SK278926B6 - Pyrrole derivatives, insecticidal and acaricidal agent containing same and their use - Google Patents

Abstract

This patent describes pyrrole derivatives with a general formula (I), where X is halogen, thiocyanato-, alkylthio-, alkylsulfinyl-, alkylsulfonyl-, halogenalkylthio- halogenalkylsulfinyl, cyano- or halogenalkylsulfonyl group, R1 is hydrogen, halogen, alkylthio-, alkylsulfinyl , alkylsulfonyl, amino, alkylcarbonylamino-, halogenalkyl carbonyl aminogroup, R2 is hydrogen, halogen, cyano-, alkyl-, halogenalkyl or alkoxycarbonylamino group, R3 is hydrogen, halogen, thiocyanato-, alkylthio-, alkylsulfinyl-, alkylsulfonyl-, halogenalkylthio-, or bis(alkylthio)methyl group, Y is halogen, halogenalkyl or halogenalkoxyl, or is Y hydrogen, in the case that X is halogen or rest R5(SO)n, where n is integer 0, 1 or 2 and R5 is alkyl or halogenalkyl, R1 and R3 mean hydrogen and R2 menas cyano group, X1 is hydrogen, halogen, alkyl, alkylthio or alkylsufinyl group, X2 and X3 mean hydrogen, and X4 is hydrogen, halogen or alkyl, while all of the above mentioned alkylgroups or the parts of them are direct or branched and they contain 1 up to 4 carbon atoms. This invention also is dealing with the insecticidal and acaricidal agents, containing the above mentioned pyrrole derivative, playing role of active compound and it also is dealing with the application of these derivative to destroy insect and mites.

Description

Technical field

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. The invention further describes the application of the compounds in agriculture, in particular as pesticides for the control of arthropods, preferably as insecticides and acaricides. The present invention provides agrochemical compositions useful for controlling arthropods, especially insects and spiders.

BACKGROUND OF THE INVENTION

Several pyrazoles (heterocycles containing 2 nitrogen atoms) are well known as insecticides. Certain compounds containing a pyrrole group (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 have insecticidal activity, such as a pyrethroid group, a carbamate group or a certain organophosphorus group. Single substituted pyrrole derivatives for use in agriculture have been described, for example, in British Pat. 2,189,242, but only for fongicidal application.

SUMMARY OF THE INVENTION

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

ISQď · xvV * ^{4 (i)}

Y in which

X represents a halogen atom, a thiocyanato group, an alkylthio group, an alkylsulfonyl group, an alkylsulfonyl group, a haloalkylthio group, a haloalkylsulfinyl group or a haloalkylsulfonyl group, in which the alkyl and haloalkyl moieties have straight or branched carbon atoms containing from 1 to 4 carbon atoms; the same or different halogen atoms from monosubstitution to complete polysubstitution, or is cyano,

R ¹ is hydrogen, halogen, alkylthio, alkylsulfinyl, alkylsulfonyl, amino, alkylcarbonylamino, haloalkylcarbonylamino or alkyltioalkylidéniminoskupinu, wherein the alkyl and haloalkyl moieties are straight or branched chains containing 1 to 4 carbon atoms, and all of said groups substituted with halo include a 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, and alkoxy moieties are linear or branched chain of 1 to 4 carbon atoms, haloalkyl groups containing one or more identical or different halogen atoms from monosubstitution to full 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, a 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 being selected from the group consisting of amino and defined alkylcarbonylamino, haloalkylcarbonylamino, alkoxycarbonylamino, alkylthioalkylthio, alkylthioalkylthioalkylthio) 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 X represents a halogen atom or 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, R ¹ and R ³ are 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 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, provided that at most two of R ¹ , R ² and R ³ are selected from the group consisting of hydrogen and defined alkyl groups, 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 symbols and with the exception of the compound in which X ⁴ , X ¹ , Y, R ¹ , X, R ² and R ³ are chlorine and X ³ and X ² are hydrogen and compounds wherein X ¹ , X ² , X ³ , X ⁴ , R ¹ and R ² X is cyano, R ³ is amino and Y is chloro.

Compounds of the general formula (I) of interest, such as insecticides and acaricides, are generally preferred.

Y represents a hydrogen atom and X represents a radical of formula R ^with 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 is hydrogen, halogen or straight or branched alkylthio group having 1 to 4 carbon atoms, R ² is cyano,

R ³ is 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 formula I of particular interest are the following:

A) compounds of formula (II),

in which

X is R ⁵ S (O) n where n is 0, 1 or 2 and R ⁵ is methyl, trifluoromethyl, difluoromethyl, fluorodichloromethyl, difluoromethyl, difluoromethyl, dichloromethyl, or fluoromethyl

R ² is CN,

R ¹ is H, F, Cl, Br, R ³ is H, F, Cl, Br,

X ¹ represents a hydrogen or chlorine atom;

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- (trifluoromethylisulfonyl) pyrrole,

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

- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (dichlorofluoromethylsultinyl) 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-4-trifluoromethylphenyl) - 2-chloro-3-cyano-4- (dichloromethylsulfonyl) -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- (dichlórfluórmetylsulfonyl) pyrrole,

- (2-chloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylsulfonyl) pyrrole,

- (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 represents a radical R ⁵ S (O) _n in which n is 0, 1 or 2 and R ⁵ represents a methyl group, a trifluoromethyl group, a difluorohoromethyl group or a fluorodichloromethyl group,

R ² is cyano,

R ¹ is H, F, Cl, Br, or an amino group

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

^X 'is H or Cl and

Y is trifluoromethyl or trifluoromethoxy.

In view of their insecticidal activity, the following compounds according to the invention are preferred: 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, l- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfonyl-5-bromopyridine.

1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (trifluoromethylthio) pyrrole,

- (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 -chloropyrrole, 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-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-trifluóimetylfenyl) -2-amino-3-triíluórmetyltio-4-cyano-5-bromopyridine. 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylthiopyrrole), 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-4- (dichlorofluoromethylthio) pyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-cyano-4- (dichlorofluoromethylsulfinyl) pyrrole and l- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (trifluoromethylsulfonyl) pyrrole.

C) Compounds having remarkably high acaricidal activity, corresponding to the general formula (I), in which:

X represents a halogen atom or a radical R ⁵ S (O) n in which n is 0, 1 or 2 and R ⁵ represents a C 1 -C 4 alkyl group, a C 1 -C 4 haloalkyl group, preferably a trihalomethyl group, in which halogen is in particular 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 cyano,

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 atoms and alkyl groups of 1 to 3 carbon atoms, preferably X ¹ and X ⁴ independently of each other being hydrogen, fluorine, chlorine or bromine or methyl group.

Particularly preferred compounds of this class of compounds are: 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (chlorodifluoromethylthiopyrrole), 1- (4-bromo-2,6-dichlorophenyl) -3-cyano- 4- (trifluoromethylthio) pyrrole, 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chlorodifluoromethylthio) pyrrole, 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chlorodifluoromethylsulfinyl) pyrrole, 1- ( 2,4,6-trichlorophenyl) -3-cyano-4- (dichlorofluoromethylthio) pyrrole, 1- (2,4,6-trichlorophenyl) -3-cyano-4- (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- (tr their chloromethylthio) pyrrole, 1- (2,4-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-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 and 1- (4-bromo-2,6-difluorophenyl) -3-cyano-4- (dichlorofluoromethylthiopyrrole).

D) Other preferred compounds of formula (1) are those in which they are present

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

R ² is CN,

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

X ¹ and X ⁴ are different from hydrogen,

X ² and X ³ are each a hydrogen atom and Y is a defined haloalkyl or haloalkoxy group.

It is an object of the present invention to provide novel insecticides and acaricides from the pyrrole derivative family and intermediates necessary for their production. It is further an object of the invention to provide very active compounds. These and other objectives can be achieved wholly or partially using the defined novel compounds.

The compounds of formula (I) may be prepared by the 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 substituents. It is understood that in the methods described the order of introduction of the various groups into the pyrrole ring can be changed and that in some cases it is necessary to protect a functional group. The resulting compounds of formula (I) may also be converted into other compounds of formula (I) by known methods.

If certain symbols appearing in the formulas are not specifically defined below in the description of the various methods by which the method according to the invention is carried out, it is understood that in such a case the respective symbol has the meaning indicated, i.e.. j. meaning defined first. 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 stated, the term amino refers to unsubstituted amino.

The invention includes certain intermediates used to make the compounds of the invention. Such preferred intermediates, prepared as described above, correspond to the general formula (IIIa),

in which

Y represents a hydrogen, chlorine or bromine atom, a trifluoromethyl group or a trifluoromethoxy group, and

X ¹ and X ⁴ independently of one another are hydrogen, chlorine, fluorine or methyl, and X ¹ are a methylthio group, with the restriction that if the means both of X ¹ and X ⁴ is H, then Y is other than hydrogen hydrogen or chlorine.

While the compounds falling within the scope of this limitation are not within the scope of the invention, they are useful as intermediates for 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

According to one embodiment of the invention, compounds of formula (I) wherein X and R ³ are hydrogen, R ² is cyano and R ¹ is amino, wherein X ¹ , X ² , X ³ , X ⁴ and Y are possible are as defined above, ie compounds corresponding to the general formula (111)

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

(IV) wherein the individual general symbols are as defined above, by reaction with a base, preferably 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

According to another embodiment of the process of the invention, compounds of formula (IV) may be prepared from an aniline derivative of formula (V),

wherein Y, X ¹ , X ² , X ³ and X ⁴ are as defined above, by reaction with formyl succinonitrile or an alkali metal salt of formyl succinonitrile. This reaction is generally carried out in an organic solvent or in water, at a temperature between 10 and 120 ° C, preferably under 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

The compounds of formula (I), wherein X is halogen, ^R1 is amino, ^R2 is cyano, ^R3 is hydrogen and the other substituents are as defined above, may be prepared by reaction of compounds of formula (III) with halogenating agents, such as sulfuryl chloride, N-chlorosuccinimide, N-bromosuccinimide, N-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 (1) wherein X is cyano, ^R1 is amino, ^R2 is cyano, ^R3 is hydrogen and the remaining substituents are as defined above, may be prepared from corresponding compounds in which 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, there may be a need to protect the amino group with a suitable protecting group.

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

C) Intermediate compounds in which X represents a formyl group may be obtained by hydrolyzing the corresponding compounds in which X represents a bis (alkylthio) methyl or bis (arylthio) methyl group, or by reacting them with a suitable alkyl nitrite followed by hydrolysis according to the procedure described E. Fujita, R. Ichikawa and K. Fuji in Tetrahedron Letters 1978, 3561. During the reaction with alkyl nitrites, it may become necessary to protect the amine function with a suitable protecting group.

D) Intermediate compounds of formula (I) wherein X is bis (alkylthio) methyl or bis (arylthio) methyl and the remaining general symbols 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) Necessary intermediates of formula (I) in which X is a hydroxyl group, R ¹ is an optionally protected amino group, R ² is a cyano group, R ³ is a hydrogen atom and X ¹ , X ² , X ³ , X ⁴ and Y have the abovementioned meaning, can be prepared from the corresponding compounds in which X is a halogen atom by conversion to a Grignard reagent or lithium derivative by standard methods followed by treatment with oxodiperoxymolybdium (pyridine) (hexamethylphosphoric triamide) (MoOPH) using the procedure described by NI Lewis and company. in J. Org. Chem. 1977, 42, 1479. Prior to the preparation of a Grignard reagent or lithium derivative, there may be a need to convert a cyano group in said 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 described Grignard reagent or lithium derivative may be reacted with a trialkyl borate followed by oxidation with hydrogen peroxide using the procedure described by MF Hawthome in J. Org. Chem. 1957, 22, 1001 or RW Hofimann and K. Ditrich in Synthesis 1983, 107.

Method 6

A) Compounds of formula (I) in which X is thiocyanato, ^R1 is amino, ^R2 is cyano, ^R3 is hydrogen and X ^1, X ^2, X ^3, X ⁴ and Y are as defined above, can 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 methanol.

B) Compounds of formula (I) where X is alkylthio or haloalkylthio, R ¹ is amino, ^R2 is cyano, ^R3 is hydrogen and X ^1, X ^2, X ^3, X ⁴ and Y are as defined above, ie, compounds corresponding to formula (IX) 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 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 can be prepared by the procedure of S. Thea and G. Cevasco in Tetrahedron Letters, 1988, 2865. Using sulfenyl chloride, the process can be described by the following reaction scheme:

represents a group R 5 (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, ie temperature, reaction time and amount of oxidizing agent used, may be varied as necessary to provide either the corresponding sulfinyl derivative (n-1) or the corresponding sulfonyl derivative (n = 2). It will be understood that sulfonyl derivatives may also be prepared from sulfinyl derivatives. In the case of certain haloalkylthio groups, for example trifluoromethylthio, it may be expedient to protect the amine function, for example in the form of the trifluoroacetamide derivative. Using, for example, trifluoroperoxyacetic acid as the oxidizing agent, the reaction may be described by the following reaction scheme:

* CF 3 CO 3 H

Method 9

Compounds of formula (I) wherein R ³ is halogen, 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 of compounds of general formula I of formula (I) wherein R ¹ is amino, R ² is cyano, R ³ is hydrogen and X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, ie compounds corresponding to said general formula (XI) ), with halogenating agents under conditions similar to those described in Method 3. This reaction may be described by the following reaction scheme:

{Hal = halogen)

Method 7

The compounds of formula (I) in which X is thiocyanato, ^R1 is amino, ^R2 is cyano, ^R3 is hydrogen and X ^1, X ^2, X ^3, X ⁴ and Y are as defined above, can be further converted to a compound of formula (I), wherein 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 are as defined above, with a base, such as sodium or potassium hydroxide, in the presence of, for example, an alkyl halide or dialkyl sulfate, in a solvent.

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 hereinabove may be prepared by reacting a compound of formula (XI) with tris (alkylthio) methane of formula (R ^and S) ₃ CH, wherein 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 temperature refluxing the solvent, optionally in the presence of an acid acceptor such as pyridine. According to a preferred embodiment of this process, acetonitrile is used as the solvent, working at 25 ° C with tris (methylthio) methane as tris (alkylthio) methane and dimethyl (methylthio) sulfonium tetrafluoroborate as Lewis acid, without an acid acceptor. This procedure can be described by the following reaction scheme:

Method 8

Compounds of formula (IX) can be converted by oxidation to compounds of formula (X) wherein X

(R’SfeCH ---- ►

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, of formula (XVI), 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:

X x

CN

Y (XVI)

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

Method 12

Compounds of formula (I) wherein R ³ is alkylsulfmyl 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 of formula (XVI) using methods similar to those described in Method 8. In those cases where X represents a group R 5 which may undergo undesirable competitive oxidation, the sulfenylation may be carried out on compounds of formula (I) according to the above procedures. ), wherein X is a halogen, preferably bromine or iodine, ^R1 is amino, ^R2 is cyano, ^R3 is hydrogen and the remaining symbols are as defined above, the intermediate is subjected to oxidation, followed by treatment with an alkyl lithium using a procedure analogous to the procedure described by C. Kruse et al. in Heterocycles 1989, 29, 79, whereupon the reaction is quenched by the addition of 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:

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, ie compounds corresponding to said general formula (XX) may be prepared from compounds of formula (I) wherein R ¹ is amino, R ² is cyano and R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, i.e. from compounds of the above formula (XIX), by diazotization, which is preferably carried out by treatment with an alkylnitrile such as tert-butylnitrile 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 0-25 ° C.

B) Compounds of formula (I) wherein R ¹ is halogen, R ² is cyano and R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above, ie compounds corresponding to said general formula of formula (XXI), may be prepared from a compound of formula (XIX) by diazotization with an alkylnitrite, for example tert, butylnitrite, in the presence of a halogen atom donor such as bromoform, carbon tetrachloride, anhydrous copper chloride or iodine.

C) Compounds of formula (I) 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, ie compounds corresponding to said general formula (XXII), can be prepared from compounds of formula (XIX) by treatment with an alkyl nitrite in the presence of a disulfide of formula RSSR, wherein R is an alkyl group as defined. The reaction is typically carried out in a solvent such as chloroform at 0 ° C using 1 to 5 equivalents of alkyl nitrile and 2 to 5 equivalents of disulfide.

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

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

Method 14

Compounds of formula (I) wherein R ¹ is alkylsulfmyl or alkylsulfonyl, R ² is cyano and R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above may be prepared by oxidation of the compounds (XXII) following the procedures described in mETHOD 12. If the X or R ³ is SR also to be maintained at the oxidation state (at the stage of sulphide), it is possible to obtain the desired compound by a similar method to that described in method 12 .

Method 15

Compounds of formula (I) wherein R ¹ is alkylcarbonylamino, haloalkylcarbonylamino or alkylthioalkylidenenimino, R ² is cyano and R ³ , X, X ¹ , X ² , X ³ , X ⁴ and Y are as defined above may be prepared from of the formula (XIX) by methods known per se.

Method 16

Compounds of formula (I) in which R 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 (I). XXVII)

X-N --- it -NH ₂ "W (XXVII)

Alternatively, the compounds of formula (I) wherein R ² is hydrogen and R ¹ , R ³ , X, X ¹ , X ² , X ^J , X ⁴ and Y have the abovementioned meaning to prepare from compounds of formula (XXV) by heating with 48% hydrobromic acid in glacial acetic acid to reflux or 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 oxidizing compounds of formula (XXIV) with Jones reagent. This procedure can be described by the following reaction scheme:

Compounds of formula (XXVII) wherein 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 (XXV) by treatment with diphenylphosphoryl azide in the presence of an organic base , such as triethylamine, in an alcoholic solvent, such as tert-butanol, to form the carbamate of formula (XXVI), which is then subjected to hydrolysis. Other methods for the preparation of a compound of formula (XXVII) from a compound of formula (XXV) by Curtius rearrangement are the conversion of a compound of formula (XXV) to an acid chloride and subsequent reaction with an azide ion source and alcohol treatment as described by J. March in Advanced Organic Chemistry, McGraw-Hill publ. (1985), p. 984. The overall rename can be described by the following reaction scheme:

Y (XXV)

DETAILED DESCRIPTION OF THE INVENTION

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.

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 acid (394 mg of pure; 2.28 mmol) in 25 mL of chloroform was stirred at room temperature for 1.5 h, then heated at reflux overnight, then an additional 45 mg (0.21 mmol) was added. m-Chloroperoxybenzoic acid and refluxing are continued for 1 hour. The heating is then discontinued, the reaction mixture is 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 the product which was chromatographed on silica gel using dichloromethane / hexane (2: 1 by volume) as eluent. The starting 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 a combination of hexane and ethyl acetate gave 240 mg of the desired sulfone as colorless needle crystals, m.p. 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 the toluene / hexane combination afforded 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 using 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylthio-5-bromopyrrole as the starting material. Example 5. 1- (2,6-Dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4-trifluoromethylsulfinyl-5-bromo-pyrrole is obtained as the product in Example 3A. 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 is obtained as the product in Example 3B. This compound, prepared as described in Example 1, melts at about 113 ° C.

Example 4

To 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 tetrahydrofuran, under stirring under nitrogen, 3.9 ml (3.4 g: 33 mmol) of t-butyl nitrite are added. After 30 minutes, the reaction mixture was heated at 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. This material after recrystallization using a combination of hexane and ethyl acetate gave 1.87 g of the desired product in m.p.

It is a colorless powder which melts at approximately 137 ° C.

Example 5

To a heterogeneous mixture of 2.4 g (5.28 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole (prepared as described in Example 8) and 40 ml of bromoform are added, under an inert gas atmosphere, 0.94 ml (820 mg: 7.92 mmol) of tert-butyl nitrite. 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 yields 780 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 8), 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, then an additional 0.30 mL (2.1 mmol) of trifluoroacetic anhydride was added. After a total of 24 hours of reaction, the reaction mixture is diluted with dichloromethane, concentrated, washed with aqueous hydrochloric acid and water, and recrystallized from a combination of hexane and ethyl acetate. 860 mg (37%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2 - [(trifluoromethyl) carbonylamino] -3-trifluoromethylthio-4-cyano-5-chloropyrrole were obtained 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). 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 room temperature for 4 days. 20 ° C and then refluxing for 1 day. After the addition of an additional 0.03 ml of acetyl chloride, refluxing is continued for another day, then the reaction mixture is 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 afforded 480 mg (29%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) after chromatography on silica gel using 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-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole (prepared as described in Example 13) in 15 ml of ethyl ether is added at 15 ml. A solution of 0.29 ml (0.48 g; 3.6 mmol) of sulfuryl chloride in 15 ml of anhydrous ethyl ether was added dropwise to it under stirring under an inert gas atmosphere. The reaction mixture was allowed to warm to 20 ° C, stirred for 2.5 days, then an additional 0.03 mL (0.4 mmol) of sulfuryl chloride was added and stirring was continued the next day. After addition of an additional 0.03 ml of sulfuryl chloride and further stirring for one day, the reaction is quenched by the addition of 28 ml of a 10% aqueous potassium carbonate solution, the phases are separated and the aqueous layer is 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, eluting with dichloromethane / hexane (2: 1, v / v) as a eluent, to give 1.30 g (80%) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino- 3-Trifluoromethylthio-4-cyano-5-chloropyrrole as a slightly pink colored solid. After recrystallization from cyclohexane, 810 mg of the desired product is obtained in the form of off-white needles melting at approximately 176 ° C.

Example 9

The reaction was carried out in a manner analogous to that of Example 8 except that 1- (2-chloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrile melting at 169 ° C was used as the reactant. as described in Example 13. 1- (2-Chloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole, m.p.

Example 10

The reaction was carried out in a manner analogous to that of Example 8 except that 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-dichlorofluoromethylthio-4-cyanopyrole, m.p. 202 DEG C., was used as the reactant. as in Example 13. 1- (2,6-Dichloro-4-trifluoromethyl-phenyl) -2-amino-3-dichloro-fluoromethyl-thio-4-cyano-5-chloro-pyrrole, m.p.

Example 11

1- (2,6-Dichloro-4-trifluoromethyl-phenyl) -2,4-bis (trifluoromethyl-thio) -3-cyano-5-aminopyrene, melting point was prepared as described in Example 13 for the preparation of the above compound using an excess of trifluoromethanesulfenyl chloride. 161 ° 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-cyanopyrole (m.p. ca 182 ° C). A solution of 1.46 g (3.6 mmol) of 80% pyridinium bromide perbromide in 15 ml of pyridine was added in 15 ml of pyridine under an inert gas atmosphere. After 30 minutes, the reaction mixture is poured into 0 ° C cooled ethyl ether and the precipitate formed is filtered off. The filtrate was washed successively with aqueous hydrochloric acid solution, aqueous sodium hydroxide solution and water, and the organic layer was dried over anhydrous magnesium sulfate and evaporated. 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

of 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-3 after chromatography on silica gel using 4: 1 hexane: ethyl acetate as eluent. -trifluoromethylthio-4-cyano-5-bromopyrrole as a white solid. After recrystallization from a combination of hexane and ethyl acetate, 910 mg of the title product is obtained as colorless needles with a melting point of about 160 ° C.

Example 13

To a solution of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-4-cyanopyrrole (2.00 g, 6.25 mmol) prepared as described above in 60 ml of dichloromethane was slowly stirred with cooling on ice. Add 10 mL of dichloromethane solution to 0.55 mL (0.85 g; 6.2 mmol) of trifluoromethanesulfenyl chloride cooled to -78 ° C. The reaction mixture was stirred at 0 ° C for 2 hours then a stream of nitrogen was added over 1 hour, then the resulting mixture was shaken with saturated aqueous 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 portions of colorless solids, weighing 900 mg and 950 mg. The solids were recrystallized from chloroform to give 680 mg and 630 mg of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethyl-4-cyanopyrole, 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-dicyanopropene 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-4-trifluoromethylphenyl) -2-amino-4-cyanopyrrole at a temperature. 176 ° C.

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

20.5 g (0.140 mol) of formylsuccinonitrile potassium salt are dissolved in about 30 ml of water, acidified with concentrated hydrochloric acid and extracted with ethyl ether. The ethereal extract was dried over anhydrous magnesium sulfate and evaporated. 3.87 g of a brown colored 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 heated at reflux overnight with removal of 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-4-trifluoromethylphenyl) amino] -2,3-dicyanopropene precipitates as yellow in the trituration with hexane. solid. This material, after recrystallization from ethanol / water, gave a product with a melting point of about 101 ° C.

Examples 14A and 14B

To a suspension of 1.17 g (3.30 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 ethyl acetate. 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 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 brown solid is obtained, which is mixed with the product of the previous reaction 1.00 g (2.8 mmol) of 1- (4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrole and 0.15 g. ml of bromine. Silica gel chromatography eluting with dichloromethane: hexane (3: 1, v / v) gave 1.40 g (52%) of 1- (4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5- bromopyrole (Example 14A) as a yellow solid. Recrystallization from hexane-ethyl acetate gave the desired product as yellowish plates melting at about 175 ° C.

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. 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, which was used in a manner analogous to that described in Example 13 to prepare 1- (2-chloro-4). (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-4-cyanopyrrole prepared according to the procedure of Example 13 was treated with (fluorodichloromethane) sulfenyl chloride as described in Example 13 (but using trifluoromethanesulfenyl chloride), to give 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-dichlorofluoromethylthio-4-cyanopyrrole (Example 16A), m.p.

This compound was treated with tert-butyl nitrite following the procedure of Example 4 to give 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylthio) pyrrole (Example 16B). mp 158 ° C.

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- (dichlorofluoromethylsulphinyl) 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. 179 ° C.

Example 19

The compound of Example 16 was treated with tert-butyl nitrite following the procedure of Example 4 to give 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-cyano-4- (dichlorofluoromethylthio) pyrrole, m.p. .

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] - was prepared using 2,6-dichloro-4-trifluoromethoxyaniline instead of 2,6-dichloro-4-trifluoromethylaniline. 2,3-dicyanopropen.

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

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

Example 8 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-trifluoromethylthiopyrole (Example 21B), m.p. Example 18 was converted to 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfonylpyrrole (Example 21 C), m.p. 187 ° C.

Examples 22A, 22Ba22C

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) ¹ - d the Lo ^r-1 -TR 4 and 1 -fluoro-phenyl) pyrrole (47.77 g, 0.101 mol, 1.0 equiv) at 0 ° C dissolved in 190 ml of trifluoroacetic acid was added to the solution 10, 8 mL (0.106 mol; 1.05 equivalents) of 30% 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. equivalents) of 30% hydrogen peroxide, the mixture was stirred at 0 ° C for 9 hours, then stored again in the refrigerator overnight. The next morning, 10.8 ml (0.106 mol; 1.05 equivalents) of 30% hydrogen peroxide was added at 0 ° C and after 3.5 hours the reaction mixture was poured into 2 liters of ice water with vigorous stirring and the resulting mixture filtered.

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 ^1- Dichloro-4'-trifluoromethylphenyl] 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 (0.173 mol; 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 again at room temperature. The mixture was allowed to warm to room temperature overnight, stirred at room temperature overnight, and an additional 9.05 mL (0.0886 mol; 1.05 equivalents) was added the next morning at 0 ° C. 30% hydrogen peroxide was added and the mixture was cooled to 0 ° C for 6 hours and 40 minutes and the resulting mixture was allowed to warm to room temperature over Saturday and Sunday stirring, then poured into 2 liters of water. Filter with ice and vigorous stirring.

The precipitated products from both of these reactions were combined and dissolved in 500 ml of dichloromethane. The solution is 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 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 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 Dissolve in 15.8 ml of tetrahydrofuran and add 2.41 g (1.0 equivalents) of solid triphenylphosphine to the solution, which turns yellow. After 2.5 hours, the cooling bath was removed and the reaction was stirred at room temperature overnight, then an additional 2.55 g (9.72 mmol; 1.06 equivalents) of triphenylphosphine was added and the resulting mixture was stirred at room temperature overnight. at room temperature, whereupon a precipitate is 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 is dried over magnesium sulphate, filtered and the solvent is 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- [2-ch] are obtained. lor-3-cyano-1- (2 ', 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, as a precipitate forms, 15 ml of dimethylformamide and 10 ml of water are added. , then 0.564 g (3.24 mmol; 3.0 equivalents) of solid sodium dithionite is added, turning the mixture to light yellow, and 0.65 g (3.1 mmol; 2.87 equivalents) is added to the cooled weighed vial. dibromodifluoromethane, which was then transferred to a colorless reaction mixture and a white precipitate began to precipitate, after 1 hour and 50 minutes 10 ml of dimethylformamide was added first, followed by an additional 0.93 g of dibromodifluoromethane, the reaction vessel was sealed and overnight After cooling to 0 ° C, the reaction mixture was poured into 200 ml of water and extracted with ethyl acetate The organic phase is washed twice with 100 ml of 5% aqueous hydrochloric acid, twice with 100 ml of saturated sodium hydrogen carbonate solution and 100 ml of saturated sodium chloride solution each time, the organic layer is dried over magnesium sulfate, filtered and the solvent is evaporated. Evaporate in vacuo. 80.7 mg of a white solid is obtained. The original aqueous phase was then filtered to collect a white solid that 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 (overall yield 0.429 g: 40%). This material was combined with the previous 80.7 mg portion and subjected to silica gel chromatography. 0.362 g of a white solid was identified as 4-bromodifluoromethylsulfenyl-2-chloro-3-cyano-1- (2 ', 6'-dichloro-4'-trifluoromethylphenyl) pyrrole (Example 22C), mp 128.3-133.7 C.

Using the procedures detailed for the synthesis of the compounds in Examples 1 to 22, or using other methods or procedures generally described, 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 Table 3 below (DAP Nos. 1 to 91: compounds of formula (I) in which X ² and X ³ are hydrogen atoms and the remaining general symbols have the meanings shown in the table) and in the table. 4 (DAP No. 92-195 of a compound of formula (I) wherein X ² and X ³ are hydrogen, X ¹ and X ² are chlorine, Y is trifluoromethyl, and the remaining general symbols are as defined in the table).

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SK 278926 Β6 <β

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Examples of other pyrrole compounds prepared analogously (DAP) of the formula I, wherein ^X and X 'are hydrogen, X ¹ and X * is Cl, and Y is a group trifluórnetylovú

DAP about. R ¹ X R ² R ³ melting point (° C) 92 nh ₂ CF ₂ C1S CN H 160.5 to 175 93 H CP ₃ SO ₂ CN H 199.5 to 201 94 H cf ₂ cis CN E 104.9 to 106.8 95 H C? ₂ C1S CN cf ₂ cis 114.5 to 117 96 nh ₂ CF.C1S ¢: CN Cl 178-181 97 H C? ₂ C1SO ₂ CN H 199.8 to 202 96 H C? ₂ C1SO ₂ CN Cl 193.1 to 195.6 99 H C? ₂ C1SO CN Cl 145.2 to 147.5 100 H CF ₂ C1S CN Cl 139.0 to 143.1 101 H CP ₃ S CN br 137-138 102 H CP ₃ SO CN br 164 to 165.5 103 H CP ₃ SO ₂ CN br 197-198 104 H CP ₂ C1SO CN H 126.8 to 129.6 105 H cf ₃ p CN H 152-153 106 nh ₂ cfci ₂ cf ₂ sec CN H 183-190

DAF melting point

d. R ¹ X R ² R ³ (C) 107 nh ₂ CC1 ₂ S CN H 189-193 108 H CTC1 ₂ CF ₂ S CN H 118.8 to 123.8 109 H cfci ₂ cf ₂ Sat ₂ CK H 157.5 to 161.9 110 H cfci ₂ cf ₂ sq CN H 182.5 to 133.9 111 nh ₂ cfci ₂ cf ₂ sec CN Cl 186.5 to 188 112 H C ₂ Cl ₂ CF ₂ S CN Cl 149.5 to 151 113 br cf ₃ p CN H 163-164 114 E CTCIjCFjS CH Cl 113.5 to 116.5 115 H CCljS CN Cl 177-182 116 H CFC1 ₂ CF ₂ SO ₂ CN Cl 147 to 150.5 117 H CC1 ₃ SO ₂ CN Cl 200-202 118 H CCljSO CN Cl 152.2 to 153.5 119 Cl CF ₃ SO CN H 161.5 to 162.5 120 nh ₂ CH ₃ S CN H 150-151 121 H cfci ₂ p CN br 117-142 122 nh ₂ cfci ₂ p CN br 195.5 to 197 123 br cf ₃ so CN H 170-172 124 H cfci ₂ so ₂ CN br 176 to 178.5 125 H CFCLjSO CN br 116.5 to 135.5

melting point

No. R ¹ X R ² R ³ (° c) 126 H SCN CN H 173 to 173.5 127 br C? ₃ SO ₂ CN H 179 to 180.5 128 E CH, S CN H 107 to 108.5 129 nh ₂ CT ₂ C1S CK br 174.5 to 178 130 br CF ₂ C1S CN Cl 129.5 to 133.5 131 H CF ₂ C1S CN br 133.5 to 137.1 132 NH. No. 01 dl H 159.5-160 133 MH ₂ CF ^ S CN SCN 169-171 134 H A C ^ S CN SCN 105 to 106.5 135 br CP ₂ C1SO CN Cl 157.5 to 159 136 H Cl CN H 105.5 to 106.5 137 H CH? SO CN H 144.5 to 145.5 13Θ H EN ₃ SO ₂ CN H 173 to 173.5 139 nh ₂ CF ₃ S CN SCH ₃ 146-148 140 H cf ₃ p CN SOCH ₃ 143-145 141 H ca ₂ ciso CN br 143 to 146.5 142 br CFC1 ₂ SC ₂ CN Cl 117.8 to 122.5 143 CFjCUNH CP ₃ S CS H 187 to 188.5 144 H CFjClSO ^ CS br 182-185

SK 278926 Β6

DAP fi. R ¹ X R ² R ³ melting point ("C) 145 H CP ₃ S CN CH ₃ S 89-91 146 H CF ₃ S CN C ^ SOg 136-138 147 H CF ₃ S0 CN CH ₃ SO ₂ 151-163 148 nh ₂ CF ₃ CC1 ₂ S CN H 200-220 149 nh ₂ and? ₃ cci ₂ p CN Cl 223.5 to 232.5 150 H CF ₃ CC1 ₂ S CN Cl 170 to 172.5 151 H CF ₃ CC1 ₂ SO ₂ CN Cl 195.6 to 197.2 152 H CF ₃ CC1 ₂ SO CN Cl 161,161,5 153 H CF ₃ S CN CF ₃ S 95-96 154 nh ₂ CH ₃ S0 CN with 130-132 155 nh ₂ ch ₃ Sat ₂ CN H 248 to 248.5 156 H CF-JSO CN C? ₃ S 145-148 157 H CN Cl 128-129 158 nh ₂ CF ₃ S CN S0CH ₃ 139-141 159 cf ₃ p CN Cl 73-74 160 HH ₂ CFC1 ₂ SO CN H 156.4 to 195 161 H cf ₃ Sat ₂ CN CF ₃ S 156-157 162 H CHjSO CN Cl 130-131 163 nh ₂ cf ₃ p CN F 164 to 164.5

melting point

no. R ¹ X R ² R ³ (° C) 164 H Cl CN Cl 129-129.5 165 CH ₃ SO CF ₃ S CN Cl 133-135 156 CH ₃ S CFC1 ₂ S CN Cl 112.2 to 124, with 167 nh ₂ CFClgSO CN Cl 163 to 169.5 168 CF ₃ COH CFjSO CN H 195 to 197.5 169 H CF ₃ S CN F 116-117 170 CH ₃ SO ₂ cfci ₂ p CN Cl 164.5 to 170.5 171 ch ₃ so cfci ₂ p CN Cl 193 to 195.7 172 nh ₂ cf ₃ so CN H 175 173 H cf ₃ p CFgH H 54-56 174 E CK ₃ SO ₂ CN Cl 165-166 175 H br CN br 127.5-128 176 H br CN H 120-121 177 nh ₂ CFC1 ₂ SO ₂ CN Cl 203 to 214.5 178 H CF ₃ SC CN T 129-130 179 br Cl CN H 121-123 180 nh ₂ C? ₃ SO ₂ CN H 258-260 181 ch ₃ so CF ₃ SO CN Cl 238-239 182 H CFjBrS CN Cl 128.3 to 133.7

ΕΑΡ melting point

δ. R ¹ X R ² (° c) 183 H CF ^ r SO and Cl 117-119 184 H Cl ₂ BrS0 ₂ CN Cl 172-181 185 H c? ₃ p CH ₃ H oil 186 H C ^ SQ ch ₃ br 106-107 187 H C? ₃ SO ₂ CH ₃ br 76-77 188 ffi ₂ CF-.beta. CH ch (sch ₃ ) ₂ 159-161 189 CäjSCM C? ₃ S CH en (sch ₃ ) ₂ 124.5 to 125.5 190 H CF ₃ S (CH _{3) 3} COCONH br 113-114 191 H C? ₃ S br br oil 192 H CF ₃ SO cs ₃ 0H ^í} 149Ί51 193 br CP ₃ S ffi ₃ br oil 194 br br H c? ₃ p oil 195 H CFjS CH I 107-109

Legend: *) Knives exist as a keto-tautoner

The present invention provides a method of 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 cattle breeding and in health against arthropods parasitic on the vertebrate, in particular on warm-blooded vertebrate animals such as man and domestic animals such as cattle, sheep, goats, horses. , pigs, poultry, dogs, cats and fish, such as the Acarina mites, including ticks such as Ixodes spp.

Boophilus spp., E.g., Boophilus microplus, Amblyomma spp.,

Hyalomma spp.

Rhipicephalus spp, such as Rhipicephalus appendiculatus,

Haemaphysalis spp., Dermacentor spp. and Omithodorus spp., for example Omithodorus moubata, and mites such as Damalinia spp., Dermahyssus gallinae, Sarcoptes spp., for example Sarcoptes scabiei, Psoroptes spp.,

Chorioptes spp., Demodcx spp. and Eutrombicula spp., Diptera, such as e.g.

Aedes spp.

Anopheles spp., Musca spp., Hypoderma spp., Gasterophilus spp. and Simulium spp., the Hemiptera order, such as, for example

Triatoma spp., The order of Phthiraptera, such as, for example

Damalinia spp. and

Linognathus spp., The Siphonaptera family, such as, e.g.

Ctenocephalides spp., Of the order Dictyoptera, such as e.g.

Periplaneta spp. and

Blatella and the Hymenoptera line, such as Monomorium pharaonis, to protect stored products such as cereal products including grain and flour, groundnuts, animal feed, lumber and household items such as carpets and textiles against arthropod attack, especially beetles, including various moths and mites such as

Ephestia spp. (Moth),

Anthrenus spp. (anthrenus), Tribolium spp., (moss), Sitophilus spp. and Acarus spp. for destroying cockroaches, ants, termites and similar arthropods in residential and industrial buildings and for mosquito larvae in waterways, wells, reservoirs and other standing or flowing water, for treating foundations, structures and soil to protect buildings against attack termites such as

Reticulitermes spp., Heterotermes spp. and

Coptotermes spp., In agriculture to combat adults, larvae and eggs of Lepidoptera pests (butterflies and moths), such as

Heliothis spp., Such as Heliothis virescens, Heliothis armigera and Heliothis zea,

Spodoptera spp. Such as Spodoptera exempta, Spodoptera littoralis and Spodoptera eridania,

Mamestra configurata (sea),

Earias spp., Such as Earias insulana,

Pectinophora spp., Such as Pectinophora gossypiella, Ostrinia spp., Such as Ostrinia nubilalis, Corn trichoplusia ni,

Pieris spp. (White butterfly),

Laphygma spp.

Agrotis spp. and Amathes spp. (Cutworms),

Wiseana spp.

Chilo spp.

Tryporyza spp. and Diatraea spp.,

Sparganothis pilleriana,

Cydia pomonella,

Archips spp.

Plutella xylostella (whitefly), against adult and beetle larvae (Coleoptera), such as

Hypothenemus hampei, Hylesinus spp. Anthonomus grandis

Acalymma spp.

Lema spp. (Cuckoo).

Psylliodes spp. (Dropčík).

Leptinotarsa decemlineata, Diabrotica spp.,

Gonocephalus spp. (Flour beetles),

Agriotes spp. (blacksmiths), Dermolepida and Heteronychus spp.,

Phaedon cochleariae, Lissorhoptrus oiyzophilus,

Meligethes spp. (spineflower), Ceutorhynchus spp. (scrytonos), Rhynchophorus and Cosmopolites spp., against Hemipter pests such as Psylla spp. (Measured).

Bemisia spp.

Trialeurodes spp. (White flies),

Aphis spp.

Myzus spp.

Megoura viciae,

Phylloxera spp.

Adelges spp.

Phorodon humuli,

Aeneolamia spp.

Nephotettix spp.

Empoasca spp. (Cikádočka).

Nilaparvata spp.,

Perkinsiella spp.

Pyrilla spp.

Aonidiella spp.

Coccus spp.

Pseudococcus spp.

Ilelopeltis spp., Lygus spp.,

Dysdercus spp.

Oxycarenus spp. and

Nezara spp., Against Hymenoptera pests such as

Athalia spp. (Sawflies),

Cephus spp. (thistle) a

Atta spp., Against diptera pests such as Hylemyia spp. (Boll).

Atherigona spp.

Chlorops spp. (green lichen), Phytomyza spp. and Ceratitis spp. (vrtuya), against Thysanoptera pests, such as

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

Sminthurus spp.a

Onychiurus spp., Against Isoptera pests, such as Odontotermes spp., (Termites) against Dermaptera pests, such as Forficula spp. (ucholak) as well as against other arthropods important in the agricultural field, such as mites, for example

Tetranychus spp. (mite), Panonychus spp., Bryobia spp. (Mite),

Eriophyes spp. (bellows) a

Polyphagotarsonemus spp., Blaniulus spp. (Bodkavka).

Scutigerella spp. (Drobnonôžka).

Oniscus spp. (hives) a

Triops spp. (Štítovka).

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

from the series of isopods, for example

Oniscus asellus,

Armadillidium vulgare,

Porcellio scaber, from the class of millipedes (Diplopoda), for example Blaniulus guttulatus, from the class of centipedes (Chilopoda), for example

Geophilus carpophagus,

Scutigera spp., From the class of the Centipede (Symphyla), for example

Scutigerella immaculata, from the order of the whiskers (Thysanura), for example

Lepisma saccharina, from the order of the Collembola, for example Onychiurus armatus, from the order of the Orthoptera, for example Blatta orientalis,

Periplaneta americana,

Leucophaea maderae,

Blattella germanica,

Acheta domesticus,

Gryllotalpa spp.

Locusta migratoria migratorioides,

Melanoplus differentialis,

Schistocerca gregaria, of the order of the Dermaptera, for example Forficula auricularia, of the order of the Isoptera, for example Reticulitermes spp., Of the series of Anoplura, for example

Phylloxera vastatrix,

Pemphigus spp.

Pediculus humanus corporis,

Haematopinus spp.

Linognathus spp., Of the mollusk (Mallophaga), for example

Trichodectes spp.

Damalinea spp., From the order of the tufts (Thysanoptera), for example

Hercinothrips femoralis,

Thrips tabaci, from the family of Heteroptera, for example

Eurygaster spp.

Dysdercus intermedius,

Piesma quadrata,

Cimex lectularius,

Rhodnius prolixus,

Triatoma spp., 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 spp.

Psylliodes chrysocephala,

Epilachna varivestis,

Atomaria spp.

Oryzaephilus surinamensis,

Anthonomus spp.

Sitophilus spp.

Otiorrhynchus sulcatus,

Cosmopolites sordidus,

Ceuthorrhynchus assimilis,

Hypera postica,

Dermestes spp.

Trogoderma spp.

Anthrenus spp.

Attagenus spp.

Lyctus spp.

Meligethes aeneus,

Ptinus spp.

Niptus hololeucus,

Gibbium psylloides,

Tribolium spp.

Tenebrio molitor,

Agriotes spp.

Conoderus spp.

Melolontha melolontha,

Amphimallon solstitialis,

Costelytra zealandica, from the order of the Hymenoptera, for example Diprion spp.,

Hoplocampa spp.

Lasius spp.

Monomorium pharaonis,

Vespa spp., Of the Diptera family, for example

Aedes spp.

Anopheles spp.

Culex spp.

Drosophila melanogaster,

Musca spp.

Fannia spp.

Calliphora erythrocephala,

Lucilia spp.

Chrysomyia spp.

Cuterebra spp.

Gastrophilus spp.

Hyppobosca spp.,

Stomoxys spp.

Oestrus spp.

Hypoderma spp.,

Tabanus spp.

Tannia spp.

Bibio hortulanus,

Oscinella frit,

Phorbia spp.

Pegomyia hyoscyami,

Ceratitis capitata,

Dacus oleae,

Tipula paludosa, from the order of the Siphonaptera, for example

Xenopsylla cheopis,

Ceratophyllus spp., Of the order Arachnida, for example

Scorpio maurus,

Latrodectus mactans, of the familyopteran (Homoptera), such as Aleurodes brassicae,

Bemisia tabaci,

Trialeurodes vaporariorum,

Aphis gossypii,

Brevicoryne brassicae,

Cryptomyzus ribis,

Doralis fabae,

Doralis pomi,

Eriosoma lanigerum,

Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.

Phorodon humuli,

Rhopalosiphum padi,

Empoasca spp.

Euscelis bilobatus,

Nephotettix cincticeps,

Lecanium comi,

Saissetia oleae,

Laodelphax striatellus,

Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp., From the order of the butterflies (Lepidoptera), for example

Pectinophora gossypiella,

Bupalus piniarius,

Cheimatobia brumata, Lithocolletis blancardella, Plutella maculipennis, Hyponomeuta padella,

Malacosoma neustria,

Euproctis chrysorrhoea,

Lymantria spp.

Bucculatrix thurberiella,

Phyllocnistis citrella,

Agrotis spp.

Euxoa spp.

Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp. Tineolla bisselliella, Tinaea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana,

Choristoneura fumiferana,

Clysia ambiguella,

Homona magnanima, Tortrix viridana.

The invention also provides a method of controlling harmful arthropods on plants by applying an effective amount of a compound of formula (I) to the plants or the environment in which they grow.

For arthropod control, the active ingredient is generally applied to sites infested by these pests at a dose of from about 0.005 kg to 15 kg of active ingredient per hectare of treated area, preferably from 0.02 kg / ha to 2 kg / ha. Under ideal conditions, depending on the pest being destroyed, lower doses may also provide adequate protection. In contrast, in adverse weather conditions, in the control of 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 species of pest being destroyed as well as on the type 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 area 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 area with water or left on the surface to flush the soil into the soil. 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, during, after sowing, or before emergence or emergence.

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

The compounds of formula (I) are capable of controlling pests eating parts of the plant remote from the site of application: for example, leaf-eating insects are destroyed by active substances applied to the roots.

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 vines, ornamental plants, park and forest trees. Examples of plants and crops that can be protected by these active substances 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, meadows and fodder crops (such as corn, sorghum and lanterns), plantations (such as tea, coffee, cocoa, banana tree, oil palm, coconut tree, rubber tree, pepper), orchards and groves (for example, with stone and peach, citrus, kiwi, avocado, mango, olives and walnuts), 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 lumber (standing timber, harvested timber, sawn timber, stored timber, timber) against attack by sawdust [e.g. Urocerus] or beetles (e.g. Scolytidae), Platypodidae (heart corals), Lyctidae, Bostrychidae, Cerambycidae or Anobiidae] or by termites [such as Reticulitermcs spp., Heterotermes spp. or Coptotermes].

The compounds of the invention may further be used to protect stored products such as grain, fruit, nuts, spices and tobacco, whether unprocessed, ground or processed into various products, against attack by seas, beetles, mites and weevils (Sitophilus granarius). Animal products such as leather, hair, hair and bristles, wool and feathers in natural or processed form (such as carpets or textile products) may also be protected against attack by seas and beetles, and stored meat and fish against beetle, mite attack and flies.

The compounds of formula (I) are particularly suitable for the control of arthropods spreading or transmitting diseases to humans and animals, for example the control of said pests and in particular to the control of ticks, moths, lice, fleas, mosquitoes and midges, troublesome and disease-carrying flies. The compounds of formula (I) are particularly useful for controlling arthropods which feed on or in the skin or sucking blood of said 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 to protect stored products, household equipment and generally accessible areas and facilities may alternatively also be used for application to growing crop plants and to the places where they grow and as seed dressings.

Suitable methods of administering the compounds of formula (I) include:

- in the case of persons or animals infected or exposed to arthropod infections, topical application of a composition containing an active substance having an immediate and / or delayed action against arthropods, such as watering, spraying, bathing, soaking, dusting, ointment, shampoo, cream and wax preparations;

- in the vicinity of general or specific places where pests may be hidden, including stored products, wood and timber, household and industrial and industrial buildings and rooms, application by spraying, fogging, dusting, smoky, waxing, painting, granulate or bait , dosing into waterways, wells, reservoirs and other running or standing water;

- domestic animals in feedingstuffs for the control of larvae, flies in their feces;

- for growing plants, foliar application in the form of spray, dust, granulate, mist and foam;

- generally in the form of suspensions of finely divided and encapsulated compounds of the general formula (I), for the treatment of soil or roots in the form of liquid grouts, dusts, granules, smoke and foam, and

- for pickling seed in the form of liquid or powdered preparations.

The compounds of formula (I) may be applied for arthropod control in the form of any type of art known in the art as suitable for the internal or external application of vertebrates or for arthropod control in rooms or even in open spaces containing at least one active ingredient a compound of formula (I) in combination with one or more compatible diluents or excipients suitable for the intended use of the composition. All of these compositions can be prepared by any method known in the art.

Compositions suitable for administration to vertebrates or humans include those suitable for oral, parenteral, percutaneous or topical administration.

Oral compositions contain one or more compounds of Formula (I) in combination with pharmaceutically acceptable carriers or excipients and / or finished coatings and are prepared, for example, in the form of tablets, pills, paste capsules, gels, dressings, premedicated food. and feed, premedicated drinking water, premedicated feed supplements, slow release boluses or other slow release forms of the active ingredient intended to remain in the gastrointestinal tract. All of these forms may contain the active ingredient in microcapsules or coated with coatings that are unstable in either an acidic or basic environment, or other pharmaceutically acceptable coatings. It is also possible to use feed premixes and concentrates containing the compounds according to the invention, in particular for the preparation of pre-medicated feed, drinking water or other materials intended for animal consumption.

Formulations for parenteral administration include solutions, emulsions or suspensions of the active ingredient in any pharmaceutically acceptable vehicle and solid or semi-solid subcutaneous implants or pellets intended for sustained sustained release of the active ingredient. These preparations can be prepared and sterilized by any suitable method known in the art.

Formulations for percutaneous and topical application include sprays, dusts, infusions, baths, lotions, ointments, shampoos, creams or waxes, and optional devices (e.g. ear tags) attached to the animals to allow an overview of the local or systemic application of the formulations to destruction of arthropods.

Solid or liquid bait compositions suitable for killing arthropods consist of one or more compounds of formula (I) and a carrier or diluent which may contain edible material or other substance that causes the arthropod to consume the composition.

In practice in agriculture, the compounds of the invention are rarely used alone, but most often form part of the respective compositions. These compositions, which can be used as insecticidal agents, contain as active ingredient the compound of the invention described above, in combination with agriculturally acceptable solid or liquid carriers and surfactants, also suitable for use in agriculture. Conventional inert carriers and conventional surfactants are used for this purpose. Said compositions form part of the invention.

These compositions may also contain all kinds of other ingredients such as protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, spray oils (especially in acaricidal applications), stabilizers, preservatives (especially fungal preservatives), complexing agents and the like. etc. as well as other known active substances having pesticidal properties (in particular insecticides or fungicides) or plant growth regulators. Generally speaking, the compounds used in the context of the invention can be combined with any solid or liquid additives customary in the field of pesticide compositions.

The dosage of the compounds used according to the invention can be varied within wide ranges, in particular depending on the type of pest being destroyed and the degree of infestation of the crops by these pests.

The compositions of the invention typically contain about 0.05 to 95% (by weight) of one or more active ingredients of the invention, about 1 to 95% of one or more solid or liquid carriers, and optionally

0.1 to 50% of one or more surfactants.

In accordance with what has been said herein, the compounds of the invention are generally combined with carriers and optionally surfactants.

As used herein, the term carrier refers to an organic or inorganic, natural or synthetic material with which the active ingredient is combined to facilitate its application to the plant, seeds or soil. Thus, this carrier is generally inert and must be usable in agriculture, especially as regards the plant to be treated. The carrier may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid mineral fertilizers such as ammonium salts and crushed natural minerals such as kaolins, talc, chalk, quartz, atapulgite, monmorillonite, bentonite or diatomaceous earth, as well as crushed synthetic minerals such as diatomaceous earth, alumina and silicates, in particular aluminum or magnesium silicates). As solid carriers for preparing granules! for example, crushed and fractionated natural rocks such as limestone, marble, pumice, sepia and dolomite, as well as synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stems, are further suitable diatomaceous earth, maize husks, calcium phosphate, powdered cork, carbon black, activated carbon, water soluble polymers, resins, waxes and solid mineral fertilizers. These solid compositions may optionally contain one or more compatible wetting, dispersing, emulsifying or coloring agents which, if solid, may serve as the diluents. The carrier may also be liquid and in this regard, alcohols, especially butanol or glycol, as well as ethers or esters thereof, especially methylene glycol acetate, ketones, especially acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone and isophorone, petroleum fractions, paraffinic or aromatic hydrocarbons , in particular xylenes or alkylnaphthalenes, mineral and vegetable oils, aliphatic chlorinated hydrocarbons, in particular trichloroethane or methylene chloride, or aromatic chlorinated hydrocarbons, in particular chlorobenzenes, water-soluble or strongly polar solvents, such as dimethylformamide, dimethylsulfide or N-methylpyrrolidone, N-methylpyrrolidone or N-methylpyrrolidone; gases and the like, as well as mixtures thereof.

The surfactant may be an emulsifier, dispersant or wetting agent of the ionic or non-ionic type, or a mixture of such surfactants. In this regard, mention may be made, for example, of polyacrylic acid salts, lignosulfonic acid salts, phenolsulfonic or naphthalenesulfonic acid salts, polycondensates of ethylene oxide with fatty alcohols, fatty acids or fatty acid esters or amines, substituted phenols (especially alkylphenols or sulphophenols), ester salts of esters. , taurine derivatives (especially alkyl taurates), esters of alcohols or polycondensates of ethylene oxide with phenols with phosphoric acid, esters of fatty acids with polyols and sulfates, sulfonates and phosphates of said compounds. The presence of at least one surfactant is generally necessary when the active ingredient and / or the inert carrier are poorly water-soluble or not water-soluble at all, water being the carrier of the respective dosage form.

The compositions of the invention may contain various other ingredients such as adhesives and colorants. Adhesives such as carboxymethylcellulose and natural or synthetic polymers in the form of powders, granules or latexes such as acacia, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids may be used in the preparation of the compositions. Other additives may be mineral and vegetable oils. Further, dyes such as inorganic pigments, for example iron oxides, titanium oxide and Berlin blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, as well as trace elements in the form of, for example, iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Compositions containing compounds of formula (I) which can be applied to kill arthropods, nematodes harmful to plants, helminths or protozoa may also contain synergistic additives (e.g., piperonyl butoxide or sesamex), stabilizers, other insecticides, acaricides, nematicides, anthelminticides or anticelminticides. agents, fungicides (whether for agricultural or veterinary use, such as benomyl or iprodione), bactericides, attractants or repellents for arthropods or vertebrates or pheromones, deodorants, flavoring agents, coloring agents and auxiliary therapeutic agents such as trace elements. These additives may improve the efficacy of the composition, its persistence on the treated surface, the safety, absorption or spectrum of action, or allow the composition to perform other useful functions in a single treatment of an animal or a certain area.

Examples of other pesticidally active compounds that may be present in the compositions of the invention or which may be used in conjunction with the compositions of the invention include acephat, chlorpyrifos, demetone S-methyl, disulfotone, ethoprophos, phenitrothion, malathion, monocrotophos, parathion, phosalone, pirimiphos-methyl, triazophos, cyfluthrin, cypermethrin, deitamethrin, fenpropathrin, fenvalerate, permethrin, aldicarb, carbosulfate, methomyl, oxamyl, pirimicarb, bendiocarb, teflubenzuron, dicofol, tetapol, endosulfan, cartos, invermectin, milbemycins, thiophanate, trichlorfom, dichlorvos, diaveridine and dimetriadazole.

Thus, for agricultural applications, the compounds of formula (I) are generally used in the form of compositions having various solid or liquid forms. Liquid compositions may be used to treat substrates or sites infested or exposed to arthropod infestations, including buildings, exterior or interior storage or production areas, containers or equipment, and still or flowing waters.

Solid homogeneous or heterogeneous formulations containing one or more compounds of formula (I), for example granules, pellets, briquettes or capsules, can be used for long-term treatment of standing or running water. A similar effect can be achieved by continuous or discontinuous dosing of the water-dispersible concentrates described above.

Formulations in the form of aerosols and aqueous or non-aqueous solutions or dispersions suitable for normal spray application, spray application or spray application using low and ultra low volumes can also be used.

Solid forms of the compositions according to the invention include dusts in which the active compound of the formula I can be up to 80%, or wettable powders or granules, in particular granules obtained by extrusion, compression, impregnation of a granular carrier or granulation of a powder formulation. the active compound of formula (I) in these wettable powders or granules being between 0.5 and 80%.

Formulations which are liquid or intended for the preparation of liquid dosage forms include solutions, in particular emulsifiable concentrates, emulsions, suspension concentrates, aerosols, wettable powders (or spray powders), dry suspension concentrates and pastes.

Emulsifiable or soluble concentrates usually contain 5 to 80% active ingredient, while the emulsion or solution suitable for application contains 0.01 to 20% active ingredient. In addition to the solvent, the emulsifiable concentrates may optionally contain 2 to 50% of suitable additives such as stabilizers, surfactants, penetration agents, corrosion inhibitors, dyes or adhesives.

From these concentrates, it is possible to dilute with water to obtain emulsions of any desired concentration of active ingredient, particularly suitable for application to plants.

Concentrated sprayable suspensions are formulated to form a stable, non-settling liquid product (finely divided) and usually contain 10 to 75% active ingredient, 0.5 to 30% surfactants, 0 1 to 10% of thixotropic agents, 0 to 30% of suitable additives such as anti-foaming agents, corrosion inhibitors, stabilizers, penetrating agents, adhesives and as a carrier a water or organic liquid in which the active ingredient is poorly soluble or not at all soluble. Certain organic solids or inorganic salts may be dissolved in the carrier, preventing additives from settling solids or preventing the freezing of water.

Wettable powders (or spray powders) are usually formulated to contain 10 to 80% active ingredient and, in addition to the solid carrier, usually contain 0 to 5% wetting agent, 3 to 10% dispersant and, if necessary, 0 to 80% one or more stabilizers; and / or other additives such as penetration agents, adhesives, anti-caking agents, dyes and the like.

For the preparation of these wettable powders, the active substance or substances are intimately mixed in suitable mixing devices with other components which may be impregnated with the porous carrier, and the mixture is ground in mills or other suitable devices of this kind. In this way, wettable powders are obtained with advantageous wettability and suspensibility. These powders can be suspended in water to form a suspension of any desired concentration, and this suspension can be very advantageously used, especially for application to plant leaves.

The water dispersible granules (granules that readily disperse in water) have a composition very close to that of wettable powders. These granules can be prepared by granulating the formulations described for wettable powders either in a wet way (the finely divided active ingredient is mixed with an inert filler and a small amount of water, for example 1 to 20% water, or with an aqueous dispersant or filler solution; dried and sieved) or dry (compression followed by crushing and sieving).

As already described, aqueous dispersions and emulsions, for example compositions obtained by diluting a wettable powder or emulsifiable concentrate of the invention with water, are within the scope of the present invention. The resulting emulsions may be of the water-in-oil or oil-in-water type and may also have a thick consistency.

All of these aqueous dispersions or emulsions or spray mixtures can be applied to crops

In any suitable manner, in particular by spraying, in doses ranging generally from 100 to 1200 liters of spray mixture per hectare.

The compounds and compositions according to the invention are expediently applied to vegetation and in particular to the roots or leaves of plants on which the pest is destroyed.

A further method of application to the compounds or compositions of the present invention is to incorporate the compounds or compositions into irrigation water. Irrigation may be by spraying (in the case of pesticides suitable for foliar application) or by irrigation or under-irrigation in the case of systemic pesticides. The application rate of active compound is generally between 0.1 and 10 kg / ha, preferably between 0.5 and 4 kg / ha. The dosage and concentration employed may vary depending upon the method of administration and the nature of the active ingredient employed.

In general, the compositions applied for the purpose of destroying arthropods, nematodes harmful to plants, helminths or protozoa usually comprise from 0.00001 to 95%, in particular from 0.0005 to 50% by weight. one or more compounds of formula (I) or all active ingredients (i.e. compounds or compounds of formula (I) together with other arthropod and nematode toxicants, anthelmintics, anticoccidially active agents, synergists, trace elements or stabilizers). The particular type of formulation and the particular application rates are chosen by the farmers themselves, whether in crop or livestock production, physicians or veterinarians, pest control staff and other professionals to achieve the desired effect (s). Solid and liquid compositions intended for topical application to wood, animals, stored products or household equipment usually contain 0.00005 to 90%, in particular 0.001 to 10% by weight. one or more compounds of formula (I). Solid and liquid compositions intended for oral or parenteral (including percutaneous) administration to animals normally contain from 0.1 to 90 wt. one or more compounds of formula (I). Pre-medicated feeds normally contain from 0.001 to 3 wt. one or more compounds of formula (I). Concentrates and feed supplements intended for mixing with feed normally contain from 5 to 90%, preferably from 5 to 50% by weight. one or more compounds of formula (I). Salt licks normally contain from 0.1 to 10 wt. one or more compounds of formula (I).

Dusts and liquid compositions intended for application to cattle, persons, objects and equipment, buildings and exterior areas may contain 0.0001 to 15%, in particular 0.005 to 2.0% by weight. one or more compounds of formula (I). Suitable concentrations of one or more compounds of formula (I) in the water to be treated are between 0.0001 and 20 ppm, in particular from 0.001 to 5.0 ppm, and such concentrations may also be used therapeutically in fish farming (over a given period of time). The edible baits may contain from 0.01 to 5%, preferably from 0.01 to 1.0% by weight. one or more compounds of formula (I).

For parenteral, oral, percutaneous or other administration to vertebrate, the dosage of the compounds of formula (I) depends on the species, age and state of health of the vertebrate, as well as on the nature and degree of actual or potential infestation by harmful arthropods, helmets or elements. For prolonged medication by oral or parenteral administration, single doses of from 0.1 to 100 mg, preferably 2.0 to 20.0 mg / kg of animal body weight or daily doses of 0.01 to 20.0 mg are generally suitable, preferably 0.1 to 5.0 mg / kg body weight of the animal. When using sustained release formulations or devices, the doses required for a period of several months can be combined and administered to the animals on a single occasion.

The agrochemical compositions containing the compounds of the invention as active ingredients, and the insecticidal and acaricidal applications and properties of representative compounds and compositions of the invention are illustrated by the following examples.

The following Examples 23 to 28 illustrate compositions useful for killing arthropods, in particular insects and spiders, nematodes, helminths or protozoa, containing as active compounds compounds of formula (I), in particular some of the compounds described in Examples 1 to 22 and Tables 3 and 4. All of the compositions described in Examples 23-28 can be diluted with water to formulations containing the active ingredients in concentrations suitable for the particular application. The percentages given in Examples 23 to 28 are percentages by weight. The auxiliary preparations, designated by trade names, have the following chemical composition:

Ethylan BCP condensation product of nonylphenol with ethylene oxide Soprophor BSU condensation product of tristyrylphenol with ethylene oxide Arylan CA 70% (w / v) calcium dodecylbenzenesulfonate solution Solvesso 150 light aromatic solvent (C _lo ) Arylan S sodium dodecylbenzenesulfonate Darvan sodium lignosulfonate Celite PF a synthetic carrier based on magnesium silicate Soprophon T36 polycarboxylic acid sodium salt Rhodigel 23 xanthan Bentone 38 an organic derivative of magnesium montmorillonite Aerosil very fine silica Example 23 A water-soluble concentrate is prepared from the following ingredients: active substance 7% Ethylan BCP 10% N-methylpyrrolidone 83%

Ethyl BCP is dissolved in a portion of N-methylpyrrolidone, the active ingredient is added and the mixture is heated with stirring until all solid components are completely dissolved. The resulting solution is then adjusted to the desired volume by adding the remainder of the solvent.

Example 24

An emulsifiable concentrate is prepared from the following ingredients:

active substance 7%

Soprophor BSU

Arylan CA 4%

N-methylpyrrolidone 50%

Solvesso 150 35%

Soprophor BSU, Arylan CA and the active substance are dissolved in N-methylpyrrolidone and the solution is made up to volume with the addition of Solvesso 150.

Example 25

A wettable powder is prepared from the following ingredients:

active substance 40% Arylan S 2% Darvan č. 2 5% Celite PF 53%

The components are mixed and blended and ground in a hammer mill to particles below 50 µm.

Example 26

An aqueous suspension is prepared from the following ingredients

concentrate: active substance 40,05% Ethylan BCP 1.00% Sopropon T36 0.20% ethylene glycol 5,00% Rhodigel 23 0,15% Water 53,69%

The components are mixed thoroughly and the mixture is ground in a ball mill until the mean particle size is less than 3 µm.

Example 27

An emulsifiable suspension concentrate is prepared from the following ingredients:

active substance 30.0%

Ethylan BCP 10.0%

Bentone 38 0.5%

Solvesso 150 59.5%

The components are mixed thoroughly and the mixture is ground in a ball mill until the mean particle size is less than 3 µm.

Example 28

The following components are prepared by dispersing water in water.

wearable granules: active substance 30% Darvan č.2 15% Arylan S 8% Celite PF 47%

The components are mixed, the mixture is ground in a fluid mill and then granulated while sprinkling with sufficient water (up to 10% w / v) in a rotary pelletizer. The resulting granulate is then freed of excess water by air-drying.

Example 29

By thoroughly mixing the following ingredients, a dust can be prepared: active ingredient 1 to 10% very fine talc 99 to 90%

The dusts can be applied to sites infested with arthropods, such as garbage dumps or landfills, stored products or household equipment, or can be administered orally to animals infested or exposed to arthropod infestations. Suitable means of distributing the dust to the area contaminated by arthropods are, for example, hand or mechanical dusters or suitable devices that the cattle itself operate.

Example 30

By thoroughly mixing the above ingredients it is possible to prepare edible bait:

active substance wheat flour molasses

0.1 to 1.0% 80.0%

19.9 to 19.0%

The edible bait may be distributed in suitable locations, such as homes and industrial buildings, in kitchens and hospital warehouses, or outside buildings where arthropods are infested, such as ants, locusts, cockroaches and flies, to eradicate those pests who bait eat.

Example 31

The following ingredients can be prepared: Active ingredient 15% dimethylsulfoxide 85%

The pyrrole derivative is dissolved in a portion of dimethylsulfoxide and adjusted to the desired volume by addition of additional dimethylsulfoxide. The resulting solution can be applied to pets infested by arthropods percutaneously by watering or, after sterilization by filtration through a 0.22 µm polytetrafluoroethylene membrane, by parenteral injection at a dose of 1.2 to 12 ml solution per 100 kg animal body weight.

Example 32

The following ingredients may be wettable

powder: active substance 50% Ethylan BCP (9 mol ethylene oxide) per mole of phenol) 5% Aerosil 5% Celite PF 40%

Ethylan BCP is absorbed onto Aerosil, mixed with the other ingredients and ground in a hammer mill. The wettable powder obtained may be diluted with water to a concentration of active compound of 0.001 to 2% (w / v) and sprayed on a place infested with arthropods, for example double-winged or nematode larvae, or sprayed either in the form of a bath for pets contaminated or at risk infestation by arthropods, helminths or protozoa, or may be administered orally to animals in drinking water to destroy arthropods, helminths or protozoa.

Example 33

A slow release drug bolus can be prepared from a granulate comprising a thickener, a binder, a slow release agent, and an active ingredient prepared by the procedure of Example 27. By pressing the mixture, it is possible to produce a bolus with a density of 2 or more and then to apply it orally to ruminants. The bolus is trapped in the cap or rumen area and over a long period of time the pyrrole derivative of the invention is continuously slowly released therefrom, controlling the infestation of domestic ruminants by arthropods, helminths or elements.

Example 34

From the following ingredients, a slow release formulation can be prepared: active ingredient 0.5 to 25% polyvinyl chloride base 75 to 99.5%

The polyvinyl chloride base is mixed with the active ingredient and a suitable plasticizer, for example dioctyl phthalate, and suitable forms, such as granules, pellets, briquettes or strips, are suitable for dispensing into stagnant water or in the case of strips , for processing into collars or ear tags for pets. All these slow release forms can be used to control harmful insects.

Similar compositions to those mentioned above can be prepared by substituting the active compound mentioned in the respective examples with an appropriate amount of any other compound of formula (I).

In the following Examples 35 to 47, the compounds of the invention are applied at various concentrations. The application of a solution, suspension or emulsion with an active substance concentration of 1 ppm per leaf corresponds approximately to an application rate of 1 g of active substance per hectare, with a spray volume of 1000 liters per hectare (application to run-off). Subsequent application to the leaf using a concentration of about 6.25 to 500 ppm corresponds to about a dose of 6 to 500 g / ha. When applied to soil, a concentration of 1 ppm, assuming a soil depth of 7.5 cm, corresponds to field application at a rate of approximately 1000 g / ha.

Example 35

Effectiveness against aphids

A mixture is prepared from the following components.

0.01 g of active ingredient

0.16 g of dimethylformamide

0.838 g of acetone

0.002 g of a surfactant mixture comprising, on the one hand, an alkylatyl polyether alcohol and, on the other hand, an alkylaryl polyether alcohol carrying 98.99 g of water on the aryl radical of the sulfo group.

This diluted aqueous mixture is sprayed with cress plants grown in flower pots on which adults and nymphs of the aphid Aphis nasturtii are present. The number of aphids in each pot is between 100 and 150. Spraying is carried out using a volume sufficient to moisten the treated plants until run-off. After spraying, the pots were kept at 20 ° C for 1 day, after which the number of live aphids was determined. 100% mortality was found when the compounds of the invention were administered at 100 ppm:

Example compounds 1, 2, 3A, 4, 5, 16C, 17, 18, 19 and 20 and DAP no. 12, 24, 33, 34, 38, 39, 42, 44, 45, 54, 57, 60, 62, 98-100, 102-104, 125, 128, 130, 131, 135, 137, 141, 142, 144, 157, 158, 162, 165, 166, and 174.

Example 36

Effectiveness against mites

The composition is prepared in a manner analogous to that of Example 35, and is also applied. In this case, however, 150 to 200 specimens of the mites (Tetranychus urticae) are infested with the bean test plant. After spraying, the test plants are kept at 30 ° C for 5 days. 100% mortality was found with the compounds of the present invention at a concentration of 100 ppm:

Example compounds 2, 3A, 16C, 17 and 18 and DAP no. 9, 20, 25, 41, 44, 46, 52, 53, 58, 59, 63, 64, 70, 74, 77-81, 83.90, 98, 99, 102, 124 and 141.

Examples 37-39

Efficacy against Spodoptera eridania

Example 37

An analogous composition to that used in Example 35 is used. Experimental insects are the 2nd instar of Spodoptera eriania found on bean (Sieva) plants approximately 15 cm high. After 5 days the following mortality rates were found:

100% mortality for the compounds of Examples no. 3A, 3B, 5, 6, 7, 8, 9, 11, 12, 15B, 16C, 17, 18, 20, 21B, and 21C and DAP NO. 42, 44, 60, 62, 64, 98-100, 102, 103, 121, 124, 125, 131, 141, 142, 144, 162, 166 and 174, applied at 100 ppm and% mortality for the compound of Example no. 13, applied at a concentration of 500 ppm.

Example 38

The formulation and application thereof are carried out in the same manner as in Example 35, but the formulation is prepared from the following ingredients:

2.5 mg of the active substance

0.05 g of dimethylformamide

9.9228 g of acetone

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

In the application of the compound of Example 1, 4 at 25 ppm in Spodoptera eridania larvae, 100% mortality was found.

Example 39

The formulation and application thereof are carried out in the same manner as in Example 38, but the formulation is prepared from the following ingredients:

0.625 mg of active substance

12.5 mg of dimethylformamide

9.9621 g acetone

0.0247 g surfactant (as in Example 35) g water

When applying the compounds of Examples no. 1 and 2 at a concentration of 6.25 ppm, 100% mortality was found in Spodoptera eridania larvae.

Examples 40-43

Efficacy against Epilachna varivestis

Example 40

The formulation is prepared in the same manner as in Example 37, but using the following ingredients:

12.5 mg of the active substance

0.25 g of dimethylformamide

9.726 g of acetone

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

The larvae of Epilachna varivestis (2.instar) found on bean plants (Sieva) with a height of approximately 15 cm are used as test insects. After 5 days, 100% mortality was found when using the compound of Example 13 applied at 125 ppm.

Example 41

The formulation is prepared in the same manner as in Example 38, but using the compound of Example 1. 8 as an active ingredient which is applied at a concentration of 25 ppm. 100% mortality of Epilachna varivestis was found.

Example 42

The formulation is prepared in the same manner as in Example 35, but using the non-brominated compound of Example 1. 15A as an active ingredient which is applied at a concentration of 100 ppm. 100% mortality of Epilachna varivestis was found.

Example 43

The formulation is prepared in the same manner as in Example 40, but from the following ingredients: 10 mg of active ingredient 0.2 g of dimethylformamide 9.7657 g of acetone

0.0243 g of a surfactant (as in Example 35) 90 g of water

The following mortality percentages for Epilachna varivestis were found:

% mortality in the case of the compounds of the examples. 15A and 15B, applied at a concentration of 100 ppm; and

100% mortality in the case of the compounds of Examples no. 1,2, 9, 17, 18 and DAP no. 42, 44, 60, 62, 64, 98, 99, 124, 125, 141, 142 and 144, applied at 100 ppm.

Examples 44-46

Effectiveness against housefly

The active ingredient in the form of 10 ml of a sugar aqueous solution containing 10% (w / w) sugar and 100 ppm of the active ingredient is processed in analogy to Example 35 to form the corresponding formulation, which is then further diluted as necessary. The following three different preparations were prepared for the test.

component example no.

44 45 46 active substance (mg) 10 10 1.25 Dimethylformamide (mg) 160 200 25 surfactant (as in Example 35) (mg) 2.15 24.3 14.25 acetone (g) 8.42 9.766 5.73 Water (g) 88.99 81 84,38 Sugar (s) 10 9 9.84

adult individuals of house flies (Musca domestica) are anesthetized with carbon dioxide and transferred to a container containing the bait composition containing the active ingredient. After 1 day at 27 ° C, the mortality of the flies was determined. The results are as follows:

Examples 44: 100% mortality in the case of the compounds of Examples no. 1,2, 3B, 4-6, 8, 9, 16C, 17-20, 21B and 21C and DAP no. 42, 44, 60, 62, 64, 98, 99, 100, 102, 103, 121, 124, 125, 131, 141, 142, 144,

162, 166 and 174, applied at 100 ppm. Example 45: 100% mortality for Example No. 12, applied at a concentration of 100 ppm.

Example 46: 100% mortality for the compounds of Examples no. 1, 2 and 5, applied at a concentration of 12.5 ppm.

Example 47

Efficacy against Diabrotica undecimpunctata

The corresponding formulation is prepared in a similar manner to Example 35 except that only 48.99 g of water is used, so that the initial active compound concentration is 200 ppm. In the test described above, the appropriate proportions are taken from the formulation and used directly so as to always achieve the desired concentration in ppm.

An appropriate volume of the composition containing 200 ppm of active ingredient (to achieve the desired final concentration of the test substance in the soil), 3.2 mL of water and five pre-germinated key maize plants are placed in a container containing 60 g of sandy loam soil. Shake the contents of the flask thoroughly to distribute the test composition evenly, then pore the well in the soil, in which 20 Diabrotica undecimpunctata eggs are placed, followed by 1 ml of vermiculite and 1.7 ml of water. In a similar manner, a control experiment was prepared using an equal amount of a mixture of water, acetone, dimethylformamide and an emulsifier containing no test compound. Next, an active control experiment is prepared using a commercial technical compound formulated into the same formulation as the standard. After 7 days, the number of live larvae of Diabrotica undecimpunctata is determined as usual.

The described compounds, present in the soil at concentrations of 1.45, 0.72 and 0.36 ppm, exhibited 100% overall activity: the compounds of Examples No. 1 and 3 were found to be 100% effective. 3B, 4 and 17-19 and DAP no. 98, 99, 101, 105, 113, 119, 121, 124, 125, 130 and 173.

Claims (8)

PATENT CLAIMS Pyrrole derivatives of general formula (I) ( ¹ ). Y in which X represents a halogen atom, a thiocyanato group, an alkyl thio group, an alkylsulfonyl group, an alkylsulfonyl group, a haloalkylthio group, a haloalkylsulfinyl group or a haloalkylsulfonyl group in which the alkyl and haloalkyl moieties have straight or branched carbon atoms containing from 1 to 4 carbon atoms; a number of the same or different halogen atoms from monosubstitution to complete polysubstitution, or is cyano, R ¹ is hydrogen, halogen, alkylthio, alkylsulfinyl, alkylsulfonyl, amino, alkylcarbonylamino, haloalkylcarbonylamino or alkyltioalkylidéniminoskupinu, wherein the alkyl and haloalkyl moieties are straight or branched chains containing 1 to 4 carbon atoms, and all of said groups substituted with halo include a 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, and alkoxy moieties are linear or branched chain of 1 to 4 carbon atoms, haloalkyl groups containing one or more identical or different halogen atoms from monosubstitution to full 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, a haloalkyl moiety contains one or several identical or different halogen atoms from mono-substitution to complete poly substitution, with at most one of R ¹ , R ² and R ³ being selected from the group consisting of amino and defined alkylcarbonylamino, haloalkylcarbonylamino, alkoxycarbonylamino bis (alkylthio) alkylidio (alkylthio) alkylidio 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 wherein X is a halogen atom or a radical of formula R ⁵ S (O) _n> wherein n is 0, 1 or 2 and R ⁵ represents an alkyl or haloalkyl group as defined, R ¹ and R ³ represent hydrogen atoms and R ² means cyano, 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 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, provided that at most two of R ¹ , R ² and R ³ are selected from the group consisting of hydrogen and defined alkyl groups, when X ⁴ and X ¹ are hydrogen and X represents a halogen atom, then R ² is different from X and at least one of X, R ¹ , R ² and R ³ are different from those remaining, 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 ² are hydrogen and compounds wherein X ¹ , X ² , X ³ , X ⁴ , R ¹ and R ² represents a hydrogen atom, X represents a cyano group, R ³ represents an amino group and Y represents a chlorine atom. Derivatives according to claim 1 of the general formula (I), in which 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 = 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 is hydrogen, halogen or a linear or branched alkylthio group having 1 to 4 carbon atoms, R ² is cyano, R ³ is 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. Derivatives according to claim 1 of the general formula (II) Y in which X is R ⁵ S (O) _n in which n is 0, 1 or 2 and R ⁵ is methyl, trifluoromethyl, difluoromethyl, fluorodichloromethyl, difluoromethyl, difluoromethyl, dichloromethyl, or fluorochloromethyl; ² is cyano, R ¹ is H, F, Cl, Br, R ³ is H, F, Cl, Br, X is H or Cl and Y is trifluoromethyl or trifluoromethoxy. 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- (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-trifluoromethylphenyl) -2-bromo-3-cyano -4- (dichloromethylsulfonyl) 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- 4-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- (dichlorofluoromethyl sulfmyljpyrol. 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-437 SK 278926 Β6 - (brómdifluórmetylsulfonyl) pyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (methylsulfinyl) pyrrole or 1- (2,6-Dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (methylsulfonyl) -pyrrole. 5. A compound 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-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- (dichlorofluoromethylsulfinyl) pyrrole, 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichlorofluoromethylsulfonyl) pyrrole 1- (4-bromo-2,6-dichlorophenyl) -3 -cyano-4- (dichlorofluoromethylthiopyrrole), 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- (trifluoromethylthio) pyrrole, 1- (2 4,6-dichlorophenyl) -3-cyano-4- (difluoromethylthio) 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-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- (chlorodifluoromethylsulfonyl) 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- (dichlórfluómetyltiojpyrol, 6. A compound according to 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-cyano-4- (trifluoromethylthio) pyrrole . 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-bromo-3-trifluoromethylthio-4-cyano-5-chloropyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -2 - [(trifluoromethyl) carbonylamino] -3-trifluoromethylthio-4-cyano-5-chloropyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -2- (methylcarbonylamino) -3-trifluoromethylthio-4-cyano-5-chloropyrrole, 1- (2,6-Dichloro-4-trifluoromethylphenyl) 2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole, 1- (2-chloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano 5-chloropyrrole, 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-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- (dichlórfluórmetyltiojpyrol, 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-4- (dichlorofluoromethylthio) pyrrole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-cyano-4- (dichlorofluoromethylsulfinyl) pyrrole or 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (trifluoromethylsulfonyl) pyrrole. An insecticidal and acaricidal composition, characterized in that it contains, as active principle, derivatives of the general formula (I) according to claim 1 in combination with one or more compatible diluents or carriers. Use of derivatives of general formula (I) according to claim 1 for controlling insects and mites.