BG60842B1 - Pyrene derivatives, method for their preparation and application - Google Patents

Abstract

The pyrrole derivatives have a general formula in which the substituents have the meanings indicated in the description. The invention also relates to methods for their preparation and their use in the formulation of high biological activity insecticidal compositions.

Description

The invention relates to novel compounds of the pyrrole chemical family, to the intermediates required for the preparation of these compounds and to methods for preparing these compounds and to the intermediates. The invention also relates to the use of said compounds in agriculture, according to the invention. -specifically as pesticides for the control of arthropods, preferably as insecticides and acaricides :. The invention also relates to compositions which find use in the control of arthropods, in particular insects and arachnids.

Many pyrazoles A heterocyclic structure containing two nitrogen atoms are well known as insecticides. As insecticides are known as, and are known to, and certain compounds containing a pyrrole (formula containing one nitrogen atom) .the group in their molecule.

• they also contain another chemical group in their molecule that is well known for having insecticidal properties, such as a pyrethroid group or a carbamate or some organophosphorus group. Simply substituted pyrrole derivatives are described as agrochemicals used as fungicides, for example in (1).

The novel pyrrole compounds according to the invention have the general formula in which X stands for halogen atom or cyano, cyano, thiocyanato, halogen κ yl, ad coke, halogen al coke, alkyl thio, alkyl sulfinyl, alkyl or sulfonyl, haloalkylthio , hadogenalkilsulfinil, halogvnalkilsulfonil, .alkenil- thio, alk enyl sulfinyl, alkenyl sulfonyl, hal ogenalk enylthio, .hadogenalkenilsulfinil, halsgenalk enylsufonyl, haloalkyl ilk ACB onyl, hal ogenalk ilt IEC carbonylamino, phenylthio, phenyl sulfinyl, phenylsulfonyl, x eteroariltio , heteroar or sulfinyl or x hetero alkaryl sulfonyl; optionally substituted by halogen, cyano or haloalkyl, and heteroaryl groups having five or; a six-membered monocyclic ring containing one or two heteroatoms, for example oxygen, sulfur or nitrogen in any combination, and optionally substituted with halogen, nitro, cyano or halogenyl or where the halogen substitution in said groups is a one or more halogen substitution atom - which may be the same or different - from mono to fully substituted, and alkyl alkyl, halogen alkyl nit, alkenyl, halogen, alkoxy and haloalkoxy groups have normal or branched chains and less than 10 char ether atoms, preferably less than 5 carbon atoms;

Rq, ^ 2 ^and ^ 3 0 ^{denote the} same substituents described for X; a hydrogen atom; an alkyl group; only one of R ₂ and can be selected from

.. formyl, xyl, and alk aldylenyl, alkoxylcarbonyl, azido, amino, alkylamino, dialkylamino, aralkylamino, aminocarbonyl but, alkyl arbonyl aminocarbonylalkylaminoalkylaminoalkylamino alkylamino arbolylamino, aryl aminocarbonylbut, benzyl idenylbut, alkylideneimino, alkoxyalkylidinimino, dialkylaminoalkylideneimino, bis / alkylthio / methyl, bis / arylthio / methyl, alkylthioalkyl, alkylthioalkyl, phenyl optionally substituted with halogen, cyano Do -haloalkyl. and a monocyclic five or six membered heteroaryl group containing one or two identical or different heteroatoms, for example oxygen, sulfur or nitrogen optionally substituted by halogen, nitro, cyano or halogenadkyl; and wherein the halogen substitution in said ¹ i

groups means the substitution by one or more halogen atoms, which may be the same or different, from mono to fully substituted. _? and the alkyl, haloalkenyl, alkenyl, haloalkenyl, alkoxy, and J haloalkyl groups have a normal or branched chain and no more than 10 carbon atoms, preferably less than 5 carbon atoms; Ύ means a halogen atom or cyano, alkyl , alkoxy, halo gene alkyloxy, alkyl yl sulfinyl, alkyl yl sulfonyl, alkyl yl thio, halogenalkylthio, halogenalkylsulfinyl, halogenoalkylsulfonyl, alkylcarbonyl, halogenoalkyl, alkenylalkenyl, alkenylalkyl, alkenyl / alkenyl alkynyl (especially propargyl), go halogenadinyl (axis) and halogenpropargide / j and where halogen substitution in these groups means substitution by one or more halogen atoms # which may be the same or different, from mono to complete polysubstitution, and the groups alkyl, halogen yl, alkenyl, hal ogenalk enyl, alkynyl, hal ogenalkynyl, adoxy, and halogenoalkok each have a normal or branched chain and less than 10 carbon atoms, preferably less than 5 carbon atoms; or γ denotes hydrogen when

X stands for halogen atom or the group Rcj (o), which is 0,1 or 2, and Rg stands for alkyl, halogenated, alkenide, or halogenatedalkyl and the halogen substitution of alkyl and alkenyl groups are as such as defined above; _; and each of them means a hydrogen atom

1 ^ 2 means cyano $

X ^, X _^,: ^and Xe ^are individually selected from the same list of h amestiteli that is specified for Y or a hydrogen atom, excluding the compounds in which X ^ = X ^ = y = R ^ = X = R - ^and at the same time ^ 3- ⁼ ^ 2 ⁼ ^ / ^AND In Y ^words: at least one of the groups R ^ ,, 1¾ ^w R ^ is selected from the group of substituents indicated for X; if they denote hydrogen, and X is halogen or cyano, then R1 is other than X; if X is hydrogen and Y is methyl then X is not bromine.

More particular novel pyrrole compounds of general formula (I) according to the present invention are those of the following:

X represents a halogen atom or a group cyano, cyanato,; giotsianato, χολ ogen tinea para coke, hal ogen _alkoxy,; al kil thio, alkyl sulfinyl, alkyl sulfyl-phonyl, hal ogenalkylthio hal hal kil sul finyl, hal gen kil sul phonyl, hal ogen kilcarbonyl, hal gen kilthiocarbonyl, phenylthio, phenyl sulfaryl phenyl sulfaryl phenyl sulphonyl sulfinyl finyl or heteroarylsulfonyl ;, wherein the phenyl group is optionally substituted by halogen, cyano or haloalkyl, and the heteroaryl groups have a monocyclic five-membered six-membered ring containing one or two heteroatoms, such as oxygen, sulfur, or nitrogen are deputy halogen, nitro, cyano or halogen kiln esters; _; and wherein halogen substitution means mono or to full substitution. and the alkyl, halogen, or alkenyl and halogenoalkoxy groups have normal or branched chains and less than 10 carbon atoms, preferably less than 5 carbon atoms; RR ^ and may be selected from the same group of substituents , which are described for a hydrogen atom ;, alkyl ;, and a substituent in which only one of R4, ·. R ^ iww

R 4 may be selected from the group consisting of: formyl, hydroxy, iminoalkylidenyl, adoxyiminoalkylidenyl, azido, amino, alkylamino, diadylamino, ar adamino, amino arVonylamino, alkylcarbonylamino, halogenoalkyl, aralkyl, alkyl il k ar They are lam, but alk idsul fonyl amino, halo genad k ylsulfonyl amino, ad ilamino arbonylamino, arylaminocarbonylamino, venzilidinimino, ad k il idenimino, ad k oxi ad k yl idenimino, di yadk fenyl amine, optionally substituted with halogen, cyano or haloalkyl, and a monocyclic five or six a membered heteroaryl group containing one or two of the same or different heteroatoms, such as oxygen, sulfur or nitrogen and optionally substituted by halogen, nitro, cyano or halogen; and wherein the halogen substitution in the above-mentioned groups means mono or to a complete polysubstitution, and the alkyl, halogenoalkyl, alkoxy and haloalkane moieties have normal or branched chains and less than 10 carbon atoms, preferably less than 5 carbon atoms;

Y stands for halogen atom, and for the group: cyano, alkyl, halogenadkyl, alkoxy, hal ogenalkok, alkyl yl sulfinyl, alkyl sulfonyl, alkyl ylthio, halogenated thio, halogenadenyl sulphinyl, halo phenyl adenyl , halogenated carbonyl, alkenyl (especially ad yl), halogenalkenyl (especially hadogenadil), alkynyl (especially propargyl) or halogenadkinyl (especially hadogenpropargyl); and wherein the halogen substitution in these groups is mono or fully substituted and the groups: alkyl, halogenalkide (alkoxy, halogenalkoxy, alkynyl, and halogenadinyl have a normal or branched chain and less than 10 carbon atoms, preferably less of 5 carbon atoms;

X1, X 2_t X3 ^and Xd have the meanings given to the same conditions as quoted above.

In general, preferred compounds of the general formula (ί) that are of importance such as insecticides and acaricides are those in which: X is a halogen atom or the group R ₅ $ / ⁰ / _n , where P is 0.1 or 2 and C 1 ₅ denotes alkyl, halogenadkyl, alkenide or halogenadenyl;

means an odor atom, a hal atom atom or an alkylthio;

r ₂ means cyano;

means a hydrogen atom or a halogen atom.

starting from a hydrogen atom, a halogen atom, a halogenalkyl, or a halogen coke, provided that when Y is a hydrogen atom as defined above in general formula (I)

is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C 1-6 alkyl, a C 1-6 alkoxy, and a C 1-6 alkylthio.

Compounds of general formula (i) which are preferred and of particular interest? are the following:

A (Compounds of general formula (n) having high insecticidal activity;

Cl

II. '

Υ, where π is 0.1 or 2, where: X is R ^ S / O /

CF ₂ Bz, ^CHf 2? ^CHCl 2 ' ^or CHCIF means H, F, Cl or B 2; denotes H, F, Cl or CF ^ O.

CF ₃ , C RUB ₂ CI »CFCI ^ but;

or CI; and γ is CFg n

CHP _g , * 5 to ₂ or va H

Among these compounds, the following are preferred:

1- / 2

1- / 2

1- / 2

1- / 2 denotes a ^CH ztsiaVs ;, means the 6-dichloro-4-trifluoromethyl in ortho phenyl methyl / -2-Chloro-S-cyano-4- / trifluoromethyl in ortho methyl thio / pyrrole;

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

, 6-dichloro-4-trifluorophenylmethyl) -2-chloro-3-cyano-4- (dichlorophenylmethyl sulfinyl) pyrrole;

methyl sulfonyl / η ir ol;

1- (2,6-dichloro-4-trifluoromethyl phenyl) -2-chloro-3-cyano-4- (chlorodifluoro) -2,6-dichloro-4-trifluorophenylmethyl) -2-chloro-3-cyano- 4- [ch] op d and fl in ormethylsulfonyl / pyrrole;

1- (2,6-Dichloro-4-trifluoro-phenylmethyl) -2-chloro-3-cyano-4- (chlorodifluoromethyl-sulfinyl) -pyrrole;

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

1- (2, 6-dichloro-4-trifluoromethylphenyl) -2-6rom-3-cyano-4- (trifluoromethyl-sulfinyl) pyrrole ;,

1- (2,6-Dichloro-4-tert-fluoro phenyl ethyl) -2-bromo-3-cyano-4- (trifluoromethylsulfonyl) lyrole;

1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (dichlorofluoromethylthio) pyrrole;

1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-6rom-3-cyano-4- (dichlorofluoromethyl) sulfonyl] pyrrole;

1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-6 rom-3-cyano-4- (dichloromethoyl) sulfonyl / pyrrole;

1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-6rom-3-cyano-4- (chlorodifluoromethyl) thio] pyrrole;

1- (2, 6-dichloro-4-trifluoromethyl-phenyl) -2-methyl-3-cyano-4- (chlorodifluoromethyl-sulfinyl) -pyral;

1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dihydrofluoromethyl sulfonyl) -5-6-pyrrole;

1- (2,6-dichlorom-4-trifluoro methyl phenyl) -2-6 rom-3-cyano-4- (chloride) and fluoromethyl sulfonyl) pyrrole;

1- (2,6-Dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethyl sulfinyl) pyrrole; '

1-12,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethyl sulfonyl) pyrrole;

1- (2-chloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylsulfonide) pyrrole;

1- (2-chloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyan-4- (dichlorofluoro-methylsulfinyl) pyrrole j

1- (2-chloro-4-trifluoromethyl-phenyl) -2-bromo-3-cyano-4- (dichlorophenylmethylsulfonyl) pyrrole;

1- (2,6-dichloro-4-trifluorophenylmethyl) -2-chloro-3-cyano-4- (dichlorophenylmethyl) and lthio] -5-methylthiopyrrole;

1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (bromodifluoromethyl) yl / η erol *,

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

1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (bromo-ylmethyl) issulfonyl / pyrrole;

1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (methylsulfinyl) pyrrole; or

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

B / Other compounds of general formula (n) with high insecticidal activity, in which: X is R ₅ S / o / _n , where n is 0,1 · or 2, and represents CH 2, CF 4, CF 6 Cl or CFCl 2 R ₂ ° means cyano; represents H, R, Cl, B4 or MH ₂ ; R3 is H, F, Cl, Βχ, CF3 or CM; represents H or Cl; and Y is CF3 or CF3O.

Preferred because of their insecticidal activity, the compounds of the present invention are:

1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (trifluoromethylsulfonyl) pyrrole;

1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (trifluoromethylsulfinyl) pyrrole;

1- (2, 6-dichloro-4-trifluoromethyl phenyl) -2-chloro-3-cyano-4-trifluoromethyl-sulfyl-5-bromopyrrole;

1- [2, 6-dichloro or 4-trifluoromethyl phenyl] -2-chloro-3-cyano-4-trifluoromethyl

- 9 sulfonyl-5-bromopropyl eryl;

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

1- (2, 6-dichloro-4-trifluoromethylphenyl) -2-6 rom-3-trifluoromethylthio-4-cyano-5-chloropyrrole

1 - / 2,6-d ihl-or-4-tr iflormomet yl f eil l / - 2 - // three fl u orm and l / k ar 6 o n and lamino / -

3-trifluoromethyl thio-4-cyano-5-chloropyrrole;

1- (2,6-Dichloro-4-trifluoro-methylphenyl) -2- (methyl-arbonylamino) -3-trifluoromethylthio-4-cyano-5-hydroxypyrrole;

1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio ~ 4-cyano-5-chloropyrrole | _;

1- (2-Chloro-4-trifluoromethyl phenyl) -2-amino-3-trifluoromethyl thio-4-cyano-5-chloropyrrole- (2,6-dichloro-4-trifluoromethyl) phenyl methyl N - 2-amino-3-dichloro fluorine methylthio-

4- cyano-5-chloropyrrole;

1- (2,6-dichloro-4-trifluoromethyl phenyl) -2,4-6is (trifluoromethylthio) -3-cyano-5-aminopyrrole;

1- (2,6-dichloro-4-trifluoromethyl phenyl) -2 * -amino-3-trifluoromethylthio-4-cyano-5-bromopyrrole;

1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4 H -anoprole;

- (4-trifluoromethyl phenyl) -2-amino-3-trifluoromethyl thio-4-cyano-5-bromopropyl

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

5- omp irol;

1- (2,6-Dichloro-4-trifluoromethyl phenyl) -2-chloro-3-cyano-4- (dichlorofluoromethyl thio) pyrrole

1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichloro fluoromethylsulfinyl) pyrrole;

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

1- (2,6-Dichloro-4-trifluoromethylphenyl) -3-cyano-4- (dichlorofluoromethylthio) - pyrrole V

1- (2,6-dichloro-4-tr and fluoromethylphenyl) -3-cyano-4- (dichlorofluoromethylsulfinyl) pyrrole; or

1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (trifluoromethylsulfonyl) pyrrole.

B / Compounds of general formula (ί) with surprisingly high acaricidal activity, where: X represents a halogen atom or a group!

th R ₅ S / O / _n, wherein n is 0,1 or 2, and represents alkyl, preferably C ₁ alkyl; halogenoalkyl, preferably trihalomethyl, preferably in the latter halogen means P, Cl or илиξ or a combination thereof, for example, CCI ^, CF ^C CI, CECI ^ or CR ^B ^; or haloalkenyl; R ^ and R ^ are each a hydrogen atom; means cyano; γ means a hydrogen atom or a halogen atom, preferably CI or Οχ; and X, X2, X3 and Xd are individually selected from the group consisting of: hydrogen, halogen, C1-C6 alkyl; With alkoxy; and C 1-6 alkylthio; and, preferably, X1 and X1, respectively, denote H, P, Cl, B1 or CH2, and and X1, each represents hydrogen,

Among these compounds, the following are more preferred: 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (chlorodiflormethylthio) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (chloro-ordifluoromethyl) thio] pyrrole; 1- (2,4, 6-trichlorophenyl) -3-cyano-4- (chlorodifluoromethylsulfinyl) pyrrole; 1- (2, 4,6-trichlorophenyl) -3-cyano-4- (dichlorophenylmethylthio) pyrrole; 1- (2,4, 6-trichlorophenyl) -3-cyano-4- (dichloro fluoromethylsulfinyl) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (dichlorophenylmethyl sulfonyl) pyrrole; 1- / _4-6rom-2? 6-dichlorophenyl / -3-cyano-4- (dichlorophenylmethylthio) pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (dichlorofluoromethylsulfinyl) pyrrole;.,

1- (4-6rom-2,6-dichlorophenyl) -3-cyano-4- (dichloromethoromethyl) sulfonyl / pyrrole;

1- (2,4,6-trichlorophenyl) -3-cyano-4-trifluoromethylthio / pyrrole;

1- (2,4,6-trichlorophenyl) -3-cyano-4- (pyrrolidine or methylsulfinyl) pyrrole;

1- (2,4,6-trichlorophenyl) -3-cyano-4- (trifluoromethylsulfonyl) pyrrole;

1- (2, 4, 6-trichlorophenyl) -3-cyano-4- (trichloromethylthio) pyrrole;

1- (2,4-dichlorophenyl) -3-cyano-4- (dichlorophenylmethylthio) pyrrole;

1- (2,4,6-trichlorophenyl) -3-cyano-4-chloropyrrole

1- (2,4,6-Trichlorophenyl) -3-cyano-4- (chloro difluoromethyl sulfonyl) pyrrole;

1- (2,6-dichlorophenyl) -3-cyano-4 - [dichlorophenylmethylthio] pyrrole;

1- (R-rom-2,6-dichlorophenyl) -3-cyano-4- (trifluoromethylsulfinyl) pyrrole;

1- (4-6rom-2,6-dichlorophenyl) -3-cyano-4- (trifluoromethyl sulfonyl) pyrrole; 1- (4-6rom-2, 6-dichlorophenyl) -3-cyano-4- (chlorodifluoromethylsulfinyl) pyrrole; 1- (4-6rom-2,6-dichlorophenyl) -3-cyano-4- (chlorodifluoromethylsulfonyl) pyrrole; 1- (4-bromo-2,6-dimethyl phenyl) -3-cyano-4- (trifluoromethyl ethyl sulfinyl) pyrrole;

1- (4-bromo-2,6-dimethylphenyl) -3-cyano-4- (trifluoromethylsulfonyl) pyrrole; or 1- (4-bromo-2,6-difluorophenyl) -3-cyano-4- (dichlorophenylmethylthio) pyrrole. D) Other preferred compounds of general formula (I) are those wherein: represents a hydrogen atom or a halogen atom, such as chlorine or bromine; means cyano ;. X stands for haloalkylthio. or haloalkylsulfinyl or haloalkylsulfonyl, preferably CF S (o), wherein n is 0.1 or 2; X and X do not represent a hydrogen atom; X ^ ^and ^ 3 oz- begin each hydrogen atom; and means haloalkyl or haloalkoxy.

se

It is an object of the invention to provide new insecticides and acaricides from the pyrrole group, as well as the intermediates from which they are derived.

It is another object of the invention to provide very active compounds. These and other objects of the invention are solved in whole or in part with the novel compounds described below.

The object of the invention is solved by the compounds of general formula (1), which can be obtained by the application or adaptation of known methods using the methods described herein (i.e., those methods which have hitherto been extracted from the chemical literature): formation of mainly a pyrrole ring, after which the substituents are replaced as necessary. It should also be clear that in the description it is used. The sequence for the introduction of the different rings may occur in different order, as well as the subsequent groups in the pyrrole if necessary. they also use a fit yashti protecting groups that will be obvious to spetsialistite.Sashto takasaedineniyata general formula / i / by known methods can be converted into other compounds of general formula / ί /.

It should be borne in mind that 'in the methods described below, the symbols in formulas, when not specifically defined, are as previously described in accordance with the first definition for each symbol in the description. The term protection means becoming a suitable non-reactive group - which, if desired, can be converted again, as well as the addition of groups that make the functional group unreactive. In the definitions, unless otherwise indicated, amino means an unsubstituted amino group.

Certain intermediates useful in the preparation of some of the compounds described herein are encompassed within the scope of the invention. Such preferred intermediates of the invention have the general formula

I, 111 a.

Υ in which y denotes H, Cl, B,, or OCF ^, and and denote separately mean

H, CI, S, CH ^ $ or CH ₃ both hydrogen, then

these types, defined by similar conditions, do not fall within the scope of the invention, but are useful as starting intermediates for the preparation of compounds of general formula (I) according to the invention.

From compounds of the general formula / 111a / are preferred those in which the mean CF ^, or OCF ^, Xoznachava H or 01 and X ₄ is CI.

METHOD 1.

According to one embodiment of the invention, compounds of the general formula (I), with which they denote hydrogen, X means cyano group ^ means amino group (NH ₂ ) and X _v X ₂ , X ₃ , X ₄ and X have the same meanings ^ as in the basic definition of the invention which means the compounds of general formula

may be obtained from dicyanopropene derivatives of the general formula

MH-CI-C-CHi-CV

Хд Хг

X have (in which the substituents as described above) are reacted with a basic substance, preferably an alkali, such as tritic amine or hydroxide or carbonate of an alkali metal. The reaction is advantageously carried out in the temperature range -80 and 150 ° C. preferably at + 40 and 100 ° C. The solvent and which may be used are, for example, liquid alcohol and, hydrocarbons, halogens, ethers, ketones, amides such as N-methylpyrrolidone or water. METHOD 2

According to another embodiment of the invention, compounds of general for14 zero / IV / can be obtained from derivatives of compounds of the aniline of the general formula / V /, wherein X ^, X _2, X ^, X ^, and γ have the same meanings as in the general definition of the invention.

N-3 by reaction with formyl succinonitrile or an alkali metal salt of formyl succinonitrile.This reaction is usually carried out in an organic solvent medium or water in the temperature range between 120 DEG C., preferably at reflux temperature, obtained by acidifying the alkali metal. its salt, which is a alkaline substance according to (2)

METHOD WITH

Compounds of general formula (X), which X is halogen, amino, cyano and hydrogen, and the other substituents have the same meanings described in the general description of the invention, can be obtained by treating the compounds of general formula (ill) with halogenating agents, such as, for example, sulfuryl chloride, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide,

Dihydromethane and acetonitrile are suitable organic solvents between -00 and + 80 ° C, preferably between -30 and + 25 ° C, if trifluoroacetamide during molecular fluorine treatment.

METHOD 4.

A / The compounds of the general formula (ΐ), Β which X stands for cyanide

of the invention can be prepared from the corresponding compounds in which

X stands for the group C = b10H, by dehydration with a substance of the

acetic anhydride, cyanuric chloride iridium P2 ^ 5 * ^ ^Ogata is

using at some of these dehydrators need amino the group yes be protected by a suitable protecting group. Used The intermediates described above in which X is

the group C = NO, can be obtained by condensing the hydroxide amine with the corresponding compounds in which X is formyl.

B) Intermediates in which X is formyl (of the general formula (VI) - see below) can be prepared by hydrolysis of the corresponding compounds in which X is bis (alkylthio) methyl or bis (aridiothio) methyl, or by treatment with a suitable alkyl nitrite, after which the resulting compound is hydrolyzed according to (3).

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

D) Intermediates of general formula (I), wherein X is bis (alkylthio) methyl or bis (arylthio) methyl, and the other substituents being the same as defined above may be obtained by reaction of a compound with .general formula (t) with tri (alkylthio) methane or tri (arylthio) methane in the presence of a Lewis acid, preferably a sulfonium salt, such as dimethyl (methylthio) sulfonium tetrafluoroborate. General conditions for this conversion are described in 4 /

METHOD 5.

A / Useful intermediates, generally referred to as hydroxy, mean optional

1 ^ 2 means' cyano group ·, | ^ ₃ means hydrogen formula (ΐ),, which X is a protected amino group, an atom and X _g , X ₂ , X ₃ , X ₄ and γ have the definitions shown in the general definition of the invention, can to be obtained from the corresponding compounds in which X is halogen by conversion to a Grignard reagent or lithium derivative according to standard methods, and then reacted with oxodiper-oxymolybdenum / pyridine // hexamethylphosphoric triamide (MOORN) by following the procedures described in the compounds described above, in turn become a suitable protection If necessary, the cyano group of which X represents halogen may be a derivative of the compound (for example, an oxazoline derivative of the corresponding compound in which the cyano group is hydrolyzed to carboxylic acid) prior to the formation of the Grignard reagent or the lithium derivative. above Grignard reagent or lithium derivative may interact with trialkyl boron after only oxidation with hydrogen peroxide _; according to the method described in (b).

B / The compounds of the general formula (ι), β which X stands for cyano, R ^ represents amino, R ₂ θ piano, R ₃ stands for hydrogen atom, and X ^ _r X ^, X ₃ , Xd and Y have the meanings given in the general definition of the invention can be obtained from the corresponding compounds in which X 3 is a starting point, R 1 represents an optional but protected amino group, R ₃ represents a hydrogen atom

In the general definition and XX _z , X ₃ , X ₄ and γ have the meanings shown in the invention by interacting with halo-cyanocyanates in the presence of a base by methods similar to that described by θ /? /, Followed by the stage of removal of the protecting group, if necessary.

B) The compounds of the general formula (I), with which X stands for alkoxy: stands for amino, R ₂ stands for cyano, R ₃ stands for hydrogen atom and X, j, X3, Xd and the meanings given are the general definition of the invention, can be prepared from the corresponding compounds in κοι το X is hydroxy, R ^ is optionally protected amino group, R ₃ represents a hydrogen atom and X ^., X _2, X _3, Xe and y have the meanings ments given in the general definition of the invention , by reaction with alkyl halide, alkyl sulfonate, diadyl sulfate and the like, optionally in the presence of of a base in a solvent such as acetone or dimethylformamide at a temperature between 25 ° C and the temperature of reflux of the solvent her taken only in neo [essary, the step of removing the protecting group.

D) Compounds of general formula (i) in which X stands for halo-genalkoxy, R1 is amino, stands for cyano, represents a hydrogen atom, and X 1, X X 4, X 4 and y have the same meanings given in the general definition of the invention can be obtained from the corresponding compounds in which X is hydroxy, R 1 represents an optionally protected amino group, R 3 represents a hydrogen atom, and X 1, R 3 ^and R 4 ^and X have the same definitions as in the general definition of the invention according to the various halogenoalkylation methods described in (c), subsequently optionally, X ", X", X4 and y have the same meanings as defined in ehodimost. from the protection removal stage.

PEDOD 6.

Compounds of the general formula (ΐ), Β which X stands for halogen-alkyl, R1 stands for amino group, stands for cyano group. R 3 represents a hydrogen atom and lazes within the general definition of the invention can be prepared from the corresponding compounds wherein X represents a formide group, a carboxylic acid or halogen function group, and an amino group! it is optionally protected.For example, the treatment of formyl compounds with diethylamino sulfur trifluoride by analogy to the method described in (9) results in a compound of the general formula (1), in which X is a difluoromethyl group and the other substituents have the descriptions described above, Oxidation of the aforementioned common compounds of the general form a / 1 / * in which X is trioxide in the medium means formyl with an oxide such as, for example, chloro sulfuric acid (Johnny's reagent) leads to intermediates with general formula (1) wherein

X is game 1.

with a carboxylic acid function, R 1 is an amino group, R _{2 is a} cyano-n-hole, R 2 represents a hydrogen atom and X 1, X 2, X 4, X 4 and mean

Y has the same meanings as defined by the general definition of the invention. It may be advantageous to protect the amino group, for example, as a derivative of trifluoroacetate amide during such oxidative reactions. The interactions of the compounds described above, in which X represents a carboxyl group, with sulfur tetrafluoride as described in (10), to afford compounds in which X represents a trifluoromethyl group and the other substituents have those described above values. Alternatively, compounds in which X is trifluoromethyl, R ^ is an amino group, R ₂ represents a cyano group, F _<3 represents a hydrogen atom and X ^, X _2, X _3, X 4 ^and X have the meanings shown in the general definition of the invention, to be obtained from compounds of general formula (ι), β which X stands for halogen, preferably iodine, and the other substituents having the above meanings by reaction with trifluoro-methyl-copper under conditions similar to those described in / and /.

METHOD 7.

Compounds of the general formula (ι), β which X stands for bromomethyl or chloromethyl, R ^. means an amino group, ι R ^ means a cyano group, R ₃ ί means a hydrogen atom and X ^, Xg, X ₃ , X ^ and have the meanings shown in the general definition of the invention, can be obtained by reacting the corresponding intermediates in which X stands for methyl group and amino group. is optionally protected with M-bromo-succinimide or M-chlorosuccinimide in a solvent medium such as tetrachloromethane at temperatures between 0 ° C and the reflux temperature of the solution. The above compounds in which X denotes a methyl group may are obtained from the intermediates of general formula (1) in which X is formyl and the other substituents have the same meanings as described above by subsequently treated with p-toluenesulfonylhydrazine and sodium cyanoborohydride according to a method similar to this, written in / 12 / ..

METHOD 8.

e) Compounds of the general formula (ι), β which X stands for halogen alkylcarbonyl, R 1 represents an amino group, f 2 R 2 means a cyano group, R ₃ represents a hydrogen atom and X 1, X ₂ , X ₇ > Xd ^and Y have the meanings defined in the general definition of the invention, meaning the compounds of general formula (VIII), can be obtained by sequential treatment of the corresponding compounds (VI), in which the amino group is optionally protected, with a halogenoalkylmethane derivative to give compounds of general formula (VII), in which X stands for Hadogenadylcarbinol of the oxidation process according to metho d, on ncai in (1 3) and, if necessary, a deprotection step. Suitable hadogenic alkylmeth derivatives include perfluoroalkyl lithium derivatives, semi-scientists according to (14)? or trimethyltrifluoromethylsilane, prepared and used according to / 15/. In this literature, reference can also be made to other hadogenic alkylmethane derivatives. The method using trimethyltrifluoromethylsilane ^ can be illustrated as follows:

B (Compounds of general formula (VIII) 'may be converted to compounds of general formula (I), in which X is a haloalkylthiocarbonyl group, R 1 represents an amino group, R 2 represents a cyano group, R ₃ represents a hydrogen atom and X 1, X ₂ , X ₃ , and y have the definitions given in the general definition of the invention by treatment with / 2,4-bis

4-Methyl oxiphenyl (-1,3-dith and a-2,4-d and phosphate-2,4-d isophyl d / (Lawson's Agents).

D, ET0D 9,

The compounds of general formula (VII) can be converted to other compounds of general formula (ΐ), Β which X stands for α-haloalkyl-α-halo genmethyl groups by treatment with a halogenating agent, such as for example ep, nyl chloride or hydrogen bromide. It may be advantageous to protect the amino group, for example, as a trifluoroacetamide derivative, to prevent the pyrrole ring halogenation during such halogenation.

GSETOD 10.

A (Compounds of the general formula (1) wherein X is thiocyanato means an amino group, R _{2 is an} ^analogous cyano group, R 2 represents a hydrogen atom and X 2. X X ^, X 4 ^and Y ^stubborn same h headed k as, in the general definition of the invention may be prepared by treating the compounds of general formula / ill / a M $ CN, wherein M is an alkali metal in the presence of bromine is medium from a solvent such as methanol.

B) Compounds of general formula (X), which X is alkyl-thio, hal-o-alkylthio, alkenylthio, halo-alkenylthio, phenylthio or heteroarylthio, R is amino, R ₂ is cyano! and R ^ represents a hydrogen atom, and XХ ^, X ^ and γ have the same meanings as in the general definition of the invention, and the phenyl and heteroaryl groups represent and / or are substituted as described herein, i.e. the compounds of general formula (IX) (c) and w ith, od y) can be obtained by reacting a compound of general formula (ill) with sulfenyl halide RS Hal, where R is alkyl, haloalkyl, alkenyl, halogenalkenyl, phenyl or heteroaryl as defined above, and Hal denotes a halogen atom, the reaction medium being liquid. Preferably an organic solvent is used, for example, dichloromethane, at a temperature of- ^{0 O} to + 100 ° C, preferably at temperatures of -80 ° C to +25 ° C. Hz ad el living, pelvis and reaction can be carried out in the presence of acid. n acceptor, for example, tertiary amine, mp. is .pyridine. Alkylsulfonylnyl chlorides are prepared according to (1b).

sulfenyl chloride, the method can presented through the following scheme P ^SN «A / ^RS imr ^{Ch /} ν ν 1 + Q SGT - -From * 4 xA ^ ^Xj xA / X ' Υ Υ / III / / IX /

YEAR 11.

The compounds of general formula (ΐ), Β which X stands for thiocyanate, means an amino group,. C ₂ represents a cyano group, R ₃ represents a hydrogen atom and X _t , X 2, X 4, X ₄ and γ have the same meanings as in the general definition of the invention, they can further be converted to compounds of the general formula (ΐ / , Which X stands for alkylthio, means

an amino group ί ^ ₂ means a cyano group, a hydrogen atom and * 1. "^ 2 '^ 3' X and γ have the same meanings as in the general definition of 4 ·

the invention by treatment with a base, for example sodium or potassium base in the presence of, for example, alkyl halide or dialkyl sulfate in a solvent medium.

METHOD 12.

The compounds of general formula (IX) can be oxidized to give compounds of general formula (x), in which X (see below) means the group RS / θΛ, where C is 1 or 2, and R has the meaning The oxidizing agent used may be hydrogen peroxide, peroxyacetic acid, trifluoroperoxyacetic acid, and N -chloroperoxybenzoic acid in a solvent medium, for example dichloro methane, acetic acid or trifluoroacetic acid40 ° and + 80 ° C, preferably from 0 ° to 25 ° C. temperature, reaction time, and amount of oxidant may be varied in order to obtain the sulfinyl

22. (n = 1) or sulfonyl (n = 2) derivatives. It is also possible to obtain sulfonyl derivatives from sulfinyl compounds, which is apparent to those skilled in the art. In some cases, it may be advantageous thio groups, for example, the trifluoromethylthio group, to protect, for example, as the trifluoroacetate trifluoroperoxyacetic acid, the moamine function method, the amide. When the oxidant

but yes ι be present i link through the following scheme: R-S V cn l. re rn U * π CN  ) C • rm 2 ** 3 “X | * s th Υ, / VII / In / x /

METHOD 13 means amino, ^ 2 means the same meanings as in the general

The compounds of the general formula / ΐ /, Β which represents halogen, cyano and X, X ^, X _2, X ^, X ^ and · γ have a definition of the invention may be prepared by treating compounds of the general formula / ΐ / , β which ^X 4 stands for amino, C ₂ means here, i.e. * cyano, C ₃ is hydrogen and X, X 4, X ₂ , X 4 have the same meanings as in the general definition of the compounds of the general formula / XI /, shown below, by treatment with halogenating agents under similar conditions as in METHOD 3

The general conversion is shown below:

CN

Hal = halogen

/ XI /

METHOD 14.

The compounds of the general formula / ί /, which is bis / alkylthio / methyl or bis / arylthio / methyl group, Ιχ is amino and X, X ^, X _2, X _d, Xe, and γ have the same meaning as in general definition of the invention are prepared by reacting a compound of the general formula / XI / three / alkkltio / methane or three / arylthio / methane, Ζ ^ θ5 / / wherein W ^a is alkyl or aryl / in the presence of a Lewis acid, for preferably a sulphonium salt, in a solvent at a temperature between 0 ° C and the reflux temperature of the solvent, optionally in the presence of an acid acceptor such as pyridine. In a more preferred method, acetonitrile at 25 ° C with tri (methylthio) methane as tri (alkylthio) methane and dimethyl (methylthio) sulfonium tetrafluoroborate as a Lewis acid without an acid acceptor is used as the solvent. Generally, the method is illustrated with the following scheme:

/ XI /

METHOD 15,

Useful intermediates of the general formula (1) in which formyl means amino, amino, cyano, and X, X, X ^, ^X 3 » ^X 4 ^and Υ have the meanings given in the general definition of the invention herein, i.e. The compounds of general formula (XIV) shown below may be prepared by hydrolysis of compounds of general formula (XIII) or by reaction with an alkylnitrite under conditions similar to those described in METHOD 4B. be presented as follows:

Μ E ΤΟ E 16.

The intermediates of the general formula (I), which R1 denotes hydroxyiminoalkylidenyl or alkoxyiminoalkylidenyl, R1 represents amino, mean cyano and X, X1, X1, X3 and y have the same meanings as in the general definition of the invention, useful as intermediates compounds are prepared by condensation of a compound of the general formula (1) in which R ₃ is alkylcarbonyl or formyl, R 2 is amino, R 2 is cyano and X, X, X X 4, X 1 and γ have the meanings given in the general definition of the invention, with hydroxylamine or O-alkyl hydroxylamine or their conjugates of acid salts in a solvent medium, for example, ethanol. The above compounds wherein R1 is alkylcarbonyl are prepared in the same manner as the compounds (XIV) using the compound 1,1,1-tri (alkylthio or arylthio). / alkane as starting compound

METHOD 17,

Useful intermediates of the general formula (I) wherein R 3 is amino, amino, R 2 are cyano and X, X,,

1. »

Xd and y have the starting point of the nitro meanings given in the general definition of the invention by reducing the corresponding compounds in which 03, e.g., hydrogen, in the presence of a noble metal as a catalyst, for example, platinum or palladium, or with hydrazine and Raney nikel.S certain combinations of R2 and X, the compounds of the general formula / ί /, wherein R ^ and R ₂ are simultaneously amino, have limited stability and may require protection of one of the amino-logs with an appropriate protecting group.Compounds of the general formula (1) in which R ₃ means nitro, R <1 means amine o, R ^ cyano and X, X ^, X ^, X ₃ , Xd and y have the meanings25 given in the general definition of the invention, are obtained by nitrating compounds of general formula (XI) with a nitrating agent, nitric acid and sulfuric acid or nitric acid in acetic anhydride or other nitrating agents. In the nitration arena, it may be necessary to protect the functional amino group in (XI) with a suitable protecting group, such as, for example, acetyl or trifluoroacetyl.

BRIDGE 15.

Various derivatives useful as intermediates of the compounds of general formula (XV) (see below) can be prepared by the following methods.

A / The compounds of the general formula / ΐ /, Β which R ₃ is alkylamino, dialkylamino or aralkylamino, R ^ represents amino, Rg is cyano and X, X, X £ »CP ^and Y have the same meanings as in the general definition of the invention , are obtained from the corresponding compounds wherein R1 is amino and the other substituents have the meanings given above by alkylation with alkyl or aralkyl halides or sulfonates in organic solvents, such as ethanol, acetonitrile, toluene ►.

The production of mono or dialkylated products can be controlled by varying with stoichiometric or reaction conditions. Alternatively, if the purpose is to obtain monoalkylamine derivatives, other methods may be used, for example, converting the amino group into an alkoxyalkyl or idenimino group by treatment with an alkylorthoester followed by reduction.

R _1L as an unsubstituted amino moiety is to be introduced; and to protect this amino group before the above-mentioned treatment with a suitable protecting group. In such cases, a compound of the general formula (I), where R 2 represents an amino , Rj is a suitably protected amino group, and the other substituents have the meanings given above, meaning that a compound of general formula (XV) is prepared and used as a repertoire. Hopefully, the protecting group in (XV) is added before nitro -reduction described in NETHER 17. Depending on the subsequent transformation affecting the amino group at R1, different protecting groups are used, as can be seen from the following examples.

B) The compounds of the general formula (ΐ), ^ which R ^ denotes aminocarbonyl amino, Rj denotes amino, R _o X4 and γ have the same meanings as in the same, are obtained from the compounds denote cyano and X, Xj, X, , X ^, the general definition, of the general formula (XV ') by phosgene treatment, followed by the step of deprotecting.

B) Compounds of general formula (I), which means alkylcarbonylamino, haloalkylcarbonylamino or arylcarbonylamino, R 1 represents amino, R 1 represents cyano, and X, X ₂ , 4, 4, ^and 4 ^{have the} meanings given in the general definition of of the invention are prepared by reacting a compound of general formula (XV) with acid chlorides of e * pi of formula R ° / C = O / CI or acid anhydrides of formula wherein R® 'is alkyl, halogenated or an aryl group as defined in the first definition of the general formula (I) followed by a deprotection step. Solvents such as acetonitrile and acid acceptors, such as pyridine, combined with suitable reaction conditions, may be used.

D / Similarly, a compound of the general formula (ΐ), which

stands for alkyl-sulfonylamino or halo-phenylsulfonylamino

Rj is amino, Rg is cyano and X, Xj, ^ ₂ > X-, X ^ and y have the meanings given in the general definition of the invention, are ordered by compounds of general formula (XV) with a protected amino group by reaction with alkyl or haloalkyl sulfonyl hadogenides or sulfonic acid anhydrides under appropriate reaction conditions, followed by a step of removing the protecting group. Suitable for protecting the amino group are alkoxyalkylideneimino group, taught by treating the compound, formate, compound. About ca water hodrodiza.

the procedure for deprotecting such groups generally includes 27 g (Compounds of the general formula (a) in which stands for alkyl aminocarbonylamino or arylaminocarbonylamino, HC represents amino, K ₂ means cyano, and X, X ^, Xg, X ₃ , X _d and γ have the same meanings as in the general definition of the invention, obtained from a compound of a suitably protected amino group of the general formula (XV) by reaction with alkyl or aryl isocyanate, in which the alkyl or aryl groups are defined in the first definition of the invention, after which the protective d upa.Podhodyashti conditions for the preparation of ureas are described in / 17 /, suitable protecting groups for the amino group! in such reactions include an alkoxyalkylideneimino deprotection group as previously described.

E (Compounds of the general formula (I), B which stands for alkoxycarbonylamino or hadogenalkoxycarbonylamino, R 4 represents amino, R 2 represents cyano, and X, X 4, X 8, X ₃ , X 4 and X have the same meanings given in the general definition of the invention are obtained from a compound. with a suitably protected amino group of the general formula (XV) by reaction with an alkylxyl formate or a hal ogenalk yl chloroformate, having taken an advance from the deprotection step.

G / l idenimino or benzylidinimino means amino, Rg means cyano, and X, ^X 1 * ^X 2. ' ^X 3 » ^X 4 ^and V have the same meanings as in the general definition of the invention, obtained by condensing a compound of a suitably protected amino group of general formula (XV) with an alkyl or aryl aldehyde in which the alkyl or aryl groups are defined in the first definition of the invention, followed by a deprotection step. Suitable conditions for obtaining Schiff bases will be selected for the condensation step as described in (18). Suitable protecting groups for the amino group are acetyl or trifluoroacetyl, a. the removal of the protecting group may be accomplished by alkaline hydrolysis or otherwise as described in (19).

2a -

Y have the same meanings given in the general definition of the invention, are obtained from a compound of a protected amino group of the general formula (XV) by condensation with an alkylorthoester followed by a deprotection step. Suitable protecting groups are. derivatives of amides or carbamates, which is described in (20) dialy (Compounds of the general formula), which means dial

^{5 of the} invention, are prepared by reacting a compound of general formula (XV) with a dialkylacetal derivative of N, N-dialkylformamide, as described in (21), followed by a deprotection step. Or, alternatively, reacting (XV) with N, N-dialkylformamide in the presence of, for example, phosphorous oxychloride under B orsmeier conditions. Suitable protecting groups include amide or carbamate derivatives.

tion, are obtained by reacting a compound of general formula (XV) with tri (alkylthio) methane in pyridine as a solvent, optionally in the presence of a suitable ketalizer, for example dimethyl / methylthio / sulphonium tetrafluoroborate.

the same meanings given in the general definition of the invention are obtained by reacting a compound of general formula (XV) with p-toluenesulfonyl azide under the conditions described in (22), except during the deprotection step. but, the compounds described above, in which R1 represents azido * may be obtained from a compound of general formula (XV) by conversion of the amino group into a diazonium salt, followed by reduction to a hydrazine group, and then treated with nitric acid, followed by removal of protection ..

IETHOD 19.

A /

R3 is phenyl or heteroaryl substituted as described in the general definition

X 1, X 2 and 5 4 have the same meanings given in the general definition of the invention, are obtained from a compound of general formula (X 1) in which the amino group is optionally protected by a suitable protecting group by reaction with a suitably substituted phenyl or heteroaryl diazonium salt under the conditions of the Gomberg-Bachman reaction described in / 23 /.

B) Alternatives to the intermediates of general formula (i), in which R1 denotes phenyl or heteroaryl substituted as described in the general definition of the invention, R1 represents amino, R3 begins cyano, and X, X4. X1, X1, X3 and Y have the meanings given in the general definition of mule (XII), in a protective aspect of the invention, derived from a compound of general formula.

which the amino group. is optionally protected by an approach group by reaction with a suitably substituted phenyl or heteroaryl halide, preferably bromide or iodide in the presence of copper under the Ulman reaction conditions described in (24).

B / Al ternative intermediates of the general formula (ι), β keto

R ₃ stands for phenyl or heteroaryl substituted as described in the basic definition of the invention

Rq stands for amino

R ₂ is cyano, and X, X 4, X 4, X 5, X 4 and γ have the same meanings given in the general definition of the invention, derived from a compound of general formula (XII), preferably bromide or iodide, by treatment with suitably substituted lantern: or heteroaryl boronic acid in the presence of η al with di (0) under conditions similar to those described in (25).

METHOD 20.

Compounds of the general formula (ι), β which stands for cyano, means amino, N 2 ^O 3 for the ^{beginning of} cyano, and X, X, X ₂ , X 1, X 2 and y have the meanings given in the general definition of the invention. of the compounds of the general formula (I), which I ₃ represents hydroxyiminomethylidenyl or alkoxyiminomethylidenyl, described in METHOD Tb2 by dehydration according to the method described in METHOD 4A.

METHOD 21 ..

The compounds of the general formula / ι /, β koyatiCh ^ is haloalkylcarbonyl or hadogenalkiltiokarbonil, Roznachava amino, ZA represents cyano, a X, X ^, X _2, X ^, Xe and y have the same meanings as in the general definition of the invention, obtained from a compound with an optionally protected amino group! of general formula (XIV) according to the procedures described in METHOD 8, followed by a deprotection step if necessary.

METHOD 22 »

A (Compounds of the general formula (ΐ), which means halo · genalkyl, R _{1 -} means amino, R ₂ means cyano, and X, X, X X 4, X 4

Y has the same meanings given in the general definition of the invention, but the group is optionally protected according to the procedures described in

METHODS 6,7 and 9? with a stage of protection depletion, if necessary. B) The compounds of general formula (N), in which alkyl means amino, amino, cyano, and X, X ^, X ^, X ^, X ^ and y have the same meanings given in the general definition of the invention are derived from compounds of general formula (XIV) in which the amino group is optionally protected by reaction with a Grignard reagent obtained from alkyl halide or alkyl lithium - converted to carbinol, followed by dehydration, resulting in a compound in which ⁸ al31 kenyl is subsequently substituted Compounds of general formula (I), in which it stands for methyl, and the other substituents have the meanings given above, are obtained from the compounds of general formula (XIV) according to the procedure described in ME I 0 D 7.

METHOD 23

Compounds is a general formula

it, alk iltio, hal ogenalk iltio, alk enil thio, hal ogenal to enilt io, pheniltio

the phenyl and the heteroaryl groups represent and / or. are substituted as described herein, i. The compounds of general formula (XVI) (see below y) are obtained from compounds of general formula (Xl) under conditions similar to those described in METHOD 1.0. The whole process can be described by the following equation:

/ XVI /

Compounds of general formula (XVI) in which R is alkyl can also be prepared from compounds of general formula (ί) in which thiocyanate is used, and the other substituents have the meanings described in (XVI) by treatment with alkyl halides or similar, according to procedures similar to those described in METHOD 11.

METHOD 24.

sul finyl, alkyl or sul phonyl, alkenyl sul finil, alkenyl sul phonyl, xal ogenad ylsul finil, xal o ginal k il sul phonil, h al o gen kenil sul finil, hal og enalk enylsulfonyl, phenyl sulfinyl, phenylsulphonyl, heteroaryl sulfinyl, xheteroaryl sulfonyl, | C represents an amino group, R ₂ represents a cyano group, and X, X 4,

X ^X 3 ^{'X 4} V ^{img17 co} ^ ^s meanings as in the general definition of the invention, and the groups phenyl and hsteroaril represent and / or are moved so as described herein may be prepared by oxidation of compounds of general formula (XVI) according to methods similar to

X means those described in METHOD 12, In these examples, when the RS group, which may be oxidized undesirably, the sulfenylation according to the above procedures can be carried out on a compound of the general formula (1), wherein X is halogen, for preferably bromine or iodine, means amino, means cyano, means hydrogen, and the other substituents have the same meaning given in the basic definition of the invention, followed by oxidation, treatment with alkylthio, by a method similar to that described in (2b). followed by cooling with cold water, whereupon A compound of general formula (XVII) is emitted «The compound of general formula (XVII) may then be subjected to sulfenylation to give compounds of general formula (XVIII). This whole process can be represented as follows:

X X

Y / XVII /

- 33 METHOD 25.

The compounds of general formula (i), which means cyano, alkoxy or haloalkoxy, Rq means amino, and λ, X, X ₂ , Xj> 4 'and the unim values given in the basic definition of the invention are derived from the compounds with the general formula (XII) wherein the amino group is optionally protected by a method similar to that described in METHOD 5, followed, if necessary, by a deprotection step.

METHOD 26.

A (Compounds of the general formula (ΐ) Β which R is hydrogen, R ₂ is cyano and R ₃ , X, X 4, X ₂ , X 4, X 1 and have the same meanings as given in the basic definition of the invention, i..e., compounds of the general formula / XX / / see below /, can be prepared from compounds of the general formula / ΐ /, Β which R ^ represents amino, R ^ is cyano, and R _3, X , X _v X ₂ , Xj, Xd and y have the same meanings given in the basic definition of the invention, i. compounds of general formula (XIX) (see below y). by diazotization, preferably with alkyl nitrite in an inert solvent, such as tetrahydrofuran or acetonitrile.This reaction can be carried out in the temperature range between -80 ° C and temperature. of the reflux condenser of the solvent, preferably between Q ^Q C and 25 ° C.

B (Compounds of the general formula (1) wherein R 2 is halogen, R ₂ is cyano, and R 4, X, X X 1, X 1 and X have the meanings,. given in the basic definition, i.e. compounds of general formula / XXI /

I / ref; below y / of the invention, are prepared from a compound of general formula (XIX) by diazotization with alkyl nitrite, for example tert-butyl nitrite, in the presence of a donor halogen atom, for example in the presence of a bromoform , tetr ahl ormethane, b erected cupric chloride or iodide.

I

B / with the compounds of the general formula (ΐ), which means thiocyanato, alkylthio, halogenalkylthio, alkenylthio, halo genalkenylthio, phenyl-34thio or heteroarylthio, Rg means cyano, and R ', X, γγ , X ₂ , X ₃ »X ^ ^and γ have the same meanings as in the basic definition of the invention. The phenyl and heteroaryl groups represent and / or are substituted as described therein, i. Compounds of general formula (XXI) (see below) are prepared from a compound of general formula (XIX) by reaction with alkyl (pyrite) in the presence of (R) CN ( ₂₎ or a disulfide of the formula wherein R is alkyl, haloalkyl , alkenyl, haloalkenyl, phenyl or heteroaryl groups described above. Typically, the reaction is carried out in a solvent medium, for example, chloroform at 0 ° C with one to five equivalents of alkyl nitrite and two to five equivalents of disulfide.

The whole process can be illustrated ^ as shown below:

/ XXI / R ^B = Halogen / XXII / R ^B = SR

METHOD 27.

Alternatively, μηογο of the compounds of general formula (XXII) can be obtained from a compound of general formula (XX) in which

means amino, according to a method similar to that described in METHOD TO. The derivation of the amino group into other functional groups can be accomplished by one of the methods described above.

METHOD 26.

The compounds of the general formula / ΐ /, Β which R is alkylsulphinyl, par k ylsulfonyl, alk enyl sulfinyl, alk enyl sulfonyl halide ogenalkil35 sulfinyl, halogenalkilsulfsnil, halogenalkenilsulfinil, halogenalkenil- sulfonyl, phenylsulfinyl, phenylsulfonyl, heteroarilsulshtinil, heteroarylsulfonyl, 1 ^ 2 means cyano and R ^, X »η, ^ 2 * ^ 3 ' ^and V ^{have the same} meanings as given in the basic definition of the invention, the phenyl and heteroaryl groups being and / or substituted as described therein , can be prepared by oxidizing compounds of general formula / XXII / by methods similar to those in MET8D 24 If X or also mean $ R group, which must be maintained at the level of sulfide oxidation, can implement a strategy similar to that described ⁱⁿ METHOD 24, to the desired compounds are obtained,

METHOD 29.

Compounds of the general formula (R), which R1 is alkylamino, dialkyl amino, aralkyl amino, amino arb onylamino, alkyl arbonyloxy, x allogenalkyl arbonyl amino, aryl arb onylamino, alkyl yl sulfonylamino, alkyl yl sulfonylamino, alkylaminocarbonylamino, arylamino arbonylamino, alkoxycarbonyl amino, haloalkoxycarb onyl amino, alkylideneimino, benzyl idenimino, alkyloxyalkylidinimino, dialkylaminoalkylideneimino, alkylthioalkylidene, alkylthioalkylidene, alkylthioalkylidenimino, alkylthioalkylidene, alkyl Xd and γ have the same meanings given in the basic e can be obtained from a method similar to that described in METHOD 18.

METHOD 30.

A) Compounds of general formula (I), wherein R 2 is formyl

R2 is cyano and R4, X,

having the same meanings given in the basic definition of the invention can be obtained from a compound of the general formula (XIX) by treatment with sodium nitro

HC-NOH, copper sulphate and HCl by a method analogous to that described in (27), if, in (XIX), R1 is an amine group, then the compound may be suitably protected, the compound above. in which RJ stands for formyl, it can be converted to a compound into which (denotes

- 36 bis (alkyl) io (methyl or bis (arylthiomethyl) according to the standard methods described in (28). Alternatively, the compounds of general formula (ι), β co-

the meanings given in the basic definition of the invention are obtained

a procedure similar to that described in METHOD 14. The conversion of bis / alkylthio / methyl a or bis / arylthio / methyl a to formyl is carried out according to a method analogous to that described in METHOD 15. The conversion of the amino group 1 into another functional group proceeds according to the πα procedures described above.

A further definition of the invention is obtained from compounds of general formulation

substituents have the meanings described above according to a method similar to

METHOD 16 ^ Compounds. in which R1 represents alkylcarbonyl may be prepared from the corresponding compounds in which R3 represents halogen by converting them to a Grignard reagent or lithium derivative with optional protection of the cyano group as described in METHOD 5. followed by reaction with aliphatic acid chloride or anhydride or alternatively, condensation with aliphatic aldehyde,

started formyl by reaction with alkyl Grignard reagent, followed by oxidation.

as given in the basic definition of the invention, is prepared from the corresponding compounds in which h.d. is siaminomethyl idenyl or alkoxyiminomethylidenyl by the method described in PiETOfl 4A.

D) Compounds of the general formula (1), in which haloalkylcarbonyl or hcl □ genalkylthioxiononyl, 1¾ means cyano and R ₇ , X, X., X ", X", X. and y have the same meanings as described in the basic DEFINITION OF THE INVENTION are obtained from a compound of general formula (i), β which R 1 represents formyl, and the other substituents are described above by treatment under conditions similar to those described in PETOD 8.

E (Compounds of general formula (I), wherein R 1 is haloalkyl or alkyl, R 2 is cyano and R 4, X, X, X 4, X 4, X 4 ^and V have the same meanings as in the basic definition of the invention, are obtained from a compound of the general formula (I), which is R, j formed or halogen, and the other substituents have the meanings described above by treatment under conditions similar to those described in METOD 22 ».

METHOD 31,

Compounds of general formula (1) in which R is phenyl or heteroaryl substituted as described in the basic definition of the invention, R 2 represents cyano and R 4, X, X 4, X 4, X 4. and y have the same meanings as given in the basic definition of the invention, are obtained from compounds of the general formula (ι), β which R 1 represents halogen, and the other substituents have the meanings described above according to a method similar to this described in METHODS 19B and 19B.

METHOD 32,

The compounds of general formula (I), which is alkoxy or haloalkoxy, R 1 represents cyano X 4 and y have the same meanings as described

Rq stands for cyanate,

R ₃ , X, x _v x ₂ , X ₃ , the main definition of the invention, is prepared from compounds of general formula (XXI) by a method similar to that described in METHOD 5,

METHOD 33.

The compounds are the general formula (1) in which stands for formyl, Rq, R? , X> ^x <| » ^X 2» ^X 3 * ^X 4 ^And X have the same meanings given in the basic definition of the invention, i. compounds of general formula (XXIV) (below, y) are obtained from compounds of general formula (I), B which ί ^ 2 denotes cyano, RC, R ^, X, X ^, X 1 ^and X have the same 3 Our basic definition is inventive, i. e. united! with the general formula / XXIII / / see below at /. by treatment with a reducing agent, preferably with diisobutylaluminum hydride in a solvent, preferably in a mixture of toluene and hexane (1: 1) by a method similar to that described in /29/. The whole process can be expressed as follows:

In / XXIII /

METHOD 34.

Useful intermediates of the general formula / ΐ /, Β which R2 means a carboxyl functional group,, F ^, X, X, ^X 2 » ^X 3 ' ^X 4

and γ have the same meanings given in the basic definition of the invention, i.e., compounds of general formula (XXV) (see below y) are prepared by oxidizing compounds of general formula (XXIV) with a reagent of

Jones.The process can be presented as follows:

X

X <X »

/ XXV /

C.EETZD 35.

The compounds of general formula / i /, wherein R ^ is hydroxyiminoalkylidenyl, alkoxyiminoalkylidenyl, x al ogenalk ylcarbonyl, halogenalkiltiokarbonil, alk yl, bis / alk yl thio / methyl, b cis / arylthio / methyl haloganadkil and R ^ R _3, X , X ^ X ₂ , X ₃ , ^x d ^and \ have the same meanings given in the basic definition of the invention, are obtained from the compounds of general formula (XXIV) or compounds of general formula (ΐ), where R ^ is halogen, and the other substituents are defined above so that the preparation is described in G1ETOD 3B by procedures similar to those described in ί'ίΕ ΤΟD 30 Α, Β, Γ and D.

NSTOD 36,

The compounds of general formula (1) in which

meant a amino,

have the same meanings as defined in the basic definition of the invention, i.e., compounds of general formula (XXVII) (see below) are obtained from compounds of general formula (XXV) by treatment with diphenylphosphoryl azide in the presence of an organic base, such as, for example, triethyl amine in a solvent-alcohol, such as tert, butanol, to give carbamate (XXVI) followed by hydrolysis.Other methods of preparing (XXVII) from (XXV) by regrouping according to Curcius, including conversion to acid chloride followed by interaction with azide ion and treatment with alcohol are described in /30/. Transformation can be represented as follows:

from:

Υ / χχνιι / / XXVI /

- 40 METHOD 37.

Compounds of general formula (I), in which R1 is alkyl-amino, dialkylamino, aralkylamino, aminocarbonylamino, alkylcarbonyl and, but, allogenalkyl arb onyl amino, aryl arb onylamino, alkyl aminosulfonyl, alkylamino, sulfonyl sulfonyl has been found to be sulfonylamino, alkylaminocarbyl onylamino, aryl ammonium arbonyl-amino, alkyloxycarbonylamino, halogen alcoxocarbonylamino, alkyldidenimino, benzylideneimino, alkoxyalkylidenealkylamidealkylaminoalkylaminoalkylaminoalkylene R ₃ , X, X ^, ^ 3 »^ 4 ^and Υ have the same meanings given in the basic definition of the invention are prepared from the compounds of general formula (XXVII) according to procedures similar to those in METHOD 18.

METHOD 38,

Compounds of the general formula (ι), β which R ^ denotes hydrogen, halogen, thiocyanato, alkylthio, halogenoalkylthio, alkenylthio, haloalkenylthio, phenylthio or heteroarylthio, R,, X, X ^, X ^, X ^, X ^ and y have the same meanings given in the basic definition of the invention, are obtained from the compounds of general formula (XXVII) by a method similar to that described in METHOD 26. Alternatively, the compounds of general formula (I), which R1 denotes hydrogen, R ^ _, R _3, X, X, X _2, X _3, Xe and y have the same meanings given in the general definition of the invention, are prepared from compounds of general form (XXV) by heating at 48% ΗΒχ in reflux glacial acetic acid or by heating in a high boiling solvent such as decahydronaphthalene or quinoline in the presence of copper.

METHOD 39.

Compounds of the general formula (I), which R1 denotes alkylsulfinyl, alkyl or sulfonyl, alkenylsulfinyl, alkenylsulfonyl, halogenalkylsulfinyl, haloalkylsulfinyl, xylenylsulfonyl, xalogensulfonyl nyl sul finyl, xalg og has poured kenyls ulfonyl, phenyl sul finil, phenyl sul phonyl, x et eroyl or sul fininyl, x eturoarylsulfonyl, R ^, R ₃ , X, X ^, X ^, X ₃ , Xd and y have the same meanings given

4- ι in the basic definition of the invention are prepared by oxidizing compounds of the general formula ίI /, which is R R denotes alkylthio, haloalkylthio, alkenylthio, halo ogenalkenylthio, phenylthio or x heteroarylthio by a method similar to that described in METHOD 24. .

ι.ΕΤύλ 40,

The compounds of general formula / 1 /, wherein Rg is phenyl or heteroaryl substituted as described in the general definition of the invention, R ^, R ", X , X, Xg, X _3, Xe and y have the same meanings as defined in the basic definition of the invention are prepared from compounds of general formula (I) in which Rg is halogen and the other substituents have the meanings described above, by a method similar to that described in PETOD 19B and 19B.

METHOD 41.

The compounds of the general formula / ι /, β which Rg is cyanato, alkoxy or haloalkoxy his, R ^, R _3, X, X, Xg, X _3, X shield meanings given in the general definition of the invention, are prepared from compounds of the general formula (ι), β which Rg stands for halogen and the other substituents are defined above by a method similar to that described in METHOD 5,

In general, the method according to the invention can be described, and y have the following way.

P ^, a process for the preparation of compounds of the general formula which X,

/ 1a /,

γ have the same meanings as in method one, finyl, alkyl sulfonyl, halogenoalkylthio, halogenalkyl sulfyl, halogenX means halogen, trifluoromethyl, cyano, thiocyanato, alkyl ylthio, alkyl ylalkenyl, alkenyl, alkenyl, alkenyl, alkenyl, alkylene halogenated alkenylsulfonyl, phenylsulfonyl, phenylsulfinyl, phenylsulfonyl, heteroaryl-thio, heteroarylsulfinyl or heteroarylsulfonyl, wherein the compound of the general formula

III in which the amino group is optionally protected and (a) reacts with a halogenating agent, optionally in the presence of a solvent, to give a compound of the general formula (Ia), in which X is halogen, after which the optional compound is reacted with trifluoromethyl copper according to known methods, to obtain a compound of general formula (Ia) in which X is trifluoromethyl;

b) is reacted with three (alkylthio) methane or three (arylthio) methane in the presence of acid (1uis), then the compound obtained: of the general formula (XXXVI), in which X is bis (alkylthio) methyl or bis (aryl) io (methyl) is loaned with a suitable alkyl nitrite followed by hydrolysis to give the compound of general formula (XXXVII) in which X is formyl, after which said compound is reacted with hydroxylamine followed by dehydration with suitable substances , such as P0 O2 according to standard methods, to give the compound c a general formula (Ia) in which X represents a cyano group;

c) is reacted with a compound of formula [* 1 $ CN, wherein I represents an alkali metal, in the presence of bromine, in a solvent, such as methanol, e.g., to give the compound of general formula (Ia), in which X means a thiocyanate group, and then said compound optionally reacts with. alkyl halide or dialkyl sulfate

- 43 the presence of a base, such as sodium or potassium, to give a compound of general formula (Ia) in which X is alkylthio, or d) is reacted with a sulfenyl chalcogenide of general formula wherein it is alkyl or halo or en alkyl, phenyl or heteroaryl, Hal represents a halogen atom, in an organic liquid reaction medium, optionally in the presence of an acid acceptor, such as a tertiary amine, to give a compound of general formula (Ia), in which X is alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, phenylthio n Onion compound or x fl er ar ylthio, ff ed koetbunezadal resident but is oxidized according to known methods, to give a compound of the general formula / 1 /, kadets X represents R $ / 0 / _n, B which π -β 1 or 2 , depending on the terms of p is the stock.

P2 * Ivtod for preparing compounds of the general formula / la /, wherein X ^, X _2, X 3, ^X e ^and Y have the same meaning as in method one, X represents microns ianato para k October, the halogens GENADI coke, which is a compound of general formula

(XXVIII), wherein the amino and cyano groups are suitably protected if necessary, and (a) reacts with halogenocyan in the presence of an acid acceptor to give a compound of the general formula (Ia) in which X is cyano;

b) reacts with an alkylating agent, optionally in the presence of a base, to give compounds of the general formula (Ia) in which X is alkoxy; or - 44 - is halogenated according to the standard methods described in (31) to give compounds of general formula (Ia) in which

X stands for halogenalk.

P ". A process for the preparation of compounds of general formula (Ia) in which X 1, O

X, X, X and Y have the same meanings as in method one, and X means -

2. 3 4 □ a halogenoalkyl (CF ₂ H, CF „, B ^CH ₂ , ClCH ^), haloalkylsulfonyl, haloalkylthiocarbonyl or α-halsgenalkyl-α-halogenmethyl, where a compound of the general formula

(VI) suitably protected, where appropriate, in which the amino and cyano groups are (a) optionally active with a fluorinating agent, such as, for example, diethyl aminosulfurtrifluoride, according to known methods, to give the compound of general formula (Ia) wherein X is difluoromethyl;

b) reacts with a suitable oxidant, such as chromium sulfuric acid, to give compounds in which X is a carboxyl group, then said compounds are reacted with a fluorinating substance, such as sulfur tetrafluoride by known methods, whereby obtains the compound of general formula (Ia), in which X is trifluoromethyl, in the form of aromatic action under Bulf-Kischner conditions or by treatment with p-toluenesulfonylhydrazide and then with sodium cyanoborohydride to give a compound in cats X represents a methyl group, then said compound is reacted with a halogenating agent such as, for example, ром-bromosuccinimide or Ν-chlorosuccinimide in a suitable solvent in order to obtain a compound of the general formula (Ia). in which X is bromomethyl or chloromethyl or methyl

-45g (reacting with a mtal 3 derivative of haloalkyl or trifluoromethyltrimstylsilane to give compounds of general formula (Ia), in which X is halogenalkylcarbinol followed by oxidation according to known methods, to give compounds of general formula (Ia) which X stands for halogenalkylcarbinol, followed by the optional reaction of said compound with a Lawson reagent to obtain compounds of the general formula (Ia), in which X stands for halogenalkyl (thiocarbonyl) or for a compound in which X stands for halogen enalkylcarbinol, reacted with a halogenating agent such as, for example, thionyl chloride or bromosodium to give compounds of the general formula (Ia) in which X is N -halogenated-halogenmethyl, all previous steps may be followed by a step to remove the protection, if necessary. P ^. Petod for the preparation of compounds of general formula

Y wherein X, X ^, _{X2, X3,} Xe ^and Y have the same conception as in method one, a halogen, formyl, 6 cis / alc ylthio or arylthio / methyl, haloalkyl, alkyl, optionally substituted phenyl or heteroaryl-thiocyanate, alkyl-thio, x-algenalkyl-thio, alk-enyl-thio, hal-ogenalkenylthio, phenylthio, hetero-ar-thio, alkyl-sulfinyl, alkyl-sulfonyl, alkenyl-sulfenyl, alkyl-sulfenyl, alkyl-sulfenyl finyl, hal ogenyl or sulphonyl, halogenoalkyl is nylsulfinide, xalc enalkenileul phonyl, phenylsulfinyl, phenyl sulphonyl, heteroarylsulfinyl or heteroarylsulfonyl, wherein a compound of general formula (Ia) in which X is cyano or amino is optionally protected in an appropriate manner if necessary * a (reacted according to method P a) to give a compound of general formula (Ib), and which R ₃ stands for halogen, then said compound optionally reacts optionally with optionally substituted heteroaryl or phenyl halide, preferably bromide or iodide in the presence of copper, according to known methods, or said compound, which means preferably bromide or iodide. optional is optionally reacted with optionally substituted phenyl or heteroaryl boronic acid in the presence of palladium according to known methods, to provide compounds of general formula (Ib), in which R 3 means optionally substituted phenyl or heteroaryl, or a compound of general formula (Ia) , in which R ₃ is halogen, reacted according to method P 1 (a), to give compounds of the general formula (1b), in which it represents trifluoromethyl;

b) is reacted according to method P ^ (b) to obtain, first, a compound of the general formula (Ib) in which R ^ represents a bis (alkylthia) methyl group or a bis (arylthio) methyl group, and then unsubstituted -

resident but a compound of the general formula (Ib) in which R is formyl (R) is reacted with optionally substituted phenyl or he-

terroaryl diazonium salt according to known methods, to provide compounds of the general formula (Ib), in which R ₃ is optionally substituted phenyl or heteroaryl; or d) is reacted according to the method P ^ (c, d) in order to obtain compounds of the general formula (Ib) in which R ₃ denotes thiocyanato, alkyl ylthio, halo generic thio, alkenyl thio, hal ogenalkylthio, phenylthio or x heteroaryl thio, followed by this optional oxidation according to method P η (d), in order to obtain the compounds of general formula (Ib) in which

means alkyl sul finyl, alkyl sulphonyl, alken sul finil, alkenyl sul phonyl, h al oginal kyl sul finil, halogen en kyl sul phonyl, hal o g enalkenyl sul finil , hal ogenalk enyl sul phonyl, phenyl sul finil, phenyl sul phonyl, x eroaryl sul finyl or ether eryl with ul phonyl, provided that X does not mean a group which

- ^ 7 may be subjected to undesired oxidation and when X is halogen, optional treatment with alkyl lithium according to known methods, followed by cooling with water and sulphonylation according to method Pq / θ, Γ /, in order to obtain compounds of general formula / 1b /,wherein

X stands for thiocyanato, alkyl ylthio, hal ogenalkyl thio, alkenyl thio, hal ogenalkenylthio, phenylthio or heteroarylthio.

P ^. A process for the preparation of compounds of the general formula (Ib) in which X, X, X2 »X ₃ , X ^ have the meanings defined in method one, and R ₃ denotes hydroxyiminoalkyl idenyl, alkoxy iminoalkyl idenyl, cyano, halogenalkylcarbonyl or haloalkylalkylalkyl or alkyl, wherein the compound of the general formula

suitably protected, if necessary, condensed with a hydroxyl amine or O-alkyl or hydroxylamine or their addition salts, in solubilized ethyl ester, to give a compound of general formula (1b) in which R ₃ denotes hydroxyiminoalkylidenyl or alkoxyiminoalkylidenyl, and when R ₃ denotes hydroxyiminomethylidenyl or alkoxyiminomethylidenyl, water or alcohol are optionally removed according to method P 2 (b) to give compound 1b (). in which R1 represents a cyano group, b / c when R ₃ is formyl according to method P ₃ (a, b, c, d), to give a compound of the general formula (1b) in which R ₃ is methyl or haloalkyl or haloalkylcarbonyl or haloalkylthiocarbonyl group, or

4S reagent for

A g inyard selected from: alkyl halogen or alkyl id, which is thereby obtained which reduces the title compound to give a compound of the general formula a (1b), B which stands for alkyl, taken up only optional protection phase

P ^. Process for the preparation of compounds of general formula

the same meanings as in method one a means amino, alkylamino, dialkylamino, aralkylamino, amino arbonylamino, alkyl arbonylamino, haloalkylcarbonylamino, arylcarbonylamino, adkylsulfonylamino, haloenalkyl sulfonylaminoalkylaminoalkylaminoalkylaminoalkylaminoalkylamine xadobenzylamine arbididamino, alkyl or substituted imino, benzylidimino, alkoxyalkyl idenimino, diadylaminoadeno or idenylthioalkylidinimino or azido, where the compound of the general formula is ·

are obtained by amino as (as monoyl or di-substituted amino groups are obtained depending on the stoichiometric ratio or reaction conditions, or by converting the amino group to alkoxyalkylideneimino, followed by reduction, in order to obtain compounds of the general formula (XXXIV), wherein

R1 represents alkylamino, dialkylamino and aradkylamino; b) with phosgene followed by ammonia to give compounds of the general formula (XXXIV) in which R 3 represents aminocarbonylamino;

c) acidic chloride or acid halide chloride or acid aryl chloride or m-anhydride, optionally in the presence of a solvent and / or organic acid as acceptor, to give a compound of the general formula (XXXIV), wherein ·? means "3alkylcarbonylamino, haloalkylcarbonyl but or arylcarbonyl" but;

d) with alkyl or haloalkylsulfonyl halides or their anhydrides under suitable conditions to obtain compounds of the general formula (XXXIV), in which R1 denotes alkylsulfonylamino or halogenadkyl sulfonylamino ;, d) with alkyl or aryl isocyanates according to known to obtain compounds of the general formula (XXXIV) in which R is-3 (alkylamino) arylamino / carbonylamino;

e) with alkyl chloroformate or halogenadkyl chloroformate according to the known methods, to obtain compounds of the general formula (XXXIV) in which (j ₃ means adoxicaric onylamino or halogenadecoxy arbonylamino;

g) with alkyl or aryl aldehyde according to known methods to teach compounds of the general formula (XXXIV) in which Z is? denotes alsJ cylidinimino or benzyl idenimino, 3 / with an alkylorthoester to give a compound of the general formula (XXXIV), wherein R ₃ is alkoxyalkylideneimino;

and / or ΤΊ, Ν-dialkylformamide or its dialkylacetal derivative, to give compounds of the general formula (XXXIV), β which

R ₃ represents dialkylaminoalkylideneimino;

k) with tri (alkylthio) methane in an organic solvent to give compounds of the general formula (XXXIV) in which R1 represents alkylthioalkylideneimino; or l / with p-toluenesulfonyl azide according to the known conversion to the diazonium salt, followed by reduction to a group followed by treatment with nitric acid, by methods or by hydrazine to give a compound of the general formula (XXXIV '), β which R ₃ means azide <group, and then, if necessary, deprotection.

P ?. A process for preparing a compound of the general formula (Ib) in which

X, X, X ₂ , X3, Xd and y have the same meanings given in method one, a

R 4 represents cyano, alkoxy or haloalkoxy, wherein the compound is of the general formula

XXXI

and X are in which the amino, cyano optionally protected groups are reacted according to method P ₂ (a), (b) and (c), to give a compound of the general formula (Ib) in which R ₃ is cyano , alkoxy or haloalkoxy.

Ρθ, A method for preparing compounds of the general formula

V

X ", X, and V have the same meanings given in me3'41 in which X, 4j, X ^, X2, /

then one means a hydrogen, halogen, thiocyanato, alkylthio, halogenated kydio, ad ken and lthio, halogen ad kenylthio, ^ enylthio, het vroaridthio, alkylile finyl, alkyl or sul phonyl, ad kenyl sul sulyl, adkenyl sul sul, adl phonyl halogen sulfonyl, phenyl sulfonyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl, phenyl ar alkyl alkyl but, knock arbonyl but, alk ilk arbonyl amino, hal ogenalk ilk a carbonyl amino, aryl arbonyl amino, alkyl or sulphonylamino, hal o genyl sulphonyl amino, ad to il aminocarbonyl amino, aryl amino ·, arb o nyl amino, alk oxic arbonyl amine, hal gen k to oxic arbonyl amino, decyl iden, but, enzyme idenimino, alk oxialc idenimino, dialkyl ami noalkyl idenimino, alkyl ilthioalkyl idenimino, i ido, bis / alk ylthio or arylthio / methyl, formyl genadylcarbonyl, halogenated alkyladenyl, halogenated or alkyl, wherein the compound of general formula 16 / or XXXIV.

16. ' or / XXXIV, it is obtained> ch baseline methods

protecting against the groups of X is removed to Ργ,, κοητοΎθμηηο the seUza, Rj, or cyano group, if necessary, / reacts with a diazotizing agent, preferably alkyl nitrite, to give an inert solvent, to give a compound of the general formula (Ic), in which R1 is hydrogen, b) is reacted with a diazotizing agent, preferably with alkyl nitrite, in the presence of a halogen as a donor to give a compound of the general formula (Ic), in which R3 means halogen, after which the said compound is reacted with a Grignard reagent or a lithium derivative, followed by reaction with an aliphatic acid chloride or anhydride thereof, for the purpose of conversion to a compound of the general formula (Ic), in which R1 represents alkylcarbonyl or the reaction of said compound according to method P4 (a) to give compounds of general formula (Ic) wherein R is phenyl or heteroaryl;

(1c) in which RJ is thiocyanato.alkylthio.haloalkylthio.alkenylthio, hal ogenalkylthio, phenylthio or heteroarylthio, then optionally the resultant compound is oxidized according to method (g) to give a compound of the general formula / in which R ^ denotes alkyl or sulphonyl, alkyl or sulphonyl, alkenyl sulphinyl, alkenyl sulphonyl, halo genalkyl sulphinyl, halo ogenalkyl sulphonyl, hal ogenalkenyl sulphinyl, halo genylnyl, phenyl sulfinyl, phenyl sulfonyl.heteroarylsulfinyl or het eroar ilsul phonyl g / reacting and according to method Pg (a to g) to give compounds of the general formula (Ic) in which R1 is alkylamino, dialkylamino, aralkylamino, amino arbonyl amino, alkyl alkyl arbonylamino, halogenoalkylcarbonyl but, aryl arbonylamino, allyl arbonylamino, ylsulfonylamino _g haloalkylsulfonylamino, alkyl yl amino arbonyl amino, aryl amino arbonyl amino but, alkoxycarbonylamino.halogenalkoxycarb o nyl amino, alkyl iden and no, ben zilidenimino, alkoxyalkyl, alkoxyalkyl, alkoxyalkyl - thioalkylidinimino or azido, or interdependent sodium nitrite and formaldoxime. copper sulfate and HCl according to known methods, to give compounds of the general formula (Ic), in which the formyl followed by (1) is reacted with alkyl Grignard reagent oxidation to convert the resulting compound to this optionally a compound of the general formula (Ic) in which R1 represents alkylcarbonyl, (2) an interaction according to method P3 _>, so as to obtain a compound of the general formula (Ic), which R1 represents hydroxyiminoalkyl idenyl, alkoxyiminoalkylidenyl or cyano or (3) interaction a process according to the method P1 (a-d) to give a compound of the general formula (Ic) in which R is halo genalkylcarbonyl, halogenalkylthiobearyl, haloalkyl or alkyl, if necessary by deprotection, or the aforementioned a compound wherein R1 is formyl _? is converted, according to standard methods, to a compound of the general formula (Ic) wherein R is bis (alkylthio or arylthio) methyl.

Pg. A process for the preparation of compounds of general formula (Ic) in which X, R ₃ , Χη, X3, X4 and y have the same meanings given in method one, and

R. J stands for cyano, alkoxy or haloalkalko, to which is a compound of the general formula

XXXII

in which X, cyano or R4 is optionally protected by known methods is reacted according to method Pa, b, c /, to give a compound of the general formula (Ic) in which R4 is cyano, alkoxy or halo , has opted for the optional de-escalation step,

P <1 £ »· A process for the preparation of compounds of the general formula (1), wherein X, Rp R ₃ , Xp X ₂ > 3 and 3 have the meanings a given in method one, and R2 denotes CHO, where a compound of general formula (Ic) is treated with a reducing agent, preferably with diisobutylaluminium hydride, in a solvent to give a compound wherein R 1 is CHO, the said compound being optionally oxidized according to known methods to give the corresponding compound with a general formula

XXXV compounds of the general formula (1) in which γ has the same meanings as in method one, and R2 denotes hydroxyiminoalkylidenyl, alkoxyiminoalkylidenyl x alogenoalkyl arbonyl, haloalkylthiocarbonyl, alkyl, haloalkyl, bis or alkylthio, where alkyl the general formula / ΐ /, which Rg. means CH0, although optional for shield X. Rj or R ^, if necessary, according to the methods known in the art, reacts according to method (a, b, c, d), / a, b / or

Ro / a / .followed, if necessary, from the de-escalation stage - Q * 7 * tata ».

Pj2_ * A method for preparing compounds of the general formula (ι), β which X,

R1, R4, Xj, X37 Xd ^and Y have the same meanings as in method one a2 = means amino, alkylamino, dialkylamino, aralkylamino, to arbonyl but, alkyl or arb onylamino, halo genalkyl arbonylamino, carbonylamino, alkyl or sul ph phenyl amino, halogenalkilsulfonilami but amino arilalkilaminokarbonilamino, arilaminokarbonilamino, alkoxycarbonylamino, halogenalkoksikarbonilamino, alkylideneimino, benzilidenimino, alkoxy siadk yl idenimino, dialkyl aminoalkyl yl yl idenimino, alk iltioalk yl idenimins azido, hydrogen, halogen, thiocyanato, alkylthio, halogenoalkyl O alkenyl alkenylthio, halogenalkeniltio, phenylthio, heteroarylthio, alkylsulfinyl, alkylsulfonyl, alkenilsulfinil, alk enyl sulfonyl, halo genalkileulfinil, halogenalkileulfonil, halogenalkenileulfinil, halogenalkenilsulfonil, phenyl sulfinyl, phenyl sulfonyl, x eteroar yl sul alkylsulfinyl, heteroaryl yl sulfonyl, optionally substituted phenyl or heteroaryl or trifluoromethyl wherein a compound of the general formula / XXXV /, after performing optional protection of X, R. ylmethyl d '' 1, ^I TS3 o _b aloud known methods,

- 55 if necessary reacted under the conditions of a Curcius re-grouping reaction, for example, by conversion to acid chloride, followed by reaction with an alkali metal azide, or with diphenylsos-foryl azide in the presence of an organic base, such as triethylamine in alcohol as a solvent to give carbamate, which can then be hydrolyzed to give the corresponding compound, in which N ₂ is amino and which is then optionally reacted according to method P 2 (a-l) or Ρθ / a-c /, then when R ₂ ⁰³ - As a halogen, the optionally prepared compound can be reacted according to method P1 (a), followed by a deprotection step if necessary.

^P 13 * ' ^Method for the preparation of compounds of the general formula (ΐ), which x »1.» ^ c, » Χ, ρ X ₂ , X ^, Xd and γ have the meanings given in method one,

a2 represents a cyano, alkoxy or haloalkoxy, wherein the compound is of the general formula

XXXVI

Y, after optional protection of X, BC, or, if necessary, reacts according to method P?, Followed by a deprotection step as necessary.

P- | ^. A process for preparing compounds of the general formulas / XXVIII /, / XXXI /, / XXXVI / and / XXXVII / according to methods P _{2, P?} , P ^ _Q or P ^,

where the corresponding halogenated compound according to methods P1 (a), $ ₄ / a /. Pg / b / or P ^ ₂ , after protection of. , the amino group if it appears in

the formula is converted to a Grignard reagent or lithium derivative, followed by reaction with trialkyl borate and oxidation by known methods, followed where necessary by removal of the protecting agents

15 *

A process for preparing a compound of the general formula

III / in which X, X 2,

X ₃ , Xd and Ύ have the same meanings given in formula (I), wherein the dicyanopropylene derivative of the general formula

NH-CM ^ C-CHi-CW

Ва interacts with a substance of basic character.

The invention also relates to compounds of the general formulas (III) and (XXVIII) to (XXXVII) in which the substituents have the same meanings as those of the preceding methods and are particularly useful as intermediates for the preparation of compounds of the general formula / I / ^II according to the methods ^P 1 ^{d0 P} 15 *

OTHER METHODS

Compounds of general formula (I) in which X is perhalogenadkylthio are further prepared according to the following methods of chlorosulfonation, reduction to disulfide and finally reduction leading to the formation of free radicals. The method is carried out as follows;

A / Compounds of general formula / XXXIX / / see below / in which

Rj, R £ j R ₃ »Y 'X- ^{x X} 2 * ^X 3 * ^{1/1 have the} meanings given in the general formula (i), can be obtained from compounds of the general formula (XXXVIII) / see below /, wherein X represents aodorod by treatment ^- with chlorosulfonic acid either neat or in the presence of an organic solvent such as chloroform, dichloromethane, carbon tetrachloride or dimetil57 formomid at a reaction temperature of from 0 ° C to 150 ° C

One specific example is the preparation of a compound of the general formula (XXXIX) (see below y) .ξ which R ₁ stands for amino, alkyl arb inyl

R.

a means amino or hal-genalkylcarbonylamino, Rg means cyano, and hydrogen, of compounds of the general formula (XXXVIII), in which "1 with amino, alkyl arb onyl amino or halsgenalkylcarbonylamino, * 2 means cyano, R ₃ stands for hydrogen and X stands for hydrogen, by volume and with chlorosulfonic acid. A typical reaction of chlorosulfonation of an aromatic compound is described in / 32 / t

χ <

/ XXXVIII / cesotU

In / XXXIX /

Compounds of the general formula / XL · / / see below y /. IN WHICH R ^, Rg, γ, Χ-ρ Xg, ^ 3 ' ^And ^ 4 ^{have sec} ! ^the meanings given in formula (ί) are derived from compounds of general formula (XXXX1X) in which R is

W hydrogen by treatment with a chlorinating agent such as chlorine,

N-chlorosuccinamide or sulfuryl chloride, in an organic solvent, such as diethyl ether, acetonitrile or dichloromethane, at a temperature to obtain a compound of the general formula (Xb), in which R1 represents amino, alkylamino iden halogenalkylamido and Rg means , by treating a compound of the general formula (XXXIX) in which R1 is amino, alkylcarbonylamino, or halogenalkyl arbonyl amino, and R8 is at -40 ° C.

cyano, and R ₃ represents hydrogen, with sulphuryl chloride, diethyl ether

B / Compounds of general formula / X1 * 1 / / see below y / .in which R, p 1 ^ 2 »Υ» X-]> ^X 2 '^ 3 ^{and X} 4 ^IM2T meanings given in formula / I () are 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 reaction medium temperature of 0 ° C to 110 ° C. A more specific example is the preparation of a compound of the general formula (Xb1) in which

R4 represents hydrogen, ag4ino, alkylcarbonyl amino or halogenalkylcarbonylamino, R2 represents cyano and R4 represents hydrogen or chlorine, from a compound of the general formula (XXXIX) in which R4 represents hydrogen, amino, alkyl or arbonyl amino or halo genalk ilk ACB onyl amino, R ^ is cyano, R ₃ represents hydrogen or chlorine, by treatment with triphenylphosphine in tetrahydrofuran at 25 ° S.Primer for the reduction of toluene to p-tolyldisulfide is described in / 33 /.

Y / XXXIX / p eductor solvent

B / Compounds of the general formula (1) in which R 1, R 2, X 1, X ₂ »

X ₃ and X 4 have the same meanings given in formula (1), and X represents a p-halogenalkylthio group, R in a fluorine, chlorine or bromine and R g in which R g is CFR ^ R g, and R? denotes cpior, chlorine bromine or perfluoroalkyl group, obtained by reacting a compound with a common pho, mule (Xb1) with perhalogenalkane of the general formula (XLIl),% C FR yRg in which Ζ means chlorine, bromine or iodine, Ry means fluorine, chlorine or bromine and Rg means fluorine, chlorine, bromine or the group of perfluoroalicyclics and with a reducer that promotes the formation of the free radical CPR ^ R ^ of the radical Zcfr ₇ r _b , preferably selected from the group of metals, comprising: zinc, cadmium, aluminum, magnesium, or sulfur oxide compound, for example, dithionite or hydroxymethylsulfin The petal dithionite, for example, an alkaline or alkaline earth metal dithionite, corresponds to the general formula (HbH), Μ / δ2θ4 / ^Β which n is 1 or 2, depending on the valence of the metal designated P. When dithionite is used with a general formula (X 1 'N') or hydroxymethylsulfinate, then a base, for example selected from the group consisting of. alkali hydroxide, alkaline earth hydroxide, ammonia, triethylbenzylamine, or salts of weak acids, such as disodium phosphate, sodium metabisulphite, sodium hydroxyl-gen sulphite, or sodium berate. and the compound of general formula (XbP), ZCFR-R /, such as, for example, acetonitrile, foramide, dimethyl formamide, dimethyl yl acetamide, hexamethylphosphoramide, N-methylpyrrolidone, dimethyl sulphoxide or sulfolane, at reaction temperature ° C to 85 ° C * Alkaline the dithionite can be added to the reaction mixture as a saturated solution in water or formam. It is also possible to add dithionite as a solid. When treated with gas which is only very poorly soluble in the reaction solvent, the pressure above the reaction mixture may increased, for example, from 1 to 50 atmospheres.A more specific example is the preparation of a compound of the general formula (I), B which stands for hydrogen, amino, alkylcarbonylamino or haloalkylcarbonylamino, R ₂ stands for cyano, R 4 stands for hydrogen or chlorine and X oz ace perhalogenalkylthio group, R ₆ $, B which R 8 stands for CFR _? R _a , and R _? denotes fluorine, chlorine or bromine, and R ... denotes an O fluorine, chlorine, bromine or perfluoroalkyl group, by reaction of a compound of the general formula / X 1 '1, in which R 1 represents hydrogen, amino, alkylamido or hal ogenalk il amido,

R 'is hydrogen or chlorine having a compound of general form ·

R ₂ denotes cyano and zero (XbP), ^ CFR ^ Rg, B which e represents chlorine, counts or iodine, R? means fluorine or chlorine, bromine and Rg means fluorine, chlorine, bromine or per fluorine alkyl group, and with sodium dithionite or disodium phosphate in dimethylformamide at 25 ° C. The reaction is represented by the following equality.

. XI »!

p reducer * Zcfr ₇ r ₈ ---------- o 33 3

X1 * 11,

The invention also relates to the chlorosulfonyl intermediates of general formula (XXXIX) and the intermediate disulfide compounds of general formula (Xb1).

REPRESENTATIVES OF THE COMPOUNDS OF THE INVENTION

Typical representative of the pyrrole compounds (PG1C) represented by the invention are compounds of the general formula (I), with which R ₂ is cyano, and the other substituents have the meanings given in Table I (PPP-). 339 /.

Other typical representatives of the pyrrole compounds (PPP) included in the scope of the invention are compounds of the general formula (I), wherein X ₂ and X ₃ denote hydrogen, X ₁ and X 4 denote chlorine, y denote CF ₃ and X, R q, R ₂ and R ₃ have the meanings given in Table II (DPS-xX 390-491).

by J co <n

m

OC

r4 ►4 hh • 4 • -H hh * 4 hh hh * 4 * 4 * 4 in in 0 0 in υ υ υ υ υ ο Ο ο Ο X X X X X X χ χ χ χ X X X X

XXXXXXXXXXXXXX .4 · 4> - (. 4 - (- (- (- (- (- (- 4 - (- (- 4 υουυοοοουοουοο

<η η hi co ο <η cn fa <n Km u CO., LTD cn fa m fa u co CO., LTD cn bu fa O co s Ο see s 0 CM Km 0 CM Km About CM Km ο Ο Ο and 0 Oh Q 0 Oh U Ο O Oh co CO., LTD CO., LTD co v> CO., LTD CO., LTD v> ω CO., LTD CO CO., LTD CO., LTD

xxxxxxxxxx

XXX

• • 0 rl - ( CM tn tn co r- « 01 r4 H

CM <n (4 H

14. H SOCF

TABLE 1

TABLE 1

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I) WHEREIN R2 = CN

REPRESENTATIVES OF HA PLROLL COMPOUNDS / PPP / C GENERAL FORMULA / 1 / IN WHICH MEANS CN

oh

him D) by GO with OT GO by FROM by him η GO co Si Yup s Si 1 and you «And See Si 1i Si Si Si Si and and υ and and and and and and. and_ _ and. and and Oh

X X X X X X X X X X X X X X * h - < hh · Hours * 4 • n • n <H —Ch hh hh • hours hh hh and υ Q and υ υ υ and and and and and and and

• Η and and Oh X X X co him co spa him co cm see see see see sch η X X X You are You are Si Si Si Si Si Fr. X in in in In In in in in in in X and Fr. Oh Fr. oh Oh Oh 0 Oh Fr. Oh Fr. and

co him co co co there by Si co Si co Si co Si and him Si and <N Yup and by Si and co Si and FROM <h Si in them Si in see Si in see Si in SEE Si Oh and Oh Fr. and Oh Oh Oh Fr. Fr. Fr. Fr. Oh and co <0 W <0 (0 W <0 V » FROM ω by by FROM by

xxx

X X X X X X X έ ?!

ύ about .......

d. g »· 0» © «h

Oops

Cm from * cm cm cm

1L «O f cm cm cm co cm

W a

<

E-

magazine

X X X X X X X X X X X X X X • h hh hh hh * -Ch hh hh hh «N hh »N »H hh and and and and and and and ϋ and and and and and and

co X CO X him Fr. and Si SEE see and Fr. Fr. V) and> V)

co

X t co and and. s. see in in Fr. Oh Fr. V) and and

see <h him him him (and X X in and and Fr. and 2 2

GO co co co CO., LTD co fa. co fa. CO., LTD co th co fa. m fa. fa. and tn See and fa. Cm tn U co fa. Oh Cm o Ο see See in see y y Cm CN Cm y CM y CM Ο Ο Ό 0 Ο o Oh In Oh Oh Oh Oh Oh Oh m W CO., LTD <0 ν> W CO., LTD CO., LTD CO., LTD CO., LTD u> w CO., LTD v>

<l see

o w CM co * Yu co r- «0 o> o CM <n <n co co co co <n <n CO., LTD co w *

σ> CO., LTD co Cm co CO Cm n co Em t CO See co co See υ Cm Cm In co Cm Q co fu U cn Cm See y CM y y CM L · y CM Cu y CM u- y Ο Oh Oh Oh Oh o o Oh Oh Oh o Oh Oh Oh co <0 W <0 <0 CO <0 CO., LTD co CO., LTD co co CO., LTD CO., LTD

. · 6 5 * “· w

th tn

X X X X X X X X X X X X X X .4 hh hh hh * 4 • 4 • 4 • Η hh hh »4 hh • 4 «Η υ ο υ ο ο υ υ υ ο υ υ ο υ U

hh hh ech hh hh hh d4 hh hh hh ^ H υ and and and and and and and and and and Oh υ and

tn

s <*> and «Η Eu see Cu Ο Fr. υ Ο co CO., LTD W

m

CO., LTD and CO., LTD bu <h Im in Ο and o co CO., LTD co

<n which m U cn tw CM fib U o o Oh co co co

tn

in, tn Oh tn Ex cm there y Oh in o co co co

tn u

CM O co th Η H

tn tn tn «N tn X X X X X o o o in in o o

OCF Cl SCF

r · CO., LTD oi o H CM tn w that r * «0 01 o Yu Yu m co CO., LTD co co co that that CO., LTD CO., LTD co r *

δ

ES δ

W

J CO <E-

ff

a.

O at o

ΪΛ

0J

<η «Η magazine <η η fa> ο fa. «Η fa r> fa co fa. υ <η fa. and <*> U. and «Η fa o cn fa in CN fa. in (Ν fa. in <M fa y <xi y ο Ο U ο Ο and ο Ο and o o U Oh co Μ co and CO., LTD CO., LTD co CO., LTD CO., LTD co CO., LTD V) co

σ> σ> I I

phenyl SO, CF

- = <

Ρ4 and

J <H z u

II D4 K

CH

W

ft. O £ a

SL a z P o ft. s o Q

And J o ch ch> ft.

and> P <Esl CH CH ft. ft}

CH ra tx>

o

Ph • = 4

PP = in E-H

Ph

1 = 1

co <n cn b co cn ΪΜ cn CO fa. cn cn k co fa. υ co U fa. υ cn fa. U cn th U s. U CM fa. CM In CM Im Oh CH Ch y CM Oh Oh Oh Oh Oh o Oh o Oh Oh o o Oh co ω cn co U JV co cn cn CO., LTD co cn co cn

co co

P tu fa.

co fa. co o o X X X cn cn X y X CM CH y y y fa. th in o in o o 1 I ¥ o U co <0 co co co o in o co cn

v>

co

- 68 TABLE 1

TABLE 1

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I) WHEREIN R * = CN

REPRESENTATIVES OF THE HA PIRAL COMPOUNDS / PPP / C GENERAL FORMULA / 1 / IN WHICH R MEANS CN

cn m fa m cn fa cn m fa cn cn Cu cn cn Cm υ <n fa o cn fa U cn fa Oh m fa fa Oh CM Cm Q CM fa y CM Cu y CM Cm y in Oh o U o o U Oh o U o o o Oh <0 CO., LTD co CO., LTD co CO., LTD co co co CO., LTD co co co co

© ΊΓ Z ¹ . o v4 CM cn w Yu co r · «0 σ> ο rM see a. c o o o o o o o o o Ο hh hh ait = 4 Ob H H r4 • 4 r4 v4 hh r4 r4 hh 14 PM n

TABLE 1

TABLE 1

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I) WHEREIN R2 = CN

REPRESENTATIVES OF THE HA PIRAL COMPOUNDS / PPP / C GENERAL FORMULA / 1 / IN WHICH Rg denotes SK

CO EP

Oh and oh

co GO him s co fa. CO., LTD fa. co fa. co and co fa. and CO hl and D) co CO., LTD bu Oh co fa. <m Km in <m fa. in <N fa fa fa y sch fa y Oh and Oh Oh Ο Ο Ο Ο in o Oh Oh Oh Oh CO., LTD co W are They are CO CO., LTD co co CA co co CA

CO., LTD co co Midrange fa. fa hi 2 2 2 M X Ή * 4 S in o you in a z o Q in that CQ

fti ΚΛ a. p >> P th b o is Pd § O Oi 0 ν4 a f-Q H with w P w os 4Z Oh p GQ <Z) Q o fc s 3 Z P o ¢ - \ o G 1 = 5 ce P ΪΛ

X X X X X X X X X X X X X X rd r * 4 - < <- < • H r- < rd rd rd rd rd rd rd in U in in υ in in in in Oh U in o in

“-Ch th th lx lx (x lx lx tx lx U o υ X cn co m n <n CO., LTD lx m lx CO., LTD tx m lx o co fa U co V * in CO., LTD lx U co lx Oh co CM Ch Q CM b y CM lx In CM th y CM fa o o o o in o Oh Oh Oh Oh in Oh Oh in that co <0 w w co W V) CO., LTD CO., LTD co V) co co

m <n n N CM CM J. lx tx b. 2 2 2 X X X X υ o you D Z 2 X X X X X

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I) WHEREIN R * = CN

REPRESENTATIVES OF HA PYROLN COMPOUNDS / PPP / C GENERAL FORMULA / 1 /, wherein Rg denotes SK (L Cl. R o

C6 about

(N CO., LTD co see Cm

B

8 8

hey hey about Z

And oh. Oh t =:

co See 8

X X X X X X X X X X X X χ X • H R < H »M rH Ή rH rd • H .4 r4 hh • Η in o o o o in CJ υ in o υ and υ ο

• 4 ζ - ζ ζ X X Ο and υ χ X X s. See See υ and υ

co co co CO., LTD co fa. «Η fa. co fw co there co to. υ co See and co fa. In co fa. Oh co there in see See in see See y Midrange iw y CM Cm y ο ο Ο Ο ο Ο Oh O U o Oh Oh About CO co V » co <0 <0 CO., LTD CO., LTD CO co co co <0

With I

gMNgMNNNgCsMgMNN

OS OS H 'KI

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I), WHEREIN R ² = CN

REPRESENTATIVES OF HA PIRAL COMPOUNDS / PPP / C GENERAL FORMULA / 1 / IN WHICH R ₂ MEANS

R o

X

CH

CH

X X X X X X X X X X X X X X —H hh —H f4 hh -h • -H • n «N hh hh -h hh —H and and and and and and and and and and and and and and

χ χ x fa fa tu X

-h -h -and m χ x and i and a a

<N JV fa him «Η fa <η «Η fa <η σ> fa m <n fa Oh fa and fa ο JV fa ο σ> fa fa y <m fa υ CM fa ο CM fat In cm fa » y and Oh Oh Oh Ο ο U ο Ο and Ο Ο and Oh co co co co co ν> CO., LTD co ν> co co co co co

smsmmsmsmsmssmsm gChhhhhhhhhhhhhhhhhhhhhh υουυυυ ζζζζζζζζ

About ^e * Ί ot m w f «0 01 o r < CM <n hg and co r * «0 CL t = > tn and tn and and co CO., LTD co CO., LTD CO., LTD co co co co CH 3 H w r < H w r4 r4 »4 r < »4 r4 H r4 r4

> = «<= <E-h

Ed co <b

X X X X X X X X X X X X X X magazine X X X X X X X X X X X X X X X

See co

magazine JV co JV JV <n co bi joint venture him See and JV See and co See and <n would and <n See in see s in see (and in see would in CN would and Fr. Fr. and Oh Oh and Oh Fr. Oh Fr. Oh and W W ff co <L SL ff ff ff CO., LTD co co co

O? J

With f

_r \ C V r ~ <L Fr. see CO., LTD para ss ^s d » d · d » with * d * Mr- n n gi hh gm n n

«О Г„ «Ο« Λ Ο r4 CM

R- b h Γ> «« β rh rh rh rh rh H rh

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I) WHEREIN R2 = CN REPRESENTATIVES OF THE PYRAL COMPOUNDS / PPP / C GENERAL FORMULA / 1 / IN WHICH R ₂ MEANS CH

tn tn bm co cn b tn co fa tn CO fa ro co fa υ tn fa in co fa o <n fa o co fa fa y CM bl y CM fa y CM Cm y CM fa y and o Oh in o o U o o U o o o o VI w CO., LTD co co co co co co CO., LTD co co co co

d> 3 w

Ed

J

CC <

H

co co co co co co ro X X X X X X X in U in υ o U U X X X X X X X

X X X X X X X X X X X X X X co co co co co co co X X X X X X X X X X X X X X in in in υ Q in in

co fa. * 4 * 4 »• 4 * 4 r4 * 4 in in o in in U in X X X X X X in

co CO., LTD co co fa. CO., LTD fa. CO., LTD bt CO., LTD there CO., LTD U co fa. U co kt U CO fa. υ CO., LTD kt CM fau o CM fa. y <N tu Q CN th y Oh in Oh Oh U Oh Oh In O o U Oh v> co <0 CO., LTD co <0 <0 CO CO., LTD co CO., LTD CO., LTD

t · «0 Ο » o H CM co * m w r- 01 0 » 0b o o o o o o o o rM w4 rM CN CM CM CM CM CM CM CM

«0 o

CM

09. H SO.CF co

Ed

J are

Η

PQ

5> 5

CC §

«Αΐ Μ

PQ e- <

Rf

η β £

X χ X χ χ χ χ χ X X £ X X X m co χ X * 4 »- < rM -4 -4 -4 hh <-m ι-Ч hh -H -H ο ο υ υ υ υ υ and and and and and and υ

<N <n cn cn <n fa cn fa cn fa cn fa cn and » and <n fiu and cn fa U co th Oh cn bl cn in see would Ο CM fa y CM fa U CM fa o in. Fr. Oh and Ο Ο U o Oh Oh Oh Oh Oh o υ V) co co co CO., LTD co co co co CO., LTD co co co co

rM CM cn * m co D » «0 A o rM CM cn "Mr. H rM rM rM rM »4 rM rM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM

-77REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I) WHEREIN R2 = CN

REPRESENTATIVES OF HA PIR0LN1H COMPOUNDS / PPP / C GENERAL FORMULA / 1 / IN WHICH R ₂ IS CN

rd rd rd υ and υ

co co co fa · k ο υ

X χ X χ X X χ χ X X X lb k fa • Η r4 rd rd rd rd rd υ and υ Ο X υ υ υ fa «Μ k fa k fa

* 4 iH ^ 4 ^ 4 ** 4 • H H ^ 4 ^ 4 iH hh hh o U in in X in Oh in Oh o υ υ Ο ο

«Η cn fa co <n fa co <n fa co co k m to in co k in co k in <n k U fa Ο Cd fa k y Cd k y Cd fa y Cd and Ο Oh Oh U Oh Oh U Oh Oh Oh Oh Oh ω You W w V) Yu W You W You ω You You

ο

Ζ ^σ .ι

Yu W r · • 0 o rd CM co • r Yu w r ~ «0 Cd Cd CM CM CM co co co co co co co co <n CM Cd CM CM CM CM CM CM CM CM CM CM CM <4

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I) WHEREIN R2 = CN

REPRESENTATIVES OF HA PIRAL COMPOUNDS / PPP / C GENERAL FORMULA / 1 / IN WHICH MEANS ΐΛ

a. Ο ο Й ρ

Ρ CO

fa

XXX

XXX

<*> cn fa fa fa co <n Oh Oh in <* » cn cn bu there fa CM CM CM <n n CO., LTD co <n fa U fa U υ U Oh Oh o fa fa bu bu in U υ co co W tn tn that U U Oh Oh in

fa fa fa fa

CQ 0 fa X

XXX fa

o

in

in

in

<n co fa <n tn fa co co fa fa CM fa CM fa CM r- (O fa CM fa CM CO., LTD fa Oh CO fa in co fa Oh Hz Oh Oh in bu y CM fa y CM fa y CM o y CM o y in o Oh In O Oh in o Oh o o Oh o o CO., LTD co CO., LTD tn tn CO., LTD w tn co co co co co tn

0 »<n

CM

o H CM <0 and co r * « 01 o ' H CM <* * * * Ό V) tn m CM CM CM CM CM CM CM CM CM CM CM CM CM

- / in TABLE 1

TABLE 1

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I) WHEREIN R * = CN

REPRESENTATIVES OF THE HA PIRAL COMPOUNDS / PPP / C GENERAL FORMULA / 1 / IN WHICH Rg denotes CH

CO EP o s

> ·

there

In it

x X X X X X X X X X X X X X > -h - < hh ^ h n hh - < hh ^ h • and hh hh - < hh Fr. and and and Fr. and and and and and and and and and him him him (x tx tx 2 2 2 and 1x s fa X X X and and and and and and X

fa fa sch fa fa CM there tx CM fa fa CM fa CM hh fa CM H fa CM r4 fa CM r4 fa sch ^ 4 ο CM ^ 4 in CM i-i in CM 4 in CM ^ h ο ο r4 o o r4 Oh o r4 in o r4 and in CM o y CM in y CM U o CM U Oh ο ο o o o o o o in o o Oh co co co co co co co co « co CA co CO., LTD

Z! What is -

* H

co • Sec w r ~ «0 0t o r4 CM CO., LTD <· Yu <0 m and W and m and and 10 IO Ό io 10 10 10 M N CM M N CM w CM CM CM CM CM CM CM

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I) WHEREIN R2 = CN

REPRESENTATIVES OF HA PIRAL COMPOUNDS / PPP / C GENERAL FORMULA / 1 / IN WHICH R ₂ IS CH tz>

0Р О 06 Р

co

B SEE SEE see s SEE see s see s. see fa see see • 4 SEE fa gm see fa -4 see fa -4 see fa - < and Yep gm and (and • 4 and fa -4 and s • 4 Fr. and ^ H and In * 4 and υ 14 and and 14 υ in see and in see υ in see and in see in in Fr. Oh and Fr. Oh and Fr. Fr. In Fr. Oh and Fr. W co co V) W W co co CO., LTD co co co co

Γ- «0 oh o • 4 CM tn w vo r- «0 <l ΙΟ w w r- r- r- r- r- c * t- r— r- r- CM CM CM CM CM CM CM <M CM CM cm CM CM

8 0. H SO-CC1F,

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I) WHEREIN R2 = CN

REPRESENTATIVES OF HA PIRAL COMPOUNDS / PPP / C GENERAL FORMULA / 1 / IN WHICH Bg = CH

^ 4 ^ h • h hh • h • n • hours • hours iH «H hh midrange hh hh υ and and υ and and and and and and and and and and

cn co D)

You're from

X X X X X X X X X X X X X X by by by by by by by by by by by by by by and and and Fr. Fr. and and and and Fr. and and υ and

Si fa. Si

SEE Si sch Si Midrange Si by <m Si hh him co Si by and fa by and d » X co X by and and hh and and co X and co X Fr. f and in sch Fr. in mid 2 X in sch X in sch X and Fr. Fr. and Oh About U and Fr. Fr. and Fr. Fr. υ co co co co CO with co co <0 co m co CO CO., LTD

about Z

I and O. Oh

S 's>

by « CM co * co r * co o> o r4 CM co co co co CO., LTD co co co co σι 01 0 » Ob Ob CM CM CM CM CM CM CM CM CM CM CM CM CM CM

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I) WHEREIN R * = CN

REPRESENTATIVES OF THE HA PIRAL COMPOUNDS / PPP / C GENERAL FORMULA / 1 / IN WHICH R ₂ = CN

r4 and

Vf * · En U Μ s cn

Oi

XXX

in

u r- <H υ u

in

in th Ex lx tn

Ex tn lx tn

in

in

in

X u

r- <u

in

in

in

in

Ex lx lx

tn co co co tn X tn X <n X tn X X o co X in co X Q tn X in r y CM X In CM X y Midrange X y CM X Oh Oh in Oh o Oh o Oh o o o o co co cn co co w co JV co co co cn

o z • o ft.

Oh

D4 tp

m co r ~ «D Okay o H Ci cn w tn 10 Okay Okay Okay Okay Okay o o o o o o o CM CM CM CM CM cn <n <n cn cn tn cn

07. H SOCH tn tn X '83 -

N cn (Λ 06

m <n cn cn cn <n cn <n cn cn «N cn cn <*> (u Im Cu fa. fa. Gu fa. fa. fa. fa. fa. Ch th Ch Q υ in U Oh Q U Q D u U Oh - o - in

X X X X X X X X X X X X X X rH r4 —C rH r4 rH Ή —C fH I—. r4 * 4 rH in in in in o in in in in o υ U U υ cn cn cn »4 rH r4 fa. fa. be X X X Oh in in fa. fa. fa. U o o X X

<n cn X cn cn X cn cn X cn cn X cn cn X in <n X υ m X in cn X Oh cn X X o CM X In CM X o CM X In CM X y in o Oh o o o o o Oh Oh Oh Oh in o cn cn co co co co CO., LTD co co CO., LTD co co cn co

o rH CM cn w Yu w r- «0 Ch H H rt H rl r < rt rH H cn cn cn cn cn cn cn cn cn cn

ο CM cn

ΗCM

CMCM cn <n

TABLE I

TABLE 1

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I) WHEREIN R * = CN

REPRESENTATIVES OF THE HA PIRAL COMPOUNDS / PPP / C GENERAL FORMULA / 1 / IN WHICH R ₂ = CH

co <n X co co X fa CM 8 fa CM r4 8 CM CM r4 8 CM fa fa CM r4 8 fa CM · - <8 CM CM 8 cm fa fa 8 <n X in CO., LTD X in CM fa U fa in CM X y CM X y CM fa y CM . there y CM fa ο o o in o Oh in o Oh o o Oh U co You co co You co CO., LTD m V> co CO., LTD <0 co

<n W «N co r- "IN Okay o rM CM co Yu co CM CM CM CM CM CM CM co co cn co co co co co co ro co co co co co co cn co co co co

Θ5

TABLE I

TABLE 1

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I) WHEREIN R * = CN

REPRESENTATIVES OF HA PIRAL COMPOUNDS / PPP / C GENERAL FORMULA / 1 / IN WHICH K _? = CN

GO &

•• hours hh hh • n hh would s X X X and and and X X X and and Fr. Si See See See See would SEE See see See SEE See see See see <4 • h Si see R. See see • hours Si see • h See see H4 hh and SEE hh and SEE • hours Fr. see and <m <4 and and and »- < and Fr. * 4 and and * h and and hh and and and see and and see and and see and and see and Fr. see sch h Fr. see Fr. see 'See and see Si and see See would and see See and see Si In see Ll and <m See In in see See in see See in see See in see See in see Oh Oh and Fr. Fr. υ Fr. Oh ϋ Fr. Fr. and Fr. Oh CO., LTD W And ff ff SL ff ff ff ff ff ff ff ff

<3 37. «0 th Спι sp Fr. n MS W <n · ·· Yu hg d * h » «0 hG 0 »hg oh nx * = <n magazine magazine magazine magazine magazine magazine magazine magazine magazine <N magazine magazine magazine

TABLE I

TABLE 1

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I), WHEREIN R ² = CN

REPRESENTATIVES OF HA PYRAL COMPOUNDS / PPP /, C GENERAL FORMULA / 1 /, IN WHICH Bg = CH

R Ο as Ο

CO., LTD <o (H co co CO., LTD co CO., LTD co co co co co co tx tx fa tx tx tx fa> tx h tx tx hi tx fa U. In Oh y y - In y. B- -Yeah In y In - In o

co αί

X X X X X X X

X X X X X X X rdrdrdrdrdrdrdrdrdrdrdrdrdrd uuuuuuuuuuuuuuu

r4 hh r4 r4 t-4 y in Oh y y CN CM fa CM lx X tx X o X y CN oo y CM th Λ tx CM lx o lx VO h In CN vo In In Oh o y Oh co co V) «3 «3

r4 Oh • H U kt X Ms. U in fa and © U m CO., LTD CO., LTD CO., LTD CN fa fa hi bi o V> 8 8 8 8

«Ο co co co h> th lx tx

8 8 8

»4 co tx tx X In In

rd CM co “Mr. «3 VO r * co O> o rd CM co Yu IZ Yu m «L. Yu V3 m Yu VO VO VO VO V © CO., LTD CO., LTD «Η co co co co cn co co co co co <n

TABLE I

TABLE 1

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF THE FORMULAE), WHEREIN R2 = CN

REPRESENTATIVES OF THE HA PIRAL COMPOUNDS / PPP / C GENERAL FORMULA / I / IN WHICH = CH

(and 004

In the village

Yu «0 with * α Fr. hh sch <n Yu are d » «0 SO are are SO SO d * r> d » Γ- Γ- d » d * Γ- r * «N magazine <n <n n <n <n η η η «Η η «Η

TABLE I

TABLE 1

REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I) WHEREIN R * = CN

REPRESENTATIVES OF THE HA PIRAL COMPOUNDS / PPP / C GENERAL FORMULA / 1 / IN WHICH R ₂ = CK

<about X

X <ο χ X hh ^ 4 ο ο ο Μ and and ο ο δ co

m Ο

XXX

XXX

at

σ>

Γ · <η

X X X X X X • Η “-Ch * 4 c-h X υ and X ο Q

XXX

h. hc J b < sch> L and η MS and MS MS and MS «Η r4 u MS Cu PM ►q co GO υ and s Si Oh th Cu υ s Cu and δ υ and δ υ in in υ and <l co CO., LTD co co co CO., LTD CO., LTD

XXX

XXX

XXX

o H CM co L. w> Γ » co co CD CO., LTD CD co CD co co co co m co co co co co co co

389. Η SCF ₃ Η C1 Η C1 Η SCH ₂ CH ₃

TABLE II

TABLE 2

OTHER REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF

FORMULA (I): WHEREIN, X ² & X3 = H; X * & X «= C1; AND Y = CF ₃ OTHER REPRESENTATIVES OF THE HA PIRAL COMPOUNDS / PPP / C GENERAL FORMULA / 1 / _; IN WHICH X ₂ AND X ₃ = H; Χ _χ AND X ₄ = C1; AND Y = SAT ₃

SUBSTITUENT GROUPS

w · Rl X r3 R ² 390. Η SCF ₃ a -------- H 391. Η SOCF ₃ Cl H 392. Η are ₂ ^c f ₃ Cl H 393. Η SCF ₃ F H 394. Η SOCF ₃ F H 395. Η are ₂ CF ₃ F H 396. Η SCF ₃ CN H 397. Η SOCF ₃ CN H 398. Η are ₂ ^cf 3 CN H 399. Η SCF ₃ CF3 H 400. Η SOCF ₃ ^CT 3 H 401. Η are ₂ cf ₃ ^σ 3 H 402. Η SCF ₃ SO ₂ CF ₃ H 403. Η SOCF ₃ are ₂ cf ₃ H 404. Η are ₂ gf ₃ are ₂ cf ₃ H 405. C1 SCF ₃ a H 406. C1 SOCF3 a H 407. C1 SO2CF3 a H 408. C1 SCF3 F H 409. C1 SOCF3 F H

TABLE II

TABLE 2

OTHER REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I): WHEREIN, # & X ³ = H; X * & X ^ CI; AND Y = CF ₃

OTHER REPRESENTATIVES OF HA PIRAL COMPOUNDS / PPP / C GENERAL FORMULA / I / IN WHICH X ₂ AND X ₃ = H, X! And X ₄ = Cl; And Y = C? ₃

SUBSTITUENT GROUPS

RPC-No. ππη-ίϊ » R1 --- REPLACEMENTS— X R3 R2 410. Cl SCF3 CN H 411. Cl SOCF3 CN H 412 Cl are ₂ cf ₃ CN H 413. CN SCF ₃ Cl H 414. CN SOCFg a H 415. CN are ₂ cf ₃ a H 416. CN SCF3 F H 417. CN SOCFg F H 418. CN N ° 2 ^CF 3 F H 41Θ. CN SCF3 H 420. CN SOCFg CF3 H 421. CN are ₂ cf ₃ CF3 H 422. F SCFg a H 423. F SOCFg a H 424. F SO ₂ CFg a H 425. H SCFg a Cl 426. H SOCFg Cl a 427. H SO ₂ CF ₃ a Cl 428. H SCF ₃ F Cl 429. H SOCFg F Cl

~

TABLE II

TABLE 2

OTHER REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF

FORMULA (I): WHEREIN, X2 & χ3 = Η; X * & X «= C1; AND Y = CF ₃

OTHER REPRESENTATIVES OF THE HA PIRAL COMPOUNDS C GENERAL FORMULA / I / / PPP /,

IN WHICH X ₂ AND X ₃ = H; Χ _χ AND X ₄ = C1; And Y = CP ₃

SUBSTITUENT GROUPS

RPC-No. PPP-ίϋ R1 X R3 R2 430. Η SOgCFg F a 431. Η SCF ₃ CN a 432. Η SOCF ₃ CN a 433. Η θ ° 2 ^αΓ 3 CN Cl 434. Η SCF3 ^from a 435. Η SOCF ₃ ^CT 3 Cl 436. Η N ° 2 ^CF 3 Cl 437. C1 SCF ₃ α a 438. C1 SOCF ₃ α Cl 439. C1 are ₂ gf ₃ α Cl 440. C1 SCF ₃ F a 441. C1 SOCF ₃ F Cl 442. C1 are ₂ cf ₃ F Cl 443. C1 SCF ₃ CN a 444. C1 SOCF ₃ CN Cl 445. C1 are ₂ cf ₃ CN Cl 446. C1 SCF ₃ ^CT 3 a 447. C1 SOCF ₃ ^σ 3 Cl 448. C1 ^CT 3 a 449. CN SCF ₃ Cl Cl

TABLE II

TABLE 2

OTHER REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I): WHEREIN, X * & X3 = H; X * & X «= C1; AND Y = CF ₃

OTHER REPRESENTATIVES HA PYRAL COMPOUNDS / PPP / C GENERAL FORMULA IN WHICH x ₂ AND X ₃ = H; Χ _χ AND X ₄ = C1; And Y = CP ₃ RPC-No. PPP-CHZ SUBSTITUENT GROUPS NAYSMGELI R1 X R3 R2 450. CN SOCFg a a 451. CN are ₂ cf ₃ a Cl 452. CN SCF ₃ F a 453. CN SOCF ₃ F Cl 454. CN are ₂ cf ₃ F a 455. CN SCF3 CN a 456. CN SOCF ₃ CN Cl 457. CN are ₂ cf ₃ CN a 458. CN SCF ₃ ^CT 3 a 459. Cl SO2CF3 F H 460. CN SOCFg a 461. CN ^σ 3 Cl 462 H SCF ₃ a CF3 463. H SCF ₃ F cf ₃ 464 H SOCF ₃ F CF3 465. H are ₂ cf ₃ F CF3 466. H SCF ₃ CN cf ₃ 467. H SOCF ₃ CN cf ₃ 468. H are ₂ cf ₃ CN cf ₃ 469. H SCF3 Cl cf ₃

TABLE II

TABLE 2

OTHER REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF

FORMULA (I): WHEREIN, X * & X3 = H; Xl & X <= C1; AND Y = CF ₃

OTHER REPRESENTATIVES OF HA PYROLYN COMPOUNDS / PPP / OF THE GENERAL FORMULA / I / IN WHICH X ₂ AND X ₃ = H; Χ _χ AND X ₄ = C1; And Y = CP ₃

SUBSTITUENT GROUPS

SUBSTITUTES

RPC-No. PPP-JS R1 X r3 R2 470. Η SOCF ₃ a CF3 471 Η Cl CF3 472 Η SCF ₃ a CH3 473. Η SOCF ₃ a CH3 474 Η are ₂ ^c f ₃ Cl CH3 476. Η SCF3 F CH3 476. Η SOCF ₃ F CH3 477. Η are ₂ gf ₃ F CH3 478. Η SCHF2 a CN 479. Η SOCHF2 a CN 480. Η SO2CHF2 Cl CN 481. Η SCHF2 H CN 482. Η SOCHF2 H CN 483. Η SO2CHF2 H CN 484. Η SO2CHC12 a CN 485. Η S0CHC12 Cl CN 486. Η SOCHC1F a CN 487. Η SO2CHCIF a CN 488. Η SCHF2 Cl Cl 489. Η SO2CHF2 a Cl

- 94 TABLE II

TABLE 2

OTHER REPRESENTATIVE PYRROLE COMPOUNDS (RPC) OF FORMULA (I): WHEREIN, X * & χ3 = Η; X ¹ & X ⁴ = C1; AND Y = CF ₃

OTHER REPRESENTATIVES HA CONTROLLED COMPOUNDS / PPP / C GENERAL FORMULA / I / IN WHICH X ₂ AND X ₃ = H; And X = Cl; AND Y = C $ ₃ ^ SUBSTITUENT GROUPS ____________ SUBSTITUTES ..'______________________________

RPC-No. R1 X R3R2

DPS - ^

490. H SOCHF2 Br CH3

491. Cl SO2CHF2 aCF3

I - 9 5 - The i-iaoSp ratio is better illustrated by the following exemplary embodiments.

Examples 1 to 22 illustrate the methods of synthesis and physical conditions of the insecticidal compounds (as well as their intermediates) according to the invention.

¹ · 1 t I * · Η » ¹ ~ t '''I ί Η' ι i- h 'Γί U. IC ii 3; I Γ i u- i Ί »i t- I»

A solution of 913 mg (2.07 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylthiopyrrole (prepared according to Example 4) and 492 mg of 80 N-meta-chloroperac sib enzoic acid (394 mg, 2.28 mmol) in 25 ml chloroform was stirred at ambient temperature for 1.5 hours and then heated at reflux overnight. An additional 45 mg / 0.21 mmol / m-chloroperoxybenzoic acid was added and refluxed for another 1 hour. The heating was then quenched with water and the reaction mixture was diluted with dichloromethane and washed with sodium bicarbonate solution. dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a colorless solid. The procedure was repeated to collect a total of 950 mg of product, which was chromatographed on silica gel, eluting with 2: 1 v / v dichloromethane. hek san «The first fractions contain 310 mg / 24 % (1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4-trifluoromethylsulfonyl-pyrrole (Example 1) as a colorless solid. Upon recrystallization from hexane-ethyl acetate afforded 240 mg of sulfone on colorless needle crystals of m.p. 198 ° C, PRINCIPLE 2.

The chromatography at the end of Example 1 was continued. The second fractions of this chromatography gave 600 mg / 48% / 1- (2,6 dichlorometh-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- Trifluoromethyl or sulphinyl-pyrrole (Example 2) as a colorless solid. Recrystallization from toluene-hexane gave 390 mg of sulfoxide as a colorless powder, m.p. 152-154,5 p.

ΠΡΗΓιΕΡΗΗ IMPLEMENTATIONS FOR AND ST.

Repeat examples 1 and 2 with 1- (2, 6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylthio-5-bromopyrrole as the starting compound according to the method of embodiment 5. The compound of Example 3A is 1- (2, 6-dichloro or 4-trifluoromethylphenyl)

2-chloro-3-cyano-4-trifluoromethyl sulfinyl-5-bromopyrrole This compound prepared according to a method similar to that of Example 2 has a m.p. about 123 ° C. The compound of example embodiment 3B is

1- [2, 6-Dichloro-4-trifluoromethyl phenyl] -2-chloro-3-cyano-4-trifluoromethylsulfonyl-5-bromopyrrole.This compound, learned by a method similar to that in the exemplary embodiment 1, there is a so-called. about 113 ° C.

EXAMPLE 4.

A solution of 3 g (6.6 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl)

2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole (prepared according to the method described in example embodiment) in 50 ml of dry tetrahydrofuran was stirred under nitrogen and 3.9 ml / 3.4 were added. g, 33 mmol / t-butyl nitrite. After 30 minutes, the reaction mixture was heated to reflux for 1 hour. It was then concentrated under reduced pressure to give 3.69 g of a solid residue. This procedure was repeated as many times as possible. , to give a total of 4.07 g of a solid residue which is chromatographed on silica gel with 1: 1 v / v dichloromethanehexane as eluent, which afforded 2.9 g / 91% / of 1- / 2,6-dichloro-

4-Tricluoromethylphenyl (2-hdr-3-cyano-4-trifluoromethyl ylthiopyrrole) (Example 4) as a colorless solid. Recrystallization from hexane-ethyl acetate yields 1.87 g of the product as a colorless powder. , so on. about 137 ° C,

EXAMPLE 5.

To a heterogeneous mixture of 2.4 g (5.28 mmol) 1- (2, 6-dichlorom-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-hydroxypyrrole) prepared according to the method of e.g. b) in 40 ml of bromoform in an inert atmosphere, 0.94 ml / 820 mg, 7.92 mmol / tert-butyl nitrite was added. After stirring at ambient temperature for 15 minutes, the reaction mixture was concentrated under reduced pressure at The latter was collected with the product of the previous reaction, which was 300 mg of the same starting pyrrole compound. The crude product was is purified by chromatography on silica gel, eluting with a 4: 1 volume / volume of x-exandyl orthiol. 1.72 g (5b% / 1- / 2, ο-dihydro-4-trifluoromethylphenyl) is obtained. 2-bromo-3-trifluoromethylthio-4-cyano-5-chloro-pyrrole (Example 5), which was recrystallized from hexane to give 780 mg of a colorless solid, melting at about 92 ° C.

EXAMPLE 6,

A solution of 1.91 g (4.21 mmol) of 1- (2,6-dichloro-4-trifluoro-methylphenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-5- chloro pyrrole (prepared according to the method described in Example 8), 77 mg (0.63'mmol)

4-dimethylaminolyridine and 20 ml of pyridine in an inert atmosphere were cooled to 0 C and 1.01 ml / 1.50 g, 7.14 mmol / trifluoroacetic anhydride were added. The mixture was stirred at 0 ° C for 1 hour and at 20 ° C for 4 hours, followed by the addition of 0.30 ml / 2.1. mmol / trifluoroacetic anhydride. After a 24-hour total reaction time, the reaction mixture was diluted with dichloromethane and concentrated. The residue was washed with aqueous HCl, then water and recrystallized from hexane-ethyl acetate to give 860 mg / 37; - N (1- (2, 6-dichloro-4-trifluoromethylphenyl) -2- (trifluoromethyl) arb onylamino / -3-trifluoromethylthio-4-cyano-o-chloropyrrole) b / in the form of a solid product of very pale green color, etc. οκο / ιο 190 ° N ..

EXAMPLE 7.

A mixture of 1.50 g (3.3 mmol) 1- (2, 6-dichloro-4-trifluoromethylphenyl)

2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole (prepared according to the method described in Example 8), 0.10 g of 4-dimethylaminopyridine,

0.33 ml / 0.32 g, 4.1 mmol / pyridine, 0.31 ml / 0.34 g, 4.3 mmol / acetyl chloride and 10 ml of acetonitrile were stirred for 4 days at 20 ° C and 1 day at reflux. Then 0.03 ml of acetide / chlsride is further added and reflux continues for another 1 day, after which the reaction mixture is cooled, diluted with dichloromethane and partitioned sequentially between 1N HCl and saturated aq. sodium bicarbonate solution »The organic layer is dried over anhydrous magnesium sulfate and evaporated, yielding 1.42 g of a beige solid. chromatography on silica gel eluting with 4: 1 volume / volume hexane-ethyl acetate recrystallization from ethanol-water afforded 480 mg (29%) of 1- (2, 6-dichloro-4-trifluoromethylphenyl) -2-methyl yl arb onylamino-3-trifluoromethyl orthio-4-cyano-5-chloropyrrole (Example 7) as colorless needle crystals, m.p. about 216 ° C.

PRIOR IMPLEMENTATION 8.

A solution of 1.50 g (3.57 mmol) 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amines-3-trifluoromethylthio-4-cyanopyrrol (prepared according to the method described in Example 13) in 15 ml of ethyl ether was cooled with stirring to -20 ° C under inert medium and a solution of 0.29 ml / 0.48 g, 3.6 mmol / sulfuryl chloride in 15 ml of anhydrous ethyl ether was added dropwise. warm to 20 ° C and stir for 2.5 days, after which additional 0.03 ml / 0.4 mmol / sulfuryl chloride was added and stirring continued for another day. 03 ml of sulfuryl chloro is added and after another day 28 ml of 10% aqueous potassium carbonate solution are added to the reaction mixture, the phases are separated and the aqueous layer is extracted with ether. The ether layers are collected, washed with water, dried over anhydrous magnesium sulphate and concentrated to give 1.56 g of a solid product of a red, light yellow color. The crude product was chromatographed on silica gel with 2 l, v / v dichloromethane-hexane as eluent, yielding 1, 30 g / 80% 8 1- / 2,6-dichloro-4-trifluoro-99 _ methylphenyl (-2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole) (example embodiment 8) as a very pale pink solid. Recrystallization from cyclohexane gave B10 mg of the product as off-white needle crystals of m.p. about 176 ° C.

EXAMPLE 9,

A method similar to that of Example 8 is used, except that 1- (2-chloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrol is used as a reagent. so on. 169 ° C, which is obtained by the method described in example embodiment 13. The final product is'. 1- (2-Chloro-4-trifluoromethyl phenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole (Example 9), m.p. about 148 ° C.

EXAMPLE 10,

A method similar to that described in Example 8 is used, except that 1- / 2,6-dichloro is used as the reagent

4-trifluoromethyl phenyl / -2-amino-3-dichloro fluoromethylthio-4-cyanopyrrole / m · top. 202 ° C), which is obtained according to embodiment 13. The final product is: 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-dichlorofluoromethylthio-4-cyano-5-chloropyrrole (W) /, mp about 207 ° C.

EXAMPLE IMPLEMENTATION 11.

The compound 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2,4-bis (trifluoromethylthio) -3-cyano-5-amino pyrrole (Example 11) has a melting point 161 C and was prepared by the method described in Example 13 (the first compound) using excess trifluoromethanesulfenyl chloride.

EXAMPLE 12,

To a cooled (0 ° C) solution of 1.53 g (3.60 mmol) of 1- (2,6-dichloro-4-trichloromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrol, obtained by the method, described in Example 13, m.p. about 182 ° C in 15 ml of pyridine in an inert atmosphere was added. 1.46 g / 3.6 mmol /

100 solutions of B0 / pyridine bromide perbromide in 15 ml of pyridine. The reaction mixture was poured into cold (0 ° C) styrene ether for one minute and the precipitate formed was removed by filtration. The filtrate was washed with aqueous HCl, aqueous sodium hydroxide and water. The organic layer was dried over anhydrous magnesium sulfate and evaporated to give '. 1.34 g solid brown colored product>^; the following was collected together with 230 mg of the product previously learned by the reaction of 300 mg (0.7 mmol) of 1- (2,6-dichloro-4-trifluoromethylsilyl) 2-amino-3-trifluoromethylthio-4- cyanopyrrol is 0.25 g of 80 / pyridine bromide perbromide. The combined products are chromatographed on silica gel and eluted with 4: 1 v / v hexane-ethyl acetate to give.

1.31 g of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-bromoprol (example 12) as a white solid color. recrystallization from hexane / ethyl acetate gave 910 mg of this product as colorless needle crystals, m.p. about 160 ° C.

PRINCIPAL IMPLEMENTATION 13. ·

A solution of 2.00 g (6.25 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amines-4-cyanopyrrol in 60 ml of dichloromethane prepared as described below is cooled when mixed with an ice bath and a slow jet, it is added; 10 ml of cold (-78 ° C) solution of dichloromethane containing 0.55 ml (0.85 g, 6.2 mmol) of trifluoromethanesulfenyl chloride.

After stirring at 0 ° C for 2 hours, a stream of nitrogen was passed through the reaction mixture for 1 hour. Separation with saturated aqueous sodium bicarbonate and water, drying over anhydrous magnesium sulfate and concentration in vacuo gave 3.14 d light-brown solid. This product was chromatographed on silica gel with 3: 2 v / v dichloromethane-hexane as eluent to give two colorless solid products, weighing 900 and 9 50 mg, respectively. These are recrystallized from chloroform to give

- IU respectively 380 and 330 mg of 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-amino-

3- trifluoromethylthio-4-cyanopyrrol (embodiment 13), m.p. eye- oh

up to 132 C.

The reagent used in this method is prepared according to the following process. A solution of 4.34 g (14.5 mmol) of 1 - [(2-dichloro-4-trifluoromethylphenyl) amino] -2,3-dicyanopropylene and 2.0 ζ ml (1.47 g, 14.5 mmol) triethylamine in 30 ml of benzene was refluxed overnight and then concentrated in vacuo. The stock was partitioned between ethyl ether and water and the ether layer was dried over anhydrous magnesium sulfate and concentrated. , yielding 3.70 g of a light brown solid. Recrystallization from ethanol-water gave 2.79 g / 60% / 1- / 2, 6-dichloro-4-trifluoromethylphenyl / -2-amino -

4- cyanopyrrole, mp about 17b ° C.

The starting 1-arylamino-2,3-d -cyano-propylene was prepared according to the following process; 20.5 g / 0.140 mol / potassium salt of formyl succinonitrile was dissolved in approximately 30 ml of water and acidified with concentrated hydrochloric acid.The resulting product was extracted with ethyl ether. The ether extract was dried over anhydrous magnesium sulfate and evaporated to give 3.87 g of a brown liquid. One was added to a solution containing 5.04 g / 22 mmol / 2,6-dichloro-4-yl fluorine methyl aniline and 40 mg of p-toluene sulfonic acid monohydrate in 50 ml of benzene. The heterogeneous reaction mixture was refluxed overnight with a water separator. The reaction mixture was then cooled and concentrated to give 7.66 g of a yellow colored liquid. After trituration with hexane, it precipitated with, b8 g (9 5%) 1 - [(2,6-dichloro-4trifluoromethylphenyl) amino] -2,3-dicyanopropylene as a yellow solid. After recrystallization with ethanol / water, / product is melting at about 101 ° C.

PRIOR IMPLEMENTATIONS 14A AND 14B.

To a suspension of 1.1.7 g (3.30 mmol) 1- (4-trifluoromethylphenyl) 102 -

2-amino-3-trifluoromethylthio-4-cyanopyrrole and 0.46 ml / 0.34 g, 3.3 mmol / triethylamine in 20 ml chloroform cooled to -20 C * was added a solution of 0.19 ml / 0, 59 g, 3.7 mmol / bromine in 5 ml of chloro form. P ection mixture was stirred at -20 ° C for 1 hour, then allowed to warm to 0 ° C. 0.04 ml / □, 1-3 g, 0.0 mmol / bromine and after 15 m stirring. The reaction cm-axis is diluted with dichloromethane and partitioned between water and saturated aqueous sodium bicarbonate. The organic layer is dried over anhydrous magnesium sulphate and after concentration yes This solid was mixed with 1.00 g (2.8 mmol) of 1- (4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrol and 0, Chromatography on silica gel and elution with 3: 1 volume / volume of dichlorometh an-xxane afforded 1, 40 g (52%) of 1- (4-trifluoromethylphenyl) -2-amino- 3-Trifluoromethylthio-4-cyano-5-bromopyrrole (Example 14A) as a yellow solid. After recrystallization from hexane-ethyl acetate, the product was obtained as light yellow plates, m.p. 175 °.

The compound 1- (4-trifluoromethylphenyl) - 2-amino-3-trifluoro-methylthio-4-cyanopyrrol (example embodiment 14B) with melting οκολο 152 ° C is obtained from 1- (4-trifluoromethylphenyl) amino / -2,3-dicyano-prolylene according to a method similar to that described in Example 13.

EXAMPLES 1.5A AND 15B>.

The compound 1 - [(2-chloro-4-trifluoromethylphenyl) amino] -2,3-dicyanopropylene was prepared by a method similar to that described in Example 13 .. This dicyano-propyl is used as the starting compound for Preparation of 1- (2-chloro-4-trifluoromethylphenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrrol (Example 1.5A), melting at about 169 ° C, following the method of ® ®]} described in example embodiment 13. This pyrrole is used to prepare 1- (2-chloro-4-trifluoromethyl phenyl) -2-amino-3-trifluoromethyl ylthio-4-cyano-5-bromlirol / example embodiment 15B / melting at about 157 ° C

- 1 Ο 3 Example Execution 14..

EXAMPLES 16A AND 16B.

The compound 1- (2, 6-dichloro-4-trifluoromethylphenyl) -2-amino-4-cyanopyrrole prepared according to embodiment 13 is treated with CFCI ₂ - <RTI ID = 0.0> JCI </RTI> according to the method of embodiment 13 (in which C 1-4 is used) $ Cl /, which yields 1- (2, 6-dichlorom-4-trifluoromethylphenyl) -2-amino-3-dichlorofluoromethylthio-4-cyanopyrrol, (example embodiment 16A), mp, about 202 ° C. ».

This compound is treated with tert-butyl N-nitrite according to the method of embodiment 4 to give 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylthio) pyrrole. Embodiment 16B), m.p. 158 ° C.

EXAMPLE 17.

The final compound of Example Embodiment 16 was reacted according to a method similar to that of Embodiments 1 and 2. using hydrogen peroxide in trifluoromethyl peroacetic acid (instead of m-chloro peroxybenzoic acid) to give 1- (2b) -dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-N- (dichlorofluoromethylsulfinyl) pyrrole (example embodiment 17), m.p. about 119 ° C.

EXAMPLE 18,

According to the method of embodiment 17, using a doubled amount of hydrogen peroxide having absorbed one compound of embodiment 16, is converted to 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichloromethomethyl sulfonyl) pyrrole (embodiment 18), melting at about 179 ° C,

EXAMPLE 19.

The first compound of Example 16 is treated with tert-butyl N-nitrite according to the method of Example 4 to give 1- (2, 6-dichloro-4-trifluoromethyl-phenyl) -3-cyano-4 - (dichloro fluoromethylthio) pyrrole (example embodiment 19), m.p. about 120 ° C.

104 [i P IM EP Η 0 IMPLEMENTATION 20.

The compound of embodiment 19 is oxidized according to the method of embodiment 17 to give 1- (2,6-dichloro-4tr-ylmethyl phenyl) -3-cyano-4- (dichloro-methylmethyl sulfinyl) pyrrole / embodiment 20), mp 150-152 ° C.

ΐΊΡ / ίηΕΡΗ / i PERFORMANCE 21A, 21B, and 21B.

Compound 1 - // 2,6-dichloro-4-trifluoromethoxyphenyl (amino) -

2,3-Dicyanopropylene is prepared according to the method described in Example 13, the last compound, replacing the compound, 6-dichloro-4-trifluorometh cyaniline with the compound 2,6-dichloro-4-trifluoromethyl aniline.

This compound is converted to 1- (2, 6-dichloro-4-trifluoromethoxy phenyl) -2-amino-4-cyanopyrrol, according to the method of example embodiment /

- the second compound.

This compound is converted to 1- (2,6-dichloro-4-trifluoromethoxy phenyl) -2-amino-3-trifluoromethylthio-4-cyanopyrid according to the method of Example 13, the first compound.

This compound was converted to 1- (2,6-dichlorom-4-trifluoromethoxyphenyl) -2-amino-3- (trifluoromethylthio) -4-cyano-5-chloropyridine (Example 21A). mp 19b-197 ° C according to the method of the exemplary embodiment.

This compound is converted to 1- (2,6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4-trifluoromethylthiopyrrole (Example 21B), mp 172 ° C according to the method of Example 4. This compound is converted to 1- (2, 6-dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfonylpyrrole (Example 21B), mp 187 ° C according to the method of Example 18.

EXAMPLES 22A, 22B, and 22B

Mixture of 2-chloro-4-chlorosulfphenyl-3-cyano-1- (2 *, 6'-dichloro-4'-trifluoromethyl-phenyl) -pyrrole and 2-chloro-3-cyano-4-dihydrofluoromethylsulfenyl - 105 1 - / 2 *, 6 &apos; -dichloro-4 &apos; -trifluoromethyl phenyl] -pyrrole with an amount of 47.77 g, 0.101 mmol, 1.0 equivalents, was dissolved in trifluoroacetic acid (120 ml) at 0 ° C. and then 30, ύH ₂ 0 ₂ (10.8 ml, 0.105 mol / 1.05 equivalents) were added dropwise. The reaction mixture was stirred at 0 ° C for 7 hours and 15 minutes, then toes was placed in a refrigeration unit (10 ^and C) overnight. Another 30% H was added the following morning _? 0 ₂ / 10.0 ml, 2,100 moles, 1.05 equivalents / at 0 ° C, the reaction mixture was stirred at 0 ° C for 2 hours and then kept in the refrigeration machine overnight. further 30% H ₂ 0 ₂ / 10.8 ml, 0.106 mol, 1.05 equivalents / at 0 ° C was added. After 3.5 hours, the reaction mixture was poured into 2 l of water-ice, stirred vigorously and then filtering ..

Similarly, a mixture of 2-chloro-4-chlorosulfphenyl-3-cyano-1/2 ', 6'-dichloro-4'-trifluoromethyl phenyl / pyrrole and 2-chloro-3-cyano- 4-Dichlorophenylmethylsulfenyl-1- (2b &apos; -dichloro-4 &apos; -trifluoro methyl phenyl) pyrrole (40, 77 g, 0.0848 mol, 1.0 eq) was dissolved in trifluoroacetic acid (188 ml). at 0 ° C. 30% H ₂ O ₂ / 17.7 ml, 0.173 mol, 2.05 equivalents / dropwise was added. The reaction mixture was stirred at 0 C for 2 hours and 45 minutes, then refrigerate (10 ° C) at night.After 8 hours stirring at 0 ° C, the ρ-reaction today is again placed in the refrigerator at night. it is allowed to warm to room temperature and then stirred overnight

The next morning, at room temperature, a further 30% H ₂ O _Q / 9.05 ml, 0.0886 mol, 1.05 eq / 0 ° C was maintained and the reaction mixture was maintained at 0 ° C for 6 hours and 40 minutes, then allowed to warm to room temperature and stirred over the weekend. The mixture was then poured into 2 l of ice-water, stirred vigorously and filtered.

The precipitates from the two reactions were mixed and dissolved in 500 ml of dichloromethane, washed with 500 ml of eod, 500 ml of 10% aqueous

MaHS0 ₃ and 500 ml of saturated sodium chloride solution. The organic phase 166 and the solvent are evaporated off by drying over Na2SO4, filtrate in a beam. 74.96 g / yield 79.9, v / solid product. The same was extracted from π ρο of 690 ml of hexane-methane / 2: 1, and 20 ml of dichloromethane were added to give 6.93 g of a solid product representing 2-chloro-4-chlorosulfonyl -3-cyano-1- (2 &apos;, 6 &apos; -dichloro-4 &apos; -trifluoromethylphenyl) -pyrrole (example embodiment 22A) .Then one co is crystallized from 103 ml of isopropanol to give 3.97 g, m. mp 187-188.5 ° C.

The compound 2-chloro-4-chloro orsulfonyl-3-cyano-1- [2 ', 6'^{; -dihlor4,} 'trifluoromethylphenyl / pyrrole / 3.97 g, 9.06 mmol,> 1.0 eq. / is taken up in tetrahydrofuran / 15.8 ml / at 0 ° S.Pribavya triphenylphosphine / 2.41 g , 1, 0 eq / solid. The solution turns yellow. After 2.5 hours. The ice bath is removed and the mixture is allowed to stir overnight at room temperature. More triphenylphosphine / 2.55 g is added. , 9.72 mmol, 1.03 eq., And the mixture was stirred at room temperature overnight. To the resulting precipitate was added ml of tetrahydrofuran and the mixture was washed twice with saturated sodium chloride solution and again was extracted, the organic phase was dried over magnesium sulfate, filtrate and the solvent was evaporated in vacuo to give. 9.44 g waxy solid in substance. It was also chromatographed on silica gel to give (3.39 g) in a narrow like product. It was then recrystallized from 140 ml of isopropanol to give (2.54 g (74.9%) bis (2-chloro-1- (2 ^, 6'-dichloro-4'-trifluoromethyl-phenyl) -pyrrol-4-yl) -disulfide (example embodiment 228), mp 218.8- 220.3 ° C.

The compound would be - (2-chloro-3-cyano-1 .- (2 ', 6'-dichloro-4'-trifluoromethylphenyl) -pyrrol-4-yl) disulfide / 0.80 g, 1.08 mmol, 1 Is dissolved in dimethylformamide (10 ml) and cooled to 0 ° C. NaHCO 3 (0.46 g, 3.24 mmol, 3.0 eq) is dissolved separately in 5 ml of water. is added to the dimethyl formamide solution. 1.5 ml of dimethylformamide and 10 ml of water are added to the resulting precipitate. Solid / 0.564 g is added.

- 107 -

3.24 mmol, 3.0 eq./ The reaction mixture is colored pale / yellow. Pour dibromodifluoromethane 65 g into a weighed and cooled vial, 65 g 3.1. mmol, 2.07 equiv./, and then poured into the reaction mixture. One of them became colorless and a white precipitate formed. After 1 hour and 50 minutes, it was added. 10 ml of dimethylformamide, followed by the addition of 0.93 g of 05 ^ 2 ^ 2, ^{and all the ion} and ^{ionic cb} E ^was sealed and then stirred at room temperature overnight. After cooling to 0 ° C, the reaction mixture was poured into 200 ml of water and extracted four times with 150 ml of ethyl ether. The organic phase is washed twice with 100 ml of 5% aqueous HCl, twice with 100 ml of saturated NaHCO 3 solution and with 100 ml of saturated sodium chloride solution. is dried over magnesium sulphate, the filter is filtered and the solvent is evaporated in vacuo to give '.' 80.7 mg of a white solid. The initially obtained aqueous phase was then filtered and a white solid was collected which precipitated overnight. It was then dissolved in dichloromethane, the solvent was evaporated in vacuo and dried, leaving yielded 0.488 g of a white colored solid (total yield 0.429 g, 40%), the latter was mixed with the solid white product (80.7 mg) obtained above and chromatographed on silica gel to give a white solid. amount of 0.362 g, which represents a 4-piece omdifl in ortho meth yl sul phenyl-2-xg ARI-cyano-1- / 2 ', ^{b'-dichloro-4} -trifduormet lfenil / pyrrole / embodiment 22B / melting point 128,3-133,7 ° C.

ADDITIONAL PREFERRED EMBODIMENTS FOR SYNTHESIS.

Following the methods described in detail above for the synthesis of the compounds of Examples 1 to 22 or the other methods generally described therein, a large number of additional examples of synthesis (DPS) of pyrrole compounds of the general formula (i) are obtained The structure of these compounds and their melting points are given in Table III (DPS-Lajz 1-91: compounds of the general formula (/), where X ₂ and X ₃ are hydrogen.

and the other substituents are listed in Table IV and Table IV

- 10Θ (DPS-1.4 ^ 92-195: compounds of the general formula (i), in which X and X1 denote hydrogen, X1 and X1 denote chlorine, y denote trifluoromethyl, and the other substituents are listed in the table).

- 109

W P Yu b

cl Ci Z P o CL s o p w P o 66 66>

b · o

X

II

X «β hh

X • 4 with H * w 66 w X £

»T

X

W CM CM 1L ιΛ ЧГ ΓΊ W * -4 <* Ί Ρ ΐΛ • -H f Ο 1 Ρ CM ιΛ Ρ ιΑ 1 1 . ί • CN ν> Ο CM YAG iD Ρ 04 ο hrs Ρ CM Ρ Ρ Ρ

<N ιΛ KO and co d * KO ο Ρ CM 1 1 1 YAG “Mr. d * r * KO ο Ρ n CM

t-t O

4T (

Yu

<7 · Pers ο YAG Ρ V r * 1 CM «Ή CM ί Os OS P D)

CM co co co co co co m

XXXXffiX— <r4 — l-c — l— οουυυυυοουουυο u k k k k k

A cf ffi ffi 0 ffi k k k k —i a 0 m ffi u k ffi k M ffi co co co co co co

X ffi X I ffi X - <-4 rd -4 <- (-4 υυυυυουυυοου • P P and υ <P P s 0C o Сь bfa o s

R s td «4

S ο Β tc

With § PQ

υ

Fr. CM Oh Oh CM O co ip o CO P CM O <0 CM to CM co 10 co co v> co co (0 Oh co Oh <0 ip P r> m m CO., LTD co co co m CM CO., LTD CM co in Oh See See fa. fa. fa. fa. bu Cm fa. Cm Cm Cm Cm and Ο Oh U υ U U Oh U Oh U Oh Oh Oh

CM

Ζ X X X X X

CM CM CM z X X 2 z 2 2

and j

I i j ΐ I

o o o o co that that that co <n co co co CM co CO., LTD that CM f4 CM r-4 CM CM CM CM CM o r4 CM in r4 o - < co iH r4 - < co o o r4 in CM U CM in cn Oh in υ υ co CM CM Oh Cm Im Cm Cm fa Cm fa Su See b < fa Cm and * Cm Oh Oh U Oh U Oh o o o υ Oh U U Oh

I

-111

I

Λ CN

TABLE III

TABLE 3

ADDITIONAL SYNTHESIZED EXAMPLES (ASE) OF PYRROLE COMPOUNDS

OF FORMULA I: WHEREIN, X ² & χ3 = Η

II 04 CQ

S3 S3

. ·

ΣΕ-<<S)

X

<L • at w CD Oh o \ see KO Fr. flO w r4 at d * magazine CD Fr. Ό · magazine at KO ^ 4 r * r4 hh hh KO CN SEE hh g «4 hh at 1 1 1 1 1 1 1 hh 1 1 1 I 1 r * co d * at KO d · 1 V 'Mr. MG 1L ΜΊ co r * at hh co KO <n d * co magazine • α » «4 ^ 4 hh hh hh see hh hh hh at

oo

hh * h Hours hh hh ^ h * h hh hh ^ h hh ^ h m υ and and and and Fr. and and and and and and Oh

<n magazine magazine <n magazine Si <n magazine (and fa. <n Si (and in s and Gu »“ Ch in in m Si in in hh Oh and CO., LTD Oh and Fr. Fr. 0 and Fr. Fr. and

see oh see O. see O. Fr. ω V) magazine and> s / s from magazine W magazine from see <m see see see see see see hh hh ^ h s / s D < magazine * h H hh from hh hh Ή and Fr. υ magazine and magazine and and and magazine Fr. and and see see Si Would Si b * Gh Si s B Gk Si th ω υ and and and and and Oh Oh 0 and and Oh and

CSI

X

ZXXXXXXXX ο * <4

CFC12S0 CN Cl Cl OCF3 Cl 116.1-120.

r4 <M M * «1 * 0 r- CO 0k O - <CM cn cn cn cn m JV JV <n cn * * * T

I

-112

M M b4

<z> Q Z P o a. s o u w P o a a> a.

in. O and SL <

βS <X and a w SJ

X n Ζ> ff

P <Ζ about

Neither

NO

О О <

σ * CM m r- < CM CD Γ * er rh m m 40 m m σ »see m Yu co fM 0ϊ CD o r4 * cn hh 1 r4 • P σ * cn 1 CD r4 »-4 (N 1 r4 1 m 1 1 σι CM m | P 1 1 CM 40 r4 1 CD • o r4 hh hh • 1 o CM cn , hh m CD 40 co o CO., LTD cn cn 40 m • 4 r4 co r4 V r4 CM ^ 4 r4 r4 rH

<4 <4 «4 - (-4 - 4 - (» 4 - (- (- .4 -

OUUU iioioioioio

X and Sc

X and

«N cn CM cn fa bu Oh Cm M f4 in Oh U Oh CD o

<n co - (V4 fa fa u m and u

m c £

CM cz

- (- (- 4 -4 - (- (* 4 - (M υυυχυυωχχχχυυο

CM Oh o o CM O CM O Oh CM o that that W that that that that that <0 that that that CO., LTD that CM CM ^ 4 f4 CM - ( CM CM -4 CM CM r4 CM CM f4 f4 o U f4 o «Η r4 in f-4 r4 U »-4 in in CM CM in X Oh Oh CM Oh in CM o Oh Cm Cm Cm Cu Cm fa Cm Cm fa Cm fa Cm Cm Cm o Oh Oh Oh Oh υ U o Oh U in Oh U U

COClOWCMCn-rulVO <w m in and in m and in

-113

o cs rH - «J r * CD Γ * m θ f » m r4 r4 o r4 m and and Oh o m CD 1 1 r4 r4 hh ^ 4 r4 ^ 4 r4 r4 r4 I 1P m 1 1 1 I 1 1 1 | 1 V « r * CM 40 10 o n and CTi CD CD σ> o cn o f “4 m and and o r> CD THU r4 hh r4 r4 r4 MS

^ 4 * 4 hh rH ^ 4 .4 r-4 r4 r4 r4 —4 r4 r4 in in in in o o in in in in in in o co m co co co CO., LTD co co co co tx r4 M tx tx tx »4 tx lx tx tx tx tx ¹ O in ffi U in Oh ffi U Oh U U U Oh e4 * 4 ^ 4 s in U X X X o X X X X X X —1 * 4 M —1 M in hh in M in X X in ffi in X ffi ffi ffi U ffi GO z 2 z z z z z z z z z Z z o o o in in in in υ in o in in in CM CM CM o o o o o o co co You You W co CO., LTD co co co CM CM CM CM CM CM CM CM CM CM »4 Oh o <- < ^ 4 r4 · - < r4 • 4 ^ 4 r4 - < co U co co in tx U U υ in U in in in co CM co co tx tx tx (X tx th lx tx tx lx tx tx D in Q in Oh υ o in U U U U U X X X X X X X X X X X X X

CFCI2SO2 CN H Cl Br Cl 212-213

- 114 -

CF2CISO2 CN H Cl Cl Cl 183.5-184.

CM CD «—4 40 o r> 1P hh CO., LTD rH • H Oh 1 1 rH 1 Oh m r * 1 1 W m 1 lH CO., LTD Yu σ \ CM , » V • rH rM rM CM 0 cn 0 • H V0 r4 CD CD r4 Oh • Η »4

CM Oh 0 co co SEE <0 CM co co hh and Ο CM 0 0 co CM CM Ο and co co co MS <0 co «Ό —1 r4 see see <η co cn in co <n r4 in o fa fa fa fa X fa fa fa U fa • -H fa 0 Ο and 0 0 in Oh U 0 0 Q Q

_I5 _

Ο o co Yu co CM V co and CO., LTD CM CD and f4 r4 r4 40 co r-4 1 1 1 1 1 o4 1 Ο ¢ 0 co o o 1 CD W co CM m Yu • ♦ 4 r4 r * < CO., LTD CM

o o <n m tn W tn fa fa in. fa fa ^ 4 in υ in U in X in

CM O cn CM CM CO., LTD </> co CO., LTD co * 4 Oh CM CM r4 hh <M in co r4 Ή Oh in r4 o co in o CM CM U fa fa fa fa fa fa fa Oh o o U Oh in o

TABLE ΙΪ

TABLE 4

ADDITIONAL SYNTHESIZED EXAMPLES (ASE) OF PYRROLE

COMPOUNDS OF FORMULA (I):

WHEREIN, X2 & χ3 = Η; X * & X * = Cl: AND Y = CF3

ADDITIONAL MEASURES FOR THE SYNTHESIS / DPS / OF PYRAL COMPOUNDS OF THE GENERAL FORMULA / 1 / IN WHICH Xg AND Xg = H; SUBSTITUENT GROUPS ^X 1 ^{and X} 4 ^{= C1} ' ^{Y = C $} 3

WEOIZEM

ASE R ¹ X R ² R ³ M.R. (° C) t tpp DGKY 92. NH2 CF2C1S CN N. 160.5-175 93. N. CF3SO2 CN N. 199.5-201 94. N. CF2C1S CN N. 104.9-106.8 95. n CF2C1S CN CF2C1S 114.5-117 96. NH2 CF2C1S CN C1 178-181 97. N. CF2CISO2 CN N. 199.8-202 98. N. CF2CISO2 CN C1 193.1-195.8 99. N. CF2C1SO CN C1 145.2-147.5 100. N. CF2C1S CN C1 139.0-143.1 101. N. CF3S CN Br 137-138 102. N. CF3SO CN Br 164-165.5 103. N. CF3SO2 CN Br 197-198 104. N. CF2C1SO CN N. 126.8-129.6 105. N. CF3S CN N. 152-153 106. NH2 CFC12CF2S CN N. 183-190 107. NH2 CCI3S CN N. 189-193 108. N. CFC12CF2S CN n 118.8-123.8 109. N. CFC12CF2SO2 CN n 157.5-161.9 110. N. CFCI2CF2SO CN n 182.5-183.9 111. NH2 CFCI2CF2S CN C1 186.5-188

ADDITIONAL SYNTHESIZED EXAMPLES (ASE) OF PYRROLE _ 117 _

TABLE Π

TABLE 4

COMPOUNDS OF FORMULA (I):

ADDITIONAL which x ₂ u

PRIm№I ^IS ON ^IS C ^ H? EZ-MU-FORMULA / I

Ho = H; X _and AND X, = CI: AND Y = CPo ^{d 1 4} SUBSTITUENT GROUPS

SUBSTITUTES x

R ¹

R ²

R ³

М.П. (° C)

Τ · »TOIL» -------

112. Η CFCI2CF2SO CN C1 149.5-151 113. Nr CF3S CN Η 163-164 114. Η CFC12CF2S CN C1 113.5-116.5 115. Η CCI3S CN C1 177-182 116. Η CFCI2CF2SO2 CN C1 147-150.5 117. Η CCI3SO2 CN C1 200-202 118. Η CCI3SO CN C1 152.2-153.5 119. C1 CF3S0 CN Η 161.5-162.5 120. ΝΗ2 CH3S CN Η 150-151 121. Η CFC12S CN Nr 117-142 122. ΝΗ2 CFC12S CN Nr 195.5-197 123. Nr CF3SO CN Η 170-172 124. Η CFC12SO2 CN Nr 176-178.5 125. Η CFC12SO CN Nr 116.5-135.5 126. Η SCN CN Η 173 _r 173.5 127. Nr CF3SO2 CN Η 179-180.5 128. Η CH3S CN Η 107-108.5 129. ΝΗ2 CF2C1S CN Nr 174.5-178 130. Nr CF2C1S CN Cl 129.5-133.5 131. Η CF2C1S CN Nr 133.5-137.1

- 118TABL11A Π

TABLE 4

ADDITIONAL SYNTHESIZED EXAMPLES (ASE) OF PYRROLE

COMPOUNDS OF FORMULA (I):

WHEREIN, X ² & X3 = H; X ² & X * = Cl: AND Y = CF3

ADDITIONAL EXAMPLES FOR THE SYNTHESIS / MRF / OF PYRAL COMPOUNDS WITH THE GENERAL FORMULA

/ 1 /, IN WHICH X ₂ AND X ₃ = H; SUBSTITUENT GROUPS ^X 1 ^{AND X} 4 ^{= C1; And Y = CP} 3 ΟΛ νΐΡΠΦ / ι'Τ'Κ'ΤΠΛ ASE tgh— R ¹ X R ³ М.П. (° C) so on. DPSY 132. NH2 Cl CN H 159.5-160 133. NH2 CF3S CN SCN 169-171 134. N. CF3S CN SCN 105-106.5 135. Br CF2CISO CN Cl 157.5-159 136. N. Cl CN H 105.5-106.5 137. n CH3SO CN H 144.5-145.5 138. n CH3SO2 CN H 173-173.5 139. NH2 CF3S CN SCH3 146-148 140. N. CF3S CN SOCH3 143-145 141. n CF2C1S0 CN Nr 143-146.5 142. Br CFC12SO2 CN Cl 117.8-122.5 143. CF3CONH CF3S CN H 187-188.5 144. N. CF2C1SO2 CN Nr 182-185 145. N. CF3S CN CH3S 89-91 146. N. CF3S CN CH3SO2 136-138 147. n CF3SO CN CH3SO2 161-163 148. NH2 CF3CC12S CN H 200-220 149. / NH2 CF3CC12S CN Cl 223.5-232.5 150. N. CF3CC12S CN Cl 170-172.5 151. N. CF3CC12SO2 CN Cl 195.6-197.2

119

ADDITIONAL SYNTHESIZED EXAMPLES (ASE) OF PYRROLE

TABLE ΙΪ

TABLE 4

COMPOUNDS OF FORMULA (I):

WHEREIN, X ² &

ADDITIONAL EXAMPLES FOR SYNTHESIS

WHAT X ₉ AND XO = H; X _and I Xd = C1: And Y = CPo

3'1 ^ SUBSTITUENT GROUPS _ YOU STOP _____

XR ²

R ¹

R ³

ASE

M.R. (° C) dii.

152. N. CF3CCI2SO CN C1 161-161.5 153. n CF3S CN CF3S 95-96 154. NH2 CH3SO CN N. 130-132 155. NH2 CH3SO2 CN n 248-248.5 156. N. CF3SO CN CF3S 145-148 157. N. CH3S CN C1 128-129 15Θ. NH2 CF3S CN S0CH3 139-141 159. CH3S CF3S CN C1 73-74 160. NH2 CFC12SO CN n 156.4-195 161. N. CF3SO2 CN CF3S 156-157 162. N. CH3SO CN C1 130-131 163. NH2 CF3S CN F 164-164.5 164. N. C1 CN C1 129-129.5 165. CH3SO CF3S CN C1 133-135 166. CH3S CFC12S CN C1 112.2-124.8 167. NH2 CFC12SO CN C1 163-169.5 168. CF3CONH CF3SO CN n 195-197.5 169. N. CF3S CN F 116-117 170. CH3SO2 CFC12S CN C1 164.5-170.5 171. CH3SO CFC12S CN C1 193-195.7

- 120TABLE II

TABLE 4

ADDITIONAL SYNTHESIZED EXAMPLES (ASE) OF PYRROLE

COMPOUNDS OF FORMULA (I):

WHEREIN, X ² & χ3 = Η: X * & χ4 = Cl: AND Y = CFs

ADDITIONAL EXAMPLES FOR SYNTHESIS / DPS / OF PYRAL COMPOUNDS 0 GENERAL FORMULA / 1 / IN WHICH X ₂ AND X ₃ = H; Xj

ASE NO. R ¹ X R ² R ³ М.П. (° C) τ.τόπ. DPS (<2 172. NH2 CF3S0 CN H Dec. above 175 173. N. CF3S CF2H H 54-56 174. N. CH3SO2 CN Cl 165-166 175. N. Br CN Nr 127.5-128 176. N. Br CN H 120-121 177. NH2 CFCI2SO2 CN Cl 203-214.5 178. N. CF3SO CN F 129-130 179. Br C1 CN H 121-123 180. NH2 CF3SO2 CN H 258-260 181. CH3 SO CF3SO CN Cl 238-239 182. N. CF2BrS CN Cl 128.3-133.7 183 N. CF2BrSO CN Cl 117-119 184. N. CF2BrSO2 CN Cl 172-181 185. n CF3S CH3 H oil 186. n CF3SO CH3 Nr 106-107 187. n CF3SO2 CH3 Nr 76-77 188. NH2 CF3S CN CH (SCH3) 2 159-161 189. CH3SCH-N CF3S CN CH (SCH3) 2124.5-125.5 190. N. CF3S (CH3) 3COCONH Nr 113-114 191. N. CF3S Nr Nr oil

-121

Table IV

Further Examples of Synthesis (MRF) of Pyrrole Compounds of General Formula (I) wherein X ₂ and X ₃ = H; substituents X _t and X ₄ = C1 and y = CF ₃ j ¹

ASE NO. R ¹ X R ² R3 m.p. (° 0 T.TOP, DPSJ 192. N. CF3SO CH3 OH * 149-151 * Mau exist as the keto tautomer 193 Nr. CF3S CH3 Nr oil 194 Nr Nr H CF3S oil 195. H CF3S CN I 107-109

122

Methods for controlling pesticides and formulations for this purpose.

An essential feature of the invention is the method of combating arthropods, in particular insects and arachnids, plant nematodes and helminths or protozoan pests, which method involves treating the site (for example, by administration or administration) with an effective amount of the compound of general formula I, in which the various substituents have the meanings already explained above. In particular, the compounds of general formula I may find application in veterinary and animal husbandry as well as in public health in the fight against arthropods, helminths or protozoa that parasitize internally or externally on vertebrates, in particular warm-blooded vertebrates, such as humans animals, ie cattle, sheep, goats, horses, pigs, poultry, dogs and cats, eg Acarina, including ticks (eg Ixodes spp., Boophilus spp. egBoophilus microplus, Amblyomma spp., Hyalomma spp., Rhipicephalus spp. eg Rhipicephalphusph. appendiculatus, Haemaphysalis spp., Dermacentor spp., Ornithodorus spp. (eg Ornithodorus moubata and worms (egDamalinia spp., Dermahyssus gallinae, Sarcoptes spp, eg Sarcoptes scabiel, Psoroptes spp., Chorioptes spp., Chorioptes spp., Chorioptes spp.) ,); Diptera (eg Aedes spp., Anopheles spp., Musca spp., Hypoderma spp., Gasterophilus spp., Simulium spp.); Hemiptera (eg Triatoma spp.); Phthirapter (egDamalinia spp., Linognathus spp.) ; Siphonaptera (egCtenocephalides spp.); Dictyoptera (egPeriplaneta spp., Blatella spp.); Hymenoptera (egMonomorium pharaonis), for example against infections of the gastrointestinal tract t caused by parasitic maggots of nematodes, for example members of the family Trichostrongylidae, Nippostrongylus brasiliensis, Trichinella spiralis, Haemonchus contortus, Trichostrongylus colubriformis, Nematodirus battus, Ostertagia circumcincta, Trichostrongylus axei, Cooperia spp.and Hymenolepis Pope for the control and treatment of diseases

123 caused by protozoa, for example Eimeria spp. e.g. 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., Toxopylasma and spp. spp., for the protection of stored products, for example, cereals, including grain and flour, peanuts, animal foods, timber and household goods, for example, carpets and textiles against attack by arthropods, in particular beetles, including cereals, moths and worms Ephestia spp. (flur moths), Anthrenus spp. (carpet beetles), Tribolium spp. (flur beetles), Sitophilus spp. (grain weevils) and Acarus spp. (mites) for the control of cockroaches, ants and termites and similar arthropod pests in attacked domestic and industrial premises and for the control of mosquito larvae in waterways, wells and reservoirs or other running or standing water; for treating foundations, buildings and soil in order to prevent them from invading termites, for example Reticulitermes spp., Heterotermes spp., Coptotermes spp. in agriculture against adults, larvae and eggs of Lepidoptera (butterflies and moths) e.g. Heliothis spp., Such as Heliothis virescens (tobacco budworm), Heliothis armigera in Heliothis zea, Spodoptera spp. such as S. exempta, S.littoralis (Egyptian cotton worm), S.eridania (southern army worm), Mamestra configurata (bertha army worm); Earias spp.e.g. E.insulana (Egyptian bollworm), Pectinophora spp.e.g.Pectinophora gossypiella (pink bollworm), Ostrinia spp., Eg O.nubilalis (European cornborer), Trichoplusiani (cabbage looper), Pieris spp. (cabbage worms), Laphygma spp. (army worms), Agrotis and Amathes spp. (cutworms), Wiseana spp. (porina moth), Chilo spp. (rice stem borer) Tryporyza spp.and Diatraea spp. (sugar cane borers and rice borers), Sparganothis pilleriana (grape berry moth), Cydia pomonella (codling moth), Archips spp. (fruit tree tortrix moth), Plutella xylostella (diamond back moth) against adults and Coleoptera larvae (beetles)

124

egHyrothenemus hampei (coffe berry borer), Hylesinus spp. (bark beetles), Anthonomus grandis (cotton boll weevil), Acalymma spp. (cucumber beetles), Lema spp., Psylliodes spp., Leptinotarsa decemlineata (Colorado potato beetle), Colorado potato beetle) spp. (corn rootworms), Gonocephalum spp. (false wire worms), Agriotes spp. (wireworms), Dermolepida and Heteronychus spp. (white grubs), Phaedon cochleariae (mustard beetle), Lissorhoptrus oryzophilus (rice water weetil), rice water weevil) (pollen beetles), Ceutorhynchus spp., Rhynchophorus in Cosmopolites spp. (root weevils); against Hemiptera egPsylla spp., Bemisia spp., Trialeurodes spp., Aphis spp., Myzus spp., Megoura viciae, Phylloxera spp., Adelges spp., Phorodon humuli (hop damson aphid), Aeneolamia spp., Nephotettix spp. rice leaf hoppers), Empoasca spp., Nilaparvata spp., Perkinsiella spp., Pyrilla spp., Aonidiella spp. (red scales), Coccus spp., Pseucoccus spp., Helopeltis spp. (mosquito bugs), Lygus spp., Dysdercus spp., Oxycarenus spp., Nezara spp. Hymenoptera e.g. Athalia spp. and Cephus spp. (saw flies), Atta spp. (leaf cutting ants); Diptera e.g. Hylemyia spp; (root flies), Atherigona spp. in Chlorops spp; (shoot flies), Phytomyza spp. (leaf miners), Ceratitis spp. (fruit flies); Thysanoptera, for example Thrips seedlings; Orthoptera, for example Locusta in Schistocerca spp., (Locusts) in crickets e.g. Gryllus spp., In Acheta spp .; Collembola e.g. Sminthurus spp.u Onychiurus spp. (Springtails), Isoptera e.g. Odontotermes spp. (Termites), Dermaptera e.g. Forficula spp. as well as other arthropods relevant for agriculture, eg Acari (mites) e.g. Tetranychus spp .; Panonychus spp.u Bryobia spp. (Spider mites), Eriophyes spp. (Gall mites), Polyphagotarsonemus spp .; Blaniulus spp. (Millipedes), Scutigerella spp. (Symphilids), Oniscus spp. (Woodlice) in Triops spp .; nematodes that attack plants and trees essential to the holding, forests and vegetable gardens, either directly or through the spread of bacterial, viral, mycoplasma or fungal diseases of plants, nematodes of the species Meloidogyne javanica such as

125

Meloidogyne spp. (E.g. M.incognita); Cyst nematodes, such as Globodera spp. (E.g. G.rostochiensis); Heterodera spp. (E.g. H. avenae); Radopholus spp. (E.g. R.similis) damaging nematodes, e.g. Pratylenchus spp. (E.g.P.pratensis); Belonolaimus spp. (E.g. B.gracilis); Tylenchulus spp. (E.g. T.semipenetrans); Rotylenchulus spp. (E.g. R.reniformis); Rotylenchus spp. (E.g. R.robustus); Helicotylenchus spp. (E.g. H.multicinctus); Hemicycliophora spp. (E.g. H.gracilis); Criconemoides spp. (E.g. C.similis); Trichodorus spp. (E.g. T.primitivus) puncturing nematodes, eg Xiphinema spp. (E.g. X.diversicaudatum), Longidorus spp. (E.g. L. elongatus); Hoplolaimus spp. (E.g.

H.coronatus); Aphelenchoides spp. (E.g. A.ritzema-bosi, A.bessevi) nematodes on stems and bulbs, for example Ditylenchus spp. (E.g. D.dipsaci) =

Other pests that can be attacked with the compounds of the invention are from the Isopoda subclass, for example Oniseus asellus, Armadillidium vulgare u Porcellio scaber, from the Diplopoda subclass, e.g. Blaniulus guttulatus, from the Chilopoda subclass, for example Geophilus carpophagx u Scutigera spe Symphyla subclass, eg Scutigerella immaculata, Thysanura subclass, e.g. Lepisma saccharian, Collembola subclass, eg Onychiurus armatus, Orthoptera subclass, e.g. , Locusta migratoria migratorioides, Melanoplus differentialis u Schistocerca gregaria, from a subclass of Dermaptera, for example Forficula auricular ia, from the Isoptera subclass, for example Reticulitermes spp., from the Anoplura subclass, e.g. Phylloxera bastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. u Linognathus spp., from the subclass of Mallophaga, for example Trichodectes spp. u Damalinea s., from the subclass of Thysanoptera, eg Hercinothrips femoralis u Thrips tabaci, from the subclass of Heteroptera, eg Eurygaster spp., Dysdercus imtermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp, from the subclass of Coleoptera,

126 e.g. , Otiorrhynchus sulcatus, Cosmoplites sordidus, Ceuthorrhynchus assimilis, Hupera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Maligethes aeneus, Ptinus sppuc, Niptus sppuc, Niptus spp. Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis u Costelytra zealandica, from a subclass of Hymenoptera, eg Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis u Vespa spp., Vespa spp. e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Callip chora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanritus, Phorinbioritus, Phorinbia, Oscinella spp., Pegomyia hyoscyani, Ceratitis capitata, Dacus oleae u Tipula paludosa, from the subclass of Siphonaptera, e.g. tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosettaspus cepus, cephospitus cepus, cephosephus pepus, cephosppetus cepus, cephosephus pepis, cephosepatus cepus, cephosepatus cepus, cephosepatus cephas, cephosephus pepis corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp ., in Psylla spp., from the subclass of Lepidoptera, eg Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis

127 chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistia citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Matestra brassicae, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestiakuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura magnumiferaiforaififerana fumiiferaifiiferaififa

The invention also relates to a method for the control of arthropods or nematode pests in plants, which involves applying to the plants or their habitat an effective amount of a compound of general formula I.

In the control of arthropods and nematodes, the active compound is usually applied at the site of attack by the arthropods or nematodes in an amount of from about 0.005 kg to about 15 kg of the active compound per 1 ha of the treated area, preferably from 0.02 kg / ha to 2 kg / ha. Under ideal conditions, depending on the pests being fought against, a lower application rate may offer the same protection. On the other hand, adverse weather conditions, pest resistance and other factors can lead to higher doses of the active substance being administered. For foliar treatment, the rate is from 0.01 kg to 1 kg / ha. The optimal dose usually depends on the type of pest to be combated, as well as the type and stage of development of the attacked plant, the width of the row and also the method of administration.

When the pest is born in the soil, the composition containing the active compound is spread evenly over the area to be treated.

128 can be handled in any convenient way. If desired, the application may generally occur on the field or on the area on which the plants or plants grow, or directly on the seeds to be protected from attack. The active substance may be washed on the soil by spraying with zod over the surface or may be left to the natural action of rainfall. During or after application, the formulation may, if desired, be dispersed mechanically in the soil, for example, in plow or disk treatment. Application may take place before planting, at planting itself., after planting, but before sprouting or after sprouting.

The compounds of general formula (i) may be applied in solid or liquid formulations to the soil, in principle, to combat those nematodes that inhabit the soil, as well as to the leaf surface, in principle, parts of plants / e.g. is / ·.

to combat those nematodes that attack the aboveground ones

-listed

The compounds of general formula (I) may also be valuable for controlling pesticides fed on those parts of the plant that are farther from the site of application, for example. Insects feeding on: t leaves ^ are killed by administration of the compounds of the invention to the roots of the plant. In addition, said compounds may reduce the attack on the plants by an anti-nutritional or repellent effect.

The compounds of general formula (I) are of particular importance for the protection of fields, fodder, plantations, greenhouses, orchards and vines, ornamental plants and trees in plantations and forests, for example cereals such as, for example, king, wheat, rice, sorghum, p amouk, tobacco, husks and salads, such as, for example, beans, beans, spruce, lettuce, lettuce, onions, tomatoes and peppers, field crops .. such as for example, to artofi, sugar

- 129 beets, peanuts, soybeans, oilseed rape. , sugarcane, pastures and fodder such as corn, sorghum, alfalfa, 'plantations' such as tea, coffee, cocoa, banana, oil palm, coconut palm, rubber, spice, orchards and groves such as ,! fruit and citrus fruits, citrus and fruit, kiwi, avocado, mango, melinas and nuts, -, vineyards, ornamental plants, flowers and vegetables and shrubs in greenhouses and in *

gardens and parks, forest trees. both deciduous and evergreen in forests, plantations and nurseries.

They are also valuable for the protection of timber «/ upright, fallen, reclaimed, stored, or construction, from wasp leaf attack / eg, / or beetles / eg, SCO did s tyctld $ ioshy ch 'idSj ceramtyc idspnolirds / or termites, for example, Rilicuil-ierwes Utieroiemti Co / ifiirmes y> />.

They have an application for protecting stored products such as cereals, fruits, nuts, spices and tobacco, be it * * t?

whole, milled or processed into products, from moths, beetles, worms and cereals (SihphiiuPyranjFius) attack. Also stored animal products such as hides, skins and wool in natural or processed form, such as carpets or textiles. 'from the attack of moths and beetles; also stored meat and fish from attack by beetles, worms and flies.

The compounds of general formula '1' may be particularly valuable for the control of arthropods, helminths or protozoa that damage or disseminate or act as carriers of diseases in humans and domestic animals, such as those mentioned above, in particular for the control of churl hedgehogs, worms, in aphids, fleas, alcoves and bivalves, insects and flies. The compounds of general formula (ί) are especially valuable for combating arthropods, helminths or protozoa that exist within domestic hs us, appearing as stoppers, or eating at or on the skin or drink the blood of animals for which the compound 's purpose may be administered orally, enterally, through the skin or topically.

Coccidiosis * a disease caused by infection by the protozoan parasites of the genus £ / mend, in a vacheal potential cause of economic loss for breeding but domestic animals and birds, especially for those kept or kept under intensive conditions.For example, large cattle, sheep, pigs and rabbits may be affected, but the disease is of particular importance in poultry, in particular chickens.

the disease in poultry is mainly transmitted by birds that peck infectious organisms in excrement located on contaminated mats or land, either through food or by drinking water. Symptoms of the disease are blood from barley, accumulation of blood in the caecum, haemorrhage in eccentricity, shortness of breath and digestive disorders. The disease often ends with the death of the animal, but those birds that survive the cruel infection ^ have their market value, albeit substantially diminished by the infection.

Taking a small amount of the compound of the general formula. I /, preferably in combination with poultry feed, has the effect of 7 in preventing or significantly reducing the defeat of coccidiosis. The compounds are effective against both forms of the caecum / caused by the bowel / by

E. awrvutinj, E. irune-Ui, E. pmmhpd and the principle caused by

E.

The compounds of general formula (ί) also exert an inhibitory effect on the oocytes, greatly reducing the number and / or spore formation of those already produced in the body.

The compositions described below ^ for lucrative use in humans and animals and for the protection of stored products, household goods, farms and environmental areas, in general, may alternatively be used for application to growing crops and their living environment and as seed coat, Suitable means of administering the compounds of general formula (ί) are:

13! for humans or our lives, met with or exposed to infection by arthropods, helminths or protozoa, by the lateral, oral or topical administration of a constituent whose active substance exerts an immediate and / or prolonged action over a period of time against arthropods, helminths or protozoa, e.g. , by incorporation into food or in the form of suitable pharmaceutical formulations for oral administration, edible baits, licking salts, dietary supplements, single dose liquid formulations, sprays, baths, disinfectants, showers, st ruins, powder, gas, shampoos, ointments, paraffin-based products, and self-medication systems in livestock; generally to the environment or to certain places where pests are hidden, including stored products, timber, household goods and domestic and industrial premises, in the form of sprays, fogs, powders, smokers, based lubricants; vapor, lacquers, baits and lures, and as aaa thin stream in waterways, wells, reservoirs and other running or standing water; to domestic animals in their feed to combat the larvae of flies feeding on faeces; to growing crops in the form of sprays, powders, granules, mists and foams, as well as suspensions of finely dispersed and k-shaped compounds of the general formula (i) for the treatment of soil and roots with liquid doses of the composition, powders, granules, smokers and foams; and as a seed coat with liquid dense suspensions and powders.

The compounds of general formula (i) can be used to combat; with arthropods, helminths or protozoa in compositions of any kind which are known and which are suitable for internal or external ingestion; initiate or adapt to combat arthropods in any premises or interior or exterior, formulations containing as active

132 substance at least one compound of general formula (1), together with one or more compatible diluents or additives that are suitable for the purpose. All of these compositions can be prepared according to conventional methods in the art.

Formulations suitable for administration to vertebrate animals or humans include formulations suitable for oral, parenteral, transdermal, for example, single liquid doses or topical administration.

Formulations for oral administration include one or more compounds of general formula (ί), together with pharmaceutically acceptable carriers or coatings, and include, for example, tablets, dragees, capsules, pastes, gels, for irrigation, medicated foods, medicated drinking water, medicated dietary supplements, slow-release boluses, or other slow-release devices, front; Any of these formulations may include the active substance, enclosed, in microcapsules or covered with acidic or alkaline or other pharmaceutically acceptable intestinal coatings. use nutritional mixtures and concentrates containing compounds of the present invention for use in formulations intended for medical diets, drinking water or the like for animal consumption.

Compositions for parenteral administration include solutions, emulsions or suspensions placed in any suitable pharmaceutically acceptable carrier and solid or semi-solid tubes, subcutaneously or tablets intended to release the active substance over a long period and may be made sterile in any way that is known in the field '.

Compositions for transdermal and topical administration include sprays, powders, baths, disinfectants and, showers, jets, greases, shampoos, creams, paraffin-based lubricants, or liquid single dose formulations and devices (e.g., ear pads /, when attached to the animal in such a way as to exercise systemic control over the arthropods.

Liquid or solid baits suitable for combating arthropods contain one or more of the compounds of general formula (i) and carrier or diluent, which may contain a nutrient or other substance that may be aroused by the arthropods. In practice, ряд agriculture rarely uses the compounds of the invention on its own. More often, these compounds are included in compositions. These compositions, which are used as insecticides, contain a compound of the invention as described above. pellets, as active ingredient together with solid or liquid carriers and surfactants acceptable for agriculture are also acceptable for agriculture. In particular, conventional carriers and surfactants may be used. These compositions are also within the scope of the invention.

These compositions may also contain any type of other ingredient and, for example, colloid protectants, adhesives, thickeners, thixotropic substances, penetrants, insecticidal oils (especially mite control agents), stabilizers, preservatives / especially those resistant to molds / binders or the like and other known active substances with pesticidal properties (especially insecticides or fungicides) or with plant growth regulating properties In general, the compounds used in the invention jMO gram atom be combined with any solid or liquid additives corresponding to the usual formulation techniques.

The norm for use of the compounds by from the design var ir a in a wide range ato the same h it depends especially by nature of harm— la who needs to Yes se destroy _? and of degree on infecting growth is—

tion with these pests.

In the community, make up. Based on the design of a new content of 134 substances according to or from

6.1 to 50% of one or more surfactants.

compliance with what has already been said _; compounds used or an inorganic substance, natural or synthetic, with which the active substance, seeds or soil.Therefore, this carrier is generally inert and must be acceptable to agriculture, especially the treated plant. * The carrier may be solid / clay, natural or synthetic silicates, silicon, resins, paraffins, solid fertilizers, eg milling, ammonium salts, and naturalUminerals, such as kaolins, clays, alkali, in aromatic, quartz, attapulite, montmore, or onit, b entonite, or infuser soil and synthetic ground materials, such as silicon, alumina, silicates, in particular, aluminum or magnesium. Suitable solid carriers for the formulation of granules are: crushed and fractured natural rocks, such as, for example, k alcite, mr amor, n emsa, sepiolite and dolomite, including synthetic granules of inorganic and organic flours, and granules of organic material such as bran, walnut shells, corn cobs, tobacco stalks; kieselguhr, maize leaf, tricalcium phosphate, cork powder, soot as absorbent and water-soluble polymers, resins, paraffins, solid fertilizers and such compositions may optionally contain one or more compatible wetting, dispersing, emulsifying or coloring agents which, if solid, may also serve as a diluent. The carrier may also be liquid: alcohols, especially butanol or glycol, as well as their ethers or esters, especially methylglycol acetate; quitones, in particular acetone, cyclohexane, methyl methyl ketone, methyl isobutyl ketone and isophorone;

petroleum fractions; paraffinic or aromatic hydrocarbons, in particular xylenes or alkylnaphthalenes, petroleum fractions, mineral and vegetable oils; aliphatic chlorinated □ hydrocarbons, ps-specs, trichloroethane or

1.35 ~ methylene chloride, or aromatic chlorinated in carbon units, in particular hdbenzenes; water soluble or highly polar solvents, such as dimethyl ilformamide, dimethyl sulfoxide or N-methylpyrrolidone, as well as water; liquefied gases and the like

The surfactant and mixtures can of these substances.

be emulsifying, dispersing or wetting of ionic or non-ionic type or a mixture of surfactants a.These may be, for example, salts of polyacrylic acids, salts and lignosulfonic acids, salts of phenolsulfonic or naphthalenesulfonic acid fatty waste oxide, fatty acids or fatty esters or fatty amines, substituted phenols (in particular alkylphenols or arylphenols), sulfoic acid esters, taurine derivatives (in particular alkyl alkylurates), phosphorous esters of alcohols of polycondensates of ethylene oxide with phenols, esters of fatty acids with _poliodi; and the sulfate, sulfonate and phosphate derivatives of said compounds. The presence of at least one surfactant is paramount when the active substance and / or excipient is only very slightly soluble in water or insoluble at all, and the carrier is water.

The compositions of the invention may further comprise various. additives such as, for example, adhesive and and, coloring agents, such as' carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latex, such as gum arabic, sex, can be used in the formulations. vinyl alcohol and polyvinyl 'acetate' as well as natural phospholipids, such as for example, kephadin and lecithin, and synthetic phospholipids. Other additives may be mineral and

136 vegetable oils. B. It may be possible to use coloring agents, such as inorganic pigments, for example, lime oxide, titanium oxide and Berlin blue, and organic dyes such as alizarin dye, azo dyes, and metal ft alcyninsine. b Agils, κοκτο, and small amounts of nutrients, such as iron salts, manganese, boron, cobalt, molybdenum, and zinc.

Compositions containing compounds of general formula (ΐ) that are used to control arthropods, plant-free, helminths, or protozoal pests? May also contain synergists (eg, piperronyl butylate or sesamex), stabilizers, other insecticides , acaricides, nematocides for plants, anthelmintics or anticoxidicides, fungicides / agricultural or other, eg, benomyl, iprodio /, bactericides that attract or repel substances or arthropods, or pheromones, or arthropods scented in more dyes, dyes, and auxiliary therapeutic agents, for example, micronutrients. They may be designed to increase the potency, resistance, safety, absorption, if necessary, of the range of pests to be combated? or to give composition other beneficial properties: for the same object of treatment or treatment.

Examples of other pesticide-active compounds that may be included in, or used in conjunction with, the compositions of the present invention are: acephate, chlorpyrifos, demeton - $ - methyl, disulfoton, etoprofos, phenyltrot ion, mel ation , moscow rotofos, nar at ion, fez al o n, p irigpifos-methyl, triazophos, digit mornings, cyper metrin, deltamethrin, fenpropatrin, fenval erat, p ermethrin, aldic arb, carbosulfan, metomil, oxamil, pirim endioc arb, tefl ub enzuron, dic offol, endosul fan, l indan, b enoximat, potato, cihixatin, tetradifon, avermectins , ivermectin, milbemycin, thiophanate, trichlorphone, dichlorvos, diaveridine and dimethiadazole.

For its application in agriculture. the compounds of general formula 1 'are therefore generally in the form of compositions which

137 may have different solid or liquid forms. Liquid formulations may be used to treat substrates or bridges, loaded and or attacked by arthropods, including rooms, and outdoor or enclosed storage or work spaces, a container and or facilities and standing or running water.

Solid homogeneous or heterogeneous compositions containing one or more compounds of general formula (I), for example, granules, tablets, briquettes or capsules, can be used to treat water (standing or flowing) for a certain period of time. is obtained by using trickle-fed or periodically fed foods consisting of the water-dispersible concentrates described above.

The formulation of aerosols and aqueous and non-aqueous solutions or dispersions which are suitable for dispersion, fog formation and low- and small-volume dispersion may also be used.

The solid forms of the compositions which may be mentioned are powdering powders / containing a compound of general formula I capable of varying up to 80% / or wettable powders or granules, especially those 'obtained by erosion, for example, imp is the granulation of the carrier in the form of granules, or granulation starting from the powder material / content of the compound of the general formula

I in these wettable powders or granules is in the range of 0.5 to 80%.

Solutions, in fairness, emulsifiable concentrates, free-flowing emulsions, aerosol and wettable powders / or spray powders / free-flowing dry compositions and pastes, may be referred to as formulations which are liquid or intended to form liquid compositions in their application.

Most often, emulsifiable or soluble concentrates contain from 5 to 80% active ingredient while ready for use.

- 138 л mulsions or solutions contain from 0.01 to 20% of the active substance. In addition to the solution, emulsifiable concentrates contain, if necessary, 2 to 30% of suitable additives, such as stabilizers, surface-active agents, penetrating substances. , corrosion inhibitors, or dyes.

By dilution is water the concentrates can produce any suitable plant-based concentrations. »The concentrated suspensions, which can be sprayed, are prepared in such a way as to constitute a stable, non-precipitating / finely ground liquid product. and usually contain from 10 to 75% of the active substance, from 0.5 to 30% of the surfactant, from 0.1. up to 10% thixotropic substance, from 0 to 30% suitable additives such as antifoams, corrosion inhibitors, stabilizers, penetrants, adhesives and as a carrier - water or organic liquid in which the active substance is almost insoluble or insoluble, some organic solids or inorganic salts may be dissolved in the carrier to prevent precipitation or as antifreeze to water.

Wetting powders / or spreading powders / are generally prepared to contain from 10 to S0% active substance and, in addition, typically contain from 0 to 5% wetting agent to the solid carrier, from 3 to 10% dispersant and, if necessary, from 0 to o U, д is из in и and more из из из из ат и / / / and / or other / < , Etc к к н π н,,,,, ващи,,,,,,,,,,,,,,,,,,,,,,,,,

In order to obtain these wettable powders, the active substance or substances are used. mixes / watt very well in suitable mixers with additional substances that can be impregnated on a porous filler and is / are / ground in a mill or other suitable crusher.Thus, wettable powders are obtained, wetting ability. and the suspending properties of which they are useful; they can be suspended in water to obtain any desired concentrations and these suspensions can be used very advantageously, in particular for application to the foliage of plants.

In dispersible granules (VDG) / granules that are easily dispersible in water / have a very similar composition to that of the wettable powders. They can be prepared by granulating the formulations described above * for wettable powders, or by wet method / comprising shredding the active substance with the excipient and, in a small amount in the ode, for example, from 1 to 20%, go with an aqueous solution of the dispersing agent or binder, then dry and sift / or by dry method / pressing, and then grinding and sieving /.

As already stated, aqueous dispersions and emulsions, for example, compositions obtained by dilution with water, wettable powder or emulsifiable concentrate according to the invention are included in the main scope of the invention. Emulsions can be of the type water-in-oil or oil-in-water , and have a thick texture.

All of these aqueous dispersions or emulsions or spreading mixtures may be applied to the cultures in any suitable manner by any suitable means, preferably by spraying, and at rates generally ranging from 100 to 1200 l of the spreading mixture / ha.

The products and compositions according to the invention are conveniently applied to the vegetation and in particular to the roots or leaf which are attacked by pests.

Another method of administering the compounds or compositions of the invention is by chemisation, which means adding the formulation containing the active substance to the irrigation water.

irrigation can be irrigated with a rain machine for the leaves of 140 children. The dosage for administration of the active substance is generally in the range of 0.1 to 10 kg / ha, preferably between 0.5 and 4 kg / ha. vary according to the method employed and the nature of the compositions used.

Generally speaking, compositions used to control arthropods, plant nematodes, holmines, or protozoan pests typically contain from 0.00001 / to 95%, in particular from 0.0005% to 50% / weight / one or more compounds of general formula (i) or all active ingredients (i.e. compounds of the following formula (i), together with other substances that are toxic to arthropods and plant nematodes, anthelmintics, anticoxidicides, trace elements or stabilizers / «In practice, the compositions used and their application rates will be selected in order to achieve the desired (s) / effect / s / of agricultural workers, breeders, veterinarian or humane doctor responsible for pest control or any other person familiar with this common issue. Hard and liquid formulations for use in animals, timber, stored products and household goods typically contain from 0.00005% by weight to 90% by weight, in particular from 0.00T to 10% by weight of one or more compounds of the general formula / l For oral parenteral or administration to animals, including transdermally, solid and liquid formulations typically contain from 0.1 to 90% by weight of one or more compounds of general formula I .. Medicaments normally contain C, 001 to 3 % by weight of one or more compounds of the general formula. I, "Concentrates and additives intended to be mixed with foodstuffs typically contain from 5 to 90% by weight, preferably from 5 to 50% by weight of one or more compounds of general formula (I). Mineral licking salts normally contain from 0 , 1 to 10% by weight of one or more compounds of general formula I

141. Powders and precision formulations for administration to animals, humans, goods, premises or outside areas may contain from 0.0001 to 15% by weight / and in particular from 0.005 to 2.0% by weight of one or more compounds of general formula / i /. Appropriate concentrations for treatment with water are between 0.0001. ppm and 20 ppm, and in particular from 0.001 ppm to 5.0 ppm, of HCV or more of the compounds of general formula (I), the same can be used therapeutically in fisheries with appropriate exposure time. contain from 0.01 to 5% by weight, in particular from 0.01 to 1.0% by weight, of one or more compounds of the general formula (i).

When administered parenterally, orally, transdermally or otherwise to vertebrates, the dosage of the compounds of the general formula (1) will depend on the type, age and health of the vertebrates, as well as the nature and extent of their actual infection with arthropods, helminths or protozoal pests. For oral or parenteral administration, a single dose of 0.1 is generally suitable. to 100 mg, preferably 2.0 to 20.0 mg per 1 kg live weight of the animal, or doses of 0.01 to 20.0 mg, preferably 0.1. up to 5.0 mg per T kg live weight of the animal in order to maintain treatment.Using dose-controlled formulations or devices for the same purpose, the required daily doses over a period of months may be combined and given the animal in a single dose.

The following specific embodiments illustrate the agrochemical compositions comprising the compounds of the invention and further the insecticidal and acaricidal applications and properties of certain compounds

142

ΠΡί / ΙιΊΕΡΗ / ϊ IMPLEMENTATIONS OF THE COMPOSITIONS / FORMULATIONS / Formulations for use against arthropods, in particular insects and arachnids, plant nematodes and helminths or protozoan mules (i), ps-sp.

The compositions described in up to 28 can be dissolved in water to form compositions that can be sprayed at a concentration suitable for this purpose. The general chemical description of the ingredients / which are given only by weight, used in the exemplary embodiments of compositions Nos 23 to 28 below is as follows:

Ethyl BRS non-phenylethylene oxide condensate Sunflower Β $ ϋ condensate of tritylphenyl and ethylene oxide Arylan SA 70% w / v calcium dodecylbenzenesulfonate solution Solveso 150 a light C 1-4 aromatic solvent Arylan S sodium dodecylbenzenesulfonate Darvan Selit WG sodium lignosulfonate synthetic magnesium silicate - as carrier Sopropon TZb polycarboxylic acid sodium salt Parent 23 polysaccharide on xanthan gum Benton 38 an organic derivative of magnesium montmorillonite Aerosil microparticle size silica EXAMPLE 23. k

A water-soluble concentrate is obtained from; Active ingredient 7% Ethyl BSR 10% M-Methyl pyrrolidone 83%

- 143chrez dissolving the Ethylan BCP in a portion of the Pi-methylpyrrolidone, followed by addition of active veshtestoo, the mixture stirred and heated sv ^ until complete raztvaryane.Pol scientist solution was made up to _l Yu0r

An emulsifiable concentrate is obtained from:

Active substance

Soprofor 5SV

Arylan SA

7%

4%

4%

N-Methylpyrrolidone

50%

Solveso 150

35% by dissolution of Soprofor Arylan

CA and the active substance in Solveso 150 until filled

FOR MEASURED IMPLEMENTATION 25.

Wetting powder is obtained from:

40 /%

Arylan 5

2%

Darvan # 2

Celite PF

53% by mixing the ingredients and grinding the mixture in a hammer mill to a particle size _? no less than 50 microns.

FOR MEASURED IMPLEMENTATION 26.

free flowing formulation solution is obtained from:

Active substance· 40,00% 'Ethylene In CP 1.00% Sopropon TZb 0.20% Ethylene glycol 5.00% Parent 23 0.15% Water 53,65%

η <Ο * Χί

144 by intimately mixing the ingredients and grinding them in a ball mill, while the average particle size of the stanza is less than 3 microns, EXAMPLE 27,.

An extulsible suspension concentrate is obtained from:

Active substance 30.0%

Ethyl BSR 10.0; s

Benton 38 0.5%

Solveso 150 59.5% by intimately mixing the ingredients and grinding them in a ball mill until the average particle size is less than 3 microns, EXAMPLE 28>

Water-dispersible granules are obtained from:

Active substance 30%

Darvan 012 15%

Art plan S 8%

Celite PF 47% by mixing the active constituents and micronizing them in a mill using fluid energy and then granulating in a rotary granulator by spraying by spraying the mixture on water in sufficient amount of water (up to 10% by weight / volume). the granules are dried in a fluid bed dryer in order to remove excess water.

EXAMPLE 29.

Sprinkling powder can be obtained by intimate mixing of:

Active substance 1. up to 10%

Talc - finely ground 99 to 90%

This powder can be applied to the site of attack by arthropods, for example, landfills, stored products or household goods or infected or attacked pest animals, or where there is a significant risk of attack by arthropods to combat arthropods by oral

Appropriate means of spreading the powder for arthropods sprinkled on the site of attack are mechanical ventilators, handhelds and self-healing devices in animal husbandry.

for example, fulfilled zo.

lure can be obtained by intimate mixing of: Active substance 0.1 dc 1.0%

Wheat flour 30%

Molasses 19.9 to 19.0%

This edible bait can be spread over the place, for example, in domestic and industrial premises, ie. kitchens, hospitals or warehouses, or outside areas, also attacked by arthropods, such as ants, grasshoppers, cockroaches and flies, by oral administration to combat arthropods * EXAMPLE 31,

A solution can be obtained from:

Active substance 15%

Dimethyl yl sulfoxide and 3 5% by dissolving the pyrrole derivative in a portion of dimethylsulfoxide and then adding more dimethyl sulfoxide to obtain the desired volume. This solution can be administered to domestic animals attacked by arthropods but as a single liquid dose ·· as an application, or after sterilization by filtration through a polytetrafluoroethylene membrane (0.22 μm pore size), by parenteral injection, at a rate of administration of 1.2 up to 12 ml solution per 100 kg live weight of the animal.

EXAMPLE 32 *

Wetting powder can be prepared by:

Active substance 50%

Ethylene HRV / 9 mole oxide per 1 mole phenol / 5%

Aerosil 5%

Celite R $ 40%

- 146 ppm absorbed on Ethylene BWR to Drorozila, κετο is mixed with the other ingredients and ground in a hammer mill to give a wettable powder that can be dissolved in water to a concentration of C, 001% to 2% by weight / volume ea is actively fused and applied at the site of attack by arthropods, for example, larvae of bivalve insects or plant nematodes by spreading, or attacked domestic animals by, or at the risk of attack by arthropods, helminths or protozoan pests by dispersal or desis fecs or by oral administration in drinking water to combat arthropods, helminths or protozoa.

EXAMPLE 33.

Slow release boluses of the active ingredient can be obtained from granules containing a thickener, binder, slow release agent and active ingredient according to example embodiment 27 when swirled with% of the composition. By pressing the mixture;

obtains a bolus with a specific gravity of 2 retention in the reticulo-gut of the stomach in order to obtain a prolonged slow release of the oral compound for a prolonged period of time in order to combat arthropods, helminths or protozoa that attack ruminants

EXAMPLE 34, Slow-dose formulation may be obtained from:

Active substance

0.5 to

2t— to

99.5% by associating the polylinyl chloride base with the active suitable plasticizer, for example, dioctyl phthalate, H compression molding or the homogeneous composition melt in suitable forms, for example, granules, tablets, briquettes or strips, suitable for example to add to standing water or when in the form of stripes (l ents), cooking poultry such as collars or ear earrings for attachment to pets to combat insectitis by slowly releasing the active agent.

- 147 i

substance.

Such compositions may be prepared by substituting the active substance in the exemplary embodiments for compositions with an appropriate amount of another compound of general formula (I) »

EXAMPLE IMPLEMENTATIONS FOR COMPOUNDS USED FOR PESTICIDE CONTROLS.

In the following embodiments 35 to 47, the compounds according to the invention are administered at different concentrations. The use of 1 ppm / concentration of the compound in parts per million of the test solution / solution, suspension or emulsion used for foliar application corresponds approximately to the administration of 1 g / ha of active ingredient, based on an approximate dispersal volume of W00 l / ha / sufficient for. leakage /.- Thus in the following fox sprays; however, application of a concentration of about 6.25 to 500 ppm corresponds to about 6 - 500 g / ha. In soil treatment, 1. ppm concentration / based on about 7.5 cm soil depth, corresponds to approximately 1000 g / ha, field spread application.

EXERCISE 35 .. '

Activity against AphLib

A mixture of:

- 0.01 g of active substance - 0.16 g of dimethylformamide

- 0.338 g of acetone

0.002 g of surfactant mixture, containing both aryl aryl-polyether alcohol and alkylaryl polyether alcohol with a sulfone group on the aryl moiety.

93.99 g of water

This water-soluble mixture is sprayed on low-growing potted plants grown on adults and larvae under incomplete conversion.

Ara / $ ndslurli <.The number of the latter for the 1st pot is 100 - 150.

148 The volume of the water mixture to be sprayed is sufficient to wet the plants until it has drained from the vessel. After spreading, the pots were kept at 20 ° C for 1 day, after which the remaining living PZs were counted. Rate _H and the mortality was 100 for the compounds of embodiments 1,2, ON, 4,5,1.68,17,18,19,20 and

28.1 30.131.1 35.1 37 j.141., 142, 1.44.1 57.1 58.1 62.16 5.166 and 1.74 at a concentration of 100 ppm.

PRINTER IMPLEMENTATION 36 «.

Worm activity /

The same formulation procedure is used as in the exemplary embodiment. 35. But in this case 150-200 two-spotted worms are bred. / 7e4ranychn $> urlt with & / on green beans, After spreading, the plants are kept for 5 days at 30 ° C.

100% mortality for the compounds of Examples 2, 3A, 16B, 1.7 and

98,99,102., 124 and 141 at a concentration of 100 ppm »

EXAMPLES 37-39

Activity against Spocio [yief2

37; The wording of the embodiment 35 is used

In this case, second-stage larvae.

are bred on 15 cm high Ph ^ seotas lupins. After five days, the following% mortality is established: 108% mortality is obtained from the coupling of the compounds of exemplary! performances No. ZA, ST, 5,6, ^ 8, 9,

100

11,1 2,15B, 16B, 17,18,20,21, B, 21B, and DPS No. 42,44,60,62,64,98-100,102, 103,121,124,125,131,141,142,144,162,166 and 174 at ppm concentration; 80% mortality was obtained by administering the compound of Example 13 at a concentration of 500 ppm

38; The same formulation procedure is used as for the dimensional implementation 35, but in this case the content of the formulation in the case is as follows:

149

- 2.5 m active substance - 0, 05 d im et al fo r m am and e - 9,9228 g of acetone - 0,0247 d surfactant / as in example—

but performance 35 /

- 90 g water

The compound of Example 4 produces 100%

mortality on ^{J <} d at a concentration of 25 ppm.

39; 'The same formulation procedure as in the exemplary embodiment 38 ^ is used except that the composition is as follows.

- 0.625 mg of active substance

- 12.5 mg dimethylformamide

- 9,9621 g of acetone - 0,0247 d surfactant / as in example

version 35 / g water

The compounds of embodiments 1 and 2 elicit 100% mortality on $ at a concentration of 6.25 ppm.

EXAMPLES 40-43.

Activity on

EjA & Schfa} larvae are bred in the second age stage on Pkjseodus fungus with an approximate height of 15 cm. After five days 100% mortality of the compound from

41ί Using the formulation procedure of Exemplary 8, 100% fill-in mortality 38 is obtained, but as an active compound this _{? 1} of exemplary on rr * U.6 &

at a concentration of 25 ppm.

42; Using the formulation procedure of Example 15A (of which bromine is removed), a filler 35 is obtained, but the compound of the active ingredient is included.

150

100% mortality at 100 ppm.

43; The same formulation procedure is used as in example embodiment 40, but in this case.

- 10 mg of active substance - 0.2 g of dimethylformamide

- 9, 7657 acetone

-0.0243 g surfactant / as in example embodiment 35 /

- 90 g water

The following% fyrfachfrt VAn mortality is noted

85% mortality caused by the compounds of embodiments 15A and 15B _? at concentration. 100 ppm and 100% mortality induced by the compounds of exemplary embodiments 1,2,9,17,18 and MRF (Yp 42,44,50, 62,64,98,99,124,125,141,142 and 144 at a concentration of 100 ppm.

EXAMPLES 44-45.,

Activity on Mused domestic ^

The toxic substance, in the form of 10 ml of an aqueous sugar solution containing 10% by weight / weight of sugar and

100 ppm of the chemical toxicant is formulated in a similar manner to this filler 35. The following is a non-diluted series of dilutions, if necessary. The following test formulations are prepared:

44 45 .46 Active substance, mg 10 10 1,25 D im e t i l fo r m am e d, m g 160 200 25 Surfactant, mg 2.15 24.3 14,25 / as in Ex. 35 / Acetone, Mr 8.42 9,765 th most common 5.73 Boda, Mr 68.99 81. 84.38 Sugar, Mr 10 9 9.84

Twenty-five MuSCe flies in the age stage were anesthetized ^with CClc and then the toxic formulation. After% mortality as follows:

For coastal performance 44:

PRBNSYT 0

MGUia stay for 1 day at 27 ° C, id -

100% mortality of the compounds of exemplary embodiments 1,2,35,4-6,3, 9,16E, 17-20,21B and 21B and MRF No. 42 44,60,62,64,9 3,99,1.00, 1.02,103,1.21 124,125,131,141,142,144,1,62,166 and 1.74 at a concentration of 100 ppm.

100% mortality of the compound of Example 12 at a concentration of 100 ppm.

100% mortality for the compounds of the exemplary embodiments 1,2 and 5 at a concentration of 12.5 ppm.

For example embodiment 45:

For example embodiment 45:

D. EXECUTIVE IMPLEMENTATION 47.

Maize leaf activity on corn.

A formulation was obtained in a similar manner to that described in example 35 / way except that only 48.99 g of water was used to purify the test compound at a concentration of 200 ppm. Then aliquot portions were used directly of this formula is the concentration required for the test, in ppm (parts per million), following the following test procedure.

In a container containing clay-sand soil (60) an aliquot of the formulation of the test compound at 200 ppm was placed (as determined for the final concentration of test compound in soil), 3.2 ml of water and five scrapings in advance. sprouted corn seedlings, The container is shaken gently to obtain a good mix of the formula tested!

which is made in the soil by a trench.Afterwards, 20 eggs of leaves are laid in the hole.

152

Then, vermiculite (1 ml) and water (1.7 ml) were added to the opening.

In the same manner, the untreated control was prepared by applying the same aliquot in the oda-acetone-dimethylformamide (emulsifier; solution), which did not contain the test compound. Additionally, one treatment was used as standard for the test. control with a commercial technical product (compound), formulated in the same way After 7 days, count the larval larvae of the leafide using the well-known extraction method.

The following compounds cause 100% mortality at soil concentrations of 1.45, 0.72 and 0.36 ppm: Compounds of Example Embodiments 3B, 4 and 17-19 and DPS KZD2 9 3,99,101,10 5,11.3,119,121: , 124.1: 25.130 and 173.

Claims (15)

1. Pyrrole derivatives of the general formula c X / | Wherein X is selected from the group consisting of halogen, cyano, cyano, thiocyanato, haloalkyl, alkoxy, halo oenalkyl, alkylthio, alkylsulfinyl, alkyl sulfonyl, halo g, and more than thio, halo over k yl sulfinyl, halogvnalkilsulfonil, hal ogenalkilkarbonil, alkenylthio, alkenilsulfinil, adkvnilsul »sulfonyl, hal ogenalk enylthio, hal ogenalkenilsulfinil, hal ogenalkenilsulfo phenyl, haloalkyl iltiokarbonil, feniltiofenilsul alkylsulfinyl, phenylsulfonyl, x e teroariltio, heteroarilsul alkylsulfinyl and heteroarylsulfonyl; the phenyl groups being optionally substituted by halogen, cyano or. halogenoalkyl, I and the heteroaryl groups are five or six membered monocyclic rings containing one or two identical or different heteroatoms: oxygen, sulfur or nitrogen, and which heteroaryl groups are optionally substituted by halogen, nitro, cyano or halogenoalkyl, and wherein the alkyl or halo groups are alkyl. ogenalkyl, alkenide, halogenalkenyl, alkyloxy and haloalkoxy have a normal or branched chain and less than 10 carbon atoms. Replacement with halogen in all these groups means substitution with one or more halogen atoms which may be the same or different, from mono-substitution to full-substitution; , Rq, R ₂ ^and R _{3 are} independently and independently of one another selected from the group consisting of one of the substituents listed for X; a hydrogen atom, an alkyl group, and a substituent which may be only one of the three radicals R ^, R ^ or R ^ and is selected from the group consisting of: formyl, hydroxyiminoalkyl idenyl, adoxyiminoalkylidenyl, azido, amino , alkylamino, dialkylamino, aralkylamino, aminocarbonylamino, the alkyl carbonylamino, halogenalkilkarbonilamino, arylcarbonylamino, alkylsulfonic sulfonyl amino, halogenalkilsulfonilamino, alkyl amino carbonylamino, arilaminok carbonylamino, benzilidenimino, alk yl idenimino, alkoxyalkylideneimino, dialkilaminoalkilidenimino, bis / alkylthio / m til, bis / arylthio / methyl, alkylthioalkylideneimino, alkoxycarbonylamino, halogenalkoxycarbonylamino, phenyl, optionally substituted with halogen, cyano or halogen-alkyl, and a heteroaryl group of five or six membered monocyclic heterocycle , sulfur or nitrogen, and which heteroaryl groups are optionally substituted by halogen, nitro, cyano or halogenoalkyl; and where the group is alkyl, haloalkenyl, alkenyl, halo genalk is nil, halogen coke and alkane which have a normal or branched chain have less than 10 carbon I atom, and halogen substitution in all these groups means substitution by one or more halogen atoms, which may be the same or different, from mono, to complete poly substitution; ) y is selected from the group consisting of: halogen, cyano, alkyl, haloalkyl, alky, halogen, alkyloalkyl, sulphonyl, alkyl or sulphonyl, alkylthio, halogenoalkylthio, halogenoalkylsulfinyl, halogenoalkylsulfinyl, halo or sulfonyl, alkylcarbonyl, halogenalkylcarbonyl, alkenyl, halogenalkenyl, haloalkynyl, and alkynyl, and wherein the groups are alkyl, alkoxy, halogenalkyl, halogenalkoxy, halogenyl or alkenyl, and alkynylalkyl having less than 10 carbon atoms, and halogen substitution in all these groups means substitution with one n or more halogen atoms, which may be the same or different, from mono-to fully substituted, or y is a hydrogen atom when X represents a halogen atom or a group R 1 / O / 'in which n is 0, 1 or 2, and R ₅ represents alkyl, halogenated, alkenyl or halogenalkenyl; and alkyl - 155 and alkenyl carbon chains and halogen substituents have the meanings defined above, R and R 'denote each hydrogen atom, and J 1 e R 4 represents a cyano group, ^{and X} 4 in ^{each case and} independently ^and independently select from the same group of substituents described for R 5 or denote a hydrogen atom, excluding the compound wherein R 4 ⁼ R i _i ⁼ R = R < jj ^{= x =} R2 ⁼ ^ 3 ^{= C} ^ ^{and at the} same time X ^ = X ₂ = H, and provided that at least one of R ^ rR ^ or Rj ^is selected from the group of substituent i which is described for. XJ ,. if X ^ and X ^ represent hydrogen and X means halogen or cyano then R ₂ ^{is not} - ^is X » ^and if X. and X ₄₁ are hydrogen and Y is melgyl then X is not in bromo. Compound of the general formula I according to claim 1, characterized in that X is selected from the group consisting of cyano, cyano, thiocyanato, haloalkyl, alkoxy, halogen coke, alkyl or halogen atom. thio, alkyl sulphinyl, alkyl sulphonyl, halogenoalkylthio, halogenoalkyl sulphinyl, hal orealkyl sulphonyl, halogen kilyl carbonyl, halogenoalkyl iliocarbonyl, phenylthio, phenyl sulphinyl, phenyl sulphonyl, phenyl sulphonyl, phenyl sulphonyl, phenyl sulphonyl _; heteroarylsulphinyl, and heteroarylsulphonyl, where the phenyl groups are optionally substituted by aryl groups are five or two identical halogen, cyano or halogenoalkyl, and hetero-six membered monocyclic rings containing different heteroatoms: or nitrogen, and the heteroaryl groups are optionally substituted by halogen, nitro, cyano or halogenoalkyl, and wherein the alkyl, haloalkyl, alkoxy and haloalkoxy groups are straight or branched chain and have less than 10 carbon atoms and halogens ¹ ki these groups is mono-or at the most complete _poly-p R ₂ ^and Rj each independently is selected from: the same substituents described for X; a hydrogen atom, an alkyl _group; and a substitute for at least only one of I? _; R ^ or which substituent is selected from the group consisting of: formyl, hydroxyiminoalkylidenyl, alkoxyimide Mr Alcodyl, azido, amino, alkylamino, dialkylamino, aminocarbonylamino, alkylcarbonylamino, arylcarbonylamino, alkyl sulfonylamino, alkylcarbonylamino arbo-nylamino, benzyl idenimino, alkyl or idenimino, alkoxy alkyl idenimino and dialkylaminoalkyl idenimino, phenyl, optionally substituted by halogen, cyano or halogen alkyl, and a heteroaryl group having a five or six membered monocyclic ring or different heteroatom k optionally substituted by halogen, nitro, cyano or and where the alkyl, haloalkyl, haloalkoxy and alkoxy groups are of the normal or branched chain and have less than 10 carbon atoms, halogen substitution but or at most complete substitution; I in all these groups are i Y is selected from a hydrogen atom or a group consisting of cyano, alkyl, hal og enyl, alk alkoxy, halogen alky, alkylsulfinyl, alkylsulfonyl alkylthio, halogenalkylthio, haloalkylsulfonyl, haloalkylalkenyl, halogonylalkyl, haloalkylalkyl, haloalkylalkenyl , alkenyl, halogenalkenyl, halogen-alkynyl and alkynyl; with the alkyl, alkoxy, haloalkyl, halogen-adoxy, haloalkynyl and alkynyl groups having a straight or branched chain and having less than 10 carbon atoms, and the halogen substitution ι of all these groups is mono- or fully-substituted; X 1, X ₂ , X ₃ ^and X 1 ^are described in claim 1 Compound of general formula I according to claim 1. or 2, characterized in that the substituents are alkyl, alkynyl, alkynyl and alkoxy, as defined by ^X, N 1; ^{, X} 2 ^{, X} 3 ^{, X} 4 '^ 1 »^ 2' ^ 3 ^and Ύ ^have less than 5 carbon atoms. 4. Compound of general formula. 1 ^g according to claim 3, characterized in that cvX denotes a halogen atom or the group RS (o) where O P Rg is alkyl, halogenalkyl, alkenyl or halogen-alkenyl n is 0,1 or 2, and 157 means an atom, a halogen atom, or an alkylthio, meaning cyano, means a hydrogen atom, or a halogen atom, starting with a hydrogen atom, a halogen atom, halogenalkyl or halogenalkoxy, provided that. Y is a hydrogen atom as defined in claim 1, and C 1-4 alkoxy and X 1, X ₂ , X ₃ and X 1 are independently and independently selected from the group consisting of a hydrogen atom, a halogen atom, C 1-6 alkyl, C 1-6 alkylthio. Compound according to claim 4, having a common * 1 E ₃ C1 as X means R ° S / o / _, where n is 0.1. ^with hours hours 6 .. same formulas a R 8 is CH ₃ , yl and 2 a , C $ ₂ C1, CFCIg, CPgPt, CHFg, CHCl 2 or CHCl 3 meant a H, F, Cl or BZ; meant a Η, ρ, SI or Βχ, meant a H or C1; and meant a With? ₃ or CF ₃ 0. Compound according to claim 5, the har acter of irrational to be: with the fact that mo N- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (trifluoromethylthio) pyrrole; · 1- (2,6-Dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (trifluoromethyl sulfonyl) pyrrole J 1- (2,6-dichloro-4-trifluoromethyl phenyl) -2-chloro-3-cyano-4- (dichloro-fluoromethyl-thio) -pyrrole; 1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoro-158-methylsulfinyl) pyrrole; 1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethyl) phosphonyl / pyrrole 1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (chlorodifluoromethyl) sulfonyl / pyrrole; 1- (2,6-Dichloro-4-trifluoromethyl phenyl) -2-chloro-3-cyano-4- (chloro-ordifluoromethyl-sulfinyl) -Irole, 1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (chlorodifluoromethyl) thio] pyrrole; 1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-bromo-3-cyano-4- (trifluoromethylsulfinyl) 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-methylmethyl) -pyrrole; 1- (2,6-dichloro-4-trifluoromethyl phenyl) -2-bromo-3-cyano-4- (dichlorophenylmethyl) sulfonyl / pyrrole; 1- (2, 6-dichlorom-4-tr and fluorine methyl phenyl) -2-6 rum-3-cyano-4- (dichloromethyl) sulfurylphenyl / pyrrole; 1- (2,6-Dichloro-4-trifluoromethyl phenyl) -2-6-pyrrol-3-cyano-4- (chlorodifluoromethyl) thio] pyrrole; 1- (2,6-Dichloro-4-trifluoromethyl phenyl) -2-6rom-3-cyano-4- [chloro] ordifluoromethylsulfinyl / pyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorophenylmethyl sulfonyl) -5-bromopyrrole; 1- (2,6-dichloro-4-trifluoromethyl phenyl) -2-bromo-3-cyano-4- (chloro-ordifluoromethyl sulfonyl) pyrrole; 1- (2,6-Dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethyl sulfinyl) pyrrole; 1- (2,6-Dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (dichlorofluoro-159-methylsulfonyl) pyrrole; 1- (2-chloro-4-trifluoromethyl or fbyl) -2-chloro-3-cyano-4- (dichlorofluoromethyl-sulfonyl) pyrrole; 1- (2-chloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethyl-sulfinyl) pyrrole; 1- (2-chloro-4-trifluoromethylphenyl) -2-6 pyr-3-cyano-4- (dichloromofluoromethylsulfonyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl phenyl) -2-chloro-N-cyano-4- (dichlorophenylmethyl) thio--5-ethylthiopyrrole; 1- (2, 6-dichlorom-4-trifluoromethyl phenyl) -2-chloro-3-c and ano-4 ~ (difluoromethyl phenyl) and o / p irol ;,. 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (bromodifluoro-methylsulfinyl) pyrrole; _; 1- (2-bd-dichl-or-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (bromodifluoromethyl-sulfonyl) -pyrrole * 1- (2,6-dichloro-4-trifluoromethyl phenyl) -2-chloro-3-cyano-4- (methylsulfinyl) pyrrole; or 1- (2,5-Dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (methylsulfonyl) -pyrrole. 7- A compound of general formula I according to claim 4, wherein X represents a halogen atom or the group RcS (θ), wherein n is 0,1 or 2, and R1 represents alkyl, haloalkyl, alkenide or haloalkenyl; R ^ and each individually and independently of one another denotes a hydrogen atom; R ₂ represents cyano; Ύ represents a hydrogen atom or a halogen atom; and X ^, X ₂ , X ^ ^and Xd are each individually and independently selected from the group consisting of hydrogen, halogen, - 160 X and Xd each individually and independently of one another denotes H, F CI, BX or CH ₃ and X ₂ and X ₃ are hydrogen. 9 ». A compound according to claim 7 or Θ, characterized in that R ₃ means C ₃ , CCI ₃ , CF 3 Cl, CPCI 3 or CR 3 B 3 » Compound _t according to claim 7, characterized in that it can be: 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (chlorodifluoromethylthio) pyrrole; 1- (4-bromo-2,6-d ylchloro phenyl) -3-cyano-4 '- (trifluoromethyl thio) pyrrole; 1- (2,4,6-trichloro-phenyl) -3-cyano-4- (chlorofluoromethylthio) pyrrole; 1- (2,4,6-Trichloro-phenyl) -3-cyano-4- (chloro-ordifl) in ethyl ethyl sulfonyl / pyrrole; 1- (2,4-, 6-trichloro-phenyl) -3-cyano-4- (dichloro-methylmethylthio) pyrrole; 1- (2,4,6-trichloro-phenyl) -3-cyano-4- (dichlorophenyl) -methylsulfinyl / pyrrole; Ti- (2,4,6-trifluoro phenyl) - 3-cyano-4- (dichloro fluoro methyl sulfonyl) pyrrole; 1) - (4-6 rom-2,6-dichloro-phenyl) -3-cyano-4- (dichloro-methylmethylthio) pyrrole; 1- (4-Bromo-2,6-d-ylchloro phenyl) -3-cyano-4- (dichloromethane) in methyl sulf sulfin / pyrrole: 1- (4-6 rom-2,6-dichlorophenyl) -3-cyano-4- (dichlorophenyl) methyl methyl sulfonyl / pyrrole; 1- (2,4,6-Trichlorophenyl) -3-cyano-4- (trifluoromethylthio) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trifluoromethylsulfinyl) pyrrole; 1- (2,4, 6-trichlorophenyl) -C 3 -cyano-4- (trifluoromethyl) sulfonyl / phenyl; 1- (2,4,6-trichlorophenyl) -3-cyano-4- (trichloromethylthio) pyrrole; 1- (2,4-Dichloro-phenyl) -3-cyano-4- (dichloro-fluoromethylthio) pyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4-chloropyrrole; 1- (2,4,6-trichlorophenyl) -3-cyano-4- [chloro] ordifl Wormethylsulfonyl / pyrrole; 1- (2,6-dichlorophenyl) -3-cyano-4- (dichlorophenylmethylthio) pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (trifluoromethylsulfinyl) pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (trifluoromethylsulfonyl) pyrrole; 1- (4-bromo-2,6-dichlorophenyl) -3-cyano-4- (chlorodifluoromethylsulfinyl) pyrrole; 1- (4R-6Rom-2,6-dichloro-phenyl) -3-cyano-4- (chloro-ordifl) in ortho-ethyl sulfonyl / pyrrole; 1- (4-bromo-2,6-dimethyl-phenyl) -3-cyano-4- (trifluoromethylsulfinyl) pyrrole; 1- (4-bromo-2,6,6-dimethyl phenyl) -3-cyano-4- (trifluoromethyl) sulfonyl / pyrrole; - 161 1- (4-6rom-2, 6-difluorophenyl) -3-cyano-4- (dichlorofluoromethylthio) pyrrole. Compound of general formula (I) according to any one of claims 1 to 4,7,8 and 9, characterized in that the substituents on N, defined as adenide and halogenalkenyl are respectively, allyl and halogenalyl, and where the substituents are us defined as alkynyl and halogenadinyl are, respectively, propargyl and halogenpropargyl. 112- A compound of general formula I according to claims 1,2 or 3, wherein R1 represents a hydrogen atom or a halogen atom; R _q is cyano, X is haloalkyl-N 'O / group, where n is 0,1 or 2; X 1 and X 1 are not hydrogen; N represents a haloalkyl or haloalkoxy group; and. X ₉ and H_ are a hydrogen atom .. 11. Compound ₁ . according to claim 12, characterized in that R ^ defined as a halogen atom denotes chlorine or bromine and X defined as halogenalkyl- / θ / _π denotes trifluoromethylthio, trifluoromethyl-sulfinyl. or trifluoromethylsulfonyl. 14 »Compound _; According to claim 2, with the general formula of _{≤ 3} , _CFA or CF _OO . A compound according to claim 2, characterized in that it can be: 1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (trifluoromethylsulfonyl) pyridine 1- (2,6-Dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (trifluoromethyl) - 162 - sulfinyl-5-bromopyrrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4-trifluoromethylsulfonyl-5-bromopyrole; 1- (2,6-Dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-fluoromethylthio / pyrrole ;, 1- (2,6-Dichloro-4-trifluoromethyl phenyl) -2-bromo-3-trifluoromethyl thio-4-pano-5-chloropyrrole; 1- (2,6-Dichloro-4-trifluoromethyl phenyl) -2- (trifluoromethyl) arbonylamino / · 3-trifluoromethyl-yl-4-cyano-5-chloropyrrole; 1- (2,6-Dichloro-4-trifluoromethylphenyl) -2- (methylcarbonylamino) -3-trifluoromethylthio-4-cyano-5-chloropyrrole; 1- (2,6-Dichloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethylthio-4-cyano-5-chloropyrrole; 1- (2-chloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethylthio-4-cyano- 5 - chlorine pyrrole; 1- (2,6-Dichloro-4-trifluoromethyl phenyl) -2-amino-3-dichlorophenylmethylthio- 4- cyano-5-chloropyrrole; 1- (2,6-dichloro-4-trifluoromethyl phenyl) -21,4-6is (trifluoromethylthio) -3-cyano-5-aminopropyl; 1- (2,6-Dichloro-4-trifluoromethyl-phenyl) -2-amino-3-trifluoromethyl-thio-4-cyano-5-bromopyrrole; 1- (2,6-dichloro-4-trifluoromethyl phenyl) -2-amino-3-trifluoromethyl-thio-4-cyanopyr ol; 1- (4-trifluoromethyl phenyl) -2-amino-3-trifluoromethyl yl thio-4-cyano-5-bromopyrrole; 1- (2-Chloro-4-trifluoromethyl phenyl) -2-amino-3-trifluoromethylthio-4-cyano- 5- bromopyrole; 1- (2,6-dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorophenyl) -3-thylthio / pyrrole j. 1- (2,6-Dichloro-4-trifluoromethylphenyl) -2-chloro-3-cyano-4- (dichlorofluoromethylsulfinyl) pyrrole; 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -2-chloro-3-cyano-4- (dichloro fluoromethyl-sulfonyl) -pyrrole; 1- (2,6-Dichloro-4-trifluoromethylphenyl) -3-cyano-4- (dichlorophenylmethylthio) pyrrole; 1- (2,6-Dichloro-4-trifluoromethylphenyl) -3-cyano-4- (dichlorophenylmethylsulf-sulfinyl) pyrrole; or 1- (2,6-Dichloro-4-trifluoromethoxyphenyl) -2-chloro-3-cyano-4- (trifluoromethyl sulfonyl) pyrrole · The compound of claim 1 of the general formula 111a, which is individually denoted by H, C1, ₽, CH _3, go ίϋΗ ^, πρπ the condition that when and Xd are each hydrogen, then it is not H or CI. A compound according to claim 16, characterized in X ^ represents H or Cl, ay means CF ^ or CF ^ O. A process for the preparation of a compound of the general formula 1a wherein X ^, X ₂ 'X _3, HF ^and Y have the same meanings as in formula / i / as in claim 1, X is halogen, trifluoromethyl, cyano, thiocyanato, alkylthio, alkylsulfinyl, alkylsulfonyl, halogenadkiltio, halogenalkil- - 164 sulphinyl), xal ogenalk or sul phonyl, alkenyl thio, hal ogenalkenylthio, halogenyl kenyl sul finil, hal oglen alkenyl sul phonyl, phenyl thio, phenyl sulphinyl, phenyl sulphonyl, heteroaryl heteroaryl, heteroaryl or sulphinyl or heteroaryl sulphonyl having a compound of the general formula wherein the substituents have the same meanings as in claim 1 and the amino group is optionally protected and a / interacts with a halogenating agent, optionally in the presence of a solvent to give a compound of general formula (Ia) in which X means halogen, after which said compound may optionally be reacted with trifluoromethylcupro, according to conventional methods, to obtain a compound of general formula (Ia) in which X is trifluoromethyl; b) reacts with three (alkylthio) methane or three (arylthio) methane in the presence of a Lewis acid, after which the compound of general Formula A. is obtained. Y wherein X is two (aryl thio) methyl, -the other substituents are, in claim 1, optionally reacted with alkylnitrite, then hydrolyzed to obtain a compound of general formula (X1), in which X is formyl. then said compound is brought into contact with hydroxylamine, dehydrated according to known methods, to give the compound of general formula (Ia) in which X is cia-165 - HO'Tpyna; c) is reacted with a compound of formula M ^ CN, b which (* 1 stands for alkali metal in the presence of a number) and a solvent to give the compound of general formula (Ia), where X represents a thiocyanate group and then an optional interaction of said compound: with an alkyl halide or dialkyl sulfate in the presence of a base in a solvent medium, wherein, in the resulting compound of general formula (Ia), X is alkylthio, or (d) is reacted with a sulfenyl halide of formula RSHal, B which R is alkyl, halogen, phenyl or heteroaryl, and Hal means a halogen atom, in an organic liquid reaction medium and optionally in the presence of an acid acceptor, to obtain a compound of the general formula (Ia) in which X is alkylthio, halogenalkylthio, alkenylthio, halogenalkenylthio, phenylthio or heteroarylthio, followed by as the resultant compound is optionally oxidized according to conventional procedures, and a compound of the general formula (Ia) is obtained, wherein X is R8 / O / _n , where n is 1 or 2. 19. A process for the preparation of compounds of general formula (Ia) depicting the same meanings as in claim 1, and X represents cyanate, alkoxy or haloalkoxy, wherein the compound of general formula 'XXVIII,. in which all the substituents are defined in claim 1 and the amino and cyano groups are suitably protected, if necessary: a) is reacted with halogenocyan in the presence of an acid acceptor to give a compound of the general formula (Ia) in which X is -66a cyanate; b) reacts with an alkylating agent, optionally in the presence of a base, to give compounds of the general formula (Ia) in which X is alkoxy; or c) is halogenated according to known methods, to give compounds of the general formula (Ia) in which X is haloalkoxy. A method of preparing compounds of general formula (Ia) according to claim 10, wherein X is in claim 1, and X is haloalkyl, haloalkylcarbonyl or haloalkylthiocarbonyl, characterized in that a compound of vol, ^X 2 * ^X 3 * ^X 4 ^And »have the same meaning as a formula ONS-r— _r cw £ VI ^χ ι ~ ΓΓ ^Χ * In which the meanings of the substituents are given in claim b and the amino are the cyano groups. are suitably protected, if necessary: a) reacted with a fluorinating substance according to conventional methods to give the compound of general formula (Ia) in which X is a difluoromethyl group; b) reacted with an oxidant to convert the -CHO group into a carboxyl group, followed by reaction of the resulting compound with the fluorinating substance according to known methods, to give the compound of general formula (Ia), in which X is trifluoro-methyl; c) is converted to a compound in which the -CHO group is displaced from a methyl group, after which the resulting compound is halogenated in a solvent medium to give a compound of the general formula (Ia) in which X is bromomethyl or chloromethyl; or d) reacts individually with a metal derivative of haloalkyl or trifluoromethylsilane to convert the group - / 6 7 ' - CHO in halogenalkilkarbinol., Oxidizing the resulting compound according to conventional methods to give compounds of the general formula wherein X represents /1a/.v hadogenalkilkarbonil after tonezadalzhitelno / £ / vaHpodlagane of said compound to the action of the reagent of ZpVlfcSSon ^»n nd which yields compounds of general formula (Ia) in which X is haloalkyl (thiocarbonyl) or (II) reacting the compound in which X is haloalkylcarbinol with a halogenating agent to give compounds of general formula (Ia) , in which X is N-haloalkyl-N-halogenmethyl, after which the steps described above are repeated, and at. need * the protected group is deprotected. 21, Process for the preparation of compounds of general formula Y in which X, Xq, X _2> X ₃ , Xd and Y have the same meanings as in claim 1a means halogen, formyl, bis / alkylthio or arylthio / methyl, haloalkyl, alkyl, optionally substituted phenyl or heteroaryl, thiocyanate, alkyl ylthio, halogenalkylthio, alkenylthio, halogenalkenidio, phenylthiol, phenylthiol, phenylthiol, phenylthiol Finn, Finnen, Finnen. general formula (Ia) in which X is recognized cyano and amino, optionally protected: a) reacted according to claim 18 (a), in which compounds of the general formula (1b) are obtained, which means halogen, and then the optional compound (ζ,) is optionally substituted. heteroaryl or phenyl halide, in the presence of MIA in accordance with conventional methods, or / and / reacts with an unsaturated · 168 -substituted phenyl or heteroaryl boronic acid in the presence of palladium according to conventional methods, to give compounds of the general formula (IB) in which R1 represents optionally substituted phenyl or heteroaryl, or (C1) reacted according to claim 18 (a), wherein cb is prepared with compounds of the general formula (Ib) in which trifluoromethyl; b) c as claimed in claim 1b (b), wherein a compound of the general formula (Ib) is initially obtained, wherein the GC is bis (alkyl-kthio) methyl or bis (arylthio) mvtyl and then, optionally, a compound of general formula (Ib), in which it stands for formyl; c) reacts with optionally substituted phenyl or heteroaryl diazonium salt according to conventional methods, to give compounds of general formula (1b), in which R 1 represents optionally substituted phenyl or heteroaryl, or g (interacts according to claim 18 (c, g), to give compounds of the general formula (Ib) in which R1 represents thiocyanate, alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, phenylthio or heteroarylthio, a salt which is optionally oxidized according to claim 18 (g) to give compounds with vol general formula / 1b / in which R ₃ is alkylsulfinyl, alkylsulfonyl, alkenyl sulfinyl, alkenylsulfonyl, halogenalkilsul alkylsulfinyl, halogenadkil sulfonyl, XAD ogenalkenilsulfini l halogenalkenilsulfonil, phenylsulfinyl, phenylsulfonyl, heteroarilsulfinid or heteroarylsulfonyl with the proviso that X does not mean R $ a group that may be undesirably oxidized .; and when X stands for halogen, optional treatment with alkyl lithium according to conventional methods, after which it is sharply cooled with water and sulfenylated according to claim 18 (c, d) to give compounds of general formula (Ib), in which X is alkylthio, halogenalkylthio, alkenylthio, halogenalkenylthio, phenidthio or heteroarylthio .. 22. A process for the preparation of compounds of general formula (Ib) in which X, X, X, X_, X, and Y have the same meanings as in claim 1 and R ₃ 1. 2 3 4 means hydroxyiminoalkylidenyl, alkoxyiminoalkyl idenyl, cyano, haloalkylcarbonyl or haloalkylthiocarbonyl or alkyl, characterized by * 4 Kg & ^x 3 XXIX. wherein R ₃ is formyl or alkylcarbonyl, the other substituents having the same meaning as they are. are protected if necessary: in claim 1, a X, cyano and amino groups (f) is fused with hydroxylamine or O-alkylhydroxylamine or their addition salts, in a solvent, to give a compound of the general formula (1b), in which means hydroxyiminoalkylidenyl or alkoxyiminoalkylidenyl, and when R 1 represents hydroxyimino-nomethylidenyl or alkoxyiminomethylidenyl, the group is transformed into cyano to give a compound of the general formula (Ib) in which R 3 stands for cyano; b) reacts when R1 represents the formyl according to claim 2Q (a, b, c or d) to give a compound of the general formula (1b) wherein R1 represents methyl, halogenadkyl, halogenalkylcarbonyl or halogen-alkylthiocarbonylJ or c) reacts when it means formyl with a Grignard reagent, starting from alkyl halide or alkylithium to produce carbinol, followed by a dehydration step to give a compound wherein R1 represents alkenyl, after which is reduced ^ in order to obtain a compound of the general formula / 1 b /, wherein R ₃ is lkil, followed optionally by a step of removing the protecting group .. 23. A method for the preparation of compounds of general formula Xi n XXXIV xU which are useful as intermediates and in which formula X, X X _2, X _3, Xe ^and Ύ ^have the same znacheniyakakto in claim!, a R ^ ⁰³ "nachava amino alkidamino, dialkylamino, aralkylamino, aminocarbonylamino, alk ilkarbo carbonyl amino, halogenoalkyl carbonyl amino, aryl arbonylamino, alkyl sulphonylamino, halogenoalkyl sulphonylamino, alkylamino arbonylamino, aryl aminocarbonylamino, alkoxycarbonylamino, alkyl benzyldenimino, alkenylalkenyldimino dialk ylaminoalk idenimino, alk ilthioadkil idenimino, dialk ylaminoalkidenes a mine, alkylthioalkylidinimino or azido, wherein the compound of the general formula Jl _t XXX Xc / M Wherein the meanings of the substituents are the same as in claim 1, and the amino group is suitably protected, is reduced to give compounds of general formula (XXXIV), wherein R ₃ is amino, said compounds interact: a) with an alkylating agent in an organic solvent medium to give a mono- or disubstituted amino group or conversion of the amino group into alkoxyalkylideneimino, which in turn is reduced to yield compounds of the general formula (XXXIV), in which R4 means alkylamino, diadkylamino or aralkyl amino; b) with phosgene and then with ammonia to give compounds of the general formula (XXXIV) in which R ₃ is aminocarbonylamino; c) acidic alkyl chlorides or acid halogenoalkyl chlorides or anhydride 171 optionally in the presence of a solvent and / or organic acids as acceptors to give a compound of the general formula (XXXIV) in which R8 is alkylcarbonylamino, haloalkylcarbonylamino or arylcarbonylamino; d) with alkyl or haloalkylsulfonyl halides or their anhydrides under suitable conditions to give compounds of the general formula (XXXIV), wherein Rg is alkylsulfonylamino or halogen alkyl alkyl sulfonyl amine and but; e) C alkyl or aryl isocyanates according to conventional methods, to give compounds of the general formula (XXXIV) in which R 8 is (alkylamino or arylamino) carbonylamino; f / c alkyl chloroformate. or halogenated chloroformate according to known methods to give a compound of the general formula (XXXIV) in which R8 is alkoxycarbonylamino or halogenadecoxycarbonyl; g) with alkyl or arylaldehyde ι according to known methods, wherein i are given compounds of the general formula (XXXIV) in which R8 is alkyl-benzyldimino or benzylidenimino; 3) with an adidortoester to give a compound of the general formula (XXXIV) in which R 8 is alkoxyalkylidenimino; and (c) Ν, Ν-dialkidformamide or its di-diacidacetate derivative, to give compounds of the general formula (XXXIV) in which R 03-initiates diadkylaminoalkylideneimino; k) with tri (adkidio) methane in an organic solvent medium to give compounds of the general formula (XXXIV) in which R is W is alkylthioalkylidenimino; or l / with p-toluenesulfonyl azide according to known methods or by conversion to the diazinium salt, followed by reduction to form a hydrazine group, after which the title compound is treated with nitric acid to give a compound of general formula (XXXIV). - .. in which R_ means an azido group; and then, if necessary, ll— SJ removes the protection. A process for the preparation of compounds of general formula (16) as defined in claim 21, wherein X, X, X ₂ , X 1, X 2 and Y have the same as in claim 1, and C 1 represents cyano , Alcohol is a Coke, characterized in that it is a compound of the general formula CH Ouch X to the same means halogen - 'XXXI in which the amino, cyano and X groups are optionally protected is reacted according to claim 1b / a, b or c / to give a compound of the general formula (1b) in which Rg is cyano, alkoxy or halo-alkoxy 25 ,. A process for the preparation of compounds of the general formula wherein X, R and y have the same meanings as in claim 1, and RC means kiltio, adenylthio, halogenalkenylthio, phenylthio, heteroarylthio, alkylsul hydrogen, halogen, thiocyanate, alkylthio, halo gen— Finn Finnn Finnnen Finnnnn Finnnnnnnnnnnnnnnnnnnnnnnnnnn alkylcarbonyl, alkali amino, dialkyl yl amino, aralkyl amino, aminocarbonylamino, alkylcarbonyl / amino hadogenalkilkarbonilamino, arylcarbonylamino, alkylsulfonylamino, XAD ogenadk yl sulfonyl amino, alk id amino ACB o carbonyl amino, arilaminok arbonil- - 173 amino, alkoxycarbonylamino, hal orenalkoxycarbonylamino, alkylideneimino, benzylidino, alkyloalkyl idenimino, dialkyl aminoalkyl idenamino, alkylthioalkyl idenamino, idyl, bis or alkyl or thiol / methyl, formyl, halogenalkylcarbonyl, halogenalkylthiocarbonyl, halogenalkyl or alkyl yl, characterized in that. compound of general formula. in which the protection of the amino group is removed after protecting the X groups, or cyano if necessary: a) is reacted with a diazotizing agent in an inert solvent medium to give a compound of the general formula (Ic) in which it stands for hydrogen; b) reacts with a diazotizing agent in the presence of halogen as a donor to give a compound of general formula (Ic) in which halogen means, then, optionally, said compound is reacted with a Grignard reagent or a lithium compound followed by an interaction with aliphatic acid anhydride in order to obtain a compound of general chloride or non-formula (1b), in which it is alkylcarbonyl or treatment of said compound according to claim 21 (g) in order to obtain compounds of general formula (1b), in which R ^ is phenyl in / reacted with a diazotizing agent in, or heteroaryl; the presence of ( ₂₎ cn ( ₂₎ or with disulfide in a solvent medium to give compounds of the general formula (Ic) in which R 1 represents thiocyanot, alkyl yl thio, haloalkylthio, alkenylthio, haloalkenylthio, phenylthio or heteroarylthio, followed by which may optionally be oxidized according to claim 18 (g) to give a compound of the general formula (Ic) in which 4η is alkyl alkyl sulfinyl, alkyl yl sulfonyl, alkenylsulfinyl, alkenylsulfonyl, halogenyl, sulfinyl, sulfinyl, sulfinyl, sulfinyl, sulfinyl, sulfinyl, halogenalkenylsulfonyl, halogenalkenyl sul finyl, halogenalkenylsulfonyl, phenyl sulphinyl l, phenyl sulfonyl, heteroaryl sulfinyl or heteroarylsulfonyl; d) is reacted according to claim 23 (a-l) to give compounds of the general formula (Ic) in which R1 is alkylamino, dialkyl amino, aralkyl amino, amino arbonyl amino, alkylcarbonyl amino, bath robe n alkyl yl carbonyl amino, arylcarbonyl amino, alkyl sulfonyl amino, halogenadenyl sulfonyl amino, alkyl aminocarbyl amino, arid aminocarbonyl amino, alkoxycarbonyl amino, xalbogen, aminocarbonyl, xal adenyl, amino dialkylaminoalkyl, dialkylaminoalkylaminoalkyl, alkylthioalkylideneimino or azido; or e) reacts with sodium nitrite and formaldoxime, copper sulfate and HCl according to known methods to give compounds of general formula (Ic), in which it means formyl, then optionally (i) reacts with an alkyl Grignard reagent and then oxidized to a compound of the general formula / 1 c /, where R ^ represents alkylcarbonyl, W / C / reacted according to claim 22, / a /, so _so as to obtain a compound of the general formula / 1b / in which R ^. denotes hydroxyiminoalkylidenyl, alkoxyiminoalkylidenyl or cyano or (C1-) reacts according to claim 20 (a-d) to give a compound of the general formula (Ic), wherein R1 represents halo-alkylcarbonyl, xa. l ogenalk il t yocarb onyl, hal o gen al k yl or methyl and then deprotection if necessary; go to the aforementioned compound, 'ί t in which R ₁ means formyl is converted according to known methods into'. is a compound of the general formula (Ic), in which it is bis (alkylthio or arylthio) methyl. ί A method for the preparation of compounds of general formula (Ic) in which ^X > R ₃ > ^X 3 »Xd ^and Y have the same meanings as in claim 1, and R4 represents cyanate, alkoxy or hadogenalkoxy, characterized by This is a compound of the general formula * li if ^eW . XXXII,. Wherein the substituents have the same meanings as in claim 1, a X, cyano or R are optionally protected by known methods, reacted according to claim 19 (a, b and c), to give a compound of the general formula (Ic) in which R 1 is cyano, alkoxy or haloalkoxy, and then optionally removing the protecting group. A method for the preparation of compounds of the general formula (1) in which X, x ₄ and γ have the same meanings as in claim 1, and Rg means CHO, characterized in that the compound of general formula (Ic) is treated with a reducing agent in a solvent medium. in order to convert the CNI group to the CHO group to give a compound in which Rg is CHO, said compound is optionally oxidized according to conventional methods, resulting in the corresponding compound of the general formula Xt-ψ-Χ, Y A process for the preparation of compounds of the general formula (ι), β which X, R ₁ , R ₃ , X 1, X 2, X ₃ , X 4 and Wim have the same meanings as in claim 1, and R 8 represents hydroxyiminoalkylidenyl, alkoxyiminoalkylidenyl. cyano, halogenoalkyl arbonyl, halogen alkyl iliothiocarbonyl, alkyl, halogen alkyl, or bis (alkylthio or arylthio) methyl, wherein the compound of the general formula (1) wherein R ₂ is CHO , optional 176 are protected in known ways, followed by inhibition 20 (a, b, c and d) of the X, R 2 or (C 1 -C compound is reacted according to or 25 / g), followed by a deprotection step, if necessary. 29. A petod for the preparation of compounds of the general formula (ι), β which X, R 1 '3' ^X 2 * ^X 3 ' ^X 4 ^and Y have the same starting materials as in claim a and R ₂ denotes amino, alkylamino, dialkylamino, aralkylamino, aminocarbonyl amino, alkylcarbonylamino, halogenoalkylcarbonylamino, aryl arbonylaminoalkylaminoalkylaminoalkylaminoalkylaminoalkylamine halogenated, halogen-free, non-ferrous, non-ferrous finil, al to il sunsil sunsil sunesil sunesil sunesil sunesil sunesil sunesil sunesil sunsil characterized in that a compound of the general formula (XXXV) according to I, claim 27, after accidental and vigorous protection of the groups X, R ^ or R ^ axo is required according to known methods, is applied under the conditions of the Curcius acid reaction chloride after cat should dance with an alkali metal azide or diphenylphosphoryl azide in the presence of an organic base and in an alcoholic solvent, co lo obtain the carbamate, which can then be hydrolyzed to yield the corresponding compound in which R ₂ represents amino, then optionally reacting according to claim 23 (a-e) or 25 (a-c), then, when R ₂ means halogen, the resulting compound optionally reacting according to claim 21 (a), followed by - - 177 if necessary at the stage of removal of protection. 30. A process for the preparation of compounds of the general formula (ΐ), which X, D □, X x X, X, and Υ have the same meanings as in claim 1, Ί * 5 I Ζ «Ο · · R ₂ means cyano, alkoxy, halogen alkoxy, characterized in that a compound of the general formula ON p / XXXVI. have the same meanings as in claim 1, followed by the groups X, or R 5 optionally protected, if necessary, reacted according to claim 24, then if said neo (5 - walkable) the said protection is removed. A method for the preparation of compounds of general formulas (XXVIII), (XXXI), (XXXII), and (XXXV) according to claims 19, 24, 28 or 30, characterized in that the corresponding compound according to claims 16 (a), 21 (a), 25 (b) or 29, after protection of the amino group, if necessary— I * Smoke, becomes a Grignard reagent Go lithium derivative, which then interacts with trialkyl borate and oxidation by known methods, and if necessary remove the protecting groups .. 32. Method for the preparation of a compound of the general formula., N “.hi. x 1¾ In _v in which X ^, X ^, x ~, Xd and Y have the same meanings ^ k as in claim 1, characterized in that dicyanoprolene of the general formula HH-CH 2 -C 4 -CM Χ, -fS-Xi CN X _r -C ^ * c Ίν V / 178 with the general formula is reacted with an alkaline agent 33 ... Method for Preparation of Compound r ₂ > a X R ₃ , y, X ₂ , X 4, X ₃ and X ₄ have the same mean perhaloalkylthio group, meaning, as characterized by / l /, which, in claim 1, is that the key is: a) reacting a compound of the general formula Rs Rs / XXXVIII /. * 5 Y is hydrogen and the other substituents are the same as in claim 1, with chlorosulfonic acid (CISO ^ H) at a temperature of from 0 ° to 150 ° C and optionally in an organic solvent medium, wherein X is the compound of general formula C0O.S XXXIX, wherein the various substituents are the same as in claim 1; b) reacting the compound of general formula (XXXIX) with a reducing substance at a temperature of from 0 ° to 10 ° C in an organic solvent to give a disulfide of general formula; wherein 'XU / a are as in claim 1i, 'and 179 in (interaction of the disulfide of the general formula (Xb1) with perhalogenadcan of the formula (Xbp), £ CFR _? R ₈ in which 2 is Cl or I, R ₇ represents F, Cl or Βχ and represents F, Cl, Bfc or perfluoroalkyl group, in the presence of a free radical-activating reducer and optionally in the presence of a base, in an organic solvent at a temperature of 20 ° to 85 ° C and optional under pressure to give a compound of the general formula (I) wherein X is perhalogenadkylthio and the other substituents are the same as in claim 1. The method of any one of claims 18 to 32, followed by the conversion of the compound thus obtained to a compound of general formula (i) according to claim 1. A method according to any one of the claims of 18 to 34, essentially so. as described 36. Compound having been obtained from 24 to 30 and 32 to above. General formula /I/.According to a method according to each 34 .. claim 1, provided from claims 18 to 22, A composition for controlling arthropods, plant nematodes, parasitic worms or protozoa, characterized in that it contains a compound of general formula (i) according to any one of claims 1 to 17 and 36 together with one or more diluents or carriers »38. Composition for use in veterinary and animal husbandry or mass healthcare, characterized in that it contains as an active substance at least one compound according to any one of claims 1 to 17 and 36. 39. An insecticidal, acaricidal or nematocidal composition comprising an effective amount of the compound of general formula (i) according to any one of claims 1 to 17 and 36., 40. Composition according to claim 39, containing from 0.05% to 95% (w / w) of the active substance; from 1 to 95% by weight of one or more agriculturally acceptable carriers; • hours 180 - and from 0.1 to 50% by weight of one or more agriculturally acceptable surfactants. 41. Composition according to claim 39 or 40, characterized in that it contains one or more ingredients selected from the group of protective colloids and, adhesives, thickeners, thixotropic substances, penetrants, insecticidal oils, stabilizers, preservatives, anti-ecetics , sequestering agents and other active ingredients, Composition according to Claims 39, 40 or 41, characterized in that the carrier is liquid or solid. 43. The composition according to claim 37, essentially as described above. A method for combating arthropods, plant nematodes, helminths or protozoan pests, characterized in that an effective amount of the compound of general formula (ί) is applied at the site of attack according to any one of claims 1. to 17 and 36 _fc 45. A method according to claim 44, characterized in that it is used in veterinary medicine or in animal husbandry or in the healthcare for the control of arthropods, helminths or protozoan pests, which parasitize internally or externally in warm-blooded vertebrate animals. The method of claim 44, for the control of arthropods or plant nematodes, characterized in that an effective amount of a compound of general formula (ί) is applied to the plants or medium where they grow. The method of combating arthropods and nematodes / according to claim 44, characterized in that the compound to be applied at the site of attack is in an amount of 0.005 kg to 15 kg per ha of cultivated area. 48. A cetode according to claim 47, wherein the compound is administered in an amount of 0.02 kg to 2 kg / ha. - 181 - The method of claim 47, wherein the compound is used in an amount of 0.01 to 1. kg / ha. 50. The mite control method according to any one of claims 44 to 49, characterized in that the compound of general formula (i) is as claimed in claims 7, 8, 9 or 10. 51. Compounds of general formulas (III), (XXVIII) to (XXXIX) and (X1 »1) in which the substituents have the same meanings as in the preceding claims, excluding the compounds in which ^X g ^{= = X} 3 ^{= X} 4 ^{= R} 1i = ^ 2- ^{= H M X = CN} * ^mN 2 ^I ' Y stands for CH "or OCH" or. CI. '