PT92521B - PROCESS FOR THE PREPARATION OF PYRROL DERIVATIVES AND INSECTICIDAL COMPOSITIONS CONTAINING THEM - Google Patents

Description

RHÔNE-POULENC AGROCHIMIE

PROCESS FOR THE PREPARATION OF PIRROL DERIVATIVES AND

INSECTICID COMPOSITIONS THAT CONTAIN THEM

BACKGROUND OF THE INVENTION

1. Scope of the Invention

The present invention relates to new compounds from the chemical family of pyrroles, as well as intermediates for the preparation of these compounds and processes for the preparation of these compounds and intermediates. The present invention also relates to the application of these compounds in agriculture, especially as pesticides to control arthropods, preferably as insecticides and as acaricides; the present invention also relates to agrochemical compositions useful for the control of arthropods, especially insects and arachnids.

2. Description of the State of the Existing Art

Many pyrazoles (compounds of the heterocyclic formula containing two nitrogen atoms) are known as insecticides. Also known as insecticides are some compounds that contain the pyrrole group (compounds whose formula contains a nitrogen atom).

/

However, these compounds also normally contain another chemical group in their formula, which is well known for having insecticidal properties per se, such as a pyrethroid group or a carbamate group, or some organo-phosphoric group. Simple substituted pyrrole derivatives have been described as agrochemicals, for example, in British Patent No. 2189242, but for fungicidal use.

SUMMARY OF THE INVENTION

The new pyrrole compounds of the present invention have the general formula (I)

in which:

X can represent a halogen atom or a cyano, cyanate, thiocyanate, halo-alkyl, alkoxy, halofen-alkoxy, alkyl-thio, alkyl-sulfinyl, alkyl-sulfonyl, halogeno-alkyl-thio, halogeno-alkyl-sulfinyl, halogeno-alkyl-sulfonyl, alkenyl-thio, alkenyl-sulfinyl, alkenyl-sulfonyl, halogeno-alkenyl-thio, halogeno-alkenyl-sulfonyl, halofen-alkenyl-sulfonyl, halogeno-alkyl-carbonyl, halogeno-alkyl-thio-carbonyl, phenyl-thio, phenyl-sulfinyl, phenyl-sulfonyl, heteroaryl-thio, heteroaryl-sulfinyl, or heteroaryl / -3 {• 5

-sulfonyl;

the phenyl groups being optionally substituted with halogen atoms, cyano or halo-alkyl groups and the pentagonal or hexagonal monocyclic hetero-aryl groups having one or two hetero atoms such as oxygen, sulfur or nitrogen atoms in any combination and being optionally substituted with halogen atoms or nitro, cyano or halo-alkyl groups; and in which the halogen substitution in all the aforementioned groups is provided by one or more halogen atoms, the same or different, ranging from mono-substitution to complete poly-substitution and in which the alkyl, halo-alkyl, alkenyl groups , halo-alkenyl, alkoxy and halo-alkoxy are straight or branched chain, generally with less than 10 carbon atoms, preferably less than 5 carbon atoms;

R ^, R ₂ and Rg can be chosen from: the same set of substituents described for X; a hydrogen atom; an alkyl group; and a substituent such that no more than one of these symbols (R ^, _R2, Rg) can represent a formyl group, hydroxyimino-alkylidenyl, alkoxyimino-alkyloxy · denilo, azido, amino, alkylamino , dialkyl-amino, aralkyl-amino, amino-carbonyl-amino, alkyl-carbonyl-amino, halogeno-alkyl-carbonyl-amino, aryl-carbonyl-amino, alkyl-sulfonyl-amino, halogeno-alkyl-sulfonyl-amino, alkyl -amino-carbonyl-amino, aryl-amino-carbonyl-amino, benzylidene-imino, alkylidene-imino, alkoxy-alkylidene-imino, dialkyl-amino-alkylidene-imino, bis (alkyl-thio) -methyl, bis (aryl- thio) -methyl, alkyl-thio-alkylideneimino, alkoxy-carbonyl-amino, halo geno-alkoxy-carbonyl-amino, a phenyl group optionally substituted with a halogen atom or a cyano or ha group

7.4logene-alkyl, plus a pentagonal or hexagonal monocyclic hetero-aryl group with one or two heteroatoms, the same or different, such as oxygen, sulfur or nitrogen atoms and optionally substituted with halogen atoms or nitro, cyano or halogen groups alkyl; and wherein the halogen substitution in the aforementioned groups is provided by one or more equal or different halogen atoms, ranging from mono-substitution to complete poly-substitution, with the alkyl, halo-alkyl, alkenyl, halo-alkenyl groups , straight or branched chain alkoxy and halo-alkoxy, generally having less than 10 carbon atoms, preferably less than 5 carbon atoms;

Y can represent a halogen atom or a cyano, alkyl, halo-alkyl, alkoxy, halo-alkoxy, alkyl-sulfinyl-alkyl-sulfonyl, alkyl-thio, halogeno-alkyl-thio, halogeno-alkyl-sulphinyl, halogeno- alkylsulfonyl, alkyl-carbonyl, halo-alkyl-carbonyl, alkenyl (especially allyl), halo-alkenyl (especially halo-allyl), alkynyl (especially propargyl), or halo-alkynyl (especially halo-propargyl); and wherein the halogen substitution in these groups is provided by one or more halogen atoms, the same or different, ranging from mono-substitution to complete poly-substitution, with the alkyl, halo-alkyl, alkenyl, halo-alkenyl groups being, alkynyl, halo-alkynyl, alkoxy and straight or branched chain halo-alkoxy, generally having less than 10 carbon atoms, preferably less than 5 carbon atoms;

or /

-5Y represents a hydrogen atom when:

X represents a halogen atom or a group of the general formula RgS (O) _n in which n represents the integer 0, 1 or 2 and Rg represents an alkyl, halo-alkyl, alkenyl or halo-alkenyl group; and wherein the carbon chain of the alkyl and alkenyl groups and the halogen substitution are as defined above;

R4 and Rg each represent a hydrogen atom; and Rg represents a cyano group;

X ^, Xg, Xg and X ^ have the meaning defined above, for Y, or each represent a hydrogen atom, with the following conditions: at least one of the symbols R ^, Rg and Rg has the meaning defined above for X; if X ^ and X ^ each represent a hydrogen atom and X represents a halogen atom or a cyano group, then Rg is different from X; if X ^ and X ^ each represent a hydrogen atom and Y represents a methyl group, then X does not represent a bromine atom.

More specifically the new pyrrolic compounds of general formula (I) according to the present invention are the following compounds in which:

X can represent a halogen atom or a cyano, cyanate, thiocyanate, halo-alkyl, alkoxy, halo-alkoxy, alkyl-thio, alkyl-sulfinyl, alkyl-sulfonyl, halogeno-alkyl-thio, halogeno-alkyl-sulfinyl, halogeno-alkyl-sulfonyl, halogeno-alkyl-carbonyl, halogeno-alkyl-thio-carbonyl, phenyl-thio, phenyl-sulfinyl, phenyl-sulfonyl, heteroaryl-thio, heteroaryl-sulfinyl, or heteroaryl-sulfonyl; where phenyl groups are optionally ζ

substituted with halogen atoms, cyano or halo-alkyl groups, the heteroaryl groups being monocyclic, pentagonal or hexagonal, with one or two heteroatoms such as oxygen, sulfur or nitrogen atoms in any combination and being optionally substituted with halogen atoms or groups nitro, cyano or halo-alkyl; and in which the halogen substitution in all the aforementioned groups varies from mono-substitution to complete poly-substitution, with the alkyl, halo-alkyl, alkoxy and halo-alkoxy groups, straight or branched chain, generally with less than 10 carbon atoms, preferably less than 5 carbon atoms;

R4, and Rg may have the meaning defined above for X, or each represents a hydrogen atom; an alkyl group; and in such a way that no more than one of these symbols (R ^ R £, Rg) can represent a formyl, hydroxy-imino-alkylidenyl, alkoxy-imino-alkylidenyl, azido, amino, alkyl-amino, dialkyl-amino group, aralkyl-amino, amino-carbonyl-amino, alkyl-carbonyl-amino, halogeno-alkyl-carbonyl-amino, aryl-carbonyl-amino, alkyl-sulfonyl-amino, halogeno-alkyl-sulfonyl-amino, alkyl-amino-carbonyl- amino, aryl-amino-carbonyl-amino, benzylidene-imino, alkylidene-imino, alkoxy-alkylidene-imino, dialkyl-amino-alkylidene-imino, phenyl optionally substituted with halogen atoms or with cyano or halo-alkyl groups, and groups pentagonal or hexagonal monocyclic heteroaryl with one or two heteroatoms, the same or different, such as oxygen, sulfur or nitrogen atoms and optionally substituted with halogen atoms, nitro, cyano or halo-alkyl groups; and where halogen substitution in the groups mentioned above varies from mono-substitution to poly-substitution

complete substitution and in which the alkyl, halo-alkyl, alkoxy and halo-alkoxy groups are straight or branched chain, generally having less than 10 carbon atoms, preferably less than 5 carbon atoms;

Y can represent a halogen atom or a cyano, alkyl, halo-alkyl, alkoxy, halo-alkoxy, alkyl-sulfinyl, alkyl-sulfonyl, alkyl-thio, halogeno-alkyl-thio, halogeno-alkyl-sulfinyl, halogeno- alkylsulfonyl, alkyl-carbonyl, halo-alkyl-carbonyl, alkenyl (especially allyl), halo-alkenyl (especially halo-allyl), alkynyl (especially propargyl) or halo-alkynyl (especially halo-propargyl); and in which the halogen substitution of these groups ranges from mono-substitution to complete poly-substitution, with the alkyl, halo-alkyl, alkoxy and halo-alkoxy groups being straight or branched, generally with less than 10 carbon atoms, preferably less than 5 carbon atoms; and

X ^, Xg> ^ 3 ^and ^ 4 have the meanings previously defined and applying the same conditions as defined before.

The generally preferred compounds of general formula (I) that are of interest as insecticides and as acaricides are compounds of general formula (I) in which:

X represents a halogen atom or a group of the general formula R ₅ S (0) _n in which n represents an integer 0, 1 or 2 and R _g represents an alkyl, halo-alkyl, alkenyl or halo-alkenyl group; R4 represents a hydrogen atom or a halogen atom or an alkylthio group;

Rg represents a cyan group;

Rg represents a hydrogen atom or a halogen atom;

Y represents a hydrogen or halogen atom, a halo-alkyl or halo-alkoxy group with the proviso that Y represents the hydrogen atom as previously defined for the general formula (I); and

X ^, Xg, Xg and X ^ each independently represent a hydrogen or halogen atom, a C ^-Cg alkyl group, C --C - alkoxy group and (C ^-Cg) alkylthio group.

More specifically, the compounds of general formula (I) preferred and of particular interest are as follows:

A) Compounds with high levels of general insecticidal activity

in which:

X represents a group of general formula RS (0), in which n n

represents integer 0, 1 or 2 and Rg represents a group CHg, CFg, CFgCl, CFClg, CFgBr, CHFg, CHClg or CHC1F;

Rg represents one group cyan; ^R 1 represents one atom hydrogen, fluorine, chlorine or bromine; ^R 3 represents one atom hydrogen, fluorine, chlorine or bromine;

represents a hydrogen or chlorine atom; and Y represents a CFg or CFgO group.

Among these compounds, the following are preferred:

1- (2,6-dichloro-4-trifluoro-methyl-phenyl) -2-chloro-3-cyano-4- (trifluoromethyl-thio) -pyrrole;

1- (2,6-dichloro-4-trifluoromethoxy-phenyl) -2-chloro-3-cyano-4- (trifluoromethyl-sulfonyl) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole;

i- (2,6-dichloro-4-trifuoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro

-fluoro-methyl-sulfonyl) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (chlorodi fluoro-methyl-sulfonyl) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4-chloro-fluoromethyl-sulfinyl) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (chloro-difluoromethyl-thio) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (romethyl-sulfinyl) -pyrrole;

i- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (romethyl-sulfonyl) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (chloro-difluoromethyl-thio) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (chloro-difluoromethyl-sulfinyl) -pyrrole;

i- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -5-bromo-pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (chloro-difluoromethyl-sulfonyl) -pyrrole;

1— (2,6-dichloro-4-trifluoromethoxy-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole;

1- (2,6-dichloro-4-trifluoromethoxy-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole;

1- (2-chloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole;

1- (2-chloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole;

1- (2-chloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro

-fluoro-methyl-thio) -5-methyl-thio-pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (bromo-difluoromethyl-thio) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (bromo-difluoromethyl-sulfinyl) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (bromo-difluoromethyl-sulfonyl) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (methylsulfinyl) -pyrrole; or 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (methyl-sulfonyl) -pyrrole.

B) Other compounds, with high insecticidal activity, of the general formula (II) in which:

X represents a group of general formula RS (0), in which n repreU II represents the integer 0, 1 or 2 and R _g represents a group CHg, CFg,

CFgCl or CFC1 ₂ ; Rg represents a cyan group;

R4 represents a hydrogen, fluorine, chlorine or bromine atom or an amino group;

Rg represents a hydrogen, fluorine, chlorine or bromine atom or a CFg or CN group;

X4 represents a hydrogen or chlorine atom; and

Y represents a CFg or CFgO group

Among these compounds, the following are most preferred:

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (trifluoromethyl-sulfonyl) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (trifluoromethyl-sulfinyl) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4-trifluoromethyl-sulfinyl-5-bromo-pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4-trifluoromethyl-sulfonyl-5-bromo-pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (trifluoromethyl-thio) -pyrrole;

-12l- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2- £ ”(trifluoromethyl) -carbonyl-amino_7-3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2- (methyl-carbonyl-amino) -3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole;

1- (2-chloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-dichloro-fluoro-methyl-thio-4-cyano-5-chloro-pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2,4-bis (trifluoromethyl-thio) -3-cyano-5-amino-pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-5-bromo-pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluorome tyl-thio-cyan in -pyrrole;

1- (4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-5-bromo-pyrrole;

1- (2-chloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl

-thio-4-cyano-5-bromo-pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole;

-13- (2,6-dichloro-4-trifluoromethyl-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole;

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole; or 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (trifluoromethyl-sulfonyl) -pyrrole.

C) The compounds of general formula (I), with surprisingly high levels of acaricidal activity, in which:

X represents a halogen atom or a group of the general formula RgS (O) _n in which n represents the integer 0, 1 or 2 and R4 represents an alkyl group, preferably C1 -C4 alkyl; halogeno-alkyl, preferably trihalogeno-methyl in which halogeno represents a fluorine, chlorine or bromine atom or combinations thereof, for example, CFg, CClg, CFgCl, CFCI2 or CFzBr; alkenyl; or halogen-alkenyl; R4 and Rg each represent a hydrogen atom;

Rg represents a cyan group;

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

X ^, Xg, Xg and X ₄ each represent independently a hydrogen atom or halogen atom ; a C ^-Cg alkyl group; C1-Cg alkoxy; and (C1 -Cg) alkylthio; and preferably X ^ and X ^ each represent a hydrogen, fluorine, chlorine or bromine atom or a CHg group and Xg and Xg each represent a hydrogen atom.

Among these compounds, the following are most preferred:

1- (4-bromo-2,6-dichloro-phenyl) -3-cyano-4- (chloro-difluoro-methyl-thio) -pyrrole;

* i- (4-bromo-2,6-dichloro-phenyl) -3-cyano-4- (trifluoromethyl-thio) -pyrrole;

1- (2,4,6-trichloro-phenyl) -3-cyano-4- (chloro-difluoromethyl-thio) -pyrrole;

1- (2,4,6-trichloro-phenyl) -3-cyano-4- (chloro-difluoromethyl-sulfinyl) -pyrrole;

1- (2,4,6-trichloro-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole;

1- (2,4,6-trichloro-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole;

1- (2,4,6-trichloro-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole;

1- (4-bromo-2,6-dichloro-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole;

i- (4-bromo-2,6-dichloro-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole;

1- (4-bromo-2,6-dichloro-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole;

1- (2,4,6-trichloro-phenyl) -3-cyano-4- (trifluoromethyl-thio) -pyrrole;

1- (2,4,6-trichloro-phenyl) -3-cyano-4- (trifluoromethyl-sulfinyl) -pyrrole;

1- (2,4,6-trichloro-phenyl) -3-cyano-4- (trifluoromethyl-sulfonyl) -pyrrole;

1- (2,4,6-trichloro-phenyl) -3-cyano-4- (trifluoromethyl-thio) -pyrrole;

1- (2,4-dichloro-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio)

-pyrrole;

1- (2,4,6-trichloro-phenyl) -3-cyano-4-chloro-pyrrole; 1- (2.4 _I 6-trichloro-phenyl) -3-cyano-4- (chloro-difluoromethyl-sulfonyl) -pyrrole;

1- (2,6-dichloro-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole;

1- (4-bromo-2,6-dichloro-phenyl) -3-cyano-4- (trifluoromethyl-sulfinyl) -pyrrole;

1- (4-bromo-2,6-dichloro-phenyl) -3-cyano-4- (trifluoromethyl-sulfonyl-pyrrole;

1- (4-bromo-2,6-dichloro-phenyl) -3-cyano-4- (chloro-difluoromethyl-sulfinyl) -pyrrole;

1- (4-bromo-2,6-dichloro-phenyl) -3-cyano-4- (chloro-difluoromethyl-sulfonyl) -pyrrole;

1- (4-bromo-2,6-dimethyl-phenyl) -3-cyano-4- (trifluoromethyl-sulfinyl) -pyrrole;

1- (4-bromo-2,6-dimethyl-phenyl) -3-cyano-4- (trifluoromethyl-sulfonyl) -pyrrole; or 1- (4-bromo-2,6-difluoro-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole.

D) Other preferred compounds of general formula (I) are those in which:

represents a hydrogen or halogen atom such as a chlorine or bromine atom;

R ₂ represents a cyano group;

X represents a halogeno-alkylthio group or a halogeno-alkylsulfinyl or halogeno-alkylsulfonyl group, preferably CF ₃ S (0) _n , where n represents the integer 0, i or 2;

-16e are different from a hydrogen atom;

X ₂ and Χ ^ each represent a hydrogen atom; and

Y represents a halo-alkyl or halo-alkoxy group.

It is an object of the present invention to provide new pyrrole family insecticides and acaricides and intermediate compounds for their preparation.

It is another object of the present invention to provide compounds with a very simple chemical formula.

It is another object of the present invention to provide highly active compounds. These and other objects of the present invention are achieved in whole or in part with the new compounds defined below.

DESCRIPTION OF THE PREFERRED ASPECTS

SYNTHESIS METHODS OR PROCESSES

The compounds of general formula (I) can be prepared by applying or adapting known methods (i.e., methods hitherto used or described in the chemical literature); generally, the formation of the pyrrole nucleus, followed whenever necessary by changing the substituents. It should also be understood that in the description of the following processes and methods, the sequences for the introduction of the different groups of the pyrrolic nucleus can be carried out in a different order and that it is possible that suitable protecting groups are necessary, which will be evident to those skilled in the art in the matter. The compounds of general formula (I) can also be converted, by known methods, to other compounds of general formula (I).

/ / -17In the following description of processes and methods, whenever the symbols appearing in the formulas are not specifically defined, it should be understood that they have the meaning defined before, according to the first definition given to each symbol in this specification . The term protection will encompass the conversion to a suitable non-reactive group, which can be reconverted when desired, as well as the addition of groups that make the functionality non-reactive. In the context of process definitions, unless otherwise specified, the term amino refers to the unsubstituted amino group.

The present invention encompasses particular intermediate compounds, useful for the preparation of the compounds now contemplated.

These preferred intermediate compounds, prepared as described now, have the general formula

in which Y represents a hydrogen, chlorine or bromine atom or a CFg or OCFg group and e each represent a hydrogen, chlorine or fluorine atom or a CHg or SCHg group with the following condition: if X ^ and X ^ each represents a hydrogen atom, so Y does not represent a hydrogen or chlorine atom. Those compounds defined with the previous condition are not

vindicated by the present invention, but are still intermediate compounds useful for the preparation of compounds of general formula (I) of the present invention.

The compounds of general formula (IIa) more specifically preferred as intermediates are those in which Y represents a CFg or OCFg group, represents a hydrogen or chlorine atom and represents 0 chlorine atom.

METHOD 1

According to an aspect of the present invention it is possible to prepare the compounds of the general formula (I) in which and R ₂ each represent a hydrogen atom, X represents a cyano group and Rg represents an amino group (NH ₂ ) and X ^, X ₂ , X31 X4 and Y have the meaning defined in the general definition of the present invention, that is, compounds of general formula

can be prepared from diciano-propene derivatives of the general formula

NH-CH = C - CH ₂ - CN CN

Y (IV) (in which the various symbols have the meaning previously defined) by reaction with a basic agent, preferably with a tertiary amine or with an alkali metal hydroxide or carbonate. The reaction is advantageously carried out at a temperature between -80 ° C and 150 ° C, preferably between 40 ° C and 100 ° C. It is possible to use liquid solvents such as alcohols, hydrocarbons, halogenohydrocarbons, ethers, ketones, amides such as N-methyl-pyrrolidone or water.

METHOD 2

According to another aspect of the present invention, it is possible to prepare the compounds of general formula (IV) from an aniline derivative of general formula (V) in which X ^, Xg, Xg, X ^ and Y have the meaning defined in the general definition of the present invention,

NH (V)

-20 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 ° C and 120 ° C, preferably at the reflux temperature.

formyl succinonitrile is a known compound prepared generally by acidifying its alkaline salt which is obtained by reacting succinonitrile with a lower alkyl format in the presence of an alkaline agent, according to K. Gewald,

Z. Chem., 1 (1961), 349.

METQDQ 3

It is possible to prepare the compounds of general formula (I) in which X represents a halogen atom, R ^ represents an amino group, Rg represents a cyano group and Rg represents the hydrogen atom and the other substituents have the meaning defined in the general definition of the present invention, treating compounds of general formula (III) with halogenating agents such as sulfuryl chloride, N-chlorosuccinimide, N-bromo-succinimide, N-iodo-succinimide, pyridinium bromide or fluoride, chlorine perbromide , bromine or molecular iodine. Organic solvents suitable for these transformations include dichloromethane and acetonitrile. The reactions are carried out at a temperature between -80 ° C and + 80 ° C, preferably at a temperature between -30 ° C and + 25 ° C. It may be advantageous to protect the amino group in the trifluoroacetamide derivative during treatment with elemental fluorine.

/ 21-

METHOD 4

A) It is possible to obtain the compounds of general formula (I) in which X represents a cyano group, R ^ represents an amino group,

R ₂ represents a cyano group and Rg represents a hydrogen atom and the other substituents have the meaning defined in the general definition of the present invention, from the corresponding compounds where X represents a group C = NOH by dehydration with agents such as anhydride acetic acid, cyanuric chloride, PgOg ^{and the} like. With some of these dehydrating agents, it may be necessary to protect the amino group with a suitable protecting group.

B) It is possible to obtain the above intermediate compounds in which X represents a C = NOH group by condensing the hydroxylamine with the corresponding compounds in which X represents a formyl group.

C) It is possible to obtain the intermediate compounds in which X represents a formyl group, that is, compounds of the general formula (VI), by hydrolysis of the corresponding compounds in which X represents a bis (alkyl-thio) -methyl or bis (aryl) group -tio) -methyl or by treatment with a suitable alkyl nitrite followed by hydrolysis according to E. Fujita, K. Ichikawa and K. Fuji, Tetrahedron Letters 1978, 3561. The protection of the starch function with an appropriate protecting group may be necessary during the reaction with alkyl nitrites.

D) It is possible to prepare the intermediate compounds of general formula (I) in which X represents a bis (alkyl-thio) -methyl or bis (aryl-thio) -methyl group, and in which the other groups have the meaning defined above, by reaction of a compound of general formula (III) ζ

/

-22 ··· ..

with a tris (alkyl-thio) -methane or tris (aryl-thio) -methane in the presence of a Lewis acid; preferably a sulfonium salt such as dimethyl (methylthio) sulfonium tetrafluoro-borate. The general conditions for these transformations can be found in Synthesis, 1984, 166.

METHOD 5

A) It is possible to prepare useful intermediate compounds of general formula (I) in which X represents a hydroxy group, R ^ represents an optionally protected amino group, R ₂ represents a cyano group, Rg represents a hydrogen atom and X ^, X ₂ , Xg, X ^ and Y have the definitions presented in the general description of the present invention, from the corresponding compounds in which X represents a halogen atom, by conversion to a Grignard reagent or a lithium derivative, using conventional methods, following thereafter treatment with oxo-diperoxy-molybdenum (pyridine) (hexamethyl-phosphoric triamide) (MoOPH) using procedures identical to those described by NJ Lewis et al., in J. Org. Chem., 42, 1977, 1479. In the compound above where X represents a halogen atom it may be necessary to convert the cyano group into an appropriately protected derivative (for example an oxazoline derivative of the corresponding compound in which the cyano group has been hydrolyzed to obtain a carboxylic acid) before the formation of the Grignard reagent or lithium derivative. Alternatively, the Grignard reagent or the lithium derivative described above can be reacted with a trialkyl borate following oxidation with hydrogen peroxide using a procedure analogous to that described by MF Hawthorne, J. Org. Chem. , 22 (1957),

-231001 or R. W. Hoffmann and K. Ditrich, Synthesis, (1983), 107.

B) It is possible to prepare the compounds of general formula (I) in which X represents a cyanate group, R ^ represents an amino group, Rg represents a cyano group, Rg represents a hydrogen atom and X4, Xg, Xg, X4 and Y have the definitions presented in the general description of the present invention, from the corresponding compounds in which X represents a hydroxy group, R4 represents an optionally protected amino group, Rg represents a hydrogen atom and X4, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention, by treatment with cyanogen halides, in the presence of a base, using methods identical to those described by D. Martin and M. Bauer, Org. Synth. 61, 35, followed by a deprotection step, if necessary.

C) It is possible to prepare the compounds of general formula (I) in which X represents an alkoxy group, R4 represents an amino group,

Rg represents a cyano group, R represents a hydrogen atom and X ^, Xg, Xg, X ₄ and Y have 0 meanings given in the definition g ral the present invention, from the corresponding compounds in which X represents a hydroxy group, R ^ represents an optionally protected amino group, Rg represents a hydrogen atom and X ^, Xg, Xg, X ₄ and Y have the meaning given in the general definition of the present invention, by treatment with an alkyl halide, alkyl sulfonates, sulfates dialkyl and the like, optionally in the presence of a base in a solvent such as acetone or dimethylformamide, at a temperature between 25 ° C and the reflux temperature of the solvent, followed by a deprotection step if necessary .

/ '24D) It is possible to prepare the compounds of the general formula (I) in which X represents a halo-alkoxy group, R ^ represents an amino group, R2 represents a cyano group, Rg represents a hydrogen atom and X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention, from the corresponding compounds in which X represents a hydroxy group, R ^ represents an optionally protected amino group, Rg represents a hydrogen atom and X ^, Xg , Xg, X ^ and Y have the meaning presented in the general definition of the present invention, using several halogen-alkylation methods described in Syntheses of Fluoroorganic Compounds, Knunyants, IL and Yakobson, G. G., Ed., Berlin, Springer-Verlag, 1985, pp. 263-269, following a deprotection step if necessary.

METHOD 6

It is possible to prepare the compounds of the general formula (I) in which X represents a haloalkyl group, R4 represents an amino group, Rg represents a cyano group, Rg represents a hydrogen atom and X4, Xg, Xg, X4 and Y have the meaning given in the general definition of the present invention, from the corresponding compounds in which X represents a formyl group, a carboxylic acid function or a halogen atom and in which the amino group is optionally protected. For example, the treatment of formyl compounds with diethylamino sulfur trifluoride, by a process analogous to that described by W. J. Middleton, J. Org. Chem. , 40 (1975), 574, provides compounds of the general formula (I) in which X represents a difluoromethyl group and the other substituents have the previously defined meaning. The oxidation of the aforementioned intermediate compounds of general formula (I) in which X represents

a formyl group, using oxidizing agents such as chromium trioxide in sulfuric acid (Jones reagent) provides intermediate compounds of general formula (I) in which X represents a carboxylic acid function, R ^ represents an amino group, Rg represents a cyano group, Rg represents a hydrogen atom and X X, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention. It may be advantageous to protect the amino function, for example, the trifluoroacetamide derivative, during these oxidation reactions. The reaction of the previous compounds, where X represents a carboxylic acid group, with straight sulfur tetrafluid, as described by G. A. Boswell et al.,

Org. React., 21, (1974), 1-124, provides compounds where X represents a trifluoromethyl group and the other groups have the previously defined meaning.

Alternatively, it is possible to prepare the compounds of the general formula (I) in which X represents a trifluoromethyl group, R ^ represents an amino group, Rg represents a cyano group, Rg represents a hydrogen atom and X ^, Xg, Xg, X ^ and Y have the meaning shown in the general definition of the present invention from compounds of general formula (I) in which X represents a halogen atom, preferably iodine, and the other symbols have the meaning previously defined, by reaction with trifluoromethyl-copper, under conditions identical to those described by DJ Burton and DM Wiemers, J. Am. Chem, Soc., 108 (1986), 832.

METHOD 7

It is possible to obtain the compounds of general formula (I) in which

X represents a bromomethyl or chloromethyl group, represents an amino group, Rg represents a cyano group, Rg represents a hydrogen atom and X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention, by treatment the corresponding intermediate compounds in which X represents a methyl group and in which the amino group is optionally protected, with N-bromo-succionimide or N-chlorosuccinimide in solvents such as carbon tetrachloride at temperatures between 0 ° C and the reflux temperature of the solvent. It is possible to obtain the previous compounds in which X represents a methyl group, from the intermediate compounds of general formula (I) in which X represents a formyl group and the other substituents have the meaning defined above, by sequential treatment with β-toluene- sulfonylhydrazine and sodium cyanoborohydride, according to a method similar to that described in J, Am, Chem. Soc., 93 (1971), 1793.

METQDQ 8

A) It is possible to obtain the compounds of general formula (I) in which X represents a halogeno-alkylcarbonyl group, R ^ represents an amino group, Rg represents a cyano group, Rg represents a hydrogen atom and X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention, that is, compounds of general formula (VIII), by sequential treatment of the corresponding compounds of general formula (VI) in which the amino group is optionally protected, with a halogen-alkyl-metal derivative, to provide compounds of general formula (VII) in which X represents a halo-alkyl-carbinol group, followed by oxidation according to the method of RJ Linderman and DM Graves described in β * ·

Tetrahedron Lett., 28 (1987), 4259 and then following a deprotection step if necessary. Suitable halogen-alkyl-metal derivatives include perfluoro-alkyl-lithium derivatives prepared according to PG Gassman and NJ O'Reilly, J. Org. Chem, 52 (1987), 2481-2490 or tetramethyl-trifluoromethyl-silane prepared according to the method described by GA Olah et al., J. Am. Chem. Soc., 111 (1989), 393. In the work cited above, it is also possible to find references to other halogen-alkyl metal derivatives. With the use of trimethyl-trifluoromethyl-silane, this process can be illustrated as follows:

8) Compounds of general formula (VIII) can be converted into compounds of general formula (I) in which X represents a halo-alkyl-thio-carbonyl group, represents an amino group, Rg represents a cyano group, Rg represents an atom hydrogen and X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention, by treatment with / 2,4-bis (4-methoxy-phenyl) -1,3-dithia-2, 4-diphosphethane-2,4-disulfide (Lawesson's Reagent).

METHOD 9

The compounds of general formula (VII) can be converted into other compounds of general formula (I) in which X represents a Λ-halo-alkyl A ^-halo-methyl group, by treatment with halogenating agents such as thionyl chloride or hydrobromic acid. It may be advantageous to protect the amino function, for example, as a trifluoroacetamide derivative, to prevent halogenation of the pyrrolic nucleus during these halogenations.

METHOD 10

A) It is possible to prepare the compounds of general formula (I) in which X represents a thiocyanate group, represents an amino group, R ₂ represents a cyano group, Rg represents a hydrogen atom and X ^, X ₂ , Xg, X ^ and Y have the meaning shown in the general definition of the present invention, by treating the compounds of general formula (III) with MSCN, where M represents an alkali metal, in the presence of bromine in a solvent such as methanol.

B) It is possible to prepare the compounds of general formula (I) in which X represents an alkyl-thio, halo-alkyl-thio, alkenyl-thio, halo-alkenyl-thio, phenyl-thio or hetero-aryl-thio group, R ^ represents an amino group, R ₂ represents a cyano group and Rg represents a hydrogen atom and X ^, X ₂ , Xg, X ^ and Y have the meaning given in the general definition of the present invention, with the phenyl and heteroaryl groups being constituted and / or substituted as described therein, that is, compounds of the general formula (IX) by reaction of a compound of the general formula (III) with a halide of

sulfenyl RSHal wherein R represents an alkyl, halo-alkyl, alkenyl, halo-alkenyl, phenyl or heteroaryl group as defined above and Hal represents a halogen atom in a liquid reaction medium. Preferably, an organic solvent, for example dichloromethane, is used at a temperature between -100 ° C and + 100 ° C, preferably between -80 ° C and + 25 ° C. Optionally this reaction can be carried out in the presence of an acid-fixing agent such as a tertiary amine, for example pyridine. It is possible to prepare the alkylsulfenyl chlorides according to S. Thea and G. Cevasco, Tetrahedron Letters, (1988), 2865. In the case of using a sulfenyl chloride, the process can be represented by the following equation:

METHOD 11

The compounds of general formula (I) in which X represents thiocyanate, R ^ represents an amino group, Rg represents a cyano group, R ^ represents a hydrogen atom and X ^, X ^, Xg, X ^ and Y have the meaning presented in the general definition of the present invention, can also be converted into compounds of general formula (I) in

s where X represents an alkylthio group, R ^ represents an amino group, Rg represents a cyano group, Rg represents a hydrogen atom and X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention, by treatment with a base such as sodium or potassium hydroxide in the presence of an alkyl halide, a dialkyl sulfate or the like, in a solvent.

METHOD 12

The compounds of general formula (IX) can be oxidized to obtain compounds of general formula (X) in which X represents a group of general formula RS (O) _n in which n represents integer 1 or 2 and R has 0 meaning previously defined. Oxidizing agents that can be used include hydrogen peroxide, peroxyacetic acid, trifluoroperoxyacetic acid and m-chloroperoxybenzoic acid in solvents such as dichloromethane, acetic acid or trifluoroacetic acid at temperatures between -40 ° C and + 80 ° C , preferably between 0 ° C and 25 ° C. The appropriate reaction conditions, that is, the temperature, reaction duration and amount of oxidant, can be changed to provide the sulfinyl (n = 1) or sulfonyl (n = 2) derivatives, as desired. It is also possible to prepare the sulfonyl derivatives from the sulfinyl compounds, as will become apparent to those skilled in the art. With some halogeno-alkylthio groups, for example trifluoromethyl-thio, it may be advantageous to protect the amino function, for example, in the trifluoroacetamide derivative. In the case of choosing, for example, trifluoroperoxyacetic acid as an oxidizer, the process can be represented by the following equation:

METHOD 13

It is possible to prepare the compounds of general formula (I) in which Rg represents a halogen atom, R ^ represents an amino group, Rg represents a cyano group and X, X ^, Xg, XgjX ^ θ Y have the meaning given in the definition general of the present invention, by treating the compounds of general formula (I) in which R ^ represents the amino group, Rg represents a cyano group, Rg represents a hydrogen atom and X, X ^, Xg, Xg, X ^ and Y have the meaning presented in the general definition of the present invention, that is, compounds of general formula (XI), the treatment being carried out with halogenating agents under conditions identical to those described in METHOD 3.

The general transformation is as follows:

(XI) (XII)

-3 2 METHOD 14

It is possible to prepare the compounds of the general formula (I) in which Rg represents a bis (alkylthio) methyl or bis (arylthio) methyl group, R4 represents an amino group, R ₂ represents a cyano group and X, X ^, X ₂ , Xg, X ^ and Y have the meaning given in the general definition of the present invention, by reacting a compound of general formula (XI) with a tris (alkyl-thio) -methane or a tris (aryl-thio) - methane, (R SJ ^ CH in the presence of a Lewis acid, preferably a sulfonium salt, in a solvent, at a temperature between 0 ° C and the reflux temperature of the solvent, optionally in the presence of a acid-fixing agent such as pyridine A preferred process uses acetonitrile at 25 ° C as a solvent with tris (methyl-thio) -methane as tris (alkyl-thio) -methane and dimethyl (methyl-thio tetrafluoroborate) ) -sulfonium as Lewis acid without acid-fixing agent The process can be represented generically as shown Next:

CN

(RaS) .CH

(XI) (XIII)

-33 METHOD 15

It is possible to prepare useful intermediate compounds of general formula (I) in which Rg represents a formyl group, R ^ represents an amino group, Rg represents a cyano group and X, X ^, Xg, Xg, X ^ and Y have the meaning shown in the general definition of the present invention, that is, compounds of the general formula (XIV) by hydrolysis of the compounds of the general formula (XIII) or by their treatment with alkyl nitrites under conditions identical to those described in Method 4C. The process can be represented generically as follows:

X read il -CN X- ll ll -CN HgN _ | l IJ_ 1 -CH (RaS) g HgN- 11 II 1 -CHO ^x i Λ ^{* X} 4 ^X l ~ • ^X 4 Xg V ^X 3 ^X g- ^X 3 Y Y (Xiii) (XIV)

METHOD 16

The intermediate compounds of general formula (I) in which Rg represents a hydroxyiminoalkylidene or alkoxyalkylidene group, R4 represents an amino group, Rg represents a cyano group and

X, Χ _χ , Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention, which constitute useful intermediate compounds, can be prepared by condensing a compound of general formula (I) in which Rg represents a alkylcarbonyl group

-34 /.

or formyl, R ^ represents an amino group, Rg represents a cyano group and X, X ^, X ₂ , Xg, X ₄ and Y have the meaning given in the general definition of the present invention, using hydroxylamine or O-alkyl- hydroxylamine or its acid addition salts in a solvent such as ethanol. The foregoing compounds in which Rg represents an alkyl-carbonyl group are prepared by a process identical to that of compounds (XIV) using as starting compound 1,1,1-tris (alkyl-thio or aryl-thio) -alkane.

METHOD 17

It is possible to prepare useful intermediate compounds of general formula (I) in which Rg represents an amino group, R ^ represents an amino group, R ₂ represents a cyano group and X, X ^, X _2> Xg, X ^ and Y have the meaning given in the general definition of the present invention, by reducing the corresponding compounds in which Rg represents a nitro group, using for example hydrogen in the presence of a noble metal catalyst such as platinum or palladium or using hydrazine and Raney nickel. With some combinations of the substituents R ₂ and X, compounds of the general formula (I) in which R 3 and R ₂ simultaneously represent an amino group may have limited stability and may need protection of one of the amino groups with a suitable protecting group. The compounds of general formula (I) in which Rg represents a nitro group, R ^ represents an amino group, Rg represents a cyano group and X, X ^,

X ₂ , Xg, X ^ and Y have the meaning given in the general definition of the present invention, they can be prepared by nitrating the compounds of general formula (XI) through the action of nitric acid and sulfuric acid or nitric acid in acetic anhydride or other agents ζ

/ -35 nitration. During some nitration reactions it may be advantageous to protect the amino function at (XI) with a suitable protecting group such as acetyl or trifluoroacetyl.

METHOD 18

It is possible to prepare several derivatives, useful as intermediate compounds, of a compound of general formula (XV) (see below):

A) It is possible to prepare compounds of general formula (I) in which Rg represents an alkyl-amino, dialkyl-amino or aralkyl-amino group, R ^ represents an amino group, Rg represents a cyano group and X, X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention, from the corresponding compounds in which Rg represents an amino group and the other substituents have the meaning previously defined, by alkylation with alkyl or aralkyl sulfonates or halides. in organic solvents such as ethanol, acetonitrile, toluene and the like. The production of mono- or dialkylated products can be controlled by manipulating stoichiometry or reaction conditions. Alternatively, if monoalkylamine products are desired, other methods such as converting the amino group to an alkoxyalkylideneimino group can be used by treatment with an orthoalkyl ester, followed by reduction. In the case where in the desired end products R ^ represents an unsubstituted amino group, it may be necessary to protect the amino group, prior to such treatment, with a suitable protecting group. In such cases, a compound of general formula (I) is prepared and used as a reagent in which Rg represents an amino group, R4 represents an appropriately protected amino group /

.-36and the other substituents have the previously defined meaning, that is, a compound of general formula (XV). Usually, the protecting group in (XV) is added before the nitro reduction step discussed in METHOD 17. Depending on the subsequent transformation desired for the amino group Rg, it is possible to choose several protecting groups, as can be seen from the examples that follow.

Β) It is possible to prepare compounds of general formula (I) in which Rg represents an amino-carbonyl-amino group, R ^ represents an amino group, Rg represents a cyano group and X, X ^, Xg, Xg, X ^ and Y have the meaning presented in the general definition of the present invention, starting from the compounds of general formula (XV) by treatment with phosgene followed by treatment with ammonia and then a deprotection step.

C) It is possible to prepare compounds of the general formula (I) in which Rg represents an alkyl-carbonyl-amino, halo-alkyl-carbonyl-amino or aryl-carbonyl-amino group, R4 represents an amino group, Rg represents a cyano group and X, X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention by reacting a compound of general formula (XV) with acid chlorides of general formula R ^b (C = O) Cl or with acid anhydrides of the general formula [R ^b (C = O) J gO in which R ^b represents an alkyl, haloalkyl or aryl group, as defined in the first definition of the general formula (I), followed by a deprotection step. It is possible to use solvents such as acetonitrile and it is also possible to use acid-fixing agents such as pyridine, under appropriate conditions.

D) Similarly, it is possible to prepare compounds of the general formula (I) in which Rg represents an alkylsulfonyl / -37-amino or halo-alkylsulfonyl-amino group, R4 represents an amino group, Rg represents a group cyano and X, X ^, Xg, Xg, X ₄ and Y have the meaning given in the general definition of the present invention, from amino-protected compounds of general formula (XV), by reaction with alkyl or halogen halides. alkyl sulfonyl or with sulfonic acid anhydrides, under appropriate conditions, following a deprotection step. Suitable amino-protecting groups for such reactions include the alkoxyalkylideneimino group obtained by treating the amino compound with an alkyl orthoformate. Deprotection procedures for these groups typically involve aqueous hydrolysis.

E) It is possible to prepare compounds of general formula (I) in which Rg represents an alkyl-amino-carbonyl-amino or aryl-amino-carbonyl-amino group, R4 represents an amino group, Rg represents a cyano group and X, X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention, from an appropriately protected amino compound of the general formula (XV), by reaction with an alkyl or aryl isocyanate in which the alkyl or aryl groups have the meaning given in the first definition of the present invention, followed by deprotection. Suitable conditions for urea formation are described by J. March in Advanced Organic Chemistry, McGraw-Hill Publ., 1985, p. 802 and the references therein. Suitable amino-protecting groups for such reactions include the alkoxyalkylideneimino group with deprotection as previously described.

F) It is possible to prepare compounds of general formula (I) in which Rg represents an alkoxycarbonyl-amino or halogeno-

-carbonyl-amino, represents an amino group, Rg represents a cyano group and X, X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention, from an appropriately protected amino compound general formula (XV), by reaction with an alkyl chloroformate or a halogeno-alkyl chloroformate following a deprotection step.

G) It is possible to prepare compounds of general formula (I) in which Rg represents an alkylideneimino or benzylideneimino group, R4 represents an amino group, R ₂ represents a cyano group and X, X ^, X ₂ , Xg, Χή and Y have the meaning given in the general definition of the present invention, by condensing an appropriately protected amino compound of general formula (XV), with an aryl- or alkyl-aldehyde in which the alkyl or aryl groups have the meaning shown in first definition of the present invention, followed by a deprotection step. The appropriate conditions for the formation of Schiff bases will be selected for the condensation step as described by J. March in ibid. P. 1165 and references therein. Suitable amino-protecting groups include acetyl or trifluoroacetyl, deprotection can be done by alkaline hydrolysis or using other methods as described by TW Greene in Protective Groups in Organic Synthesis, J. Wiley Publ., 1981, p. 254 and references therein.

Η) It is possible to prepare compounds of general formula (I) in which Rg represents an alkoxyalkylideneimino group, R ^ represents an amino group, Rg represents a cyano group and X, X ^, Xg, Xg,

X4 and Y have the meaning given in the general definition of the present invention, from an amino-protected compound of formula

(XV) by condensation with an orthoalkyl ester followed by a deprotection reaction. Suitable protecting groups include carbamate or amide derivatives as described by T. W. Greene, ibid. P. 223 and 249.

I) It is possible to prepare compounds of general formula (I) in which Rg represents a dialkyl-amino-alkylideneimino group, represents an amino group, Rg represents a cyano group and X, X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention, by reacting a compound of general formula (XV) with a dialkylacetal derivative of an N, N-dialkylformamide as described by TW Greene, ibid. , p 275, followed by a deprotection step. Alternatively, (XV) is reacted with an N, N-dialkylformamide in the presence of an agent such as phosphorous oxychloride, under Vilsmeier conditions.

Suitable protecting groups include carbamate or amide derivatives.

J) It is possible to prepare compounds of general formula (I) in which Rg represents an alkylthio-alkylideneimino group, R4 represents an amino group, Rg represents a cyano group and X, X ^,

Xg, Xg, X ₄ and Y have the meaning given in the general definition of the present invention, reacting a compound of general formula (XV) with a tris (alkylthio) methane using pyridine as a solvent, optionally in the presence of a catalyst suitable, for example, dimethyl (methyl-thio) sulfonium tetrafluoroborate

K) It is possible to prepare compounds of general formula (I) in which Rg represents an azido group, R ^ represents an amino group, Rg represents a cyano group and X, X ^, Xg, Xg, X ^ and Y have the meaning shown in the general definition of the present invention,

A compound of the general formula (XV) is reacted with β-toluenesulfonyl azide under the conditions described by J. March, ibid. ,P. 573 and references therein, followed by a deprotection step. Alternatively, it is possible to prepare the previously described compounds in which Rg represents an azido group, from a compound of general formula (XV) by converting the amino group to a diazonium salt followed by reduction to provide a hydrazino group, following then treatment with nitrous acid to provide the azide and followed by a deprotection step.

METHOD 19

A) It is possible to prepare useful intermediate compounds of general formula (I) in which Rg represents a substituted phenyl or heteroaryl group as described in the general definition of the present invention, R4 represents an amino group, Rg represents a cyano group and X, X ^, Xg, Xg, X ^ and Y have the meaning presented in the general definition of the present invention, from a composition of general formula (XI) in which the amino group is optionally protected with a suitable protecting group, by means of treatment with an appropriately substituted phenyl- or heteroaryl-diazonium salt, under the Gomberg-Bachmann reaction conditions, as described by M. Swainsbury in Tetrahedron, 36 (1980), 3327-3359 and references therein.

B) Alternatively, it is possible to prepare the intermediate compounds of general formula (I) in which Rg represents a substituted phenyl or heteroaryl group as described in the general definition of the present invention, R4 represents an amino group, Rg re / f -41 ^κ ---- * 'has a cyano group and X, X ^, X ₂ , Xg, X ^ and Y have the meaning defined in the general definition of the present invention, from a compound of general formula (XII) in which the amino group is optionally protected with a suitable protecting group by treatment with an appropriately substituted phenyl or heteroaryl halide, preferably a bromide or an iodide in the presence of copper, under the Ullmann reaction conditions, as described by M. Swainsbury, ibid. .

C) Alternatively, it is possible to prepare the intermediate compounds of general formula (I) in which Rg represents a substituted phenyl or heteroaryl group as described in the general description of the present invention, R4 represents an amino group, R ₂ represents a cyano group and X, X ^, X ₂ , Xg, X ^ and Y have the meaning indicated in the general definition of the present invention, from a compound of general formula (XII), preferably a bromide or an iodide, by treatment with an acid phenyl- or heteroaryl-boronic appropriately substituted in the presence of palladium (0), under conditions identical to those described by V. Snieckus et al. in Tetrahedron Letters, 29 (1988), 2135 and references therein.

METHOD 20

It is possible to prepare compounds of general formula (I) in which Rg represents a cyano group, R ^ represents an amino group, R ₂ represents a cyano group and X, X ^, X ₂ , Xg, X ^ and Y have the meaning given in the general definition of the present invention, from compounds of general formula (I) in which Rg represents a hydroxyimino-methylidenyl or alkoxyimino-methylidenyl group described in METHOD 16, by dehydration, in accordance with procedures 42 ^ · Procedures described in METHOD 4A.

METHOD 21

It is possible to prepare compounds of the general formula (I) in which Rg represents a halo-alkyl-carbonyl or halo-alkyl-thio-carbonyl group, R4 represents an amino group, Rg represents a cyano group and X, X4, Xg, Xg, X ^ and Y have the meaning presented in the general definition of the present invention from a compound of general formula (XIV) of an optionally protected amino group, using the procedures described in METHOD 8, followed by a deprotection step if required.

METHOD 22

A) It is possible to prepare compounds of general formula (I) in which Rg represents a halo-alkyl group, R ^ represents an amino group, Rg represents a cyano group and X, X ^, Xg, Xg, X ^ and Y have the meaning presented in the general definition of the present invention, from the compounds of general formula (XII) ου (XIV) in which the amino group is optionally protected, using the procedures described in METHODS 6, 7 and 9, with deprotection in the case of needed.

B) It is possible to prepare compounds of general formula (I) in which Rg represents an alkyl group, R ^ represents an amino group, Rg represents a cyano group and X, X ^, Xg, Xg, X ^ and Y have the meaning shown in the general definition of the present invention, from compounds of general formula (XIV) in which the amino group is optionally protected, by reaction with a Grignard reagent derived from an alkyl halide or with a compound

-43-alkyl lithium to provide a carbinol, followed by a dehydration step to provide a compound in which Rg represents an alkenyl group, followed by reduction. It is possible to prepare compounds of general formula (I) in which Rg represents a methyl group and the other substituents have the meaning previously defined, from compounds of general formula (XIV) using the procedure described in METHOD 7.

METHOD 23

It is possible to prepare compounds of general formula (I) in which Rg represents a thiocyanate, alkyl-thio, halo-alkyl-thio, alkenyl-thio, halo-alkenyl-thio, phenyl-thio or heteroaryl-thio group, R4 represents a amino group, Rg represents a cyano group and X, X ^, Xg, Xg, X ^ and Y have the meaning given in the general description of the present invention and in which the phenyl and heteroaryl groups are constituted and / or substituted as previously described, that is, compounds of general formula (XVI), from compounds of general formula (XI) under conditions identical to those described in METHOD 10. The overall process can be represented by the following equation:

(XI) (XVI) f -44It is also possible to prepare compounds of general formula (XVI) in which R represents an alkyl group from compounds of general formula (I) in which Rg represents a thiocyanate group and in which the other symbols have the meaning defined in (XVI), by treatment with alkyl halides or similar, using procedures identical to those described in

METHOD 11.

METHOD 24

It is possible to prepare compounds of general formula (I) in which Rg represents an alkylsulfonyl, halo-alkenyl-sulfinyl, halo-alkenyl-sulfonyl, phenyl-sulfinyl, phenyl-sulfonyl, heteroaryl-sulfinyl, heteroaryl-sulfonyl, R3 group represents an amino group, Rg represents a cyano group and X, X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention and in which the phenyl and heteroaryl groups are constituted and / or substituted as previously described by oxidation of compounds of general formula (XVI) according to methods identical to those described in METHOD 12. In cases where X represents an RS group which may undergo an undesired competitive oxidation, sulfenylation can be carried out, according to the previous procedures, a compound of general formula (I) in which X represents a halogen atom, preferably bromine or iodine,

R ^ represents an amino group, Rg represents a cyano group, Rg represents a hydrogen atom and the other substituents have the meaning given in the general definition of the present invention, followed by oxidation and followed by treatment with alkyl- using a procedure identical to that described by C.

Kruse et al. In Heterocycies, 29 (1989), 79, then diluting (quench) with water to obtain a compound of general formula (XVII). The compound (XVII) can then be sulfenylated to provide compounds of the general formula (XVIII). The overall process can be represented as follows:

(XVII) (XVIII)

METHOD 25

It is possible to prepare compounds of the general formula (I) in which Rg represents a cyanate, alkoxy, or haloalkoxy group, R4 represents an amino group, Rg represents a cyano group and X, X4, Xg, Xg, X ₄ and Y have the meaning presented in the general definition of the present invention, from compounds of general formula (XII) in the / -46 which ο amino group is optionally substituted, using procedures identical to those described in METHOD 5, followed by a deprotection step if necessary.

METHOD 26

A) It is possible to prepare compounds of general formula (I) in which R ^ represents a hydrogen atom, Rg represents a cyano group, and Rg, X, X ^, Xg, Xg, X ^ and Y have the meaning given in the definition general of the present invention, that is, compounds of general formula (XX), from compounds of general formula (I) in which R ^ represents an amino group, Rg represents a cyano group and Rg, X, X ^, Xg, Xg, X ₄ and Y have the meaning given in the general definition of the present invention, that is, compounds of the general formula (XIX), by diazotation, preferably with an alkyl nitrite such as β-butyl nitrite within a 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 solvent, preferably at a temperature between 0 ° C and 25 ° C.

Β) It is possible to prepare compounds of general formula (I) in which R ^ represents a halogen atom, Rg represents a cyano group and Rg, X, X ^, Xg, Xg, X ₄ and Y have the meaning given in the general definition of the present invention, that is, compounds of general formula (XXI) from a compound of general formula (XIX) by diazotizing with an alkyl nitrite, for example, t-butyl nitrite in the presence of a halogen atom donor such as bromoform, carbon tetrachloride and anhydrous cupric chloride or iodide.

C) It is possible to prepare compounds of the general formula (I) in which it represents a thiocyanate, alkyl-thio, halo-alkyl-thio, alkenyl-thio, halo-alkenyl-thio, phenyl-thio or heteroaryl-thio group, Rg represents a cyano group and Rg, X, X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention and in which the phenyl and heteroaryl groups are constituted and / or substituted as previously described, that is, compounds of general formula (XXII), from a compound of general formula (XIX) by treatment with an alkyl nitrite in the presence of (SCN) g or of a disulfide of general formula RSSR in which R represents an alkyl, halogen- alkyl, alkenyl, halo-alkenyl, phenyl or heteroaryl as defined above. Typically the reaction is carried out in a solvent such as chloroform at 0 ° C using between one and five equivalents of alkyl nitrite and between two and five equivalents of disulfide.

The overall processes can be illustrated as follows:

CN

Y

N

Xl

X ₂

Y

(XX) R _C = H (XXI) R _c = Halogen (XXII) R _C = SR (XIX) /

/ -48 /. · *

METHOD 27

Alternatively, it is possible to prepare several compounds of general formula (XXII) from a compound of general formula (XX) in which Rg represents an amino group, using a procedure identical to that described in METHOD 10. The conversion of the group can be carried out amino to provide other functional groups according to the present invention, using one of the procedures previously described.

METHOD 28

It is possible to prepare compounds of general formula (I) in which R R represents an alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, alkenylsulfonyl, halogeno-alkylsulfinyl, halogeno-alkylsulfonyl, halogeno-alkenylsulfinyl , halogeno-alkenyl-sulfonyl, phenyl-sulfinyl, phenyl-sulfonyl, heteroaryl-sulfinyl or heteroaryl-sulfonyl, R ^ represents a cyano group and Rg, X, X ^, Xg1 ^ 31 X4 θ Y have the meaning given in the general definition , with phenyl and heteroaryl groups being constituted and / or substituted as described, by oxidation of compounds of general formula (XXII) according to methods described in METHOD 24. If groups X or Rg are also SR groups that must be maintained at oxidation level of the sulfide, a strategy similar to that described in METHOD 24 can be adopted to provide the desired compounds.

METHOD 29

It is possible to prepare compounds of general formula (I) in which

R ₁ represents an alkyl-amino, dialkyl-amino, aralkyl-amino group

no, amino-carbonyl-amino, alkyl-carbonyl-amino, halo-alkyl-carbonyl-amino, aryl-carbonyl-amino, alkyl-sulfonyl-amino, halo-alkyl-sulfonyl-amino, alkyl-amino-carbonyl-amino, aryl-amino-carbonyl-amino, alkoxy-carbonyl-amino, halo-alkoxy-carbonyl-amino, alkylidene-imino, benzylidene-imino, alkoxy-alkylidene-imino, dialkyl-amino-alkylidene-imino, alkyl-thio-alkylidene- imino or azido, Rg represents a cyano group and Rg, X, X ^, Xg, Xg, X ^ and Y have the meaning presented in the general definition of the present invention, from a compound of general formula (XIX), using procedures identical to those described in METHOD 18.

METHOD 30

A) It is possible to prepare compounds of general formula (I) in which R ^ represents a formyl group, Rg represents a cyano group and Rg, X, X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention, from a compound of general formula (XIX) by treatment with sodium nitrite, HC = NOH, copper sulfate and HCl by a process analogous to that described by W.

F. B e and c h J. Chem, Soc, (1954), 1297.

In the case that Rg represents an amino group in (XIX), adequate protection can be provided. The foregoing compound in which R4 represents a formyl group can be converted into a compound in which R4 represents a bis (alkylthio) methyl or bis (arylthio) methyl group using standard thio-acetalation methods as described by TW Greene ibid. P. 130 and references therein. Alternatively, it is possible to prepare compounds of general formula (I) in which R3 represents a bis (alkylthio) methyl or bis (aryl-thio) methyl group, Rg represents a cyano group, Rg represents

an amino group and X, X ₁ , Xg, X _g , X ^ and Y have the meaning given in the general definition of the present invention, from a compound of general formula (XX) in which R _g represents an amino group, using a procedure identical to that described in METHOD 14. The conversion of the bis (alkyl-thio) -methyl or bis (aryl-thio) -methyl group to formyl can be carried out using procedures analogous to those described in METHOD 15. The conversion of the amino function in other functional groups of the present invention it can be carried out using one of the procedures previously described.

B) It is possible to prepare compounds of the general formula (I) in which it represents a hydroxyiminoalkylidene or alkoxyiminoalkylidene group, Rg represents a cyano group and Rg, X, X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention, from compounds of general formula (I) in which R R represents an alkylcarbonyl or formyl group and the other substituents have the meaning previously defined, using procedures identical to those described in the METHOD 16. The previous compounds in which it represents an alkylcarbonyl group can be prepared from the corresponding compounds in which it represents a halogen atom by conversion to a Grignard reagent or a lithium derivative, with optional protection of the cyano group as described in the METHOD 5, following the reaction with an aliphatic acid chloride or anhydride, or alternatively, condensation with an aliphatic aldehyde followed by oxidation. Alternatively, it is possible to prepare the compounds in which it represents an alkylcarbonyl group from the corresponding compounds in which R4 represents a formyl group, by reaction with an alkyl Grignard reagent, followed by oxidation.

C) It is possible to prepare compounds of general formula (I) in which R ^ represents a cyan group, Rg represents a cyan group and Rg, X, X ^, Xg, Xg, X ₄ and Y have the meaning given in the general definition of present invention, from the corresponding compounds in which R ^ represents a hydroxyimino-methylidenyl or alkoxyimino-methylidenyl group, using processes identical to those described in METHOD 4A).

D) It is possible to prepare compounds of general formula (I) in which R R represents a halo-alkyl-carbonyl or halo-alkyl-thio-carbonyl group, Rg represents a cyano group and Rg, X,

X ^, Xg, Xg, X ₄ and Y have the meaning given in the general definition of the present invention, from a compound of general formula (I) in which R ^ represents a formyl group and the other substituents have the meaning previously defined , by treatment under conditions identical to those described in METHOD 8.

Ε) It is possible to prepare compounds of general formula (I) in which R ^ represents a halo-alkyl or alkyl group, Rg represents a cyano group and Rg, X, X ^, Xg, Xg, X ₄ and Y have the meaning shown in the general definition of the present invention, from a compound of general formula (I) in which R R represents a formyl group or a halogen atom and the other symbols have the meaning previously defined, by treatment under conditions identical to those described in the METHOD 22.

METHOD 31

It is possible to prepare compounds of general formula (I) in which

R ^ represents a substituted phenyl or heteroaryl group according to / -5 2) indicated in the general description of the present invention, Rg represents a cyano group and Rg, X, X ^, Xg, Xg, X ^ and Y have the meaning given in the definition general of the present invention from compounds of general formula (I) in which R um represents a halogen atom and the other symbols have the meaning previously defined, using procedures identical to those described in METHODS 19B) and 19C).

METHOD 32

It is possible to prepare compounds of general formula (I) in which R ^ represents a cyanate, alkoxy or halo-alkoxy group, Rg represents a cyano group and Rg, X, X ^, Xg, Xg, X ^ and Y have the meaning shown in the general definition of the present invention, from compounds of general formula (XXI), using procedures identical to those described in METHOD 5.

METHOD 33

It is possible to prepare compounds of general formula (I) in which Rg represents a formyl group, R4, Rg, X, X4, Xg, Xg, X4 and Y have the meaning given in the general definition of the present invention, that is, compounds of general formula (XXIV), from compounds of general formula (I) in which Rg represents a cyano group, R ^, Rg, X, X ^, Xg, Xg, X ₄ and Y have the meaning shown in the description of the present invention, that is, compounds of the general formula (XXIII), by treatment with a reducing agent, preferably with diisobutyl aluminum hydride in a solvent, preferably a mixture of toluene and hexane 1: 1 , using a procedure similar to that described by S. Trofimenko in J. Org.

Chem. , 29

(1964), 3046. Following is the global process:

(XXIII) (XXIV)

METQDQ 34

It is possible to prepare useful intermediate compounds of general formula (I) in which Rg represents a carboxylic acid function, R4, Rg, X, X4, Xg, Xg, X4 and Y have the meaning given in the general definition of the present invention, that is, compounds of general formula (XXV), oxidizing compounds of general formula (XXIV) using Jones reagent. The global process has the following representation:

(XXIV) (XXV) /

54 METHOD 35

It is possible to prepare compounds of general formula (I) in which it represents a hydroxyimino-alkylidenyl, alkoxyimino-alkylidenyl, halo-alkyl-carbonyl, halo-alkyl-thio-carbonyl, alkyl, bis (alkyl-thio) group - methyl, bis (aryl-thio) -methyl or halo-alkyl and R R, Rg, X, X ^, X ₂ , Xg, X ^ and Y have the meaning given in the general definition of the present invention, from compounds of general formula (XIV) or compounds of general formula (I) in which R ₂ represents a halogen atom and the other symbols have the meaning previously defined, the preparation of which is described in METHOD 38, using procedures identical to those described in METHOD 30A) B) D) and E).

METHOD 36

It is possible to prepare compounds of general formula (I) in which R ₂ represents an amino group, R ^, Rg, X, X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention, i.e. , compounds of general formula (XXVII) from compounds of general formula (XXV), by treatment with diphenyl-phosphoryl-azide in the presence of an organic base such as triethylamine in an alcoholic solvent such as tert-butanol for provide a carbamate (XXVI) following hydrolysis. There are other methods for the preparation of (XXVII) from (XXV) by means of a Curtius rearrangement which include conversion to the acid chloride following the reaction with the azide ion and treatment with an alcohol as described by J March in Advanced Organic Chemistry, McGraw-Hill Publ., 1985, p. 984. The global transformation is as follows:

/

(XXV) (XXVI) (XXVII)

METHOD 37

It is possible to prepare compounds of general formula (I) in which Rg represents an alkyl-amino, dialkyl-amino, aralkyl-amino, amino-carbonyl-amino, alkyl-carbonyl-amino, halogeno-alkyl-carbonyl-amino, aryl group -carbonyl-amino, alkyl-sulfonyl-amino, halo geno-alkyl-sulfonyl-amino, alkyl-amino-carbonyl-amino, aryl-amino-carbonyl-amino, alkoxy-carbonyl-amino, halo-alkoxy-carbonyl-amino , alkylidene-imino-benzylidene-imino, alkoxy-alkylidene-imino, dialkyl-amino-alkylidene-imino, alkyl-thio-alkylidene-imino or azido and R R, Rg, X, X ^, Xg. Xg, X ^ and Y have the meaning given in the general definition of the present invention, from the compounds of general formula (XXVII), using procedures identical to those described in METHOD 18.

METHOD 38

It is possible to prepare compounds of general formula (I) in which Rg represents a hydrogen or halogen atom, a thiocyanate, alkyl thio, halo-alkyl-thio, alkenyl-thio, halo-alkenyl-thio, phenyl-thio group or heteroaryl-thio and R ^, Rg, X, X ^, Xg, /

.-56Xg, X ^ and Y have the meaning presented in the general definition of the present invention, from the compounds of general formula (XXVII), using procedures identical to those described in METHOD 26. Alternatively, it is possible to prepare compounds of general formula ( I) in which Rg represents a hydrogen atom and R ^, Rg, X, X ^, Xg, Xg, X ^ and Y have the meaning given in the general definition of the present invention, from the compounds of general formula (XXV) , by heating under reflux with 48% HBr in glacial acetic acid or by heating in a high boiling solvent such as decalin or quinoline in the presence of copper.

METHOD 39

It is possible to prepare compounds of general formula (I) in which R R represents an alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, alkenylsulfonyl, halogeno-alkylsulfinyl, halogeno-alkylsulfonyl, halogeno-alkenylsulfinyl , halogen-alkenyl-sulfonyl, phenyl-sulfinyl, phenyl-sulfonyl, heteroaryl-sulfinyl, heteroaryl-sulfonyl, R ^, Rg, X, X ^, Xg, Xg, X ^ and Y have the meaning presented in the general definition of the present oxidizing compounds of general formula (I) in which Rg represents an alkyl-thio, halo-alkyl-thio, alkenyl-thio, halo-alkenyl-thio, phenyl-thio or heteroaryl-thio group, using procedures identical to those described in METHOD 24.

METHOD 40

It is possible to prepare compounds of general formula (I) in which

Rg represents a substituted phenyl or heteroaryl group as referred to in the general definition of the present invention and R4, Rg, X, X4, /

-57Xg, Xg, X ₄ and Y have the meaning given in the general definition of the present invention, from compounds of general formula (I) in which Rg represents a halogen atom and the other substituents have the meaning previously defined, using procedures identical to those described in METHODS 19B and 19C.

METQDQ 41

It is possible to prepare compounds of general formula (I) in which Rg represents a cyanate, alkoxy or haloalkoxy group and R4,

Rg, X, X ^, Xg, Xg, X ₄ and Y have the meaning given in the general definition of the present invention, from compounds of general formula (I) in which Rg represents a halogen atom and the other symbols have the previously defined meaning, using procedures identical to those described in METQDQ 5.

Overall, the process of the present invention can be defined as described below:

P ^. A process for the preparation of compounds of general formula

at

1, which X ^, Xg, X represents

Xg, X ^ and Y have the meaning defined in the Method a halogen atom or a trifluoromethyl group, /

58 cyano, thiocyanate, alkyl-thio, alkyl-sulfinyl, alkyl-sulfonyl, halogeno-alkyl-thio, halogeno-alkyl-sulfinyl, halogeno-alkyl-sulphonyl, alkenyl-thio, halogeno-alkenyl-thio, halogeno-alkenyl-sulfinyl, halogen-alkenyl-sulfonyl, phenyl-thio, phenyl-sulfinyl, phenyl-sulfonyl, heteroaryl-thio, heteroaryl-sulfinyl or heteroaryl-sulfonyl, in which a compound of general formula is reacted

(whose amino group is optionally protected):

(a) with a halogenating agent, optionally in the presence of a solvent, to obtain a compound of the general formula (Ia) in which X represents a halogen atom, then reacting that compound with trifluoromethyl-copper for a known process, to obtain a compound of general formula (Ia) in which X represents a trifluoromethyl group;

(b) with a tris (alkyl-thio) -methane or tris (aryl-thio) -methane in the presence of a Lewis acid, then reacting the compound obtained of the general formula (XI) in which X represents a group bis (alkyl-thio) -methyl or bis (aryl-thio) -methyl, with a suitable alkyl nitrite following hydrolysis, to obtain a compound of the general formula (XXXVII) in which X represents a forX group

-59myl, and then reacting that compound with hydroxylamine followed by dehydration with suitable agents such as PgO4, by a known process, to obtain a compound of general formula (Ia) in which X represents a cyano group;

(c) with a compound of general formula MSCN, representing M an alkali metal, in the presence of bromine, in a solvent such as methanol, to obtain a compound of general formula (Ia) in which X represents a thiocyanate group and then that compound is reacted with an alkyl halide or with dialkyl sulfate in the presence of a base such as sodium hydroxide or potassium hydroxide in a solvent, to obtain a compound of general formula (Ia) in which X represents an alkylthio group; or (d) with a sulfenyl halide of the general formula RSHal in which R represents an alkyl, halo-alkyl, phenyl or heteroaryl group, Hal represents a halogen atom, in an organic liquid reaction medium, optionally in the presence of an acid fixation such as a tertiary amine, to obtain a compound of general formula (Ia) in which X represents an alkyl-thio, halo-alkyl-thio, alkenyl-thio, halo-alkenyl-thio, phenyl-thio group or heteroaryl-thio, then optionally oxidizing, by a known process, the compound obtained to obtain a compound of general formula (Ia) in which X represents a group of general formula RS (O) _n in which n represents the integer 1 or 2, depending on the reaction conditions.

Pg. A process for the preparation of compounds of general formula (Ia) in which X ^, Xg, Xg, X ^ and Y have the meaning defined in

-60Method 1, X represents a cyanate, alkoxy or halo-alkoxy group, in which a compound of the general formula is reacted

(XXVIII) (where the amino and cyano groups are adequately protected if necessary):

(a) with cyanogen halide in the presence of an acid-fixing agent to obtain a compound of formula (Ia) in which X represents a cyanate group;

(b) with an alkylating agent, optionally in the presence of a base, to obtain a compound of formula (Ia) in which X represents an alkoxy group; or (c) by a known halo-alkylation process, according to Syntheses of Fluoroorganic Compounds, Knunyants, I.

L. and Yakobson, G. G., Ed., Berlin, Springer Verlag, 1985, pp. 263-269, to provide compounds of the general formula (Ia) in which X represents a haloalkoxy group.

Pg. A process for the preparation of compounds of general formula (Ia) in which X ^, Xg, Xg, X ^ and Y have the meaning defined in Method 1 and X represents a haloalkyl group [CFgH, CFg, BrCHg, s

CICHg], halo-alkyl-carbonyl, halo-alkyl-thio-carbonyl or phyl-halo-alkyl-halo-methyl, in which a compound of the general formula is reacted

(where the amino and cyano groups are adequately protected if necessary):

(a) with a fluorination agent such as diethylamino sulfur trifluoride, by a known process, to provide a compound of general formula (Ia) in which X represents a difluoromethyl group;

(b) with a suitable oxidizing agent such as chromium trioxide in sulfuric acid, to obtain a compound in which X represents a carboxylic acid group, then subjecting that compound to a fluorination agent such as sulfur tetrafluoride, by a known process, to obtain a compound of general formula (Ia) in which X represents a trifluoromethyl group.

(c) under the conditions of Wolff-Kishner, or according to a variant such as treatment with? -toluenesulfonylhydrazide followed by sodium cyanoborohydride, to obtain a compound in which X represents a methyl group, then subjecting that compound to a halogenating agent such as N-bromo-succinimide

or N-chlorosuccinimide in a suitable solvent to provide a compound of general formula (Ia) in which X represents a bromomethyl or chloromethyl group; or (d) sequentially with a halogen-alkyl-metal derivative or with trifluorotrimethyl-silane to obtain a compound of formula (Ia) in which X represents a halo-alkyl-carbinol group, followed by oxidation by a process known to obtain a compound of general formula (Ia) in which X represents a halogeno-alkylcarbonyl group, then subjecting that compound to Lawesson's reagent to provide compounds of general formula (Ia) in which X represents a halogeno- alkyl (thio-carbonyl), or the compound in which X represents a halo-alkyl-carbinol group is reacted with halogenating agents such as thionyl chloride or hydrobromic acid, to obtain a compound of general formula (Ia) in which X represents a tf-halogeno-alkyl - </ - halogeno-methyl group following all of these previous steps a deprotection step if necessary.

P4. A process for the preparation of compounds of general formula

(Ib) in which X do 1 and Rg ^X 1 ' ^X 2' ^X 3 ' ^X 4 ^and Y ^The meaning defined in the Method represents a halogen atom or a formyl group,

-63bis (alkyl-thio or aryl-thio) -methyl, halo-alkyl, alkyl, phenyl or optionally substituted heteroaryl, thiocyanate, alkyl-thio, halo-alkyl-thio, alkenyl-thio, halogeno-alkenyl-thio, phenyl- thio, heteroaryl-thio, alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, alkenylsulfonyl, halogeno-alkylsulfinyl, halogeno-alkylsulfonyl, halogeno-alkenylsulfinyl, halogeno-alkenylsulfonyl, phenylsulfinyl, phenylsulfonyl, heteroaryl-sulfinyl or heteroaryl-sulfonyl, in which a compound of formula (Ia) is reacted (in which the X, cyano and amino groups are optionally protected by a suitable process if necessary):

(a) according to method P ^ (a) to obtain a compound of general formula (Ib) in which Rg represents a halogen atom, then reacting that compound with an optionally substituted phenyl or heteroaryl halide , preferably a bromide or an iodide in the presence of copper, by a known process, and then the compound is reacted, in which Rg preferably represents a bromine or iodine atom, with a phenyl- or heteroaryl-boronic acid optionally substituted, in the presence of palladium, by a known process, to obtain a compound of general formula (Ib) in which Rg represents an optionally substituted phenyl or heteroaryl group, or else a compound of general formula (Ia) is reacted in which Rg represents a halogen atom, according to method P4 (a), to obtain a compound of general formula (Ib) in which Rg represents a trifluoromethyl group;

(b) according to method P ^ (b) to first obtain a compound of general formula (Ib) in which Rg represents a bis-

(alkyl-thio) -methyl or a bis (aryl-thio) -methyl group and then a compound of general formula (Ib) in which Rg represents a formyl group;

(c) with a phenyl- or heteroaryl-diazonium salt optionally substituted, by a known process, to obtain a compound of formula (Ib) in which Rg represents an optionally substituted phenyl or heteroaryl group; or (d) according to method P ^ (c, d), to obtain a compound of general formula (Ib) in which Rg represents an alkyl-thio, halo-alkyl-thio, alkenyl-thio, halogeno- alkenyl-thio, phenyl-thio or heteroaryl-thio, which is then optionally oxidized according to method P4 (d), to obtain a compound of general formula (Ib) in which Rg represents an alkylsulfinyl, alkyl group -sulfonyl, alkenylsulfinyl, alkenylsulfonyl, halogeno-alkylsulfinyl, halogeno-alkylsulfonyl, halogeno-alkenylsulfinyl, halogeno-alkenylsulfonyl, phenylsulfinyl, phenylsulfonyl, heteroaryl-sulfinyl or heteroaryl-sulfonyl , with the proviso that X does not represent an RS group, which can undergo undesired oxidation, and then in the case of X representing a halogen atom, treatment with alkyl lithium is carried out by a known process, diluting ( quench) then with water and undergoing a sulfenylation reaction according to method P ^ (c, d) to obtain compounds of general formula (Ib) in which X represents an alkyl-thio, halo-alkyl-thio, alkenyl-thio, halo-alkenyl-thio, phenyl-thio or heteroaryl-thio group.

Pg. A process for the preparation of compounds of general formula (Ib) in which X, X ^, X ₂ , Xg, X ^ and Y have the meaning defined in

Method 1 and Rg represents a hydroxyimino-alkylidenyl, alkoxyimino-alkylidenyl, cyano, halo-alkyl-carbonyl or halo-alkyl-thio-carbonyl or alkyl group, in which a compound of general formula is reacted

^X "T il pCN h ₂ n — V II I Lr ₃ ^x i ~ Ti THE p ^X 4 (XXIX) χ ₂ -ί T Y in which Rg represents one group formyl or alkylcarbonyl and the

X, cyan and amino groups are protected by an appropriate process if necessary:

(a) by condensation with hydroxylamine or with 0-alkylhydroxylamine or with its addition salts in a solvent such as ethanol to obtain a compound of formula (Ib) in which Rg represents a hydroxyimino group -alkylidenyl or alkoxyimino-alkylidenyl, and if Rg represents a hydroxyimino-methylidenyl or alkoxyimino-methylidenyl group, the elements of water or an alcohol are removed according to the P ^ method ( b) to obtain a compound of general formula (Ib) in which Rg represents a cyano group;

(b) in the case that Rg represents a formyl group, according to the method Pg (a, b, c, d) to provide a compound of general formula (Ib) in which Rg represents a methyl or haloalkyl group or halo-alkyl-carbonyl or halo-alkyl-thio-carbonyl;

ου (c) if Rg represents a formyl group, with a Grignard reagent derived from an alkyl halide or with an alkyl lithium to provide a carbinol, followed by a dehydration step to obtain a compound in which Rg represents an alkenyl group, followed by reduction in order to obtain a compound of general formula (Ib) in which Rg represents an alkyl group, optionally following a deprotection step.

Ρθ. A process for the preparation of compounds of general formula

(XXXIV) useful as intermediate compounds in which X, X ^, Xg, Xg, X ^ and Y have the meaning defined in Method 1 and Rg represents an amino, alkyl-amino, dialkyl-amino, aralkyl-amino, amino- carbonyl-amino, alkyl-carbonyl-amino, halo-alkyl-carbonyl-amino, aryl-carbonyl-amino, alkyl-sulfonyl-amino, halo-alkyl-sulfonyl-amino, alkyl-amino-carbonyl-amino, aryl-amino- carbonyl-amino, alkoxy-carbonyl-amino, alkylidene-imino, benzylidene-imino, alkoxy-alkylidene-imino, dialkyl-amino-alkylidene-imino, alkyl-thio-alkylidene-imino or azido, in which the reaction of a compound of general formula

where the amino group is protected by a suitable process, to obtain a compound of the general formula (XXXIV) in which Rg represents an amino group, by reacting that compound with:

(a) appropriate alkylating agents, in organic solvents, obtaining the mono- or disubstituted amino group according to the stoichiometric proportion or reaction conditions or by converting the amino group into an alkoxyalkylideneimino group following reduction to obtain a compound of general formula (XXXIV) in which Rg represents an alkyl-amino, dialkyl-amino or aralkyl-amino group;

(b) phosgene, followed by ammonia to obtain a compound of the general formula (XXXIV) in which Rg represents an amino-carbonyl-amino group;

(c) acid alkyl chlorides or acid halogen alkyl chlorides or acid aryl chlorides or their anhydrides, optionally in the presence of a solvent and / or organic acid fixing agents, to provide a compound of formula (XXXIV) in that Rg represents an alkyl-carbonyl-amino, halo-alkyl-carbonyl-amino, aryl-carbonyl-amino group:

(d) alkyl or halo-alkylsulfonyl halides t -68or the respective anhydrides under appropriate conditions, to obtain a compound of formula (XXXIV) in which Rg represents an alkyl-sulfonyl-amino or halo-alkyl- sulfonyl-amino;

(e) alkyl or aryl isocyanates, by a known process, to obtain a compound of general formula (XXXIV) in which Rg represents a (alkyl-amino or aryl-amino) -carbonyl-amino group;

(f) alkyl chloroformate or halo-alkyl chloroformate, by a known process, to obtain a compound of general formula (XXXIV) in which Rg represents an alkoxy-carbonyl-amino or halo-alkoxy-carbonyl-amino group;

(g) alkyl- or aryl-aldehyde, by a known process, to obtain a compound of general formula (XXXIV) in which Rg represents an alkylideneimino or benzylideneimino group;

(h) an orthoalkyl ester to obtain a compound of the general formula (XXXIV) in which Rg represents an alkoxyalkylideneimino group;

(i) N, N-dialkylformamide or a dialkyl-acetal derivative thereof to obtain a compound of the general formula (XXXIV) wherein Rg represents dialkyl-amino-alkylideneimino;

(j) tris (alkylthio) -methane, in an organic solvent to obtain a compound of general formula (XXXIV) in which Rg represents an alkyl-thio-alkylideneimino group; or (k) £ -toluene-sulfonyl-azide, by a known process or by conversion to a diazonium salt, followed by reduction to

A hydrazine group is obtained, followed by treatment with nitric acid to provide a compound of the general formula (XXXIV) in which Rg represents an azido group, followed by a deprotection step if necessary.

Py. A process for the preparation of compounds of general formula (Ib) in which X, X ^, X ₂ , Xg, X ^ and Y have the meaning defined in Method 1 and Rg represents a cyanate, alkoxy or halo-alkoxy group, in a compound of the general formula is reacted

in which the amino, cyano and X groups are optionally protected by a suitable process, according to Method P ₂ (a), (b), (c), to obtain a compound of general formula (Ic) in which Rg represents a cyanate, alkoxy or halo-alkoxy group.

Pg. A process for the preparation of compounds of general formula

Y (Ib) ζ

'-70 in which X, Rg, X ^, Xg, Xg, X ^ and Y have the meaning defined in Method 1 and R ^ represents a hydrogen or halogen atom or a thiocyanate, alkyl-thio, halo-alkyl- thio, alkenyl-thio, halo-alkenyl-thio, phenyl-thio, heteroaryl-thio, alkyl-sulfinyl, alkyl-sulfonyl, alkenyl-sulfinyl, alkenyl-sulfonyl, halogeno-alkyl-sulfinyl, halogeno-alkyl-sulfonyl, halogeno- alkenylsulfinyl, halo-alkenylsulfonyl, phenylsulfinyl, phenylsulfonyl, heteroaryl-sulfinyl, heteroaryl-sulfonyl, heteroaryl or phenyl optionally substituted, alkyl-carbonyl, alkyl-amino, dialkyl-amino, aralkyl-amino, amino- carbonyl-amino, alkyl-carbonyl-amino, halo-alkyl-carbonyl-amino, aryl-carbonyl-amino, alkyl-sulfonyl-amino, halo-alkyl-sulfonyl-amino, alkyl-amino-carbonyl-amino, aryl-amino- carbonyl-amino, alkoxy-carbonyl-amino, halo-alkoxy-carbonyl-amino, alkylideneimino, benzylideneimino, alkoxyalkylideneimino, dialkyl-amino-alkylideneimino, here 1-thio-alkylideneimino, azido, bis (alkyl-thio or aryl-thio) -methyl, formyl, halo-alkyl-carbonyl, halo-alkyl-thio-carbonyl, halo-alkyl or alkyl, in which it is reacted a compound of general formula

(lb) ου (XXXIV) prepared according to methods at P? (where 0 amino group

-71 is unprotected after protecting group X, Rg or cyan, if necessary):

(a) with a diazotizing agent, preferably with an alkyl nitrite, in an inert solvent, to obtain a compound of general formula (Ic) in which R4 represents the hydrogen atom;

(b) with a diazotizing agent, preferably an alkyl nitrite, in the presence of a halogen atom donor to obtain a compound of general formula (Ic) in which R4 represents a halogen atom, by reacting then that compound with a Grignard reagent or a lithium derivative, followed by reaction with an aliphatic acid chloride or anhydride thereof to provide conversion to a compound of general formula (Ic) in which R4 represents an alkyl group -carbonyl, or that compound is reacted according to Method P ₄ (a) to obtain a compound of general formula (Ic) in which R 4 represents a phenyl or heteroaryl group;

(c) with a diazotizing agent, preferably with an alkyl nitrite, in the presence of (SCN) g or a disulfide in a solvent such as chloroform, to obtain a compound of general formula (Ic) in the which R ^ represents a thiocyanate, alkyl-thio, halo-alkyl-thio, alkenyl-thio, halo-alkenyl-thio, phenyl-thio or heteroaryl-thio group and is optionally oxidized according to Method P ^ (d ) to obtain a compound of the general formula (Ic) in which R3 represents an alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, alkenylsulfonyl, halo-alkylsulfinyl, halo-alkylsulfonyl, halo-alkenyl group -sulfinyl, halogen-alkenyl-sulfonyl, phenyl-sulfonyl

-72nyl, phenyl-sulfonyl, heteroaryl-sulfinyl or heteroaryl-sulfonyl;

(d) according to the Pg (ak) method to obtain a compound of general formula (lc) in which it represents an alkyl-amino, dialkyl-amino, aralkyl-amino, amino-carbonyl-amino, alkyl-carbonyl- amino, halo-alkyl-carbonyl-amino, aryl-carbonyl-amino, alkyl-sulfonyl-amino, halo-alkyl-sulfonyl-amino, alkyl-amino-carbonyl-amino, aryl-amino-carbonyl-amino, alkoxy-carbonyl- amino, halogeno-alkoxycarbonyl-amino, alkylideneimino, benzylideneimino, alkoxyalkylideneimino, dialkyl-amino-alkylideneimino, alkyl-thio-alkylideneimino or azido;

(e) with sodium nitrite and formaldoxime, copper sulfate and hydrochloric acid, by a known process, to obtain a compound of general formula (lc) in which R R represents a formyl group, and then reacts with a reagent of Grignard and then oxidized to provide conversion to a compound of general formula (lc) in which R4 represents an alkylcarbonyl group and then reacted according to method P4 to obtain a compound of general formula (lc) in which R R represents a hydroxyimino-alkylidenyl or alkoxyimino-alkylidenyl group and in the case of R4 represents a formyl group it is reacted according to the Pg (ad) method to provide a compound of general formula (lc) in which R3 represents a halo-alkyl-carbonyl, halo-alkyl-thio-carbonyl, halo-alkyl or alkyl group, followed by a deprotection step if necessary; the previous compound in which R R represents a formyl group is converted, by a known process, into a compound of formula

-73 general (Ic) in which R R represents a bis (alkyl-thio or -aryl-thio) -methyl group.

Ρθ. A process for the preparation of compounds of general formula (Ic) in which X, Rg, X ^, Xg, Xg, X ^ and Y have the meaning defined in Method 1 and R ^ represents a cyano, alkoxy or halo-alkoxy group , in which a compound of general formula is reacted

x- li 'il -CN HO · II II - ^r 3 ^X l ' -Air -χ ₄ (XXXII) x ₂ · V - ^χ 3 Y in which groups X, cyan and Rg are optionally protected by

a known process according to method Pg (a, b, c) to obtain a compound of general formula (Ic) in which R R represents a cyanate, alkoxy or halo-alkoxy group, followed by a deprotection step optional.

P ^ g. Process for the preparation of compounds of general formula (I) in which X, R ^, Rg, X ^, Xg, Xg, X ^ and Y have the meaning defined in Method 1 and Rg represents a CHO group, in which a compound of general formula (Ic) with a reducing agent, preferably with diisobutyl aluminum hydride, in a suitable solvent to provide a compound in which Rg represents a CHO group, optionally oxidizing that compound by a known process to provide the corresponding compound of general formula (XXXV).

(XXXV)

P ^^. Process for the preparation of compounds of general formula (I) in which X, R ^, Rg, X ^, Xg, Xg, X ^ and Y have the meaning defined in Method 1 and Rg represents a hydroxyiminoalkylidenyl group, alkoxyimino-alkylidenyl, halo-alkyl-carbonyl, halo-alkyl-thio-carbonyl, alkyl, halo-alkyl or bis (alkyl-thio or aryl-thio) -methyl, in which a compound of general formula ( I) in which Rg represents a CHO group, after optionally protecting groups X, R ^, or Rg by a known process, if necessary, according to the method Pg (a, b, c, d ), P ₅ (a, b) ου Ρθ (θ), followed by a deprotection step if necessary.

P ^ g. A process for the preparation of compounds of general formula (I) in which X, R ^, Rg, X ^, Xg, Xg, X ^ and Y have the meaning defined in Method 1 and Rg represents a hydrogen or halogen atom or an amino, alkyl-amino, dialkyl-amino, aralkyl-amino, amino-carbonyl-amino, alkyl-carbonyl-amino, halo-alkyl-carbonyl-amino, aryl-carbonyl-amino, alkyl-sulfonyl-amino, halogen group -alkyl-sulfonyl-amino, alkyl-amino-carbonyl-amino, aryl-amino-carbonyl-amino, alkoxy-carbonyl-amino, alkylideneimino,

-75-benzylidene-imino, alkoxy-alkylidene-imino, dialkyl-amino-alkylidene-imino, alkyl-thio-alkylidene-imino, azido, thiocyanate, alkyl-thio, halo-alkyl-thio, alkenyl-thio, halogeno-alkenyl-thio , phenyl-thio, heteroaryl-thio, alkyl-sulfinyl, alkyl-sulfonyl, alkenyl-sulfinyl, alkenyl-sulfonyl, halogeno-alkyl-sulfinyl, halogeno-alkyl-sulfonyl, halogeno-alkenyl-sulfinyl, halogeno-alkenyl-sulfonyl, phenyl -sulfinyl, phenyl-sulfonyl, heteroaryl-sulfinyl, heteroaryl-sulfonyl, or an optionally substituted phenyl or heteroaryl group, in which a compound of the general formula (XXXV) is reacted, after having optionally protected the groups X, R4 or Rg by a known process and if necessary, under conditions suitable for the Curtius rearrangement, for example, by conversion to an acid chloride following the reaction with an alkali metal azide or diphenylphosphoryl azide, in the presence of a organic base such as triethylamine in an alcoholic solvent to obtain a carbamate which can then be hydrolyzed to provide the corresponding compound in which R ₂ represents an amino group, and then reacted, optionally, according to the Pg (ak) or Pg (ac) method, and then if R ₂ represents a halogen atom, it is optionally reacted according to method P ₄ (a), followed by a deprotection step, if necessary.

P ^ g. A process for the preparation of compounds of general formula (I) in which X, R ^, Rg, X ^, X ₂ , Xg, X ^ and Y have the meaning defined in Method 1 and R ₂ represents a cyanate, alkoxy group or halo-alkoxy, in which a compound of the general formula is reacted

ν -76-

(XXXVI) after optionally protecting groups X, or Rg if necessary, according to method P?, Following a deprotection step if necessary.

P ^ 4 · A process for the preparation of compounds of general formulas (XXVIII), (XXXI), (XXXVI) and (XXXVII), according to the methods Pg, Ργ, Ρθ or P ^ g in which the corresponding halogenated compound according to the methods P ^ (a), P ₄ (a), P _g (b) or P ₁₂ 'after the amino group has been protected, if present, it is converted into a Grignard reagent or a derivative of lithium, followed by reaction with a trialkyl borate and oxidation by a known process, followed by a deprotection step if necessary.

P ^ g. A process for the preparation of compounds of general formula

CN

X ₄ ^X 3 (III) in which X ^, Xg, Xg, X ^ and Y have the meaning defined in general formula (I), in which a diciano-propene derivative of general formula is reacted

with a basic reagent.

Ρ ^ θ. The present invention also relates to compounds of general formulas (III) and (XXVIII) to (XXXVII), in which the various symbols have the meaning defined in the previous methods, these intermediate compounds being useful for the preparation of compounds of general formula ( I) according to the procedural methods ^P 1 ^{to P} 15 *

OTHER METHODS

The compounds of the general formula (I) in which X represents a perhalogen-alkylthio group, are further prepared using the following chlorosulfonation process, reduction to a disulfide and finally the reduction provided by the free radical. The process is as follows:

A) The compounds of general formula (XXXIX), in which R ^, Rg, Rg, Y, X ^, Xg, Xg and X ^ have the meaning previously defined for general formula (I), can be prepared from with-

stations of general formula (XXXVIII) in which X represents a hydrogen atom, making the treatment with chlorosulfonic acid either pure or in the presence of an organic solvent such as chloroform, dichloromethane, carbon tetrachloride or dimethylformamide, at a temperature comprised between 0 ° C and 150 ° C. A more specific example may be the preparation of a compound of the general formula (XXXIX) in which R ^ represents an amino, alkyl-carbonyl-amino or halo-alkyl-carbonyl-amino group,

Rg represents a cyano group and Rg represents a hydrogen atom, from compounds of the general formula (XXXVIII) in which R ^ represents an amino, alkyl, carbonyl-amino or halo-alkyl-carbonyl-amino group, Rg represents a group cyano, Rg represents a hydrogen atom and X represents a hydrogen atom, by treatment with chlorosulfonic acid. For the chlorosulfonation of an aromatic compound, a representative procedure is described in J. March, Advanced Organic Chemistry, McGraw-Hill Publ., 1968, p. 402.

(XXXVIII) (XXXIX)

Compounds of formula (XL) wherein R ^, R, Y, X ^, ^{X2, X} 3 ^{'and X} 4 t ™ ⁰ as previously defined for the force-79mula general (I) may be prepared from the of compounds of the general formula (XXXIX) in which Rg represents a hydrogen atom, by treatment with a chlorinating agent such as chlorine, N-chlorosuccinimide, sulfuryl chloride, etc., in an organic solvent such as diethyl ether, acetonitrile or dichloromethane, at a temperature between -70 ° C and 25 ° C. A more specific example may be the preparation of compounds of general formula (XL) in which R) represents an amino, alkyl-starch or halo-alkyl-amino group and Rg represents a cyano group, by treatment of a compound of formula (XXXIX) in which R R represents an amino, alkyl-carbonyl-amino or halo-alkyl-carbonyl-amino group and Rg represents a cyano group and Rg represents the hydrogen atom, using sulfonyl chloride in diethyl ether at -40 ° C

(XXXIX) (XL)

B) Compounds of general formula (XLI) in which R ^, Rg, Y, Χχ, Xg, Xg and X ₄ have the meaning previously defined for general formula (I), can be prepared from compounds of general formula (XXXIX), by treatment with a reducing agent such as triphenylphosphine, in the presence of an organic solvent such as tetrahydrofuran, toluene or dichloromethane, at a temperature between 0 ° C and 110 ° C. A more specific example may be the preparation of compounds of the general formula (XLI) in which it represents a hydrogen atom or an amino, alkyl-carbonyl-amino or halo-alkyl-carbonyl-amino group, Rg represents a cyano group and Rg represents a hydrogen or chlorine atom, from a compound of the general formula (XXXIX), in which R4 represents a hydrogen atom or an amino, alkyl-carbonyl-amino, or halo-alkyl-carbonyl-amino group , Rg represents a cyano group and Rg represents a hydrogen or chlorine atom, by treatment with triphenylphosphine in tetrahydrofuran, at 25 ° C. For the reduction of toluene to provide Î ± -tolyl disulfide, a representative example of a procedure is described in GA Olah et al., J Org Chem., 45 (1980), 4792

C10 ₂ S fl ll ^r 2 - S read il K ₂ Rl- -V- ^R 3 í reducing agent Rl- —IL J go - ^R 3 ^x r -► solvent ^X l- -X4 ^X 2 ' ^x 3 ^X 2 ' V " ^X 3 Y Y 2 (XXXIX) (XLI) C) The compounds general formula (I) at what ^R l- Rg

^ 1 ' ^X 2' ^X 3 ^{and X} 4 ^{0 s} i9 ⁿ ifi ^ca d ° previously defined in the general formula (I) and X represents a perhaloalkyl-thio group,

RgS where Rg represents CFR? Rg and R? represents a fluorine, chlorine or bromine atom and Rg represents a fluorine, chlorine or bromine atom or a perfluoro-alkyl group, which can be prepared by reacting a compound of the general formula (XLI) and a perhalogen alkane compound of general formula (XLII), ZCFR ^ Rg, in which Z represents a chlorine, bromine or iodine atom, R? represents a fluorine, chlorine or bromine atom and Rg represents a fluorine, chlorine or bromine atom or a perfluoro-alkyl group, with a reducing agent that can promote the formation of the free radical CFRyRg from ZCFRyRg, chosen preferably among the group of metals consisting of zinc, cadmium, aluminum, manganese, or a compound with a sulfur oxide, for example, dithionites or hydroxymethylsulfinates. The alkali metal dithionite or the alkaline earth metal dithionite or the metal dithionite corresponds to the general formula (XLIII), M (SgO ^ j) in which n can represent an integer 1 or 2 depending on the valence of the metal M. When if a dithionite of general formula (XLIII) or a hydroxymethylsulfinate is used, it is necessary to add a base chosen from alkali metal hydroxides, alkaline earth metal hydroxides, ammonia, triethyl benzyl ammonium or weak acid salts such as phosphate disodium, sodium metabisulfite, sodium hydrogen sulfite or sodium borate. The reaction is carried out in a solvent (which can solubilize dithionite or hydroxymethylsulfinate and the compound (XLII), ZCFR ^ Rg), such as acetonitrile, formamide, dimethylformamide, dimethylacetamide, hexamethyl phosphoramide , N-methylpyrrolidone, dimethyl sulfoxide or sulfolane, at a temperature between 20 ° C and 85 ° C. The alkali metal dithionite can be added to the reaction mixture in the form of a solution saturated in water or in form. It is also possible to add dithionite in the solid state. In the case of working with a gas that is only slightly soluble in the reaction solvent, the reaction pressure can be increased from 1 atmosphere to 50 atmospheres. A more specific example may be the preparation of compounds of the general formula (I) in which it represents a hydrogen atom or an amino, alkyl-carbonyl-amino or halo-alkyl-carbonyl-amino group, Rg represents a cyano group, Rg represents a hydrogen or chlorine atom and X represents a perhalogen-alkylthio group, RgS where Rg represents CFRyRg and R? represents a fluorine, chlorine or bromine atom and Rg represents a fluorine, chlorine or bromine atom or a perfluoro-alkyl group, reacting a compound of the general formula (XLI) in which R4 represents a hydrogen atom, or an amino, alkyl-starch or halo-alkyl-starch group, Rg represents a cyano group and Rg represents a hydrogen or chlorine atom, and a compound of the general formula (XLII), ZCFRyRg where Z represents a chlorine atom, bromine or iodine, Ry represents a fluorine, chlorine or bromine atom and Rg represents a fluorine, chlorine or bromine atom, or a perfluoro-alkyl group, with sodium dithionite and disodium phosphate, in dimethylformamide, at temperature 25 ° C. The reaction is represented by the following equation:

(XLI) (XLII) (I) chlorosulfonyl intermediate compound of the general formula (XXXIX) and the disulfide intermediate compound of the general formula (XLI) form an additional part of the present invention.

REPRESENTATIVE COMPOUNDS OF THE PRESENT INVENTION

The specific representative pyrrole compounds (CPR) contemplated within the scope of the present invention are the compounds of general formula (I) in which Rg represents a cyano group and the other symbols have the meaning defined in TABLE I (CPR-Ns 1-389) .

Other specific representative pyrrole compounds (CPR) within the scope of the present invention are the compounds of general formula (I) in which Xg and Xg each represent a hydrogen atom, X4 and X4 each represent a chlorine atom, Y represents a group CFg and X, R ^, Rg and Rg have the meaning defined in TABLE 2 (CPR-N9390-491).

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

CJ

CJ

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OE GENERAL FORMULA (I), IN WHICH ω

ui = 3

H

W

Iw m

W ω

O

O.

= 3

CE

CS co x

CN

X

CO

CE «o tu o

all you

CJ «O tu

O ro tu çj to tu

The «You

You

You

What to do

you

ÇJ you

CJ you

CJ you

The α α

CJ <j

<n m cn «M s X X to to to cn ro O O O you you you X O O you CM CM CM ÇJ ÇJ ÇJ u x X 2 2 ? : α O O Ç O O O O O CJ CJ t ) n «0 co CO α O CJ 2

ro

<n cn <n ro to bb ro lb <n ro lb to bb r Ass O (Π b < U bb you cn O cn lu U bu y CM fau y CM O y bu CM bu y CM O O O u O O O O O O O O O O w co co ω CO co OT CO co CO w co CO

H3) N 33 o

II

CN

CE

I

CE

CL

Ç_)

Λ <M

The ro «o

CM ro «o * <o« o m

«The w

"O

ΓΙΟ «0

IO o> o

IO w

CM

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

OCF_C1 SCF /

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

IX

B

X

Hello

X <N «η η 2 2

Ο ο ο ι — 1 γ-Η r-d • Η • Η • Η Ç Ç Ç ΓΟ <ϋ ω ω Ζ Μη Μη Μη

υ ιι

CJ

S οι

«Μ

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

98. SCF_ SO_CF

REPRESENTATIVE PIRROL COHPOSTOS (CPR) OF GENERAL FORMULA (I), IN WHICH

.ί,

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH «η <η ίθ <η b

ϋ σ »« η

ΓΟ <η b

V <η b

U σι b

U

□ C

M m r> o & & Β δ δ δ u

(M s

as h

CO h

O

II

CM

Ç

93 • ..... i '

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

V)

UJ w

m tn w

ο

Q.

QC

CS cn x

CM

X cc cn cn cn cn cn cn b b

CJ O cn b

CJ «n <n bu

CJ cn <n cn <* b bu (u b

8 8 8 b

CJ

CM

O

V)

<n cn D m bu cn B cn bu f * <n bu O cn B O cn b O <n ki bu U (M bu O CM b o <N bu CJ O O O U O O 0 δ O O O (0 M W U) tn K cn «o € 0 to w

«N cn b b

O O

CM

CM

X X

2

CM cn b

O

CM o

cn cn b

υ

V) u

II

CM

QC

I oc

Q_

Ç_)

CM

«0 Λ O rH CM cn m CM CM cn «N «N cn cn Λ rH rt rt H

cn

T-l «n r-C cn

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

THE

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

/ -96CO

X

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OE GENERAL FORMULA (I), IN WHICH w

LU = 3 κω

CD ω

ω ο

ο.

=) cr ω

co

X

CD

X

CO cc

Ή

OC ro b

O to b

U to to

ro <n co ro k co k CO you co k r α CO B O co ro B U co B O co k CM k O <M k k O <M k u CM k Q O O O O U O O O ϋ O O O O CO (0 co «0 V) co co (O co VJ W V)

CN

CN to b

U

CN

Ο co u

II

Μ cr

I ac

The.

O

m C0 r ~ O σ> O rN CN n * n C0 r ~ CN CN CN CN CN co CO co m "O co co co CN CN CN CN CN CM CN CN CN CN CN CN CN

co

CN

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

103

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OE GENERAL FORMULA (I), IN WHICH

JTOO OS

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

-105PIRROL REPRESENTATIVE COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

322. F SOCH

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

-109-

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH w

LU

K w

m = 3 w

Grandfather

O.

Z3

CE

Μ ^-

X

CO

X> Cd

X co oc □ c

CO co tu α

with you

The co tu

The «the co tu α

CO you

U co co b

α

CO

CO co b

υ co

O

II ass

CE

I □ c

CL o

• Ή r-1 O α O <J u u <N CM bu CM B s B X u m X O CN m B u CM bu m bu LO CM B O B U B y CN LO O CM U O O O O O W w co (0 co V>

σ>

σ>

bu bu «Ο ro o

- bu

I 8

«4 CM co w m to 1* «0 Ot O rM m m m m m m m m m LO S0 "O co co co co co co co co (Π co

CM

LO

CO «o

LO «O

110PIRROL REPRESENTATIVE COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH

378. H C (-S) CF

-111-

REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I), IN WHICH THE

II

CM ce

X X O υ η n CM r> n CM X X X X X X the y O P P P u υ u Ό O the o O ffi QC w w

oc

CL

O

Ot t »n

<n oo «n

CM «D co

co m r> 00 σι 00 «0 «0 oo 00 00 00 co <n m co m <n

-112-

TABLE 2

OTHER REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I) IN WHICH X ₂ Ε X ₃ = Η; Χ _χ EX ₄ = Cl; Ε Y = CF _g

SUBSTITUTE GROUPS

CPR-N2 ^R 1 X ^R 3 ^R 2 390. H SCF ₃ α H 391. H SOCFg Cl H 392. H S ° 2 ^CF 3 Cl H 393. H scf ₃ F H 394. H SOCFg F H 395. H so ₂ cf ₃ F H 396. H scf ₃ CN H 397. H SOCFg CN H 398. H S ° 2 ^CF 3 CN H 399. H scf ₃ cf ₃ H 400. H socf ₃ CF „ 3 H 401. H so ₂ cf ₃ ay H 402. H scf ₃ SO ₂ CF ₃ H 403. H SOCFg SO ₂ CF3 H 404. H SO ₂ CF ₃ 80 ₂ σ · ₃ H 405. Cl SCF3 The H 406. Cl S0CF3 Cl H 407. Cl SO2CF3 The H 406. Cl SCF3 F H 409. Cl SOCF3 F H

/ -113-

TABLE 2

OTHER PIRROL COMPOUNDS REPRESENTATIVES (CPR) OF FORMULA GENERAL AT QUAL X ₂ EX ₃ = H; X _t EX ₄ = Cl; Ε Y = ^CF 3 SUBSTITUTE GROUPS CPR-N2 ^R 1 X ^R 3 ^R 2 410. Cl SCF3 CN Η 411. Cl SOCF3 CN Η 412. Cl so ₂ cf ₃ CN Η 413. CN scf ₃ Cl Η 414. CN socf ₃ α Η 415. CN so ₂ cf ₃ σ Η 416. CN scf ₃ F Η 417. CN SOCFg F Η 418. CN only ₂ CF ₃ F Η 419. CN scf ₃ ^σ 3 Η 420. CN socf ₃ cf ₃ Η 421. CN SO ₂ CF3 cf ₃ · Η 422. F scf ₃ α Η 423. F SOCFg α Η 424. F S ° ₂ CF ₃ α Η 425. H scf ₃ α α 426. H socf ₃ α C1 427. H ^ 3 α C1 428. H SCF3 F C1 429. H socf ₃ F C1

TABLE 2

OTHER PIRROL COMPOUNDS REPRESENTATIVES (CPR) OF FORMULA GENERAL AT QUAL X ₂ EX ₃ = Η; X ₁ EX ₄ = Cl; Ε Y = ^CF 3 SUBSTITUTE GROUPS CPR-N2 ^R 1 X ^R 3 ^R 2 430. H so ₂ eF ₃ F α 431. H SCF ₃ CN α 432. H socf ₃ CN Cl 433. H ^ 2 ^ 3 CN Cl 434. H scf ₃ ^CT 3 Cl 435. H socf ₃ ^σ 3 α 436. H s ° ₂ cf ₃ ^σ 3 Cl 437. Cl scf ₃ α α 438. Cl socf ₃ α Cl 439. Cl S0 ₂ cf ₃ α Cl 440. Cl scf ₃ F α 441. Cl socf ₃ F α 442. Cl so ₂ cf ₃ F α 443. Cl scf ₃ CN α 444. Cl SOCFg CN α 445. Cl ^ 2 ^ 3 CN α 446. Cl SCF ₃ ^ 3 α 447. Cl socf ₃ ^σ 3 C1 448. Cl so ₂ cf ₃ ^σ 3 α 449. CN scf ₃ α C1

-115-

TABLE 2

OTHER PIRROL COMPOUNDS REPRESENTATIVES (CPR) OF FORMULA GENERAL AT QUAL X ₂ EX ₃ = H; Xj EX ₄ = Cl; And Y = ^CF 3 SUBSTITUTE GROUPS CPR-N2 ^R 1 X ^R 3 ^R 2 450. CN SOCFg α α 451. CN s ° ₂ CF ₃ α Cl 452. CN scf ₃ F Cl 453. CN SOCFg F Cl 454. CN so ₂ cf ₃ F Cl 455. CN SCF3 CN α 456. CN SOCFg CN α 457. CN so ₂ cf ₃ CN α 458. CN scf ₃ ^CT 3 Cl 459. Cl SO2CF3 F Η 460. CN SOCFg <* 3 α 461. CN so ₂ cf ₃ Cl 462. H scf ₃ α CF3 463. H scf ₃ F CF3 464. H socf ₃ F CF3 465. H so ₂ cf ₃ F CF3 466. H scf ₃ CN CF3 467. H SOCFg CN CF3 468. H SOgCFg CN CF3 469. H SCF ₃ α CF3

-116PART 2

OTHER REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I) IN WHICH X ₂ Ε X ₃ = H; Xj EX ₄ = CI; Ε Y = CFg

SUBSTITUTE GROUPS

CPR-N2 ^R 1 X ^R 3 ^R 2 470. H SOCFg α cf ₃ 471. H Cl cf ₃ 472. H SCFg Cl ch ₃ 473. H SOCFg Cl ch ₃ 474. H so ₂ cf ₃ Cl ch ₃ 478. H SCF ₃ F ch ₃ 476. H SOCFg F ch ₃ 477. H so ₂ cf ₃ F ch ₃ 478. H SCHF2 Cl CN 479. H SOCHF2 α CN 480. H SO2CHF2 α CN 481. H SCHF2 Η CN 482. H SOCHF2 Η CN 483. H SO2CHF2 Η CN •O·"· H SO2CHCI2 α CN 485. H S0CHC12 α CN 486. H SOCHOF α CN 487. H SO2CHC1F α CN 488. H SCHF2 α α 489. H SO2CHF2 α Cl

TABLE 2 / -1179

OTHER REPRESENTATIVE PIRROL COMPOUNDS (CPR) OF GENERAL FORMULA (I) IN WHICH X ₂ EX ₃ = H; Xj EX ₄ = Cl; EY = CFg

SUBSTITUTE GROUPS

CPR-N2

490. H

491.

Cl

SOCHF2

SO2CHF2

Etr

Cl

CH3

CF3

DETAILED EXAMPLES OF COMPOUND SYNTHESIS

Examples 1 to 22 below further illustrate the methods of synthesis and the physical properties of insecticidal compounds (and their chemical intermediates) according to the present invention.

EXAMPLE 1

A solution of 910 mg (2.07 mmol) of i- (2,6-dichloro-4-trifluoro-methyl-phenyl) -2-chloro-3-cyano-4 was stirred at room temperature for 1.5 hours -trifluoro-methyl-thio-pyrrole (prepared according to the procedure described in EXAMPLE 4) and 492 mg of 80% meta-chloro-peroxy-benzene acid (394 mg; 2.28 mmoles in 25 ml of chloroform, and then it was heated under reflux overnight, an additional 45 mg (0.21 mmol) of m-chloro-peroxy-benzoic acid was added and maintained under reflux for 1 hour. Heating was stopped and diluted the reaction mixture with dichloromethane and washed with an aqueous solution of sodium hydrogencarbonate The organic layer was dried over anhydrous MgSO4 and concentrated under reduced pressure to provide a colorless solid residue. obtain a total of 950 mg of product which was subjected to chromatography on silica gel, eluting with a 2: 1 v / v mixture of dichloromethane / hexane. The first fractions contained 310 mg (24%) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4-trifluoromethyl-sulfonyl-pyrrole (EXAMPLE 1) in solid and colorless state.

Recrystallization from a hexane / ethyl acetate mixture gave 240 mg of sulfone in the form of colorless needles whose melting point is 198 ° C.

f-119EXAMPLE 2

The chromatography was performed at the end of EXAMPLE 1. The last fractions of that chromatography provided 600 mg (48% 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4-trifluoromethyl -sulfonyl-pyrrole (EXAMPLE 2) in solid and colorless state Recrystallization from a toluene / hexane mixture gave 390 mg of sulfoxide as a colorless powder, mp 152 ° -154.5 ° C.

EXAMPLES 3A and 3B

EXAMPLES 1 and 2 were repeated using 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4-trifluoromethyl-thio-5-bromo-pyrrole as the starting compound prepared according to the procedure for EXAMPLE 5. The compound of EXAMPLE 3A is 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4-trifluoromethyl-sulfinyl-5-bromo- pyrrole. This compound, prepared according to a procedure identical to that of EXAMPLE 2, has a melting point close to 123 ° C. The compound of EXAMPLE 3B is 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4-trifluoromethylsulfonyl-5-bromo-pyrrole. This compound, prepared according to a procedure identical to that of EXAMPLE 1, has a melting point of about 113 ° C.

EXAMPLE 4

Under a nitrogen atmosphere, a solution of 3 g (6.6 mmol) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano was stirred 5-chloro-pyrrole (prepared according to the procedure described in EXAMPLE 8) in 50 ml of tetrahydrofuran

Λ.

anhydrous and 3.9 ml (3.4 g; 33 mmol) of t-butyl nitrite was added. After 30 minutes, the reaction mixture was heated under reflux for about 1 hour and then concentrated under reduced pressure to provide 3.69 g of a solid residue. This process was repeated in order to obtain a total of 4.07 g of solid residue which was subjected to chromatography on silica gel using a 1: 1 v / v mixture of dichloromethane / hexane as eluent to provide 2, 9 g (91%) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4-trifluoromethyl-thio-pyrrole (EXAMPLE 4) in solid and colorless state. Recrystallization from a hexane / ethyl acetate mixture gave 1.87 g of product as a colorless powder whose melting point is about 137 ° C.

EXAMPLE 5

To a heterogeneous mixture of 2.4 g (5.28 mmol) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-5-chloro- pyrrole (prepared according to the procedure described in EXAMPLE 8) in 40 ml of bromoform, under an inert atmosphere, 0.94 ml (820 mg; 7.92 mmol) of t-butyl nitrite was added. After 15 minutes of stirring at room temperature, the reaction mixture was concentrated under reduced pressure to provide 3.9 g of residue. This residue was combined with the product of a previous reaction of 300 mg of the same pyrrole used as the starting compound. The crude product was chromatographed on silica gel, eluting with a 4: 1 v / v hexane / dichloromethane mixture. 1.72 g (56%) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole were separated (EXAMPLE 5), which was recrystallized from hexane to provide 780 mg of product in solid and colorless state whose melting point is certain

92 ° C.

EXAMPLE 6

A solution of 1.91 g (4.21 mmol) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amiηο-3-trifluoromethyl-thio was cooled to 0 ° C. 4-cyano-5-chloro-pyrrole (prepared according to the procedure described in EXAMPLE 8), 77 mg (0.63 mmol) of 4-dimethylamino-pyridine and 20 ml of pyridine under an inert atmosphere and then added 1.01 ml (1.50 g; 7.14 mmol) of trifluoroacetic anhydride are added. The reaction mixture was allowed to stir at 0 ° C for 1 hour and then at 20 ° C for 4 hours and then an additional 0.30 ml (2.1 mmol) of trifluoroacetic anhydride was added. . After a total period of 24 hours, the reaction mixture was diluted with dichloromethane and concentrated. The residue was washed with aqueous hydrochloric acid and then with water and recrystallized from a mixture of hexane / ethyl acetate to provide 860 mg (37%) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) ) -2 - [(trifluoromethyl) -carbonyl-amino] -3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole (EXAMPLE 6) in solid and slightly green state, the melting point being about 190 ° C .

EXAMPLE 7

A mixture of 1.50 g (3.3 mmol) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) - was stirred for 4 days at 20 ° C and for 1 day at reflux temperature. 2-amino-3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole (prepared according to the procedure described in EXAMPLE 8), 0.10 g of 4-dimethylamino-pyridine, /

ζ -122> '

0.33 ml (0.32 g; 4.1 mmoles) of pyridine, 0.31 ml (0.34 g; 4.3 mmoles) of acetyl chloride and 10 ml of acetonitrile. Then an additional 0.03 ml of acetyl chloride was added and reflux was maintained for an additional day, then the reaction mixture was cooled, diluted with dichloromethane and partitioned between an aqueous solution of acid IN hydrochloric acid and a saturated aqueous solution of sodium hydrogen carbonate. The organic layer was dried over anhydrous magnesium sulfate and evaporated to provide 1.42 g of a beige solid. Chromatography on silica gel eluting with a 4: 1 v / v mixture of hexane / ethyl acetate, followed by recrystallization from an ethanol / water mixture provided 480 mg (29%) of 1- (2,6-dichloro -4-trifluoromethyl-phenyl) -2-methyl-carbonyl-amino-3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole (EXAMPLE 7) in the form of colorless needles whose melting point is about 216 ° Ç.

EXAMPLE 8

Under an inert atmosphere, a stirred solution of 1.50 g (3.57 mmol) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino- was cooled to -20 ° C. 3-trifluoromethyl-thio-4-cyano-pyrrole (prepared according to the procedure described in EXAMPLE 13) in 15 ml of diethyl ether and then a 0.29 ml solution (0) was added dropwise , 48 g; 3.6 mmoles) of sulfuryl chloride in 15 ml of anhydrous ethyl ether. Then the reaction mixture was allowed to warm to 20 ° C and stirred for 2.5 days, then an additional 0.03 ml (0.4 mmol) of sulfuryl chloride was added and stirring was continued for 1 more day. An additional 0.03 ml of sulfuryl chloride was added and after a further day of reaction the reaction was stopped with 20 ml of an aqueous solution of '-123 />

10% potassium carbonate. The phases were separated and the aqueous layer was extracted with ether. The etheric layers were combined, washed with water, dried over anhydrous magnesium sulfate and concentrated to provide 1.56 g of a bronze-colored solid. The crude product was chromatographed on silica gel using a 2: 1 v / v mixture of dichloromethane / hexane as eluent to provide 1.30 g (80%) of 1- (2,6-dichloro-4- trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole (EXAMPLE 8) in the solid state and with a slightly pink color. Recrystallization from a cyclohexane mixture provided 810 mg of product in the form of off-white needles whose melting point is about 176 ° C.

EXAMPLE 9

A process identical to that of EXAMPLE 8 was used except that 1- (2-chloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-pyrrole was used (mp 169 ° C) as a reagent, which was prepared by a process as described in EXAMPLE 13. The final product obtained was 1- (2-chloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio- 4-cyano-5-chloro-pyrrole (EXAMPLE 9), e.g. f. about 148 ° C.

EXAMPLE 10

A process identical to that of EXAMPLE 8 was used except that 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-dichloro-fluoro-methyl-thio-4-cyano -pyrrole (mp 202 ° C) as a reagent, which was prepared by a process as described in EXAMPLE 13. The final product obtained was

1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-dichloro-fluoro-methyl-thio-4-cyano-5-chloro-pyrrole (EXAMPLE 10), m.p.

207 ° C.

EXAMPLE 11 compound 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2,4-bis (trifluoromethyl-thio) -3-cyano-5-amino-pyrrole (EXAMPLE 11) has a melting point of 161 ° C and was prepared according to the procedure of EXAMPLE 13 (first compound) using an excess of trifluoromethane-sulfenyl chloride.

EXAMPLE 12

To a cold solution (0 ° C) of 1.53 g (3.60 mmol) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4- cyano-pyrrole (prepared according to the procedure described in EXAMPLE 13, the melting point being about 182 ° C) in 15 ml of pyridine, a solution of 1.46 g (3, 6 mmoles) of 80% pyridinium bromide perbromide in 15 ml of pyridine. After 30 minutes, the reaction mixture was poured into cold ethyl ether (0 ° C) and the precipitate that formed was removed by filtration. This filtrate was washed with an aqueous hydrochloric acid solution, an aqueous sodium hydroxide solution and water. The organic layer was dried over anhydrous magnesium sulfate and evaporated to provide 1.34 g of a brown solid. This solid was combined with 230 mg of product from a previous reaction of 300 mg (0.7 mmol) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoro-methyl- thio-4-cyano-pyrrole with 0.29 g of pyridinium bromide perbromide at ζ

-125 / 80%. The consolidated products were chromatographed on silica gel eluting with 4: 1 v / v hexane / ethyl acetate to provide 1.31 g (73%) of 1- (2 _; 6-dichloro-4-trifluoromethyl-phenyl) - 2-amino-3-trifluoro-methyl-thio-4-cyano-5-bromo-pyrrole (EXAMPLE 12) in solid and white color. Recrystallization from a hexane / ethyl acetate mixture provided 910 mg of this product in the form of colorless needles whose melting point is about 160 ° C.

EXAMPLE 13

A stirred solution of 2.00 g (6.25 mmol) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-4-cyano-pyrrole in 60 ml was cooled in an ice bath of dichloromethane, prepared as indicated below and a cooled (-78 ° C) solution of dichloromethane containing 0.55 ml (0.85 g, 6.2 mmol) of trifluoromethane-sulfenyl chloride was added slowly. After stirring for 2 hours at 0 ° C, a stream of nitrogen was passed through the reaction mixture for 1 hour. It was partitioned between a saturated aqueous solution of sodium hydrogen carbonate and water, dried over anhydrous magnesium sulfate and concentrated in vacuo to provide 3.14 g of a light brown solid. This solid was chromatographed on silica gel using 3: 2 v / v dichloromethane / hexane as eluent to provide two samples of colorless solid weighing 900 mg and 950 mg. Recrystallization from chloroform gave 680 mg and 630 mg of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-pyrrole respectively ( EXAMPLE 13) whose melting point is about 182 ° C.

, / - 126Λ

The reagent used in this process was prepared according to the following procedure: A solution of 4.64 g (14.5 mmoles) of l - [(2,6-dichloro-4-trifluoromethyl-) was heated under reflux overnight. phenyl) -amino] -2,3-dicyano-propene and 2.02 ml (1.47 g;

14.5 mmoles) of triethylamine in 30 ml of benzene and then concentrated in vacuo. The residue was partitioned between ethyl ether and water and the ether layer was dried over anhydrous magnesium sulfate and concentrated to provide 3.79 g of a light brown solid. Recrystallization from an ethanol / water mixture provided 2.79 g (60%) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-4-cyano-pyrrole whose melting point is about 176 ° C.

Starting l-aryl-amino-2,3-dicyano-propene was prepared according to the following procedure: A sample of

20.5 g (0.140 mmol) of formyl-succinonitrile potassium salt in about 30 ml of water and acidified with concentrated aqueous hydrochloric acid. It was then extracted with diethyl ether, the ether extract was dried over anhydrous magnesium sulfate and evaporated to provide 3.87 g of a brown liquid. This liquid was added to a solution containing 5.04 g (22 mmol) of 2,6-dichloro-4-trifluoromethyl-aniline and 40 mg of para-toluenesulfonic acid monohydrate in 50 ml of benzene. The heterogeneous reaction mixture was heated under reflux overnight, and the water was separated. Then, the reaction mixture was cooled and concentrated to provide 7.66 g of a yellow liquid. Trituration with hexane precipitated 6.68 g (95%) of l - [(2,6-dichloro-4-trifluoromethyl-phenyl) -amino] -2,3-dicyano-propene in the solid, yellow state. Recrystallization from ethanol / water provided a sample whose melting point is 101 ° C.

EXAMPLES 14A and 14B

To a suspension of 1.17 g (3.30 mmol) of 1- (4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-pyrrole and 0.46 ml (0.34 g ; 3.3 mmoles) of triethylamine in 20 ml of chloroform cooled to -20 ° C, a solution of 0.19 ml (0.59 g; 3.7 mmoles) of bromine in 5 ml of chloroform was added . The reaction mixture was stirred at -20 ° C for 1 hour and then allowed to warm to 0 ° C. An additional 0.04 ml (0.13 g; 0.8 mmol) of bromine and after 15 minutes of further stirring, the reaction mixture was diluted with dichloromethane and partitioned between water and a saturated aqueous solution of hydrogen carbonate. sodium. The organic layer was dried over anhydrous magnesium sulfate and concentrated to provide 1.11 g of a brown solid. This product was combined with a previous reaction of 1.00 g (2.8 mmoles) of 1- (4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-pyrrole with 0 , 15 ml of bromine. Chromatography on silica gel eluting with a 3: 1 v / v dichloromethane / hexane mixture provided 1.40 g (52%) of 1- (4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio -4-cyano-5-bromo-pyrrole (EXAMPLE 14A) in solid and yellow color. Recrystallization from a hexane / ethyl acetate mixture provided the product in the form of light yellow platelets whose melting point is about 175 ° C.

1- (4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-pyrrole (EXAMPLE 14B) whose melting point is about 152 ° C can be prepared from 1 - / (4-trifluoromethyl-phenyl) -amino / -2,3-dicyano-propene according to a process identical to that described in EXAMPLE 13.

EXAMPLES 15A and 15B

1- (2-Chloro-4-trifluoromethyl-phenyl) -aminq7-2,3-diciano-propene was prepared according to the same procedure as described in EXAMPLE 13. This diciano-propene was used to prepare

1- (2-chloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-pyrrole (EXAMPLE 15A) whose melting point is about 169 ° C, using a process identical to that described in EXAMPLE 13. This pyrrole was used to prepare 1- (2-chloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-5-bromo- pyrrole (EXAMPLE 15B) whose melting point is about 157 ° C, according to the procedure of EXAMPLE 14.

EXAMPLES 16A and 16B 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-4-cyano-pyrrole prepared according to EXAMPLE 13 was treated with CFCl ·, -SC1, according to the procedure EXAMPLE 13 (which used CFgSCl) to obtain 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-dichloro-fluoro-methyl-thio-4-cyano-pyrrole ( EXAMPLE 16A) whose melting point is about 202 ° C.

This compound was treated with /-butyl nitrite according to the procedure of EXAMPLE 4 to provide 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro- fluoro-methyl-thio) -pyrrole (EXAMPLE 16B) whose melting point is about 158 ° C.

EXAMPLE 17

The last compound of EXAMPLE 16 was reacted according to a process identical to the process of EXAMPLES 1 and 2 using hydrogen peroxide in trifluoromethyl-peracetic acid (instead of m-chloro-peroxy-benzoic acid) to obtain 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole (EXAMPLE 17) whose melting point is about 119 ° C.

EXAMPLE 18

According to the procedure for EXAMPLE 17, using a double amount of hydrogen peroxide, the last compound of EXAMPLE 16 was transformed into 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3- cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole (EXAMPLE 18) whose melting point is about 179 ° C.

EXAMPLE 19

The first compound of EXAMPLE 16 was treated with t-butyl nitrite according to the procedure of EXAMPLE 4 to provide 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -3-cyano-4- (dichloro-4) fluoro-methyl-thio) -pyrrole (EXAMPLE 19) whose melting point is about 120 ° C.

EXAMPLE 20

The compound of EXAMPLE 19 was oxidized according to the procedure of EXAMPLE 17, to obtain 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) ) -pyrrole (EXAMPLE 20); mp 150 ° -152 ° C.

EXAMPLES 21A, 21B and 21C

1 - [(2,6-dichloro-4-trifluoromethoxy-phenyl) -amino] -2,3-dicyano-propene was prepared according to the procedure used for the last compound in EXAMPLE 13, using 2,6-dichloro -4-trifluoromethoxy aniline instead of 2,6-dichloro-4-trifluoromethyl aniline.

This compound was converted to 1- (2,6-dichloro-4-trifluoromethoxy-phenyl) -2-amino-4-cyano-pyrrole according to the procedure used for the second compound of EXAMPLE 13.

/ (-130 This compound was converted to 1- (2,6-dichloro-4-trifluoromethoxy-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-pyrrole according to the procedure used for the first compound EXAMPLE 13.

This compound was converted to 1- (2,6-dichloro-4-trifluoromethoxy-phenyl) -2-amino-3- (trifluoromethyl-thio) -4-cyano-5-chloro-pyrrole (EXAMPLE 21A), mp 196 ° -197 ° C, according to the EXAMPLE 8 process.

This compound was converted to 1- (2,6-dichloro-4-trifluoromethoxy-phenyl) -2-chloro-3-cyano-4-trifluoromethyl-thio-pyrrole (EXAMPLE 21B) whose melting point is about 172 ° C, according to the procedure of EXAMPLE 4. This compound was converted to 1- (2,6-dichloro-4-trifluoromethoxy-phenyl) -2-chloro-3-cyano-4-trifluoromethyl-sulfonyl-pyrrole (EXAMPLE 21C) whose melting point is about 187 ° C, according to the procedure of EXAMPLE 18.

EXAMPLES 22A, 22B and 22C

A mixture of 2-chloro-4-chloro-sulfenyl-3-cyano-1— (2 *, 6'-dichloro-4'-trifluoromethyl) was dissolved in trifluoroacetic acid (190 ml) at 0 ° C -phenyl) -pyrrole and 2-chloro-3-cyano-4-dichloro-fluoro-methyl-sulfenyl-1- (2 ', 6 ^, -dichloro-4'-trifluoromethyl-phenyl) -pyrrole (47.77 g; 0.101 mmol; 1.0 equivalent). 30% hydrogen peroxide (10.8 ml; 0.106 mmol; 1.05 equivalent) was added dropwise. The reaction mixture was stirred at 0 ° C for 7 hours and 15 minutes and then placed in a refrigerator (10 ° C) overnight. More 30% HgOg (10.8 ml; 0.106 mmol; 1.05 equivalent) was added at 0 ° C the following morning. The reaction was stirred at 0 ° C for 9 hours and then placed in a refrigerator overnight.

(-131 More 30% HgOg (10.8 ml; 0.106 mmole; 1.05 equivalent) was added at 0 ° C the following morning. After 3.5 hours the reaction mixture was poured into 2 liters of ice / water, stirred vigorously and then filtered.

Similarly, a mixture of 2-chloro-4-chloro-sulfenyl-3-cyano-1- (2 ', 6'-dichloro-) was dissolved in trifluoroacetic acid (188 ml) at 0 ° C 4'-trifluoromethyl-phenyl) -pyrrole and 2-chloro-3-cyano-4-dichloro-fluoro-methyl-sulfenyl-1- (2 ', 6'-dichloro-4'-trifluoromethyl-phenyl) -pyrrole (40 , 77 g; 0.0848 mmol; 1.0 equivalent). Dropwise added ^to it HgOg (17.7 mL, 0.173 mmol, 2.05 equivalent). The reaction mixture was stirred at 0 ° C for 2 hours and 45 minutes and then placed in a refrigerator (10 ° C) overnight. After stirring for 8 hours at 0 ° C, the reaction mixture was put back in a refrigerator overnight. The reaction mixture was then allowed to return to room temperature and stirred overnight at room temperature. The next morning, more 30% HgOg (9.05 ml; 0.0886 mmole; 1.05 equivalent) was added at 0 ° C and the reaction was maintained at 0 ° C for 6 hours and 40 minutes and then allowed to return to room temperature and stirred over the weekend. The reaction mixture was poured into 2 liters of ice / water, stirred vigorously and then filtered.

The precipitates from the two reactions were combined and dissolved in 500 ml of dichloromethane, washed with 500 ml of water, 500 ml of 10% aqueous NaHSOg and 500 ml of saturated aqueous chloride solution. sodium. The organic phase was dried over sodium sulfate, filtered and the solvent was evaporated

to obtain 74.96 g (79.9% yield) of a solid. This solid was recrystallized from 690 ml of hexane / dichloromethane (2: 1) to which was added 20 ml of dichloromethane to obtain 6.98 g of a solid identified as 2-chloro-4-chlorosulfonyl-3- cyano-1- (2 ', 6'-dichloro-4 ¹ -trifluoromethyl-phenyl) -pyrrole (EXAMPLE 22A). This compound was then recrystallized from 103 ml of isopropanol to provide 3.97 g; mp 187 ° -188.5 ° C.

2-chloro-4-chlorosulfonyl-3-cyano-1- (2 ', 6'-dichloro-4'-trifluoromethyl-phenyl) -pyrrole (3.97 g; 9.06 mmol) was dissolved , 0 equivalent) in tetrahydrofuran (15.8 ml) at 0 ° C. Triphenylphosphine (2.41 g, 1.0 equivalent) was added in the solid state. The solution changed to yellow. After 2.5 hours, the ice bath was removed and the reaction mixture was allowed to stir at room temperature overnight. More triphenylphosphine (2.55 g; 9.72 mmoles; 1.06 equivalent) was added and the reaction mixture was allowed to stir at room temperature overnight. A precipitate formed, 3 ml of tetrahydrofuran was added and the reaction mixture was washed twice with a saturated aqueous solution of sodium chloride and extracted again. The organic phase was dried over MgSO4, filtered and the solvent was evaporated in vacuo to provide 9.44 g of a waxy solid. This solid was chromatographed on silica gel to provide 3.39 g of a waxy solid. This solid was then recrystallized from 140 ml of isopropanol to provide 2.54 g (74.9%) of bis [2-chloro-3-cyano-1- (2 ', 6'-dichloro-4'-trifluoromethyl- phenyl) -pyrrol-4-yl] -disulfide (EXAMPLE 22B), mp 218.8 ° -220.3 ° C.

Bis [2-chloro-3-cyano-1- (2 ', 6'-dichloro-4'-trifluoromethyl-phenyl) -pyrrol-4-yl] -disulfide (0.80 g; 1.08 mmole;

/ '-1331.0 equivalent) in dimethylformamide (10 ml) and cooled to 0 ° C. NagHPO ^ (0.46 g; 3.24 mmoles; 3.0 equivalents) was dissolved in 5 ml of water and then added to the dimethylformamide solution. A precipitate formed and 15 ml of dimethylformamide and 10 ml of water were added. NagSgOO solid (0.564 g; 3.24 mmoles; 3.0 equivalents) was added. The reaction color changed to faint yellow. Dibromodifluoromethane (0.65 g; 3.1 mmol; 2.87 equivalents) was added to a cooled tare flask and then transferred to the reaction mixture. The reaction mixture became colorless with a white precipitate.

After 1 hour and 50 minutes, 10 ml of DMF was added and then another 0.93 g of CBr ₂ F _{2 was added} and then the reaction vessel was sealed and allowed to stir at room temperature overnight . After cooling to 0 ° C, the reaction mixture was added to 200 ml of water and extracted four times with 150 ml of ethyl ether. The organic phase was washed twice with 100 ml of a 50% aqueous hydrochloric acid solution, twice with 100 ml of a saturated aqueous solution of sodium hydrogencarbonate and with 100 ml of a saturated aqueous solution of sodium chloride. The organic phase was dried over MgSO4, filtered and the solvent was evaporated in vacuo to provide 80.7 mg of a white solid. Then, the initial aqueous phase was filtered to collect a white solid that had precipitated overnight. That solid was dissolved in dichloromethane, the solvent was evaporated in vacuo and dried to provide 0.348 g of a white solid (total yield 0.429 g; 40% yield). This product was combined with the 80.7 mg sample and chromatographed on silica gel to provide 0.362 g of a white solid identified as 4-bromo-difluoromethyl-sulfenyl-2-

'-134-chloro-3-cyano-1- (2', 6'-dichloro-4'-trifluoromethyl-phenyl) -pyrrole (EXAMPLE 22C), mp 128.3 ° -133.7 ° C.

ADDITIONAL SYNTHESIS EXAMPLES

Using the procedures previously described in detail for the synthesis of the compounds of EXAMPLES 1 to 22 or using other methods or synthetic processes now generally described, several additional synthetic examples (EAS) of the pyrrole compounds of general formula ( I) The structures of these compounds and their corresponding melting points are shown in TABLE 3 (ESA Ns. 1-91: compounds of general formula (I) in which Xg and Xg each represent a hydrogen atom and the other symbols have the indicated meaning) and in TABLE 4 (ESA N2s 92-195: compounds of general formula (I) in which Xg and Xg each represent a hydrogen atom, X ^ and X ^ each represent a chlorine atom, Y represents a trifluoromethyl group and the other symbols have the indicated meaning).

CJ

O

D O O O O Q LO CM to IO O LO LO * CM · * CO LO τΗ co ν1 LO LO 00 vH 1 O 1 T ^- 1 CO O CM O tH O 1 saw CM LO 1 LO O t i □ · » O » CM O □ LO O CM LO rd CM O CO O CM ν1 vH ν1 CM

O

CD IX τ — I

I o

IX o

cn o

V vH

The in o Όr — I

O o

IX rH

The in cn

CD

Ή

The nr

IX o

V cn t — I I o

CM cn t — I /

f

-135 ·

The in o

Μ ^-

CM o

cn cn «M

ADDITIONAL SYNTHESIS EXAMPLES (EAS) OF PIRROL COMPOUNDS

cn <n cn cn cn cn X X X X X X ^ 4 rM ^ 4 «Η CJ CJ CJ CJ CJ CJ υ U O u u CJ υ CJ

x

II ω

x

LU

CM

X w

UJ <

x

UJ o

LU

O

V)

X

W cn o

X

X

CD cn cc

CM (X □ c i

cn «t

UJ

P P P P u P u u Ll P fM P Ll P 0 n 0 0 0 0 0 0 0 0 CJ 0 0 0 tO to ro fO cn ro X X X X X X »“ 4 -ç Ή fH •H «—I rH O U α u u u cj CJ CJ u υ u CJ α * • 4 rM -1 Ή rH "H O u X X CJ u X (J X O X O X O

CJ

CJ

CJ

CJ

CJ

CJ

CJ

CJ

CJ

CJ

CM CM to to CM CO € 0 O O O O fH Ç f4 O CM fM to to co to co co to to O to O co fM r-4 ro Γ0 cn to cn cn to ro fM to fM (O O u bu bu Lu bu Ass you bu bu bu bu bu Ass Ass bu U O CJ U U CJ α U U υ U U O U

CM

X

CM cn »co

CM fM CM X X X X X X X Z z

CM cn

ADDITIONAL SYNTHESIS EXAMPLES (EAS) OF PIRROL COMPOUNDS

Z

-137c_j

O

LL

X

O O O O LD O O 77) O CD 00 O O C73 Ç\] LO CO cn rH cn r * » CO CD O t — 1 r ^. v1 vH vH CD tH Od C \ J v-1 1 1 I I 1 1 1 1 O O O O O O O 1 O O hx co tn r · ^ cn co r-x O co cn co CD co hx 00 vH vH vH Ή v4 OJ v4

O

CD O vi

I o

• V co o

ra o

CD

ADDITIONAL SYNTHESIS EXAMPLES (EAS) OF PIRROL COMPOUNDS

cn oo o

CD σ>

it is

ra cn o

c \ j o XI vI I o, ra vH ro x

LU

CM

X <

tc

LU

CD <

x o

LL

LU> -

CO <o CO co co co bu co C0 Ui bu co B B B O ú u U »-4 O O M B O υ M r4 U O u ffi U u O O cn U O O ffl u O

ω

LU ω

m w

w o

X

CC u

ra x

C \ J

X

I

CD tn en

X o

the tn en

X o

CM CM CM O O O O O tn cn cn tn tn cn cn tn tn tn cn CM CM CM CM Csl CM CM CN ^ 4 ^ 4 CM •H V) r4 tn r4 r * 4 w rH "H u u ^ 4 O co O co O O O CO U υ u CM CM u u. u bu u. bu bu bu u u bu B bu bu bu O O u u O U u O O O CJ U U υ

CN

X σι

CN co rH CN «O« O co * «O CO m

co co co

CO

CB co σι o co *

CN

-138 * ·

CL

ADDITIONAL SYNTHESIS EXAMPLES (EAS) OF PIRROL COMPOUNDS

II x

x

UI

CM w X UI _l t- z < l-l 3 3 σ H < w H z w * m 3 H w _l w "Ç ο ff X UI 3 CD Ε < _J 3 X ff O U. UI O CD

> x cc

CM

X

I x

LU

ο ο X ο ο O * ιη * ο ο ο n O O CM σ> LD (Ο X LD QC CM CO CO 00 rd 00 <D Ο τ — 1 ο QC γΗ 1 νΗ νΗ ο ο I 00 ο 1 V νΗ 1 ο 1 1 cn 00 ο | CM Ο ιη 1 ο ιη ο Ο σ> CM ιη O CM CO νΗ ο 00 · » ο τΗ rd τ — 1 O O r \ j ** X * Ή X 00 ίΩ 00 CT3 00 X CO X έΗ τΗ 00 * 3 · Ή CM τ — 1 τΗ * Η • Μ rH rd rd rd r- | rd ο υ α α υ ο υ α υ ο ο O υ α m ro ζ X υ η you CM (υ ro ro CM ro co ro ο υ U rd Ass you ο lu Μ rd rd kl lu Ass ο Ο α ο υ Ο ο you η υ (J n you you ιο <ο ro ΓΟ ro ro ζ X X X rd rd rd υ υ υ ο α ο ο Ζ υ you you O z X Ή ι — 1 rH ιΗ rd rd U ο υ ο ζ you υ υ X Ζ X ζ O υ O ζ 2 2 2 ζ 2 2 2 2 2 2 2 2 2 υ υ Ο you υ Ο α α υ υ υ O O you CM <Μ <Μ CM ο Ο Ο ο ο ο O <0 10 V) 10 ΙΛ co V) V) C0 co V) co <o CO CM (Μ <Μ rH CM CM rd <Μ <Μ rd CM CM ο ο υ rH υ rd u rd rd you υ <Μ <Μ ο X ο ο CM α you CM you υ Lu Lu you Lu lu lu lu lu (u Ass you lu you you Ο υ α α you α υ ο ο υ you you you you CM <Μ CM CM Ζ Ζ Z Z ζ s X X X X X 2 X X X X 2 2 <η • Π W Γ * 00 σι Ο rd «Μ ro * m u> ιη m uo tn m m IO

CL

the o

O rd O O O O O O O O O O O CD ^ r CO r ^ rd IO CD O CD co LO rd v-1 O rd LO to to O O CO rd CO 1 1 rd rd rd rd rd rd rH rd rd co CM 1 O O 1 1 1 I 1 1 1 1 1 -fd 1 O to ID O O O O O O O O O (D O · » · * r ** » CM CD CD O CO LO CD 00 O CM co CD O co O rd to LO LO O CD co rd 00 rd rd rd rd rd rd rd rd CM

Ή v-1

ADDITIONAL SYNTHESIS EXAMPLES (EAS) OF PIRROL COMPOUNDS

II ω

X

LU

CM w X LU H Z < H 3 3 σ l · - < H H- z w « m 3 H W «Λ < O oc 0. LU 3 to QC < _J 3 Z QC O U. UI 3 to

cn

QC

C \ J □ c □ c i

cn c

<o f0 n co Γ0 CO r> fO co B Rd Id B B B M B B bu B you B Id O u 0 O U O 0 U O O O O υ 0

kl —I ffi u kl

X ffi kl kl

D O »—I kl

U ffi ki ffi X

CD O CD O O O CD O O fd O co C0 to C0 w V) w CO co CO CD «0 CD CD CD CD CM CM CM CD CD Rd O O CD Rd Rd r-4 Rd rM •H Rd Rd CO O co w Rd O O u O O O υ O O <o CD ro <n u bu bu bu bu B B B bu bu bu bu B B u O U O U U O O U O U O U u O

r ^ sDOtor-tNcnwmwr ^ aooto tntnmcekowcececocecece ko r ~

ADDITIONAL SYNTHESIS EXAMPLES (EAS) OF PIRROL COMPOUNDS

O O O LO O O oo O · » 00 C \ J 'si * 00 LO n C \ 1 co in vH τ — 1 Ή co 09 rd 1 1 1 1 xH | O O O O O 1 O O 00 00 O O O CO LO 09 C \ J it co vH * · Ή τ — 1 vd 09 <M

co

ADDITIONAL SYNTHESIS EXAMPLES (EAS) OF PIRROL COMPOUNDS

Γ5

X

LU

C \ l

X <

= 3 a

<

<

CC

LU ω

<

_i

Z3

CC o

LU

LU

The ω

LU

W

CO = 3 w

w o

O.

= 5

OC co co cr c \ i

CC

CC

I

X «t

O O n cn m n n u. H hl H H •H U O O u u X O

w n

H

CJ

Ll ca

Ll

O

Ll ca u

ffi

CJ

CN

The w

CN w w LO W CO rH O CN CN rH O v> •H · - ( O υ r4 u m O U CN CN u m hl H H hi H hi H U O CJ U The O O

CN x

co γοο

Hello o

σι

TABLE 4

ADDITIONAL SYNTHESIS EXAMPLES (EAS) OF PIRROL COMPOUNDS

GENERAL FORMULA I, IN WHICH X _? EX _g = H; Xj EX ₄ = Cl; EY = CFg

SUBSTITUTE GROUPS /

f-142-

EAS-N ^ ^R 1 X ^R 2 ^R 3 M.p. (° C) 92. NH2 CF2C1S CN H 160.5 ° -175 ° 93. H CF3SO2 CN H 199.5 ° -201 ° 94. H CF2C1S CN H 104.9 ° -106.8 ° 95. H CF2CIS CN CF2C1S 114.5 ° -117 ° 96. NH2 CF2CIS CN Cl 178 ° -181 ° 97. H CF2CISO2 CN H 199.8 ° -202 ° 98. H CF2CISO2 CN Cl 193.1 ^O -195.8 ° 99. H CF2CISO CN Cl 145.2 ° -147.5 ° 100. H CF2CIS CN Cl 139.0 ° -143.1 ° 101. H CF3S CN Br 137 ° -138 ° 102. H CF3SO CN Br 164 ° -165.5 ° 103. H CF3SO2 CN Br 197 ° -198 ° 104. H CF2CISO CN H 126.8 ° -129.6 ° 105. H CF3S CN H 152 ° -153 ° 106. NH2 CFCI2CF2S CN H 183 ° -190 ° 107. NH2 CCI3S CN H 189 ° -193 ° 108. H CFCI2CF2S CN H 118.8 ° -123.8 ° 109. H CFCI2CF2SO2 CN H 157.5 ° -161.9 ° at the. H CFCI2CF2SO CN H 182.5 ° -183.9 ° 111. NH2 CFCI2CF2S CN Cl 186.5 ° -188 °

/ _

TABLE 4

ADDITIONAL SYNTHESIS EXAMPLES (EAS) OF PIRROL COMPOUNDS

GENERAL FORMULA I, IN WHICH Xg E Xg = H; Xj EX ₄ = Cl: EY = CF _g

SUBSTITUTE GROUPS

EAS-N2 ^R 1 X ^R 2 ^R 3 M.p. (° C) 112. H CFCI2CF2SO CN Cl 149.5 ° -151 ° 113. Br CF3S CN H 163 ° -164 ° 114. H CFCI2CF2S CN Cl 113.5 ° -116.5 ° 115. H CCI3S CN Cl 177 ° -182 ° 116. H CFCI2CF2SO2 CN Cl 147 ° -150.5 ° 117. H CCI3SO2 CN Cl 200 ° -202 ° 118. H CCI3SO CN Cl 152.2 ° -153.5 ° 119. Cl CF3SO CN H 161.5 ° -162.5 ° 120. NH2 CH3S CN H 150 ° -151 ° 121. H CFCI2S CN Br 117 ° -i42 ° 122. NH2 CFCI2S CN Br 195.5 ° -197 ° 123. Br CF3SO CN H 170 ° -172 ° 124. H CFCI2SO2 CN Br 176 ° -178.5 ° 125. H CFCI2SO CN Br 116.5 ° -135.5 ° 126. H SCN CN H 173 ° -173.5 ° 127. Br CF3SO2 CN H 179 ° -180.5 ° 128. H CH3S CN H 10 ° -1O8.5 ° 129. NH2 CF2C1S CN Br 174.5 ° -178 ° 130. Br CF2C1S CN Cl 129.5 ° -133.5 ° 131. H CF2C1S CN Br 133.5 ° -137.1 °

-144

TABLE 4

ADDITIONAL SYNTHESIS EXAMPLES (EAS) OF PIRROL COMPOUNDS OF GENERAL FORMULA I, IN WHICH Xg AND Xg = H; Xj EX ₄ = Cl; EY = CF _g

SUBSTITUTE GROUPS

EAS-N3 ^R 1 X Rg ^R 3 M.p. (° C) 132. NH2 Cl CN H 159.5 ° -160 ° 133. NH2 CF3S CN SCN 169 ° -171 ° 134. H CF3S CN SCN 105 ° -106.5 ° 135. Br CF2CISO CN Cl 157.5 ° -159 ° 136. H Cl CN H 105.5 ° -106.5 ' 137. H CH3SO CN H 144.5 ° -145.5 ' 138. H CH3SO2 CN H 173 ° -173.5 ° 139. NH2 CF3S CN SCH3 146 ° -148 ° 140. H CF3S CN SOCH3 143 ° -145 ° 141. H CF2C1SO CN Br 143 ° -146.5 ° 142. Br CFC12SO2 CN Cl 117.8 ° -122.5 143. CF3CONH CF3S CN H 187 ° -188.5 ° 144. H CF2C1SO2 CN Br 182 ° -185 ° 145. H CF3S CN CH3S 89 ° -91 ° 146. H CF3S CN CH3SO2 136 ° -138 ° 147. H CF3SO CN CH3SO2 161 ° -163 ° 148. NH2 CF3CC12S CN H 200 ° -220 ° 149. NH2 CF3CC12S CN Cl 223.5 ° -232.5 150. H CF3CC12S CN Cl 170 ° -172.5 ° 151. H CF3CC12SO2 CN Cl 195.6 ° -197.2

-145 TABLE 4

ADDITIONAL SYNTHESIS EXAMPLES (EAS) OF PIRROL COMPOUNDS OF

GENERAL FORMULA I, IN WHICH Xg E Xg = Η; EX ₄ = Cl; Ε Y = CFg

SUBSTITUTE GROUPS

EAS-N2 ^R 1 X ^R 2 ^R 3 M.p. (° C) 152. H CF3CCI2SO CN Cl 161 ° -161.5 ° 153. H CF3S CN CF3S 95 ° -96 ° 154. NH2 CH3SO CN H 130 ° -132 ° 155. NH2 CH3SO2 CN H 248 ° -248.5 ° 156. H CF3SO CN CF3S 145 ° -148 ° 157. H CH3S CN Cl 128 ° -129 ° 158. NH2 CF3S CN SOCH3 139 ° -141 ° 159. CH3S CF3S CN Cl 73 ° -74 ° 160. NH2 CFCI2SO CN H 156.4 ° -195 ° 161. H CF3SO2 CN CF3S 156 ° -157 ° 162. H CH3SO CN Cl 130 ° -131 ° 163. NH2 CF3S CN F 164 ° -164.5 ° 164. H Cl CN Cl 129 ° -129.5 ° 165. CH3SO CF3S CN Cl 133 ° -135 ° 166. CH3S CFC12S CN Cl 112.2 ° -124.8 ° 167. NH2 CFC12SO CN Cl 163 ° -169.5 ° 168. CF3CONH CF3SO CN H 195 ° -197.5 ° 169. H CF3S CN F 116 ° -117 ° 170. CH3SO2 CFC12S CN Cl l64.5 ° -170.5 ^< 171. CH3SO CFC12S CN Cl 193 ° -195.7 °

/ / -14 6

TABLE 4

ADDITIONAL SYNTHESIS EXAMPLES (EAS) OF PIRROL COMPOUNDS OF GENERAL FORMULA I, IN WHICH X _g EX _g = Η; EX ₄ = Cl; EY = CF _g

SUBSTITUTE GROUPS

EAS-NS ^R 1 X r ₂ ^R 3 M.p. (° C) 172. NH2 CF3SO CN H dec. over 175 173. H CF3S CF2H H 54 ° -56 ° 174. H CH3SO2 CN Cl 165 ° -166 ° 175. H Br CN Br 127.5 ° -128 ^O 176. H Br CN H 12 ° -121 ° 177. NH2 CFCI2SO2 CN Cl 203 ° -214.5 ° 178. H CF3SO CN F 129 ° -130 ° 179. Br Cl CN H 121 ° -123 ° 180. NH2 CF3SO2 CN H 258 ° -260 ° 181. CH3SO CF3SO CN Cl 238 ° -239 ° 182. H CF2BrS CN Cl 128.3 ° -133.7 ° 183. H CF2BrSO CN Cl 117 ° -119 ° 184. H CF2BrSO2 CN Cl 172 ° -181 ° 185. H CF3S CH3 H oil 186. H CF3SO CH3 Br 106 ° -107 ° 187. H CF3SO2 CH3 Br 76 ° -77 ° 188. NH2 CF3S CN CH (SCH3) 2 159 ° -161 ° 189. CH3SCH = N CF3S CN CH (SCH3) 2 124.5 ° -125.5 190. H CF3S (CH3) 3COCONH Br 113 ° -114 ° 191. H CF3S Br Br oil

TABLE 4

ADDITIONAL SYNTHESIS EXAMPLES (EAS) OF PIRROL COMPOUNDS OF GENERAL FORMULA I, IN WHICH X _? E Xg = H; Xj EX ₄ = Cl: EY = CFg

SUBSTITUTE GROUPS

EAS-N2 ^R 1 X r ₂ ^R 3 M.p. (° C) 192. H CF3SO ch ₃ OH * 149 ° -151 ° * Can exist as keto tautomer 193. Br CF3S ch ₃ Br oil 194. Br Br H CF3S oil 195. H CF3S CN I 107 ° -109 °

/

4148 METHODS OF USE AND PESTICIDAL COMPOSITIONS

According to one aspect of the present invention, a method is provided for the control of arthropods, especially insect and arachnid pests, plant nematodes, and helminths or protozoa, in a given location, which consists of treating this local (for example, by application or administration) with an effective amount of a compound of general formula (I) in which the various symbols have the previously defined meaning. In particular, it is possible to use the compounds of general formula (I) in the field of veterinary medicine and livestock and in the maintenance of public health, against arthropods, helminths or protozoa that are internal or external vertebrate parasites, particularly in vertebrates of warm blooded, for example, in humans and domestic animals, for example cattle, sheep, goats, horses, swine, dogs, cats and in poultry, deserving special reference for example Acarinos, including ticks (for example Ixodes spp. , Boophilus spp. For example Boophilus microplus, Amblyomma spp., Hyalomma spp., Rhipicephalus spp. For example Rhipicephalus appendiculatus, Haemaphysalis spp., Ornmaodoror spp., Ornithodorus spp. For example Ornithodorus moubata) and mites , Dermahyssus qallinae, Sarcoptes spp. For example Sarcoptes scabiei, Psoroptes spp., Chorioptes spp ;, Demodex spp., Eutrombicula spp.,); Diptera (for example Aedes spp., Anopheles spp., Musca spp., Hypoderma spp., Gasterophilus spp., Simulium spp.); Hemiptera (for example Triatoma spp.); Phthrirapter (for example Damalinia spp., Linognathus spp.); Siphonaptera (for example Ctenocephalides spp.); Dictiopters (for example Periplaneta spp., Blatella spp.); Himenopteros (for example Monomorium pharaonis);

/ '-143can also be used, for example, against infections of the gastrointestinal tract caused by parasitic nematode worms, for example, members of the family Trichostronqylidae, Nippostronqylus brasiliensis, Trichinella spiralis, Haemonchus confortus, Trichostronqylus colubriftata, Nematodirus battiata, Nematodirus battiata, Nematodirus batta Trichostronqylus axei, Cooperia spp. and Hymenolepis nan; they can also be used in the control and treatment of diseases caused by protozoa, for example, Eimeria spp. for example Eimeria tenella, Eimeria acervulina, Eimeria brunetti, Eimeria maxima and Eimeria necatrix, Trypanosoma cruzi, Leishamania spp., Plasmodium spp., Babesia spp., Trichomonadidae spp., Histomonas spp., Giardia spp., Toxoplasma spp. and Theileria spp .; in the protection of stored products, for example, cereals, including grains and flour, peanuts, animal fodder, wood and household goods, for example carpets and textiles, against the attack of arthropods, most especially cockroaches, including weevils, moths and mites , for example Ephestia spp. (flour moth), Anthrenus spp. (carpet beetle), Tribolium spp. (flour beetle), Sitophilus spp. (cereal weevils) and Acarus spp. (mites), in the control of cockroaches, ants and termites and of similar arthropod pests in infested domestic and industrial properties and in the control of mosquito larvae in watercourses, wells, reservoirs or other running or stagnant water; they can be used to treat foundations, structures and soils to prevent attack on buildings by termites, for example, Reticulitermes spp., Heterotermes spp., Coptotermes spp .; in agriculture against adults, larvae and eggs of Lepidoptera (butterflies and moths) for example Helio this spp. such as Heliothis virescens (tobacco worm, Heliothis f

-150armigera and Heliothis zea, Espodópteros spp. such as S. exempta,

S. littoralis (Egyptian cotton worm), S. eridania (cereal noctuids), Mamestra configurata (cereal caterpillars); Earias spp. for example E. insulana (Egyptian cotton caterpillars), Pectinophora spp. for example Pectinophora gossypiella (shallow cotton caterpillar), Ostrinia spp. such as 0. nubilalis (European corn borer), Trichoplusiani (cabbage locust), Pieris spp. (cabbage worm), Laphygma spp. (cereal caterpillar), Agrotis and Amathes spp, (travela), Wiseana spp. (porina moth), Chilo spp. (grain stem borer) Tryporyza spp. and Diatraea spp. (sugarcane borer and rice borers), Sparganothis pilleriana (grape berry moth), Cydia pomonella (apple moth), Archips spp. (phytophagous moths from fruit trees), Plutella xylostella (diamond tail moth); against adults and larvae of Coleoptera (beetles) for example Hypothenemus hampei (coffee berry borer), Hylesinus spp. (bark beetles), Anthonomus grandis (cotton weevils), Acalymma spp. (cucumber beetles), Lema spp., Psylliodes spp., Leptinotarsa decemlineata (Colorado potato beetle), Diabrotica spp. (grain rootworm), Gonocephalum spp. (pseudo-filiform worms), Agriotes spp. (threadlike worms), Dermolepida and Heteronychus spp. (white caterpillars), Phaedon cochleariae (mustard slave), Lissorhoptrus oryzophilus (aquatic rice weevil), Meligethes spp. (pollen beetles), Ceutorhynchus spp., Rhynchophorus and Cosmopolites spp. (root weevils); against Hemiptera eg Psylla spp., Bemisia spp., Trialeurodes spp., Aphis spp., Myzus spp., Megoura viciae,

Phylloxera spp., Adelges spp., Phorodon humuli (hop aphids), Aeneolamia spp., Nephotettix spp. (locusts on rice leaves), Empoasca spp., Nilaparvata spp., Perkinsiella spp., Pyrilla spp., / -151r

Aonidiella spp. (mealybugs), Coccus spp., Pseucoccus spp., Helopeltia spp. (mosquitoes), Lygus spp., Dysdercus spp., Oxycarenus spp., Nezara spp .; Hymenoptera, for example Athalia spp. and Cephus spp. (saw flies), Atta spp. (leaf ants); Diptera for example Hylemyia spp. (flies from plant roots), Atherig on a spp. and Chlorops spp. (flies from aerial parts of plants), Phytomyza spp. (leaf miners), Ceratitis spp. (fruit flies); Tisanopterans such as Thrips tabaci; Orthopterans such as Locusta and Schistocerca spp., (Grasshoppers) and crickets, for example Gryllus spp., And Acheta spp .; Collembolas for example Sminthurus spp. and Onychiurus spp. (locusts), Isoptera, for example Odontotermes spp. (termites), Dermápteros, for example Forficula spp. (lacrainha) and still other arthropods significant for agriculture such as Acari (mites) for example Tetranychus spp., Panonychus spp. and Bryobia spp. (arachnid mites), Eriophyes spp. (gall mites), Polyphagotarsonemus spp .; Blaniulus spp. (centipedes), Scutigerella spp. (myriapods), Oniscus spp. (bugworms) and Triops spp .; (crustaceans); nematodes that attack plants and trees of importance for agriculture, forestry and horticulture, either directly or by spreading bacterial, viral, mycoplasmic or fungal diseases of plants, root knot nematodes such as Meloidogyne spp. (for example M, unknown); cyst nematodes such as Globodera spp. (for example G. rostochiensis); Heterodera spp. (for example H. avenae); Radopholus spp. (for example R, similis); nematodes of lesions such as Pratylenchus spp. (for example P. pratensis); Belonolaimus spp. (for example B. Gracilis); Tylenchulus spp. (for example T. semipenetrans); Rotylenchulus spp. (for example R. reniformis); Rotylenchus spp. (for example R. robustus); Helicotylenchus spp. (for example H. multicinctus);

Hemicycliophora spp. (for example H. gracilis); Criconemoid spp. (for example C. similis); Trichodorus spp. (for example T. primitivus); bayonet nematodes such as Xiphinema spp. (for example X. diversicaudatum), Longidorus spp. (for example L. elongatus); Hoplolaimus spp. (for example H, coronatus); Aphelenchoides spp. (for example A. ritzemabozi, A. besseyi); stem and bulb anguils such as Ditylenchus spp. (for example D, dipsaci).

There are other pests that can be controlled with the compounds of the present invention and which include: In the order of the Isopods we have, for example, Oniseus asellus, Armadillidium vulgare and Porcellio scaber. In the order of the Oiplopods we have, for example, Blaniulus guttulatus. In the order of the Chilopods we have, for example, Geophilus carpophagus and Scutigera spex. In the order of the Simfilas we have, for example, Scutigerella immaculata. In the order of Tisanuras we have, for example, Lepisma saccharian. In the order of the Collemsa we have, for example, Onychiurus armatus. In the order of the Orthoptera we have, for example, Blatta orientalis, American Periplaneta, Leucophaea maderae, Blatella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria. In the order of Dermápteros we have, for example, P orficula auricularia. In the order of the Isopters we have, for example, Reticulitermes spp .. In the order of the Anopluros we have, for example, Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp ..- In the order of Malophages we have, for example, Trichodectes spp. and Damalinea spp .. In the order of Tysanopteros we have, for example, Hercinothrips femoralis and Thrips tabaci. In the order of the Heteroptera we have, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus

and Triatoma spp .. In the order of the Coleoptera, we have, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Epischiapisia, Spagiapisidae. , Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmoplites sordidus, Ceuthorrhynchus assimilis, False hypera, D er mestes spp., Trogoderma spp., Anthrenus spp., Lythusus spp., Lythusus spp. Niptus hololeucrus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp. Melolontha melolontha, Amphimallon solstitialis and Costelytra Zealandica. In the order of the Hymenoptera we have, for example, Diprion spp. Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp ..

In the order of Diptera we have, 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 hyoscyani, Ceratitis capitata, Dacus oleae and Tipula paludosa. In the order of the Siphonapter we have, for example, Xenopsylla cheopis and Ceratophyllus spp .. In the order of the Arachnids we have, for example, Scorpip maurus and Latrodectus mactans. In the order of the Homopterans, we have, for example, Aleurodes brassicae, Bemisia tabaci, Irialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphumpumhumhumpumhumhumpumum, Myrosiphumpena, Myrosiphumpumum, Mumiphumhumpumum, Mumiphumhumpumhumhumpumhumpumhumpumhumpumhumpumhumpumhumpumhumpumhumpumhumpumhumpumhumpumhumpum. padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella ί -154Ζ aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp .. In the order of the Lepidoptera we have, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, 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., Trichoplusiani, Carpocapsa pomonella, Pieris spp., Chilo , Pyrausta nubilalis, Ephestiakuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiquells, Magnum homona and Tortix viridana

The present invention also provides a method for controlling pests of arthropods or plant nematodes, which consists of applying to these plants or the environment in which an effective amount of a compound of general formula (I) develops.

For the control of arthropods and nematodes, generally, the active compound is applied to the place where it is intended to control the infestation of arthropods or nematodes, in a proportion between approximately 0.005 kg and 15 kg of active compound per hectare of treated site, preferably between 0.02 kg / ha and 2 kg / ha. Under ideal conditions, depending on the pest to be controlled, a smaller proportion may offer adequate protection. On the other hand, adverse weather conditions, pest resistance and other factors may require the use of the active ingredient in higher proportions. In the case of foliar application, a proportion comprisedζζ '' -155- can be used

between 0.01 kg and 1 kg / ha. The optimal proportion normally depends on the type of pest to be controlled and also on the type and stage of development of the infested plant, the spacing of the rows and also the method of application.

When the plague appears in the soil, the formulation containing the active compound will be distributed evenly over the area to be treated. If desired, it can be applied generically on the field or on the growth area or very close to the seed or plant to be protected from attack. The soil can be irrigated with the active component by sprinkling water over the area or it can be allowed to infiltrate through the natural action of rain. If desired, during or after application, the formulation can be mechanically distributed over the soil, for example plowing with a plow or with a disc. The application can be done before planting, during planting or after planting but always before sprouts appear or after they have appeared.

The compounds of general formula (I) can be applied to the soil in solid or liquid compositions, mainly to control the neetoids that grow there, but it can also be applied on the foliage mainly to control the nematodes that attack the aerial parts of the plants (for example Aphelenchoides spp and Ditylenchus spp, previously mentioned).

The compounds of general formula (I) can be valuable to control pests that feed on parts of the plant far from the point of application, for example, insects that feed on leaves are killed by the compounds of the present invention when applied to the roots. In addition, these compounds can reduce attacks on plants due to anti-food or repellent effects.

/ -156The compounds of general formula (I) are particularly valuable in protecting fields, fodder, plantations, greenhouses, orchards and vineyards, crops of ornamental plants and plantations and forests, for example, cereals (such as maize, wheat, rice , sorghum), cotton, tobacco, vegetables and greens for human consumption (such as crops of beans, cola, cucumbers, lettuce, onions, tomatoes and pepper), sowing crops (such as potatoes, beets, peanuts, soybeans , rapeseed), sugar cane, pastures and forages (such as corn, sorghum, lucerne), plantations (such as tea, coffee, cocoa, banana, palm, coconut, rubber, spices), orchards and thickets ( such as stone and seed fruits, citrus fruits, kiwis, avocados, mangoes, olive and walnut trees), vineyards, ornamental plants, flowers and vegetables and shrubs in greenhouses and in gardens and parks, trees (both deciduous and evergreen) in forests, plantations and nurseries.

These compounds are also valuable for the protection of wood (on site, cut, converted, stored or structural) against the attack of dipterans (eg Urocerus) or beetles (eg, scolitoids, platypodids, lictids, bostrichids, cerambicides, anobiids) ) or termites, for example, Reticulitermes spp., Heterotermes spp, Coptotermes spp.

They can be used to protect stored products such as cereals, fruits, nuts, spices and tobacco, whether they are in their natural form, crushed or incorporated into products, against attacks by moths, beetles, mites and weevils (Stophilus granarius) . They also serve to protect stored animal products such as fur, fur, wool and leather under the

its natural or converted forms (for example, in the form of carpets or textiles) against moth and beetle attacks; they also protect meat and fish from attacks by beetles, mites and flies.

The compounds of general formula (I) can be particularly valuable for the control of arthropods, helminths or protozoa which, by spreading or spreading diseases, are harmful to humans or domestic animals, for example, those mentioned above, and more especially for the control of ticks, mites, lice, fleas, mosquitoes and bites, pests and myiases of flies. The compounds of general formula (I) are particularly useful for controlling arthropods, helminths or protozoa that are present inside host domestic animals or that feed under or on the skin or that suck the animal's blood and can be administered oral, parenteral, percutaneous or topical to satisfy this objective. Coccidiosis, a disease caused by infections caused by parasitic protozoa of the genus Eimeria, is an important potential cause of economic damage in animals and poultry, particularly when raised under intensive conditions. For example, cattle, sheep, pigs and rabbits can be affected, but the disease is especially important in poultry, particularly in the case of chickens.

In poultry farming the disease is generally spread by birds that capture the infectious organism in manure or in dumps or contaminated soil or in the food or water they drink. * The disease manifests itself through haemorrhea, accumulation of blood in the cecal region, passage from blood to manure, weakness and digestive disorders. The disease often ends with the death of the animal, but the bird that survives serious infections has a substantially reduced market value as a result of the infection.

The administration of a small amount of a compound of general formula (I), preferably in combination with poultry feed, can effectively prevent or greatly reduce the incidence of coccidiosis. The compounds are effective against both the cecal form (caused by E. tenella) and the intestinal forms (caused mainly by E. acervulina, E. brunetti, E. ma xima and E. necatrix).

The compounds of general formula (I) can also exert an inhibitory effect on oocysts by greatly reducing their number and / or sporulation of those produced.

The compositions described below for topical application to humans and animals and for the protection of stored products, household goods, properties and areas of the general environment can be used alternatively, for application to growing crops and crop development sites and further as a seed coating. Suitable means for the application of the compounds of general formula (I) include:

for people or animals infested or exposed to infestation by arthropods, helminths or protozoa, parenteral or topical application of compositions in which the active ingredient exhibits an immediate and / or prolonged action over time against arthropods, helminths or protozoa, for example, by incorporation in food or in pharmaceutical formulations suitable for oral ingestion.

-159 edible baits, licking salts, dietary supplements, draining formulations, sprinkles, baths, dips, showers, jets, powders, ointments, liquid soaps, creams, waxes and livestock self-treatment systems; for application to the general environment or to specific places where pests may proliferate, including stored products, wood, household goods and industrial and domestic properties, in the form of sprays, mists, powders, fumigations, waxes, varnishes, granules and decoys , and in drip systems in waterways, wells, reservoirs and other running or stagnant water; for application to domestic animals, they will be incorporated into food to control the larvae of flies that feed on their faeces; for growing crops, foliar sprays, powders, granules, mists and foams will be used; it is also possible to use suspensions of compounds of general formula (I) finely divided and encapsulated for soil and root treatments using liquid remedies, powders, granules, fumigations and foams; and use up

-á liquid masses and powders to coat seeds.

The compounds of general formula (I) can be applied to control arthropods, helminths or protozoa in compositions of any type known in the art and which are suitable for internal or external administration to vertebrates, or can also be used in applications for the control of arthropods in any interior or exterior properties, incorporating as active ingredient at least one compound of general formula (I) in association with one or more diluents or adjuvants comparable

appropriate for the intended purpose. All of these compositions can be prepared by any process known in the art.

Compositions suitable for administration to vertebrates or humans include preparations suitable for oral, parenteral, percutaneous administration, for example, by draining or topical.

Compositions for oral administration incorporate one or more of the compounds of general formula (I) in association with pharmaceutically acceptable vehicles or coatings and include, for example, lozenges, pills, capsules, pastes, gels, liquid medicines, medicated foods, drinking water medicated, medicated dietary supplements, large slow-release pill and other slow-release devices designed to be retained within the gastro-intestinal tract. Any of these formulations can incorporate the active ingredient contained in micro-capsules or coated with acidic or alkali labile enteric coatings or other pharmaceutically acceptable enteric coatings. Food and concentrated premixtures containing the compounds of the present invention can also be used for use in the preparation of medicated diets, drinking water or other materials intended for consumption by animals.

Compositions for parenteral administration include solutions, emulsions or suspensions in any suitable pharmaceutically acceptable carrier and granules or solid or semi-solid subcutaneous implantations designed to release the active ingredient over an extended period, which can be prepared and sterilized by any process appropriate known in the field

161-

quality.

Compositions for percutaneous and topical administration include sprays, powders, baths, dips, showers, jets, fats, liquid soaps, creams, waxes or preparations and devices for animals in order to provide local or systemic control of arthropods.

Solid or liquid lures suitable for controlling arthropods consist of one or more compounds of the general formula (I) and a vehicle or diluent which can incorporate a food substance or other substances that induce the arthropod to consume them. If compounds according to the present invention are used in agriculture, they are rarely applied alone. Most often these compounds are part of compositions. Such compositions which can be used as insecticidal agents contain as active ingredient a compound according to the present invention, as described above, in association with solid or liquid vehicles acceptable in agriculture and with surfactants which are equally acceptable in agriculture. In particular, it is possible to use the usual inert vehicles and the usual surfactants. These compositions are also part of the present invention.

These compositions can also contain other kinds of ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, spray oils (especially for acaricidal use), stabilizers, preservative agents (especially fungi preservatives), sequestering agents or the like, as well as other active ingredients with pesticidal properties (particularly

/ secticides or fungicides) or that have plant growth regulating properties. More generally, the compounds used in the present invention can be combined with all solid or liquid additives corresponding to the usual formulation techniques.

The doses of the compounds used in the present invention can vary from wide limits, depending particularly on the pest to be eliminated and the known degree of infestation of the cultures with these pests.

In general, the compositions according to the present invention normally contain between 0.05 and 95% (by weight) of one or more active ingredients according to the invention, approximately between 1 and 95% of one or more solid or liquid vehicles. and optionally about 0.1 to 50% of one or more surfactants.

According to what has already been specified, the compounds used in the present invention are generally combined with vehicles and optionally with surfactants.

In the present specification vehicle means an organic or inorganic ingredient, natural or synthetic, with which the active ingredient is combined to facilitate its application to plants, seeds or soil. As a result, this vehicle will generally be inert and should be acceptable in agriculture, particularly for the treated plant. The vehicle can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, for example, crushed ammonium salts and natural minerals such as kaolin, clays, talc, marl, quartz, atapulgite, montmorillonite, bentonite or diatomaceous earth, and crushed synthetic minerals such as silica, alumina, silicates

especially aluminum or magnesium silicates. As solid vehicles for granules suitable, for example, are crushed and crushed natural rock materials such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic flours, and granules organic materials such as sawdust, coconut husks, corncobs and tobacco stalks; diatomaceous earth, corn husks, tricalcium phosphate, cork powder, absorbent carbon black and water-soluble polymers, resins, waxes and solid fertilizers, and these solid compositions may, if desired, contain one or more wetting, dispersing agents, compatible emulsifiers or dyes, which, if they are solid, can also serve as diluents. The vehicle can also be a liquid: alcohols, in particular butanol or glycol, as well as their ethers or esters, in particular methyl glycol acetate, ketones, in particular acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone and isofurone ; oil fractions; paraffinic or aromatic hydrocarbons, particularly xylenes or alkyl naphthalenes, oils from petroleum fractions, 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, dimethyl sulfoxide or] ^ - methylpyrrolidone and also water; liquefied and similar gases and mixtures thereof.

surfactant can be an emulsifying agent, a dispersing agent or a hemectating agent of the ionic or nonionic type or a mixture of these surfactants. It is possible to re--164, wound, for example, salts of polyacrylic acids, salts of lignosulphonic acids, salts of phenol-sulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with esters fatty or with fatty amines, substituted phenols (particularly alkyl-phenols or aryl-phenols), salts of sulfosuccinic acid esters, taurine derivatives (particularly alkyl taurates), phosphoric esters of alcohols or polycondensates of ethylene oxide with phenols, fatty acid esters with polyols and sulfate, sulfonate and phosphate functional derivatives of the above compounds. The presence of at least one surfactant is generally essential when the active ingredient and / or the inert carrier are only slightly soluble in water or insoluble in water and the carrier of the application is water.

The compositions of the present invention can also contain various additives such as adhesives and dyes. Adhesion agents such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or latex, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other adhesives can be mineral and vegetable oils. It is possible to use dyes such as inorganic pigments, for example, iron oxide, titanium oxide and Prussia Blue, and organic paints such as alizarin paints, azo radical paints. and metallic phthalocyanine inks, as well as rare nutrients such as iron, manganese, boron, copper, cobalt, molybdenum and zinc salts.

-165Compositions containing the compounds of general formula (I), susceptible of application for the control of pests of arthropods, plant nematodes, helminths or protozoa may also contain synergistic agents (for example, piperonyl butoxide or sesamex), stabilizing substances , other insecticides, acaricides, plant nematocides, anthelmintics or anti-coccidians, fungicides (for agriculture or veterinary, as appropriate, for example, benomyl, iprodione), bactericides, pheromones or attractive or repellents for arthropods or vertebrates, odorizers , flavoring agents, coloring agents and auxiliary therapeutic agents, for example, rare elements. These can be designed to improve potency, persistence, safety, absorption when desired, the spectrum of controlled pests or to allow the composition to perform other useful functions in the same animal or in the same treated area.

Examples of other active compounds such as pesticides that can be incorporated or used in conjunction with the compositions of the present invention are: acephate, chlorpyrifos, demoton-S-methyl, di-sulfoton, etoprofos, fenitrotion, malation, monocrotofos, paration, phosalone, pyrimiphos-methyl, triazophos, cyfluthrin, cypermethrin, deltamethrin, fenpropatrin, fenvalerate, permethrin, aldicarb, carbsulfan, metomyl, oxamyl, pyrimicarb, bendiocarb, teflubenzuron, dicofol, endo-sulfan, hexane, hexane, hexane, hexane, benzene avermectins, ivermectin, milbemycins, thiophanate, trichlorfon, dichlorvos, diaveridine and dimetriadazole.

For their agricultural application, the compounds of general formula (I) are generally presented in the form of compositions which can take various solid or liquid forms. The compositions

-166liquids can be used for the treatment of substrates or sites infested or likely to be infested by arthropods, including outdoor or indoor properties, storage or processing areas, containers or equipment and stagnant or running water.

Solid homogeneous or heterogeneous compositions containing one or more compounds of general formula (I), for example granules, agglomerates, briquettes or capsules can be used for the treatment of stagnant or flowing water for a certain period of time. A similar effect can be achieved using dripping or intermittent feeding of water-dispersible concentrates, as now described.

It is also possible to use compositions in the form of aerosols and aqueous or non-aqueous solutions or dispersions suitable for spraying, fumigation and for spraying low or ultra-low volume.

The solid forms of compositions that can be mentioned are powders for sprinkling (with a content of compound of general formula (I) capable of reaching 80%) or wettable powders or granules, particularly those obtained by extrusion, compaction or impregnation of a granular vehicle or by granulation from a powder (the content of the compound of general formula (I) in these humectable powders or granules can be between 0.5 and 80%).

Solutions, in particular emulsifiable concentrates, emulsions, fluidizable compositions, aerosols, wettable powders (or spray powders), fluidizable compositions and pastes are examples of forms of compositions that

are liquid or are intended to provide liquid compositions upon application.

Emulsifiable or soluble concentrates also often incorporate between 5 and 80% of active ingredient whereas emulsions or ready-to-apply solutions in that case contain between 0.01 and 20% of active ingredient. In addition to the solvent, emulsifiable concentrates may contain, if necessary, between 2 and 50% of suitable additives such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, dyes and adhesives.

Emulsions of any desired concentration, and which are particularly suitable for application to plants, can be obtained from these concentrates by diluting with water.

Concentrated suspensions that can be applied by spraying are prepared to provide a stable fluid product that will not solidify (fine grinding) and normally contain between 10 and 75% of active ingredient, between 0.5 and 30% of surfactants, among 0.1 and 10% of thixotropic agents, between 0 and 30% of suitable additives such as defoaming agents, corrosion inhibitors, stabilizers, penetrating agents, adhesion agents and as a vehicle, water or a liquid is used organic in which the active ingredient is poorly soluble or insoluble; it is possible to dissolve some solid organic or inorganic salts in the vehicle to help prevent solidification or for the purpose of constituting antifreeze for water.

Wettable powders (or spray powders) are normally prepared to contain between 10 and 80% active ingredient and

-168 commonly contain, in addition to the solid vehicle, between 0 and 5% of a wetting agent, between 3 and 10% of a dispersing agent and, when necessary, between 0 and 80% of one or more stabilizers and / or other additives such such as penetrating agents, adhesives or anti-solidifying agents, dyes or the like.

To obtain these wettable powders, the active ingredient or ingredients are mixed very well in suitable mixers, using additional substances that can be impregnated in the porous filler and grinding is carried out using mills or other suitable crushers. This provides wettable powders whose wettability and suspendability are advantageous; they can be suspended in water to provide any desired concentration and that suspension can be used very advantageously, in particular for application to the foliage of plants.

Water-dispersible granules (GDA) (granules that are easily dispersible in water) have a composition that is substantially close to that of humectable powders. Its preparation can be done by granulating the formulations described for wetting powders, either by wetting (making the finely divided active ingredient contact with the inert filler and a little water, for example 1 to 20%, or with a aqueous solution of the dispersing agent or binder, followed by drying and sieving), or dry (compaction followed by grinding and sieving).

As previously mentioned, aqueous dispersions and emulsions, for example compositions obtained by diluting a humectable powder or an emulsifiable concentrate according to the present invention, are considered to fall within the general scope of the compositions

provisions that can be used in the present invention. Emulsions can be of the water-in-oil or oil-in-water type and can have a thick consistency.

All of these aqueous dispersions or emulsions or spray mixtures can be used in crops, by any suitable means, mainly by spraying, in proportions generally comprised between 100 and 1200 liters of spray mixture per hectare.

The products and compositions according to the present invention are conveniently applied to vegetation and in particular to roots or leaves with pests to be eliminated.

Another method of applying the compounds or compositions according to the present invention is chemo-irrigation, that is, the addition of a formulation containing the active ingredient to the irrigation water. This irrigation can be done by spraying for foliar pesticides or irrigation of the soil or irrigation of the subsoil for systemic pesticides can be done. The application dose of the active ingredient is generally between 0.1 and 10 kg / ha, preferably between 0.5 and 4 kg / ha. More particularly, the proportions and concentrations may vary according to the method of application and the nature of the compositions used.

In general, compositions for application to control pests of arthropods, plant nematodes, helminths or protozoa normally contain between 0.00001% and 95%, more particularly between 0.0005% and 50% by weight of one or more compounds of general formula (I) or of total active ingredients (ie compounds of general formula (I) together with other substances toxic to arthropods and plant nematodes, anti (-170-helminths, anti -coccidians, synergists, trace elements or stabilizers). The compositions actually used and their rate of application will be selected in order to achieve the desired effects by the farmer, the livestock farmer, the medical or veterinary specialist, the operator who does pest control or by any other person specialized in the matter. Solid and liquid compositions for topical application to animals, wood, stored products and goods Household products normally contain between 0.00005% and 90%, more particularly between 0.001% and 10% by weight of one or more compounds of the general formula (I). For oral or parenteral administration to animals, including the percutaneous form of administration, the solid and liquid compositions normally contain between 0.1% and 90% by weight of one or more compounds of general formula (I). Medicated feed rations normally contain between 0.001% and 3% by weight of one or more compounds of general formula (I). Concentrates and supplements for mixing with food rations normally contain between 5% and 90% and preferably between 5% and 50% by weight of one or more compounds of the general formula (I). Mineral licking salts normally contain between 0.1% and 10% by weight of one or more compounds of the general formula (I).

Powders and liquid compositions for application to livestock, people, miscellaneous goods, properties or outdoor areas may contain between 0.0001% and 15%, and more especially between 0.005% and 2.0% by weight of one or more compounds of general formula (I). The appropriate concentrations in the treated waters are between 0.0001 ppm and 20 ppm, and more especially between 0.001 ppm and 5.0 ppm of one or more compounds of general formula (I), and therapeutic use can also be made in fish farming using times of /

'-171exposure appropriate. Edible baits may contain between 0.01% and 5%, and preferably between 0.01% and 1.0% by weight of one or more compounds of the general formula (I).

When administering parenteral, oral or percutaneous or other means to vertebrates, the dosage of the compounds of general formula (I) will depend on the species, the age and health of the vertebrate and also on the nature and the actual or potential degree of infestation by arthropod, helminth or protozoan pests. Generally, a single dose between 0.1 and 100 mg, preferably between 2.0 and 20.0 mg per kg of body weight of the animal, or doses between 0.01 and 10 mg, is considered suitable for oral or parenteral administration. 20.0 mg, preferably between 0.1 and 5.0 mg per kg of body weight per day for continued medication. If controlled-release devices or formulations are used, the daily doses necessary for a period of several months can be combined and administered to the animals on a single occasion.

The following specific examples illustrate agrochemical compositions containing the compounds of the present invention, with the application of insecticidal and acaricidal properties of some of these compounds.

COMPOSITIONS (FORMULATIONS) = EXAMPLES OF USE

The compositions that follow from EXAMPLES 23 to 28 illustrate compositions for use against arthropod pests, especially insects and arachnids, plant nematodes, and helminths or protozoa, which incorporate compounds of formula (I) as an active ingredient, especially the compounds (-172 <·· * described in PREPARATION EXAMPLES 1 TO 22 and TABLES 3 AND 4.

The compositions described in COMPOSITION EXAMPLES 23 to 28 can be individually diluted in water to provide a sprayable composition in concentrations suitable for use in the field. The generic chemical descriptions of the ingredients (for which all the following percentages are calculated by weight) used in EXAMPLES OF COMPOSITIONS 23 TO 28 exemplified below, are as follows:

Ethilan BCP: condensate of ethylene oxide / nonyl phenol Soprophor BSU: condensate of tristyryl-phenol and ethylene oxide Arylan CA: 70% w / v solution of dodecylbenzene- -calcium sulfonate Solvesso 150 aromatic solvent C ^ g light Arylan S: sodium dodecylbenzene sulfonate Darvan sodium lignosulphonate Celite PF synthetic magnesium silicate vehicle Sopropon T36 sodium salt of polycarboxylic acid Rhodigel 23 polysaccharide / xanthan gum Bentone 38: organic derivative of montmorillonite magnesium Aerosil silicon dioxide with particles of

microfine dimensions.

EXAMPLE 23

A water-soluble concentrate was prepared from:

Active ingredient 7%

ETHYLAN BCP 10%

N-methylpyrrolidone 83% by dissolving ETHYLAN BCP in a portion of N-methylpyrrolidone and then adding the active ingredient with heating and stirring until dissolved. The volume of the resulting solution is adjusted by adding the remaining part of the solvent.

EXAMPLE 24

An emulsifiable concentrate was prepared from:

Active ingredient 7%

Soprophor BSU 4%

Arylan CA 4%

N-methylpyrrolidone 50%

Solvesso 150 35% by dissolving Soprophor BSU, Arylan CA and the active ingredient in N-methylpyrrolidone and then adding Solvesso 150 to adjust the volume.

EXAMPLE 25

A wettable powder was prepared from:

Active ingredient 40% ARYLAN S 2% Darvan No. 2 5% Celite PF 53%

mixing the ingredients and crushing the mixture in a hammer mill until particles smaller than 50 microns are obtained.

EXAMPLE 26

A fluidisable aqueous formulation was prepared from:

Active ingredient 40.00%

Ethylan BCP 1.00%

Sopropon T36 0.20%

Ethylene glycol 5.00%

Rhodigel 23 0.15%

Water 53.65% by mixing the ingredients thoroughly and grinding in a ball mill until average particle sizes of less than 3 microns are obtained.

EXAMPLE 27

An emulsifiable suspension concentrate was prepared from:

Active ingredient

30.0%

Ethylan BCP 10.0%

Bentone 38 0.5%

Solvesso 150 59.5% by intimately mixing the ingredients and grinding them in a ball mill until particles with average dimensions of less than 3 microns are obtained.

EXAMPLE 28

Water-dispersible granules were prepared from:

Active ingredient 30%

Darvan No. 2 15%

Arylan S 8%

Celite PF 47% by mixing the ingredients, micronising in a fluid energy mill and then granulating in a rotary granulator, spraying with sufficient water (up to 10% w / v). The resulting granules are then dried in a fluid bed dryer to remove excess water.

EXAMPLE 29

A powder for sprinkling was prepared by mixing intimately:

Active ingredient 1 to 10%

90% superfine talc / -176This powder can be applied to a place infested with arthropods, for example, in waste or dumps, in stored products or household goods or in infested animals or who are at risk of infestation by arthropods, to carry out the control of these arthropods by oral ingestion. Suitable means of distributing dust over the arthropod infestation site include mechanical blowers, hand sprayers and livestock self-treatment devices.

EXAMPLE 30

An edible bait can be prepared by intimately mixing:

Active ingredient 0.1 to 1.0%

Wheat flour 80%

Molasses 19.9 to 19.0%

This edible bait can be distributed in a location, for example, in domestic and industrial properties such as kitchens, hospitals or warehouses, or outside areas infested by arthropods, for example, ants, grasshoppers, cockroaches and flies, to control these arthropods by oral intake.

EXAMPLE 31

A solution can be prepared containing:

Active ingredient 15%

Dimethylsulfoxide 85% by dissolving the pyrrolic derivative in a portion of dimethylsulfoxide

'-177e and then adding more dimethyl sulfoxide until the desired volume is obtained. This solution can be applied to domestic animals infested by arthropods, percutaneously or in the form of a draining application or, after sterilization by filtration through a polytetrafluoroethylene membrane (pores with dimensions of 0.22 microns), by parenteral injection, an application rate comprised between 1.2 and 12 ml of solution per 100 kg of the animal's body weight.

EXAMPLE 32

It is possible to prepare a wettable powder from:

Active ingredient 50%

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

Aerosil 5%

Celite PF 40% by adsorbing Ethylan BCP on Aerosil, mixing with the other ingredients and crushing the mixture in a hammer mill to provide a wettable powder, which can be diluted with water to obtain an active compound concentration between 0.001% and 2% w / v, then applied to the site of infestation with arthropods, for example, with larvae of diptera or plant nematodes, by sprinkling, or to infested domestic animals or who are at risk of infestation with arthropods, helminths or protozoa, by spraying or. by diving, or by oral administration through drinking water, in order to provide control of these arthropods, helminths or protozoa.

-178EXAMPLE 33

A large slow-release pill can be prepared from granules containing a thickening agent, a binder, a slow-release agent and the active ingredient prepared according to EXAMPLE 27, in variable percentage compositions. By compressing the mixture, it is possible to prepare a large pill with a relative density of 2 or higher, which can be administered orally to ruminant domestic animals for retention inside the reticulo-rumen to provide a slow and continuous release of the pyrrolic compound over a period of time. extended period to provide control of infestation of ruminant domestic animals by arthropods, helminths or protozoa.

EXAMPLE 34

It is possible to prepare a slow release composition from:

Active ingredient 0.5 to 25%

75 to 99.5% polyvinyl chloride base by mixing the polyvinyl chloride base with the active compound and a suitable plasticizer, for example, dioctyl phthalate, and extruding or melting the homogeneous composition into suitable configurations, for example , grains, granules, briquettes or tapes suitable, for example, for addition to stagnant water or, in the case of tapes, for the manufacture of necklaces and loop labels to be attached to domestic animals in order to provide control of insect pests through of slow release

-179 /

of the active compound.

It is possible to prepare identical compositions by replacing the active ingredient in the composition examples with the appropriate amount of another compound of general formula (I).

PESTICIDAL METHODS AND EXAMPLES OF USE

In EXAMPLES 35 to 47 below, the compounds according to the present invention are applied in different concentrations. The use of a solution or suspension or leaf emulsion at a concentration of 1 ppm (concentration of the compound in parts per million of the applied test solution) corresponds approximately to the application of the active ingredient in a proportion of 1 g / ha, based on a volume of sprinkling approximately 1000 liters / ha (enough to drain). In this way, in the following applications of foliar sprays varying between 6.25 and 500 ppm we will have the value corresponding to 6-500 g / ha. For soil applications, a soil concentration of 1 ppm, based on about 7.5 cm of soil depth, a proportion corresponding to approximately 1000 g / ha of disseminated application in the field is obtained.

EXAMPLE 35

Activity on Aphids:

A mixture was prepared with:

- 0.01 g of active ingredient

- 0.16 g of dimethylformamide

- 0.838 g of acetone

- 0,002 g of a surfactant mixture consisting of an alkyl aryl polyether alcohol and an alkyl aryl polyether alcohol having the latter sulfonic groups in the aryl radical.

- 98.99 g of water

This diluted aqueous mixture was sprinkled on dwarf nasturtium plants, where aphids (Aphis nasturtii) were created in the nymph and adult phases. The number of aphids per pot was 100-150. The volume of sprayed aqueous mixture was sufficient to let the plants run. After spraying, the pots were stored at 20 ° C for one day, after which the aphids were counted. The percentage of mortality determined was 100% for the compounds of EXAMPLES 1, 2, 3A, 4, 5, 16C, 17, 18, 19 and 20 and ASE N2 _S 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 , at a concentration of 100 ppm.

EXAMPLE 36

Activity on Mites

The same formulation procedure as in EXAMPLE was used

35. However, in this case, 150-200 thrombidiform mites (Tetranychus urticae) were created on green bean plants. After spraying, the plants were kept at 30 ° C for 5 days. The percentage of mite mortality was 100% for the compounds of EXAMPLES 2, 3A, 16C, 17 and 18 and ASE N2s 9, 20, 25, 41, 44, 46, 52, 53, 58, 59, 63, 64 , 70, 74, 77-81, 83, 90, 98, 99, 102, 124 and 141, in a concentration of 100 ppm.

z '-181 EXAMPLES 37-39

ACTIVITY ON COCONUT NOCTUIDEOS

37: The same formulation as in EXAMPLE 35 was used. In this case, larvae from the second stage of development of cereal noctuids (Spodoptera eridania) were created on Sieva beans approximately 15 cm high. After 5 days, the following percentages of mortality were obtained: 100% mortality was obtained with the compounds of EXAMPLES 3A, 3B, 5, 6, 7, 8, 9, 11, 12, 15B, 16C, 17, 18 , 20, 21B, 21C, and ASE N2 _S 42, 44, 60, 62, 64, 98-100, 102, 103, 121, 124, 125, 131, 141, 142, 144, 162, 166 and 174, for a concentration of 100 ppm and a mortality of 80% was obtained for the compound of EXAMPLE 13 at a concentration of 500 ppm.

38: The same formulation procedure as EXAMPLE 35 was used, except in this case it contains the following:

- 2.5 mg of active ingredient

- 0.05 g of dimethylformamide

- 9.9228 g of acetone

- 0.0247 g of surfactant (as in EXAMPLE 35)

- 90 g of water composed from EXAMPLE 4 provided 100% mortality on cereal noctuids, in a concentration of 25 ppm.

39: The same formulation procedure as EXAMPLE 38 was used, except in this case it contains the following:

- 0.625 mg of active ingredient

- 12.5 mg of dimethylformamide

- 9.9621 g of acetone

- 0.0247 g of surfactant (as in EXAMPLE 35)

- 90 g of water

The compounds of EXAMPLES 1 and 2 provided 100% mortality in cereal noctuids, at a concentration of 6.25 ppm.

EXAMPLES 40-43

Activated on the Mexican Bean Beetle

40: The same EXEM formulation procedure was used

PLO 37, with the exception that in this case it contains the following:

- 12.5 mg of active ingredient

- 0.25 g of dimethylformamide

- 9.726 g of acetone

- 24.1 mg of surfactant (as in EXAMPLE 35)

- 89.988 g of water

Mexican bean scarab larvae (Epilachna varivestis, muls) were grown in the second stage of development, on Sieva beans approximately 15 cm high. After 5 days, the following percentage of mortality was obtained: 100% mortality for the compound of EXAMPLE 13 at a concentration of 125 ppm.

41: Using the formulation procedure of EXAMPLE 38, but containing the compound of EXAMPLE 8 as an active ingredient, 100% mortality was obtained on the Mexican bean beetle, to a concentration of 25 ppm.

-18342: Using the formulation procedure of EXAMPLE 35, but containing the non-brominated compound of EXAMPLE 15A as an active ingredient, 100% mortality was obtained on the Mexican bean beetle, at a concentration of 100 ppm.

43: The same formulation procedure as in EXAMPLE 40 was used, except in this case it contains:

- 10 mg of active ingredient

- 0.2 g of dimethylformamide

- 9.7657 g of acetone

- 0.0243 g of surfactant (as in EXAMPLE 35)

- 90 g of water

The following mortality percentages were obtained for the Mexican bean beetle: 80% mortality for the compounds of EXAMPLES 15A and 15B, at a concentration of 100 ppm and 100% mortality for the compounds of EXAMPLES 1, 2, 9, 17, 18, and ASE N2 _S 42, 44, 60, 62, 64, 98, 99, 124, 125, 141, 142 and 144 for a concentration of 100 ppm.

EXAMPLES 44-46

Domestic Fly Activity

The toxic formulation was made in the form of a sugary aqueous solution, in a volume of 10 ml containing 10% w / w sugar and a concentration of 100 ppm chemical toxic by the same procedure as in EXAMPLE 35. the preparation of several serial dilutions as needed. To perform the tests, the following 3 different formulations were prepared:

/ -184-

EXAMPLE

44 45 46 Active ingredient, 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, g 10 9 9.84 Twenty-five flies were anesthetized adults (Musca domestic) using carbon dioxide carbon and then made up your

transfer to a decoy cup containing the toxic formulation. After one day at 27 ° C, the percentage of fly mortality was measured and the following was verified:

For 0 EXAMPLE 44: 100% mortality provided by For 0 EXAMPLE 45: compounds of EXAMPLES 1, 2, 3B, 4-6, 8, 9, 16C, 17-20, 21B and 21C and ASE N2 _S 42, 44, 60, 62, 64, 98, 99, 100, 102, 103, 121, 124, 125, 131, 141, 142, 144 ,. 162, 166 and 174, at a concentration of 100 ppm. 100% mortality provided by For 0 EXAMPLE 46: compound of EXAMPLE 12 to a concentration of 100 ppm. 100% mortality provided by

compounds of EXAMPLES 1, 2 and 5, to a concentration of 12.5 ppm.

EXAMPLE 47

ACTIVITY ON COCONUT ROOT NOCTUIDEOS

A formulation was prepared by a process identical to that used in EXAMPLE 35 except that in this case only 48.99 g of water was used providing an initial concentration of 200 ppm for the test compound. Then aliquots of this formulation were used directly, according to the desired test concentration, in ppm (parts per million) by weight, according to the following test procedure.

To a pot containing 60 g of sandy loam soil, an aliquot of the tested compound formulation was added at a concentration of 200 ppm (as appropriate for the final concentration of the compound tested in the soil), 3.2 ml of water and five seeds of pre-germinated corn. The vessel was shaken well to obtain a uniform distribution of the tested formulation. After this operation, twenty noctuid eggs from the roots of the cereals were placed in a cavity made in the soil. Then vermiculite (1 ml) and water (1.7 ml) were poured into this cavity. By an identical process, an untreated control sample was prepared by applying an identical aliquot of water / acetone / DMF emulsifying solution that did not contain any compound to be tested. In addition, a control sample treated with a commercially known compound was used as a standard assay, and the formulation was carried out in the same way. After 7 days, live larvae of root noctuids were counted using the well-known Berlese funnel extraction method.

The compounds listed below provided 100% /

<186control for soil concentrations of 1.45; 0.72 and 0.36 ppm: compounds of EXAMPLES 3B, 4 and 17-19 and ASE Nos. 98, 99, 101, 105, 113,

119, 121, 124, 125, 130 and 173.

Claims (33)

1.- Process for the preparation of compounds of general formula in which X represents a halogen atom or a cyano, cyanate, thiocyanate, halo-alkyl, alkoxy, halo-alkoxy, alkyl-thio, alkyl-sulfinyl, alkyl-sulfonyl, halogeno-alkyl-thio, halogeno-alkyl-sulfini group lo, halogeno-alkylsulfonyl, halogeno-alkyl-carbonyl, alkenyl-thio, alkenyl-sulfinyl, alkenyl-sulfonyl, halogeno-alkenyl-thio, halogeno-alkenyl-sulfinyl, halogeno-to 1-cenyl-sulfonyl, halogeno -alkyl-thio-car-188bonyl, phenyl-thio, phenyl-sulfinyl, phenyl-sulfonyl, heteroaryl-thio, heteroaryl-sulfinyl or heteroaryl-sulfonyl; wherein the phenyl groups are optionally substituted with halogen atoms or cyano or halo-alkyl groups and the heteroaryl groups are pentagonal or hexagonal rings containing one or two heteroatoms, the same or different, selected from oxygen, sulfur or nitrogen atoms, and whose heteroaryl groups are optionally substituted with halogen atoms or nitro, cyano or halogen-alkyl groups; and where the alkyl, halo geno-alkyl, alkenyl, halo-alkenyl, alkoxy and halo-alkoxy groups are straight or branched, with less than 10 carbon atoms, and where the halogen substitution in all of these groups is done by a or more halogen atoms, which can be the same or different, from mono-substitution to complete poly-substitution; R1, Rg and R3 each independently represent a radical of the same set of substituents described for X; a hydrogen atom; an alkyl group; and a substituent such that no more than one of the symbols R]., Rg and R3 represents a formyl, hydroxyimino-alkylidenyl, alkoxyimino-alkylidenyl, azido, amine, alkyl-amino, dialkyl-amino, aralkyl group -ami-189no, amino-carbonyl-amino, alkyl-carbonyl-amino, halogeno-alkyl-carbonyl-amino, aryl-carbonyl-amino, alkyl-sulfonyl-amino, halogeno-alkyl-sulfoni1-amino, alkyl-amino-carbonyl -amino, aryl-amino-carbonyl-amino, benzylidene-imino, alkylidene-imino, alkoxy-alkylidene-imino, dialkyl-amino-alkylidene-imino, bis (alkyl-thio) -methyl, bis (aryl-thio) - methyl, alkyl-thio-alkylideneimino, alkoxy-carbonyl-amino, halo-alkoxy-carbonyl-amino, a phenyl group optionally substituted with a halogen atom or with a cyano or halo-alkyl group, and a heteroaryl group having a unicycle ring. pentagonal or hexagonal co, containing one or two heteroatoms, the same or different, chosen from oxygen, sulfur or nitrogen atoms and whose heteroaryl group is optionally substituted with halogen atoms or with nitro, cyano or halo-alkyl groups; and in which groups there. lo, halo-alkyl, alkenyl, halo-alkenyl, halo-alkoxy and alkoxy are straight or branched chain, with less than 10 carbon atoms, the halogen substitution in all these groups being provided by one or more halogen atoms, which can be the same or different, from mono-substitution to complete poly-substitution; Y represents a halogen atom or a group -190 cyano, alkyl, halo-alkyl, alkoxy, halo-alkoxy, alkyl-sulfinyl, alkyl-sulfonyl, alkyl-thio, halogeno-alkyl-thio, halogeno-alkyl-sulfinyl, halogeno-alkyl-sulfonyl, alkyl-carbonyl, halogeno -alkylcarbonyl, alkenyl, halo-alkenyl, halo-alkynyl, and alkynyl; and in which the alkyl, alkoxy, halogen-alkyl and halo-alkoxy groups are straight or branched, with less than 10 carbon atoms, the halogen substitution in all of these groups being provided by one or more halogen atoms, which can be the same or different, from mono-substitution to complete poly-substitution; or Y represents a hydrogen atom when: X represents a halogen atom or a group of the general formula R.5S (O) _n , in which n represents the integer 0, 1 or 2 and R5 represents an alkyl, halo-alkyl, alkenyl or halo-alkenyl group; the carbon chains being of the alkyl and alkenyl groups and the halogen substitutions as defined above; R1 and R3 each represent a hydrogen atom; and R ₂ represents a cyan group; and Χχ, X ₂ , X3 and X4 have the meaning previously defined for Y or each represent a hi-191 hydrogen atom; with the following conditions: at least one of the symbols Rp R2 and R3 has the meaning defined before for X; if X4 and X4 each represent a hydrogen atom, and X represents a halogen atom or a cyano group, so R2 is different from X; if X4 and X4 each represent a hydrogen atom and Y represents a methyl group, then X does not represent a bromine atom, characterized by the fact that: A) for the preparation of compounds of general formula (I) in which R4 represents an amino group, R2 represents a cyano group and R3 represents a hydrogen atom, that is compounds of the general formula in which Χχ, X2, X3, X4 and Y have the meaning defined for the general formula I, X represents a halogen atom or a trifluoromethyl, cyano, -192thiocyanate, alkylthio, alkylsulfinyl, alkylsulfonyl, halogeno-alkyl-thio, halogenoalkyl-sulfinyl, halogeno-alkyl-sulfonyl, al-cenii-thio, halogeno-aicenii-thio, halogeno-alkenyl-sulfinyl, halogeno- alkenylsulfonyl, phenylthio, phenylsulfinyl, phenylsulfonyl, heteroaryl-thio, heteroaryl-sulfinyl or heteroaryl-sulfonyl, by reacting a compound of the general formula in which the amino group is optionally protected: (a) with a halogenating agent, optionally in the presence of a solvent, to provide a compound of the general formula (Ia) in which X represents a halogen atom, then reacting that compound with trifluoromethyl-copper, by a known process, to providing compounds of the general formula (Ia) in which X represents a trifluoromethyl group; -193 (b) with a tris (alkyl-thio) methane or tris (aryl-thio) -methane in the presence of a Lewis acid, then reacting the compound obtained of the general formula (XI) in which X represents a bis ( alkyl-thio) -methyl or bis (aryl-thio) -methyl with a suitable alkyl nitrite, followed by hydrolysis, to obtain a compound of the general formula (XXXVII) in which X represents a formyl group, and then contacting said compound with hydroxyl-amine following dehydration with suitable agents such as P2O5, for ^a known process, to obtain a compound of formula (Ia) in which X represents a cyano group; (c) with a compound of general formula MSCN, in which M represents an alkali metal, in the presence of bromine, in a solvent such as methanol to obtain a compound of general formula (Ia) in which X represents a group thiocyanate and then reacting that compound with an alkyl halide or with a dialkyl sulfate in the presence of a base such as sodium hydroxide or potassium hydroxide in a solvent, to obtain a compound of general formula (Ia) in which X represents an alkylthio group; or (d) with a sulfenyl halide of the general formula RSHal, in which R represents an alkyl, halo-alkyl, phenyl or hetero-aryl radical, Hal represents a halogen atom, in an organic liquid reaction medium, optionally in the presence of an acid-fixing agent such as a tertiary amine, to obtain a compound of general formula (Ia) in the -194qual X represents an alkyl-thio, halo-alkyl-thio, alkenyl-thio, halo-alkenyl-thio, phenyl-thio or heteroaryl-thio group, then optionally oxidizing, by a known process, the compound obtained to obtain a compound of general formula (Ia) in which X represents a group of general formula RS (O) _n in which n represents the integer 1 or 2, depending on the reaction conditions; B) for the preparation of compounds of general formula (Ia) in which Χχ, X £, X3, X4 and Y have the meaning defined for general formula (I), X represents a cyanate, alkoxy, or halo-alkoxy group, reacting a compound of general formula (XXVIII) in which the symbols Xj, X2, X3, X4 and Y have the meaning defined above, -195in which the amino and cyano groups are adequately protected when necessary: (a) with a cyanogen halide in the presence of an acid-fixing agent to obtain a compound of formula (Ia) in which X represents a cyanate group; (b) with an alkylating agent, optionally in the presence of a base, to obtain a compound of the general formula (Ia) in which X represents alkoxy, or (c) by a known halo-alkylation process, according to Syntheses of Fluoroorganic Compounds, Knunyants, I. L. and Yakobson, G. G., Ed., Berlin, Springer-Verlag, 1985, pp. 263-269, to obtain a compound of general formula (Ia) in which X represents a haloalkoxy group; C) for the preparation of compounds of general formula (Ia) in which X ^, X2, X3, X4 and Y have the meaning defined for general formula (I), X represents a haloalkyl group [CF2H, CF3, BrCH2 , CICH2], halo-alkyl-carbonyl, halo-alkyl-thio-carbonyl or α-halo-alkyl-α-halo-methyl, if a compound of general formula is reacted -196- in which Χχ, X ₂ , X3, X4 and Y have the meaning defined before, in which the amino and cyano groups are adequately protected if necessary: (a) with a fluorination agent such as diethylamino sulfur trifluoride, by a known process, to obtain a compound of general formula (Ia) in which X represents a difluoromethyl group; (b) with a suitable oxidizing agent such as chromium trioxide in sulfuric acid to obtain a compound where X represents a carboxylic acid group, then subjecting that compound to a fluorination agent such as sulfur tetrafluoride, through a known process, to -197 to obtain a compound of the general formula (Ia) in which X represents a trifluoromethyl group; (c) under Wolff-Kishner conditions, or using a variant such as treatment with p-toluene-sulfonyl-hydrazide followed by sodium cyanoborohydride, to obtain a compound in which X represents a methyl group, subjecting that compound is then added to a halogenating agent such as N-bromo-succinimide or N-chlorosuccinimide, in a suitable solvent, to obtain a compound of formula (Ia) in which X represents a bromomethyl group or chloromethyl; or (d) sequentially with a halogen-alkyl-metal or trifluoro-trimethyl-silane derivative to obtain a compound of general formula (Ia) in which X represents a halo-alkyl-carbinol group following oxidation by a process known, to obtain a compound of general formula (Ia) in which X represents a halo-alkylcarbonyl group, then subjecting that compound to Lawesson's reagent to obtain a compound of general formula (Ia) in which X represents a halogeno-alkyl (thio-carbonyl) group or a compound in which X represents a halogeno-alkyl-carbinol group is reacted with a halogenating agent such as thionyl chloride or hydrobromic acid, to obtain a compound of general formula (Ia) in which X represents an α-halo-alkyl-α-halo-methyl group, followed by all the previous steps, another deprotection step if necessary; -198D) for the preparation of compounds of general formula (I) in which Rj represents an amino group and R1 represents a cyano group, that is, compounds of general formula R. CN (Tb) in which X, Xj, X2, X3, X4 and Y have the meaning defined for the general formula (I) and R3 represents a halogen atom or a formyl group, bis (alkyl-thio or aryl-thio) -methyl, halo-alkyl , alkyl, optionally substituted phenyl or optionally substituted heteroaryl, thiocyanate, alkyl-thio, halo-alkyl-thio, alkenyl-thio, halogen-alkenyl-thio, phenyl-thio, heteroaryl-thio, alkyl-sulfinyl, alkyl-sulfonyl, alkenylsulfinyl, alkenylsulfonyl, halogeno-alkylsulfinyl, halogeno-alkylsulfonyl, halogeno-alkenylsulfinyl, halogeno-alkenylsulfonyl, phenylsulfinyl, phenylsulfonyl, heteroaryl-south-199finyl or heteroaryl-sulfonyl, a compound of general formula (Ia) is reacted in which groups X, cyano and amino are optionally protected by a suitable process if necessary: (a) according to A) a) to obtain a compound of the general formula (lb) in which R3 represents a halogen atom, after which this compound is reacted with an optionally substituted phenyl or heteroaryl halide, preferably a bromide or an iodide in the presence of copper by a known process, or said compound is then reacted in which R3 preferably represents a bromine or iodine atom with an optionally substituted phenyl- or heteroaryl-boronic acid in the presence of palladium, by a known process, to obtain a compound of general formula (lb) in which R3 represents an optionally substituted phenyl or heteroaryl group, or a compound of general formula (Ia) is then reacted in which R3 represents a halogen atom according to claim A) a) to obtain a compound of general formula (lb) in which R3 represents a trifluoromethyl group; (b) according to A) b) to obtain first a compound of general formula (lb) in which R3 represents a bis (alkylthio) methyl group or a bis (aryl-thio) methyl group and then a compound of general formula (lb) in which R3 represents a formyl group; -200 (c) with a phenyl- or heteroaryl-diazonium salt optionally substituted by a known process to obtain a compound of general formula (Ib) in which R3 represents an optionally substituted phenyl or heteroaryl group or (d) according to A) c), d), to obtain a compound of general formula (Ib) in which R3 represents an alkyl-thio, halo-alkyl-thio, alkenyl-thio, halo-alkenyl-thio, phenyl-thio group or heteroaryl-thio, followed by oxidation according to A) d) to obtain a compound of general formula (Ib) in which R3 represents an alkylsulfinyl, alkylsulfonyl, alkenylsulfinyl, alkenylsulfonyl group , halogeno-alkylsulfinyl, halogeno-alkyl-sulfonyl, halogeno-alkenyl-sulfinyl, halogeno-alkenyl-sulfonyl, phenyl-sulfinyl, phenyl-sulfonyl, heteroaryl-sulfinyl or heteroaryl-sulfonyl, with the proviso that X does not represent a group RS that may undergo an undesired oxidation reaction and then in the case of X representing an atom of halogen is treated with alkyl lithium by a known process, then diluted (quench) with water and sulfenylation according to A) c), d), to obtain a compound of general formula (Ib) in which X represents an alkyl-thio, halo-alkyl-thio, alkenyl-thio, halo-alkenyl-thio, phenyl-thio or hetero group -aryl-uncle; E) for the preparation of compounds of general formula (Ib) in which X, Xp X ₂ , X3, X4 and Y have the meaning defined for general formula (I) and R3 represents a hydroxy-imi-201no-alkylidenyl group, alkoxyimino-alkylidenyl, cyano, halo-alkyl-carbonyl or halo-alkyl-thio-carbonyl or alkyl, if a compound of general formula is reacted in which R3 represents a formyl or alkyl-carbonyl group and the X, cyano and amino groups are protected by a suitable process if necessary: (a) by condensation with hydroxylamine or with O-alkylhydroxylamine or its acid addition salts, in a solvent such as ethanol, to obtain a compound of the formula (Ib) in which R3 represents a group hydroxyimino-alkylidenyl or alkoxyimino-alkylidenyl, and when R3 represents a hydroxyimino-methylidenyl or alkoxyimino-methylidenyl group, the elements of water or an alcohol are eliminated according to A) b) to get a -202 compound of general formula (Ib) in which R3 represents a cyano group; (b) according to C) a), b), c), d), when R3 represents a formyl group, to obtain a compound of formula (Ib) in which R3 represents a methyl or halo-alkyl group or halo-alkyl-carbonyl or halo-alkyl-thio-carbonyl; or (ç ) common reagent in Grignard derived from a halide alkyl or with one alkyl lithium, when R3 represents a group formyl, for get one carbinol, followed by a dehydration step to provide a compound in which R3 represents an alkenyl group, followed by reduction to obtain a compound of general formula (Ib) in which R3 represents an alkyl group, optionally followed by a deprotection step . 2. A process for the preparation of compounds of formula (I) according to claim 1, wherein R ^, R2, R3, Y, Χχ, ^{x3 0 Ex} 4 are as defined in claim 1 for formula general (I) and X represents a perhalogen-alkylthio group, characterized by the fact that it comprises the following steps: a) reaction of a compound of general formula (XXXVIII) -203- (XXXVIII) (XXXIX) in which X represents a hydrogen atom, with chlorosulfonic acid at a temperature between 0 ° C and 150 ° C and optionally in an organic solvent, to obtain a compound of the general formula (XXXIX) in which X represents a group - SO 2 Cl and R, R2 / R3, Y, Χχ, ^ 2 · ^x 3 ^ex 4 have the meaning defined in claim 1 pa ra general formula (I); b) reaction of a compound of the general formula (XXXIX) reducing agent ---- d j ssn 1 vfin11; (XI T) (xxxjx) -204in which X represents a -SO ₂ C1 group, with a reducing agent at a temperature between 0 ° C and 110 ° C in an organic solvent to obtain the disulfide compound of the general formula (XLI) in which Rj, R ₂ , R3, Y, Χχ, X ₂ , ^x 3 θ * 4 have the meaning defined in claim 1 for the general formula (I); and reaction of a disulfide compound of general formula (XLI) in which Rq, R ₂ , R3, Y, X] _, X ₂ , X3 and X4 have the meaning defined in claim 1 for the general formula (I), with a perhalogen alkane of the general formula (XLI), ZCFRçRg, in which Z represents a chlorine, bromine or iodine atom, R7 represents a fluorine, chlorine or bromine atom and R represents a fluorine, chlorine or bromine atom or a perfluoro-alkyl group in the presence of a reducing agent free radical generator and optionally in the presence of a base, in an organic solvent, at a temperature between 20 ° C and 85 ° C and optionally under pressure, to obtain a compound of formula (I) in which X represents a perhalogen-alkylthio group and Rj, R ₂ , R3, Y, Χχ, X ₂ , X3 and X4 have the meaning defined in claim 1 for the general formula (I). 3 - Process for the preparation of compounds of general formula (I) according to claim 1, in which: X represents a halogen atom or a cyano, cyanate, thio-cyanate, halo-alkyl, alkoxy, halo-alkoxy, alkyl-thio, alkyl-sulfinyl, alkyl-sulfonyl, halo-alkyl-thio, halo-alkyl-sulfinyl group , halogeno-alkylsulfonyl, halogeno-alkyl-carbonyl, halogeno-alkyl-thio-carbonyl, phenyl-thio, phenyl-sulfinyl, phenyl-sulfonyl, heteroaryl-thio, heteroaryl-sulfinyl and heteroaryl-sulfonyl; wherein the phenyl groups are optionally substituted with halogen atoms or with cyano or halo-alkyl groups, the heteroaryl groups being pentagonal or hexagonal monocyclic rings, containing one or two equal or different heteroatoms chosen from oxygen, sulfur or nitrogen atoms, -206e being the heteroaryl groups optionally substituted with halogen atoms or with nitro, cyano or halo-alkyl groups; and where the alkyl, halo-alkyl, alkoxy and halo-alkoxy groups are straight or branched chains, with less than 10 carbon atoms, and where the halogen substitution in all of these groups ranges from mono-substitution to complete poly-substitution; Rp R2 and R3 have the meaning defined above for X; or each represents a hydrogen atom; an alkyl group; and a substituent such that no more than one of the symbols Rp R2 and R3 represents a formyl, hydroxyimino-alkyl idenyl, alkoxyimino-alkylidine, azido, amino, alkyl-amino, dialkyl-amino group, aralkyl-amino, amino-carbonyl-amino, alkyl-carbonyl-amino, halogeno-alkyl-carbonyl-amino, aryl-carbonyl-amino, alkyl-sulfonyl-amino, halogeno-alkyl-sulfonyl-amino, alkalkyl-amino-carbonyl- amino, aryl-amino-carbonyl-amino, benzylidene-imino, alkylidene-imino, alkoxy-alkylidene-imino and dialkyl-amino-alkylidene-imino, an optionally substituted phenyl group or a halogen atom or with a cyano or halogen group alkyl, or a heteroaryl group having a pentagonal or hexagonal monocyclic ring, containing one or two equal or different he-207teroatoms chosen from oxygen, sulfur or nitrogen atoms, and whose heteroaryl group is optionally substituted with a halogen atom or with a nitro, copoly or halo-alkyl group; and where the alkyl, halo-alkyl, halo-alkoxy and alkoxy groups are straight or branched chain, with less than 10 carbon atoms, with the hydrogen substitution in these groups varying from mono-substitution to complete poly-substitution ; Y represents a halogen atom or a cyano, alkyl, halo-alkyl, alkoxy, non-alkoxy, alkyl-sulfinyl, alkyl-sulfonyl, alkyl-thio, halogeno-alkyl-thio, halogeno-alkyl-sulfinyl, halogeno- alkylsulfonyl, alkyl-carbonyl, halo-alkyl-carbonyl, alkenyl, halo-alkenyl, halo-alkynyl and alkynyl; and in which the alkyl, alkoxy, halo-alkyl and halo-alkoxy groups are straight or branched, with less than 10 carbon atoms, the halogen substitution in these groups being variable from mono-substitution to complete poly-substitution; and Χχ, Xg, X3 and X 4 have the meaning for the general formula (I) in claim 1, the same conditions as in claim 1 applying, characterized in that correspondingly substituted starting compounds are used. -2084, - Process for the preparation of compounds of general formula (I), according to claims 1 or 3, in which the alkyl, alkenyl, alkynyl and alkoxy radicals of the substituents represented by X, Χχ, X2, X3, X4 , R4, R2 R3 and Y have less than 5 carbon atoms, characterized by the use of correspondingly substituted starting compounds. 5. - Process for the preparation of compounds of general formula (I), according to claim 4, in which: X represents a halogen atom or a group of the general formula R5S (O) _n in which n represents the integer 0, 1 or 2 and R5 represents an alkyl, halo-alkyl, alkenyl or halo-alkenyl group; Rx represents a hydrogen or halogen atom or an alkylthio group; R2 represents a cyano group; R3 represents a hydrogen or halogen atom; Y represents a hydrogen or halogen atom, a halo-alkyl or halo-alkoxy group, with the proviso that Y represents a hydrogen atom as defined in claim 1; and Χχ, X2, X3 and X4 each independently represent a hydrogen or halogen atom or a C2-C3 alkoxy C2-C3 or al-209alkyl (C1-C3) -io alkyl group, characterized by the fact that use correspondingly substituted starting compounds. 6. The process according to claim 5 for the preparation of compounds of general formula (II) in which X represents a group in which no CH3, CHF ₂ , CHC1 ₂ or CHC1F group is present; ^R 1 represents one atom ro or bromine; ^r 3 represents one atom ro or bromine; *1 represents one atom ro; and of general formula RsS (O) _n integer 0, 1 or 2 and R5 re CF3, CF ₂ C1, CFC1 ₂ , CF ₂ Br, hydrogen, fluorine, hydrogen estrus, fluorine, hydrogen estrus or cloY represents a group CF3 or CF3O, -210 characterized by the use of correspondingly substituted starting compounds. 7.- Process according to claim 6, for the preparation of: 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (trifluoromethyl-thio) pyrrole; 1- (2,6-dichloro-4-trifluoromethoxy-phenyl) -2-chloro-3-copy no-4- (trifluoromethyl-sulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-thio) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (chloro-difluoro-methyl-sulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (chloro-difluoro-methyl-sulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (chloro-difluoro-methyl-thio) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (trifluoro-methyl-sulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (trifluoromethyl-sulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (dichloro-fluoro-methyl-thio) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cia-211ηο-4- (dichloro-fluoro-methyl-sulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (chloro-difluoro-methyl-thio) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (chloro-difluoro-methyl-sulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -5-bromo-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (chloro-fluoromethyl-sulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethoxy-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethoxy-phenyl) -2-chloro-3-copy no-4- (dichloro-fluoro-methyl-sulfonyl) pyrrole; 1- (2-chloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) pyrrole; 1- (2-chloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) pyrrole; 1- (2-chloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-thio) -5-methyl-thio-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (bromo-difluoro-methyl-thio) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (bromo-difluoromethyl-sulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cia-212no-4- (bromo-difluoromethyl-sulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (methylsulfinyl) pyrrole; or 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (methylsulfonyl) pyrrole, characterized in that correspondingly substituted starting compounds are used. 8.- Process for the preparation of compounds of general formula (I), according to claim 5, wherein, X represents a halogen atom or a group of general formula RsS (O) _n in which n represents the integer 0, 1 or 2 and R5 represents an alkyl group, preferably C1-C4 alkyl; halogeno-alkyl, preferably trihalogeno-methyl in which halogeno means F, Cl, Br or their combinations, for example, CF3, CCI3, CF2CI, CFCI2 or CF ₂ Br; alkenyl; or halogen-alkenyl; R3 and R3 each represent a hydrogen atom; R ₂ represents a cyano group; Y represents a hydrogen or halogen atom, preferably chlorine or bromine; and Χχ, X ₂ , X3 and X4 each independently represent a hydrogen or halogen atom; or a C1-C3 alkyl group; C1-C3 alkoxy; and (C1-C3) alkylthio; and preferably Χχ and X4 represent 213 each have a hydrogen, fluorine, chlorine or bromine atom or a methyl group and X £ and X3 each represent a hydrogen atom; characterized by the use of correspondingly substituted starting compounds. 9.- Process according to claim 8, for the preparation of: 1- (4-bromo-2,6-dichloro-phenyl) -3-cyano-4- (chloro-difluoro romethyl-thio) -pyrrole; 1- (4-bromo-2, β-dichlorophenyl) -3-cyano-4- (trifluoromethyl-thio) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chloro-difluoromethyl-thio) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chloro-difluoromethyl-sulfinyl) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole; 1- (4-bromo-2,6-dichloro-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (dichloro-fluoro-214ro-methyl-sulfonyl) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trifluoromethyl-thio) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trifluoromethyl-sulfuryl) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trifluoromethyl-sulphonyl) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trichloromethyl-thio) -pyrrole; 1- (2,4-dichlorophenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4-chloro-pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chloro-difluoromethyl-sulfonyl) -pyrrole; 1- (2,6-dichlorophenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio) -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- (chloro-difluoromethylsulfinyl) -pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (chloro-difluoromethyl-sulfonyl) -pyrrole; 1- (4-bromo-2,6-dimethylphenyl) -3-cyano-4- (trifluoromethylsulfinyl) -pyrrole; 1- (4-bromo-2,6-dimethylphenyl) -3-cyano-4- (trifluoromethylsulfonyl) -pyrrole; or -2151- (4-bromo-2,6-difluorophenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole, characterized in that correspondingly substituted starting compounds are used. 10. Process for the preparation of compounds of general formula (I) according to claim 3, in which the alkyl and alkoxy radicals of the groups represented by X, X] _, X2, X3, X4, Ri, R2, R3 and Y have less than 5 carbon atoms, characterized by the use of correspondingly substituted starting compounds. 11. Process for the preparation of compounds of general formula (I) according to claim 3 or 10, wherein the substituents Y defined as alkenyl and halo-alkenyl are, respectively, allyl and halo-allyl, and in which the Y substituents defined as alkynyl and halo-alkynyl are, respectively, propargyl and halo-propargyl, characterized in that correspondingly substituted starting compounds are used. 12. Process for the preparation of compounds of general formula (I) according to claim 3 or 10 wherein: R1 represents a hydrogen or halogen atom; R2 represents a cyano group; -216X represents a halo-alkyl-S (0) _{n group} , where n represents the integer 0, 1 or 2; Χχ and X4 do not represent hydrogen atoms; Y represents a halogen-alkyl or non-alkoxy halogen group; and X2 and X3 each represent a hydrogen atom, characterized in that correspondingly substituted starting compounds are used. 13. The process of claim 12, wherein: Rq represents a halogen atom selected from chlorine or bromine; and X represents a halogen-alkyl-S (0) group _not selected from trifluoromethyl-thio; trifluorome tylsulfinyl or trifluoromethylsulfonyl, characterized in that correspondingly substituted starting compounds are used. 14. The process of claim 3 for preparing: 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (trifluoromethyl-sulfonyl) -pyrrole); 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (trifluoromethyl-sulfinyl) -pyrrole; -2171- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-ciaηο-4-trifluoromethyl-sulfinyl-5-bromo-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4-trifluoromethyl-sulfonyl-5-bromo-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) 2-chloro-3-cyano-4- (trifluoromethyl-thio) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2 - [(trifluoromethyl) -carbonyl-amino] -3-trifluoromethyl-thio-4-cyano-5-chloro-pyrol; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2- (methyl-carbo-1-amino) -3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole; 1- (2-chloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoro-methyl-thio-4-cyano-5-chloro-pyrol; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-dichloro-fluoro-methyl-thio-4-cyano-5-chloro-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2,4-bis (trifluoro-methyl-thio) -3-cyano-5-amino-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoro-methyl-thio-4-cyano-5-bromo-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-pyrrole; 1- (4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-5-bromo-pyrrole; 1- (2-chloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoro-218romethyl-thio-4-cyano-5-bromo-pyrroy; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole; or 1- (2,6-dichloro-4-trifluoromethoxy-phenyl) -2-chloro-3-cia no-4- (trifluoromethyl-sulfonyl) -pyrrole, characterized in that correspondingly substituted starting compounds are used. 15.- Method to control pests of arthropods (especially insects or arachnids), plant nematodes, helminths or protozoa in a place, characterized by the fact that: a) for the control of arthropod and nematode pests, an effective amount of between 0.005 and 15 kg of compost per hectare of treated site, preferably between 0.02 kg and 2 kg, and more advantageously applied to the site to be treated between 0.01 kg and 1 kg per hectare of a compound of general formula (I) prepared by the process according to claim 1 or 14; or -219b) if a warm-blooded vertebrate animal is administered an effective amount, between 0.01 and 20.0 mg per kg of body weight and per day, preferably between 0.1 and 5.0 mg / kg and per day, of a compound of general formula (I), prepared by the process according to claim 1 or 14. 16.- Method according to claim 15, for controlling pests of arthropods or plant nematodes, characterized in that a compound of general formula (I) prepared by the process according to claim is used 1 or 3. 17. A method for controlling mites, according to claim 15 or 16, characterized in that a compound of general formula (I) prepared by the process according to claim 8 or 9 is used. 18. Process for the preparation of compositions used as insecticidal, acaricidal or nematocidal agents, characterized in that an effective amount of one or more compounds of general formula (I) prepared by the process according to any one of claims 1 and 3 to 14, preferably comprised between 0.05% and 95% by weight, with an amount comprised between 1% and 95% by weight of one or more liquid or solid vehicles acceptable in agriculture; and with between 0.1% and 50% by weight of one or more agriculturally acceptable surfactants. -22019.- Process according to claim 18, characterized in that one or more ingredients selected from the group consisting of protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, spray oils are additionally incorporated into the composition. , stabilizers, preservatives, form preservatives, sequestering agents and other pesticidal active ingredients. Lisbon, July 3, 1995 The Official Industrial Property Agent -221 - (dichloro-fluoro-methyl-sulfonyl) -5-bromo-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (chloro-difluoromethyl-sulfonyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethoxy-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethoxy-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole; 1- (2-chloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole; 1- (2-chloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole; 1- (2-chloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-thio) -5-methyl-thio-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (bromo-difluoro-methyl-thio) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (bromo-difluoromethyl-sulfinyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (bromo-difluoromethyl-sulfonyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (methylsulfinyl) -pyrrole; or 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (methyl-sulfonyl) pyrrole _T wherein using correspondingly substituted starting compounds. 19. - Process for the preparation of compounds of general formula (I), according to claim 16, in which: X represents a halogen atom or a group of the general formula RgS (O) _n in which n represents the integer 0, 1 or 2 and R4 represents an alkyl group, preferably C1 -C4 alkyl; halogeno-alkyl, preferably trihalogeno-methyl in which halogeno means F, Cl, -Br or combinations thereof, for example, CFg, CClg, CFgCl, CFClg or CFgBr; alkenyl; or halogen-alkenyl; R4 and Rg each represent a hydrogen atom; Rg represents a cyan group; Y represents a hydrogen or halogen atom, preferably chlorine or bromine; and X ^, Xg, Xg and X ^ each independently represent a hydrogen or halogen atom; or a C ^-Cg alkyl group; C ^-Cg alkoxy; and (C1 -Cg) alkylthio; and preferably X ₁ and X 4 each represent a hydrogen, fluorine, chlorine or bromine atom or a methyl group and Xg and Xg each represent a hydrogen atom; characterized by the use of correspondingly substituted starting compounds. 20. - Process according to claim 19, for preparing: * 1- (4-bromo-2,6-dichloro-phenyl) -3-cyano-4- (chloro-difluoromethyl-thio) -pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (trifluoromethyl-thio) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chloro-difluoromethyl-thio) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chloro-difluoromethyl-sulfinyl) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole; 1- (4-bromo-2,6-dichloro-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio-pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trifluoromethyl-thio) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trifluoromethylsulfinyl) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trifluoromethyl-sulfonyl) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trichloromethyl — thio) -pyrrole; 1- (2,4-dichlorophenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4-chloro-pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chloro-difluoromethyl-sulfonyl) -pyrrole; 1- (2,6-dichlorophenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio) -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- (chloro-difluoromethylsulfinyl) -pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (chloro-difluoromethyl-sulfonyl) -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- (dichloro-fluoro-methyl-thio) -pyrrole, characterized in that correspondingly substituted starting compounds are used. 21.- Process for the preparation of compounds of general formula (I) according to claim 14, in which the alkyl and alkoxy radicals of the groups represented by X, Xg, Xg, Xg, X ^, Rg Rg, Rg and Y have less than 5 carbon atoms, characterized by the fact that correspondingly substituted starting compounds are used. 22. A process for the preparation of compounds of general formula (I) according to claim 14 or 21, wherein the substituents Y defined as alkenyl and halo-alkenyl are, respectively, allyl and halo-allyl, and in which the Y substituents defined as alkynyl and halo-alkynyl are, respectively, propargyl and halo-propargyl, characterized in that correspondingly substituted starting compounds are used. 23. The process for preparing compounds of the general formula (I) according to claim 14 or 21 wherein: Rg represents a hydrogen or halogen atom; Rg represents a cyan group; X represents a halogen-alkyl-S (0) group, where n represents the integer 0, 1 or 2; Xg and X ₄ do not represent hydrogen atoms; Y represents a halo-alkyl or halo-alkoxy group; and Xg and Xg each represent a hydrogen atom, characterized in that correspondingly substituted starting compounds are used. 24. The process of claim 23, wherein: R4 represents a halogen atom selected from chlorine or bromine; and X represents a halo-alkyl-S (O) group selected from trifluoromethyl-thio, trifluoromethyl-sulfinyl or trifluoromethyl-sulfonyl, characterized in that correspondingly substituted starting compounds are used. 25. The process of claim 14 for preparing compounds of the general formula in which X represents a group of general formula R ₅ S (O) _n in which n represents the integer 0, 1 or 2 and represents a CHg, CFg, CFgCl or CFC1 _{2 group} ; R ₂ represents a cyano group; R4 represents a hydrogen, fluorine, chlorine or bromine atom or an amino group; Rg represents a hydrogen, fluorine, chlorine or bromine atom or a CFg or CN group; '' -227represents a hydrogen or chlorine atom; and Y represents a CF4 or CF4O group, characterized in that correspondingly substituted starting compounds are used. 26. The process of claim 14 for preparing: 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (trifluoromethyl-sulfonyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (trifluoromethyl-sulfinyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4-trifluoromethyl-sulfinyl-5-bromo-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4-trifluoromethyl-sulfonyl-5-bromo-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (trifluoromethyl-thio) -pyrrole; 1— (2,6-dichloro-4-trifluoromethyl-phenyl) -2-bromo-3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-Z ”(trifluoromethyl) -carbonyl-amino_7-3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2- (methyl-carbonyl-amino) -3-trifluoromethyl-thio-4-cyano-5-chloro-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino_3-trifluoro-methyl-thio-4-cyano-5-chloro-pyrrole; 1- (2-chloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoro-methyl- -thio-4-cyano-5-chloro-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-dichloro-fluoro-methyl-thio-4-cyano-5-chloro-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2,4-bis (trifluoro-methyl-thio) -3-cyano-5-amino-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoro-methyl-thio-4-cyano-5-bromo-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-pyrrole; 1- (4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-5-bromo-pyrrole; 1- (2-chloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-5-bromo-pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro-fluoro-methyl-sulfonyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-thio) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -3-cyano-4- (dichloro-fluoro-methyl-sulfinyl) -pyrrole; or 1- (2,6-dichloro-4-trifluoromethoxy-phenyl) -2-chloro-3-cyano-4- (trifluoromethyl-sulfonyl) -pyrrole, characterized in that correspondingly substituted starting compounds are used. 27.- Process according to claim 1, for the preparation of compounds of general formula (Illa) in which Y represents a hydrogen, chlorine or bromine atom or a CFg group, or OCFg and X ^ and X ^ each independently represent a hydrogen, chlorine or fluorine atom or a CHg or SCHg group, with the proviso that, if X ^ and X ^ each represent a hydrogen atom, then Y does not represent a hydrogen or chlorine atom, preferably X ^ represents a hydrogen or chlorine atom and Y represents a CFg or CFgO group, characterized by the use of correspondingly substituted starting compounds. 28.- Method to control pests of arthropods (especially insects or arachnids), plant nematodes, helminths or protozoa in a place, characterized by the fact that: a) for the control of arthropod and nematode pests, an effective amount of between 0.005 and 15 kg of compost per hectare of treated site, preferably between 0.02 kg and 2 kg and more advantageously, is applied to the site to be treated between 0.01 kg and 1 kg per hectare of a compound of general formula (I) prepared according to claim 1 or 27; or (b) administering to a warm-blooded vertebrate animal an effective amount of between 0.01 and 20.0 mg per kg of body weight and per day, preferably between 0.1 and 5.0 mg / kg and per day, of a compound of general formula (I), prepared according to claim 1 or 27. 29. The method of claim 28 for controlling arthropod or plant nematode pests, characterized in that a compound of general formula (I) prepared according to claim 1 or 14 is used. Method for controlling mites, according to claim 28 or 29, characterized in that a compound of general formula (I) prepared according to claim 19 or 20 is used. 31. - Process for the preparation of pharmaceutical compositions, especially usable in veterinary medicine and in livestock and in the maintenance of public health, characterized by the fact that an amount between 0.00005 and 90% by weight of at least one is mixed compound prepared according to any one of claims 1 and 14 to 27, with a pharmaceutically acceptable carrier. 32. Process for the preparation of compositions used as insecticidal, acaricidal or nematocidal agents, characterized in that an effective amount of one or more compounds of general formula (I) prepared according to any one of claims 1 and 14 is mixed. to 27, preferably between 0.05% and 95% by weight, with an amount between 1% and 95% by weight of one or more liquid or solid vehicles acceptable in agriculture; and between 0.1% and 50% by weight of one or more agriculturally acceptable surfactants. 33. The method of claim 22, wherein one or more ingredients selected from the group consisting of protective colloids, adhesives, thickeners, thyrotropic agents, penetrating agents, spray oils are additionally incorporated into the composition. , stabilizers, preservatives, form preservatives, drying agents and other pesticidal active ingredients,