, preferably an acyl nitrite, in the presence of SCN ₂ or a disulfide in a solvent such as chloroform to give compounds of the formula Ic in which R ^{1 is} thiocyanate, alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, phenylthio or rieteroarylthio, and optionally subsequent oxidation according to process 1 (d) to a compound of formula Ic wherein R ^{1 is} alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, akenylsulfonyl, haloalkenylsulfinyl, haloalkylsulfonyl, haloalkylsulfinyl, haloalkenylsulfonyl, phenylsulfinyl, phenylsulfonyl, heteroarylsulfinyl or heteroarylsulfonyl;

(d) according to process 6 21 (a) to (k) to give compounds of the formula Ic in which R ^{1 is} alkylamino, dialkylamino, aralkylamino, aminocarboxylamino, alkylcarbonylamino, haloalkylcarbonylamino, arylcarbonylamino, alkylsulfonylamino, haloalkylsulfonylamino, alkylaminocarbonylamino, arylaminocarbonylamino, alkoxycarbonylamino, Haloalkoxycarbonylamino, alkylidenimino, benzylidenimino, alkoxyalkylidenimino, dialkylaminoalkylidenimino, alkylthioalkylidenimino or azido,

or _/

(e) reacting with sodium nitrite and formaldoxime, copper sulfate and HCl in known manner to give compounds of the formula Ic in which R 'is formyl, followed by reaction with an alkyl Grignard reagent and subsequent oxidation to give compounds of the formula Ic, in dor R 'is alkylcarbonyi, subsequent reaction according to process 5 to give a compound of formula Ic in which R ^{1 is} Hydroxyimlnoalkylidenyl or Alkoximinoalkylidenyl, and when R' is phenyl, reaction according to ancestors 3 (a) to (d) to a compound of Formula lc in which R 'is haloalkylcarbonyl, haloalkylthiocarbonyl, haloalkyl or aryl, and optionally. Subsequent Schutzgrupponabspaltung, wherein the above compound, in the formula R ^{1 is} formyl, is converted in a conventional manner into a compound of formula Ic, in the R ¹ bis (alkylthio) methyl or bis (arylthio) methyl bedoutot.

Method 9

The process for the preparation of the compounds of the formula Ic in which X, X ', X ² , X ³ , X ⁴ , R ³ and Y are the same as in method 1 and R' is cyanato, alkoxy or haloalkoxy, is characterized by reacting a Compound of formula XXXII,

(XXXII), X ³

in which X, Cyano or R ^{3 are} optionally protected in a manner known per se, according to claim 2 (a), (b), (c), to a compound of formula Ic in which R 'is cyanato, alkoxy or haloalkoxy means, and optionally. subsequent SchutzgruppenabspaltuTig.

Method 13

The process for preparing the compounds of the formula I in which X, X ¹ , X ² , X ³ , X ⁴ , R ¹ , R ³ and Y is the same as in formula I and R ^{2 is} CHO is characterized of the formula Ic with a reducing agent, preferably Diisobutylalumlniumhydrid, in a solvent to give the corresponding compound in thep- formula R ² CHO, which if necessary, in a conventional manner to the corresponding compound of formula XXXV

-CO ₂ H

is oxidized.

Method 11

The process for preparing the compounds of formula I, wherein X, X ^1, X ^2, X ^3, X ^4, R ', R ³ and Ydasselbe as in formula I and R ² is hydroxyiminoalkylidenyl, Alkoximinoalkylidenyl, haloalkylcarbonyl, haloalkylthiocarbonyl, alkyl, Haloalkyl, bis (alkylthio) -methyl or bis (arylthio) -methyl, is characterized by reacting a compound of formula I, in which R ^{2 is} CHO, if necessary after protection of the groups X, R 'or R ³ with a protective group according to method 3 (a), (b), (c), (d). Process (a), (b) or Process 8 (e) and, if necessary, subsequent protecting group: cleavage.

Method 12

The process for the preparation of compounds of the formula I, in which

X, X ¹ , X ² , X ³ , X ⁴ , R ', R ³ and Y are the same as in Method 1

R ^{2 is} amino, alkylamino, dialkylamino, aralkylamino.aminocarbonylamino, alkylcarbonylamino, haloalkylcarbonylamino, arylcarbonylamino, alkylsulfonylamino, haloalkylsulfonylamino, alkylaminocarbonylamino, arylaminocarbonylamino, alkoxycarbonylamino, alkylidenimino, benzylidenimino, alkoxyalkylidenimino, dialkylaminoalkylidenimino, alkylthioalkylidenimino, azido, hydrogen, halogen, thiocyanates, alkylthio, haloalkylthio, A) kenylthio, haloalkenylthio, phenylthio, heteroarylthio, alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, alkenylsulfony), haloalkylsulfinyl, haloalkylsulfonyl, haloalkenylsulfinyl, haloalkenylsulfonyl, phenylsulfinyl, phenylsulfonyl, heteroarylsulfinyl, heteroarylsulfonyl or optionally substituted phenyl or heteroaryl,

is characterized by reacting a compound of formula XXXV, if necessary after protection of the groups X, R ¹ or R ³ in a conventional manner with a protective group, under conditions for the Curtius rearrangement, for example by conversion to a corresponding acid chloride and subsequent reaction with an alkali metal azide, or with diphenylphosphoryl azide in the presence of an organic base such as triethylamine in an alcoholic solvent to the corresponding carbamate, and optionally. subsequent hydrolysis to the corresponding compound, in the formula R ^{2 is} amino, which then, if necessary. According to process 6 (a) to (k) to method 8 (a) to (c) reacted wildly and, if R ^{2 is} halogen, if appropriate, reaction according to process 4 (a) and, if necessary, subsequent deprotection.

Method 13

The process for preparing the compounds of formula I ₁ In which X, X ¹ , X ² , X ³ , X ⁴ , R ¹ , R ³ and Y are the same as in method 1 and R ^{2 is} cyanato, alkoxy or haloalkoxy, is characterized by reacting a compound of formula XXXVI,

(XXXVI)

if necessary after protection of the groups X, R ¹ or R ³ with a protective group, according to method 7 and, if necessary, subsequent deprotection.

Method 14

The process for preparing the formulas XXVIII, XXXI, XXXII and XXXV according to processes 2, 7, 10 or 13 is characterized by conversion of the corresponding halogenating compound according to processes 1 (a), 4 (a), 8 (b) or 12, after protection of an existing amino group, in a corresponding Grignard reagent or lithium derivative and subsequent reaction with a trialkyl borate and oxidation in a conventional manner and, if necessary, subsequent deprotection.

Method 15

The process for the preparation of the compounds of formula III,

^H X

^H 2 ^N -

in which X ¹ , X ² , X ³ , X ⁴ and Y denote the same w'e in formula I, is characterized by reacting a Dicyanopropenderivats of formula IV

NH-CH = C-CH ₉ -CN

I *

(IV)

Y with a basic agent.

Method 16

The invention further relates to the compounds of formulas III and XXVIII to XXXVII, wherein the various substituents have the same meaning as in the aforementioned methods; These compounds are useful as intermediates for the preparation of "Vorbindungen of formula I according to the methods 1 to 15.

The compounds of the formula I in which X represents a & Ferhalogenalkylthiogruppe can, apart from the above-mentioned procedures, also be prepared by the process explained below, which is based on the chlorosulfonation, reduction to the corresponding disulfide and final, free radical-assisted reduction. The procedure is carried out as follows:

(A) The compounds of the general formula XXXIX, in which the substituents R ¹ , R ² , R ³ , Y, X ¹ -, X ² , X ³ and X ⁴ denote the same as in formula I, can be prepared from compounds of the general formula XXXVIII, inderX hydrogen, are prepared at a reaction temperature in the range of 0 to 15O ⁰ C, by treatment with chlorosulfonic acid either neat or in the presence of an organic solvent such as chloroform, dichloromethane, carbon tetrachloride or dimethylformamide. A specific example of this is, for example, the preparation of a compound of the general formula XXXIX in which R ^{1 is} amino, alkylcarbonylamino or haloalkylcarbonylamino, R ^{2 is} cyano and R ^{3 is} hydrogen, from compounds of the general formula XXXVIII in which R ^{1 is} amino, alkylcarbonylamino or haloalkylcarbonylamino , R ^{2 is} cyano, R ^{3 is} hydrogen and X is hydrogen, by treatment with chlorosulfonic acid. A representative procedure for the chlorosulfonation of aromatic compounds is described in the literature (J.March, "Advanced Organic Chemistry", McGraw-Hill Publ. [1968], 402).

ClO ₂ S

(XXXVIII) [XXXDQ

The compounds of general formula XL, ^{4 are} the same as obon signify in which R ^1, R ^1, Y, X ^1, X ^2, X ³ and X in formula I may be prepared from compounds of general formula XXXIX ₁ in de ^r R ³ is hydrogen is prepared by treatment with a chlorinating agent such as chlorine, N-chlorosuccinimide, sulfuryl chloride, etc. in an organic solvent such as diethyl ether, acetyl nitrile or dichloromethane at a reaction temperature of -70 to 25 ⁰ C. A specific example of this is the preparation of compounds of general formula XL, in which R 'is amino, alkylamido or haloalkylamido and R ^{2 is} cyano, by treatment of a compound of general formula XXXIX in which R ^{1 is} amino, alkylcarbonylamino or haloalkylcarbonylamino, R ² Cyano and R ³ hydrogen, with sulfuryl chloride in diethyl ether at -4O ⁰ C:

CIO2S

C102S

rl

chlorinating

: -►

(XXXlX) (XL)

B) The compounds of the general formula XLI, in which the substituents R ¹ , R ² , Y, X ¹ , X ² , X ³ and X ^{4 are the} same as those in formula I, can be prepared from the precursors of general formula XXXIX by treatment with a reducing agent such as triphonylphosphine in the presence of an organic solvent such as tetrahydrofuran, toluene or dichloromethane at a reaction temperature of 0 to 110 ⁰ C are prepared. A more specific example of this is the preparation of compounds of general formula XLI, in which R ^{1 is} hydrogen, amino, alkylcarbonylamino or haloalkylcarbonylamino, R ^{2 is} cyaro, and R ^{3 is} hydrogen or chlorine, from compounds of general formula XXXIX, in which R ' hydrogen, amino, alkylcarbonylamino odor haloalkylcarbonylamino, ^R2 is cyano and R ³ is hydrogen or chlorine, by treatment with triphenylphosphine in tetrahydrofuran at 25 ⁰ C. A typical example of the procedure for the reduction of toluene to p-Tolyldisulfid is (described in the literature GA Elah et al., J. Org. Chem. 45 [1980] 4792).

Rl-! "JL-R3

X ¹ X ² -

N '

Reclusion with solvent

X ³

(XXXIX)

C) The compounds of general formula I in which R ', R ² , Y, X', X ² , X ³ and X ^{4 are the} same as in formula I and X is a perhaloalkylthio group R ⁶ S, in which R ^{6 is} CFR ⁷ R ⁸ , where R ^{7 is} F, Cl or Br and R ^{8 is} F, Cl, Br or a perfluoroalkyl group, can be prepared by reacting a compound of the general formula XLI with a perhaloalkane compound of the general formula XLII, ZCFR ⁷ R ⁸ , in the Z Cl, Br or J, R 'represents R, Cl or Br, and R ^{8 represents} F, Cl, Br or a perfluoroalkyl group, with a reducing agent which promotes the formation of the free radical CFR ⁷ R ⁸ from ZCFR ⁷ R ⁸ , and which is preferably selected from the metals zinc, cadmium, aluminum and manganese and the compounds having SO structure, for example dithionites or hydroxymethylsulfinates. The alkali metal dithionites or alkaline earth metal or dithionites correspond to the general formula XLIII, M _n (S ₂ O ₄ ), in which η, depending on the valency of the metal M, is equal to or 2. When a dithionite of the general formula XLIII or a hydroxymethylsulphinate is used, a base must be added which is selected from alkali hydroxides, alkaline earth hydroxides, ammonia, triethylbenzylammonium, weak acid salts such as disodium phosphate, sodium metabisulfite, sodium bisulfite or sodium borate.

The reaction is carried out in a solvent which is capable of facilitating the dithionite or hydroxymethyl difluate and the compound of Formol XLII, ZCFR ⁷ R ', for example, acetonitrile, formamide, dimethylformamide, dimethylacotamide, hexamethylphosphoramide, N-methylpyrrolidone, dimethylsulfoxide or sulfolane , and that at a reaction temperature of 20 to 85 ⁰ C.

The alkali dithionite may be added to the deadening mixture in the form of a saturated solution in water or formamide. It is also possible to add the dithionite as a solid. When operating with a gas that is only slightly soluble in the reaction solvent, the reaction pressure can be increased from atmospheric to 50 bar. A more specific example of this reaction is the preparation of compounds of general formula I in which R 'is hydrogen, amino, alkylcarbonylamino or haloalkylcarbonylamino, ^R2 is cyano, R ³ is hydrogen odor Cl and X is a Perhalogenalkylthiogruppe, R ⁶ S, wherein R ^{e is} CFR ⁷ R ⁸ and R ^{7 is} F, Cl or Br and R ^{8 is} F, Cl, Br or a perfluoroalkyl group, by reaction of a compound of general formula XLI in which R ^{1 is} hydrogen, amino, alkylamido or haloalkylamido, R ² Cyano and R ^{3 are} hydrogen or Cl, with a Verb ,, ..: ng the general Formol XLII, ZCFR ⁷ R ⁸ , in the Z Cl, Br or J, R ⁷ F, Cl or Br and R ¹ F, Cl , Br or a perfluoroalkyl group, in the presence of sodium dithionite and disodium phosphate in dimethylforrnium at 25 ° C. This reaction can be represented by the following equation:

ZCFR ⁷ R ⁸

Reduktiuns-

mLLLeJ

base

(XLI)

(XLII)

The intermediate chlorosulfonyl compound of formula XXXIX and the intermediate disulfide compound of formula XLI

also covered by the subject invention.

Table 1 (compounds RPC Nos. 1 to 389 below) lists specific typical inventive pyrrole derivatives of the formula I in which R ² denotes cyano, the remaining substituents being specified in detail.

More special and typical pyrrole derivatives according to the invention of the formula I in which X ² and X ³ is hydrogen, X ¹ and X ^{4 is} chlorine and Y is CF ₃ and X, R ^1, R ² and R are given ³ in detail, are shown in Table 2 listed (connections

RPC-No. 390-491).

Table 1

Representative pyrrole compounds (RPC) of formula I with R ² ·

Substituent meanings

RPC-No. R ' X R ³ X ¹ X ² Y X ³ X ⁴ 1 H SCF ₃ F Cl H CF ₃ H Cl 2 H SOCF ₃ F Cl H CF ₃ H Cl 3 H SO ₂ CF ₃ F Cl H CF ₃ H Cl 4 H SCF ₃ br Cl H CF ₃ H Cl Oil H SOCF ₃ br Cl H CF ₃ H Cl 6 H SO ₂ CF ₃ br Cl H CF ₃ H Cl 7 H SCF ₃ I Cl H CF ₃ H Cl 8th H SOCF ₃ I Cl H CF ₃ H Cl 9 H SO ₂ CF ₃ I Cl H CF ₃ H Cl 10 H SCF ₃ CF ₃ Cl H CP, H Cl 11 H SOCF ₃ CF ₃ Cl H CF ₃ H Cl 12 H SO ₂ CF ₃ CF ₃ Cl H CF ₃ H Cl 13 H SCF ₃ CH ₃ Cl H CF ₃ H Cl 14 H SOCF ₃ CH ₃ Cl H CF ₃ H Cl 15 H SO ₂ CF ₃ CH ₃ Cl H CF ₃ H Cl 16 H SCF ₃ OCH ₃ Cl H CF ₃ H Cl 17 H SOCF ₃ OCH ₃ Cl H CF ₃ H Cl 18 H SO ₂ CF ₃ OCH ₃ Cl H CF ₃ H Cl 19 H SCF ₃ OCF ₃ Cl H CF ₃ H Cl 20 H SOCF ₃ OCF ₃ Cl H CF ₃ H Cl 21 H SO ₂ CF ₃ OCF ₃ Cl H CF ₃ H Cl 22 H SCF ₃ OCF ₂ CI Cl H CF ₃ H Cl 23 H SOCF ₃ OCF ₂ CI Cl H CF ₃ H Cl 24 H SO ₂ CF ₃ OCF ₂ CI Cl H CF ₃ H Cl 25 H SCF ₃ OCF ₂ H Cl H CF ₃ H Cl 26 H SOCF ₃ OCF ₂ H Cl H CF ₃ H Cl

RPC-No. R ¹ X R ³ X ¹ X ² Y X ³ X ⁴ 27 H SO ₂ CF ₃ OCF ₂ H Cl H CF ₃ H Cl 28 H SCF ₃ CHO Cl H CF ₃ H Cl 29 H SOCF ₃ CHO Cl H CF ₁ H Cl 30 H SO ₂ CF ₃ CHO Cl H CF ₃ H Cl 31 H SCF ₃ CN Cl H CF ₃ H Cl 32 H SOCF ₃ CN Cl H CF ₃ H Cl 33 H SO ₂ CF ₃ CN Cl H CF ₃ H Cl 34 H SOCF ₃ SCF ₃ Cl H CF ₃ H Cl 35 Il SOCF ₃ SO ₂ CH ₃ Cl H CF ₃ H Cl 36 H SCF ₃ SO ₂ CH ₃ Cl H CF ₃ H Cl 37 H SO ₂ CF ₃ SO ₂ CH ₃ Cl H CF ₃ H Cl 38 H ST ₃ COCF ₃ Cl H CF ₃ H Cl 39 H SOCF ₃ COCF ₃ Cl H CF ₃ H Cl 40 H SO ₂ CF ₃ COCF ₃ Cl H CF ₃ H Cl 41 H SOCF ₃ N (CHj) ₂ Cl H CF ₃ Il Cl 42 H SO ₂ CF ₃ N (CHj) ₂ Cl H CF ₃ H Cl 43 H SCF ₃ Cech Cl H CF ₃ H Cl 44 H SOCF ₃ CH ₂ CaCH Cl H CF ₃ H Cl 45 NH ₂ SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 46 NH, SOCF ₃ Cl Cl H CF ₃ H Cl 47 NH ₂ SOCFa br Cl H CF ₃ H Cl 48 NH ₂ SO ₂ CF ₃ br Cl H CF ₃ H Cl 49 CH ₃ CONH SCF ₃ Cl Cl H CF ₃ H Cl 50 CH ₃ CONH SOCF ₃ Cl Cl H CF ₃ H Cl 51 CH ₃ CONH SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 52 Cl SCF ₃ Cl Cl H CF ₃ H Cl 53 Cl SOCF ₃ Cl Cl H CF ₃ H Cl 54 Cl SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 55 F SCF ₃ Cl Cl hl CF ₃ H Cl 56 F SOCF ₃ Cl Cl H CF ₃ H Cl 57 F SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 58 I SCF ₃ Cl Cl H CF ₃ H Cl œ9 I SOCF ₃ Cl Cl H CF ₃ H Cl 60 I SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 61 CF ₃ SCF ₃ Cl Cl H CF ₃ H Cl 62 CF ₃ SOCF ₃ Cl Cl H CF ₃ H Cl 63 CF ₃ SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 64 CH ₃ SCF ₃ Cl Cl H CF ₃ H Cl 65 CH ₃ SOCF ₃ Cl Cl H CF ₃ H C! 66 CH ₃ SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 67 CCH ₃ SCF ₃ Cl Cl H CF ₃ H Cl 68 OCH ₃ SOCF ₃ Cl Cl H CF ₃ H Cl 69 OCH ₃ SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 70 OCF ₂ CI SCF ₃ Cl Cl H CF ₃ H Cl 71 OCF ₂ CI SOCF ₃ Cl Cl H CF ₃ H Cl 72 OCF ₂ CI SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 73 OCF ₂ H SCF ₃ Cl Cl H CF ₃ H Cl 74 OCF ₂ H SOCF ₃ Cl Cl H CF ₃ H Cl 75 OCF ₂ H SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 76 CN SCF ₃ Cl Cl H C ^ ₃ H Cl 77 CN SOCF ₃ Cl Cl H CF ₃ H Cl 78 CN SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 79 N ₃ SCF ₃ CL Cl H CF ₃ H Cl 80 N ₃ SOCF ₃ ci Cl H CF ₃ H Cl 81 N ₃ SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 82 phenyl SCF ₃ Cl Cl H CF ₃ H Cl 83 phenyl SOCF ₃ Cl Cl H CF ₃ H Cl 84 phenyl SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 85 1 -pyrrolyl SCF ₃ Cl Cl H CF ₃ H Cl 86 1-pyrrolyl SOCF ₃ Cl Cl H CF ₃ H Cl 87 1-pyrrolyl SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 88 SCH ₃ SCF ₃ Cl Cl H CF ₃ H Cl 89 SOCF ₃ Cl Cl Cl H CF ₃ H Cl 90 SCH ₃ SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 91 SO ₂ CF ₃ SOCF ₃ Cl Cl H CF ₃ H Cl 92 SO ₂ CF ₃ SO ₂ CF ₃ Cl Cl H CF ₃ H Cl

Continuation Table 1

RPC-No. R ¹ X R ³ X ¹ X ² Y X ³ X ⁴ 93 CACH SCF ₃ Cl Cl H CF ₃ H Cl 94 CACH SOCF ₃ Cl Cl H CF ₃ H Cl 95 CACH SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 96 SCF ₃ SCF ₃ Cl Cl H CF ₃ H Cl 97 SCF ₃ SOCF ₃ Cl Cl H CF ₃ H Cl 98 SCF ₃ SO ₂ CF ₃ Cl Cl H CF ₃ H Cl 99 H SCF ₃ H Cl H CF ₃ H Cl 100 H SOCF ₃ H Cl H CF ₃ H Cl 101 H SO ₂ CF ₃ H Cl H CF ₃ H Cl 102 NH ₂ SCF ₃ H Cl H CF ₃ H Cl 103 NH ₂ SOCF ₃ H Cl H CF ₃ H Cl 104 NH ₂ SO ₂ CF ₃ H Cl H CF ₃ H Cl 105 Cl SCF ₃ H Cl H CF ₃ H Cl 106 Cl SOCF ₃ hl Cl H CF ₃ H Cl 107 Cl SO ₂ CF ₃ H Cl H CF ₃ H Cl 108 F SCF ₃ H Cl H CF ₃ H Cl 109 F SOCF ₃ Il Cl H CF ₃ H Cl 110 F SO ₂ CF ₃ H Cl H CF ₃ H Cl 111 B. SCF ₃ H Cl H CF ₃ H Cl 112 br SOCF ₃ H Cl H CF ₃ H Cl 113 br SO ₂ CF ₃ H Cl H CF ₃ H Cl 114 CF ₃ SCF ₃ H Cl H CF ₃ H Cl 115 CF ₃ SOCF ₃ H Cl H CF ₃ H Cl 116 CF ₁ SO ₂ CF ₃ H Cl H CF ₃ H Cl 117 CN SCF ₃ H Cl H CF ₃ H Cl 118 CN SOCF ₃ H Cl H CF ₃ H Cl 119 CN SO ₂ CF ₃ H Cl H CF ₃ H Cl 120 br SCF ₃ SCF ₃ Cl H CF ₃ H Cl 121 NH ₂ SCF ₃ SCF ₃ Cl H CF ₃ H Cl 122 Cl SCF ₃ F Cl H CF ₃ H Cl 123 Cl SOCF ₃ F Cl H CF ₃ H Cl 124 Cl SO ₂ CF ₃ F Cl H CF ₃ H Cl 125 br SCF ₃ F Cl H CF ₃ H Cl 126 br SOCF ₃ F Cl H CF ₃ H Cl 127 br SO ₂ CF ₃ F Cl H CF, H Cl 128 CF ₃ SCF.- F Cl H CF ₃ H Cl 129 CF ₃ SOCF ₃ F Cl H CF ₃ H Cl 130 CF ₃ SO ₂ CF ₃ F Cl H CF ₃ H Cl 131 CN SCFj F Cl H CF ₃ H Cl 132 CN SOCF ₃ F Cl H CF ₃ H Cl 133 CN SO ₂ CF ₃ F Cl H CF ₃ H Cl 134 NH ₂ SCF ₃ F Cl H CF ₃ H Cl 135 NH ₂ SOCF ₃ F Cl H CF ₃ H Cl 136 NH ₂ SO ₂ CF ₃ F Cl H CF ₃ H C! 137 H SCF ₃ Cl Cl H OCF ₃ H Cl 138 H SOCF ₃ Cl Cl H OCF ₃ H Cl 139 H SO ₂ CF ₃ Cl Cl H OCF ₃ H Cl 140 H SCF ₃ H Cl H OCF ₃ H Cl 141 H SOCF ₃ H Cl H OCF ₃ H Cl 142 H SO ₂ CF ₃ H Cl H OCF ₃ H Cl 143 NH ₂ SCF ₃ ci Cl H OCF ₃ H Cl 144 NH ₂ SOCF ₃ Cl Cl H OCF ₃ H Cl 145 NH ₂ SO ₂ CF ₃ Cl Cl H OCF ₃ H Cl 146 NH ₂ SCF ₃ H Oil H OCF ₃ H Cl 147 NH ₂ SOCF ₃ H ct H OCF ₃ H Cl 148 NH ₂ SO ₂ Cr, H Cl H OCF ₃ H Cl 149 H 3CF ₃ F Cl H CCF ₃ H Cl 150 H SOCF ₃ F Cl H OCF ₃ H Cl 151 H SO ₂ CF ₃ F Cl H OCF ₃ H Cl 152 H SCF ₃ CN Cl H GCF ₃ H Cl 153 H SOCF ₃ CN Cl H OCF ₃ H Cl 154 H SO ₂ CF ₃ CN Cl H OCF ₃ H c " 155 Cl SCF ₃ H Cl H OCF ₃ H Cl 156 Cl SOCF ₃ H Cl H OCF ₃ H Cl 157 Cl SO ₂ CF ₃ H ci H OCF ₃ H Cl

R ¹ X R ³ X ¹ X ² Y -42- X ³ 289,920 Cl SCF ₃ F Cl H OCF ₃ H Continuation Table 1 Cl SOCF ₃ F Cl H OCF, H X ⁴ RPC-No. Cl SO ₂ CF ₃ F Cl H OCF ₃ H Cl 158 NH, SCF ₃ H Cl H CF ₃ H Cl 159 NH, SOCF ₃ H Cl H CF ₃ H H 160 NH, SO ₂ CF ₃ H Cl H CF ₃ H H 161 NH, SCF ₃ Cl Cl H CF ₃ H H 162 NH ₂ SOCF ₃ Cl Cl H CF ₃ H H 163 NH, SO ₂ CF ₃ Cl Cl H CF ₃ H H 164 ' NH, SCF ₃ br Cl H CF ₃ H H 165 NH, SOCF ₃ br Cl H CF ₃ H H 166 NH, SO ₂ CF ₃ br Cl H CF ₃ H H 167 H SCF ₃ H Cl H CF ₃ H H 168 H SOCF ₃ H Cl H CF ₃ H H 169 H SO ₂ CF ₃ H Cl H CF ₃ H H 170 H SCF ₃ Cl Cl H CF ₃ H H 171 H SOCF ₃ Cl Cl H CF ₃ H H 172 H SO ₂ CF ₃ Cl Cl H CF ₃ H H 173 Il SCF ₃ F Cl H CF ₃ H H 174 H SOCF ₃ F Cl H CF ₃ H H H SO ₂ CF ₃ F Cl H CF ₃ H H 176 NH, SCF ₃ H H H CF ₃ H H 177 NH, SOCF ₃ H H H CF ₃ H H 178 NH, SO ₂ CF ₃ H H H CF ₃ H H 179 NH, SCF ₃ SCF ₃ H H CF ₃ H H 180 NH, SCF ₃ Cl H H CF ₃ H H 181 NH, SOCF ₃ Cl H H CF ₃ H H 182 NH, SO ₂ CF ₃ Cl H H CF ₃ H H 183 NH, SCF ₃ br H H CF ₃ H H 184 NH, SOCF ₃ br H H CF ₃ H H 185 NH, SO ₂ CF ₃ br H Il CF ₃ H H 186 H SCF ₃ Cl H H CF ₃ H H 187 H SOCF ₃ Cl H H CF ₃ H H 188 H SO ₂ CF ₃ Cl H H ' CF ₃ H H 189 H SCF ₃ F H H CF ₃ H H 190 H SOCF ₃ F H H CF ₃ H H 191 H SO ₂ CF ₃ F H H CF ₃ H H 192 H SCF ₃ CF ₃ H H CF ₃ H H 193 H SOCF ₃ CF ₃ H H CF ₃ H H 194 H SO ₂ CF ₃ CF ₃ H H CF ₃ H H 195 Cl SCF ₃ Cl H H CF ₃ H H 196 Cl SOCF ₃ Cl H H CF ₃ H H 197 Cl SO ₂ CF ₃ Cl H H CF ₃ H H 198 br SCF ₃ Cl H H CF ₃ H H 199 br SOCF ₃ Cl H H CF ₃ H H 200 br SO ₂ CF ₃ Cl H H CF ₃ H Cl 201 NH, SCF ₃ H CH ₃ H br H Cl 202 NH, SOCF ₃ H CH ₃ H br H Cl 203 NH, SO ₂ CF ₃ H CH ₃ H br H CH ₃ 204 H SCF ₃ H CH ₃ H br H CH ₃ 205 H SOCF ₃ H CH ₃ H br H CH ₃ 206 H SO ₂ CF ₃ H CH ₃ H br H CH ₃ 207 H SCF ₃ Cl CH ₃ H br H CH ₃ 208 H SOCF ₃ Cl CH ₃ H br H CH ₃ 209 H SO ₂ CF ₃ Cl 0H3 H br H CH ₃ 210 NH, SCF ₃ H Cl H Cl H CH ₃ 211 NH, SOCF ₃ H Cl H Cl H CH ₃ 212 NH, SO ₂ CF ₃ H Cl H Cl H Cl 213 H SCF ₃ Cl Cl H Cl H Cl 214 H SOCF ₃ Cl Cl H Cl H Cl 215 H SO ₂ CP ₃ Cl C! H Cl H Cl 216 NH, SCF ₃ H ci H Cl H Cl 217 NH ₂ SOCF ₃ H Cl H Cl H Cl 218 NH, SO ₂ CF ₃ H Cl H Cl H H 219 H 220 H 221

Continuation Table 1

RPC-No. R ¹ X R ¹ X ¹ X ² Y X ³ X ⁴ 222 NH ₂ SCF ₃ SCF ₃ Cl H Cl H H 223 NH ₂ SOCF ₃ Cl Cl H Cl H H 224 NH ₂ SC! ^: ₃ Cl Cl H Cl H H 225 NH ₂ • SO ₂ CF ₃ Cl Cl H Cl H H 226 H SCF ₃ Cl Cl H Cl H H 227 H SOCF ₃ Cl Cl H Cl H H 228 ' H SO ₂ CF ₃ Cl Cl H Cl H H 229 NH ₂ SCF ₃ H H H Cl H H 230 H SCF ₃ Cl Cl H CF ₃ H br 231 H SOCF ₃ Cl Cl H CF ₃ H br 232 H SO ₂ CF ₃ Cl Cl H CF ₃ H br 233 H SCF ₃ Cl F H CF ₃ H F 234 H SOCF ₃ Cl F H CF ₃ H F 235 H SO ₂ CF ₃ Cl F H CF ₃ H F 236 H SCF ₃ Cl F F CF ₃ F F 237 H SOCF ₃ Cl F F CF ₃ F F 238 H SO ₂ CF ₃ Cl F F CF ₃ F F 239 H SCF ₃ br F F CF ₃ F F 240 H SOCF ₃ br F F CF ₃ F F 241 H SO ₂ CF ₃ br F F CF ₃ F F 242 H SCF ₃ Cl Cl H PCS H Cl 243 H SOCF ₃ Cl Cl H 3CF ₃ H Cl 244 H SO ₂ CF ₃ Cl Cl H SCF ₃ H Cl 245 H SCF ₃ Cl Cl H SO, CF ₃ H Cl 246 H SOCF ₃ Cl Cl H SO ₂ CF ₃ H Cl 247 H SO ₂ CF ₃ Cl Cl H SO ₂ CF ₃ H Cl 248 NH ₂ SCCI ₂ F H Cl H CF ₃ H Cl 249 NH ₂ SOCCI ₂ F H Cl H CF ₃ H Cl 250 NH ₂ SO ₂ CCI ₂ F H Cl H CF ₃ H Cl 251 NH ₂ SCCI ₂ F Cl Cl H CF ₃ H Cl 252 NH ₂ SOCCI ₂ F Cl Cl H CF ₃ H Cl 253 NH ₂ SO ₂ CCI ₂ F Cl Cl H CF ₃ H Cl 254 NH ₂ SCCI ₂ F F Cl H CF ₃ H Cl 255 NH ₂ SOCCI ₂ F F Cl H CF ₃ H Cl 256 NH ₂ SO ₂ CCI ₂ F F Cl hl CF ₃ H Cl 257 H SCCI ₂ F H Cl H CF ₃ H Cl 258 H SOCCI ₂ F H Cl H CF ₃ H Cl 259 H SO ₂ CCI ₂ F H Cl H CF ₃ H Cl 260 H SCCI ₂ F CF ₃ Cl H CF ₃ H Cl 261 H SOCCI ₂ F CF ₃ Cl H CF ₃ H Cl 262 H SO ₂ CCI ₂ F CF ₃ Cl H CF ₃ H Cl 263 H SCCI ₂ F CN Cl H CF ₃ H Cl 264 H SOCCI ₂ F CN Cl H CF ₃ H Cl 265 H SO ₂ CCI ₂ F CN Cl H CF ₃ H Cl 266 CN SCCI ₂ F H Cl H CF ₃ H Cl 267 CN SOCCI ₂ F H Cl H CF ₃ H Cl 268 CN SO ₂ CCI ₂ F H Cl H CF ₃ H Cl 269 NH ₂ SCCIF ₂ H Cl H CF ₃ H Cl 270 NH ₂ SOCCIF ₂ H Cl H CF ₃ H Cl 271 NH ₂ SO ₂ CCIF ₂ H Cl H CF ₃ H Cl 272 NH ₂ SCCIF ₂ Cl Cl H CF ₃ H Cl 273 NH ₂ SOCCIF ₂ Cl Cl H CF ₃ H Cl 274 NH ₂ SO ₂ CCIF ₂ Cl Cl H CF ₃ H Cl 275 H SCCF ₂ Cl Cl H CF ₃ H Cl 276 H SOCCIF ₂ Cl Cl H CF ₃ H Cl 277 H SO ₂ CCIr ₂ Cl Cl H CF ₃ H Cl 278 H SCCIF ₂ F Cl H CF ₃ H Cl 279 H SOCCIF ₂ F Cl H CF ₃ H Cl 280 H SO ₂ CCIF ₂ F Cl H CF ₃ H Cl 281 F SCCIF, F Cl H CF ₃ H Cl 282 F SOCCIF ₂ F Cl H CF ₃ H Cl 283 F SO ₂ CCIF ₂ F Cl H CF ₃ H Cl 284 br SCCIF ₂ SO ₂ CH ₃ Cl H CF ₃ H Cl 285 br SOCCIF ₂ SO ₂ CH ₃ Cl H CF ₃ H Cl

R ¹ X R ³ X ¹ X ² Y -44- X ³ 289,920 br SO ₂ CCIF ₂ SO ₂ CH ₃ Cl H CF ₃ H Continuation Table 1 NH ₂ SCN H Cl H CF ₃ H X ⁴ RPC-No. NH ₂ SCH ₃ H Cl H CF ₃ H Cl 286 NH ₂ SOCH ₃ H Cl H CF ₃ H Cl 287 NH ₂ SO ₂ CH ₃ H Cl H CF ₃ H Cl 288 NH ₂ SCH ₃ Cl Cl H CF ₃ H Cl 289 NH ₂ SOCH ₃ Cl Cl H CF ₃ H Cl 290 NH ₂ SO ₂ CH ₃ Cl Cl H CF ₃ H Cl 291 NH ₂ 3CH ₃ F Cl H CF ₃ H Cl 292 NH ₂ SOCH ₃ F Cl H CF ₃ H Cl 293 NH ₂ SO ₂ CH ₃ F Cl H CF ₃ H Cl 294 NH ₂ SCH ₃ CF ₃ Cl H CF ₃ H Cl 295 NH ₂ SOCH ₃ CF ₃ Cl H CF ₃ H Cl 296 NH ₂ SO ₂ CH ₃ CF ₃ Cl H CF ₃ H Cl 297 H SCH ₃ H Cl H CF ₃ H Cl 298 H SOCH ₃ H Cl H CF ₃ H Cl 299 H SO ₂ CH ₃ H Cl H CF ₃ H Cl 300 H SCH ₃ Cl Cl H CF ₃ H Cl 301 H SOCH ₃ Cl Cl H CF ₃ H Cl 302 H SO ₂ CH ₃ Cl Cl H CF ₃ H Cl 303 H SCH ₃ F Cl H CF ₃ H Cl 304 H SOCH ₃ F Cl H CF ₃ H Cl 305 H SO ₂ CH ₃ F Cl H CF ₃ H Cl 306 Cl SCH ₃ H Cl H CF ₃ H Cl 307 Cl SOCH ₃ H Cl H CF ₃ H Cl 308 Cl SO ₂ CH ₃ H Cl H CF ₃ H Cl 309 Cl SCH ₃ Cl Cl H CF ₃ H Cl 310 Cl SOCH ₃ Cl Cl H CF ₃ H Cl 311 Cl SO ₂ CH ₃ Cl Cl H CF ₃ H Cl 312 Cl SCH ₃ F Cl H CF ₃ H Cl 313 Cl SOCH ₃ F Cl H CF ₃ H Cl 314 Cl SO ₂ CH ₃ F Cl H CF ₃ H Cl 315 Cl SCH ₃ CF ₃ Cl H CF ₃ H Cl 316 Cl SOCH ₃ CF ₃ Cl H CF ₃ H Cl 317 Cl SO ₂ CH ₃ CF ₃ Cl H CF ₃ H Cl 318 F SCH ₃ H Cl H CF ₁ H Cl 319 F SOCH ₃ H Cl H CF ₃ H Cl 320 F SO ₂ CH ₃ H Cl H CF ₃ H Cl 321 F SCH ₃ F Cl H CF ₃ H Cl 322 F SOCH ₃ F Cl H CF ₃ H Cl 323 F SO ₂ CH ₃ F Cl H CF ₃ H Cl 324 F SCH ₃ Cl Cl H CF ₃ H Cl 325 F SCCH ₃ Cl Cl H CF ₃ H Cl 326 F SO ₂ CH ₃ Cl Cl H CF ₃ H Cl 327 NH ₂ SCF ₂ CCI ₂ F H Cl H CF ₃ H Cl 328 MH ₂ SOCF ₂ CCI ₂ F H Cl H CF ₃ H Cl 329 NH ₂ SO ₂ CF ₂ CCI ₂ F H Cl H CF ₃ H Cl 330 NH ₂ SCF ₂ CCI ₂ F Cl Cl H CF ₃ H Cl 331 NH ₂ SOCFjCCI ₂ F Cl Cl H CF ₃ H Cl 332 NH ₂ SO ₂ CF ₂ CCI ₂ F Cl Cl H CF ₃ H Cl 333 NH ₂ SCF ₂ CCI ₂ F F Cl H CF ₃ H Cl 334 NH ₂ SOCF ₂ CCI ₂ F F Cl H CF ₃ H Cl 335 NH ₂ SO ₂ CF ₂ CCI ₂ F F Cl H CF ₃ H Cl 336 H SCF ₂ CCI ₂ F H Cl H CF ₃ H Cl 337 H SOF ₂ CCI ₂ F H Cl H CF ₃ H Cl 338 H SO ₂ CF ₂ CCI ₂ F H Cl H CF ₃ H Cl 339 H SCF ₂ CCI ₂ F Cl Cl H CF ₃ H Cl 340 H SOCF ₂ CCI ₂ F Cl Cl H CF ₃ H Cl 341 H SO ₂ CF ₂ CCI ₂ F Cl Cl H CF ₃ H Cl 342 F SCF ₂ CCI ₂ F H Cl H CF ₃ hl Cl 343 F SOCF ₂ CCI ₂ F H Cl H CF ₃ H Cl 344 F SO ₂ CF ₂ CCI ₂ F H Cl H CF ₃ H Cl 345 F SCF ₂ CCI ₂ F Cl Cl H CF ₃ H Cl 346 F SOCF ₂ CCI ₂ F Cl Cl H CF ₃ H Cl 347 Cl 348 Cl 349

Continuation Table 1

RPC-No. R ¹ X R ³ X ¹ X " Y ^XY X ⁴ 350 F SO, CF, CCI, F Cl Cl H CF ₃ H Cl 351 H SCF ₂ CHF, Cl Cl H CF ₃ H Cl 352 H SOCF ₁ CHF, Cl Cl H CF ₃ H Cl 353 H SO ₂ CF ₂ CHF, Cl Cl H CF ₃ H Cl 354 H SC, F ₆ Cl Cl H CF ₃ H Cl 355 H SOC ₆ F ₆ Cl Cl H CF ₃ H Cl 356 H SO ₂ C ₈ F ₆ Cl Cl H CF ₃ H Cl 357 H OCF ₃ Cl Cl H CF ₃ H Cl 358 H OCF ₃ F Cl H CF ₃ H Cl 359 F OCF ₃ H Cl H CF ₃ H Cl 360 F OCF ₃ Cl Cl H CF ₃ H Cl 361 F OCF ₃ F Cl H CF ₃ H Cl 362 Cl OCF ₃ H Cl H CF ₃ H Cl 363 Cl OCF ₃ Cl Cl H CF ₃ H Cl 364 Cl OCF ₃ CF ₃ Cl H CF ₃ H Cl 365 H 0CF, H Cl Cl H CF ₃ H Cl 366 H OCF ₂ H F Cl H CF ₃ H Cl 367 NH, C (= 0) CF ₃ Cl Cl H CF ₃ H Cl 368 NH, C (= S) CF ₃ Cl Cl H CF ₃ H Cl 369 NH, CI = O) CF ₃ F Cl H CF ₃ H Cl 370 NH, CI = S) CF ₃ F Cl H CF ₃ H Cl 371 NH, CI = O) CF ₃ br Cl H CF ₃ H Cl 372 NH, CI = S) CF ₃ br Cl H CF ₃ H Cl 373 H CI = O) CF ₃ Cl Cl H CF ₃ H Cl 374 H CI = S) CF ₃ Cl Cl H CF ₃ H Cl 375 H CI = O) CF ₃ F Cl H CF ₃ H Cl 376 H CI = S) CF ₃ F Cl H CF ₃ H Cl 377 H CI = O) CF ₃ CF ₃ Cl H CF ₃ H Cl 378 H CI = S) CF ₃ CF ₃ Cl H CF ₃ H Cl 379 H CF ₃ Cl Cl H CF ₃ H Cl 380 H CF ₃ CN Cl H CF ₃ H Cl 381 H SCCL ₂ F H Cl H Cl H OCH ₃ 382 H SOCCL ₂ F H Cl H Cl H OCH ₃ 383 H SCF ₃ H H H Cl H OCH ₂ CH ₃ 384 H SCF ₂ CI H Cl H Cl H br 385 H SOCF ₁ CI H Cl H Cl H br 386 H SCF ₃ H H H Cl H br 387 H SCF ₂ CI H Cl H Cl H SCH ₃ 388 H SCCL ₂ F H Cl Ή Cl H SCH ₃ 389 H SCF ₃ H Cl H Cl H SCH ₂ CH ₃

Table 2

Further representative pyrrole compounds (RPC) of the formula I where X ² , X ³ = H; X ¹ , X ⁴ = Cl and Y = CF ₃

Substituent meanings

RPC-No.

390 391 392 393 394 395 396 397 398 399 400 401 402 403 404 405 406

H H H H H H H H H H H H Cl Cl

SCF ₃

SOCF ₃

SO ₂ CF ₃

SCF ₃

SOCF ₃

SO ₂ CF ₃

SCF ₃

SOCF ₃

SO ₂ CF ₃

SCF ₃

SOCF ₃

SO ₂ CF ₃

SCF ₃

SOCF ₃

SO ₂ CF ₃

SCF ₃

SOCF ₃

CN

CN

CN

CF ₃

CF ₃

CF ₃

SO ₂ CF ₃

SO ₂ CF ₃

SO ₂ CF ₃

H H H H H H H H H H H H H H

Continuation Tabulation 2

RPC-No. R 'XR ³ R ^;

407 Cl SOjCFj Cl H

408 Cl SCF ₃ FH

409 Cl SOCF ₃ FH

410 Cl SCF ₃ CN H

411 Cl SOCF ₃ CN M

412 Cl SOjCF ₃ CN H • 413 CN SCF ₃ Cl H

414 CN SOCF ₃ Cl H

415 CN SOjCF ₃ Cl H

416 CN SCF ₃ FH

417 CN SOCF ₃ FH

418 CN SOjCFj F H

419 CN SCF ₃ CF ₃ H

420 CN SOCF ₃ CF ₃ H 121 CN SOjCF ₃ CF ₃ H

422 F SCF ₃ Cl H

423 F SOCF ₃ Cl H

424 F SO ₂ CF ₃ Cl H

425 H SCF ₃ Cl Cl

426 H SOCF ₃ Cl Cl

427H SO ₂ CF ₃ Cl Cl

428 H SCF ₃ F Cl

429 H SOCF ₃ F Cl

430H SO ₂ CF ₃ F Cl

431 H SCF ₃ CN Cl

432 H SOCF ₃ CN Cl

433 H SOjCF ₃ CN Cl

434 H SCF ₃ CF ₃ Cl

435 H SOCF ₃ CF ₃ Cl

436 H SOjCF ₃ CF ₃ Cl

437 Cl SCF ₃ Cl Cl

438 Cl SOCF ₃ Cl Cl

439 Cl SO ₂ CFj Cl Cl

440 Cl SCF ₃ F Cl

441 Cl SOCF ₃ F Cl

442 Cl SO ₂ CF ₃ F Cl

443 Cl SCF ₃ CN Cl

444 Cl SOCF ₃ CN Cl

445 Cl SO ₂ CF ₃ CN Cl

446 Cl SCF ₃ CF ₃ Cl

447 Cl SOCF ₃ CF ₃ Cl

448 Cl SOjCF ₃ CF ₃ Cl

449 CN SCF ₃ Cl Cl

450 CN SOCF ₃ Cl Cl

451CN SO ₂ CF ₃ Cl Cl

452 CN SCF ₃ F Cl

453 CN SOCF ₃ F Cl

454 CN SO ₂ CF ₃ F Cl

455 CN SCF ₃ CN Cl

456 CN SOCF ₃ CN Cl

457 CN SO ₂ CF ₃ CN Cl

458 CN SCF ₃ CF ₃ Cl

459 Cl SOjCF ₃ FH

460 CN SOCF ₃ CF ₃ Cl

461 CN SOjCF ₃ CF ₃ Cl

462. H SCF ₃ Cl CF,

463 H SCF ₃ F CF ₃

464 H SOCF ₃ F CF ₃

465 H SO ₂ CF ₃ F CF ₃

466 H SCF ₃ CN CF ₃

467 H SOCF ₃ CN CF ₃

468 H SO ₂ CF ₃ CN CF ₃

469 H SCF ₃ Cl CF ₃

470 H SOCF ₃ Cl CF ₃

471H SO ₂ CF ₃ Cl CF ₃

-47- 289 Continuation Table 2

RPC-No, R ¹ XR ³ R ¹

472 H SCF ₃ Cl CH ₃

473 H SOCF ₃ Cl CH ₃

474H SO ₁ CF ₃ Cl CH ₃

475 H SCF ₃ F CH ₃

476 H SOCF ₃ F CH ₃

477 H SO ₂ CF ₃ F CH ₃ '478 H SCHF ₂ Cl CN

479 H SOCHF ₂ Cl CN

480 H SO ₂ CHF ₂ Cl CN

481 H SHF ₂ H CN

482 H SOCHF ₂ H CN

483 H SO ₂ CHF ₂ H CN

484 H SO ₂ CHCl ₂ Cl CN

485 H SOCHCI ₂ Cl CN

486 H SOCHCIF Cl CN

487 H SO ₂ CHCIF Cl CN

488 H SCHF ₂ Cl Cl

489 H SO ₂ CHF ₂ Cl Cl

490 H SOCHF ₂ Br CH ₃ 491 Cl SO ₂ CHF ₂ Cl CF ₃

embodiments

The invention will be explained in more detail below with reference to examples. Examples 1 to 22 below illustrate the synthesis and physical properties of insecticidally active compounds and their intermediates according to the invention.

example 1

A solution of 910 mg (2.07 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylthiopyrrole (prepared by the method of Example 4) and 492 mg of an 80% solution of m-chloroprobenzoic acid (394 mg, 2.28 mmol) in 25 ml of chloroform was stirred at room temperature for 1.5 h and then heated at reflux overnight. Thereafter, another 45 mg (0.21 mmol) of m-chloroperoxybenzoic acid was added, followed by heating at reflux for 1 h. Thereafter, the heating was interrupted; the reaction mixture was diluted with dichloromethane and washed with an aqueous solution of bicarbonate. The organic phase was dried over anhydrous MgSO ₄ and evaporated under reduced pressure to give a colorless solid as residue

 This procedure was repeated to give a total of 950 mg of product which was chromatographed on silica gel using ice eluent a 2: 1 (v / v) mixture of dichloromethane and hexane. The early fractions contained 310mg (24%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-

trifluoromethylsulphonylpyrrole (Example 1), which is a colorless solid. Recrystallization from hexane-ethyl acetate gave 240 mg of the sulf ms as colorless needles; F.198 ° C.

Example 2

The chromatography performed at the end of the procedure of Example 1 was continued. The later fractions thereof gave 600 mg (48%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfinylpyrrole (Example 2) as a colorless solid. Recrystallization from toluene-hexane provided 390 mg of the sulfoxide in the form of a colorless powder;

152 to 154.5 F. ⁰ C.

Examples 3A and 3B

Examples 1 and 2 were repeated with 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-r.yano-4-trifluoromethylthio-5-bromopyrrole starting material prepared according to the ancestor of Example 5 was. The compound of Example 3A is 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfinyl-5-bromopyrrole. This compound, prepared using a similar procedure to Example 2, has a melting point of about 123 ^° C. The compound of Example 3B is 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro 3-cyano-4-trifluoromethylsulfonyl-5-bromopyrrole. This compound, which was prepared by a similar method as in Example 1, has a melting point of about 113 ° C.

Example 4

A solution of 3 g (6.6 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-chlorobromine (prepared by the method of Example 8) in 50 ml of dry tetrahydrofuran was stirred under a nitrogen atmosphere and admixed with 3.9 ml (3.4 g, 33 mmol) of i-butyl nitrite. After 30 minutes, the reaction mixture was refluxed for about 11 minutes and then evaporated under reduced pressure to give 3.69 g of a solid as a residue. This procedure was repeated to give a total of 4.07 g of solid residue, which was chromatographed on silica gel using as eluent a 1: 1 (v / v) mixture of dichloromethane and hexane;

-48- 28!) 920

thereby, 2.9 g (91%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-trifluoromethyl-thiopyrrole (Example 4) was obtained in the form of a colorless solid. Recrystallization from hexane-ethyl acetate gave 1.87 g of the product as a colorless powder; F. about 137 ⁰ C.

example

A heterogeneous C. ..ι of 5.4 g (5.28 mmol) of 1- (2,6-dichloro-4-tiifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole (prepared by the method of Example 8) in 40 ml of bromoform were added under an inert atmosphere with 0.94 ml (820 mg, 7.92 mmol) of t-butylnitrite. After stirring for 15 minutes at room temperature, the crude mixture was evaporated under reduced pressure to give 3.9 g of residue. The residue was combined with the product of a corresponding earlier reaction of 300 mg of the same pyrrole as starting material. This crude product was chromatographed on silica gel, eluting with a 4: 1 (v / v) mixture of hexane and dichloromethane. This separated 1.72 g (56%) of 1- (2,6-dichloro-4-trifluoromethyl-phonon) -2-bromo-3-trifluoromethylthio-4-cyano-5-chloropyrrole (Example 5) which was recrystallized from hexane, whereby 780 mg of the product were obtained in the form of a colorless solid; F. about 92 ° C.

Examples

A solution of 1.91 g (4.21 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole (prepared by the method of Example 8), 77 mg (0.63 mmol) of 4-dimethylaminopyridine and 20 mg of pyridine were cooled to ⁰ ° C. under an inert atmosphere, whereupon 1.01 ml (1.50 g, 7.14 mmol) of trifluoroacetic anhydride were added. The reaction mixture was then stirred at ⁰ ° C. for 1 hour and at 20 ° C. for 4 hours, followed by addition of another 0.30 ml (2.1 mmol) of trifluoroacetic anhydride. After a total of 24h reaction time, the reaction mixture was diluted with dichloromethane and evaporated. The residue was washed with aqueous HCl and then with water and recrystallised from hexane-ethyl acetate to give 860 mg (37%) of 1- (2,6-dichloro-4-trifluoromethyl-phonyl) -2- (trifluoromethyl) -carbonylamino-S-trifluoromethylthio cyano-6-chloropyrrole (Example 6) was obtained as a slightly green solid; F. about 190 ⁰ C.

Example 7

A mixture of 1.50 g (3.3 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole (prepared by the method of Example 8). , 0.10 g 4-dimethylaminopyridine, 0,33ml (0.32 g; 4.1 mmol) of pyridine, 0.31 ml (0.34 g; 4,3mmol) of acetyl chloride and 10 ml of acetonitrile were 4d at 2O ⁰ C and 1 d at Stirred reflux. A further 0.03 ml of acetylchloroyl was added to the well, followed by refluxing for a further day; then the reaction mixture was cooled, diluted with dichloromethane, and the organic phase was extracted with aqueous 1N HCl and then with a saturated aqueous sodium bicarbonate solution. The organic phase was dried over anhydrous magnesium sulfate and evaporated to give 1.42 g of a beige solid. Chromatography on silica gel using a 4: 1 (v / v) mixture of hexane and ethyl acetate followed by recrystallization from ethanol-water gave 480 mg (29%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2- methylcarbonylamino-3-trifluoroniethylthio-4-cyano-5-chloropyrrole (Example 7) in the form of colorless needles; F. about 216 ⁰ C.

Example 8

A solution of 1.50 g (3.57 mmol) of 1-i2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole (prepared by the method of Example 13) in 15 ml of ethyl ether was added stirring and cooled in an inert atmosphere at 2O ⁰ C and a solution of 0.29 ml (0.48 g; 3,6mmol) of sulfuryl chloride in anhydrous 15 ml of ether tropfenwek 9 was added. The reaction mixture was then warmed to 20 ⁰ C and stirred for 2.5d, after which another 0.03 ml (0.4 mmol) of sulfuryl chloride were added and a further day stirring. Subsequently, 0.03 ml of sulfuryl chloride were added again, whereupon after a further day the reaction was stopped with 28 ml of a 10% aqueous K.Miumcarbonatlosung. The phases were separated; the aqueous phase was extracted with ether. The ethereals were combined, washed with water, dried over anhydrous magnesium sulfate and evaporated to give 1.50 g of a brown solid. The crude product was chromatographed on silica gel using a 2: 1 (v / v) mixture of dichloromethane and hexane as eluent to give 1.30 g (80%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2- amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole (Example 8) as a light pink solid. Recrystallization from cyclohexane gave 810 mg of the product as pale white needles; F. about 176 ° C.

Example 9

The procedure was as in Example 8 with the difference that 1- (2-chloro-4-trifluoromethylthylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole (mp. 169 ⁰ C) was used as a reactant, which according to a Procedure was prepared according to Example 13. The final product was 1- (2-chloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-c / ano-5-chloropyrrole (Example 9); F. about 148 ° C.

Example 10

The procedure was as in Example 8 with the difference that 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-dichlorofluoromethylthio-4-cyanopyrrol (F. 202 ⁰ C) was used as a reactant, the was prepared by a method according to Example 13. The final product was i- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-dichlorofluoromethylthio-4-cyano-5-chloroprene (Example 10); F. about 207 ° C.

Example 11

1- (2,6-dichloro-4-trifluoromethylphenyl) -2,4-bis (trifluoromethylthio) -3-cyano-5-aminopyrrole (Example 11) was prepared by the method of Example 13 (I. Compound) using an excess prepared on trifluoromethanesulfenyl chloride; F. 161 ⁰ C.

Example 12

To a cold (O ⁰ C) solution of 1.53 g (3.60 mmol) of 1- (2, e-D-chloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole (prepared by the method of Example 13; F. about 182 ⁰ C) in 15ml pyridine Pyrldiniumbromld-perbromld was added in 15 ml of pyridine under an inert atmosphere Oino solution of 1.46 g (3,6mmol) of 80%. After 30 min, the reaction mixture was poured into cold (O ⁰ C) ethyl ether; The precipitate formed was filtered off. The filtrate was washed with aqueous HCl, aqueous NaOH and water. The organic phase was dried over anhydrous magnesium sulfate and evaporated to give 1.34 g of a brown solid. This product was treated with 230 mg of a product from a previous reaction of 300 mg (0.7 mmol) of 1- (2, e-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole and 0.29 g of 80% pyridinium bromide. Perbromide united. This total product was chromatographed on silica gel using a 4: 1 (V7V) mixture of hexane and ethyl acetate as eluent. There was thus obtained 1.31 g (73%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-aminol-3-trifluoromethylthio-4-cyano-5-bromopyrrole (Example 12) as a white solid. Recrystallization from hexane / ethyl acetate gave 910 mg of this product as colorless needles; F. about 16O ⁰ C.

Example 13

A solution of 2.00 g (6.25 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-4-cyanopyrrole in 60 mL of dichloromethane, prepared as explained below, was added with stirring cooled in a Eisbp.s and with 10ml of a cold (-78 ⁰ C) dichloromethane solution in slow stream containing 0.55 ml (0.85 g, 6.2 mmol) trifluoromethanesulfonyl chloride. After stirring for 2 h at ⁰ ° C., nitrogen was passed through the reaction mixture for 1 h. After extraction with saturated aqueous sodium bicarbonate solution and water and drying over anhydrous magnesium sulfate and evaporation in vacuo, 3.14 g of a tan solid was obtained. Chromatography on silica gel using a 3: 2 (v / v) * mixture of dichloromethane and hexane as eluent gave two colorless solids of 900 and 95 oun mass, respectively. This material was recrystallized from chloroform, whereupon 680 and 630 mg of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole (Example 13) were obtained; F.etwa182 ° C.

The starting material used in this procedure was prepared by the following procedure: A solution of 4.64 g (14.5 mmol) of i-ß.e-Dichloro-trifluoromethylphenyD-amino ^. S-dicyanopropene and 2.02 mg (1.47 g, 14 , 5mmol) triethylamine in 30ml benzene was heated at reflux overnight and then evaporated in vacuo. The residue was partitioned between ethyl ether and water; the ether phase was then dried over anhydrous magnesium sulfate and evaporated to give 3.79 g of a tan solid. Recrystallization from ethanol-water gave 2.79 g (60%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-4-cyanopyrrole; F. about 176 ° C.

The starting i-arylamino-.s-dicyanopropene was prepared by the following procedure: 20.5 g (0.140 mol) of the potassium salt of formyl succinonitrile were dissolved in about 30 ml of water, which was then acidified with concentrated hydrochloric acid. This mixture was then extracted with ethyl ether; The ether extracts were dried over anhydrous magnesium sulfate and evaporated to give 3.87 g of a brown liquid. This product was added to a solution containing 5.04 g (22 mmol) of 2,6-dichloro-4-trifluoromethylaniline and 40 mg of p-toluenesulfonic acid monohydrate in 50 ml of benzene. The heterogeneous reaction mixture was then refluxed overnight, with water being separated. The reaction mixture was then cooled and evaporated to yield 7.66 g of a yellow liquid. Trituration with hexane precipitated 6.68 g (95%) of i-lZ.e-dichloro-trifluoromethylphenyl-amino-1-5-dicyenopropene as a yellow solid. Recrystallization from ethanol / water gave a purified sample; F. about 101 "C.

Examples 14A and 14B

A suspension of 1.17g (3.30mmol) of 1- (4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole and 0.46ml (0.34g, 3.3mmol) of triethylamine in 20ml of chloroform which was added After cooling to ⁰ ° C., a solution of 0.19 ml (0.59 g, 3.7 mmol) of bromine in 5 ml of chloroform was added. The reaction mixture was stirred at -20 ° C for 1 h and allowed to warm to ⁰ ° C. Then another 0.04rr.l (0.13g, 0.8mmol) of bromine was added; after stirring for a further 15 minutes, the reaction mixture was diluted with dichloromethane and extracted with water and a saturated aqueous sodium bicarbonate solution. The organic phase was dried over anhydrous magnesium sulfate and evaporated to give 1.11 g of a brown solid. This material was combined with the product of a preliminary reaction of 1.00 g (2.8 mmol) iW-trifluoromethylphenyD ^ -amino-S-trifluoromethylthio ^ -cyanopyrrole and 0.15 ml of bromine. Chromatography on silica gel using a 3: 1 (v / v) mixture of dichloromethane and hexane as eluent gave 1.40 g (52%) of 1- (4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano 5-bromopyrrole (Example 14A) in the form of a yellow solid. Recrystallization from hexane-ethyl acetate gave a product in the form of light yellow platelets, mp ca. 175 ^° C.

1- (4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole (Example 14B), mp. About 152 ° C, can be prepared from 1- (4-trifluoromethylphenyl) amino) -2,3-dicyanopropene prepared according to the method described in Example 13.

Examples 15A and 15B

1 - (2-Chloro-4-trifluoromethyl-phenyl) -amino-2,3-dicyanopropene was prepared by the method of Example 13. This dicyanopropene compound was used to prepare 1- (2-chloro-4-trifluoromethylpienyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole (Example 15A) prepared by the method of Example 13; F. about 169 ⁰ C. This pyrrole (Example 15B) was used to prepare 1- (2-chloro-4-trifluoromethylphenyl) -2-amino-S-trifluoromethylthio ^ -cyano-e-bromopyrrole used by the method of Example 14 was produced; F. about 157 ⁰ C.

Examples 16A and 16B

1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-4-cyanopyrrole prepared according to Example 13 was prepared by the method of Example 13 (using CF ₃ SCI) with CFCl ₂ - SCI treated to give 1- (2,6, dichloro-4-trifluoromethylphenyD ^ -amino-S-dichlorofluoromethylthio) -cyanopyrrole (Example 16A), mp ~202 ° C. This compound was prepared by the method of Example 4 with t -Butylnitrit beha ndelt, where 1 - (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4 - (dichloromethylthio) pyrrole was obtained (example 16B); F. about 158 ⁰ C.

Example 17

The latter compound of Example 16 was reacted in a manner similar to Examples 1 and 2 using hydrogen peroxide in trifluoromethyl porosacetic acid (instead of chloroperoxybenzoic acid) to give 1- (2,6-D-OHM-trifluoromethylphenyl-N-chloro-S -cyono-dichloro-fluoro-diylsulfine-4-pyrrole {Example 17); F. about 119 ⁰ C.

Example 18

Following Example 17, the latter compound of Example 16 was prepared using a double amount of hydrogen peroxide in 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-1-1- (dichlorofluoromethylsulfonyl) - pyrrole (Example 18) converted; F. about 179 ° C.

Example 19

The former compound of Example 16 was treated with t-butyl nitrite following the procedure of Example 4 to give 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-cyano-4- (dichlorofluoromethylthio) -pyrrole (Example 19) has been;

Example 20

The compound of Example 19 was oxidized by the method of Example 17 to give 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-cyano-4- (dichlorofluoromethylsulfinyl) -pyrrole (Example 20); F. 150-152 ⁰ C.

Examples 21A, 21B and 21C

1- (2,6-dichloro-4-trifluoromethoxyphenyl) -amino-2,3-dicyanopropene was prepared according to the procedure described for the latter compound of Example 13, wherein instead of 2,6-dichloro-4-trifluoromethylaniline 2.6 -DicMor-4-trifluoromethoxyaniline was used.

This compound was converted to 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-amino-4-cyanopyrrole by the ancestor described for the second precursor of Example 13.

This compound was again converted to 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole following the procedure described for the former compound of Example 13.

This compound was converted to 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-amino-3-trifluoromethylthio-cyano-S-chloropyrrole (Example 21A) by the method of Example 8; F. 196-197 ⁰ C.

This compound was finally converted to 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4-trifluoromethylthiopyrrole (Example 12B) by the method of Example 4; F. 172 ⁰ C.

This compound was further converted to 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfonylpyrrole (Example 21 C) by the method of Example 18; F. 187 ^° C.

Examples 22A, 22R and 22C

A mixture of 2-chloro-4-chlorosulfenyl-3-cyano-1 • (2 ', 6'-dichloro-4-trifluoromethylphenyl) -pyrrole and 2-chloro-3-cyano-4-dichlorofluoromethylsulfenyl-1- (2' , 6'-dichloro-4'-trifluoromethylphenyl) -pyrrole (47.77 g: 0.101 mol, 1.0 eq.) Was golewed in trifluoroacetic acid (190 mL) at ⁰ ° C. Thereafter, 30% H ₂ O ₂ (10.8 mL, 0.106 mol, 1.05 eq.) Was added dropwise. The reaction mixture was then stirred at ⁰ ° C. for 7.25 h and then allowed to sit in the refrigerator (10 ° C.) overnight, followed by further 30% H ₂ O ₁ (10.8 mL, 0.106 mol, 1.05 eq the next morning at ⁰ ° C. The reaction mixture was then stirred for 9 hours in OX and then allowed to stand in the refrigerator overnight, after which 30% H ₂ O ₂ (10.8 ml, 0.106 mol, 1.05 eq. ) was added at ⁰ ° C. After 3.5 hours the reaction mixture was finally poured into 2 l of ice water;., the reaction mixture was stirred vigorously and then filtered in a similar manner, a mixture of 2-chloro-4-chlorosulfenyl-3-cyano-1-. (2'-6'-dichloro-4'-trifluoromethylphenyl) -pyrrole and 2-chloro-3-cyano-4-dichlorofluoromethylsulfenyl-1- (2'6'-dichloro-4'-trifluoromethylphenyl) -pyrrole (40.77g 0.0848 mol, 1.0 equiv) in trifluoroacetic acid (188mi) on OX, followed by the dropwise addition of 30% H ₂ O ₂ (17.7 mL, 0.173 mol, 2.05 eq) sets. The reaction mixture was then stirred at ⁰ ° C 2,75h and then overnight in a refrigerator (1O ⁰ Cj left. After stirring for 8 h at ⁰ ° C., the reaction mixture was then again left in the refrigerator overnight. There-. Reaction mixture was then allowed to warm to room temperature and stirred again at room temperature overnight. Thereafter, 30% H ₂ O ₂ (9.05 mL, 0.0886 mol, 1.05 eq.) Was added the following morning at ⁰ ° C, after which the reaction mixture was kept at OX for 40 min. then allowed to warm to room temperature and stirred for one weekend. The maintained reaction mixture was finally poured into 2 1 of ice water; the resulting mixture was stirred vigorously and then filtered.

The precipitates of both reactions were combined and dissolved in 500 ml of dichloromethane; the solution was washed with 500 ml of water, 500 ml of 10% NaHSO ₃ and 500 ml of saturated NaCl solution. The organic phase was dried over Na ₂ SO ₄ and filtered. Evaporation of the solvent gave 74.96 g (79.9% yield) of a solid. This product was recrystallized from 690 ml of a 2: 1 mixture of hexane and dichloromethane to which 20 ml of dichloromethane had been added to give 6.98 g of a solid which was obtained as 2-chloro-4-chlorosulfonyl-3-cyano-1. (2 ', 6'dichloro-4'-trifluoromethylphenyl-pyrrole! Example 22A) was identified. This product was then recrystallized from 103 ml of isopropanol to give 3.97 g of product; 187 to 188.5 F. ⁰ C.

2-Chloro-4-chlorosulfonyl-3-cyano-1- (2 ', 6'-dichloro-4'-trifluoromethylphenyl) -pyrrole (3.97g, 9.06mmol, 1.0eq.) Was dissolved at ⁰ ° C dissolved in THF (15.8ml). Subsequently, triohenylphosphine (2.41 g, 1.0 eq.) Was added in solid form. The solution then turned yellow. After 2.5 hours, the ice bath was removed and the reaction was allowed to warm to room temperature with stirring overnight. Further triphenylphosphine (2.55 g, 9.72 mmol, 1.06 eq.) Was added followed by stirring the reaction overnight at room temperature. Thereafter, a precipitate was formed; then 3 ml THF was added and the reaction mixture was washed twice with saturated NaCl solution and reextracted. The resulting organic phase was dried over MgSO ₄ and filtered; After evaporation of the solvent in vacuo, a waxy solid was obtained in an amount of 9.44 g. This product was chromatographed on silica gel to give 3.39 g of a waxy solid. This product was then recrystallized from 140 ml of isopropanol to give 2.54 g (74.9 g) of bis (2-chloro-3-cyano-1- (2 ', 6'-dichloro-4 "-trifluoromethylphenyl) -pyrrol-4 -yl) -disulfide (example 22B); 218.8 to 220.3 F. ⁰ C.

Bis (2-chloro-3-cyano-1- {2 ', 6'-dichloro-4-trifluoromethylphenyl-4-vinyl-4-sulfo) -disulfide (0.80 g; 1.08 mmol, 1.0 eq.) Was added in DMF (10ml) solved; the solution was cooled to ⁰ ° C. Then, Na ₃ HPO ₄ (0.46 g, 3.24 mmol, 3.0 eq.) Was dissolved in 5 mL of water, whereupon the solution was added to the DMF solution. As a precipitate formed, 15 mL of OMF and 10 mL of water were added. Solid Na ₂ SjO- (0.564 g, 3.24 mmol, 3.0 equiv.) Was then added, whereupon the reaction mixture turned a pale yellow color. Thereafter, dibromodifluoromethane (0.65 g, 3.1 mmol, 2.87 eq.) Was added to a cold, tared vial, which was then soaked in the reaction mixture. The reaction mixture then became colorless, forming a white precipitate. After 1 h 50 min, 10 ml DMF and then another 0.93 g CBr ₂ F _{2 were} added; the reaction vessel was connected ": ¹ closed and stirred overnight at room temperature. After cooling to OX, the reaction mixture was then added to 200 ml of water; the resulting mixture was extracted four times with 150 ml of ethyl ether. The organic phase was washed twice with 100 ml of 5% aqueous HCl, washed twice with 100 ml of saturated NaHCO ₃ solution and with 100 ml of saturated NaCl solution. The organic phase was then dried over MgSO ₄ and filtered; Evaporation of the solvent in vacuo gave 80.7 mg of a white solid. The initial aqueous phase was then filtered to yield a white solid which had precipitated overnight. This product was dissolved in dichloromethane; After evaporation of the solvent in vacuo and drying, 0.348 g of a white solid was obtained (total yield 0.429 g, 40%). This product was combined with the first product of 80.7mg; This material was chromatographed on silica gel to give 0.362 g of a white solid which was as 4-bromodifluoromethylsulfenyl-2-chloro-3-cyano-1- (2 ', 6'-dichloro-4'-trifluoromethylphenyl) -pyrrole (Example 22C). was identified; F. ⁰ 128.3 to 133.7 C.

More synthesis fogles

In accordance with the procedures detailed above for the synthesis of compounds of Examples 1 to 22 according to the invention or other general methods or processes which have been described above, a number of other pyrrole compounds of the formula I have been synthesized. The structure of these compounds and the corresponding melting points are shown in Tables 3 and 4 combined (Table 3, compounds (ASE] -No 1-91;. Compounds of formula I in which X ² and X ³ denote hydrogen, where the remaining substituents Tabel'o t, compounds [ASEJ Nos. 92 to 195; compounds of the formula I in which X 'and X ^{3 are} hydrogen, X ¹ and X ^{4 are} chlorine and VTrifluoromethyl, the remaining substituents being defined as indicated are).

Table 3

Further synthesis examples of compounds according to the invention (ASE) of the formula I where X ² , X ³ = H

of substituents

ASENo. R ¹ X R ² R ³ X ¹ Y X ⁴ F. (X) 1 NH ₂ CF ₃ S CN Cl CH ₃ br CH ₃ 215 to 215.5 2 H CF ₃ S CN Cl CH ₃ br CH ₃ 120.5 to 122 3 H CF ₃ SO CN H CH ₃ br CH ₃ 102 to 103.5 4 H CF ₃ SO ₂ CN H CH ₃ br CH ₃ 144.5 to 145 5 H CF ₃ SO CN Cl CH ₃ br CH ₃ 152-153 6 H CF ₃ SO ₂ CN Cl CH ₃ br CH ₃ 164 to 165.5 7 H CF ₃ S CN H Cl br Cl 207 to 208.5 8th H CF ₃ S CN Cl Cl br Cl 174-176 9 H CF ₂ CIS CN H Cl br Cl 113 10 H CF ₃ SO CN Cl Cl br Cl 140.5 to 141 11 NH ₂ CFjCIS CN H Cl Cl Cl 169.5 to 170 12 H CF ₃ SO ₂ CN Cl Cl br Cl 174 13 NHY CFCIjS CN H Cl br Cl 192-194 14 NHY CFCI ₂ S CN Cl Cl br Cl 239 to 240.5 15 H CFCI ₂ S CN Cl Cl br Cl 212.5 to 214 16 NH ₂ CF ₂ CIS CN CF ₂ CIS Cl Cl Cl 206-207 17 NHY CFCI ₂ S CN CFCI ₂ S Cl br Cl 214.5 to 218 18 H CF ₂ CISO CN H Cl br Cl 124.5 to 125.5 19 NHY CFCI ₂ S CN H Cl Cl Cl 177-178 20 H CF ₃ S CN hl Cl br Cl 111-112 21 H CFCI ₂ SO CN Cl Cl br Cl 174.5 to 175.5 22 H CFCIjS CN CFCI ₂ S Cl br Cl 143 23 H CFCIjS CN Cl Cl Cl Cl 190-191 24 H CFCI ₂ SO cn Cl Cl Cl Cl 151-152 25 H CF ₃ SO ₂ CN Cl CH ₃ S CF ₃ Cl 175.5 to 178 26 H CF ₂ CISO CN Cl Cl Cl Cl 143 27 H CF ₂ CIS CN Cl Cl Cl Cl 174 ?8th NH ₂ CFCI ₂ S CN H Cl OCF ₃ Cl 126 to 126.5 29 NH ₂ CFCI ₂ S CN Cl Cl OCF ₃ Cl 187-189 30 H CF ₃ S CH = O H Cl CF ₃ Cl 73-74 31 H CFCIjSO ₂ CN Cl Cl br Cl 195-196 32 H CF ₃ S CN Cl CH ₃ S CF ₃ Cl 117-118 33 H CFCl ₂ SO ₂ CN Cl Cl Cl Cl 189-190 34 H CFCI ₂ S CN H Cl OCF ₃ Cl 66-67 35 H CFCI ₂ S CN Cl Cl OCF ₃ Cl 137-139

Table 3 - continued

ASE no.

X ¹

X ⁴

F. (X)

36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 S7 68 69 70 71 72 73 74 7b 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91

H CF ₃ S CN H H CFCI ₂ S CN Cl H CFCl ₂ SO ₂ CN H H CFCIjSO CN H H CF ₂ CIS CN Cl H CFjCIS CN H H CFCIjSO CN Cl NHY CFCI ₂ S CN Cl H CFCl ₂ SO ₂ CN Cl H CFjCISO JN Cl H CF ₂ CISO CN H H CFCI ₂ S CN Cl H CFHCISO ₂ CN Cl H CFCI ₂ S CN Cl NHY CFCI ₂ S CN H H CF ₂ CISO ₂ CN H H CFCI ₂ S CN H H CFCI ₂ SO CN H H CF ₂ CISO ₂ CN Cl NH ₂ CFCI ₂ S CN Cl NH, CFCI ₂ S CN br H CFCI ₂ S CN Cl H CFCI ₂ SO: CN H H CFCI ₂ S CN H H CFCIjSOj CN Cl H CFCI ₂ S CN br H CFCIjSO CN Cl H CFCI ₂ SO CN H H CFCl ₂ SO ₂ CN br H CFCI ₂ SO CN br H CF ₃ S CN br H CFjCIS CN Cl H CF ₃ SO ₂ CN br H CF ₃ SO CN br H CFCIjSOj CN H H CF ₂ CISO ₂ CN Cl H CF ₂ CISO CN Cl H CF ₃ SO ₂ CN H H CF ₃ S CN H H CH ₃ S CN H H CFCIjS CN H H CF ₃ SO CN H H CF ₃ SO ₂ CN H H CCI ₃ S CN H H CFCIjS CN H H Cl CN H H CFCI ₂ S CN H H CFjCISOj CN H H CFCI ₂ SO CN br H CF ₃ SO ₂ CN CF ₃ S H CFCIjS CN br H CFCIjSOj CN br NHY CF ₂ CIS CN br H CFjCIS CN br H CFCIjS CN H NH ₂ CF ₃ CCI ₂ S CN H

Cl

CH ₃ SO

Cl

Cl

Cl

Cl

Cl

CH ₃

Cl

Cl

Cl

CH ₃ S

CH ₃ S

CH ₃

Cl

Cl

Cl

Cl

hl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

ci

OCF ₃

OCF ₃

OCF ₃

CO ₂ CH ₃

OCF ₃

CO ₂ CH ₃

CF ₃ O

CF ₃ O

Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl C! Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl

c:

C!

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

127-128.5 184-202 144-145 134-136

189.5-190.5 95-96

118.1-120.2 220

143.6-152.9 154 133-133.5

126.8-129.1 51.5-65 130-136 181-182 199 123

146.5-147 188-188.5 190-191 182-184 84-85

189.5 to 190

140.5-141 137-144 102-107 116-118 156-157 150-151 153-155 105-106 99-100 138-139 wax

212-213

129-132

92-95

183.5-184 80.5-81 114-116

106.5 to 107

130

165

147

96

146-147 121-121.5

183.5 to 184.5

115-118

50-52

1.38-140

128-130

150-153

60-63

131 to 132.5

162.8 to 188.1

Table 4

Further synthetic examples of the invention compounds (ASE) of formula I with X ² and X ³ - H; X ¹ and X ⁴ = Cl and Y = CF ₃

Subsiltuentenbedeutungen

ASENo.

R =

F. ( ⁰ C)

92 NH ₂ CFjCIS CN H 160.5 to 175 93 H CF ₃ SO ₂ CN H 199.5 to 201 94 H CFjCIS CN H 104.9 to 106.8 95. H CF ₂ CIS CN CFjCIS 114.5 to 117 96 NHY CF ₂ CIS CN Cl 178-181 97 H CFjCISO ₂ CN H 199.8 to 202 98 H CF ₂ CISO ₂ CN Cl 193.1 to 195.8 99 H CF ₂ CISO CN Cl 145.2 to 147.5 100 H CF ₂ CIS CN Cl 139.0 to 143.1 101 H CF ₃ S CN br 137-138 102 H CF ₃ SO CN br 164 to 165.5 103 H CF ₃ SO ₂ CN br 197-198 104 H CF ₂ CISO CN H 126.8 to 129.6 105 H CF ₃ S CN H 152-153 106 NH ₂ CFCIjCFjS CN H 183-190 107 NH ₂ CCI ₃ S CN H 189-193 108 H CFCIjCFjS CN H 118.8 to 123.8 109 H CFCIjCFjSOj CN H 157.5 to 161.9 110 H CFCIjCF ₂ SO CN H 182.5 to 183.9 111 NH ₂ CFCIjCFjS CN Cl 186,5-18P 112 H CFCIjCF ₂ SO CN Cl 149.5 to 151 113 br CF ₃ S CN H 163-164 114 H CFCI ₂ CF ₂ S CN Cl 113.5 to 116.5 115 H CCIjS CN Cl 177-182 116 H CFCIjCFjSOj CN Cl 147 to 150.5 117 H CCI ₃ SO ₂ CN Cl 200-202 118 H CCI ₃ SO CN Cl 152.2 to 153.5 119 Cl CF ₃ SO CN H 161.5 to 162.5 120 NH ₂ CH ₃ S CN H 150-151 121 H CFCIjS CN br 117-142 122 NH ₂ CFCIjS CN br 195.5 to 197 123 br CF ₃ SO CN H 170-172 124 H CFCIjSO ₂ CN br 176 to 178.5 125 H CFCI ₂ SO CN br 116.5 to 135.5 126 H SCN CN H 173 to 173.5 127 br CF ₃ SO ₂ CN H 179 to 180.5 128 H CH ₃ S CN H 107 to 108.5 129 NH ₂ CF ₂ CIS CN br 174.5 to 178 130 br CF ₂ CIS CN Cl 129.5 to 133.5 131 H CF ₂ CIS CN br 133.5 to 137.1 132 NHY Cl CN H 159.5 160 133 NHY CF ₃ S CN SCN 169-171 134 H CF ₃ S CN SCN 105 to 106.5 135 br CF ₂ CISO CN Cl 157.5 to 159 136 H Cl CN H 105.5 to 106.5 137 H CH ₃ SO CN H 144.5 to 145.5 138 H CH ₃ SO ₂ CN H 173 to 173.5 139 NH ₂ CF ₃ S CN SCH ₃ 146-148 140 H CF ₃ S CN SOCH ₃ 143-145 141 H CF ₂ CISO CN br 143 to 146.5 142 br CFCl ₂ SO ₂ CN Cl 117.8 to 122.5 143 CF ₃ CONH CF ₃ S CN H 187 to 188.5 144 H CF ₂ CISO ₂ CN br 182-185 145 H CF ₃ S CN CH ₃ S 89-91 146 H CF ₃ S CN CH ₃ SO ₂ 136-138 147 H CF ₃ SO CN CH ₃ SO ₂ 161-163 148 NH ₂ CF ₃ CCIjS CN H 200-220 149 NH ₂ CF ₃ CCI ₂ S CN Cl 223,5-232.5 150 H CF ₃ CCIjS CN Cl 170 to 172.5 151 H CF ₃ CCI ₂ SO ₂ CN Cl 195.3 to 197.2 152 H CF ₃ CCIjSO CN Cl 161 to 161.5 153 H CF ₃ S CN CF ₃ S 95-96

Continuation Tabule 4

ASENo. R ¹ X R ¹ R ³ F. ( ⁰ C) 154 NH ₂ CH ₃ SO CN H 130-132 155 NH ₂ CH ₃ SO ₂ CN H 248 to 248.5 156 H CF ₃ SO CN CF ₃ S 145-148 157 H CH ₃ S CN Cl 128-129 158 NH ₂ CF ₃ S CN SOCH ₃ 139-141 159 CH ₃ S CF ₃ S CN Cl 73-74 160 ' NH ₂ CFCI ₂ SO CN H 156.4 to 195 161 H CF ₃ SO ₂ CN CF ₃ S 156-157 162 H CH ₃ SO CN Cl 130-131 163 NH ₂ CF ₃ S CN F 164 to 164.5 164 H Cl CN Cl 129 to 129.5 165 CH ₃ SO CF ₃ S CN Cl 133-135 166 CH ₃ S CFCI ₂ S CN Cl 112.2 to 124.8 167 NH ₂ CFCI ₂ SO CN Cl 163 to 169.5 168 CF ₃ CONH CF ₃ SO CN H 195 to 197.5 169 H CF ₃ S CN F 116-117 170 CH ₃ SO ₂ CFCI ₂ S CN Cl 164.5 to 170.5 171 CH ₃ SO CFCI ₂ S CN Cl 193 to 195.7 172 NH ₂ CF ₃ SO CN H Dec. over 175 173 H CF ₃ S CF ₂ H H 54-56 174 H CH ₃ SO ₂ CN Cl 165-166 175 H br CN br 127.5 to 128 176 H rr CN H 120-121 177 NH ₂ CFCl ₂ SO ₂ CN Cl 203 to 214.5 178 H CF ₃ SO CN F 12S-13O 179 br Cl CN H 121-123 180 NH; CF ₃ SO ₂ CN H 258-260 181 CH ₃ SO CF ₃ SO CN Cl 238-239 182 H CF ₂ BrS CN Cl 128.3 to 133.7 183 H CF ₂ BrSO CN Cl 117-119 184 H CF ₂ BrSO ₂ CN Cl 172-181 185 H CF ₃ S CK ₃ H Gi 186 H CF ₃ SO CH ₃ br 106-107 187 H CF ₃ SO ₂ CH ₃ br 76-77 188 NH ₂ CF ₃ S CN CH (SCH ₃ I ₂ 159-161 189 CH ₃ SCH = N CF ₃ S CN CH (SCH ₃ I ₂ 124.5 to 125.5 190 H CF ₃ S (CH ₃ I ₃ COCONH br 113-114 191 H CF ₃ S br br oil 192 H CF ₃ SO CH ₃ OH" 149-151 193 br CF ₃ S CH ₃ br 194 br br H CF ₃ S 195 H CF ₃ S CN I 107-109

* may be a, keto tautomarous

The invention relates to a method for the local control of diseases caused by arthropods, in particular insects and arachnids, plant nematodes, Helminth.-m and protozoa, consisting in the fact that the corresponding site (eg or administration) with an effective amount of a compound of general formula I as defined above. The compounds of general formula I can be used in particular in the field of veterinary medicine and livestock husbandry as well as in public health care against arthropodone, helminths and protozoa, the internal or external parasites in vertebrates and in particular warm-blooded Vertobraten, for example, in humans and pets , for example in cattle, sheep, goats, horses. Pigs, poultry, dogs and cats. The compounds of general formula I can, for. Ticks (eg, Ixodes spp., Boophilus spp., Eg, Boophilus microplus, Amblyomme spp., Hyolnmma spp., Rhiplcephalu: spp., Eg, Rhlpicepiialus eppendiculatus, Haemaphysalis spp., Dermacentor spp , Ornithodorus spp., (Eg, Ornit'ioc * jrus moubata), and Miiben (eg, Damalinla spp., Dermahyssus gallluae, Sarcoptes spp., Eg, Sarcoptes scabiei, Psoroptes spp., Chorioptes spp , Demo ^ ex spp., Eutrombicula spp.); Dip'era (eg Aedes spp., Anopheles spp., Musca spp., Hypoderma spp., Gasterophlus !, pp., Simulium spp.); Hemiptc ' a (eg Triatoma spp.), Phthlrapter (eg Damalinla spp., Llnognathus spp.), Siphonaptera (eg Ctenocephalides spp.), Dlctyoptera (eg Periplaneta spp., Blatella spp.) and liymenoptera (eg Monomorium phti.-aonls).

The compounds of the general formula I can be used , for example, against -jarasitic nematodes which cause infections of the gastrointestinal tract, for example against members of the trichostrongylitis family, Nippostrongylus bmsiliensis, Trichinelle splralis, Haemoncius nontortus, Trlchostrongyus colubriformis , Nematodirus battus, Ostertagia cicumcincta, Trichostrongylus ax), Cooperla spp. and Hymenolepfs i,. * na.

The compounds of the general formula I can also be used in the control and treatment of diseases caused by protozoa, such as. B. against Elmekrla spp., Z. B. Eimerla tonella, Eimerla acervullna, Elmorla brunetti, Eimerla maxima and Eimerla necatrlx, Trypanosoma cruzl, Lelshamanla spp., Plasmodium spp., Babosia spp., Trlchomonadidae spp., Hlstomonas spp., Glardla spp., Toxoplasma spp ,, Entamoeba hystolytlca and Teltarai spp. The compounds of general formula I may further for the protection of stored goods, such as. Cereals, including cereals and flour, peanuts, cattle feed, wood and household items, e.g. Carpets and textiles used against attack by arthropods, in particular against beetles including weevils, moths and mites, for example against Ephestla spp. (Meal moths), Anthrenus spp. (Carpet beetles), Trlboll jm spp. (Meal beetles) , Sltophllus spp. (Grain beetle) and Acarus spp. (Mites).

Further use of the compounds of general formula I in the control of cockroaches, ants and termites and similar harmful arthropods in infested domestic and industrial premises, in the control of mosquito larvae in waterways, wells, reservoirs or other standing or flowing waters and in the Treatment of foundations, structures and floors to prevent infestation of such buildings by termites such. Retlculltermes spp., Heterotear spp. and Coptotermes spp.

The compounds of general formula I can also be used favorably in agriculture against the following pests: Adult, larvae and eggs of Lepldoptera (butterflies and moths, moths), z. Heliothis spp., Such as Heliothis vlrescens (tobacco budworm), Heliothis armlgera and Heliothis zea, Spodoptera spp., Such as Heliothis spp. BS exempta, S. llttoralls (Egyptian cotton worm), S. erldanla (southern army worm), Mamestra configurate (bertha army worm); Earla * spp., Z. BE insulin (Egyptian seed bollworm), Pectlnophora spp., Ζ. B. Pectlnophora gossypiella (pink cottonworm), Ostrlnla spp., Z. Bo nobllalls (European corn borer), Trlchopliislanl (coopers), Pleris spp. (Cabbage worm), Laphygma spp. (army worm), Agrotis and Amathes spp. (Cuttingworms), Wlseana spp. (Porinafalter), ChIIo spp. (Rice Drill), Tryporyza spp. and Dlatraea spp. (Cane sugar and roach drill), Sparganothls plllerlana (budworm), Cydia pomonella (codling moth), Archlps spp. (Fruit tree peel wrapper), Plutoila xylostella (cabbage leaf); Adults and larvae of coleoptera (beetles), e.g. Hypothenemus hampei (coffee pots), Hyleslnus spp. (Bark beetle), Antonomus grandis (cotton weevil), Acalymma spp. (Cucumber beetle), Lema spp., Psyl'lodas spp., Leptinotaraa decemlineata (Colorado potato beetle), Dlabrotlca spp. (Corn rootworm), Gonocophalum spp. (false wireworm), Agrlotes spp. (Deworm worms), Dermoleplda and Heteronychus spp. (white caterpillars), Phaedon cochleariae (mustard beetle), Llssorhoptrus oryzophilus (rice water beetle), Mellgothes spp. (Pollen beetle), Ceutorhynchus spp., Rhynchophorus and Cosmopolites spp. (Weevil); Hemiptera, eg Psylla spp., Bemlsla spp., Trlaleurodes spp., Aphis spp., Myzus spp., Magoura viclae, Phylloxera spp., Adelges spp, Phorodon humull (hops aphid), Aeneolamla spp., Nephotettlx spp. (Rice-Leaper), Empoasca spp., Nilaparvata spp., Perklnsllla spp., Pyrllla spp., Aenldiolla spp. (red scale insects), Coccus spp., Psoucoccus spp., Helopeltls spp. (Mosquito beetle), Lygus spp., Dysdercus spp., Oxycarenus spp., Nezara spp., Hymenoptera, eg Athalla spp. urH Cephus spp. (Sawflies or cereal sawflies), Atta spp. (Leaf cutting ants); Diptera such as B. Hylemyla spp. (Root flies, onion flies, cornflower flies), Atherigona spp. and Chlorops spp. (Shoot fly), Phytomyza spp. (Minier fly), Ceratitls spp. (Fruit flies); Thysanoptera such as Thrlps tabaci; Orthoptera such as Locusta and Schistocerca spp. (Grasshoppers) and Grillon, z. B. Gryllus spp. and Acheta spp .; Collembola, z. B. Sminthurus spp. and Onychiurus spp. (Jump tails), Isortera, eg Odontotermes spp. (Termites), Dermaptera, eg Forficula spp. (Earwigs) and other important in agriculture arthropods, such. B. Acaria (mites), z. Tetranychus spp., Panonychus spp. and Bryobla spp. (Spider mites), Eriophyes spp. (Gall mites), Polyphegotarsonemus spp., Blanlulus spp. (Centipedes), Scutlgerella spp. (Symphilids), Onlscus spp. (Wood louse) and Triops spp. (Crustacea); Non-rodents infesting plants and trees of importance to agriculture, forestry and horticulture, directly or through the spread of bacterial, viral, mycoplasma or fungal plant diseases, root knot nematodes wio Moloidogyne spp. (eg M. Incognita); Cyst nematodes such as Globodera spp. (eg BG rostochiensis); Heterodera spp. (eg BH avenae); Radopholus spp. (eg R. üimllis); Lesion nematodes such as Pratylenchus spp. (eg BP pratensls); Belonolalmus spp. (eg BB gracilis); Tylenchulus spp. (eg T. semlpenetrans); Rotylenchuluispp. (eg R. r.anlformls); Rotylenchus spp. (eg R. robustus); Helicotylenchus spp. (eg BH multlclnctus); Heml cycliophora spp. (e.g., BH jjracllis); Crlconomoldes spp. (eg BC similis); Trlchodorus spp. (eg BT primltivus); Sword nematodes like Xlphlnema supp. (eg X. diverslcaudatum), Longidorus spp. (e.g., BL elongatus); Hoplolaimus spp. (eg BH coronatus); Aphelencholdes spp. (for example BA rltzema-bosi, A. besseyl) as well as about stem and tuber calves, such as eg. B. Dltylenchus spp. (eg BD dipsaaf).

The compounds according to the invention can also be used to control other pathogens: From the order of the isopods, for example Onlseus asellus, Armadillidlum vulgare and Porcolllo scaber; from the order of diplopods, for example Blaniulus guttulatus; from the order of the Chilopoden for example Geoohilus carpophagus and Scutigera spex; from the order of Symphyla for example Scutigerella immaculata; from dr, order of Thysanura, for example, Lepfsma sacharlan; from the order of the Collembola, for example, Onychiurus armatus; from the order of Orthoptera for example Blatte orlentalis, Periplaneta americana, Leucophao. ήβταβ, Blatella germanica, Acheta domesticus, Gryllotalpa spp., Locusta mlgratoria mlgratorioldos, Melanoplus dif., .., and Schlestocera g: egarla; from the order of the Dermaptera, for example, Forficula auricularta; from the order of Isoptera for example Reticulitermes spp .; from the order of Anoplura for example Phylloxera vastotrix, Pemphigus spp., Pediculus humanus corporls, Haematopinus spp. and Linognathus spp .; from the order of Malloohaga for example Trichodectes spp. and Damalinea spp .; from the order of Thysanoptera, for example, Herclnothrips femoralls and Thrlps tabaci; from the order of Heteroptera, for example Eurygaster spp., Dysdercus intermedlos, Plesma | uadrata, Clmex lectularius, Rhodnius prolixus and Triatoma spp .; from the order Coleoptera for example Anobium punetatum, Rhlzopertha domlnica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochlenrlae, Diabrotica spp., Psylliodes chrysoeephala, Epilachna varlvestis, Atomana spp., Oryzaephilus sirinamensis, Anthonomus spp. , Sitophilus spp., Otiorrhynchus sulcatus, Cosmoplites sordldus, Ceuthorrhynchus assimus, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Maligethes aeneus, Ptinus spp., Niptus hüloleucrus, Gibbium psylloldes, Tribolium spp., Tenebrio molltor, Agriotes spp., Conoderus spp., Melolontha mclolontha, Amphlmallon solstitlalis and Costelytra zealandlca; from the order of Hymenoptera, for example, Diprion spp., Hoplocarnpa spp., Lasius spp., Monomorium pharaonii, and Vespa spp .; from the order of Diptera for example Aedes spp., Anopheles spp., Culex spp. Drosophila

melanogaster, Musca spp., Fannla spp., Calllphora erythrocephala, Lucilia spp., Chrysomyia 8pp., Cutorebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp, Tabanus spp., Tannia spp., BIblo hortulanue, Osclnella frit, Phorbla spp., Pegomyla hyoncyanl, Ceratltl »capitate, Dacut oleae, and Tlpula paludoea; from the order of Siphonaptera boispleleweleo xenoptylla cheopl "and Certatophyllus spp .; from the order of Arachnlden for example Scorpio maurus and Latrodectus mactans; from the order of the Homoptora for example Aleurodes brasslcao, Bemlsla tabaci, Trialeurodes vaporarlorum, Aphls gostypll, Brevlcoryno brasslcao, Cryptomyzus ribls, Doralls fabae, Doralls poml, Erlosoma lanlgerum, Hyalopterus arundinls, Macroslphum avenae, Myzus spp., Phorodon humull, Rhopaloslphum padi, Empoasca spp., Euscelisbilobatue, Nephotettlx clnctlceps, Lecanlum cornl, Salssetla oleae, Laodelphax striatllllus, Nilaparvata lugens, Aenldiella aurantll, Aspldlotue hodorao, Pseudococcus spp. and Psylla spp .; from the order of the Leipidoptera for example Pectinophora gossyplella, Bupalus plnlarius, Chelmatobla brumata, Llthocolletls blancardella, Hyponomeuta padella, Plutoila macullpennls, Malacosoma neustrla, Euproctis chrysorrhea, Lymantria spp., Bucculatrlthurberlolla, Phyllocnstis citrella, Agrotis spp., Euxoa spp., Feltia spp , Earlas Insulana, Heliothis spp., Paphygma exlgua, Mamestra brasslcae, Panolis flame, Prodenla litura, Spodoptora sp.t., Trlchopluslana, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalls, Ephestla kuehnlella, Galleria mellonella, Tlnenla bisselliella, Tinea pelllonolla, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia arnblguella, Homona magnanlme and Tortix vlrldana. The invention further relates to methods for controlling plant-destructive arthropods and nematodes which comprise the application of an effective amount of at least one compound of general formula I to the plants or the medium in which they grow.

For the control of arthropods and nematodes, the active ingredient is generally applied where the corresponding arthropod or nematode infestation is to be controlled using an amount of from about 0.005kg to about 15kg of active ingredient per hectare of treated area, preferably 0.02kg / ha to 2 kg / ha. Under ideal conditions, depending on the nature of the pests to be attacked, even the lower specified amount may provide adequate protection. And on the other hand, adverse weather conditions, pest resistance and other factors may require the use of the active ingredient in a higher amount. When applied to leaves, amounts of from 0.01 kg to 1 kg / ha can be used. The optimum amount usually depends on the type of pests to be controlled and on the type and growth of the affected plants, the row spacing and the type of application.

If the pests are in the soil, the formulation containing the active ingredient may be distributed evenly over the area to be treated in any suitable manner. If desired, the application can also be made over a large area of the field or a plant-cultivated area. The application can also be made in the immediate vicinity of seeds or plants that are to be protected from infestation. The active ingredient can also be washed by spraying the surface in question with water in the soil; it is also possible to have the active ingredient washed in the soil by the natural rainfall. During or after use, the formulation may, if desired, be mechanically distributed in the soil, for example by plowing or harrowing. The application can be made before. during οι'ργ after plant success, but before germination or after germination.

The compounds of general formula I can be applied to the soil in the form of solid or liquid compositions, so as to combat in principle those nematodes which are in the soil; to further control such nematodes infesting aerial parts of plants (as listed above, eg, Aphelenchoides spp., and Ditylenchus spp.), the compounds of general formula I can also be applied to foliage. The compounds of general formula I are also of great value in the control of pests that feed on parts of plants remote from the site of use of the compounds. So z. B. b'attfressende insects killed by the fact that the compounds in question are applied to the Wuneln. In addition, these compounds can reduce the infestation of the plants by having an anti-seizing effect or a repellent development.

The compounds of general Formei I are particularly useful for the protection of crops including, fodder plants from fields, plantations, in KuKu ¹ en, greenhouses, orchards and vineyards, ornamental plants, tree plantations and forest trees, for example. Cereals such as corn, wheat, rice, cotton, tobacco, vegetables and salads, such as beans, cabbage, squash, lettuce, onions, tomatoes and peppers, crops such as potatoes, sugar beets, peanuts, soybeans, rapeseed, sugar cane, willow and fodder plants such as maize, sorghum, alfalfa, plantations such as tea, coffee, cocoa, bananas, oil palms, coconut palms, rubber trees, spices, orchards and woody plants such as stonefruits, citrus, kiwi, avocado, mango, olives and walnuts, Vineyards, ornamental plants, flowers and shrubs under glass, in gardens and in parks, of forest trees (deciduous as well as evergreen) in forests, plantations and nurseries and the like. The compounds of general formula I are also valuable for the protection of wood (standing, felled, processed, stored timber or lumber) from infestation by sawfly and leaf wasps (eg Urocerus) or beetles (eg Scolytids, Platypodids, Lyctids, Bostrychids, Cerambycides, Anobiiden) or termites, z. B. Retlciilltermes spp., Heterotermes spp. and Coptotermes snp.

The compounds of general formula I may also be used to protect stored products from moth, beetle, mite and swarm beetle infestation, e.g. As grains, fruits, nuts, spices and tobacco, in whole or in ground state or in the form of corresponding processed products. Furthermore, the compounds according to the invention can also be used to protect stored animal products such as hides, hair, wool and leather in natural or processed form (eg as carpets or textiles) from moth and beetle infestation; even stored meat and stored fish can be protected in this way from beetles, mites and flies.

The compounds of general formula I are of particular value in the control of Arlhropoden, helminths or protozoa, rlie directly cause diseases or act as vectors in the spread of diseases in humans and pets, such as those mentioned above. In particular, the compounds are also useful in the control of ticks, mites, mice, fleas, mosquitoes and biting, nuisance and myasitis causing flies, e.g. As biting flies and coffee flying, advantageously applicable.

The compounds of the general formula I are particularly suitable for controlling arthropods, helminths or protozoa which live in domestic animals as host animals or are ingested with food or live in or on the skin or suck the blood of the animals. For this purpose, the compounds are administered orally, parenterally, psrcutan or locally.

Coccidioso is a disease caused by infection with parasitic protozoa of the genus Elmerla; This disease is an important cause of economic losses in keeping domestic animals and birds, especially those raised or kept under intensive conditions. From this disease can ζ. B. cattle, sheep, pigs and rabbits are infested; However, this disease is of particular concern in poultry farming and especially in chickens.

This poultry disease is generally spread by the poultry picking the infectious organism in the form of manure on contaminated litter or hay or soil, or otherwise ingesting it with food or drinking water. The disease is characterized by haemorrhage, accumulation of blood in the cecum, blood in the excrement, weakness and indigestion. The disease often ends with the death of the infected animal; Furthermore, poultry that has survived serious infections has a significantly lower market value as a result of the infection.

The administration of a small amount of a compound of general formula I, advantageously in combination with poultry feed, effectively prevents the infestation with coccidiosis or significantly reduces the risk of infection. The compounds are active against both the cecal form (caused by E. tenella) and the intestinal forms (mainly caused by E. acervullna, E. brunettl, E, maxima and E. necatrlx).

The compounds of the general formula I also exert an inhibiting effect on the oocytes by considerably reducing the number and / or sporulation of the oocytes.

The compositions described below for topical use in humans and animals as well as for the protection of stored goods, household goods, buildings and open spaces may generally also be used for crops, suitable acreage as well as for the protection of seed.

Suitable methods for the use of compounds of the general formula I are, for example:

The parenteral, oral or topical application of compositions in which the active ingredient has an immediate and / or prolonged activity over a period of time against arthropods, helminths or protozoa in humans or animals infected with or exposed to arthropods, helminths or protozoa , z. By ingestion or in suitable orally acceptable pharmaceutical formulations, baits, salt stones, aerosol additives, pour-on formulations, sprays, baths, dip baths, showers, molding applications, dusts, greases, shampoos, creams, wax greases, and self-care systems for farm animals; application to the environment in general or to specific places or areas where pests lurk, including stored goods, wood, household goods and private and industrial buildings, in the form of sprays, mists, dusts, smoke, wax smears, varnishes, granules and baits, in I orm certain dosage forms for waterways, wells, reservoirs and other flowing or standing waters; Use as food supplement for pets for controlling fly larvae that feed on their faeces; Application of growing crops in the form of blubber sprays, dusts, granules, mists and foams; also as suspensions of finely divided and encapsulated compounds of the general formula I for the treatment of soil and roots by liquid impregnation, dusts, granules, hulls and foams; finally also in the form of liquid sludges and dusts for seed treatment.

The compounds of general formula I can be used in compositions of any known type for the control of arthropods, helminths or protozoa, which are used for internal or external use of vertebrates or for the control of Art'iropoden in any building or interior or exterior free surfaces suitable; they contain as active ingredient at least one compound of general formula I in addition to one or more diluents or excipients compatible therewith, which are suitable for the intended use. All such compositions can be prepared in any known manner.

Compositions suitable for use in human or human responders are, for example, preparations suitable for oral, parenteral, topical or percutaneous administration, for example by infusion.

Compositions for oral administration contain one or more compounds of general formula I in addition to pharmaceutically acceptable carriers or wrappers and include, for example, tablets, pills, capsules, pastes, gels, drench, drug-containing foods, drinking water provided with active ingredient, food or feed containing active ingredient Feed additives, BoIi or other slow-release formulations intended to be retained in the gastrointestinal tract. The active ingredient may be enclosed in microcapsules or coated with coatings applied to the digestive tract which are acid labile or alkali labile or consist of other pharmaceutically acceptable materials. The compounds according to the invention can also be present in food premixes and corresponding concentrates used for the preparation of active ingredient-containing dietary or edible additives, active ingredient-containing drinking water or other active ingredient-containing materials which are absorbed by animals.

Compositions for parenteral administration include, for example, solutions, emulsions or suspensions in any suitable pharmaceutically acceptable carrier, as well as solid or semi-solid subcutaneous implants or pellets designed to deliver the active ingredient over an extended period of time; These compositions can be prepared and sterilized by any known method.

Compositions for percutaneous and local administration include, for example, sprays, dusts, baths, baths, showers, compositions for molding, fats, shampoos, creams, lubricating waxes or infusion preparations, and devices (eg, ear-mounted devices) external to animals can be mounted so as to allow a local or systemic control of arthropods.

Suitable key or liquid baits for controlling arthropods contain one or more compounds of all the formula I as well as a carrier or diluent; These include food substances or anc eer substances that induce uptake by the arthropods.

In practical application in agriculture verb to the invention ^are: nHunnen rarely used alone.

They are mostly components of corresponding compositions. These compositions, which can be used as insecticidal agents, contain a composition of the invention as described above as a substance in combination with agriculturally acceptable solid or liquid carriers and surfactants, and conventional carriers and conventional surfactants can be used in particular. These compositions are also part of the subject invention.

Such compositions may also include allo Arton woofer Bostandtoilo onthelton, boisplolewoiso Scluiukolloido, Adhäbivn, thickener, thxxotropic probe, ponotrating agent, spray oils (besondors for use as Acariclde), stabilizers, preservatives (Insbeeondoro gegon mold), Komploxblldnor u. Like., Well woitoro, known active ingredients with pestlcidone properties (Insecticide odor particular Fungicldo) odor with Eigmschafton, with clonon a regulation of plant growth is possible. Still more generally, the orogenic moieties according to the present invention may be combined with either solid or liquid additive according to the conventional formulation of wordon.

Diousedioededione of the orbital bound prefilmone may be administered within three grams of Gronzon variioron, in particular depending on the nature of the disease to be controlled and the usual degree of agrofuktone. In allgomoinon onthalton dio orc according to the invention compositions übllchorwoise otwa 0.05 to 95 Ma. •% oinou odor mohrbrer orfindungsgomäßor active ingredients, otwa 1 to 95Ma .-% oinos or mohroror festor odor liquid carrier sowio optionally otwa 0.1 to 50Ma. % oinos or mohroror surfactants.

Wio boreits obon orwähnt, wordon the invention orangungsgomäß angowandton Vorhinderungon combined in allgomoinon with carriers and possibly. Surfactants.

By "support" is meant organic or inorganic, natural or synthetic matter, combined with donor active ingredient to facilitate its application to plants, seeds or soil. Such carriers are therefore generally inert and must be agriculturally acceptable, especially with regard to the bohandolton plants. Dor Trägor may be solid (clays, natural or synthetic silicates, silicic acid, horzo, waxy, fosto fertilizers, for example ammonium salts, and ground natural minerals such as kaolins, clays, talc, lime, quartz, attapulgite, montmorillonite, bertonite or diatomoonordo, ground synthotico mineral ion such as silica, alumina and silicates, especially aluminum silicate or mapnesiumsilicate). Examples of solid carriers for granules are zljoinorto and fractionated natural rocks such as citrite, marble, bimsstoin, seplolite and dolomite, as well as synthetic granules of inorganic or organic flours and granules of organic materials such as sawdust, coconut shell, corncob and tobacco gums, and diatomaceous earth. Gotroidoschnlon, Schoton odor pods, tricalcium phosphate, powdered cork, activated carbon and water-soluble polymers, resins, waxes, solid fertilizers and. Likewise, solid solid compositions may, if necessary, contain one or more compatible wetting agents, dispersants, emulsifying agents, or coloring agents which, when solid, may also serve as diluents. The carriers may also be liquid, for example alcohols, in particular outnol or glycol, and their ethers and esters, in particular methylglycolacotate, furthermore ketones, in particular acetone, cyclohexanone, methyl ethyl ketone, Mothylisobutylketon and isophorone; Petroleum fractions; paraffinic or aromatic hydrocarbons, in particular xylenes or alkylnaphthalenes, petroleum fractions, inorganic and vegetable oils; aliphatically chlorinated hydrocarbons, in particular trichlorothane or methylene chloride, or aromatic chlorinated hydrocarbons, in particular chlorobenzenes; water-soluble or strongly polar solvents such as dimethylformamide, dimothylsulfoxide or N-methylpyrrolidone and water; liquefied gases u. Like. And their mixtures.

The surfactant may be an emulsifier, a dispersant or wetting agent and may be of ionic or nonionic type; Forner may also be mixtures of such surfactants. These include, for example, salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic acids or naphthalenesulfonic acids, polycondensation products of ethylene oxide with fatty alcohols, fatty acids, fatty esters or fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivative (in particular alkyl taurates), phosphoric esters of alcohols or polycondensation products of ethylene oxide with phenols, esters of fatty acids with polyols and functional sulfate, sulfonate and phosphate derivatives of the above compounds. The presence of at least one surfactant is generally essential if the active ingredient and / or the inert carrier have little or no water solubility and the vehicle for the application is water.

The compositions of the invention may further contain various additives, wio adhesives and colorants. In corresponding formulations can be used as adhesives, for example carboxymethylcellulose and natural and synthetic polymers in the form of powders, ridge, jiaten or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as also natural phospholipids such as cephalins and lecithins and synthetic phospholipids werdon. Further additives are, for example, inorganic and vegetable oils. It is also possible to use colorants, for example, inorganic pigments, for. For example, iron oxide, titanium oxide and Prussian blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes. In addition, trace elements required for nutrition may also be added in the form of salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. Compositions containing compounds of general formula I and used for controlling arthropods, plant nematodon, helminthon or protozoa may also contain synergistic substances (eg piperonyl butoxide or sesamex), stabilizing substances, other insecticides, acaricides, plant nematocides, anthelmintics or anticoccidiosis, fungicides (agricultural or veterinary, eg benomyl, lprodione), bactericides, attractants or repellents for anhropods or vertebrates or pheromones, fragrances (deodorants), flavorings, colorants and therapeutic adjuncts, e.g. B. trace elements. These additives may be selected to increase the efficacy, persistence, safety, possibly the ingestion of the pest and the range of pests controlled, or to provide the composition with any beneficial effects on the treated animal or on the treated area.

Examples of other pesticidally active compounds which can be used in or in connection with the compositions according to the invention are acephate, chlorpyrifos, demeton-S-methyl, disulfone, ethoprofos, fenitrothion, malathion, monocrotophos, parathion, phosalones, pirimiphos-methyl, triazophos, cyfluthrin , Cypermothrin, Deltamethrin, Fenpropathrin, Fenvalerate, Permethrin, Aldicai b, Carbosulfan, Methomyl, Oxamyl, Pirimicarb, Bendiocarb, Teflubenzuron, Dicofol, Endosulfan, Lindane, Benzoximate, Cartap, Cyhexatin, Tetradifone, Avermectins, Ivermectin, Milbemycins, Thiophanates, Trichlorfone üichlorvos, Diaveridine and dimetriadiazole.

For prewiring in agriculture, the compounds of formula I are therefore generally in the form of Used compositions which may be in various fosten or liquid forms. liquid Compositions may be suitable for the treatment of arthropodone-affected or, as appropriate, bifunctional Substrates or places are vermondot, including buildings, outdoor or indoor liogendon Lagorflächon odor Vorarboitungsflächon, containers or equipment and standing or Flioßondon waters. Fosto homogeneous or hotorogeno compositions contain an odor mohroro compounds dor allgomoinon Formol I;

They are, for example, in the form of granules, pollots, briquettes or capsules, which can be wounded to treat sturdy odorflioßondon Gowiissorn währond oinor for a specific period of time. A similar effect can also be achieved in water Hisporglerbaro Concentrate as described above with the aid of drip or other

Dispensers dispensed in water wordon. The compositions may also be in the form of aerosolon, aqueous or nonaqueous solutions or disporsionone

Pre-wetting or dioxygenating, spraying, atomizing or low or ultra-low volume spraying are suitable.

As fosto forms of compositions, powder for dusting (containing Compound of Formol I up to

80%) or wettable powder odor granules, in particular those obtained by extrusion, compactors, impregnating a granulated carrier or granulating from a powder, the content of

Compounds of formula I in these wettable powders or granules is between 0.5 and 80%. Solutions, in particular emulsifiable concentrates, emulsions, flowable compositions, aerosols, bonotzbare Powders, dry flowable compositions and pastes are to be regarded as forms of compositions

mention that are liquid or have been prepared from donon in liquid compositions.

Inulinulable or soluble concentrates also generally contain from 5 to 80% of active ingredient, while emulsions or solutions which are ready for use in this case contain from 0.01 to 20% of active ingredient. In addition to the solvent, the emulgiorbaren

Concentrates, if necessary, from 2 to 50% of suitable additives, such as stabilizers, large active agents, Containing agent, corrosion inhibitors, colorants or adhesives. From these Konzontraten emulsions of any required concentration can be prepared by dilution with water

which are particularly suitable for use on plants.

The concentrated suspensions, applied by spraying inside, are prepared so that a stable,

flowable product is obtained, which does not settle (fine grinding); usually contain 10 to 75% active ingredient, 0.5 to 30% surfactant, 0.1 to 10% thixotropic agent and 0 to 30% suitable additive wio antifoam,

Corrosion inhibitors, stabilizers, penetrating agents, adhesives and, as a carrier, water or an organic Liquid in which the active substance is sparingly soluble or insoluble; Furthermore, various organic solids or

inorganic salts have been dissolved in the carrier, which either contribute to the prevention of sedimentation or as

Antifreeze for water serve. The wettable powders are usually prepared to contain 10 to 80% active ingredient; sio

usually contain, in addition to the solid support, 0 to 5% of a wetting agent, 3 to 10% of a dispersing agent and, if necessary, 0 to 80% of one or more stabilizing agents and / or other additives such as penetrating agents,

Adhesives, anti-caking agents, colorants and the like. The active substance (s) are used to prepare these wettable powders in suitable mixing devices

thoroughly mixed with additional substances with which the porous filler can be impregnated; Grinding is done with mills or other suitable crushers. As a result, wettable powders are obtained whose

Wettability and suspensibility are advantageous; they can be suspended in water to any concentration

become; the corresponding suspensions can be applied in a very advantageous manner, in particular to the leaves of plants.

Water-dispersible granules (WG) which are readily dispersible in water have a composition which in the

substantially equal to that of the wettable powders. They may be prepared by granulating formulations as described above for the wettable powders using either the wet route (contacting the finely divided active ingredient with the inert filler and some water, e.g., 1 to 20%, or with an aqueous solution of a

Dispersant or binder and then drying and sieving) or the dry way can be labeled

(More compact and then grinding and sieving).

As already mentioned, the inventive concept also includes aqueous disporsionone and emulsions, for. B. compositions,

obtained by diluting a wettable powder or emulsifiable concentrate according to the invention with Wacser, the emulsions may be of the water-in-oil or of the oil-in-water type and have a thick consistency.

These aqueous dispersions or emulsions or spray mixtures can be applied to crops or crops in crops

in any suitable manner, mainly by spraying, using amounts generally of the order of 100 to 1200 liters per hectare.

The products and compositions according to the invention can be used favorably on plants, in particular on Roots or leaves where appropriate pests are to be controlled. Another application for compounds or compositions according to the invention consists in the addition of a

the active ingredient-containing formulation to irrigation water. This irrigation can be done by sprinkler equipment

Treatment with foliar pesticides or by soil irrigation or underground irrigation for

systemic pesticides take place. The application dose of the active ingredient is generally between 0.1 and 10 kg / ha and preferably between 0.5 and 4 kg / ha. In particular, the amounts and concentrations may vary depending on the mode of use and the type of compositions used.

In general, the compositions for use in controlling harmful arthropods, plant nematode, Helminths or protozoa usually 0.00001 to 95Ma .-% and in particular 0.0005 to G0Ma .-% of one or more Compounds of general formula I or total active ingredient content, d. H. the compound (s) of general formula I.

together with other substances which are toxic to arthropods and plant nematodes, Anthelmintica,

Anticoccio agents, synergists, trace elements or stabilizers. The particular compositions used and

the frequency of use can be trained by the farmer or the farmer, the medically or veterinarily trained

Users, dom or pest control or other expert persons depending on the intended effects

to be selected. Solid and liquid compositions for tropical application to animals, wood, stored goods or household goods usually contain 0.00005 to 90% by weight and in particular 0.001 to 10% by weight of one or more compounds of the general formula I. For oral or parenteral incl. Percutaneous Administration to animals contains solid and liquid compositions, normally 0.1 to 90% by weight, of one or more compounds of general formula I. Feed containing animal feed normally contains 0.001 to 3% by weight of one or more compounds of general formula I. Concentrates and Feed additives for blending with fodder usually contain from 5 to 90% by weight and preferably from 5 to 50% by weight of one or more compounds of general formula I. Mineral salt pickles normally contain 0.1 to 10% by weight of one or more compounds of the general formula I.

Dusts and liquid compositions for use on livestock, persons, goods, rooms or open areas may contain from 0.0001 to 15% by mass and in particular from 0.005 to 2.0% by mass of one or more compounds of the general formula I. Suitable concentrations for a treatment of waters are between 0.001 and 20 ppm and in particular between 0.001 and 5.0 ppm, based on one or more compounds of the general formula I. Furthermore, they can also be used therapeutically in fish farming with a suitable exposure time. Feeding baits may contain from 0.01% to 5% by weight and preferably from 0.01% to 1.0% by weight of one or more compounds of general formula (I). When administered to vertebrates parenterally, orally or percutaneously or otherwise, the dose of the compounds of general formula I depends on the species, age and health of the vertebrate and the nature and extent of the presence or potential attack by arthropods, helminths or protozoa. A single dose of 0.1 to 100 mg and preferably 2.0 to 20.0 mg per kilogram body mass of the animal or doses of 0.01 to 20.0 mg and preferably 0.1 to 5.0 mg per kilogram body mass per animal Day with continued medication are generally suitable for oral or parenteral administration. By using formulations or devices that slow down drug release, the daily doses required over a period of months can be combined and administered once to the animals.

The following specific examples illustrate agrochemical compositions containing such agents of the present invention, as well as the insecticidal and acaricidal applications and properties of some compounds.

Examples of Ready-to-Use Compositions and Formulations The following Examples 23 to 28 illustrate examples of use against harmful arthropods, particularly insects and arachnids, plant nematodes and helminths or protozoa containing as active ingredients compounds of general formula I, in particular compounds as described in the Preparation Examples The compositions described in Examples 23 to 28 can each be diluted with water, ready-to-use compositions being available at concentrations suitable for field application.

The additives used in Examples 23 to 28 are listed below with their generic chemical names, all percentages being based on mass:

Ethylene BCP: ethylene oxide-nonylphenol condensation product

Soprophor BSU: Condensation product of tristyrylphenol with ethylene oxide

Arylan CA: 70% (M / V) solution of calcium dodecylbenzenesulfonate

Solvesso150:! Organic Cio-aromatic solvent

Arylan S: sodium dodecylbenzenesulfonate

Darvan: sodium lignosulfonate

ColitePF: Synthetic carrier made of magnesium silicate

SoproponT36: sodium salt of polycarboxylic acids

Rhodigel 23: Xanthan polysaccharide gum

Bentone 38: organic derivative of magnesium montmorillonite

Aerosil: Microfine silica.

Example 23

Preparation of a water-soluble concentrate from:

active substance 10 ° /: EthylanBCP 83 ° / < N-methylpyrrolidone

by dissolving the ethylan BCP in a portion of the N-methylpyriolidone and then adding the active ingredient with heating and stirring until dissolved. The resulting solution is adjusted to the final volume by adding the residual solvent.

Example 24

Preparation of an emulsifiable concentrate from:

active substance 7% Soprophor BUS 4% Arylan CA 4% N-methylpyrrolidone 50% Solvesso150 35%

by dissolving soprophor BSU, arylan CA and the active ingredient in N-methylpyrrolidone and then adding Solvesso 150 and adjusting the final volume.

Example 25

Preparation of a wettable powder from:

Active ingredient 40%

ArylanS 2%

DarvanNr.2 5%

Gelite PF 53%

by mixing the ingredients and grinding the mixture in a hammer mill on a Partikelgioßo under δΟμσι.

Example 26

Preparation of an aqueous, flowable formulation

active substance 40.00% Ethylene BCP 1.00% SoproponT36 0.20% ethylene glycol 5.00% Rhodigel 23 0.15% water 53.65%

by intimately mixing the ingredients and milling in a ball mill to a mean particle size below 3 pm.

Example 27

Preparation of an emulsifiable suspension concentrate

Active ingredient 30.0%

ethylene BCP 10.0%

Bentone 38 0.5%

Solvesso150 59.5%

by intimately mixing the ingredients and milling in a ball mill to a mean particle size below 3 pm.

Example 28

Preparation of a water-dispersible granules

Active ingredient 30%

DarvanNr.2 15%,

Arylan 8%

CelitePF 57%

by mixing the ingredients, micronizing in a fluid energy mill and then granulating in a rotary pelletizer by spraying sufficient water (up to 10% [M / V]). The resulting granules are dried in a fluid bed dryer to remove excess water.

Example 29

Preparation of powder for dusting by intimately mixing

Active ingredient 1 to 10%

superfine talc 99 to 90%.

This powder can be applied locally to arthropod-infested sites, e.g. B. on Schuttabladeplätzen, waste dumps, stored goods or household goods or even in arthropods infected or endangered animals by fighting by oral intake. Suitable means for dispersing the powder for dusting at the site of arthropod infestation are, for example, mechanical blowing devices, hand-operated shakers and devices for self-treatment of livestock.

Example 30 "

Production of a feed bait by intimately mixing

active substance 0.1 to 1.0% wheat flour 80.0% molasses 19.9 to 19.0%.

This bait can be distributed to arthropod-infested sites, for example, in private and industrial buildings, such as kitchens, hospitals, warehouses, or on open land to control, for example, ants, grasshoppers, cockroaches, and fleas, taken orally.

Example 31

Preparation of a solution

Active ingredient 15%

Dimethyl sulfoxide 85%

by dissolving the Pyrroldorivats in a part of the dimethyl sulfoxide and subsequent addition of further dimethyl sulfoxide to the desired volume. This solution may be percutaneously applied to arthropod-infested domestic animals by infusion or, after sterile filtration through a polytetrafluoroethylene membrane. (Pore size 0.22pm), by parenteral injection, with the application dose being 1.2 to 12 ml of solution per 100 kg body mass of the animal.

Example 32

Preparation of a wettable powder mis

Active ingredient 50%

Ethylene BCP (9 moles of ethylene oxide per mole of phenol) 5%

Aerosil 5%

Celite PF 40%

by absorbing the ethylene BCP on the Aerosil, mixing with the remaining ingredients and grinding the mixture in a hammer mill to obtain a wettable powder which can be diluted with water to a concentration of 0.001 to 2% (M / V) of active ingredient. This composition may then be applied by spraying to a location affected by arthropods, for example Diptera larvae or plant nematodes. Skin affected by arthropods, helminths, or protozoa, or any other suitable pets, may be treated with this composition by spraying, or by dipping or by oral administration in drinking water to control arthropods, helminths, or protozoa.

Example 33

A slow-release bolus may be prepared from granules containing a compacting agent, a binder, a slow release agent, and the active ingredient prepared according to Example 27, wherein the percentage composition may vary. By pressing the mixture, a bolus having a density of 2 g / ml or more can be obtained, which can be orally administered to ruminant pets. The bolus is retained by these animals in the Netzpansen and gives it over a longer period, the pyrrole compound continuously slowly and thus combats the infestation of ruminant pets by arthropods, helminths or protozoa.

Example 34

Preparation of a slow-release composition

Active ingredient 0.5 to 25%

Polyvinyl chloride base 75 to 99.5%

by mixing the polyvinyl chloride base with the active ingredient and a suitable plasticizer, e.g. Dioctyl phthalate, and melt extrusion or casting of the homogeneous composition into suitable forms, e.g. Granules, pellets, briquettes or strips suitable, for example, for addition to stagnant waters or, in the case of strips, for incorporation into collars or ear tags for attachment to domestic animals, in order to control harmful insects by slow release of the active substance ,

Similar compositions can be prepared by replacing the active ingredient in the above examples with an appropriate amount of another active ingredient of the formula I.

Application belsplele for use as pesticides

The following Examples 35 to 37 relate to the use of compounds of the invention at various concentrations. The application of 1 ppm (concentration of the compound in parts per million parts of the applied test solution) of a solution or suspension or emulsion for foliar treatment corresponds approximately to an application of 1 g of active ingredient per hectare, based on an approximate injection volume of 1000 l / ha (sufficient to drain). Accordingly, in the following applications, spray amounts of about 6.25 to 500 ppm applied to the sheets correspond to about 6 to 500 g / ha. For soil application, 1 ppm of Soil Concentrate "on the basis of approximately 7.5 cm soil depth corresponds to an approximate quantity of 1000 g / ha of hot field application.

Example 35

Efficacy against aphids:

It was made from a mixture

0.01 g of active ingredient

0.16 g of dimethylformamide

0.838 g of acetone

0.0002g of a surfactant mixture of an alkylaryl polyether alcohol and a

Alkylarylpolyether alcohol with sulfone groups in the aryl radical and 98.99 g of water.

This dilute aqueous mixture was sprayed onto dwarf nasturtium in pots on which adult and nymphal-stage woodcorn aphids (Aphls nasturtll) had been grown. The number of aphids per pot was 100 to 150. The volume of the sprayed aqueous mixture was sufficient to moisten the plants so that the liquid drained from them. After spraying, the pots were left for one day at 2O ⁰ C, after which the living aphids were counted. The percent mortality was 100% for the compounds of Examples 1,2,3A, 4, 5, 16C, 17,18,19 and 20 and Compound Nos. 12,24,33,34,38,39,42,44 , 45.54, 57.60, 62.98, 100, 102, 104, 125, 128, 130, 131, 135, 137, 141, 142, 114, 155, 152, 165, 166, 166 and 174 at a concentration of 100 ppm.

Example 36

Efficacy against mites:

The procedure was as in Example 35. In this case, however, 150 to 200 double-stained mites (Tetranychusurticae) were grown on tender green beans. After spraying the plants were maintained for 5 days at 3O ⁰ C. The percent mortality of the mites was 100% for the compounds of Examples 2,3A, 16C, 17 and 18 and compounds Nos. 9,20,25,41,44,46,52,53, 58,59,63,64, 70,74,77-81,83,90,98,99,102,124 and 141% concentration of lOOppm.

Examples 37 to 39

Efficacy against Southern Army Worm

Example 37

The same formulation as in Example 35 was used. In this case, larvae of Southern Army-Worm (Spodoptera eridania) in the second instar were grown on Sieva beans about 15 cm in height. The following percent mortalities were obtained after 5 days: 100% mortality was found for the compounds of Examples 3 A ₁ 'id, 5,6,7,8,9,11,12,15B.16C, 17,18,20, 21B, 21C and Compound Nos. 42,44,60,62,64,98-100,102,103,121,124,125,131, 141,142,144,162,166 and 174 at a concentration of 100ppm: 80% mortality was achieved by the compound of Example 13 at 500 ppm.

Example 38

The same formulation ancestor was used as in Example 35 with the difference that the following composition was present:

2.5 mg of active ingredient

0.05 g of dimethylformamide

9.9228 g of acetone

0.0247g surfactant (as in Example 35)

90g of water.

The compound of Example 4 gave 100% mortality in Southern Army-Worm at 25ppm.

Example 39

The same formulation procedure was used as in Example 38 with the difference that the following composition was present:

0.625mg active ingredient 12.5mg dimethylformamide

9.9621 g of acetone

0.0247g surfactant (as in Example 35) 90g water

 The compounds of Examples 1 and 2 gave 100% mortality in Southern Army Worm at 6.25 ppm.

Example 40

The same formulation procedure was used as in Example 37 with the difference that the following composition was present:

12.5 mg active ingredient

0.25 g of dimethylformamide

9.726g acetone

24.1 mg surfactant (as in Example 35) 89.988 g water.

Larvae of the Mexican bean beetle (Epllachna varivestis, muls) in its second appearance were grown on Sieva beans about 15 cm high. The following percent mortality was obtained after 5 days: 100% mortality was obtained with the compound of Example 13 at 125 ppm.

Example 41

The same formulation procedure was used as in Example 38, except that the composition contained the compound of Example 8 as the active ingredient. With this composition, a 100% mortality was achieved in Mexican bean beetle at 25ppm.

Example 42

The same formulation procedure was used as in Example 35 except that the nonbrominated compound of Example 15AaI's active ingredient was used. There was a 100% mortality in Mexican bean beetle at 100 ppm.

Example 43

The glelcho formulation method was used as in Example 40, except that the resulting composition was 10mm of active ingredient

0.2 g of dimethylformamide

9.7657 g of acetone

0.0243g surfactant (as in Example 35) 90g water.

The following percentage mortalities were obtained in the Mexican bean beetle: 80% igo mortality by the compounds of Example 15A and 15B at 100 ppm and 100% mortality by the precursors of Examples 1,2,9,17,18 and Compounds No. 42,44,60, 62.64,98,99,124,125,141,142 and 144 at 100ppm.

Examples 44-46

Efficacy against houseflies

The poison in the form of 10 ml of an aqueous sugar solution containing 10% by mass of sugar and 100 ppm of the chemical poison was formulated in a similar manner as in Example 35. From this, further serial dilutions were made as required. The following 3 different formulations were prepared for testing:

44 example 46 10 45 1.25 Active ingredient (mg) 160 10 25 Dimethylformamide (mg) 200 surfactant 2.15 14.25 (as in Example 35) (mg) 8.42 24.3 5.73 Acetone (g) 88.99 9.766 84.38 Water (g) 10 81 9.84 Sugar (g) 9

Twenty-five adult flies (Musca domestlca) were anesthetized with carbon dioxide and then transferred to a bait box containing the poison formulation. After one day at 27 ^° C. the mortality of the flies was determined; it was as follows: For Example 44: 100% mortality by the compounds of Examples 1,2,3B, 4-6,8,9,16C, 17-20,21B and 21C and the

Compounds 42,44,60,62,64,98,99,100,102,103,121,124,125,131,141,142.162,166 and 174 at 100ppm. For example 45: 100% mortality by the compound of Example 12 at 100 ppm. For Example 46: "J0% mortality by the compounds of Examples 1, 2 and 5 at 12.5 ppm.

Example 47

Efficacy against Southern Corn Rootworm:

A formulation was prepared in a similar manner to Example 35, except that in this case only 48.99 g of water were used, giving an initial test compound concentration of 2300 ppm. Aliquots of this formulation were then used directly according to the required test concentration, in ppm, by weight, according to the subsequent test procedure.

Into a pot containing 60g of a sandy loam soil, an aliquot of the formulation was added with 200ppm of the test compound (appropriate for the final concentration of the test compound in the soil), 3.2ml of water and 5 pre-seeded seedlings. The pot was then shaken thoroughly to achieve even distribution of the test formulation. Subsequently, 20 eggs of the pest were placed in a well provided in the soil. Vermiculite (1 ml) and water (1.7 ml) were then added to these Vertiofui g . Similarly, an untreated control experiment was prepared in which an aliquot of equal size was applied from a solution of water, acetone, DMF and emulsifier containing no test compound. In addition, another control experiment with a commercial technical compound was formulated in the same way, which was used as a test standard. After 7 days, the living larvae were counted using the well-known "Berleso" funnel-eating procedure.

The following compounds all gave 100% control at soil concentrations of 1.45, 0.72 and 0.36 ppm: Compounds of Examples 3B, 4 and 17 to 19 and Compounds Nos. 98, 99, 101, 105, 113, 119, 121, 124, 125, 130 and 130

Claims (18)

1. Insecticide, acaricide or nematocide compositions, characterized by an effective amount of a compound of formula I, in which mean X is halogen, cyano, cyanato, thiocyanato, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, haloalkylcarbonyl, alkenylthio, alkenylsulfinyl, alkenylsulfonyl, haloalkenylthio, haloalkenylsulfinyl, haloalkenylsulfonyl, haloalkylthiocarbonyl, phenylthio, phenylsulfinyl, phenylsulfonyl, heteroarylthio Heteroarylsulfinyl or heteroarylsulfonyl, where the phenyl groups are optionally substituted by halogen, cyano or haloalkyl groups, the heteroaryl groups are five- or six-membered monocyclic rings having one or two heteroatoms selected from oxygen, sulfur and nitrogen, and optionally halogen, nitro, Cyano or haloalkyl groups, and the alkyl, haloalkyl, alkenyl, haloalkenyl, alkoxy and haloalkoxy groups listed above are straight-chain or branched and have 1 to 10 carbon atoms, the halogen substitution in all of these groups, one or more or different halogen atoms may exist and monosubstitution may be present until complete polysubstitution; R ¹ , R ² and R ^{3 are} independently the same as defined above for X and hydrogen or alkyl, where one of the substituents R ¹ , R ² and R ³ may be selected from formyl, hydroxyiminoalkylidenyl, alkoximinoalkylidenyl, azido, amino, alkylamino, dialkylamino, Aralkylamino.aminocarbonylamino, alkylcarbonylamino, haloalkylcarbonylamino, arylcarbonylamino, alkylsulfonylamino, haloalkylsulfonylamino, alkylaminocarbonylamino, arylaminocarbonylamino, benzylidenimino, alkylidenimino, alkoxyalkylidenimino, dialkylaminoalkylidenimino, bis (alkylthio) methyl, bis (arylthio) methyl, alkylthioalkylidenimino, alkoxycarbonylamino, haloalkoxycarbonylamino, phenyl which is optionally substituted with halogen, cyano or haloalkyl, and heteroaryl groups having a five- or six-membered monocyclic ring having one or more heteroatoms selected from oxygen, sulfur and nitrogen and optionally substituted with halogen, nitro, cyano or haloalkyl groups . wherein the abovementioned alkyl, haloalkyl, alkenyl, haloalkenyl, haloalkoxy and alkoxy groups are straight-chain or branched and have 1 to 10 carbon atoms, the halogen substitution in all of these groups consisting of one or more identical or different halogen atoms and mono-substitution may be present for complete polysubstitution; Y is halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylsulfinyl, alkylsulfonyl, alkylthio, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl, said alkyl, alkoxy, haloalkyl and haloalkoxy groups are straight-chain or branched and have 1 to 10 carbon atoms and the halogen substitution in all of these groups consists of one or more identical or different ^ η halogen atoms and monosubstitution may be present until complete polysubstitution, or a hydrogen atom, if
X is a halogen atom or a group R ⁵ S (O) _n , where η is 0.1 or 2 and R ^{6 represents} alkyl, haloalkyl, alkenyl or Ha.'ogenalkenyl and the alkyl and alkenyl carbon chains and the halogen substitution are as defined above, R ¹ and R ^{3 are} each a hydrogen atom and
R ^{2 is} cyano,
and X ¹ , X ² , X ³ and X ^{4 are} independently the same as defined above for Y or a hydrogen atom, with the following conditions: At least one of the substituents R ¹ , R ² and R ³ is selected from the meanings defined above for X;
if X ⁴ and X ¹ H and X is halogen or cyano,
R ^{2 is} different from X;
and if X ⁴ and X ^{1 are} hydrogen and
Y means methyl
X no bromine and preferably 0.05 to 95% by weight of one or more active ingredients, 1 to 95% by weight of one or more agriculturally acceptable carriers and 0.1 to 50% by weight of one or more agriculturally acceptable surfactants. 2. Compositions according to claim 1, characterized by one or more additives which are selected from protective colloids, adhesives, thickeners, thixotropic agents, penetrants, spray oils, stabilizers, preservatives, anti-mold agents, complexing agents and other pesticidally active substances. Compositions according to Claim 1, characterized in that they contain compounds of the formula I in which: X is halogen, cyano, cyanato, thiocyanato, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, Halogßnalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, haloalkylcarbonyl, haloalkylthiocarbonyl, phenylthio, phenylsulfinyl, phenylsulfonyl, Heteroarylthio, heteroarylsulfinyl or heteroarylsulfonyl, where the phenyl optionally with halogen , Cyano or haloalkyl groups and the 'heteroaryl groups represent five- or six-membered monocyclic rings and one or two selected from oxygen, sulfur and nitrogen heteroatoms and optionally substituted with halogen, nitro, cyano or haloalkyl groups, said alkyl, Haloalkyl, alkoxy and haloalkoxy groups are straight-chain or branched and have 1 to 10 carbon atoms and the halogen substitution in all of these groups consists of one or more identical or different halo atoms and mono-substitution ~o too complete ger polysubstitution may be present R ¹ , R ² and R ^{3 are} independently the same as defined above for X and hydrogen or alkyl, wherein one of the substituents R \ R ² and R ³ may be selected from formyl, hydroxyiminoalkylidonyl, alkoximinoalkylidenyl, azido, amino, alkylamino, dialkylamino, aralkylamino , Aminocarbonylamino, alkylcarborylamino, haloalkylcarbonylamino, arylcarbonylnomino, alkylsulphonylamino, haloalkylsulphonylamino, alkylalkenocarbonylamine, arylaminocarbonylamino, benzylideneimino.alkylideneimino, alkoxyalkylideneimino, dialkylaminoalkylideneimino, phenyl which is optionally substituted by halogen, cyano or haloalkyl, and heteroaryl groups having a or six-membered monocyclic ring having one or two heteroatoms selected from oxygen, sulfur and nitrogen and optionally substituted with halogen, nitro, cyano or haloalkyl groups, said alkyl, haloalkyl, haloalkoxy and alkoxy groups being straight or branched, and 1 up to 10 carbon have off atoms and the halogen substitution in all of these groups consists of one or more identical or different halogen atoms and mono-substitution may be present until complete polysubstitution, Y is halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylsulfinyl, alkylsulfonyl, alkylthio, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl, said alkyl, alkoxy, haloalkyl and haloalkoxy groups are straight or branched and have 1 to 10 carbon atoms and the halogen substitution in all of these groups consists of one or more identical or different halogen atoms and monosubstitution are present until complete polysubstitution , can
and X ¹ , X ² , X ³ and X ^{4 are the} same as in claim 1, wherein the same conditions apply as in claim. 4. Compositions according to claim 1 or 3, characterized in that they contain compounds of formula I in which the alkyl, alkenyl, alkynyl and alkoxy moieties of X, X ¹ , X ² , X ³ , X ⁴ , R ¹ , R ² , R ³ and Y have substituents less than 5 carbon atoms. 5. Compositions according to claim 4, characterized in that they contain compounds of the formula I in which X is a halogen atom or a group R ⁵ S (O) _n , where η is 0.1 or 2 and R ^{6 is} alkyl, haloalkyl, alkenyl or haloalkenyl, R ^{1 is} a hydrogen atom, a halogen atom or alkylthio, R ^{2 is} cyano,
R ^{3 is} a hydrogen atom or a halogen atom, Y is a hydrogen atom, a halogen atom, haloalkyl or haloalkoxy, with the proviso that Y is a hydrogen atom under the conditions defined in claim 1, and X ¹ . X ^2, X ³ and X ⁴ independently represent a hydrogen atom, a halogen atom, C ₁ ^ ₃ alkyl, C ₁ ^ ₃ -alkoxy or C, _ ₃ alkylthio. 6. Compositions according to Claim 5, characterized in that they contain compounds of the formula I in which XR ⁵ S (O) _n , where η is 0.1 or 2 and R ^{5 is} CH ₃ , CF ₃ , CF ₂ Cl, CFCl ₂ , CF ₂ Br, CHF ₂ , CHCl ₂ or CHCIF, R ^{1 is} H, F, Cl or Br,
R ^{3 is} H, F, Cl or Br, X ^{I is} H or Cl,
X ² H, X ³ H,
X ⁴ Cl
and Y CF ₃ or CF ₃ O. Compositions according to Claim 6, characterized in that they contain the following compounds: 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (trifluoromethylthio) pyrrole; 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (trifluoromethylsulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluormethylpheiiyl) -2-chloro-3-cyano-4- (dichlorofluoromethylthio) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorfluormethylsulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorfluormethylsulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (chlordifluormethylsulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-chlorodifluoromethylsulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (chlorodifluoromethylthio) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (trifluoromethylsulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (trifluoromethylsulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (dichlorofluoromethylthio) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (dichlorfluormethylsulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluormethylph3nyl) -2-bromo-3-cyano-4- (dichlorfluormethylsulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (chlorodifluoromethylthio) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (chlorodifluoromethylsulfinyl) pyrrole; brornpyrrol; 1- (2,6-dichloro-4-trifluoromethylphenol) -2-bromo-3-cyano-4- (chlorodifluoromethyl-8-sulfonyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3- cyano-4- (dichlorfluormethylsulfinyl) pyrrole; 1- (2-chloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorfluormethylsulfonyl) pyrrole; 1- (2-chloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorfluormethylsulfinyl) pyrrole; 1 .- (2-chloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (dichlorfluormethylsulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylthio) -5-methylthiopyrrol; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (bromdifluormethylthio) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (bromdifluormethylsulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (bromdifluormethylsulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3: yano-4- (methylsulfinyl) -pyrrole and 1- (2,6-dicilor-4-trifluoromethylphenyl) -2-chloro 3-cyano-4- (methylsulfonyl) -pyrro !. 8. Compositions according to claim 5, characterized in that they contain compounds of the formula I in which X is a halogen atom or a group R ⁵ S (O) _n , where η is 0.1 or 2 and R ^{5 is} alkyl, preferably C 1-4 alkyl, haloalkyl, preferably trihalomethyl, wherein the halogen atoms are F, Cl, Br or combinations thereof, e.g. , CF ₃ , CCI ₃ , CF ₂ Cl, CFCl ₂ or CF ₂ Br, alkenyl or haloalkenyl, R ¹ and R ³ each represent a hydrogen atom, R ² cyano, Y is a hydrogen atom or a halogen atom, preferably Cl or Br, and X ¹ , X ² , X ³ and X ^{4 are} independently hydrogen, halogen, C 1-4 alkyl, C _1-3 alkoxy or C _1-3 alkylthio, wherein X ¹ and X ^{4 are} preferably independently H, F, Cl, Br or CH ₃ and X ² and X ^{3 are} each hydrogen. 9. Compositions according to claim 8, characterized in that they contain the following compounds: 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (chlorodifluoromethylthio) pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (trifluoromethylthio) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chlorodifluoromethylthio) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chlorodifluoromethylsulfinyl) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichloi-fluoromethylthio) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichlorfluormethylsulfinyl) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichlorfluormethylsulfonyl) pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (dichlorofluoromethylthio) pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (dichlorfluormethylsulfinyl) pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (dichlorfluormethylsulfonyl) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trifluoromethylthio) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trifluoromethyl-sulfinyl) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trifluoromethyl-sulfonyl) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trichloromethylthio) pyrrole; 1- (2,4-dichlorophenyl) -3-cyano-4- (dichlorofluoromethylthio) -pyriol; 1- (2,4,6-trichlorophenyl) -3-cyano-4-chloropyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chlordifluormethylsulfonyl) pyrrole; 1- (2,4,6-dichlorophenyl) -3-cyano-4 (dichlorofluoromethylthio) pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (trifluoromethylsulfinyl) pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (trifluoromethylsulfonyl) pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (chlordifluormc> thylsulfinyl) pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (chlordifluormethylsulfonyl) pyrrole; 1- (4-bromo-2,6-dimethylphenyl) -3-cyano-4- (trifluoromethyl-sulfinyl) pyrrole; 1- (4-Bromo-2,6-dimethylphenyl) -3-cyano-4- (trifluoromethyl-sulfonyl) -pyrrole and 1- (4-bromo-2,6-difluorophenyl) -3-cyano-4- (dichlorofluoromethylthio ) -pyrrole. 10. Compositions according to claim 3, characterized in that they contain compounds of formula I, wherein the alkyl and alkoxy moieties of X, X ¹ , X ² , X ³ , X ⁴ , R ¹ , R ² , R ³ and Y defined groups have less than 5 carbon atoms. 11. A composition according to claim 3 or 10, characterized in that they contain compounds of formula I, wherein the defined as alkenyl and haloalkenyl substituents Y allyl or haloallyl and the substituents Y defined as alkynyl and haloalkinyl mean propargyl or Halopenpropargyl. Compositions according to Claim 3 or 10, characterized in that they contain compounds of the formula I, in which R ^{1 is} a hydrogen atom or a halogen atom,
R ² cyano, X is a group of haloalkyl-S (O) n,
where η is 0.1 or 2, X ^I and X ^{4 are} a substituent other than hydrogen, Y is a haloalkyl or haloalkoxy group and
X ² and X ^{3 is} a hydrogen atom. 13. A composition according to claim 12, characterized in that they contain compounds of formula I wherein the substituent R ¹ defined as halogen atom is a chlorine or bromine atom and the substituent X defined as haloalkyl-S (O) _n group trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl represent. 14. Compositions according to claim 3, characterized in that they enthalien compounds of formula I, in which mean: XR ⁵ S (O) _n , where η is 0.1 or 2 and R ^{5 represents} CH ₃ , CF ₃ , CF ₂ Cl or CFCl ₂ ,
R ² cyano, R ¹ H, F, Cl, Broder NH ₂ ,
R ^{3 is} H, F, Cl, Br, CF ₃ or CN, X ^{I is} H or Cl,
X ² H, X ³ H,
X ⁴ Cl
and Y CF ₃ or CF ₃ O. Compositions according to Claim 3, characterized in that they contain the following compounds: 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (trifluoromethylsulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (trifluoromethylsulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfinyl-5-bromopyrrole; 1- (2,6-Dichljr-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfonyl-5-bromopyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (trifluoromethylthio) pyrrole; 1- \ 2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-trifluoromethylthio-4-cyano-5-chloropyrrole; 1- (2,6-dichloro-4-trifluormethylphenyi) -2- (trifluoromethyl) carbonylamino-3-trifluoromethylthio-4-cyano-5-chloropyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2- (methylcarbonylamino) -3-trifluoromethylthio-4-cyano-5-chloropyrrole; 1- (2,6-dichloro-4-irifluormethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole; 1- (2-chloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-dichloromethylthio-4-cyano-5-chloropyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2,4-bis (trifluoromethylthio) -3-cyano-5-aminopyrrole; 1- (2,6-dichloro-4trifluormethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-bromopyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole; 1- (4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5- bromopyrrole; 1- (2-chloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-bromopyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3- cyano-4- (dichlorofluoromethylthio) -pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylsulfinyl) -pyrrole; 1- (2,6-dichloro-4 trifluoromethylphenyl) -2-chloro-3-cyano-4- (you orfluormethylsulfonyl) -pyrrole!; 1- (2 ₍ 6-Dichloro-4-trifluoromethylphenyl) -3-cyano-4- (dichlorofluoromethylthio) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -3-cyano-4- (dichloro-fluoro-methylsulfinyl ) -pyrrolone and 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofibromomethylsulfonyl) -pyrrole. Composition according to Claim 1 or 3, characterized in that it is intended to control plant diseases caused by arthropods or nematodes by applying an effective amount of the compounds of formula I to the plants or to a medium in which they grow. Composition according to Claim 16, characterized in that it is used for the local application of the corresponding compound in the area in which the arthropod or nematode infection is to be controlled, in an amount effective between 0.005 and 15 kg of the compound per hectare of surface to be treated and preferably an amount of from 0.02 to 2 kg, and more preferably from 0.01 to 1 kg / ha. 18. Process for the preparation of the compounds of the formula I. in which mean X is halogen, cyano, cyanato, thiocyanato, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, HalogenalkylcarbonyljAlkenylthiOjAlkenylsulfinyljAlkenylsulfonyl, Halogenalke ylthio, haloalkenylsulfinyl, haloalkenylsulfonyl, Halogenalkenylthiocarbonyl, Phonylthio, phenylsulfinyl, phenylsulfonyl, heteroarylthio, heteroarylsulfinyl or heteroarylsulfonyl, wherein the phenyl groups are optionally substituted with halogen, cyano or haloalkenyl groups, the heteroaryl groups are five- or six-membered monocyclic rings having one or two heteroatoms selected from oxygen, sulfur, and nitrogen, and optionally with halogen, nitro, cyano or haloalkenyl groups and the abovementioned alkyl, haloalkyl, alkenyl, haloalkenyl, alkoxy and haloalkoxy groups are straight-chain or branched and have from 1 to 10 carbon atoms, the halogen substituents being from 1 to 10 carbon atoms in which all of these groups consist of one or more identical or different halogen atoms and monosubstitution may be present until complete polysubstitution; R ¹ , R ² and R ^{3 are} independently the same as defined above for X as well as hydrogen or alkyl, wherein one of the substituents R ¹ , R ² and R ³ may be selected from formyl,. Hydroxyiminoalkylidenyl, alkoxyiminoalkylidenyl, azido, amino, alkylamino, dialkylamino, aralkylamines, aminocarbonylamino.alkylcarbonylamino, haloalkylcarbonylamino, arylcarbonylaminoalkylsulfonylamino, haloalkylsulfonylamino, alkylaminocarbonylamino, arylaminocarbonylamino, benzylidenimino, alkylidenimino, alkoxyalkylidenimino, dialkylaminoalkylidenimino, bis (alkylthio) methyl, bis (arylthio) -methyl, alkylthioalkylidenimino, alkoxycarbc; ylamino, haloalkoxycarbonylamino, phenyl which is optionally substituted by halogen, cyano or haloalkyl and heteroaryl groups having a five- or six-membered monocyclic ring which has one or more heteroatoms selected from oxygen, sulfur and nitrogen and optionally substituted by halogen, nitro, cyano or Substituted haloalkyl groups, wherein the abovementioned alkyl, haloalkyl, menkyl, haloalkenyl, haloalkoxy and alkoxy groups are straight-chain or branched and have 1 to 10 carbon atoms, the halogen substitution in all of these groups consisting of one or more identical or different halogen atoms and mono-substitution may be present for complete polysubstitution; Y is halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylsulfinyl, alkylsulfonyl, alkylthio, ketoalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyi, alkenyl, haloalkenyl, alkynyl or haloalkynyl, said alkyl, alkoxy, haloalkyl and haloalkoxy groups are straight or branched and have 1 to 10 carbon atoms and the halogen substitution in all of these groups consists of one or more identical or different halogen atoms and monosubstitution are present until complete polysubstitution or a hydrogen atom, if X is a halogen atom or a group R ⁵ S (O) _n ,
where η is 0.1 or 2 and R ^{G represents} alkyl, haloalkyl, alkenyl or haloalkenyl and the alkyl and alkenyl carbon chains and the halogen substitution are as defined above, R ¹ and R ³ each represent a hydrogen atom and R ^{2 is} cyano, X ^I X ² , X ³ and X ^{4 are} independently the same as defined above for Y or a hydrogen atom where the following conditions exist: at least one of the substituents R ¹ , R ¹ and R ³ is selected from the meanings defined above for X,
if X ⁴ and X ¹ H and
X is halogen or cyano,
R ^{2 is} different from X, and
if X ⁴ and X ^{1 are} hydrogen and
Y is methyl,
X does not mean bromine,
characterized in that A) with the proviso that in the compounds of formula IR ¹ amino, R ^{2 is} cyano, R ^{3 is} hydrogen
and X is halogen, trifluoromethyl, cyano, thiocyanato, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkenylthio, haloalkenylthio, haloalkenylsulfinyl, haloalkenylsulfonyl, phenylthio, phenylsulfinyl, phenylsulfonyl, heteroarylthio, heteroarylsulfinyl or heteroarylsulfonyl,
a compound of formula III in which X ¹ , X ² , X ³ , X ⁴ and Y have the above meaning and the amino group is optionally protected, (A) with sinem halogenating agent, if appropriate in the presence of a solvent, to give a compound of the formula Ia (La), in which X represents halogen and, if appropriate, subsequent reaction of this compound with trifluoromethyl copper in a manner known per se to give compounds of the formula Ia in which X represents trifluoromethyl; (b) with a tris (alkylthio) methane or tris (arylthio) methane in the presence of a Lewis acid and then reacting the resulting compound of formula Xl, wherein X is bis (alkylthio) methyl or bis (arylthio) methyl a suitable alkyl nitrite and subsequent hydrolysis to give a compound of the formula XXXVII, in which X is formyl, and optionally subsequent contacting of this compound with hydroxylamine and subsequent dehydration with suitable agents such as P2O5 in a manner known per se to give a precursor of the formula Ia, wherein X represents a cyano group; (c) with a compound of the formula MSCN wherein M is an alkali metal, in the presence of bromine in a solvent such as methanol to form a compound of formol Ia in which X is a thiocyanato group and optionally subsequent reaction of this compound with an alkyl halide or a dialkyl sulphate in the presence of a base such as NaOH or KOH in a solvent to give a compound of the formula Ia in which X is alkylthio, or (d) with a sulfenyl halide of the formula RSHaI in which R is alkyl, haloalkyl, phenyl or heteroaryl and Hal represents a halogen atom, in an organic liquid reaction medium, optionally in the presence of an acid acceptor such as a tertiary amine, to give a compound of the formula Ia in which X is alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, phenylthio or heteroarylthio, and optionally subsequent Oxidation of the compound obtained in a manner known per se to give a compound of the formula a, in which X represents RS (O) _n , where η is 1 or 2, depending on the reaction conditions, or B) with the proviso that R ^{1 is} amino, R ^{2 is} cyano, R ^{3 is} hydrogen and X is cyanato, alkoxy or haloalkoxy, a compound of formula XXVIII (XXVIII) wherein X ¹ , X ² , X ³ , X ⁴ and Y have the meaning defined above and the amino group and the cyano group are optionally suitably protected, (a) with a cyanogen halide in the presence of an acid acceptor to give a compound of formula Ia, wherein X is cyanato; (b) with an alkylating agent, if appropriate in the presence of a base, to give compounds of the formula Ia in which X is alkoxy, or (c) is reacted by per se known haloalkylation to compounds of formula I a, in which X is haloalkoxy, or C) provided that R ^{1 is} amino, R ^{2 is} cyano, R ^{3 is} hydrogen, X is haloalkyl (CF ₂ H, CF ₃ , BrCH ₂ , CICH ₂ ), haloalkylcarbonyl, haloalkylthiocarbonyl or α-haloalkyl-ahalogenomethyl,
a compound of Formol Vl OHC-i r ~ CN (Vl), in which X ¹ , X ² , X ³ , X ⁴ and Y have the above meaning and the amino group and the cyano group are optionally protected in suitable catfish, (A) with a fluorinating agent such as diethylaminosulfur trifluoride in a conventional manner to a Vorbindung the formula I a, wherein X is a difluoromethyl group; (b) with a suitable oxidizing agent such as chromium trioxide in sulfuric acid to Vorbindungen, in doren Formol X represents a Carboxylgi 'ippe, and subsequent reaction of these compounds with a fluorinating agent such as sulfur tetrafluoride in known Weisr, to compounds of formula I a, in the Xor Tritluoromethyl; (c) under Wolff-Kishner conditions or a variant thereof, such as treatment with p-toluenesulfonylhydrazide and then with sodium cyanoborohydride to give a compound in which formula X represents a methyl group, followed by reaction with a halogenating agent such as N-bromosuccinimide or N-chlorosuccinimide in a suitable solvent to give a compound of the formula Ia, in which X is bromomethyl or chloromethyl, odor (d) sequentially adding a haloalkylmetal dorivate or trifluorotrimethylsilane to compounds of formula Ia wherein X represents haloalkylcarbinol followed by oxidation in a manner known per se to compounds of formula Ia in which X is haloalkylcarbonyl and then reacting the obtained compounds with Lawesson's reagent Compounds of the formula Ia in which X is haloalkylthiocarbonyl, or reaction of the compound in which Fornel X represents haloalkylcarbinol with halogenating agents such as thionyl chloride or hydrogen bromide to give compounds of the formula Ia in which X represents ahaloalkyl-ahalogeno-thyl, in which if necessary, all of the aforementioned steps are followed by deprotection, reaction, or D) with the proviso that R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} halogen, formyl, bis (alkylthio) methyl, bis (arylthio) methyl, haloalkyl, alkyl, optionally substituted phenyl or heteroaryl, thiooyanato, alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, phenylthio, hoteroarylthio, alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl Alkenylsulfonyl, halo-alkylsulfinyl, haloalkylsulfonyl, haloalkenylsulfinyl, haloalkonylsulfonyl, phenylsulfinyl, thenylsulfonyl, heteroarylsulfinyl or heteroarylsulfonyl, a compound of formol la, in which X cyano and amino optionally in suitable Woiso are protected, (A) according to variant A) (a) zj compounds of the formula Ib χ -ι r ^C CN 3 Ib, in which R ^{3 represents} halogen, subsequent reaction of these compounds with an optionally substituted heteroaryl or phonyl halide, preferably a bromide or iodide in the presence of copper in a conventional manner, or subsequent reaction of this compound, in which R ^{3 is} preferably bromine or iodine represents, with an optionally substi'.uierton phenyl or Hütoroaryldihydroxyborane in the presence of palladium in a manner bokannten manner to compounds of formula I b in which R ^{3 is} an optionally substituted phenyl or heteroaryl group, or subsequent reaction of a compound of Formula la in which R ^{3 is} halogen, according to variant A) (a) to compounds of the formol Ib, in which R ^{3 is} trifluoromethyl; (B) according to variant A) (b) to give a compound of formula I b in which R ^{3 is} bis (alkylthio) methyl or bis (arylthio) methyl, and then a compound of formula I b in which R ³ Formyl means; (c) with an optionally substituted phenyl or Hetoroaryldiazoniumsalz in a conventional manner to compounds of formula I (b) in which R ^{3 is} optionally substituted phenyl or heteroaryl, or (d) according to variant A) (c), (d) to compounds of the formula Ib in which R ^{3 is} alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, phenylthio or heteroarylthio, optionally subsequent oxidation according to variant A) (d) to compounds of the formula Ib in which R ^{3 is} alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, alkenylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenylsulfinyl, haloalkenylsulfonyl, phenylsulfinyl, phenylsulfonyl, heteroarylsulfinyl or heteroarylsulfonyl, with the proviso that X is not an RS group which is undesirable Subject to oxidation, subsequent treatment, when X is a halogen, with an alkyl lithium in a conventional manner and subsequent aqueous quenching and sulfenylation according to variant A) (c), (d) to compounds of formula I b in which X is alkylthio, Haloalkylthio, alkenylthio, haloalkenylthio, phenylthio or heteroarylthio, is reacted, odor E) untor dor requirement that R ^{1 is} amino, R ^{2 is} cyano and R ³ Hydroxyiminoalkylidenyl, Alkoximinoalkylldenyl, cyano, haloalkylcarbonyl, Halogonalkylthiocarbonyl or alkyl mean, a compound of formula XXIX in which R ^{3 is} formyl or alkylcarbonyl and X cyano and amino are suitably protected, (A) by condensation with hydroxylamine or an O-alkylhydroxylamine or an addition salt of these compounds in a solvent such as ethanol to a compound of formula Ib in which R ³ Hydroxyiminoalkylidenyl or Alkoximinoalkylidenyl, and, when R ³ Hydroxyiminomethylidenyl or Alkoximinomethvlidenyl, separation of Water or alcohol components according to variant A) (b) to give a compound of the formula Ib in which R ^{3 is} cyano; (b) when R ^{3 is} formyl, according to variant C) (a), (b), (c), (d) and obtaining a compound of formula Ib in which R ^{3 is} methyl, haloalk / 1, haloalkylcarbonyl or haloalkylthiocarbonyl . or (c) when R ^{3 is} formyl, with a Grignard reagent derived from an alkyl halide or an alkyllithium to the corresponding carbinol, then dehydration to a compound in which R ^{3 is} alkenyl and subsequent reduction to corresponding compounds of the forms! ib, in which R ^{3 is} alkyl, and optionally subsequent deprotection is rearranged, or F) with the proviso that R ^{1 is} amino, R ^{2 is} cyano and R ^{3 is} cyanato, alkoxy or haloalkyl, y,
a compound of formula XXXI (XXXI) in which amino, cyano and X are optionally suitably protected, according to variant B) (a), (b), (c) to a compound of the formula Ic in which R ^{3 is} cyanato, alkoxy or haloalkoxy, is implemented, or
G) provided that R ^{1 is} hydrogen, halogen, thiocyanates, alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, phenylthio, heteroarylthio, alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, alkenylsulfonyl, haloalkylsulfinyl. Arylsulfinyl, heteroarylsulfonyl, optionally substituted phenyl or heteroaryl, alkylcarbonyl, alkylamino, dialkylamino, aralkylamino, aminocarbonylamino, alkylcarbonylamino, haloalkylcarbonylamino, arylcarbonylamino, alkylsulfonylamino, halogenoalkylsulfonyl, Haloalkylsulfonylamino.alkylaminocarbonylaminecarbylaminocarbonylamino, alkoxycarbonylamino, haloalkoxycarbonylamino, alkylidenemino, benzylidenimino, alkoxyalkylidenimino, dialkylaminoalkylidenimino, alkylthioalkylidenimino, azido, bis (alkylthio) methyl, bis (arylthio) methyl, formyl, haloalkylcarbonyl, haloalkylthiocarbonyl, haloalkyl or alkyl, and R ^{2 is} cyano, a compound Car Formula I b or XXXIV (Ib or XXXIV), in which the amino group is freed from the protective group if necessary after protection of the groups X, R ³ or cyano, (a) with a diazotizing agent, preferably an inert solvent, to give a compound of formula Ic in which R is hydrogen; (b) with a Diazoticrungsmittel, preferably an alkyl nitrite, in the presence of a halogen donor to obtain a compound of formula I c wherein R ¹ represents halogen, subsequently reacting this compound with a Grignard reagent or lithium derivative followed by reaction with an aliphatic acid chloride or a corresponding anhydride with conversion into a compound of the formula I c, in which R ^{1 is} alkylcarbonyl, or reaction of this compound according to variant D) (a) to obtain compounds of the formula Ic in which R ^{1 is} phenyl or heteroaryl; (c) with a diazotizing agent, preferably an alkyl nitrite, in the presence of SCH? or a disulfide in a solvent such as chloroform to give compounds of the formula Ic in which R ^{1 is} thiocyanato, alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, phenylthio or heteroarylthio, and optionally subsequent oxidation A) (d) to give a compound of the formula I. c, wherein R ^{1 is} alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, alkenylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenylsulfinyl, halo-alkenylsulfonyl, phenylsulfinyl, phenylsulfonyl, heteroarylsulfinyl or heteroarylsulfonyl; (d) according to variant F) (a) to (k), to give compounds of the formula Ic in which R ^{1 is} alkylamino, dialkylamino, aralkylamino, aminocarbonylamino, aikylcarbonylamino, haloalkylcarbonylamino, arylcarbonylamino, alkylsulfonylamino, haloalkylsulfonylamino, alkylaminocarbonylamino, arylaminocarbonylamino, alkoxycarbonylamino, Haloalkoxycarbonylamino, alkylidenimino, benzylidenimino, alkoxyalkylidenimino, dialkylaminoalkylidenimino, alkylthioalkylidenimino, or azido, or (E) with sodium nitrite ur.d formaldoxime, copper sulfate and HCl in a conventional manner to compounds of formula Ic in which R ^{1 is} formyl, followed by reaction with an alkyl Grignard reagent and subsequent oxidation with conversion into compounds of formula Ic in which R ^{1 is} alkylcarbonyl, subsequent reaction according to claim 20 to a compound of formula Icindering R ^{1 is} hydroxyiminoalkylidenyl or alkoximinoalkylidenyl, and, when R ^{1 is} phenyl, reaction according to variant C) (a) to (d) to give a compound of formula Ic, in the R ¹ haloalkylcarbonyl, haloalkylthiocarbonyl, haloalkyl or aryl, and optionally subsequent deprotection, wherein the above compound, in the formula R ^{1 is} formyl, in per se got ner way into a compound of formula I c is converted, in the R ¹ bis (alkylthio) methyl or bis (arylthio) methyl, is reacted, or H) Provided that R ¹ cyanates alkoxy or haloalkoxy and R ^{2 is} cyano
a compound of formula XXXII (XXXII) in which X, cyano or R ^{3 are} optionally protected in a manner known per se, according to variant B) (a), (b), (c) to give a compound of formula I c in which R ^{1 is} cyanato, alkoxy or haloalkoxy means, and optionally subsequent deprotection implemented will, or provided that R ^{2 is} CHO, reacting a compound of the formula Ic with a reducing agent, preferably diisobutylaluminum hydride, in a solvent to give the corresponding compound in the formula R ² CHO, which may optionally be prepared in a manner known per se to give the corresponding compound of the formula XXXV CO ₀ I _v l ^ N ^ v ⁴ (XXXV) / 3 is oxidized, or
J) with the proviso that R ^{2 is} hydroxyiminoalkylidenyl, alkoximinoalkylidenyl, haloalkylcarbonyl, haloalkylthiocarbonyl, alkyl, haloalkyl, bis (alkylthio) methyl or bis (arylthio) methyl, a compound of the formula I in which R ^{2 is} CHO, if appropriate after protection of the groups X, R ¹ or R ³ with a protective group according to variant C) (a), (b), (c), (d), variant E) (a), (b) or variant H) (e) and, if necessary, subsequent deprotection, is carried out, K) on condition that R ^{2 is} amino, alkylamino, dialkylamino, aralkylamino, aminocarbonylamino, alkylcarbonylamino, haloalkylcarbonylamino, arylcarbonylamino, alkylsulfonylamino, haloalkylsulfonylamino, alkylaminocarbonylamino, arylaminocarbonylamino, alkoxycarbonylamino, alkylidenimino, benzylidenimino, alkoxyalkylidenimino, dialkylaminoalkylidenimino, alkylthioalkylidenimino, azido, hydrogen, halogen, thiocyanato, alkylthio, haloalkylthio, Alkenylthio, haloalkenylthio, phenylthio, heteroarylthio, alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, alkenylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenylsulfinyl, haloalkenylsulfonyl, phenylsulfinyl, phenylsulfonyl, heteroarylsulfinyl, heteroarylsulfonyl or optionally substituted phenyl or heteroaryl, reacting a compound of the formula XXXV, after protection of the groups X, R ¹ or R ³ in a manner known per se with a protective group, under conditions for the Cuitius rearrangement, for example by conversion g in a corresponding acid chloride and subsequent reaction with an alkali metal azide, or with diphenylphosphoryl azide in the presence of an organic base such as triethylamine in an alcoholic solvent to give the corresponding carbamate, and optionally subsequent hydrolysis to the corresponding compound, in the formula of amino, then optionally according to variant F) (a) to (k) to Variani H) (a) to (c) is reacted, and, if R ^{2 is} halogen, optionally reaction according to variant D) (a) and, if necessary, subsequent deprotection, or L) under the condition that R ² cyanato, alkoxy or Haloalkoxy means a compound of formula XXXVI Ι I OH-R ³ (XXXVI) optionally after protection of the groups X, R ¹ or R ^{3 is} reacted with a protective group, according to variant F) and, if necessary, subsequent deprotection, or M) with the proviso that X is a perhaloalkylthio group, a (a) reaction of a compound of formula XXXVIII ClSO ₃ H (XXXVIII) (XXXIX), in which X is hydrogen, with chlorosulfonic acid at a temperature between 0 and 150 ⁰ C and optionally in an organic solvent to a compound of formula XXXIX, in whichX-SO ₂ CI and R ¹ , R ² , R ³ , Y, X ¹ , X ² , X ³ and X ^{4 are the} same as in formula I,
(b) reaction of the compound of formula XXXIX c? .o ₂ s R ¹ Reducing agent solvent (XXXIX; (XLI) in the X-SO ₂ Cl, with a reducing agent at a temperature between and 11O ⁰ C in an organic solvent to the corresponding disulfide compound of the formula XLI in which R ¹ , R ² , R ³ , Y, X ¹ , X ² , X ³ and X ⁴ are defined as in formula I, and
(c) reaction of the disulfide compound of formula XLI reduction
medium base JSL (XLI) (XLII) (I), wherein R ¹ , R ² , R ³ , Y, X ¹ , X ² , X ³ and X ^{4 are} as defined for formula I, with a perhaloalkane of formula XLII, ZCFR ⁷ R ⁸ , wherein Z is CL, Br or J, R ^{7 is} F, Cl or Br and R ^{8 is} F, Cl, Br or a perfluoroalkyl group, in the presence of a free radical-promoting reducing agent and optionally in the presence of a base in an organic solvent at a temperature between 20 and 85 ° C and optionally under pressure to give a compound of the formula I in which X is a perhaloalkylthio group and R ¹ , R ² , R ³ , Y, X ¹ , X ² , X ³ and X ^{4 are} as defined above. Field of application of the invention The invention relates to compositions containing as active ingredients novel compounds of the pyrrole series which are suitable for the control of arthropods and in particular insects and arachnids, especially in agriculture. Characteristic of the known state of the art Numerous pyrazoles, d. H. Compounds having heterocyclic rings with two nitrogen atoms are well known as insecticides. Further, some compounds containing a pyrrole group (a heterocyclic ring having a nitrogen atom) are also known as insecticides. However, these known compounds usually also contain in their formula other chemical groups whose insecticidal properties are known per se, for example a pyrethroid group or a carbarnate group or organophosphoric acid groups. Simple substituted pyrrole derivatives have already been described as agricultural chemicals for use as fungicides, for example in GB-A-2,189,242. Object of the invention The invention provides highly effective insecticidal, acaricide or nematocidal compositions which contain new pyrrole compounds as active ingredients. Explanation of the essence of the invention The invention has for its object to produce new insecticid and acaricid active compounds from the family of pyrroles and to provide highly effective pesticide compositions. According to the invention, insecticidal, acaricidal or nematocidal compositions are provided which contain pyrrole compounds of general formula I,