CZ284089B6 - Pyrrole derivatives and insecticidal and acaricidal agent in which the derivatives are comprised - Google Patents

Abstract

The present invention relates to pyrrole derivatives of formula I wherein X is halogen, thiocyanato, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, cyano- or haloalkylsulfonyl, R.sup.1. is hydrogen, halogen, alkylthio-, alkylsulfinyl, alkylsulfonyl, amino-, alkylcarbonylamino-, haloalkylcarbonylamino- or alkylthioalkylidenimino; is hydrogen, halogen, cyano, alkyl, haloalkyl or alkoxycarbonylamino; is hydrogen, halogen, thiocyanato, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio or bis / alkylthio / methyl, Y is halogen, haloalkyl or haloalkoxy, or hydrogen. The present invention also relates to an insecticidal and arcaricidal composition comprising said pyrrole derivative as an active ingredient and using said derivatives to control insects and mites. ŕ

Description

The invention relates to novel compounds belonging to the group of pyrroles, to intermediates for the preparation of these compounds and to a process for the preparation of these compounds and intermediates. Furthermore, the invention describes the application of said compounds in agriculture, in particular as pesticides for controlling arthropods, preferably as insecticides and acaricides. The present invention relates to agrochemical compositions useful for controlling arthropods, in particular insects and arachnids.

Numerous pyrazoles (heterocycles containing 2 nitrogen atoms) are well known as insecticides. Some pyrrole-containing compounds (heterocycle containing 1 nitrogen atom) are also known as insecticides. However, these substances usually also contain other chemical groups in their molecule which are known to exhibit insecticidal activity themselves, such as a pyrethroid group, a carbamate group or an organophosphorus group. Simply substituted pyrrole derivatives for use in agriculture have been described, for example, in British Patent No. 2,189,242, but only for fungicidal application.

The novel pyrrole derivatives according to the invention correspond to the general formula I

X

(I) in which

X is halogen, thiocyanato, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl, wherein the alkyl and haloalkyl moieties have straight or branched chain containing 1 to 4 carbon atoms and all of the above halogen substituted groups contain one or several of the same or different halogen atoms from monosubstitution to complete polysubstitution, or represents a cyano group,

R ¹ is hydrogen, halogen, alkylthio, alkylsulfinyl, alkylsulfonylovouskupinu, amino, alkylcarbonylamino, haloalkylcarbonylamino or alkylthioalkylideniminoskupinu in which the alkyl and haloalkyl moieties are straight or branched chains containing 1 to 4 carbon atoms and all of the above groups substituted with halo include one or several identical or different halogen atoms from monosubstitution to complete polysubstitution,

R ² is hydrogen, halogen, cyano, alkyl, haloalkyl or alkoxycarbonylamino, the alkyl and haloalkyl groups and alkoxy moieties are straight or branched chains containing from 1 to 4 carbon atoms and haloalkyl groups contain one or more identical or different halogen atoms from monosubstitution to full polysubstitution,

- 1 GB 284089 B6

R ³ is hydrogen, halogen, thiocyanato, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio group or a bis (alkylthio) methyl group in which the alkyl and haloalkyl moieties are straight or branched chains containing 1 to 4 carbon atoms, and haloalkyl moiety contains one or several identical or different halogen atoms from monosubstitution to complete polysubstitution, with at most one of R ¹ , R ² and R ³ selected from the group consisting of amino and alkylcarbonylamino as defined above, haloalkylcarbonylamino, alkoxycarbonylamino, alkylthioalkylidenimino and bisthioalkylidenimino; methyl groups,

Y represents a halogen atom, a haloalkyl group or a haloalkoxy group, wherein the haloalkyl and haloalkoxy groups have straight or branched chains of 1 to 4 carbon atoms and contain one or more identical or different halogen atoms from monosubstitution to complete polysubstitution, or Y represents a hydrogen atom when wherein X is a halogen atom or a radical of formula R ³ S (O) _n wherein n is 0, 1 or 2 and R 'is an alkyl or haloalkyl group as defined above. R ¹ and R ³ represent hydrogen and R ² is CN,

X ¹ represents a hydrogen atom, a halogen atom, an alkyl group, an alkylthio group or an alkylsulfonyl group, wherein the alkyl groups and moieties have a straight or branched chain of 1 to 4 carbon atoms,

X and X ³ are hydrogen and

X ⁴ represents a hydrogen atom, a halogen atom or a straight or branched (C 1 -C 4) alkyl group, provided that at most two of R ¹ , R ² and R ³ are selected from the group consisting of hydrogen and alkyl as defined above when X ⁴ and X ¹ are hydrogen and X is halogen then R ² is different from X and at least one of X, R ¹ , R ² and R ³ is different from the other, except for the compound in which X ⁴ , X ¹ , Y, R ¹ , X, R ² and R ³ are chlorine and X ^{3 and} X "are hydrogen.

Generally preferred compounds of the invention of interest as insecticides and acaricides are those of formula (1) above wherein:

Y represents a hydrogen atom and X represents a radical of formula R ⁵ S (O) n, where n is 0, 1 or 2 and R ⁵ represents an alkyl or haloalkyl group as defined in 1, R ¹ and R ³ represent hydrogen atoms and R ² cyano, or

Y represents a halogen atom or a haloalkyl or haloalkoxy group as defined in point 1,

X represents a halogen atom,

R ¹ represents a hydrogen atom, a halogen atom or a straight or branched (C 1 -C 4) alkylthio group.

R ² is CN,

-2GB 284089 B6

R ³ represents hydrogen or halogen,

X ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkylthio group having 1 to 3 carbon atoms,

X ² and X ³ represent hydrogen atoms and

X ⁴ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.

Particularly interesting compounds of the formula I are of particular interest:

A) compounds of formula II

X ¹ ------ Cl

(ii) in which:

X is R ⁵ S (O) n wherein n is 0, 1 or 2 and R ⁵ is methyl, trifluoromethyl, difluorochloromethyl, fluorodichloromethyl, difluorobromomethyl, difluoromethyl, dichloromethyl or fluorochloromethyl,

R ² is CN,

R ¹ represents a hydrogen, fluorine, chlorine or bromine atom,

R ³ represents hydrogen, fluorine, chlorine or bromine,

X ^I represents hydrogen or chlorine and

Y is trifluoromethyl or trifluoromethoxy, which exhibit high insecticidal activity.

Preferred compounds of this class of compounds are:

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-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- (dichlorofluoromethylsulfonyl) pyrrole, 1- (2,6 -dichloro-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-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-tri fluoromethylphenyl) -2-bromo-3-cyano-4- (dichlorofluoromethylsulfonyl) pyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (dichlorofluoromethylsulfinyl) 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, 1- (2,6-dichloro-1-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylsulfonyl) -5-bromopyrrole,

1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (chlorodifluoromethylsulfonyl) pyrrole,

1- <2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylsulfinyl) pyrrole,

1- <2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylsulfonyl) pyrrole, 1- (2-chloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4 - (dichlorofluoromethylsulfonyl) pyrrole, 1- (2-chloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylsulfinyl) pyrrole, 1- (2-chloro-4-trifluoromethylphenyl) -2-bromo- 3-cyano-4- (dichlorofluoromethylsulfonyl) pyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylthio) -5-methylthiopyrrole, 1- (2,6-dichloro- 4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (bromodifluoromethylthio) pyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (bromodifluoromethylsulfinyl) pyrrole, 1 - (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (bromodifluoromethylsulfonyl) 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 with high insecticidal activity, corresponding to the general formula II, in which:

X is R ⁵ S (O) _n wherein n is 0, 1 or 2 and R ⁵ is methyl, trifluoromethyl, difluorochloromethyl or fluorodichloromethyl,

R ² is CN,

-4GB 284089 B6

R * represents a hydrogen, fluorine, chlorine or bromine atom or an amino group,

R ³ represents hydrogen, fluorine, chlorine or bromine, trifluoromethyl or cyano,

X ¹ represents a hydrogen or chlorine atom and

Y is trifluoromethyl or trifluoromethoxy.

In view of their insecticidal activity, the following compounds of the invention are preferred:

1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano- (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-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-trifluoromethylphenyl) -2 - [(trifluoromethyl) carbonylamino] -3-trifluoromethylthio-4 —Cyan-5-chloropyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -2- (ethylcarbonylamino) -3-trifluoromethylthio-4-cyano-5-chloropyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) 2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole; 1- (2-chloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole; 6-dichloro-4-trifluoromethylphenyl) -2-amino-3-dichlorofluoromethan ylthio-4-cyano-5-chloropyrrole 1- (2,6-dichloro-trifluoromethylphenyl) -2,4-bis (trifluoromethylthio) -3-cyano-5-aminopyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) 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-trifluoromethylphenyl) -2-chloro-3-cyano- 4- (dichlorofluoromethylsulfonyl) pyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -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 a remarkably high acaricidal activity, corresponding to the general formula (I) in which:

X is halogen or R ⁵ S (O) _n wherein n is 0, 1 or 2 and R ⁵ is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, preferably trihalomethyl in which the hal gene is especially fluorine, chlorine,

Bromine or combinations thereof, for example, trifluoromethyl, trichloromethyl, difluorochloromethyl, fluorodichloromethyl or difluorobromomethyl,

X ² , X ³ , R ¹ and R ³ are hydrogen atoms,

R ² is CN,

Y represents a hydrogen atom or a halogen atom, preferably chlorine or bromine, and

X ¹ and X ⁴ are independently selected from the group consisting of hydrogen, halogen and C 1 -C 3 alkyl, preferably X ¹ and X ⁴ are each independently hydrogen, fluoro, chloro, bromo or methyl group.

Particularly preferred compounds of this class of compounds are:

1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (chlorodifluoromethylthio) pyrrole, 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (trifluoromethylthio) pyrimidine, 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- (dichlorofluoromethylsulinyl) pyrrole, 1- (2,4 6-trichlorophenyl) -3-cyano-4- (dichlorofluoromethylsulfonyl) pyrrole, 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (dichlorofluoromethylthio) pyrrole, 1- (4-bromo-2) 6-dichlorophenyl) -3-cyano-4- (dichlorofluoromethylsulfinyl) pyrrole, 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (dichlorofluoromethylsulfonyl) pyrrole, 1- (2,4,6) -trichlorophenyl) -3-cyano-4- (trifluoromethylthio) pyrrole, 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trifluoromethylsuifinyl) 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- fdichlorfluormethylth io) pyrrole, 1- (2,4,6-trichlorophenyl) -3-cyano-4-chloropyrido-1,1- (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) pyrrole, 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-cyano-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.

-6GB 284089 B6

D) Other preferred compounds of Formula 1 are those wherein:

R ¹ represents a hydrogen atom or a halogen atom such as chlorine or bromine,

R ² is CN,

X is haloalkylthio or haloalkylsulfinyl or haloalkylsulfonyl, preferably CF ₃ S (O) _n , wherein n is 0, 1 or 2,

X ^I and X ⁴ are different from hydrogen,

X ² and X ³ are each hydrogen and

Y is haloalkyl or haloalkoxy as defined above.

SUMMARY OF THE INVENTION It is an object of the present invention to provide novel insecticides and acaricides from the group of pyrrole derivatives and intermediates necessary for their production. It is an object of the present invention to provide highly effective compounds. These and other objectives can be achieved in whole or in part using the novel compounds defined below.

The compounds of formula (I) may be prepared by application or adaptation of known methods (i.e., methods previously used or described in the chemical literature). Generally, a pyrrole ring is formed and then optionally substituted or substituted. It will be understood that in the methods described below, it is possible to change the order of introduction of different groups on the pyrrole ring and that in some cases certain functional groups need to be protected. The resulting compounds of formula I can also be converted into other compounds of formula I by known methods.

If, in describing the various methods by which the method of the invention is carried out, some of the symbols appearing in the formulas are not specifically defined in the following, it is believed that in such a case, the respective symbol is as defined above, i.e. the first defined meaning. The term protection includes the conversion of the respective functional group into a suitable non-reactive group which, if desired, can be converted back to the original group as well as the addition of groups which render the original functional group unreactive. Unless otherwise indicated, the term amino refers to unsubstituted amino.

The invention includes certain intermediates used to produce the compounds of the invention. Such preferred intermediates prepared as described below correspond to the general formula IIIa

-7EN 284089 B6

--- _C1

Y (lilac) in which

Y is hydrogen, chlorine or bromine, trifluoromethyl or trifluoromethoxy;

X ¹ and X ⁴ independently represent hydrogen, chlorine or fluorine atom or a methyl group, or X ¹ is also a methylthio group, with the restriction that means when both X ¹ and X ⁴ are hydrogen, then Y is other than a hydrogen or chlorine atom.

While the compounds within the scope of the above limitation are not within the scope of the invention, they are useful as intermediates in the preparation of the compounds of formula I according to the invention.

Particularly preferred intermediates are compounds of formula IIIa wherein Y is trifluoromethyl or trifluoromethoxy, X ¹ is hydrogen or chlorine and X ⁴ is chlorine.

Method 1

In one embodiment of the process of the invention, compounds of formula I wherein X and R ³ are hydrogen are possible. R ² is cyano and R ¹ is amino, wherein X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, i.e., compounds corresponding to formula III

-8EN 284089 B6

(ΙΠ), prepared from dicyanopropene derivatives of general formula IV

NH - CH = C - CH ₂ - CN

(IV), wherein each of the general symbols is as defined above, by reaction with a base, preferably with an alkali, such as a tertiary amine or an alkali metal hydroxide or carbonate. The reaction is preferably carried out at a temperature between -80 and 150 ° C, preferably 40 to 100 ° C. The reaction may be carried out in a solvent such as a liquid alcohol, a hydrocarbon, a halogenated hydrocarbon, a ketone, an amide such as N-methylpyrrolidone, or water.

Method 2

In another embodiment of the process of the invention, compounds of formula IV may be prepared from an aniline derivative of formula V

-9EN 284089 B6

(V), wherein Y, X ¹ , X ² , X 1 and X ⁴ are as defined above, by reaction with formyl succinonitrile or 5 alkali metal salts of formyl succinonitrile. This reaction is generally carried out in an organic solvent or in water, at a temperature between 10 and 120 ° C, preferably at reflux.

Formyl succinonitrile is known and is generally prepared by acidifying its alkali metal salt, which is obtained by reacting succinonitrile with a lower alkyl formate in the presence of an alkaline reagent according to the procedure described by K. Gewald in Z. Chem. 1961, 1, 349.

Method 3

Compounds of formula (1) in which X represents a halogen atom. R ¹ is amino, R ² is cyano, R ³ is hydrogen and the remaining substituents are as defined above, can be prepared by reacting compounds of formula III with halogenating agents such as sulfuryl chloride. N-chlorosuccinimide. N-bromosuccinimide. N 2 O is iodosuccinimide, pyrimidium bromide perbromide or molecular fluorine, chlorine, bromine or iodine. Suitable organic solvents for these reactions are, for example, dichloromethane and acetonitrile. Said reactions are carried out at a temperature between -80 and + 80 ° C, preferably between -30 and +25 ° C. It may be advantageous to protect the amino group during the reaction with elemental fluorine in the form of trifluoroacetamide derivatives.

Method 4

A) Compounds of formula I wherein X is cyano, R ¹ is 30 amino, R ² is cyano, R ³ is hydrogen and the remaining radicals are as defined above may be prepared from the corresponding compounds wherein X is a moiety C = NOH, by dehydration with suitable agents such as acetic anhydride, cyanuric chloride or phosphorus pentoxide. When using some of these dehydrating agents, it may be necessary to protect the amino group with a suitable protecting group.

B) The above intermediate compounds wherein X is C = NOH can be obtained by condensation of hydroxylamine with the corresponding compounds wherein X is a formyl group.

C) Intermediate compounds in which X represents a formyl group may be obtained by hydrolysis of the corresponding compounds in which X represents a bis (alkylthio) methyl or bis (arylthio) methyl group or by reaction thereof with a suitable alkyl nitrite followed by hydrolysis according to the procedure described E. Fujita. K. Ichikawa and K. Fuji in Tetrahedron Letters

- 10GB 284089 B6

1978, 3561. During the reaction with alkyl nitrites, it may be necessary to protect the amine function with a suitable protecting group.

D) Intermediate compounds of formula I wherein X is bis (alkylthio) methyl 5 or bis (arylthio) methyl and the remaining formulas are as defined above may be prepared by reacting a compound of formula III with tris (alkylthio) methane or tris (arylthio) methane in the presence of a Lewis acid, preferably a sulfonium salt, such as dimethyl (methylthio) sulfonium tetrafluoroborate. General reaction conditions for this procedure can be found in Synthesis 1984, 166.

Method 5

A) The required intermediates of formula I in which X represents a hydroxyl group, R ¹ 15 is optionally protected amino, R ² is CN, R ³ represents a hydrogen atom and X ^1, X ^2, X, ^J, X ⁴ and Y have the abovementioned meanings , corresponding compounds in which X is a halogen atom may be prepared by conversion to a Grignard reagent or lithium derivative according to standard methods followed by treatment with oxodiperoxymolybdenium (pyridine) (hexamethylphosphoric triamide) (MoOPH) using the procedure described by NJ 20 Lewis and spol. Org. Chem. 1977, 42, 1479. Prior to the preparation of a Grignard reagent or lithium derivative, it may be necessary to convert a cyano group in the above compound wherein X is a halogen atom to a suitably protected derivative (e.g., an oxazoline derivative in which the cyano group has been converted to a carboxyl group). . Alternatively, the Grignard reagent or lithium derivative described above may be reacted with a trialkyl borate 25 followed by oxidation with hydrogen peroxide using the procedure described by MF.

Hawthome in J. Org. Chem. 1957, 22, 1001 or R. W. Hoffmann and K. Ditrich in Synthesis 1983, 107.

Method 6

A) Compounds of formula I wherein X is thiocyanato, R ¹ is amino, R ² is cyano, R ³ is hydrogen and X ¹ , X ² , X ³ , X ⁴ and Y are as defined above may be prepared by reacting compounds of formula III with a compound of formula

MSCN wherein M represents an alkali metal, in the presence of bromine, in a suitable solvent such as 40 in methanol.

B) Compounds of the formula I * in which X is alkylthio or haloalkylthio, R ¹ is amino, R ² is CN, R ³ is a hydrogen atom and X ^1, X ^2, X ^3, X ⁴ and Y have the above meanings, i.e., compounds corresponding to Formula IX below, may be prepared by reacting a compound of Formula III with a sulfenyl halide of Formula

RSHal in which R represents an alkyl or haloalkyl group as defined above and Hal represents a halogen atom, in a liquid reaction medium. The reaction medium is preferably an organic solvent, for example dichloromethane, and is operated at a temperature of from -100 to + 100 ° C, preferably from -80 to +25 ° C. This reaction may optionally be carried out in the presence of an acid acceptor, such as a tertiary amine, for example pyridine. The necessary alkylsulfenyl chlorides are

Can be prepared by the method of S. Thea et al. Cevasco v Tetrahedron Letters, 1988, 2865. Using sulfenyl chloride, the above procedure can be described by the following reaction scheme:

Y (ΠΙ),

(IX), io Method 7

Compounds of formula I in which X is thiocyanato, R ^L is amino, ^R2 is cyano, ^R3 is hydrogen and X ^1, X ^2, X ^3, X ⁴ and Y have the above meanings, can be further converted to compounds of formula I in which X is an alkylthio group, ^R1 is amino, ^R2 is cyano, ^R3 is hydrogen and X ¹ X ² X ³ X ⁴ and Y have the above meanings, with a base such as sodium or potassium hydroxide , in the presence of, for example, an alkyl halide or dialkyl sulfate, in a solvent.

- 12GB 284089 B6

Method 8

Compounds of formula (IX) can be converted by oxidation to compounds of formula (X) below, wherein X is RS (O) _n , wherein n is 1 or 2 and R is as defined above. Oxidizing agents useful for this purpose include hydrogen peroxide, peroxyacetic acid, trifluoroacetic acid, and m-chloroperoxybenzoic acid. The reaction is carried out in solvents such as dichloromethane, acetic acid or trifluoroacetic acid at a temperature between -40 and + 80 ° C, preferably between 0 and 25 ° C. The reaction conditions, i.e., temperature, reaction time and amount of oxidizing agent used, can be varied as desired to provide either the corresponding sulfinyl derivative (n = 1) or the corresponding sulfonyl derivative (n = 2). It is understood that sulfonyl derivatives can also be prepared from suldinyl derivatives. In the case of certain haloalkylthio groups, for example trifluoromethylthio, it may be desirable to protect the amine function, for example in the form of a trifluoroacetamide derivative.

CF-jCO-jH

(VII),

(X),

- 13 GB 284089 B6

Method 9

Compounds of formula (I) wherein R ³ represents a halogen atom. R ¹ is amino, ^R2 is cyano and X, X ^1, X ^2, X ^3, X ⁴ and Y are as hereinbefore defined, may be prepared by reacting compounds of formula I wherein R ¹ is amino, R ² is CN, R ³ represents a hydrogen atom and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, i.e., compounds corresponding to formula XI below, with halogenating agents under conditions similar to those described in Method 3. This reaction may be described by the following reaction scheme:

X ⁴

CN

Method 10

Compounds of formula I wherein R ³ is bis (alkylthio) methyl, R ¹ is amino, R ² is cyano and X, X ¹ , X ² , X ³ , X ^{4 and} Y are as defined above may be prepared by reaction compounds of formula XI with tris (alkylthio) methane of formula (R ^and S) ₃ CH where R ^a is an alkyl group, in the presence of a Lewis acid, preferably a sulfonium salt, in a solvent at a temperature between 0 ° C and the boiling point of the solvent below with a reflux condenser, optionally in the presence of an acid acceptor, such as pyridine. In accordance with a preferred embodiment

Acetonitrile is used as solvent in this process, working at 25 ° C with tris (methylthio) methane such as tris (alkylthio) methane and dimethyl (methylthio) sulfonium tetrafluoroborate as Lewis acid, without an acid acceptor. The above process can be described by the following reaction scheme:

(R ^and S) ₃ CH

X ------------- _CN

Method 11

Compounds of formula I wherein R ³ is thiocyanato, alkylthio or haloalkylthio, R ¹ is amino, R ² is cyano and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, i.e. of formula (XVI) below, may be prepared from compounds of formula (XI) under conditions similar to those described in Method 6. This procedure may be described by the following reaction scheme:

- 15 GB 284089 B6

Compounds of formula XVI in which R is an alkyl group may also be prepared from compounds of formula I in which R ³ is thiocyanato and the remaining symbols are as in formula XVI, by reaction with alkyl halides or the like, using procedures analogous to those described herein. the procedures described in Method 7.

Method 12

Compounds of formula I wherein R ³ is alkylsulfinyl or alkylsulfonyl, R ¹ is amino, R ² is cyano and X, X ¹ , X ² , X ³ , X ^{4 and} Y are as defined above may be prepared by oxidation of compounds XVI, using methods similar to those described for Method 8. In those cases where X is an RS group that may be subjected to undesirable competitive oxidation, the sulfenylation of the above procedures may be carried out on compounds of Formula I wherein X is a halogen atom, preferably bromine or iodine. R ¹ is amino, R ² is cyano R ³ is hydrogen and the remaining symbols are as defined above, the intermediate is subjected to oxidation treatment followed slkyllithia using a procedure analogous to procedures described by C. Kruse Aspol, Heterocycles 1989, 29, 79, whereupon the reaction is stopped by adding water. The resulting compound of formula XVII can then be sulfenylated to the corresponding compound of formula XVIII. The overall procedure can be described by the following reaction scheme:

- 16GB 284089 B6

(XVII)

Y

RS

H ₂ N

CN

n

R

- 17GB 284089 B6

Method 13

A) Compounds of formula I wherein R ¹ is hydrogen. R ² is cyano, and R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, i.e. compounds of formula XX below may be prepared from compounds of formula I wherein R 2 ¹ is amino, ^R2 is cyano and ^R3, X, X ^1, X ^2, X ^3, X ⁴ and Y are as hereinbefore defined, i.e. the compounds corresponding to the following above general formula XIX diazotising which is preferably carried out with alkyl nitrite such as a target, butyl nitrite in an inert solvent such as tetrahydrofuran or acetonitrile. This reaction can be carried out at a temperature between -80 ° C and the reflux temperature of the reaction solvent, preferably between 0 and 25 ° C.

B) Compounds of formula I wherein R ¹ represents a halogen atom. R ² is CN and R \ X, X ^1, X ^2, X ^3, X ⁴ and Y are as hereinbefore defined, i.e. compounds corresponding to the below mentioned general formula XXI can be prepared from a compound of formula XIX diazotising an alkyl nitrite such as t, butyl nitrite, in the presence of a halogen atom donor such as bromoform, carbon tetrachloride, anhydrous copper chloride or iodine.

C) Compounds of formula 1 wherein R ¹ is alkylthio, R ² is cyano and R ³ , X, X ¹ , X ² , X ³ , X ^{4 and} Y are as defined above, i.e. compounds corresponding to formula XXII below can be prepared from compounds of formula XIX by treatment with an alkyl nitrite in the presence of a disulfide of the formula RSSR, wherein R is an alkyl group as defined above. The reaction is typically carried out in a solvent such as chloroform at 0 ° C using 1 to 5 equivalents of alkyl nitrite and 2 to 5 equivalents of didulfide.

The overall procedure described above can be illustrated by the following reaction scheme:

(XX), R ^c = H (XXI) R ^c = halogen (XXII) R = ^C SR

Method 14

Compounds of formula I in which R ¹ is alkylsulfinyl or alkylsuifonylovou group, R ² represents cyano and R ^3, X, X ^1, X ^2, X ^3, X ⁴ and Y are as hereinbefore defined may be prepared by oxidation of compounds of general formula XXII according to procedures described in method 12. If the X or R ³ also represents a group R, that is to remain

In this oxidation stage (in the sulfide stage), the desired compounds can be obtained in a similar manner to that described in Method 12.

Method 15

Compounds of formula I wherein R ¹ is alkylcarbonylamino, haloalkylcarbonylamino or alkylthioalkylideniminoskupinu, R is cyano and R, ^J, X, X ^1, X ^2, X ^3, X ⁴ and Y have the above meanings, can be prepared from a compound of Io of formula (XIX) by methods known per se.

Method 16

Compounds of formula I wherein R ² is hydrogen or halogen and R ¹ , R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above may be prepared from compounds of formula XXVII

(XXVII)

Alternatively, the compounds of formula (I) wherein R ² is hydrogen and R ¹ , R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above , prepared from compounds of formula XXV below by heating with 48% hydrobromic acid in glacial acetic acid to reflux or 25 by heating in a high boiling solvent such as decalin or quinoline in the presence of copper.

Useful intermediate compounds of formula XXV wherein 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 formula XXIV with Jones reagent. This procedure can be described by the following reaction scheme:

- 19GB 284089 B6

(XXIV)

Compounds of formula XXVII in which R ^1, R ^3, X, X ^1, X ^2, X ^3, X ⁴ and Y are as hereinbefore defined may be prepared from compounds of formula XXV by treatment with diphenylphosphorylazide in the presence of an organic base such as triethylamine , in an alcoholic solvent, such as a target, butanol, to form the carbamate of formula XXVI below, which is then subjected to hydrolysis. Other methods for the preparation of a compound of formula XXVII from a compound of formula XXV by means of a Curtius rearrangement are the conversion of compounds of formula XXV to an acid chloride and subsequent reaction with an azide ion source and treatment with alcohol as described by J. March in Advanced Organic Chemistry (1985), p. 984. The overall conversion can be described by the following reaction scheme.

XXVII

The invention is illustrated by the following non-limiting examples.

Examples 1 to 22 illustrate the synthetic methods and physical properties of the insecticidally active compounds of the invention and their chemical intermediates.

-20GB 284089 B6

Example 1

A solution of 910 mg (2.07 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylthiopyrrole (prepared as described in Example 4) and 492 mg of 80% m-chloroperoxybenzoic acid of the acid (394 mg of pure; 2.26 mmol) in 25 mL of chloroform was stirred at room temperature for 1.5 h, then heated at reflux overnight, followed by an additional 45 mg (0.21 mmol). m-chloroperoxybenzoic acid and refluxing were continued for 1 hour. The heating was then discontinued, the reaction mixture was diluted with dichloromethane and washed with aqueous sodium bicarbonate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a colorless solid residue. This procedure was repeated to give a total of 950 mg of product which was chromatographed on silica gel using dichloromethane / hexane (2: 1 by volume) as eluent. The initial fractions contained 310 mg (24%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfonylpyrrole, which resulted as a colorless solid. Recrystallization from hexane / ethyl acetate gave 240 mg of the desired sulfone as colorless needles with a melting point of 198 ° C.

Example 2

The chromatography described at the end of Example 1 is continued. 600 mg (48%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfinylpyrrole are obtained as a colorless solid from the later eluted chromatography fractions. Recrystallization of this material from toluene / hexane gave 390 mg of the desired sulfoxide as a colorless powder, mp 152-154.5 ° C.

Examples 3A and 3B

The procedure described in Examples 1 and 2 was repeated except that 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylthio-5-bromopyrrole prepared as described in Example 1 was used as starting material. Example 5. 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfinyl-5-bromopyrrole is obtained as the product in Example 3. This compound, prepared as in Example 2, melts at about 123 ° C.

1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfonyl-5-bromopyrrole was obtained as the product in Example 3B. This compound, prepared as in Example 1, melts at about 113 ° C.

Example 4

K. a solution of 3 g (6.6 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole (prepared as described in Example 8) in 50 ml of dry of tetrahydrofuran, under stirring under nitrogen, was added 3.9 mL (3.4 g; 33 mmol) of tert. Butylnitrite. After 30 minutes, the reaction mixture was heated to reflux for about 1 hour and then concentrated under reduced pressure to give 3.69 g of a solid residue. This procedure was repeated to give a total of 4.07 g of a solid residue which was chromatographed on silica gel using a mixture of equal volumes of dichloromethane and hexane as eluent. 2.9 g (91%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylthiopyrrole were obtained as a colorless solid. Recrystallization from hexane / ethyl acetate gave 1.67 g of the desired product as a colorless powder, melting at about 137 ° C.

-21 GB 284089 B6

Example 5

To a heterogeneous mixture of 2.4 g (5.26 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole (produced as described in Example 8) and 40 g. 0.94 ml (820 mg; 7.92 mmol) of tert-butyl nitrite are added in an inert gas atmosphere under an inert gas atmosphere. After stirring at room temperature for 15 minutes, the reaction mixture was concentrated under reduced pressure to give 3.9 g of a residue. This material was combined with the product obtained in the previous reaction using 300 mg of the same starting pyrrole. The crude product was chromatographed on silica gel using hexane / dichloromethane (4: 1, v / v) as the eluent. 1.72 g (56%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-trifluoromethylthio-4-cyano-5-chloropyrrole are obtained, which after recrystallization from hexane gives 760 mg of the desired product. as a colorless solid melting at about 92 ° C.

Example 6

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 as described in Example 6), 77 mg (0.63 mmol) of 4-dimethylaminopyridine and 20 ml of pyridine were cooled to 0 ° C under an inert gas atmosphere and treated with 1.01 ml (1.50 g; 7.14 mmol) of trifluoroacetic anhydride. The reaction mixture was stirred for 1 hour at 0 ° C and then for 4 hours at 20 ° C, followed by an additional 0.30 mL (2.1 mmol) of trifluoroacetic anhydride. After the reaction was allowed to proceed for a total of 24 hours, the reaction mixture was diluted with dichloromethane, concentrated, washed with an aqueous hydrochloric acid solution and water, and recrystallized from a combination of hexane and ethyl acetate. There was obtained 660 mg (37%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2 - [(trifluoromethyl) carbonylamino] -3-trifluoromethylthio-4-cyano-5-chloropyrrole as a greenish solid, m.p. 190 ° 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-4-chloropyrrole (prepared as described in Example 8), 0.10 g of 4-dimethylaminopyridine, 0.33 ml (0.32 g; 4.1 mmol) of pyridine and 0.31 ml (0.34 g; 4.3 mmol) of acetyl chloride in 10 ml of acetonitrile are stirred at 20 ° C for 4 days and then 1 day at reflux. After the addition of an additional 0.03 ml of acetyl chloride, refluxing was continued the next day, after which the reaction mixture was cooled, diluted with dichloromethane and partitioned several times between 1N aqueous hydrochloric acid and saturated aqueous sodium bicarbonate. The organic layer was dried over anhydrous magnesium sulfate and evaporated to give 1.42 g of a beige solid. This material gave 480 mg (29%) of 1- (2,6-dichloro-1-trifluoromethylphenyl) after chromatography on silica gel with hexane / ethyl acetate (4: 1 by volume) as the eluent, followed by recrystallization from ethanol / water. 2-Methylcarbonylamino-3-trifluoromethylthio-4-cyano-5-chloropyrrole as colorless needle crystals, m.p. 216 ° C.

Example 8

A solution of 1.50 g (3.57 mmol) of 1- (2,6-dichloro-1-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole (prepared as described in Example 13) in 15 ml of ethyl ether is treated with while stirring under an inert gas atmosphere, it is cooled to -20 DEG C. and a solution of 0.29 ml (0.48 g; 3.6 mmol) of sulfuryl chloride in 15 ml of anhydrous ethyl ether is added dropwise and the reaction mixture is allowed to warm to 20 DEG After stirring for 2.5 days, an additional 0.03 mL (0.4 mmol) of sulfuryl chloride was added and stirring continued the next day.

After stirring for one day, the reaction was quenched by the addition of 28 ml of 10% aqueous potassium carbonate solution, the phases were separated and the aqueous layer was extracted with ether. The ethereal phases are combined, washed with water and, after drying over anhydrous magnesium sulphate, concentrated. 1.56 g of a reddish-brown solid are obtained. The crude product was chromatographed on silica gel using 5: 2 dichloromethane / hexane as eluent to give 1.30 g (80%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino- 3-trifluoromethylthio-4-cyano-5-chloropynol as a slightly pink solid. After recrystallization from cyclohexane, 610 mg of the desired product is obtained in the form of off-white needles melting at about 176 ° C.

Example 9

The procedure is analogous to that in Example 6 except that 1- (2-chloro-Y-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole is used as the reactant, m.p. Example 13. 1- (2-Chloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole, m.p.

Example 10

The reaction was carried out in a manner analogous to Example 8, except that 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-dichlorofluoromethylthio-4-cyanopyrrole, m.p. 202 DEG C., was used as the reactant. as described in Example 13. 1- (2,625 dichloro-4-trifluoromethylphenyl) -2-amino-3-dichlorofluoromethylthio-4-cyano-5-chloropyrrole, m.p.

Example 11

1- (2,6-Dichloro-4-trifluoromethyl-phenyl) -2,4-bis (trifluoromethyl-thio) -3-cyano-5-aminopyrrole, m.p. 161 DEG C., prepared according to the procedure described in Example 13 for the preparation of the former, using an excess of trifluoromethanesulfenyl chloride. C.

Example 12

To a cold (0 ° C) solution of 1.53 g (3.60 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole (m.p. 182 ° C); according to procedure 40 described in Example 13) in 15 ml of pyridine, a solution of 1.46 g (3.6 mmol) of 80% pyridinium bromide perbromide in 15 ml of pyridine was added under an inert gas atmosphere. After 30 minutes, the reaction mixture is poured into ethyl ether cooled to 0 ° C and the precipitate formed is filtered off. The filtrate was washed successively with aqueous hydrochloric acid, aqueous sodium hydroxide, and water, and the organic layer was dried over anhydrous magnesium sulfate and evaporated. 45 1.34 g of a brown solid are obtained, which is mixed with 230 mg of the product from the previous reaction.

300 mg (0.7 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole with 0.29 g of 80% pyridinium bromide perbromide. This mixture of products afforded 1.31 g (73%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-, after chromatography on silica gel with hexane / ethyl acetate (4: 1 by volume) as eluent. 350 trifluoromethylthio-4-cyano-5-bromopyrrole as a white solid. Recrystallization from a combination of hexane and ethyl acetate gave 910 mg of the above product as colorless needle crystals with a melting point of about 160 ° C.

-23EN 284089 B6

Example 13

K. A solution of 2.00 g (6.25 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-4-cyanopyrrole, prepared as described below, in 60 ml of dichloromethane is stirred and cooled under stirring. of ice-cold solution of 10 ml of dichloromethane solution 0.55 ml (0.85g; 6.2 mmol) of trifluoromethanesulfenyl chloride cooled to -78 ° C was added slowly. The reaction mixture was stirred at 0 ° C for 2 h. A stream of nitrogen was added for 1 h. The resulting mixture was shaken with a saturated aqueous solution of sodium bicarbonate and water. The organic phase is dried over magnesium sulphate and concentrated in vacuo. 3.14 g of a brownish solid is obtained which, when chromatographed on silica gel with dichloromethane / hexane (3: 2 by volume) as eluent, yields 2 parts of colorless solids, weighing 900 mg and 950 mg. These were recrystallized from chloroform to give 680 mg and 630 mg of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethyl-4-cyanopyrrole, m.p.

The starting material used in this process is produced as follows:

A solution of 4.64 g (14.5 mmol) of 1 - [(2,6-dichloro-4-trifluoromethylphenyl) amino] -2,3-dicyanpropene and 2.02 ml (1.47 g; 14.5 mmol) of triethylamine in 30 ml of benzene was heated at reflux overnight and then concentrated in vacuo. The residue was partitioned between ethyl ether and water, the ether layer was dried over anhydrous magnesium sulfate and concentrated. 3.79 g of a brownish solid are obtained, which after recrystallization from ethanol / water gives 2.79 g (60%) of 1- (2,6-dichloro-N-trifluoromethylphenyl) -2-amino-4-cyanopyrrole, m.p. 176 ° C.

The starting 1-arylamino-2,3-dicyanopropene is prepared as follows:

20.5 g (0.140 mol) of formylsuccinonitrile potassium are dissolved in about 30 ml of water, acidified with concentrated hydrochloric acid and extracted with ethyl ether. The ether extract was dried over anhydrous magnesium sulfate and evaporated. 3.87 g of a brown liquid material are obtained, which is added to a solution of 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 refluxed overnight to separate the reaction water, then cooled and concentrated. 7.66 g of a yellow liquid residue are obtained, from which 6.68 g (95%) of 1 - [(2,6-dichloro-trifluoromethylphenyl) amino] -2,3-dicyanpropene precipitates as a yellow solid upon trituration with hexane. substances. This material was recrystallized from ethanol / water to give a product with a melting point of about 101 ° C.

Examples 14A and 14B

K. a suspension of 1.17 g (3.3G mmol) of 1- (4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole and 0.46 ml (0.34 g, 3.3 mmol) of triethylamine in 20 ml of chloroform, After cooling to -20 ° 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 hour, then allowed to warm to 0 ° C. An additional 0.04 mL (0.13 g, 0.8 mmol) of bromine was added and stirring was continued for 15 h. minutes. The resulting mixture was diluted with dichloromethane and shaken with water and saturated aqueous sodium bicarbonate. The organic layer was dried over anhydrous magnesium sulfate and concentrated. 1.11 g of a brown solid is obtained, which is mixed with the product of the preceding reaction, 1.00 g (2.8 mmol) of 1- (4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole and 0.15 g. ml of bromine. Chromatography on silica gel using dichloromethane / hexane (3: 1 by volume) as eluent gave 1.40 g (52%) of 1- (4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5- bromopyrrole (Example 14A) as a yellow solid. Recrystallization from hexane / ethyl acetate gave the desired product as yellowish plates, m.p. 175 ° C.

-24GB 284089 B6

Following a procedure analogous to that described in Example 13, 1- (4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole (Example 14B) was obtained from 1 - [(4-trifluoromethylphenyl) amino] -2,3-dicyanopropene (Example 14B), m.p. 152 ° C.

Examples 15A and 15B

Following a procedure analogous to that described in Example 13, 1 - [(2-chloro-4-trifluoromethylphenyl) amino] -2,3-dicyanopropene was prepared and used in a manner analogous to that described in Example 13 to prepare 1- (2-chloro-M (Trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole (Example 15A) melting at about 169 ° C. This pyrrole was used as described in Example 14 to prepare 1- (2-chloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-bromopyrrole (Example 15B) melting at about 157 ° C.

Examples 16A and 16B

1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-amino-N-cyanopyrrole, prepared according to Example 13, was treated with (fluorodichloromethane) sulfenyl chloride as described in Example 13 (but using trifluoromethanesulfenyl chloride). 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-dichlorofluoromethylthio-4-cyanopyrrole (Example 16A), m.p.

This compound was treated with tert-butyl nitrite as described in Example 4 to yield

1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylthio) pyrrole (Example 16B), m.p.

Example 17

The latter compound of Example 16 is subjected to a reaction analogous to that of Examples 1 and 2, but using hydrogen peroxide in trifluoromethylperacetic acid (instead of m-chloroperoxybenzoic acid). 1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylsulfinyl) pyrrole, m.p.

Example 18

Following the procedure of Example 17 but using twice the amount of hydrogen peroxide, the latter compound of Example 16 was converted to 1- (2,6-dichloro-4-trifluoromethylphenyl) -

2-chloro-3-cyano-4- (dichlorofluoromethylsulfonyl) pyrrole, m.p.

Example 19

The first compound of Example 16 was treated with tert-butyl nitrite as described in Example 4 to give 1- (2,6-dichloro-N-trifluoromethylphenyl) -3-cyano-4- (dichlorofluoromethylthio) pyrrole, m.p. C.

-25GB 284089 B6

Example 20

The product of Example 19 was oxidized using the procedure described in Example 17. 1- (2,6-Dichloro-4-trifluoromethyl-phenyl) -3-cyano-4- (dichlorofluoromethylsulfinyl) -pyrrole, m.p. 150-152 ° C.

Examples 21A, 21B and 21C

Using the procedure described for the preparation of the latter compound of Example 13, 1 - [(2,6-dichloro-4-trifluoromethoxyphenyl) amino] -2,3- was prepared using 2,6-dichloro-4-trifluoromethoxyaniline instead of 2,6-dichloro-N-trifluoromethylaniline. dicyanpropene.

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

This material was converted to 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole as described for the first compound of Example 13.

This compound was converted to 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-amino-3- (trifluoromethylthio) -4-cyano-5-chloropyrrole (Example 21A), m.p. 196-197 °. C.

The product was converted to 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4-trifluoromethylthiopyrrole (Example 21B), m.p. of Example 18 was converted to 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfonylpyrrole (Example 2IC), m.p. 187 ° C.

Examples 22A, 22B and 22C

A mixture of 2-chloro-4-chlorosulfenyl-3-cyano-1- (2,6'-dichloro-4'-trifluoromethylphenyl) pyrrole and 2chloro-3-cyano-4-dichlorofluoromethylsulfenyl-1- (2 ', 6'-dichloro) (4'-Trifluoromethylphenyl) pyrrole (47.77 g, 0.101 mol. 1.0 equivalents) was dissolved in 190 mL trifluoroacetic acid at 0 ° C and 10.8 mL (0.106 mol; 1.05 equivalents) 30% was added to the solution. hydrogen peroxide. The reaction mixture was stirred at 0 ° C for 7 hours and 15 minutes, stored in a 10 ° C refrigerator overnight, and an additional 10.8 mL (0.106 mol, 1.5 mL) was added at 0 ° C the next morning. of hydrogen peroxide (30%), the mixture was stirred at 0 ° C for 9 hours and then stored in a refrigerator overnight. The following morning, at 0 ° C, 10.8 mL (0.106 mol; 1.05 equivalents) of 30% hydrogen peroxide was added again, and after 3.5 hours the reaction mixture was poured into 2 L of ice water with vigorous stirring and the resulting mixture filters.

Similarly, 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'-trifluoromethyl-phenyl) -pyrrole (40.77 g; 0.0848 mol; 1.0 equivalents) was dissolved in 188 mL of trifluoroacetic acid at 0 ° C and 17.7 mL was added dropwise. ml (0.173 mol; 2.05 equivalents) of 30% hydrogen peroxide. The reaction mixture was stirred at 0 ° C for 2 hours 45 minutes, then stored in a 10 ° C refrigerator overnight, stirred at 0 ° C for an additional 8 hours, and then refrigerated overnight. The resulting mixture was allowed to warm to room temperature, stirred overnight at room temperature, the following morning at 0 ° C, an additional 9.05 mL (0.0886 mol, 1.05 equivalents) of 30% hydrogen peroxide was added and the mixture stirred at room temperature. is cooled to 0 ° C for 6 hours and 40 minutes. The resulting mixture was allowed to warm to room temperature over Saturday and Sunday, then poured into 2 liters of ice-water and filtered after vigorous stirring.

-26EN 284089 B6

The precipitated products from both reactions were combined and dissolved in 500 ml of dichloromethane. The solution was washed with 500 ml of water, 500 ml of 10% aqueous sodium bisulfite solution and 500 ml of saturated sodium chloride solution. The organic phase was dried over sodium sulfate, filtered and the solvent was evaporated. 74.96 g (79.9% yield) of a solid material is obtained, which, after recrystallization from 690 ml of hexane / dichloromethane (2: 1), to which 20 ml of dichloromethane is added, yields 6.98 g of the solid material identified as 2. -chloro-4-chlorosulfonyl-3-cyano-1- (2 ', 6'-dichloro-4'-trifluoromethylphenyl) pyrrole (Example 22A). After recrystallization from isopropanol (103 ml), 3.97 g of product, m.p. 187 DEG-188.5 DEG C., is obtained.

3.97 g (9.06 mmol, 1.0 equivalents) of 2-chloro-4-chlorosulfonyl-3-cyano-1- (2 ', 6'-dichloro-4'-trifluoromethylphenyl) pyrrole at 0 ° C dissolved in 15.8 ml of tetrahydrofuran and 2.41 g (1.0 equivalents) of solid triphenylphosphine was added to the solution, which turned yellow. After 2.5 hours, the cooling bath was removed and the reaction was stirred at room temperature overnight. An additional 2.55 g (9.72 mmol; 1.06 equivalents) of triphenylphosphine was added thereto, and the resulting mixture was stirred at room temperature overnight. at room temperature, whereupon a precipitate formed. After addition of 3 ml of tetrahydrofuran, the reaction mixture is washed twice with saturated sodium chloride solution, which is back-extracted with tetrahydrofuran. The organic phase was dried over magnesium sulfate, filtered and the solvent was evaporated in vacuo. 9.44 g of a waxy solid is obtained, which, after chromatography on silica gel, yields 3.39 g of a waxy solid, from which, after recrystallization from 140 ml of isopropanol, 2.54 g (74.9%) of bis-β-chloro- is obtained. S-Cyano-1- (6-dichloro-4'-trifluoromethylphenyl) pyrrol-4-yl] disulfide (Example 22B), m.p. 218.8-220.3 ° C.

0.80 g (1.08 mmol: 1.0 equivalents of bis [2-chloro-3-cyano-1- (2 ', 6'-dichloro-4'-trifluoromethylphenyl) pyrrol-4-yl) disulfide was dissolved in 10 ml of dimethylformamide, the solution is cooled to 0 ° C and 0.46 g (3.24 mmol; 3.0 equivalents) of sodium monohydrogen phosphate dissolved in 5 ml of water are added. Water (10 ml) was added followed by solid sodium dithionite (0.564 g, 3.24 mmol, 3.0 equivalents) and the mixture turned light yellow and 0.65 g (3.1 mmol, 2.87) was added to the cooled weighed ampoule. of dibromodifluoromethane, which is then transferred to a colorless reaction mixture and a white precipitate begins to precipitate. After stirring at room temperature overnight, the reaction mixture was poured into 200 ml after cooling to 0 ° C The organic phase was washed twice with 100 ml of 5% aqueous hydrochloric acid, twice with 100 ml of saturated sodium bicarbonate solution and 100 ml of saturated sodium chloride solution each time, the organic layer was dried over magnesium sulfate, filtered and the solvent was evaporated in vacuo. 80.7 mg of a white solid is obtained.

The original aqueous phase was then filtered to collect a white solid which precipitated overnight. This solid was dissolved in dichloromethane, the solvent was evaporated in vacuo and the residue dried. 0.348 g of a white solid is obtained (total yield 0.429 g, 40%). This material was mixed with the preceding 80.7 mg and chromatographed on silica gel. 0.362 g of a white solid was identified as 4-bromodifluoromethylsulfenyl-2-chloro-3-cyano-1- (2 ', 6'-dichloro-4'-trifluoromethylphenyl) pyrene (Example 22C), m.p. 128.3-133.7 Deň: 32 ° C.

Using the procedures detailed above for the synthesis of the compounds in Examples 1 to 22, or using other methods or procedures generally described above, a variety of other analogously prepared pyrrole compounds (DAP) of Formula I are prepared. The structures of these compounds and their melting points are shown in the following table. 3 (DAP Nos. 1 to 91; compounds of formula I wherein X ^: and X ³ are hydrogen and the remaining formulas have the meanings listed in the table) and Table 4 (DAP Nos. 92 to 195; compounds of formula I in which X *

-27CZ 284089 B6 and X ³ are hydrogen atoms, X ¹ and X ⁴ are chlorine atoms. Y represents a trifluoromethyl group and the remaining general symbols have the meanings given in the table).

Table 3

Examples of other analogously prepared pyrrole compounds (DAP) of formula I wherein X ² and X ³ are hydrogen atoms

DAP meanings of melting point symbols

No. R ¹ X R ² R ³ X ¹ Y X ⁴ (° C) 1 nh ₂ CF ₃ S CN Cl ch ₃ Br ch ₃ 215-252.5 2 H cf ₃ p CN Cl ch ₃ Br ch ₃ 120.5 to 122 3 H CFjSO 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 to 153 6 H cf ₃ Sat ₂ CN Cl ch ₃ Br ch ₃ 164-165.5 7 H cf ₃ p CN H Cl Br Cl 207 to 208.5 8 H cf ₃ p CN Cl Cl Br Cl 174 to 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 cf ₂ cis CN H Cl Cl Cl 169.5 to 170 12 H cf ₃ Sat ₂ CN Cl Cl Br Cl 174 13 nh ₂ cfci ₂ p CN H Cl Br Cl 192 to 194 14 nh ₂ cfci ₂ p CN Cl Cl Br Cl 239-240.5 15 Dec H cfci ₂ p CN Cl Cl Br Cl 212.5-214 16 nh ₂ cf ₂ cis CN CF ₂ CIS Cl Cl Cl 206 to 207 17 nh ₂ CFCbS CN CFČ1 ₂ S Cl Br Cl 214.5-218 18 H CF.CÍSO CN H Cl Br Cl 124.5 to 125.5 19 Dec nh ₂ CFC1 ₂ S CN H Cl Cl Cl 177 to 178 20 May H cf ₃ p CN H Cl Br Cl 111 to 112 21 H CFCbSO CN Cl Cl Br Cl 174.5 to 175.5 22nd H CFCbS CN CFC1 ₂ S Cl Br Cl 143 23 H CFC1 ₂ S CN Cl Cl Cl Cl 190 to 191 24 H CFCbSO CN Cl Cl Cl Cl 151 to 152 25 H CF ₃ SO ₂ CN Cl ch ₃ s cf ₃ Cl 175.5 to 178 26 H ca ₂ ciso CN Cl Cl Cl Cl 143 27 Mar: H cf ₂ cis CN Cl Cl Cl Cl 174 28 nh ₂ CFČ1 ₂ S CN H Cl ocf ₃ Cl 126 to 126.5 29 nh ₂ CFCUS CN Cl Cl ocf ₃ Cl 187 to 189 30 H cf ₃ p CH = O H- Cl cf ₃ Cl 73 to 74 31 H cfci ₂ so ₂ CN Cl Cl Br Cl 195 to 196 32 H cf ₃ p CN Cl ch ₃ s cf ₃ Cl 117 to 118 33 H cfci ₂ so ₂ CN Cl Cl Cl Cl 189 to 190 34 H cfci ₂ p CN H Cl ocf ₃ Cl 66 to 67 35 H cfci ₂ p CN Cl Cl ocf ₃ Cl 137 to 139 36 H cf ₃ p CN H Cl Be Cl 127 to 128.5 37 H cfci ₂ p CN Cl ch ₃ so cf ₃ Cl 184 to 202 38 H cfci ₂ so ₂ CN H Cl ocf ₃ Cl 144 to 145 39 H CFCbSO CN H Cl ocf ₃ Cl 134 to 136 40 H CF ₂ C1S CN Cl Cl Br Cl 189.5 to 190.5 41 H cf ₂ cis CN H Cl Cl Cl 95 to 96

-28Table 3 - continued

DAP meanings of melting point symbols

C. R ¹ X R ² R X ¹ YX ⁴ (° C) 42 H CFCI ₂ SO CN Cl Cl ocf ₃ Cl 118.1 to 120.2 43 nh ₂ cfci ₂ p CN Cl ch ₃ co ₂ ch ₃ Cl 220 44 H cfci ₂ so ₂ CN Cl Cl ocf ₃ Cl 143.6 to 152.9 45 H ca ₂ ciso CN Cl Cl Br Cl 154 46 H ca ₂ ciso CN H Cl Cl Cl 133 to 133.5 47 H cfci ₂ p CN Cl ch ₃ s cf ₃ Cl 126.8 to 129.1 48 H cfhciso ₂ CN Cl ch ₃ s cf ₃ Cl 51.5 to 65 49 H cfci ₂ p CN Cl ch ₃ co ₂ ch ₃ Cl 130 to 136 50 NH? cfci ₂ p CN H H cf ₃ Cl 181 to 182 51 H cf ₂ number ₂ CN H Cl Br Cl 199 52 H CFČ1-S CN H Cl Cl Cl 123 53 H cfci ₂ so CN H Cl Cl Cl 146.5 to 147 54 H cf ₂ number ₂ CN Cl Cl Br Cl 188 to 188.5 55 NH? cfči ₂ p CN Cl H cf ₃ Cl 190 to 191 56 nh ₂ cfci ₂ p CN Br H cf ₃ Cl 182 to 184 57 H cfci ₂ p CN Cl H cf ₃ Cl 84 to 85 58 H cfci ₂ so ₂ CN H Cl Cl Cl 189.5 to 190 59 H CFCbS CN H Cl Br Cl 140.5 to 141 60 H CFC1 ₂ SO ₂ CN Cl H cf ₃ Cl 137 to 144 61 H cfci ₂ p CN Br H cf ₃ Cl 102 to 107 62 H cfci ₂ so CN Cl H cf ₃ Cl 116 to 118 63 H cfci ₂ so CN H Cl Br Cl 156 to 157 64 H cfci ₂ so ₂ CN Br H cf ₃ Cl 150 to 151 65 H cfci ₂ so CN Br H cf ₃ Cl 153 to 155 66 H cf ₃ p CN Br H cf ₃ Cl 105 to 106 67 H cf ₂ cis CN Cl H cf ₃ Cl 99 to 100 68 H cf ₃ Sat ₂ CN Br H cf ₃ Cl 138 to 139 69 H cf ₃ so CN Br H cf ₃ Cl wax 70 H cfci ₂ so ₂ CN H Cl Br Cl 212 to213 71 H cf ₂ number ₂ CN Cl H cf ₃ Cl 129 to 132 72 H ca ₂ ciso CN Cl H cf ₃ Cl 92 to 95 73 H cf ₃ Sat ₂ CN H Cl Br Cl 183.5 to 184 74 H cf ₃ p CN H Cl Cl Cl 80.5 to 81 75 H ch ₃ s CN H Cl Br Cl 114 to 116 76 H cfci ₂ p CN H F Br F 106.5 to 107 77 H cf ₃ so CN H Cl Cl Cl 130 78 H cf ₃ Sat ₂ CN H Cl Cl Cl 165 79 H CCIjS CN H Cl Cl Cl 147 80 H CFC1 ₂ S CN H H Cl Cl 96 81 H Cl CN H Cl Cl Cl 146 to 147 82 H CFC1 ₂ S CN H H Cl Η 121 to 121.5 83 H cf ₂ ciso ₂ CN H Cl Cl Cl 183.5 to 184.5 84 H cfči ₂ so CN Br H cf ₃ Cl 115 to 118 85 H ca ₃ sol ₂ CN CF ₃ S H cf ₃ Cl 50 to 52 86 H cfci ₂ p CN Br Cl cf ₃ o Cl 138 to 140 87 H cfci ₂ so ₂ CN Br Cl cf ₃ o Cl 128 to 130 88 NH cf ₂ cis CN Br H cf ₃ Cl 150 to 153

-29GB 284089 B6

Table 3 - continued

DAP meanings of melting point symbols

C. R ¹ X R ² R ³ X ¹ Y X ⁴ (° C) 89 H CF, C1S CN Br H cf ₃ Cl 60 to 63 90 H CFČ1, S CN H Cl H Cl 131 to 132.5 91 NH, cf ₃ c'ci ₂ sec CN H Cl Cl Cl 162.8 to 188.1

Table 4

Examples of other analogously prepared pyrrole compounds (DAP) of formula I wherein X ² and X ³ are hydrogen, X ^{1 and} X ⁴ are chlorine and Y is trifluoromethyl meanings

DAP C. R ¹ X R ² R ³ melting point (° C) 92 NH, CF, C1S CN H 160.5 to 175 93 H CF ₃ SO ₂ CN H 199.5 to 201 94 H CF, C1S CN H 104.9 to 106.8 95 H CF, C1S CN CF, C1S 114.5 to 117 96 NH, CF, C1S CN Cl 178 to 181 97 H CF, C1SO, CN H 199.8 to 202 98 H CF, C1SO, CN Cl 193.1 to 195.8 99 H CF, ClSO CN Cl 145.2 to 147.5 100 ALIGN! H CF, C1S CN Cl 139.0 to 143.1 101 H CF ₃ S CN Br 137 to 138 102 H cf ₃ so CN Br 164-165.5 103 H cf ₃ so. CN Br 197 to 198 104 H CF ₂ C1SO CN H 126.8 to 129.6 105 H cf ₃ p CN H 152 to 153 106 NH ₂ cfci, cf ₂ p CN H 183 to 190 107 nh ₂ CC1 ₂ W CN H 189 to 193 108 H CFC, CF, S CN H 118.8 to 123.8 109 H CFC1, CF, SO CN H 157.5 to 161.9 110 H CFC1, CF, SO CN H 182.5 to 183.9 111 nh ₂ CFC, CF, S CN Cl 186.5 to 188 112 H CFC, CF, S CN Cl 149.5 to 151 113 Br CF ₃ S CN H 163 to 164 114 H CFC, CF, S CN Cl 113.5 to 116.5 115 H CC1 ₃ Š CN Cl 177 to 182 116 H CFC1, CF, SO CN Cl 147-150.5 117 H CC1 ₃ pest, CN Cl 200 to 202 118 H CC1 ₃ SO CN Cl 152.2 to 153.5 119 Cl CF ₃ SO CN H 161.5 to 162.5 120 NH, CH ₃ S CN H 150 to 151 121 H CFC1, S. CN Br 117 to 142 122 NH, CFCI, S. CN Br 195.5 to 197

-30GB 284089 B6

Table 4 - continued

DAP C. R ¹ X R ² R ³ melting point (° C) 123 Br CF ₃ SO CN Η 170 to 172 124 H CFCbSO, CN Br 176-178.5 125 H CFC1 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, C1S CN Br 174.5 to 178 130 Br CF, CIS CN Cl 129.5 to 133.5 131 H CF ₂ C1S CN Br 133.5 to 137.1 132 NH, Cl CN H 159.5 to 160 133 nh ₂ cf ₃ p CN SCN 169 to 171 134 Η cf ₃ p CN SCN 105 to 106.5 135 Br ca ₂ ciso CN Cl 157.5 to 159 136 Η Cl CN H 105.5 to 106.5 137 H CHjSO CN H 144.5 to 145.5 138 H CH ₃ SO, CN H 173 to 173.5 139 NH, cf ₃ p CN sch ₃ 146 to 148 140 H cf ₃ p CN statues ₃ 143 to 145 141 H CF, CISO CN Br 143 to 146.5 142 Br CFČ1 ₂ SO, CN Cl 117.8 to 122.5 143 CF ₃ CONH cf ₃ p CN H 187-188.5 144 H CF, C1SO, CN Br 182 to 185 145 H cf ₃ p CN CH ₃ S 89 to 91 146 H cf ₃ p CN ch ₃ Sat ₂ 136 to 138 147 H cf ₃ so CN ch ₃ so. 161 to 163 148 NH, cf ₃ cci, p CN H 200 to 220 149 NH, cf ₃ cci, p CN Cl 223.5 to 232.5 150 H ca ₃ ca ₂ sec CN Cl 170-172.5 151 H cf ₃ cci, sat. CN Cl 195.6 to 197.2 152 H ca ₃ ca ₂ sat CN Cl 161, 161.5 153 H cf ₃ p CN cf ₃ p 95 to 96 154 NH, ch ₃ so CN H 13Gaž 132 155 nh ₂ ch ₃ so. CN H 248 to 248.5 156 H cf ₃ so CN CF ₃ S 145 to 148 157 H ch ₃ s CN Cl 128 to 129 158 NH, cf ₃ p CN statues ₃ 139 to 141 159 CH ₃ S cf ₃ p CN Cl 73 to 74 160 NH, CFC1, SO CN H 156.4 to 195 161 H CFjSÓ, CN CF ₃ S 156 to 157 162 H ch ₃ so CN Cl 130 to 131 163 NH ₂ cf ₃ p CN F 164-164.5 164 H Cl CN Cl 129 to 129.5 165 CH ₃ SO cf ₃ p CN Cl 133 to 135 166 ch ₃ s CFC1, S. CN Cl 112.2 to 124.8 167 NH, CFC1, SO CN Cl 163-169.5 168 CFjCONH CFjSÓ CN H 195 to 197.5 169 H cf ₃ p CN F 116 to 117 170 CH ₃ SO ₂ cfci ₂ p CN Cl 164.5 to 170.5

-31 GB 284089 B6

Table 4 - continued

DAP C. R ¹ X R ² R ³ melting point (° C) 171 CHjSO CFCLS CN Cl 193-195.7 172 nh ₂ CF ₃ SO CN H 175 173 H cf ₃ p cf ₂ H 54 to 56 174 H ch ₃ Sat ₂ CN Cl 165 to 166 175 H Br CN Br 127.5 to 128 176 H Br CN H 120 to 121 177 nh ₂ CFC1 ₂ SO ₂ CN Cl 203-214.5 178 H ca ₃ sol CN F 129 to 130 179 Br Cl CN H 121 to 123 180 nh ₂ cf ₃ Sat ₂ CN H 258 to 260 181 CHjSO cf ₃ so CN Cl 238 to 239 182 H CF ₂ BrS CN Cl 128.3 to 133.7 183 H CF ₂ BrSO CN Cl 117 to 119 184 H CF ₂ BrSO-> CN Cl 172 to 181 185 H cf ₃ p ch ₃ H oil 186 H cf ₃ so ch ₃ Br 106 to 107 187 H CF ₃ SO, ch ₃ Br 76 to 77 188 nh ₂ cf ₃ p CN CH (SCH _{3) 2} 159 to 161 189 ch ₃ sch = n cf ₃ p CN CH (SCH _{3) 2} 124.5 to 125.5 190 H cf ₃ p (CH3) ₃ COCONH Br 113 to 114 191 H cf ₃ p Br Br oil 192 H CF ₃ SO ch ₃ OH *) 149 to 151 193 Br CF ₃ S ch ₃ Br oil 194 Br Br H CF ₃ S oil 195 H CF ₃ S CN AND 107 to 109

Legend: *) may exist as a keto-tautomer

The present invention provides a method for controlling harmful arthropods, in particular insects and mites, at a particular site, which comprises treating the site with an effective amount of a compound of formula (I), in which the individual symbols are as defined above. In particular, the compounds of formula (I) may be used in veterinary medicine, in livestock breeding and in health care against arthropods parasitizing externally on vertebrate animals, in particular on warm-blooded vertebrates, such as humans and domestic animals such as cattle, sheep, goats, horses, pigs, poultry, dogs, cats and fish such as mites (Acarina), including ticks such as

Ixodes spp. (tick)

Boophilus spp. (tick), for example Boophilus microplus. Amblyomma spp. (drinker), Hyalomma spp.,

Rhipicephaius spp., Such as Rhipicephalus appendiculatus,

Haemaphysalis spp. (tick),

Dermacentor spp. (drinker) and

Omithodorus spp., Such as Omithodorus moubata, and other species such as Damalinia spp.,

-32GB 284089 B6

Dermanyssus gallinae,

Sarcoptes spp., For example Sarcoptes scabiei

Psoroptes spp. (pastry),

Chorioptes spp. (scab),

Demodex spp. a

Eutrombicula spp., Of the order Diptera, for example

Aedes spp. (mosquito),

Anopheles spp. (anofeles),

Musea spp. (fly),

Hypoderma spp. ,

Gasterophilus spp. (syrup) a

Simulium spp. (flycatcher), the order of Hemipter, such as

Triatoma spp., Of the order Phthiraptera, such as e.g.

Damalinia spp, a

Linognathus spp. (louse) of the order Siphonaptera, such as

Ctenocephalides spp. (flea), of the order Dictyoptera, such as

Períplaneta spp. (cockroach) and

Blatella (rus) and Hymenoptera (bees, ants and wasps), for example

Monomorium pharaonis in protecting stored products such as cereal products including grain and flour, groundnuts, animal feed, lumber and household goods such as carpets and textiles against attack by arthropods, especially beetles, including various moths and mites such as for example

Ephestia spp. (flour moth),

Anthrenus spp. (towel),

Tribolium spp. (darkling beetle),

Sitophilus spp. (pilus) a

Acarus spp. for the control of cockroaches, ants, termites and similar arthropods in residential and industrial buildings and for the control of mosquito larvae in waterways, wells, reservoirs and other standing or running water, for the treatment of foundations, structures and soil to protect buildings against attack by termites, such as

-33 GB 284089 B6

Reticulitermes spp. (termite),

Heterotermes spp

Coptotermes spp., In the field of agriculture against Lepidoptera, butterflies, such as adults, larvae and eggs,

Heliothis spp. (asphalt), such as Heliothis virescens. Heliothis armigera and Heliothis zea, Spodoptera spp., As Spodoptera specimen. Spodoptera littoralis and Spodoptera eridania, Mamestra configurata,

Earias spp. (moth) like Earias insulana,

Pectinophora spp., Such as Pectinophora gossypiella,

Ostrinia spp., Such as Ostrinia nubilalis,

Trichoplusia ni,

Pieris spp. (whites),

Laphygma spp.

Agrotis spp. and Amathes spp. (worms), Wiseana spp.,

Chilo spp.

Tryporyza spp, and Diatraea spp.,

Sparganothis pilleriana,

Cydia pomonella,

Archips spp.

Plutella xylostella (foreskin), against adults and beetle larvae (Coleoptera), such as

Hypothenemus hampei,

Hylesinus spp. (bark beetle),

A thonomus grandis,

Acalymma spp.,

Lema spp. (tap),

Psylliodes spp. (flea beetle),

Leptinotarsa decemlineata, Colorado potato beetle, Diabrotica spp.,

Gonocephalus spp. (darkling beetle),

Agriotes spp. ,

Dermolepida and Heteronychus spp.,

Phaedon cochleariae,

Lissorhoptrus oryzophilus,

Meligethes spp. (lightning bolt),

Ceutorhynchus spp. ,

Rhynchophorus and Cosmopolites spp., Against Hemipter pests such as

Psylla spp. (mera)

Bemisia spp.

Trialeurodes spp. (whitefly),

Aphis spp. (aphid),

Myzus spp. (aphid),

Megoura viciae,

Phylloxera spp. (aphid),

Adelges spp. ,

Phorodon humuli,

Aeneolamia spp ..

-34GB 284089 B6

Nephotettix spp.

Empoasca spp. (cross),

Nilaparvata spp.,

Perkinsiella spp.

Pyrilla spp.

Aonidiella spp.

Coccus spp.

Pseudococcus spp. (July)

Helopeltis spp.

Lygus spp. ,

Dysdercus spp ..

Oxycarenus spp. and

Nezara spp., Against Hymenoptera pests, such as e.g.

Athalia spp. (pilatka),

Cephus spp. (thistle) a

Atta spp., Against Diptera pests, such as e.g.

Hylemyia spp. (flower flies),

Atherigona spp ..

Chlorops spp. (green grass),

Phytomyza spp. (burr) a

Ceratitis spp. (propellers) against Thysanoptera pests, such as

Thrips tabaci, against Orthoptera, such as locusta and Schistocerca spp. And crickets (for example Gryllus spp. And Acheta spp.), Against Collembola pests, such as they are for example

Sminthurus spp. (flap) and

Onychiurus spp. (larva), against Pests (Isoptera), such as

Odontotermes spp., Against Dermaptera pests such as

Forficula spp. (earwig) as well as against other arthropods important in the agricultural field such as mites, for example

Tetranychus spp. (spider mite),

Panonychus spp ..

-35 GB 284089 B6

Bryobia spp. (spider mite),

Eriophyes spp. (bellows) a

Polyphagotarsonemus spp., Infra

Blaniulus spp. (millipedes),

Scutigerella spp. (millipede),

Oniscus spp. (shade) a

Triops spp. (postman).

Other pests that can be controlled with the aid of the compounds of the invention include:

from the order of the Isopods, for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber;

from the class of the Diplopoda, for example Blaniulus guttulatus;

from the class of the Centipede (Chilopoda), for example Geophilus carpophagus, Scutigera spec.

from the centipede class (Symphyla), for example

Scutigerella immaculata;

Thysanura, for example Lepisma saccharina, Collembola, for example Onychiurus armatus, Orthoptera, for example Blatta orientalis, Periplaneta americana )

Leucophaea maderae, Domestic Russian (Blattella germanica), Cricket (Acheta domesticus), Gryllotalpa spec., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria,

-36GB 284089 B6 from the order of the Dermaptera, for example the common earwig (Forficula auricularia), the order of the Isoptera, for example the Reticulitermes spec.;

from the order of the Anoplura, for example Phylloxera vastatrix, Pemphigus spec., Pediculus humanus corporis, Haematopinus spec.,

Linognathus spec .;

from the order of the Mallophaga, for example the Trichodectes spec.

Damalinea spec .:

from the order of the Thysanoptera, for example Hercinothrips femoralis, Thrips tabaci, Heteroptera, Eurygaster specus, Dysdercus intermedius, Pexma quadrata, Piesma quadrata (Rectius prolixus),

Triatoma spec., From the order of the beetles (Coleoptera), for example, Anobium punctatum, Rhizopertha dominica,

Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica ..

European flea beetle (Psylliodes chrysocephala), Epilachna varivestis, Atomaria spec., Oryzaephilus surinamensis, Anthonomus spec., Sitophilus spec., Otiorrhynchus sulcatus

-37GB 284089 B6 Cryptoidea (Ceuthonhynchus assimilis), Hypera postica, Dermestes spec.

Trogoderma spec., Anthrenus spec., Attagenus spec., Lyctus spec., Meligethes aeneus, Ptinus spec., Niptus hololeucus, Gibbium psylloides (Tribolium spec.), European darkling (Tenebrio molitor), Click beetle (Agriotes spec.), Conoderus spec ..

Common Chafer (Melolontha melolontha), Summer Chafer (Amphimallon solstitialis), Costelytra zealandica, Hymenoptera, for example Diprion spec., Hoplocampa spec., Lasius spec., Monomorium pharaonis, hornet (Vespa spec.);

from the order Diptera. for example mosquito (Aedes spec.), anofeles (Anopheles spec.), mosquito (Culex spec.), fruit fly (Drosophila melanogaster), fly (Musea spec.), sunflower (Fannia spec.), buzzard (Calliphora erythrocephala) (Lucilia spec.), Chrysomyia spec., Cuterebra spec., Hamster (Gastrophilus spec.), Hyppobosca spec., Thistle (Stomoxys spec.), Hamster (Oestrus spec.), Hamster (Hypoderma spec.), Horsefly (Tabanus spec.) .),

Tannia spec., Bibberry hortulanus (Oscinella frit),

Phorbia spec., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa;

284089 B6 from the order of the Siphonaptera, for example, Xenopsylla cheopis, Ceratophyllus spec.

from the order of Arachnida, for example

Scorpio maurus, Latrodectus mactans, of the order Homoptera, for example Aleurodes brassicae,

Bemisia tabaci, Greenland Aphid (Trialeurodes vaporariorum), Aphis gossypii, Brevicoryne brassicae, Currant Aphid (Cryptomyzus ribis), Doralis fabae, Doroma pomi, , aphids (Hyalopterus arundinis),

Macrosiphum avenae,

Myzus spec., Phorodon humuli, Rhopalosiphum padi, Empoasca spec., Euscelis bilobatus,

Nephotettix cincticeps,

Lecanium comi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spec., Psylla spec.

from the order of the butterflies (Lepidoptera), for example

Pectinophora gossypiella, Dark-leaved Carpet (Bupalus piniarius), Cheimatobia brumata, Apple Fingernail (Lithocolletis blancardella) Apple Moth (Hyponomeuta padella), Field Brush (Plutella maculipennis), Golden Moth (Malacosoma neustr) Muscovy Euproctis chrysorrhoea, Ly man tria spec., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spec., Euxoa spec.

Feltia spec.,

-39GB 284089 B6

Earias insulana, Heliothis spec., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura.

Spodoptera spec.,

Trichoplusia ni,

Carpocapsa pomonella, White (Pieris spec.),

Chilo spec., Corn Moth (Pyrausta nubilalis), Meal Moth (Ephestia kohniella), Wax Moth (Galleria mellonella), Wardrobe Moth (Tineolla bisselliella), Fur Mole (Tinea pellionella), Hofmannophila pseudospretella, Cacoecana reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

The invention also relates to a method of controlling harmful arthropods on plants, comprising administering to the plants or the environment in which they grow an effective amount of a compound of formula I.

To control arthropods, the active ingredient is generally applied to the sites contaminated by these pests at a dosage of about 0.005 kg to 15 kg of active ingredient per hectare of area treated, preferably from 0.02 kg / ha to 2 kg / ha. Under ideal conditions, depending on the pest to be controlled, lower doses may provide adequate protection. On the other hand, in adverse weather conditions, in combating resistant pests and depending on other factors, higher doses of the active ingredient may be required. For foliar application, rates from 0.01 kg to 1 kg / ha can be used. The optimum dosage usually depends on the type of pest to be controlled as well as on the species and growth stage of the infested plant, the row spacing and the method of application.

In the case of the control of soil insects, the active ingredient-containing composition is distributed evenly over the surface to be treated in any suitable manner. If desired, it is possible to treat the entire area of the field or site where the crop is grown, or the application can be carried out in close proximity to the seeds or plants to be protected. The active ingredient can be washed into the soil by spraying the treated surface with water or left on the surface to wash it down with rain. During or after application, the composition may optionally be mechanically dispersed in the soil, for example by plowing or by means of a cultivator. Application can be carried out before sowing, during sowing, after sowing but before or after emergence.

The compounds of formula (I) may be applied in the form of solid or liquid formulations to the soil to control nematodes found in the soil, but may also be applied to a leaf to control nematodes attacking aerial parts of plants, such as Aphelenchoides and Ditylenchus.

By combining the formula I, they are capable of controlling pests eating parts of the plant remote from the application site, for example, leaf-eating insects are destroyed by active substances applied to the roots.

-40GB 284089 B6

In addition, the active compounds described can reduce the attack on plants by their insect repellent effects.

The compounds of formula I are particularly well suited for the protection of fields, meadows, plantations, greenhouses, orchards and vineyards, ornamental plants, park and forest trees. Examples of plants and crops that can be protected by these active ingredients include cereals (such as corn, wheat, rice and sorghum), cotton, tobacco. vegetables (such as beans, crucifers, cucumbers and pumpkins, lettuce, onions, tomatoes and peppers), field crops (such as potatoes, sugar beets, peanuts, soya, oilseed rape), sugar cane, grassland and fodder crops (such as corn, sorghum and alfalfa), plantations (such as tea, coffee, cocoa, banana, oil palm, coconut palm, rubber tree, spices), orchards and groves (for example, with stone fruit and plantations, citrus, kiwi, avocado, mango, olive and walnut trees), vineyards, ornamental plants, greenhouse, garden and park flowers and shrubs and forest trees (both deciduous and evergreen) in forests and nurseries.

The compounds of the invention may also be used to protect wood and sawn timber (standing timber, harvested timber, sawn timber, stored timber, timber) against attack by sawflies (e.g. Urocerus) or beetles (e.g. Scolytidae, Platypodidae (Bark beetles)). corals, Lvctidae, Bostrychida, Cerambycidae or Anobiidae J or termites [such as Reticulitermes spp. , Heterotermes spp, or Coptotermes].

Furthermore, the compounds of the invention can be used to protect stored products such as grains, fruits, nuts, spices and tobacco, whether unprocessed, ground or processed into various products, against attack by moths, beetles, mites and weevils (Sitophilus granarius). Animal products such as hides, hair, hair and horsehair, wool and feathers in natural or processed form (such as carpets or textile products) may also be protected against attack by moths and beetles, and stored meat and fish against beetles, mites and flies .

The compounds of the formula I are particularly suitable for combating arthropod spreading or transmitting diseases to humans and domestic animals, for example for controlling the abovementioned pests and in particular for controlling ticks, moths, lice, fleas, mosquitoes and midges, difficult and disease-transmitting flies. The compounds of formula I are particularly useful for controlling arthropods which feed on or in the skin or suck the blood of the aforementioned animals. For this purpose, the compounds described can be administered orally, parenterally, percutaneously or topically.

The compositions described below for topical application to humans or animals, or for the protection of stored products, household equipment and generally accessible areas and facilities, may alternatively also be used for applications on growing crop plants and on their growing sites and as seed dressings.

Suitable methods for administering the compounds of formula I include.

in the case of persons or animals infected or exposed to arthropods, the topical application of an active ingredient composition exhibiting an immediate and / or protracted effect against arthropods, such as irrigating, spraying, bathing, soaking, dusting, ointment, shampoo, cream and wax preparations;

in the case of surrounding areas in general or specific places where pests can hide, including stored products, wood and lumber, household and residential and industrial buildings and application rooms by spraying, fogging, dusting, smoldering, waxing, painting, granulate or bait, dosing into waterways, wells, reservoirs and other running or standing water;

To pet animals in the feed for the control of fly larvae in their feces, for growing plants foliar application in the form of spray, dust, granulate, fog and foam;

generally in the form of suspensions of finely divided and encapsulated compounds of formula (1), for treating soil or roots in the form of liquid dressings, dusts, granules, fumes and foams, and for seed dressings in the form of liquid or powdered preparations.

The compounds of formula I may be applied to combat arthropods in the form of compositions of any type known in the art as suitable for internal or external application to vertebrates or to control arthropods in both indoor and outdoor areas containing at least one compound of the formula Also in combination with one or more compatible diluents or carriers.

Claims (8)

PATENT CLAIMS Pyrrole derivatives of the general formula I (O) wherein: X is halogen, thiocyanato, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl, wherein the alkyl and haloalkyl moieties have straight or branched chain containing 1 to 4 carbon atoms and all of the above halogen substituted groups contain one or several of the same or different halogen atoms from monosubstitution to complete polysubstitution, or represents a cyano group, R ¹ is hydrogen, halogen, alkylthio, alkylsulfinyl, alkylsulfonyl, amino, alkylkarbonylsminoskupinu, haloalkylcarbonylamino or alkylthioalkylideniminoskupinu in which the alkyl and haloalkyl moieties are straight or branched chains containing 1 to 4 carbon atoms and all of the above groups substituted with a halogen containing one or more of the same or different halogen atoms from monosubstitution to complete polysubstitution, -42 GB 284089 B6 R ² is hydrogen, halogen, cyano, alkyl, haloalkyl or alkoxycarbonylamino, the alkyl and haloalkyl groups and the alkoxy moieties of having straight or branched chains containing 1 to 4 carbon atoms, and haloalkyl groups contain one or more identical or different atoms halogens from monosubstitution to complete polysubstitution, R ³ is hydrogen, halogen, thiocyanato, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio group or a bis (alkylthio) methyl group in which the alkyl and haloalkyl moieties are straight or branched chains containing 1 to 4 carbon atoms, and haloalkyl moiety contains one or several identical or different halogen atoms from monosubstitution to complete polysubstitution, with at most one of R ¹ , R ² and R ³ selected from the group consisting of amino and alkylcarbonylamino as defined above, haloalkylcarbonylamino, alkoxycarbonylamino, alkylthioalkylidenimino and bisthioalkylidenimino; methyl groups, Y represents a halogen atom, a haloalkyl group or a haloalkoxy group, wherein the haloalkyl and haloalkoxy groups have straight or branched chains of 1 to 4 carbon atoms and contain one or more identical or different halogen atoms from monosubstitution to complete polysubstitution, or Y represents a hydrogen atom; that X is a halogen atom or a radical of formula R'S (O) _n wherein n is 0, 1 or 2a R ³ is an alkyl or haloalkyl group as defined above, R ¹ and R ³ are hydrogen atoms and R is cyano, X ¹ represents a hydrogen atom, a halogen atom, an alkyl group, an alkylthio group or an alkylsulfinyl group, wherein the alkyl groups and moieties have a straight or branched chain of 1 to 4 carbon atoms, X ² and X ³ are each hydrogen and X ⁴ represents a hydrogen atom, a halogen atom or a straight or branched (C 1 -C 4) alkyl group, with the restriction that at most two of R ¹ , R ² and R ³ are selected from hydrogen and alkyl as defined above when X ⁴ and X ¹ are hydrogen and X is halogen then R ² is different from X and at least one of X, R ¹ , R ² and R ³ is different from the other, except for the compound in which X ⁴ , X ¹ , Y, R ¹ , X, R ² and R ³ are chlorine and X ³ and X are hydrogen. Pyrrole derivatives according to claim 1 of the general formula I, in which Y is hydrogen and X is a radical of the formula R ⁵ S (O) _n, wherein n is 0, 1 or 2 and R 'represents an alkyl or haloalkyl group as defined in claim 1, R ¹ and R ³ are hydrogen and R ² CN or Y represents a halogen atom or a haloalkyl or haloalkoxy group as defined in claim 1, -43EN 284089 B6 X represents a halogen atom, R ¹ represents a hydrogen atom, a halogen atom or a straight or branched (C 1 -C 4) alkylthio group, R ² is CN, R ³ represents hydrogen or halogen, ίο X ¹ is hydrogen, halogen, alkyl of 1-3 carbon atoms or alkylthio of 1 to 3 carbon atoms, X ² and X ³ represent hydrogen atoms and 15 X ⁴ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms. Pyrrole derivatives according to claim 1 of the general formula II (Π), in which 25 X is R ⁵ S (O) _n wherein n is 0, 1 or 2 and R ⁵ is methyl, trifluoromethyl, difluorochloromethyl, fluorodichloromethyl, difluorobromomethyl, difluoromethyl, dichloromethyl or fluorochloromethyl, 30 R ² is CN, R ¹ represents a hydrogen, fluorine, chlorine or bromine atom, R znamená means a hydrogen, fluorine, chlorine or bromine atom, X ¹ represents a hydrogen or chlorine atom; Y is trifluoromethyl or trifluoromethoxy. -44EN 284089 B6 Pyrrole derivatives according to claims 1 and 3 selected from the group consisting of 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-1,1- (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- (dichlorofluoromethylsulfonyl) pyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (chlorodifluoromethylsulfonyl) pyrrole-1,1- (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-1,1- (2, 3-cyano-4- (chlorodifluoromethylthio) pyrrole) 6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (trifluoromethylsulfinyl) pyrrole-1,1- (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- (dichlorofluoromethylsulfonyl) pyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (dichlorofluoromethylsulfinyl) pyrrole, 1- (2,6-dichloro-4- trifluoromethylphenyl) -2-bromo-3-cyano-4- (chlorodifluoromethylthio) pyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) methylphenyl) -2-bromo-3-cyano-4- (chlorodifluoromethylsulphinyl) pyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano- (dichlorofluoromethylsulfonyl) -5-bromopyrrole, 1 - ( 2,6-Dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (chlorodifluoromethylsulfonyl) pyrrole-1,1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano - (dichlorofluoromethylsulfinyl) pyrrole, 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylsulfonyl) pyrrole, 1- (2-chloro-4-trifluoromethylphenyl) -2- chloro-3-cyano-4- (dichlorofluoromethylsulfonyl) pyrrole, 1- (2-chloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylsulfinyl) pyrrole, 1- (2-chloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (dichlorofluoromethylsulfonyl) pyrrole-1,1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylthio) -5-methylthiopyrrole, 1 - (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (bromodifluoromethylthio) pyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano- 4- (bromodifluoroethylsulfinyl) pyrrole, 1- (2,6-dichloro-4) -trifluoromethylphenyl) -2-chloro-3-cyano-1- (bromodifluoromethylsulfonyl) pyrrole-1,1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (methylsulfinyl) pyrrole; or 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (methylsulfonyl) pyrrole. Pyrrole derivatives according to claim 1 selected from the group consisting of 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- (chlorodifluoromethylthio) pyrrole. -45 GB 284089 B6 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chlorodifluoromethylsulfinyl) pynol, 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichlorofluoromethylthio) pyrrole, 1- (2 4,6-trichlorophenyl) -3-cyano-1- (dichlorofluoromethylsulfinyl) pyrrole, 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichlorofluoromethylsulfonyl) pyrrole, 1- (4-bromo-2) 6-dichlorophenyl) -3-cyano-4- (dichlorofluoromethylthio) pyrrole, 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (dichlorofluoromethylsulfinyl) pyrrole, 1- (4-bromo-2, 6-dichlorophenyl) -3-cyano-4- (dichlorofluoromethylsulfonyl) 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- (2,4,6-dichlorophenyl) -3-cyano-4- (dichlorofluoromethylthio) pyrrole, 1- (2,4,6-trichlorophenyl) -3-cyano-4-chloropyrrole 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chlorodifluoromethylsulfonyl) pyrrole, 1- (2,6-dichlorophenyl) -3-cyano-4- (dichlorofluoromethylthio) pyrrole, 1- (4- bromine- 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- (chlorodifluoromethylsulfinyl) pyrrole, 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (chlorodifluoromethylsulfonyl) pyrrole, 1- (4-bromo-2,6-dimethylphenyl) -3-cyano-4- (trifluoromethylsulfinyl) pyrrole, 1- (4-bromo-2,6-dimethylphenyl) -3- cyano-4- (trifluoromethylsulfonyl) pyrrole or 1- (4-bromo-2,6-difluorophenyl) -3-cyano-4- (dichlorofluoromethylthio) pyrrole. The pyrrole derivatives of claim 1 selected from the group consisting of 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-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfonyl-5-bromopyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3 -cyan-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-chloropyrrole, 1- (2-chloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5 -chlorpyrrole -46GB 284089 B6 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- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-bromopyrtol, 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-bromopylamino-1,1- (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 - (dichlorofluoromethylsulfonyl) pyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-cyano-1- (dichlorofluoromethylthio) pyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-cyano- 4- (dichlorofluoromethylsulfinylpyrrole or 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3- cyano-4- (trifluoromethylsulfonyl) pyrrole. 7. An insecticidal acaricidal composition comprising, as active ingredient, a pyrrole derivative of the formula I as claimed in claim 1 in combination with one or more compatible diluents or carriers. Use of the pyrrole derivatives of the general formula I according to claim 1 for controlling insects and mites.