SK279269B6 - Methods of insect, acarid and nematodes extirpation; methods of plant protection, agents, arylpyrroles, method and intermediates for preparation thereof - Google Patents

Abstract

Methods of insect, acarid and nematode extirpation; a method for protecting growing plants from the said pests by applying arylpyrrole compounds of the formula (I) wherein the symbols are, as defined in the Claims. The invention also is directed to an insecticidally, acaricidally or nematicidally effective agent prepared on the basis of the said compounds, to the novel arylpyrrole compounds themselves and to a method and intermediates for some of the novel arylpyrrole compounds preparation.

Description

The invention relates to a method of controlling insects, nematodes and mites, to a method of protecting growing plants from attack by these pests using certain arylpyrrole compounds. Furthermore, the invention relates to an insecticidal, acaricidal and nematicidal composition based on these compounds, novel arylpyrrole compounds per se, a method and intermediates for the manufacture of some of these novel arylpyrrole compounds. Said arylpyrrole compounds are very effective insecticidal, acaricidal and nematicidal agents useful for controlling insects, mites and nematodes and for protecting agronomic crops, whether growing or harvested, from damage by these pests.

BACKGROUND OF THE INVENTION

While there is extensive literature dealing with various natural and synthetic pyrrols, such as antibacterial and fungicidal agents, the arylpyrrols of the present invention differ from the known compounds in their structure and / or insecticidal activity.

Among the known pyrrole compounds, for example, pyrrolidine of the formula can be mentioned

(US 4,495,358). No insecticidal effect has been reported with these substances.

4,5-Dihalopyrrol-2-yl-di-trihalomethyl ketones have also been described (U.S. Pat. No. 3,963,746). Although some acaricidal activity has been declared for these compounds, the comparative experiments described herein have not shown these compounds to be effective insecticides, acaricides and nematicides.

Certain aryl / cyano and aryl / nitropyrrols having a trisubstituted pyrrole functionality are known from Japanese Patent Application J 69001528-B. These compounds are declared as muscle relaxants. The compounds of the invention differ therefrom in that they contain a tetrasubstituted pyrrole functional group and exhibit an insecticidal effect.

Certain pyrroles are also known from US 4,563,472, but neither do they contain a tetrasubstituted pyrrole functional group and have no insecticidal effect.

Also included in the scope of the heterocyclic semiconductors described in Japanese patent application J 62098562-A are certain pyrroles. Finally, certain pyrroles are also included in EP 206 523. The compounds are declared as fungicides. They differ significantly from the compounds of the invention in their structure.

SUMMARY OF THE INVENTION

In one aspect, the present invention provides a method for controlling insects, nematodes and mites, comprising contacting insects, nematodes and mites with the insecticidal, nematocidal or acaricidally effective amount of an arylpyrrole compound in a place where they are propagated. of formula (I)

where

X represents a hydrogen, fluorine, chlorine, bromine or iodine atom or a trifluoromethyl group;

Y represents a fluorine, chlorine, bromine or iodine atom, a trifluoromethyl group or a cyano group;

W is cyano or nitro;

A represents a hydrogen atom, a C 1 -C 4 alkyl group optionally substituted by one to three halogen atoms, one hydroxy group, one C 1 -C 4 alkoxy group or one C 1 -C 4 alkylthio group, one phenyl group optionally substituted by alkyl (C 1 -C 3), (C 1 -C 3) alkoxy or (C 1 -C 3) halogen, followed by one phenoxy optionally substituted by 1 to 3 halogen atoms or one benzyloxy group optionally substituted by one halogen; C 3 -C 4 alkenyl, optionally substituted with 1 to 3 halogen atoms, cyano, C 3 -C 4 alkynyl optionally substituted with one halogen atom, C 1 -C 4 dialkylaminocarbonyl in each alkyl moiety carbon atoms or cycloalkylaminocarbonyl having 4 to 6 carbon atoms in the cycloalkyl moiety;

L is hydrogen, fluorine, chlorine or bromine; and

M and R are each independently hydrogen, (C1-C3) alkyl, (C1-C3) alkoxy, (C1-C3) alkylthio, (C1-C3) alkylsulfonyl, (C1-C3) alkylsulfonyl; up to 3 carbon atoms, cyano, fluorine, chlorine, bromine or iodine, nitrosine, trifluoromethyl, the radical of formula RJCF2Z, R ^CO or NRŠR ⁴ , or M and R bonded in adjacent positions together with the carbon atoms to which they are attached linked, they can form a ring in which MR represents a residue

Z is S (O) _n or oxygen;

R1 represents a hydrogen atom, a fluorine atom, a difluoromethyl group, a fluorochloromethyl group or a trifluoromethyl group;

r 2 is C 1 -C 3 alkyl, C 1 -C 3 alkoxy or NR ³ R ⁴ ;

r 3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;

R ⁴ represents a hydrogen atom, a C 1 -C 3 alkyl group or the radical R 4 CO;

R 5 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms and n is an integer of 0, 1 or 2.

According to a second aspect, the present invention also provides a method of protecting growing plants from insect, nematode and mite infestation by applying insecticidally, nematocidally or acaricidally effective, defined insects to the leaves of the plants or to the soil or water in which they grow. amount of arylpyrrole compound.

The invention also relates to an insecticidal, acaricidal and nematicidal composition which contains an arylpyrrole compound as defined above.

A further object of the invention are novel arylpyrrole compounds of formula (I), wherein the individual symbols are as defined above, but X is not a hydrogen atom.

C 4 -C 6 Cycloalkylaminocarbonyl means a C 4 -C 6 cycloalkylamino group bonded directly to the carbonyl group via a nitrogen atom.

A preferred group of novel arylpyrrols according to the invention are compounds of formula (II)

IN (IT) in which R

A, L, M, R, W, X and Y are as defined above.

A further preferred class of novel arylpyrroles according to the invention are compounds of formula (III)

in which

A, L, M, R, W, X and Y are as defined above.

Another group of preferred arylpyrroles according to the invention is represented by compounds of formula (IV)

in which

A, L, M, R, W, X and Y are as defined above.

Yet another group of preferred arylpyrroles of the invention are compounds of formula (V)

(V) in which

A, L, M, R, W, X and Y are as defined above and of formulas (VI) and (VII)

A, L, M, R, W, X and Y are as defined above

Preferred arylpyrroles of formula (I) according to the invention are those in which A represents a hydrogen atom or a (C 1 -C 4) alkoxymethyl group, W represents a cyano or nitro group, L represents a hydrogen or fluorine atom, X and Y independently of one another M is hydrogen, fluorine, chlorine or bromine, and R is fluorine, chlorine or bromine, trifluoromethyl or trifluoromethoxy.

Preferred compounds of formula (II) which are particularly effective as insecticidal, acaricidal and / or nematicidal agents are those in which A represents a hydrogen atom or a (C 1 -C 4) alkoxymethyl group, L represents a hydrogen atom, M is hydrogen, fluorine, chlorine or bromine, R is fluorine, chlorine or bromine, trifluoromethyl or trifluoromethoxy, W is cyano and X and Y are each independently chlorine, bromine or trifluoromethyl.

Other compounds of formula (II) which are highly effective as insecticides, acaricides and / or nematicides are those in which A represents a hydrogen atom or a (C 1 -C 4) alkoxymethyl group, L represents a hydrogen atom, M represents a hydrogen atom, a fluorine atom, R is fluorine, chlorine or bromine, trifluoromethyl or trifluoromethoxy, W is nitro and X and Y are each independently chlorine, bromine or trifluoromethyl.

Illustrative examples of the insecticidally, acaricidally and nematocidally active arylpyrroles of the present invention include the following compounds:

4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile,

4,5-dichloro-2- [p- (trifluoromethoxy) phenyl] pyrrole-3-carbonitrile, 4-bromo-5-chloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile,

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5-bromo-4-chloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile,

4,5-dichloro-2- (o-chlorophenyl) pyrrole-3-carbonitrile,

2- (p-bromophenyl) -4,5-dichloropyridine-3-carbonitrile,

4,5-dichloro-2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile,

4,5-dibromo-2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile,

4,5-dibromo-2- (o-chlorophenyl) pyrrole-3-carbonitrile,

4,5-dibromo-2- (p-chlorophenyl) pyrrole-3-carbonitrile,

4,5-dichloro-2- (2,4-dichlorophenyl) pyrrole-3-carbonitrile,

4,5-dibromo-2- (2,4-dichlorophenyl) pyrrole-2-carbonitrile,

2,3-dibromo-4-nitro-5-phenylpyrrole,

2- (p-bromophenyl) -4,5-dichloro-3-nitro-pyrrol,

2,3-dichloro-4-nitro-5- (α, α, α-trifluoro-p-tolyl) pyrrole,

4,5-dichloro-2- (m-chlorophenyl) pyrrole-3-carbonitrile,

4,5-dichloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile,

4,5-dichloro-2-phenylpyrrole-3-carbonitrile,

2,3-dichloro-5- (p-chlorophenyl) -4-nitropyrrole,

2-bromo-3-chloro-5- (p-chlorophenyl) -4-nitropyrrole,

2,3-dibromo-5- (p-chlorophenyl-4-nitropyrole),

2.3-dichloro-4-nitro-5-phenylpyrrole,

3-Bromo-2-chloro-4-nitro-5- (a, a, a, -trifluoro-p-tolyl) pyrrole, 5-chloro-2- (3,4-dichlorophenyl) -1- (methoxymethyl) - 4- (trifluoromethyl) pyrrole-3-carbonitrile, 5-bromo-2- (m-fluorophenyl) -3-nitro-4- (trifluoromethyl) pyrrole,

2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile,

3-bromo-5- (m-fluorophenyl) -4-nitro-2- (trifluoromethyl) pyrrole,

4-bromo-2- (p-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile,

4-chloro-2- (3,5-dichloro-4-methylphenyl) -3-nitro-5- (trifluoromethyl) pyrrole,

2- (2-bromo-4-chlorophenyl) -1- (2-propynyl) -4,5-bis- (trifluoromethyl) pyrrole-3-carbonitrile,

2- (2,5-difluorophenyl) -3-nitro-4,5-bis (trifluoromethyl) pyrrole,

5- [p- (trifluoromethoxy) phenyl] pyrrole-2,4-dicarbonitrile,

5- (p-dimethylaminophenyl) -4-nitropyrrole-2-carbonitrile, 3-bromo-5- (p-chlorophenyl) pyrrole-2,4-dicarbonitrile,

4-bromo-2- (p-chlorophenyl) -5-nitropyrrole-3-carbonitrile,

5- (p-Methylthiophenyl) -3- (trifluoromethyl) pyrrole-2,4-dicarbonyl nitrile,

1-Allyl-4-nitro-5- (α, α, α-trifluoro-p-tolyl) -3- (trifluoromethyl) pyrrole-2-carbonitrile,

4-chloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile,

2- (m-methanesulfonylphenyl) -4- (trifluoromethyl) pyrrole-3-carbonitrile,

2- (3-chloro-4-methyl-phenyl) -l-methyl-3-nitro-4- (trifluoromethyl) pyrrole,

2-phenylpyrrole-3,4-dicarbonitrile,

5- (p-ethanesulfinylphenyl) -4-nitropyrrole-3-carbonitrile,

2-bromo-5-phenylpyrrole-3,4-dicarbonitrile,

2-chloro-5- (3,5-dichlorophenyl) -4-nitro-pyrrol-3-carbonitrile,

-benzyl-4-nitro-5- (p-chlorophenyl) -2- (trifluoromethyl) pyrrole-3-carbonitrile,

2-chloro-5- (m-bromophenyl) pyrrole-3-carbonitrile,

2-bromo-1- (p-chlorophenoxy) methyl-5- (p-chlorophenyl) -3-nitro-pyrrol,

2,4-dibromo-5-phenylpyrrole-3-carbonitrile, 5- (p-bromophenyl) -2,4-dichloro-3-nitropyrrole,

2-bromo-5- (3-bromo-4-methylphenyl) -1- (n-propyloxy) methyl-4- (trifluoromethyl) pyrrole-3-carbonitrile,

2-bromo-5- (p-chlorophenyl) -3-nitro-4- (trifluoromethyl) pyrrole, 5- [m- (difluoromethoxy) phenyl] -2- (trifluoromethyl) pyrrole-3-carbonitrile,

5- (2,3-dichlorophenyl) -l-methoxymethyl-3-nitro-2- (trifluoromethyl) pyrrole,

4-chloro-5- (P-naphthyl) -2- (trifluoromethyl) pyrrole-3-carbonitrile,

3-Bromo-2- (3,4-dichlorophenyl) -4-nitro-5- (trifluoromethyl) pyrrole, 5- (2-bromo-5-ethylphenyl) -2,4-bis- (trifluoromethyl) pyrrole-3- carbonitrile, 1-ethyl-2- (p-fluorophenyl) -4-nitro-3,5-bis- (trifluoromethyl) pyrrole, 1 - [(2,6-dichlorophenoxy) methyl] -5- (m-chlorophenyl) pyrrole 2,3-dicarbonitrile

3-nitro-5- (α, α, α-trifluoro-p-tolyl) pyrrole-2-carbonitrile,

4-chloro-5- (4-chloro-2-methylphenyl) pyrrole-2,3-dicarbomtril,

4-bromo-5- (3,4-dibromophenyl) -2-nitropyrrole-3-carbonitrile, 1 - [(1-methoxy) ethyl] -5- (p-chlorophenyl) -4- (trifluoromethyl) pyrrole-2, 3-dicarbonitrile,

5- (p-isopropylphenyl) -2-nitro-4- (trifluoromethyl) pyrrole-3-carbonitrile,

4-chloro-5- (3,4-difluoromethylenedioxyphenyl) pyrrole-3-carbonitrile,

3-bromo-2- (3-chloro-4-cyanophenyl) -4-nitropyrrole.

1 - [(3,4-dichlorobenzyloxy) methyl] -2- (m-bromophenyl) pyrrole-4-carbonitrile,

2- (3,5-dichloro-4-methylphenyl) -4-nitro-3-trifluoromethylpyrrole,

2-phenylpyrrole-3,4-dicarbonitrile,

2- (2-bromo-4-chloro-phenyl) -4-nitro-pyrrol-3-carbonitrile,

2-bromo-5-phenylpyrrole-3,4-dicarbonitrile,

5-chloro-2- (3,4-dibromophenyl) -1-methyl-4-nitropyrrole-3-carbonitrile,

2- (p-chlorophenyl-5- (trifluoromethyl) pyrrole-3,4-dicarbonitrile,

2- (o-bromophenyl) -4-nitro-5- (trifluoromethyl) pyrrole-3-carbonitrile,

3-bromo-5- (3-chloro-4-methoxy) pyrrole-2-carbonitrile,

-bromo-5- (m-bromophenyl) -2-nitropyrole,

3,4-dibromo-5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile,

2- (3-chloro-4-cyanophenyl) -5-nitro-3,4-dichloropyrrole,

3-chloro-1- (p-methoxybenzyl) -5- (3,4-difluorophenyl) -4- (trifluoromethyl) pyrrole-2-carbonitrile,

3-bromo-5- (3,5-dibromo-p-tolyl) -2-nitro-4- (trifluoromethyl) pyrrole,

1- (2,3,3-trichloralyl) -5- (p-chlorophenyl) -3- (trifluoromethyl) pyrrole-2-carbonitrile,

2- (p-iodophenyl) -5-nitro-4- (trifluoromethyl) pyrrole,

4-chloro-5- (m-isopropylphenyl) -3- (trifluoromethyl) pyrrole-2-carbonitrile,

3-bromo-1-methyl-2- (3-fluoro-4-methylphenyl) -2-nitro-3- (trifluoromethyl) pyrrole,

5- (p-bromophenyl) -1-isopropyl-3,4-bis- (trifluoromethyl) pyrrole-2-carbonitrile,

2- (3,4-dichloro-4-methylthio) -5-nitro-3,4-bis- (trifluoromethyl) pyrrole,

5- (m-difluoromethoxyphenyl) pyrrole-2,3-dicarbonitrile, 5- (3-bromo-4-cyanophenyl) -2-nitropyrrole-3-carbonitrile,

4-chloro-1-methoxymethyl-5- (p-bromophenyl) pyrrole-2,3-dicarbonitrile,

4-bromo-5- (2,6-dichloro-4-methylthio) -2-nitropyrrole-3-carbonitrile,

1 - [(p-bromophenoxy) methyl] -5- (m-trifluoromethyl) -4- (trifluoromethyl) pyrrole-2,3-dicarbonitrile,

5- (α-naphthyl) -2-nitro-4- (trifluoromethyl) pyrrole-3-carbonitrile,

4-bromo-5- (3-bromo-4-trifluoromethylphenyl) pyrrole-2-carbonitrile,

3-chloro-2- (2,3-dichlorophenyl) -5-nitropyrrole,

5- (m-cyanophenyl) -3- (trifluoromethyl) pyrrole-2-carbonitrile,

2- (3-bromo-4-isopropoxy) -5-nitro-3- (trifluoromethyl) pyrrole,

5- (p-chlorophenyl) pyrrole-2,4-dicarbonitrile,

2- (3,4-dichlorophenyl) -5-nitropyrrole-3-carbonitrile,

3-bromo-5- (3,4-dichlorophenyl) pyrrole-2,4-dicarbonitrile,

4-bromo-2- (3,4-dichlorophenyl) -5-nitropyrrole-3-carbonitrile,

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5- (3,4-dibromophenyl) -3- (trifluoromethyl) pyrrole-2,4-dicarbonitrile,

2- (m-chlorophenyl) -5-nitro-4- (trifluoromethyl) pyrrole-3-carbonitrile,

5-bromo-3- (3,5-dichloro-4-difluoromethoxy-phenyl) -pyrrole-2-carbonitrile,

2-Bromo-4- (2,5-dibromophenyl) -5-nitro-pyrrol,

2,3-dibromo-4- (p-chlorophenyl) pyrrole-5-carbonitrile,

2,3-dichloro-4- (3,5-difluorophenyl) -5-nitropyrrole, 5-bromo-3- (p-chlorophenyl) -1-hydroxyethyl-4- (trifluoromethyl) pyrrole-2-carbonitrile,

2-chloro-5-nitro-3- (trifluoromethyl) -4- (m-trifluoromethylphenyl) pyrrole,

3- (3-bromo-4-chlorophenyl) -5- (trifluoromethyl) pyrrole-2-carbonitrile,

3- (3-chloro-4-fluorophenyl) -2-nitro-5- (trifluoromethyl) pyrrole,

4-bromo-3- (p-chlorophenyl) -1-methylthiomethyl-5- (trifluoromethyl) pyrrole-2-carbonitrile,

3- (4-bromo-3-cyanophenyl) -4-chloro-2-nitro-5- (trifluoromethyl) pyrrole,

4- (p-chlorophenyl) -2,3-bis- (trifluoromethyl) pyrrole-2-carbonitrile,

3- (2,3-dichlorophenyl) -2-nitro-4,5-bis- (trifluoromethyl) pyrrole,

- (3,4-dichlorophenyl) pyrrole-2,5-dicarbonitrile,

4- (2-bromo-4-methylphenyl) -5-nitropyrrole-2-carbonitrile,

3-bromo-4- (3,5-dichloro-4-methylthiophenyl) pyrrole-2,5-dicarbonitrile,

4- (m-bromophenyl) -3-chloro-5-nitropyrrole-2-carbonitrile,

3- (p-acetamidophenyl) -4- (trifluoromethyl) pyrrole-2,5-dicarbonitrile,

4- (m-bromophenyl) -5-nitro-3- (trifluoromethyl) pyrrole-2-carbonitrile,

4-chloro-3- (3,4-dichlorophenyl) -1- (1-propenyl) pyrrole-2-carbonitrile,

3-bromo-4- (p-dimethylaminophenyl) -5-nitro-pyrrol,

1- (3,4-Dichlorobenzyl) -3- (p-chlorophenyl) -4- (trifluoromethyl) pyrrole-2-carbonitrile,

2-nitro-3- (p-tetrafluoroethoxyphenyl) -4- (trifluoromethyl) pyrrole,

3- (3-bromo-4-isopropylphenyl) pyrrole-2,4-dicarbonitrile,

4- (p-ethylsulfonylphenyl) -5-nitropyrrole-3-carbonitrile,

-bromo-1- (2-methoxyethyl) -4- (2,4,6-trichlorophenyl) pyrrole-2,4-dicarbonitrile,

2-chloro-4- (2,3-dichlorophenyl) -5-nitropyrrole-3-carbonitrile,

3- (p-fluorophenyl) -5- (trifluoromethyl) pyrrole-2,4-dicarbonitrile,

4- (p-iodophenyl) -5-nitro-2-trifluoromethyl) pyrrole-3-carbonitrile,

5-chloro-4- [p- (N-methylacetamido) phenyl] pyrrole-2-carbonitrile, 5-bromo-4- (o-bromophenyl) -1-propargylpyrrole-2-carbonitrile,

2-bromo-3- (o-bromophenyl) -5-nitropyrole,

4- (p-chlorophenyl) -3,5-dichloro-1- (2,3,3-trichloralyl) pyrrole-2-carbonitrile,

3-bromo-5-chloro-4- (p-chlorophenyl) -2-nitropyrrole,

5-bromo-4- [p- (2,2-dichloro-1,1-difluoroethoxy) phenyl] -3- (trifluoromethyl) pyrrole-2-carbonitrile,

2-chloro-3- (2-bromo-4-ethylthiophenyl) -5-nitro-4- (trifluoromethyl) pyrrole,

3- (3-bromo-4-acetylphenyl) -5- (trifluoromethyl) pyrrole-2-carbonitrile, 1-cyano-3- (3,4-dibromophenyl) -5-nitro-2- (trifluoromethyl) pyrrole, 3- bromo-1-methoxymethyl-4- (1H-trifluoromethyl) -5- (trifluoromethyl) pyrrole-2-carbonitrile,

3- (p-chlorophenyl) -4-iodo-5-nitro-2- (trifluoromethyl) pyrrole,

4- (p-bromophenyl) -1 - [(1-ethoxy) ethyl] -3,5-di- (trifluoromethyl) pyrrole-2-carbonitrile,

3- (2-bromo-4-methoxy-phenyl) -5-nitro-2,4-di- (trifluoromethyl) pyrrole,

3- (p-chlórdifluórmetoxyfenyl) pyrrole-2,5-dicarbonitrile,

2- (p-isobutyrylaminophenyl) -5-nitropyrrole-2-carbonitrile,

3-bromo-4- (3,4-dimethoxyphenyl) pyrrole-2,5-dicarbonitrile,

4-chloro-3- (p-chlorophenyl) -1-isopropyloxy (carbonylmethyl) -5-nitropyrrole-2-carbonitrile,

3- (o-bromophenyl) -4- (trifluoromethyl) pyrrole-2,5-dicarbonitrile, 1- (2-chloroethyl) -3- (3,4-dichlorophenyl) -4- (trifluoromethyl) pyrrole-2-carbonitrile,

4- (4-bromo-3-trifluoromethoxyphenyl) -3-chloropyrrole-2-carbonitrile,

3-bromo-4- (2,4-dichlorophenyl) -1-isopropyl-2-nitropyrrole,

4- (3-methoxy-4-cyanophenyl) -3- (trifluoromethyl) pyrrole-2-carbonitrile, 1- (3,4-dichlorobenzyl) -4- (2-methyl-4-iodophenyl) -2-nitro-3 -trifluórmetylpyrol.

1-methyl-4- [3,5-di- (trifluoromethyl) phenyl] pyrrole-2,3-dicarbonitrile,

4- (3,4-dichlorophenyl) -2-nitro-pyrrol-3-carbonitrile,

4- (m-bromophenyl) -1-carbomethoxymethyl-5-chloropyrrole-2,3-dicarbonitrile,

5-bromo-4- (2,6-dichloro-4-methanesulfinylphenyl) -2-nitropyrrole-3-carbonitrile,

4- (p-chlorophenyl) -1- (2,2,2-trifluoroethyl) -5- (trifluoromethyl) pyrrole-2,3-dicarbonitrile,

4- (3,5-dichlorophenyl) -2-nitro-5- (trifluoromethyl) pyrrole-3-carbonitrile,

2-chloro-4- (3-chloro-4-H-methylacetamidophenyl) pyrrole-3-carbonitrile,

2-Bromo-4- (3-bromo-4-n-propylphenyl) -3-nitro-pyrrol,

2,5-dichloro-4- (3,5-dichloro-4-methylthiophenyl) pyrrole-3-carbonitrile,

2,5-dibromo-1- (2,4-dibromophenoxymethyl) -3- (p-chlorophenyl-4-nitropyrole),

4- (3-bromo-4-cyanophenyl) -2-chloro-5- (trifluoromethyl) pyrrole-3-carbonitrile,

2-bromo-1-methyl-3-nitro-4- (α, α, α-trifluoro-p-tolyl) pyrrole,

4- (p-chlorophenyl) -l- (n-butyloxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile,

4- (3,4-methylenedioxyphenyl) -3-nitro-2- (trifluoromethyl) pyrrole,

5-chloro-4- (3-chloro-4-trifluoromethoxyphenyl) -2- (trifluoromethyl) pyrrole-3-carbonitrile,

2-bromo-3- (3,4-dichlorophenyl) -1-ethylthiomethyl-4-nitro-5- (trifluoromethyl) pyrrole,

4- [p- (tetrafluoroethoxy) phenyl] -2,5-di (trifluoromethyl) pyrrole-3-carbonitrile,

3- (3-bromo-4-acetoxyphenyl) -1- (3,4-dichlorophenoxymethyl) -4-nitro-2,5-di- (trifluoromethyl) pyrrole,

4- (p-bromophenyl) -1 - [(2-methoxy) ethyl] pyrrole-2,3-dicarbonitrile,

4- (m-isopropionamidophenyl) -3-nitropyrrole-2-carbonitrile,

5-bromo-4- (2-chloro-4-methylthio) pyrrole-2,3-dicarbonitrile,

5-chloro-4- (p-chlorophenyl) -l-hydroxyethyl-3-nitro-pyrrol-2-carbonitrile,

4- (3,5-dibromo-4-cyanophenyl) -5- (trifluoromethyl) pyrrole-2,3-dicarbonitrile,

4- (4-chloro-2-methylphenyl) -1-isopropylthiomethyl-3-nitro-5- (trifluoromethyl) pyrrole-2-carbonitrile,

5-bromo-4- (3,4-dichlorophenyl) -1- (difluoromethyl) pyrrole-3-carbonitrile,

2-chloro-3- (m-difluoromethoxyphenyl) -4-nitropyrole,

- (2,4-dibromophenoxymethyl) -4- (m-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile,

3- (3-bromo-4-ethoxy) -4-nitro-2- (trifluoromethyl) pyrrole, 3- (2,4,6-trichlorophenyl) pyrrole-2,4-dicarbonitrile, 3- (4-bromo-3) (chlorophenyl) -1- (difluoromethyl) -4-nitropyrrole-25

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carbonitrile,

5-bromo-3- (p-chlorophenyl) -1- (isobutyloxymethyl) pyrrole-3-carbonitrile,

3- (4-bromo-3-methylphenyl) -5-chloro-4-nitro-pyrrol-2-carbonitrile,

3- (2-naphthyl) -5- (trifluoromethyl) pyrrole-2,4-dicarbonitrile,

3- (3-cyano-4-methylphenyl) -1-methyl-4-nitro-5- (trifluoromethyl) pyrrole-2-carbonitrile,

2,3-dichloro-5- (3,4-dichlorophenyl) -4-nitropyrrole, 2- (3,5-dibromo-4-methoxyphenyl) -4,5-dichloropyrrole-3-carbonitrile,

2,3-dichloro-4-nitro-5- (2,4,6-trifluorophenyl) -4-nitropyrrole,

4,5-dibromo-2- (2,3,6-trifluorophenyl) -3-carbonitrile,

4,5-dichloro-2- (3,4-dichlorophenyl) -1- (ethoxymethyl) pyrrole-3-carbonitrile,

4,5-dibromo-1-methyl-2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile,

4,5-dichloro-2- (3,4-dichlorophenyl) -1-ethylpyrrole-3-carbonitrile,

2,3-dichloro-4-nitro-5- [p- (trifluoromethoxy) phenyl] pyrrole,

4,5-dichloro-2- [m- (trifluoromethoxy) phenyl] pyrrole-3-carbonitrile,

4,5-dichloro-2- (3,4-dichlorophenyl) -1-methylpyrrole-3-carbonitrile,

2,3-dichloro-5- (p-chlorophenyl) -1-methyl-4-nitropyrrole,

4-bromo-5-chloro-2- (p-chlorophenyl) -1-methylpyrrole-3-carbonitrile,

5-chloro-2- (3,4-dichlorophenyl) -4-fluoropyrrole-3-carbonitrile,

2-bromo-5- (p-chlorophenyl) -1- (ethoxymethyl) -4-fluoropyrrole-3-carbonitrile,

3-Bromo-5- (p-chlorophenyl) -2-fluoro-4-nitropyrrole.

α- (2,2-dialkoxyethylamino) - [5-cyanostyrene] and α- (2,2-dialkoxyethylamino) -β-nitrostyrene compounds in which each alkoxy moiety each contains 1 to 4 carbon atoms correspond to the following general formula

L

in which

Alk is C 1 -C 4 alkyl, W is cyano or nitro, L is hydrogen, fluoro, chloro or bromo and M and R are each independently hydrogen, C 1 -C 3 alkyl, alkoxy (C 1 -C 3) alkyl, (C 1 -C 3) alkylthio, (C 1 -C 3) alkylsulphonyl, (C 1 -C 3) alkylsulphonyl, cyano, fluorine, chlorine, bromine or iodine atom, nitro, trifluoromethyl, residue of formula R 1 CF 2, R 2 CO or NR 3 r 4, or M and R, attached at adjacent positions together with the carbon atoms to which they are attached, may form a ring in which MR represents a residue

Z is S (O) _n or oxygen;

R 'represents a hydrogen atom, a fluorine atom, a difluoromethyl group, a fluorochloromethyl group or a trifluoromethyl group;

r 2 is C 1 -C 3 alkyl, C 1 -C 3 alkoxy or NR 3 R 4;

R 3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;

R 4 represents a hydrogen atom, a C 1 -C 3 alkyl group or the radical R 4 CO;

R ⁵ represents a hydrogen atom or a C 1 -C 3 alkyl group and n is a number of 0, 1 or 2.

A preferred group of β-substyrene compounds of the invention are those compounds of the formula wherein W is cyano, L is hydrogen, chlorine or bromine, M is hydrogen, fluorine, chlorine or bromine, or methoxy, and R is hydrogen, fluorine, chlorine or bromine, trifluoromethyl, nitro, trifluoromethoxy or methoxy, or M and R bonded in adjacent positions together with the carbon atoms to which they are attached may form a ring in which MR is the radical of the formula

Another preferred group of β-substyrstyrene compounds of the invention are those compounds of the formula wherein W is nitro, L is hydrogen, chlorine or bromine, M is hydrogen, fluorine, chlorine or bromine, or methoxy and R is hydrogen , fluorine, chlorine or bromine, trifluoromethyl, nitro, trifluoromethoxy or methoxy, or M and R bonded in adjacent positions together with the carbon atoms to which they are attached may form a ring in which MR is the radical of the formula

although these compounds of the invention are referred to as β-cyanostyrenes and β-nitrostyrenes, they may also be referred to as dialkyl acetals.

Some of the preferred dialkylacetals of the invention are (E) and (Z).

1. p-chloro-3 - [(formylmethyl) amino] cinnamonitrile diethyl acetal;

2. β - [(formylmethyl) amino] -3,4-dimethoxycinnamonitrile diethyl acetal;

3. (Z) -methyl-p- (2-cyano-1 - [(formylmethyl) amino] vinyl) benzoate diethyl acetal;

4. (Z) 4 - [(formylmethyl) amino] -1-naphthalenacrylonitrile diethyl acetal;

5. (Z) -4 - [(formylmethyl) amino] -p-methylcinnamonitrile diethyl acetal,

6. N- (formylmethyl) -. Beta.-methyl-.alpha .- (nitromethylene) benzylamine diethyl acetal;

7. N- (formylmethyl) -3,4-dimethoxy-α- (nitromethylene) benzylamine diethyl acetal;

8. N- (formylmethyl) -α- (nitromethylene) -2-naphthalenemethylamine diethyl acetal;

9. methyl-p - (α - [(formylmethyl) amino] - (P-nitrovinyl) benzoate-p-diethyl acetal;

10. N- (formylmethyl) -3,4-dimethoxy-α- (nitromethylene) benzylamine dimethylacetal;

11. (E) and (Z) p-Chloro-4 - [(formylmethyl) amino] cmamonitrile dimethylacetal;

SK 279269 Β6

12. p - [(formylmethyl) amino] -3,4-dimethoxycinnamonitrile dimethylacetal,

13. 3,4-Dichloro-β - [(formylmethyl) amino] cinnamonitrile diethyl acetal a

14. p-Trifluoromethyl-β - [(formylmethyl) amino] cinnamonitrile diethyl acetal.

The β-cyanostyrenes, also referred to as cinamonitrildialkylacetals, can be prepared by reacting a substituted or unsubstituted benzoylacetonitrile with 2,2-dialkoxyethylamine of 1 to 4 carbon atoms in each alkoxy moiety, in the presence of an aromatic solvent to give α (2,2-dialkoxyethylamino) The β-cyano-substyrene having 1 to 4 carbon atoms in each alkoxy moiety, which can be reacted with trifluoroacetic acid to form 2-substituted phenylpyrrole-3-carbonitrile. Chlorination of the resulting cyanophenylpyrrole with sodium hypochlorite or sulfuryl chloride in an inert solvent yields insecticidal, acaricidal and nematicidal 4,5-dichloro-2-substituted phenylpyrrole-3-carbonitrile. Conversion to the intermediate pyrrole can also be accomplished by treatment with concentrated hydrochloric acid at a temperature of between about 20 and 40 ° C. The reactions can be described by the following reaction scheme.

Y

I aronetic ra.pŕSi.dlo

In this reaction scheme, A represents a hydrogen atom, a C 1 -C 4 alkyl group optionally substituted by one C 1 -C 4 alkoxy group, one C 1 -C 4 alkylthio group, one to three halogen atoms, or a phenyl group optionally substituted by one or more carbon atoms. C 1-4 alkyl, C 1-4 alkoxy or halogen, C 3 -C 4 alkenyl optionally substituted with 1 to 3 halogen atoms, or C 3 -C 4 alkynyl, X R b is C 1 -C 4 alkyl and L, R and M are as defined above.

Certain novel arylpyrrole compounds of formula (I) wherein A is hydrogen, W is cyano and X, Y, L, M and R are as defined above may be prepared by reaction of N-formyl-DL-phenyl-glycine or substituted H -formylphenylglycine of general formula (VIII)

X ^W 2 ^H ¥ --- CH ^X = MHCH = 0 (VIII). in which R

L is hydrogen, fluorine, chlorine or bromine and M and R are each independently hydrogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, alkylsulfinyl of 1 to 3 carbon atoms, alkylsulphonyl of 1 to 3 carbon atoms, cyano, F, Cl, Br or I, a nitro group, a trifluoromethyl group, a radical of formula R'CFjZ, r2C0 or NR ³ R ^4, or R, and M, bonded in adjacent positions together with the carbon atoms to which they are attached may form a ring in which MR represents a residue

Z is S (O) _n or oxygen;

R1 represents a hydrogen atom, a fluorine atom, a difluoromethyl group, a fluorochloromethyl group or a trifluoromethyl group;

R 2 is C 1 -C 3 alkyl, C 1 -C 3 alkoxy or NR 3 R 4;

r 3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;

R ⁴ represents a hydrogen atom, a C 1 -C 3 alkyl group or the radical R 4 CO;

R 5 represents a hydrogen atom or a C 1 -C 3 alkyl group and n is a number of 0, 1 or 2, with at least an equivalent amount of 2-chloroacrylonitrile and 2 to 3 equivalents of acetic anhydride. The reaction is carried out at elevated temperature, preferably at about 70 to 100 ° C.

The reaction can be described by the following reaction scheme:

Substituted phenylpyrrole-3-carbonitrile is readily converted to the corresponding 4-halo-, 5-halo- or 4,5-dihalo-2-substituted-phenylpyrrole-3-carbonitrile of formula (II) by reaction with at least 1 or 2 equivalents sulfuryl halide, bromine or chlorine in the presence of a solvent such as dioxane, tetrahydrofuran, acetic acid or a chlorinated hydrocarbon solvent.

The preparation of monohalogenated pyrrole-3-carbonitrile requires the use of about one equivalent of the halogenating agent, while two to three equivalents of the halogenating agent are required to prepare dihalopyrrole-3-carbonitrile. When sulfuryl chloride or sulfuryl bromide is used for this purpose, the reaction is generally carried out at a temperature below about 40 ° C, and preferably between about 0 and 30 ° C, and elemental bromine is then usually operated at about 30 to 40 ° C. Other halogenating agents that may be used in this reaction include sodium hypochlorite, tert-butyl hypochloride, N-bromosuccinimide, N-iodosuccinimide, and the like. The reaction can be described by the following reaction scheme.

The carbonitriles of formula (II) according to the invention may also be prepared by reacting substituted or unsubstituted benzoylacetonitrile with 2,2-dialkoxyethylamine of 1 to 4 carbon atoms in each alkoxy group, in the presence of an aromatic solvent, resulting in the formation of α- (2,2-dialkoxyethylamino) 1-p-cyano-substyrene having 1 to 4 carbon atoms in each alkoxy group, which is then converted to 2-substituted-phenylpyrrole-3 by treatment with trifluoroacetic acid or concentrated hydrochloric acid at a temperature between about 20 and 40 ° C. - carbonitrile of formula (II). This reaction may be described by the following reaction scheme wherein R ⁹ is C 1 -C 4 alkyl and L, R and M are as defined above.

In accordance with the invention, the 3-nitro-2-phenylpyrrole and 3-nitro-2-substituted-phenylpyrrole compounds of formula (II) may also be prepared by reacting α-nitroacetophenone or substituted α-nitroacetophenone with 2,2-dialkoxyethylamine containing in each alkoxy parts 1 to 4 carbon atoms. The reaction is generally carried out in the presence of an inert organic solvent, preferably an aromatic solvent, at elevated temperature to give α- (2,2-dialkoxyethylamino) -β-nitrostyrene or substituted α- (2,2-dialkoxyethylamino) -β-nitrostyrene, wherein each alkoxy moiety contains 1 to 4 carbon atoms, which is then converted to 3-nitro-2-phenylpyrrole or 3-nitro-2-substituted-phenylpyrrole of formula (II) by treatment with a mineral acid such as hydrochloric or hydrobromic acid. Reaction of the nitrophenylpyrrole thus prepared with sodium hypochlorite in the presence of an inert organic solvent at reduced temperature affords 2,3-dichloro-4-nitro-5-phenyl- or -5-substituted phenylpyrrole of formula (II).

The reactions can be described by the following reaction scheme.

NaOCl

Tert-Butylbenzoyl and aubstituted benzoyl cyanoacetates

L

It has now been found that in addition to several methods described in the literature for the preparation of substituted and unsubstituted benzoylacetonitriles, these compounds can also be prepared by reacting an appropriately substituted benzoyl halide with an alkali metal hydride and an alkyl cyanoacetate such as tert-butyl cyanoacetate to form tert-butyl (benzoyl or benzoyl). This reaction can be described by the following reaction scheme.

+

NaH + / C-OCH 2 -j CH 3,

CN

L M R melting point H H 4-CF ₃ 146-147 H H 4-F 98-100 H H 4-CN 127-128 H H 4-CF ^ chjo 136 - 13? H H 4-SO p CH 127-139 The 3-F 4-F 91-94 The H 4-CH ₃ S 117-119.5 H H 4-CHF _? CFpO 92-94 3-01 5-Cl 4-chjo -

Benzoylacetonitrile (B)

L

CH

L

(C)

The cyanoacetic acid ester thus formed can then be converted to substituted or unsubstituted benzoylacetonitrile by heating in toluene containing p-toluenesulfonic acid (PTSA). This reaction may be described by the following reaction scheme.

L

PTSA

L

Examples of tert-butyl (benzoyl and substituted benzoyl) cyanoacetates used in the described reactions and examples of the resulting benzoyl nitriles are shown in the following tables.

Tert-Butyl- (b-nMyl · ub-t, bentoyl) cyan * citrates

L M R melting point H H 4-C1 128.5 to 129.5 H 3-01 4-Cl 10? - 107 H H 2-C 153-155 H H 4-OCF ₃ 79-81 The H 4-0F ₃ 44 - 45 H 2-C1 4-01 66 - 67 H H 3-01 80-83 H H 4-CN 126-128 H H 4-Γ 70 - BO H H 4-S0 _? CH 129-132 H 3-F 4-F 74-75 H H 3-CF ₃ 58 - 60 H H 4-CH 103.5 to 106 H H 4-MO ₂ 119-124 3-C1 5-Cl 4-OCH ₃ -

L

M r Melting point ('C)

H 3-Cl 4-Cl

4-OCF 3 -Br

- 94

BI - 84

113-115

N-substituted arylpyrroles of formula (I) may be prepared by reacting an appropriately substituted arylpyrrole of formula (I) wherein A is hydrogen and L, M, R, W, X and Y are as defined above with an appropriate alkylating agent and a suitable alkylating agent. with a base such as brominated alkanol having 1 to 4 carbon atoms and potassium tert-butoxide. This reaction yields an arylpyrrole having the same substituents as the starting material but, in addition to them, a C 1 -C 4 hydroxyalkyl group on nitrogen. Instead of C 1 -C 4 bromoalkanol, cyanogen bromide can be used in this reaction to give the corresponding arylpyrrole of formula (I) substituted on the nitrogen with cyano. These reactions can be described by the following reaction scheme in which BrAlkOH is C1 -C4 bromoalkanol,

K ⁺ O t -Bu is potassium tert-butoxide, L, M, R, W, X and Y are as defined in formula (I) and A is C 1 -C 4 hydroxyalkyl or C 2 cyano.

2-Phenylpyrrole-3,4-dicarbonitrile, 2-bromo-5-phenylpyrrole-3,4-dicarbonitrile and their phenyl-substituted derivatives can be obtained by reacting fumaronitrile with bromine in the presence of a chlorinated hydrocarbon such as chloroform at elevated temperature and subsequent reaction of the resulting bromofumaronitrile nitrile with N- (trimethylsilyl) methyl-

5-methylbenzenethioimidate or a substituted derivative thereof in the presence of hexamethylphosphoramide at elevated temperature to give 2-phenylpyrrole-3,4-dicarbonitrile. Bromination of the 3,4-dicarbonitrile thus prepared affords 2-bromo-5-phenylpyrrole-3,4-dicarbomtril or the corresponding phenyl-substituted derivative when the appropriately substituted H- (trimethylsilyl) methyl-5- is used in the previous reaction. metylbenzéntioimidát. The process described can be described by the following reaction scheme. In this reaction scheme, HMPA is hexamethylphosphoramide and TMS is trimethylsilyl.

Br ₂ / CHC1 ₃ / _R

C KBr)

In the examples that illustrate the process of the invention, the schemes are utilized and these examples provide guidance on the preparation of other compounds of the invention not specifically mentioned herein.

The arylpyrrols of the invention effectively kill insects, mites and nematodes. Thus, the compounds can be used to protect growing or harvested crop plants from attack by said pests.

In practice, about 10 to about 10,000 ppm, preferably from about 100 ppm, are generally applied to the plants, harvested crops or soil on which they are grown to provide effective protection of said crops from insect, mite and / or nematode attack. up to 5000 ppm of arylpyrrole of general formula (I) (this term includes all isomeric arylpyrrole of formulas (II), (III), (IV), (V), (VI) and (VII)) dispersed in water or other cheap liquid carrier. The compounds of the invention may also be used to protect lawns on sports grounds and racecourses from attack by various pests such as caterpillars and others, for example Blissus leucopterus.

The arylpyrrols of the formula (I) according to the invention are also effective in controlling insects, nematodes and mites when applied to the leaves of plants and / or to the soil or water in which the plants grow, at a dose ranging from about 0.125 kg of active substance per hectare to 4; 0 kg of active substance per hectare. Of course, higher application rates of arylpyrroles of formula (I) may also be used to protect crops from insect, nematode and mite infestations, but these higher rates are generally not necessary and harmful to the environment.

While the arylpyrrols of the invention themselves are effective in controlling insects, nematodes and mites, they can be used in combination with other chemicals including other insecticides, nematicides and acaricides. For example, the arylpyrrols of the invention can be effectively used in conjunction with or in combination with phosphates, carbamates, pyrethroids, formamidines, chlorinated hydrocarbons, halobenzoylureas and the like.

The 2-aryl-3-cyano-4,5-dihalopyrrols prepared from the β-cyanostyrene compounds of the invention are effective in killing insects, mites and nematodes, and can also be used to protect growing and harvested crops from attack by said pests.

In practice, about 10 to about 10,000 ppm, preferably from about 100 to about 10,000 ppm, is generally applied to plants, harvested crops or soil on which they are grown to effectively protect said useful crops from insect, mite and / or nematode attack. 5000 ppm of halogenated arylpyrrole dispersed in water or other cheap liquid carrier.

Said halogenated arylpyrrols are also effective in killing insects, nematodes and mites when applied to plant leaves and / or to the soil or water where the plants are growing, at a rate ranging from about 0.125 kg active ingredient per hectare to 4.0 kg active ingredient substances per hectare. Obviously, higher application rates of halogenated arylpyrroles may also be used to protect crops from insect, nematode and mite infestations, but such higher doses are generally unnecessary and harmful to the environment.

Said arylpyrrols may advantageously be formulated into dry compact granules, suspension concentrates, granular preparations, wettable powders, emulsifiable concentrates, powders, powder concentrates, microemulsions and the like, all of which can be used to protect plants by application.

to soil, water and / or plant leaves. These compositions contain the compounds of the invention in admixture with inert, pharmacologically usable solid or liquid diluents.

For example, wettable powders, dusts and powder concentrates of the invention can be prepared by co-grinding about 3 to 20 weight percent of an arylpyrrole of formula (I) with about 3 and 20 weight percent anionic surfactant. One suitable anionic type surfactant is sodium sulfosuccinic acid dialkyl ester, in particular an OTB aerosol surfactant (American Cyanamid Company). These compositions also contain about 60 to 94% by weight of an inert solid diluent such as montmorillonite, attapulgite, chalk, talc, kaolin, diatomaceous earth, limestone, some of the silicates and the like.

Compressed granules which are particularly suitable for application to soil or water can be prepared by grinding about equal parts, usually about 3 to 20 parts, of arylpyrrole and a solid surfactant with about 60 to 94 parts of gypsum. The mixture is then compressed into small granules, about 24/48 mesh or larger.

Other suitable solid surfactants used in the manufacture of the compositions herein are also nonionic block copolymers of ethylene oxide and propylene oxide. These block copolymers are marketed by BASF Wyandotte Corporation under the designation Pluronic 10R8, 17R8, 25R8, F38, F68, F77 or F87. These copolymers are particularly suitable for preparing compressed granules.

In addition to powders and the above-mentioned concentrated preparations, wettable powders and water-dispersible suspension concentrates may also be used. These suspension concentrates are preferably applied to the leaves of the protected plants as aqueous preparations by spraying. These sprays can also be applied to insect and mite pests or to the source of their food.

When the arylpyrrole-containing solid compositions of the invention are used for combined treatment with other pesticidal agents, such compositions may be applied sequentially or a composition comprising a mixture of the two components may be applied.

Similarly, the arylpyrrole-containing liquid compositions of the invention may be mixed with compositions containing other pesticidal agents just prior to application (tankmix), or both may be applied sequentially separately, in the form of liquid sprays. The liquid spray formulations of the invention should contain about 0.001 to 0.1% by weight of the active arylpyrrole of the invention.

The invention is illustrated by the following examples, which are not intended to limit the scope of the invention in any way.

Signal intensities in IR spectra are indicated by the following symbols:

w weak, m medium, with strong, w wide belt.

Signal shapes in NMR spectra are indicated by conventional abbreviations.

Example 1

2-Phenylpyrrole-3-carbonitrile

The following procedure is analogous to the method described in J. Org. Chem., 43, 4273-4276 (1978). 30.00 g of P1-formylphenylglycine, together with 2-chloroacrylonitrile and acetic anhydride, are heated at 90 DEG C. for 1.5 hours. The clear reaction solution was concentrated in vacuo to give 42.5 g of a brownish orange semi-solid. The product is partially purified by silica gel chromatography. According to the proton NMR spectrum, this was a mixture of 73% 2-phenylpyrrole-3-carbonitrile and 27% 2-phenyl-3-cyano-5-methylpyrrole. After recrystallization from chloroform and recrystallization twice from 1,2-dichloroethane, 1.69 g of an off-white solid is obtained, which is 96% by 2-phenylpyrrole-3-carbonitrile according to the proton NMR spectrum. Mp 148-152 ° C.

Microanalysis (MW 168.19): calculated C 78.55, H 4.79, N 16.66; Found: C, 78.52; H, 4.73; N, 16.54.

Example 2

4,5-Dichloro-2-phenylpyrrole-3-carbonitrile and 5-chloro-2-phenylpyrrole-3-carbonitrile

CH

To a solution of 2.00 g (11.9 mmol) of 2-phenyl-3-cyanopyrrole in 80 mL of methylene chloride, 1.90 mL (3.19 g; 23 mL) was added dropwise over 5 minutes while cooling with water and stirring with a magnetic stirrer. 6 mmol) of sulfuryl chloride. The temperature of the mixture is maintained between 5 and 10 ° C during the addition. Stirring at 5 to 10 ° C was continued for 90 minutes, then the reaction mixture was vacuum filtered to isolate 1.28 g of a solid at 192.5 to 195 ° C, identified as 5-chloro-2-phenylpyrrole. 3-carbonitrile. The filtrate is diluted with 400 ml of ethyl acetate, washed twice with 200 ml of water, dried over sodium sulfate, clarified with charcoal, filtered, concentrated in vacuo and the residue triturated with hexane. 0.60 g (21.3% yield) of a pink-red solid is obtained which, after recrystallization from 5 ml of hot acetone, yields 0.32 g (yield 9%) of 4,5-dichloro-2-phenylpyrrole-3-carbonitrile as m.p. 254-255 ° C.

IR (nujole suspension) γ _max : 3165 (bs), 3120 (s), 2245 (s), 1570 (m), 1513 (m), 1440 (s), 1252 (m), 1069 (m), 996 (m), 920 (m), 768 (s), 698 (s), 665 (s) cm -1.

1 H-NMR (dimethylsulfoxide, δ values): 7.73 (d, J = 6.6 Hz, 1.97H, 2 phenyl protons on C 2 and C 8), 7.52 (t, J = 7.3 Hz,

SK 279269 Β6

2.04 H, two phenyl protons on C3 and C5), 7.44 (t, J = 7.3 Hz, 1.02H, one phenyl proton on C4).

C-NMR (DMSO, δ values): 137.51 ₍₂ C pyrrole carbon), 129.25 (C-4 carbon, phenyl), 129.04 (C 3 -C 5 carbons, and phenyl), 128.37 (C Carbon phenyl), 125 , 88 (C ₂ -C and the phenyl carbons), 114.32 (either C 5 carbon pyrrole or the nitrile carbon group), 114.14 (either C 5 carbon pyrrole or the nitrile carbon group), 110.72 (C-4 pyrrole carbon), 89, 78 (C3 carbon pyrrole).

Microanalysis (MW 237.09): calculated 55.72% C, 2.55% H, 11.82% N, 29.91% Cl; Found: C 55.78, H 2.59, N 11.12, Cl 29.74.

Example 3

P-P-Chloro - [(formylmethyl) amino] cinnamonitrile diethyl acetal

4 of the phenyl ring carbon), 129.34 (Z), and 129.89 (e) (either a C ₂ or C 3 -C and C 5 of the phenyl ring), 128.94 (Z), and 128.63 (e) (C ₂ either and C 8 or C 3 and C 5 of the phenyl ring), 121.19 (Z) and 119.50 (E) carbon of the nitrile group), 99.43 (Z) and 100.63 (E) (β-enamine carbon), 61, 88 (Z) and 63.25 (E) (methane of the acetal residue), 62.64 (Z) and 63.03 (E) (methylene carbons of ethoxy groups), 46.32 (Z) and 47.33 (E) (ethylene carbon of ethylamino), 15.26 (methyl carbons of ethoxy).

Microanalysis (MW 294.78): calculated C 61.11, H 6.50, N 9.51, Cl 12.03, found C 61.25, H 6.29, 34% N, 12.35% Cl,

Example 4

2- (p-chlorophenyl) pyrrole-3-carbonitrile

ABOUT

about-/

A solution of 250.00 g (1.39 mol) of p-chlorobenzoylacetonitrile and 203 ml (185.95 g; 1.39 mol) of 2,2-diethoxyethylamine in 1300 ml of dry toluene was heated at reflux for 20 hours equipped with Dean- Stark pen in which 23.8 ml (95.2% of theory) of water was collected. The hot cloudy, dark brown solution containing a large amount of undissolved solids was filtered through a pad of diatomaceous earth and after dilution with 200 ml of ethyl acetate was filtered through a silica gel column (7 cm x 13.5 cm). The filtrate was concentrated in vacuo to give 354.38 g (86.4% crude yield) of a clear dark oil which solidified slowly. After recrystallization from hot cyclohexane, the solid material yielded 324.26% (79.1% yield) of an orange waxy solid. The NMR spectrum indicated that this product consisted of 78% (Z) -isomer and 23% (E) -isomer of p-chloro-β - [(methylmethyl) amino] cinnamonitrile diethyl acetal. The product melts at 60-72 ° C. The following analytical data applies to another sample prepared in an analogous manner.

IR (mull in nujolejy _{m and} x: 3327 (s), 3065 (m), 2197 (s), 1600 (s), 1530 (s), 1314 (m), 1265 (m), 1173 (m), 1154 ( m), 1128 (s), 1100 (s), 1060 (s), 1022 (s), 939 (m), 895 (m), 844 (s), 768 (m), 730 (m) cm).

1 H-NMR (chloroform, δ values): 7.47 (d, J = 8.6 Hz, 2.12H, two aromatic protons), 7.37 (d, J = 8.6 Hz, 2.12H, two) aromatic protons), 5.10 (E) and 4.86 (Z) (bt, 1.25H, 1H, NH), 4.69 (Z) and 4.60 (E) (t, J = 5.1 Hz, 1.05H, one methine proton and acetal carbon), 4.07 (E) and 4.05 (Z) (s, 0.83H, β-cnamine proton), 3.71 (E) and 3.68 (Z) (q, J = 7.1 Hz, 2.22H, two methylene protons of one of the two ethoxy groups), 3.56 (Z) and 3.53 (E) (q, J = 7.1 Hz, 2 , 22H, two methylene protons of one of the two ethoxy groups), 3.18 (t, J = 5.1 Hz, 1.77H, two methylene protons of the ethylene acetal group), 1.20 (t, J = 7.1 Hz, 4 , 90H, six methyl protons of one of the two ethoxy groups).

C-NMR (chloroform, δ values): 161.21 (α-enamine carbon), 136.29 (Z) and 134.60 (E) (either C] or C4 of the phenyl ring), 134.08 (Z) and 132.30 (E) (either Ci or (> ol. biotno 294.10)) (see 11.4.02)

CK

(»1, haotnoti 202.64)

To 108 ml of trifluoroacetic acid was added 5.00 g (0.183 mol) of solid p-chloro-O - [(formylmethyl) amino] cinamonitrile dictylacetal, with stirring at 23 ° C, over 5 minutes. This addition induces an exothermic reaction associated with a temperature rise to 38 ° C. After 32 minutes a solid product began to precipitate. After the addition was complete, the reaction mixture was stirred for a further 30 minutes, then filtered in vacuo and the solid material was washed first with trifluoroacetic acid, then with a mixture of ethyl acetate and hexane and then with hexane. 16.83 g (45.4%) of an off-white solid are obtained, m.p. 165-166 ° C. The following analytical data were obtained for an analogously prepared sample.

IR (nujole suspension) / _max : 3275 (bs), 2225 (s), 1502 (s), 1410 (m), 1275 (m), 1200 (m), 1108 (s), 1023 (m), 999 (m), 908 (m), 843 (s), 752 (s), 695 (s), 620 (s) cm -1.

1 H-NMR (acetone, δ values): 11.22 (very broad s, 0.99H, one proton in the NH group of the pyrrole residue), 7.82 (d, J = 8.9 Hz, 2.46H, two aromatic) phenyl protons), 7.51 (d, J = 8.9 Hz, 2.46H, two aromatic phenyl protons), 7.02 (t, J = 2.6 Hz, 1.01 H, one pyrrole proton on C5 6.58 Ct, J = 2.6 Hz, 0.77H, one pyrrole proton per C4).

C NMR (acetone, δ values): 13.73 ₍₂ C pyrrole carbon), 134.42 (C-4 carbon of p-chlorophenyl), 129.93 (methine carbons at positions 3 and 5 of the phenyl ring), 128.07 ( methic carbons at positions 2 and 6 of the phenyl ring), 121.21 (C5 carbon pyrrole), 117.93 (nitrile carbon), 113.78 (C4 carbon pyrrole), 90.86 (C3 carbon pyrrole).

Microanalysis (MW 202.64): Calculated: 65.19% C, 3.48% H, 13.83% N, 17.50% Cl; Found: C, 64.18; H, 3.52; N, 13.63; Cl, 17.74.

Using the described procedure or using concentrated hydrochloric acid instead of trifluoroacetic acid, the following compounds are obtained:

M and / or R melting point CC) used acid 4-C1 165-166 Iconc. HCl, CF3COOH 3,4-di-Cl 216-221 CFjCOOH 2-01 156-157 CFjCOOH 4-OCF 143-145 CFjCOOH 4-CFj 179-180 CFjCOOH 2,4-11-01 197-199 CFjCOOH 3-C1 150-156 CFjCOOH 4-CN 210-212 CFjCOOH 4-F 167-170 horses. HC1 4-SO ₂ CH ₃ 221-221.5 CFjCOOH 3.4-41-F 173 - 175.5 CFjCOOH 3-CFj 166-168 CFjCOOH 4-COOCHJ 155.5 - 15B CFjCOOH 4-CH 117-137 CFjCOOH 4-KO ₂ 174-177 CFjCOOH

Example 5

4,5-Dichloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile

CM

127.11 (C] carbon of p-chlorophenyl), 114.49 (carbon of the nitrile group), 114.10 (C5 carbon of pyrrole), 110.92 (C4 carbon of pyrrole), 90.09 (C3 carbon of pyrrole).

Microanalysis (MW 271.54): calculated 48.65% C, 1.86% H, 10.32% N, 39.17% C1, found 49.22% C, 2.12% H, 9.85 % N, 39.03% Cl.

Example 6

To a stirred mixture of 0.8 g of 2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile in 70 mL of chloroform was added 2 mL of bromine. The mixture was stirred overnight to give a white solid which was filtered off. According to thin layer chromatography (ethyl acetate-hexane 1: 1) the product is a single component. The prepared substance melts above 230 ° C.

N, 7.11; Br, 40.61; Found: C, 36.40, H, 1.08, N, 6.99, Br.

Following the procedures described in Examples 5 and 6, the following compounds were prepared by substituting 2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile with an appropriately substituted phenylpyrrole-3-carbonitrile:

x ck

To a mechanically stirred solution of 2- (p-chlorophenyl) pyrrole-3-carbonitrile (16.83 g, 83.1 mmol) in glacial acetic acid (450 mL) was added dropwise 14.7 mL (24.70) at 36 ° C over 18 min. g (183.0 mmol) of sulfuryl chloride. The addition induced a slight exothermic reaction associated with a temperature rise to 39 ° C. After a further 16 minutes, the reaction mixture is filtered; the collected solids were washed first with acetic acid and then with water and recrystallized from hot ethyl acetate. The resulting product melts at 259-261 ° C. Additional samples of this product were prepared by similar procedures. Analytical data for one of these products is given below.

IR (nujoleja suspension _max : 3170 (bs), 3100 (m), 2225 (s), 1508 (m), 1097 (m), 825 (s), 717 (a), 660 (m) cm -1)).

1 H-NMR (dimethylsulfoxide, δ values): 7.72 (d, J = 8.6 Hz, 2.0OH, two aromatic protons), 7.56 (d, J = 8.6 Hz, 2.00H, two) aromatic protons).

C-NMR (dimethylsulfoxide, δ values): 136.01 (C2 carbon pyrrole), 133.92 (C4 carbon p-chlorophenyl), 129.09 (C3 and C5 carbons of p-chlorophenyl), 127.41 (C4 carbon p) chlorophenyl)

L M R X Y melting point (’( H The 4-NO ₂ br br 274-277 you M 4-F Cl Cl > 220 H H 4-F br br > 220 H you 4-SO ₂ CH 3 Cl Cl > 230 H 3-F 4-F Cl Cl > 230 H 3-F 4-F br br > 220 2-C1 3-C1 4-01 Cl Cl 2-Br 3-Br 4-Br br br H H 4-OCKj Cl Cl 222-225 H H 4-OCF br br 231-232 H H 4-OCF Cl H

L M R X Y melting point (· < H H 4-CN br br > 230 H H 4-CN Cl Cl > 240 H E 4-SO ₂ CH ₃ br br > 230 H M 4-H ° ₂ Cl Cl 246-249 The 3-C1 4-F br br > 260 H H 3-CSL Cl Cl > 230 U H 4-COCH ₃ Cl Cl 251-254 H CH »CH Cl Cl 244-247 H H _4-CH3 Cl Cl 215-217 H 2-C1 4-Cl br br > 230 H H 3-Cl Cl Cl > 230 U 2-C1 4-C1 Cl Cl > 230 H H 4-Cl br br 273-274 H H 2-C1 br br > 230 H H 4-cr ₃ Cl Cl > 230 H H 4-Br Cl Cl 7 235 H H 2-C1 Cl Cl > • 230 H 3-Cl 4-Cl Cl Cl > 235 H H H Cl Cl 254-255 H H 4-Cl Cl Cl 255-257 H H 4-CF3 br br > 230 H H 4-Cl Cl br 262-263 (decomposition) H H 4-Cl br Cl 250-2J8 (roskled) H 3-Cl 5-C1 Cl Cl > 230 H 3-Cl 4-Cl Cl br > 230 2-C1 4-Cl 5-F Cl Cl 20T-210

Example 7

3-Nitro-2-phenylpyrrole

5.7 g (0.0345 mol) of .alpha.-nitroacetophenone are dissolved in 100 ml of toluene and 4.6 g (0.0345 mol) of diethyl acetal and aminoacetaldehyde are added. The reactants were introduced into a quarter-liter round bottom flask equipped with a DeanStark collar. The tray was filled with molecular sieve (4 x ΊΟ-W m) and the mixture was heated under reflux for 18 hours. Evaporation of the toluene in vacuo afforded 8.36 g of brown oily α- (2,2-diethoxyethylamino) -p-nitrostyrene.

To this oily material was added 50 ml of concentrated hydrochloric acid, and the flask was circulated to turn the oily material into a yellow suspension. After 10 minutes, the solid product was filtered off. 2.48 g of a yellow solid are obtained, which, after recrystallization from a mixture of ether, ethyl acetate and hexane, yields 2.08 g (31%) of the product in two fractions, m.p. 190-192 ° C.

IR: 1485 cm-1 (NO ₂ )

H-NMR (CDCl3 / d6): 6.73 (m, 2H), 7.46 (m, 5H).

Example 8

2,3-Dichloro-4-nitro-5-phenylpyrrole

or » ₂

To a mixture of 1.56 g (0.0083 mol) of 3-nitro-2-phenylpyrrole in 60 ml of dioxane was added dropwise 25.9 g (0.0182 mol) of commercial sodium hypochlorite while cooling in ice. The reaction mixture was stirred for 5 minutes, then acidified with concentrated hydrochloric acid and water and diethyl ether were added. The layers were separated, the upper organic layer was washed with water and, after drying over anhydrous magnesium sulfate, concentrated in vacuo. 2.21 g of a yellow solid are obtained, which is purified by chromatography on silica gel using a gradient elution with ethyl acetate / hexane mixtures containing an increasing portion of ethyl acetate. Evaporation of the appropriate fractions gave 0.77 g (36%) of a yellow solid, m.p. 190-190.5 ° C.

H, 2.35; N, 10.90. Found: C, 46.96; H, 2.86; N, 10.02.

Using the procedures of Examples 7 and 8, respectively, using the appropriately substituted α-nitroacetophenone and 2,2-dialkoxyethylamine, wherein each alkoxy moiety contains 1 to 4 carbon atoms, yields the corresponding substituted α- (2,2-dialkoxyethylamino) -β-nitrostyrene, which by treatment with hydrochloric acid, hydrobromic acid or trifluoroacetic acid to give 3-nitro-2-substituted-phenylpyrrole The reaction of this substituted phenylpyrrole with sodium hypochlorite in dioxane yields the corresponding chloro analogs, while the reaction of this substituted phenylpyrrole with bromine in chloroform gives The products are included in the following overview.

X>!

B

L K

R XI

HH

H 4-Cl

E4-C

KH

3-014-Cl

H 4-Br

BB

H ClCL

X ClCl

X BrBr and BrBr

C CLCl and cici

4-CT ₃ ClCl temperature * heating *

CC)

19o-1JO.5

$ 214-21

803-204 <ro »key4

148.5 to 149

219-220 (roskltd 222-223 (roskled 166-168)

SK 279269 Β6

Example 9

4,5-Dichloro-2- (3,4-dichlorophenyl) -l-methylpyrrole-3-carbonitrile

Cl «

Cl C »

In a 100 mL flask, 2 g of 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile was dissolved in 60 mL of dry tetrahydrofuran to a clear brown solution to which was added 1 equivalent of tert. of potassium butoxide. After a few minutes, the mixture turns into a clear solution, to which 1 equivalent of methyl iodide is added via syringe. The reaction mixture was heated at reflux for 4 hours, then stirred at room temperature overnight. The next day, 50 mL of water was added and the resulting mixture was extracted four times with 50 mL of chloroform each. The organic phases are combined and, after drying over magnesium sulphate, concentrated. The white solid was purified by flash chromatography on silica gel, eluting with ethyl acetate / hexane (1.80 g, 86% yield) as a white solid, mp 154-156 ° C.

The procedure described above replaces 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile with appropriately substituted phenylpyrrole-3-carbonitriles or 3-nitro-2-subst. the following compounds are obtained by phenylpyrrole.

A L · M R X x melting point (’C) c (ca ₃ > ₃ H U 4-CRJ Cl Cl c « ₃ H H 4-CTJ Cl Cl 99-100 CHjSCgHj H 3-C1 4-C1 Cl Cl 74-75 0 Cghj-OC-CHG H 3-C1 4-01 Cl Cl 118-120 C ^ -OCHg H The 4-CF ₃ Cl Cl 99-100 CH H H 4-OCH br br 112-115 CH · * H H 4-C1 br br 197 - 201 CgHjOCHg H H 4-OCF-j Cl Cl 46 - 47 ch ₃ H B 4-0CF ₃ CL Cl 72-73 C ₆ ^H 5- ^CB 1 H H 4-OCF ₃ CL Cl oil C ₂ H ₂ OCH ₂ H H 4-C1 Cl CL - boy ₂ cb ₂ U 3-C1 4-C1 Cl CL 143-145 NC R 3-C1 4-C1 Cl Cl 251-252 H 3-C1 4-01 Cl CL 68-89 Cl 0-CK ₂ E 3-01 4-CL Cl Cl 118-120 IC-C-CHG H 3-C1 4-C1 Cl Cl 115-116 ca ₃ H H 4-CL br CF. J 126-139 H H 4-C1 br CP ₃ 91-92 CjHj -OC ^ H 3-01 4-C1 Cl Cl X18 - 120 ^C 2 ^H 5 ^OCH 2 H H 4-C1 br br 104-105 C ^ -CIL. H H 4-C1 br br 81-82 CB ₃ H The 4-01 br br 197 - 201 CN H E 4-0F ₃ Cl Cl 138-139 CJL ^ -OCUj H H 4-CJ * ₃ br cr ₃ 104-105 H H 4-CFj H cf ₃ 76 - 77 CGH ^ OCH H 3-C1 4-C1 br 3 80-81

X X H A M CN / L X melting temperature (C • | a / b B , M R X A It ch ₃ H H 4-C1 Cl CL 152-153 CjHjOCHj The 3-C1 4-C1 Cl Cl 128-130 ° ₂ “5 y 3-C1 4-01 Cl Cl 137-138 CH ₃ B 3-C1 4-CL Cl CL 154-156 ch ₃ H H 4-CFj br br 145-146 C _{6 -} 5-CH ₂ H H 4-CFj br br 145-147 The 3-a 4-C1 CL CL 95 - 96 C-CH-CHG The 3-C1 4-C1 CL Cl 6? - 70 ch ₂ -c-ch ₂ H 3-01 4-C1 Cl Cl Cl CH'C Chg H 3-C1 4-C1 Cl Cl 147-MB CH ₃ SCH ₂ H 3-C1 4-01 Cl Cl

Example 10 1-Benzyl-4,5-dibromo-2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile

In a 100 ml flask, mix 1.5 g of 4,5-dibromo-2-a, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile and 50 ml of dry tetrahydrofuran and mix the resulting dark dark solution with stirring add 1 equivalent of potassium tert-butoxide. After a few minutes, the resulting solution became clear, then 0.65 g of benzyl bromide was added via syringe. The reaction mixture is heated at reflux overnight and the following day a sample is taken and subjected to thin layer chromatography (a mixture of equal parts of ethyl acetate and hexane,

EN 279269 Β6 which indicates the presence of both starting material and product. The reaction mixture was worked up as follows.

Water (50 ml) was added and the resulting mixture was extracted with chloroform (4 x 50 ml). The organic phases are combined, washed four times with 50 ml of a 10% aqueous sodium hydroxide solution each time, the organic layer is dried over magnesium sulphate and evaporated. The brown solid obtained after crystallization from ethyl acetate / hexane gave 0.75 g (40.7%) of the desired product melting at 145-147 ° C with decomposition.

Example 11

4,5-Dichloro-2- (3,4-dichlorophenyl) -l- (ethoxymethyl) pyrrole-3-carbonitrile

Dissolve 1.0 g (0.003 mol) of 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile in 10 ml of dry tetrahydrofuran and add 0.37 g (0.0033 mol) first. potassium tert-butoxide and then 0.312 g (0.0033 mol) of chloromethyl ethyl ether. The resulting mixture was stirred at room temperature for about 1 hour and then poured into a large volume of water to precipitate the product. The white solid was collected and dried to give 1.0 g (91%) of the title compound, mp 128-130 ° C.

Example 12

4-Chloro-3-cyano-2- (p-chlorophenyl) pyrrole

To a solution of 17.87 g (88.2 mmol; 1.00 equivalents) of 2- (p-chlorophenyl) -3-cyanopyrrole in 800 mL of dioxane was added dropwise with magnetic stirring at 20 ° C over 30 minutes 250.15 g. (5.25% by weight) sodium hypochlorite (13.13 g; 176.4 mmol; 2.00 equivalents). The reaction mixture was stirred at room temperature for 30 minutes, then poured into 2200 ml of water, the resulting mixture was freed from a small amount of solid black by vacuum filtration and the filtrate acidified to pH 2 with concentrated hydrochloric acid. Wash with water to give 22.1 g of a brown solid which is treated with 100 mL of 5% aqueous sodium hydroxide, dissolving most of the material and leaving only a small amount of black solid undissolved.

This black material was dissolved in 100 ml of ethyl acetate, washed with 75 ml of 5% aqueous sodium hydroxide solution, water and saturated aqueous sodium chloride solution each time, the ethyl acetate layer was dried over magnesium sulfate, clarified with charcoal and evaporated on a rotary evaporator. vacuo. 1.10 g (yield 5.3%) of a slightly orange-brown solid are obtained, which, after recrystallization from ethyl acetate-chloroform, yields 0.51 g (yield 2.4%) of an off-white solid 4-chloro-3-cyano-2-. (p-chlorophenyl) pyrrole, m.p. 251-253.5 ° C.

Example 13

Preparation of 5-bromo-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile

2.0 g (0.008 mol) of 2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile were dissolved in 100 ml of dioxane with heating to 40-50 ° C, the resulting solution was cooled to 30 ° C and added thereto. 1.3 g (0.008 mol) of bromine. After stirring at room temperature for 1 hour, the resulting solution was evaporated in vacuo to give 2.2 g (88%) of a gray colored solid, melting at 233-236 ° C with decomposition.

In an analogous manner 5-bromo-2- (3,4-dichloro) -3-nitropyrole was prepared using 2- (3,4-dichlorophenyl) -3-nitropyrrole as starting material.

Example 14

Preparation of 5-bromo-4-chloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile

0.158 8 (0.005 mol) of 5-bromo-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile was dissolved in 5 ml of tetrahydrofuran, an equivalent amount of tert-butyl hypochlorite was added and the solution was stirred overnight.

The reaction solution is poured into water and the precipitate formed is collected. 0.052 g (30%) of the desired product is obtained, m.p.

In an analogous manner, 2-bromo-3-chloro-5- (3,4-dichlorophenyl) -4-nitropyrole can be prepared starting from 2-bromo-5- (3,4-dichlorophenyl) -4-nitropyrrole.

SK 279269 Β6

Example 15

Preparation of 5-bromo-4-chloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile

To a solution of 0.17 g (0.67 mmol; 1.00 equivalents) of 4-chloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile in 100 mL of chloroform at 22 ° C under magnetic stirring for 30 minutes a solution of 0.20 mL (0.62 g; 3.88 mmol; 5.79 equivalents) of bromine in 5 mL of chloroform was added dropwise. There is no exothermic reaction during the addition. The resulting mixture was stirred at room temperature for 3.25 hours, then the clear red reaction solution was evaporated in vacuo. 0.28 g of off-white solid material is obtained which, when mixed with a mixture of hexane and methylene chloride and subsequent vacuum filtration, yields 0.23 g of off-white feather solid product melting at 262 DEG-263 DEG C. with decomposition.

Example 16

Preparation of 5-chloro-4-bromo-2- (p-chlorophenyl) pyrrole-3-carbonitrile

To a solution of 1.00 g (4.22 mmol; 1.00 equivalents) of 5-chloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile in 300 mL of chloroform is added dropwise over a period of 30 minutes at 45 ° C with magnetic stirring. minute solution of 0.40 mL (1.24 g; 7.76 mmol; 1.84 equivalents) of bromine in 25 mL of chloroform. There is no exothermic reaction during the addition and a small amount of solid material precipitates at the end of the addition. The reaction mixture was stirred at room temperature for 19.5 hours and then evaporated in vacuo to give 1.49 g of a slightly orange-white solid which was stirred with a mixture of hexane and methylene chloride. After vacuum filtration, 1.33 g (100% yield) of a feathered white solid is obtained, melting at 250-258 ° C with decomposition.

Example 17

Preparation of 5-chloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile

To a solution of 2.40 g (11.8 mmol: 1.00 equivalents) of 2- (p-chlorophenyl) pyrrole-3-carbonitrile in 65 mL of glacial acetic acid at 35 ° C with magnetic stirring was added dropwise using a syringe. over 5 minutes, 0.75 mL (1.26 g; 9.34 mmol; 0.79 equivalents) of sulfuryl chloride. About 5 minutes after the addition was complete, a solid material precipitated from the reaction solution. The reaction mixture was stirred at room temperature for 45 minutes, then filtered and the solid product was washed thoroughly with cold acetic acid. 2.08 g (74% yield of crude product) of an off-white solid are obtained which, after recrystallization from 75 ml of hot acetic acid, yields 1.63 g (yield 58%) of the product with a purity of 97% by weight and a melting point of 261 ° C.

Example 18

Preparation of 2- (3,4-dichlorophenyl) -1-methylpyrrole-3-carbonitrile

CM

In a 100 ml flask, 2.0 g of 2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile was dissolved in 50 ml of dry tetrahydrofuran and 1 equivalent of potassium tert-butoxide was added. To the resulting slightly cloudy solution was added 1 equivalent of methyl iodide by pipette while the solution was lightly lit. The flask was fitted with a drying tube and the mixture was stirred at room temperature overnight.

The next morning, a light colored precipitate is in the flask. After addition of 50 ml of water, a clear solution is formed first, from which a solid precipitate is formed. This solid material was filtered off and compared to the starting material by thin layer chromatography (25% ethyl acetate in hexane). The chromatogram shows one new spot progressing faster than the starting material. The product obtained is dried overnight in a vacuum oven at 50 ° C to give 1.31 g (62% yield) of the title compound, m.p. 140-142 ° C.

Example 19

Preparation of 4,5-dichloro-2- (3,4-dichlorophenyl) -1-methylpyrrole-3-carbonitrile

Cl CN

CH,

In a 50 ml round bottom flask, 0.5 g of 2- (3,4-dichlorophexyl) -1-methylpyrrole-3-carbonitrile was mixed with 35 ml of glacial acetic acid. The mixture is gently heated with an immersion cooker to dissolve all the pyrrole.

To the resulting clear solution, 2 equivalents of sulfuryl chloride was added by pipette, and the resulting solution was stirred at room temperature for 12 hours. After 12 hours, the reaction solution is poured into 50 ml of water, the precipitated white precipitate is filtered off and dried in a vacuum oven at 50 ° C for 3 hours.

The solid material obtained was identical to that of Example 9 by thin layer chromatography (25% ethyl acetate in hexane) and IR. The yield of the product was 0.36 g (56%).

Example 20

Preparation of 4,5-dichloro-2- (3,4-dichlorophenyl) -1- (2-hydroxyethyl) pyrrole-2-carbonitrile

Cl CN

To a mixture of 2.0 g (6.5 mmol) of 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile and 0.88 g (7.8 mmol) of potassium tert-butoxide in 50 mL of dioxane, under stirring and reflux, was added 0.98 g (7.8 mmol) of bromoethanol. The reaction mixture is stirred at reflux for 12 hours, cooled, diluted with 50 ml of water and extracted several times with chloroform. The combined chloroform extracts were dried (MgSO 4) and concentrated in vacuo. The solid residue was dissolved in ethyl acetate with heating, then the solution was cooled, leaving the predominantly pyrrole to form. The mother liquor is concentrated and the residue is recrystallized from 20% ethyl acetate in hexane. 0.31 g of a white solid is obtained, m.p. 143-145 ° C.

H, 2.29; N, 8.00; Cl, 40.57. Found: C, 44.77; H, 2.29; N, 8.06; Cl, 40.14.

Example 21

Preparation of 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-1,3-dicarbonitrile

To a solution of 1.52 g (5 mmol) of 3-cyano-4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole in 20 mL of anhydrous tetrahydrofuran was added portionwise 617 mg (55 mmol) of potassium tert-butoxide. After 30 minutes, a solution of 583 mg (5.5 mmol) of cyanogen bromide in 1 mL of tetrahydrofuran was added and the reaction was allowed to stand at room temperature overnight. The solvent was removed by rotary evaporation, the residue was stirred with water and extracted with ethyl acetate. The organic layer was washed with water and saturated sodium chloride solution, dried over magnesium sulfate, evaporated and the residue was crystallized from ethyl acetate. 1.0 g of white crystalline product is obtained, m.p. 250.5-252.0 ° C.

ID (nujol): 2255.2245 cm ’» (CN).

13 C-NMR (CDCl 3): 102.7 (N-CN), 113.7 (3-CN).

Mass spectrum; 331.9 (M + 1). For C12H3CP4N3 (330.99) calculated C 43.54, H 0.91, N 12.70, Cl 42.85; Found: C, 43.62; H, 0.93; N, 12.63; Cl, 41.95.

Example 22

Preparation of 4,5-dichloro-2- (3,4-dichlorophenyl) -1- (3-iodo-2-propynyl) -pyrrole-3-carbonitrile

To a mixture of 1.92 g (5.5 mmol) of 4,5-dichloro-2- (3,4-dichlorophenyl) -1- (2-propynyl) pyrrole-3-carbonitrile and 500 ml of methanol is added first with stirring. ml of 10% aqueous sodium hydroxide and then 0.70 g (2.7 mmol) of iodine. The reaction mixture is stirred for 12 hours, then acidified and diluted with 200 ml of water. The precipitated solid material is filtered off and recrystallized from methanol. 0.51 g of white crystalline product is obtained, m.p. 115-116 ° C.

This reaction can also be used to convert any of the substituted N-alkylarylpyrroles of formula (III), (IV), (V), (VI) or (VII) of the invention to the corresponding N-substituted-3-iodo-2-propylarylpyrrole according to the invention.

Example 23

To a solution of 3.0 g (0.0127 mol) of 2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile in 100 ml of tetrahydrofuran was slowly added 5.7 g (0.0254 mol) of N-iodosuccinimide. The reaction mixture was stirred at 25 ° C for several hours until a thin layer chromatography (silica gel; ether-petroleum ether-acetic acid 100: 100: 1) indicated complete reaction. The resulting mixture was evaporated in vacuo to a residue containing pyrrole and succinimide. The crude solid was dissolved in 500 ml of ether and shaken 400 ml of water five times to remove the succinimide. The ether phase is dried over sodium sulphate and evaporated in vacuo. 2.0 g (32.3%) of a gray-brown solid are obtained, from which red vapors are released on heating and having a melting point above 230 ° C.

Example 24

Preparation of 2-phenyl-1-pyrroline-4-carbonitrile

A solution of 0.65 ml (0.01 mol) acrylonitrile and 2.4 g (0.01 mol) N- (trimethylsilyl) methyl-S-methylbenzenethioimidate in 100 ml tetrahydrofuran was cooled to -5 in an ice / acetone cooling bath. A solution of 1.0 ml of a 1N tetrahydrofuran solution of tetrabutylammonium fluoride in 20 ml of tetrahydrofuran is added dropwise over 30 minutes under a nitrogen atmosphere. The resulting solution was stirred at -5 ° C for a further 30 minutes, then allowed to cool slowly to room temperature, stirred for an additional 18 hours, then the solvent was evaporated under reduced pressure. The residue was partitioned between ether and water and the aqueous layer was extracted with fresh ether. The combined organic phases are washed with water and then with a saturated sodium chloride solution, dried over magnesium sulphate and, after filtration, the filtrate is cooled to give 1.2 g (70% of theory) of an off-white solid having the same spectral data as the material described Tsuge [J. Org. Chem. 52, 2523 (1987)].

Analysis: for C10 1HH10NN% requires C, 77.65; H, 5.88; N, 16.47. Found: C, 77.55; H, 5.83; H, 16.39.

Mp 95-97 ° C.

Example 25

Preparation of 2-phenylpyrrole-4-carbonitrile

In a nitrogen atmosphere, 0.23 g (0.001 mol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and 0.1 g (0.001 mol) of 2-phenyl are dissolved in 13 ml of 1,2-dimethoxyethane. of 1-pyrrolidine-4-carbonitrile to a clear orange solution, to which 0.08 ml (0.001 mol) of pyridine is added in a single portion, with a slight exothermic reaction (temperature rise to approximately 28 ° C) and immediate green-brown precipitate .

The resulting suspension was stirred at room temperature for 18 hours at which time most of the solvent was evaporated. The brownish semisolid residue was partitioned between ether and dilute sodium carbonate solution, the red-brown aqueous layer was extracted twice with ether, the combined ether phases were washed with water and saturated sodium chloride solution, dried over magnesium sulfate and the solvent was evaporated under reduced pressure. A white semi-solid residue is obtained which, after recrystallization from ethylene dichloride with decolourisation of charcoal, gives 0.1 g of lavender-colored crystals.

The same product is obtained directly in a single step by condensation of α-chloroacrylonitrile with N- (trimethylsilyl) methyl-S-methylbenzenethioimidate using tetrabutylammonium fluoride as a catalyst (a procedure analogous to the preparation of 2-phenyl-1-pyrroline-4-carbonitrile described above).

Analysis calculated for: C H [H vypočítN requires C, 78.57; H, 4.76; N, 16.67; found: C, 78.65; H, 4.70; N, 16.43. Mp 155-158 ° C.

Example 26

Preparation of 2,4-dibromo-5-phenylpyrrole-3-carbonitrile

To a stirred solution of 0.84 g (0.05 mol) of 2-phenylpyrrole-4-carbonitrile in 20 ml of chloroform was added dropwise a solution of 0.6 ml (0.012 mol) of bromine in 5 ml of chloroform over 20 minutes under nitrogen. The resulting solution was stirred at room temperature for 18 hours, then the solvent was evaporated under reduced pressure. After recrystallization from dichloroethane (charcoal purification), the solid residue yielded 0.6 g of the desired final product melting at 239-242 ° C.

Analysis Found: C]] H ₍₂ jBr2N calculated 40.49% C, 1.84% H, 49.08% Br, 8.59% N. Found 39.88% C, 1.87% H, 48, 81% Br, 8.48% N.

2,4-dibromo-5- (p-chlorophenyl) pyrrole-3-carbonitrile, melting at 270-272 ° C with decomposition, was also prepared as described in Examples 24, 25 and 26.

Example 27

3 ', 4'-dichloro-3- (l, 3-dioxolan-2-yl) propiophenone

ci

THF room temperature

To a vigorously stirred mixture of magnesium shavings (0.64 g, 26 mmol) and tetrahydrofuran (10 mL) in a 100 mL three-necked round-bottom flask equipped with a thermometer, 60 mL dropping funnel and nitrogen inlet was added at 25 °. C dropwise 4.7 g (26 mmol) of 2- (2-bromomethyl) -1,3-dioxolane in 40 ml of tetrahydrofuran. The rate of addition was controlled to maintain the temperature of the mixture below 50 ° C. The reaction mixture was then stirred at 25 ° C for 1 hour.

120 ml of tetrahydrofuran are mixed with 5.0 g (22 mmol) of potassium 3,4-dichlorobenzoate under a nitrogen atmosphere, the prepared Grignard solution is rapidly decanted from unreacted magnesium shavings and added dropwise to the suspension of potassium 3,4-dichlorobenzoate with rapid stirring. . The mixture was stirred at 25 ° C for 24 h, then 50 mL of diethyl ether and 15 mL of 3N hydrochloric acid were added and the layers were separated. The organic layer is washed with saturated aqueous sodium bicarbonate until neutral, then washed once more with 10 ml of sodium chloride solution, dried over sodium sulfate and evaporated on a rotary evaporator. A beige-colored, semi-solid residue is obtained which, after chromatography on silica gel with hexane / ethyl acetate (3: 1) as eluent, yields 4.3 g (60%) of the desired ketoacetal as a white solid, m.p. 115-117 ° C. .

Example 28

Preparation of 3- (3,4-dichlorobenzoyl) propionaldehyde

To 30 ml of a 0.2 M oxalic acid solution prepared by dissolving 0.9 g of oxalic acid dihydrate in 30 ml of water) and 5 ml of ethanol is added 10 g (26 mmol) of 3 ', 4'-dichloro-3- (1,3- dioxolan-2-yl) propiophenone. The reaction mixture was heated at reflux for 1 hour, then allowed to cool, most of the ethanol was removed by rotary evaporation and 100 ml of diethyl ether was added to the residue along with 20 ml of saturated aqueous sodium bicarbonate solution. The layers are separated, the organic phase is dried over magnesium sulphate and evaporated on a rotary evaporator. Chromatography on silica gel using hexane / ethyl acetate (3: 1) as eluent gave 6.3 g (75%) of the desired ketoaldehyde as a white solid.

Example 29

Preparation of 2- (3,4-dichlorophenyl) pyrrole

ci

To a suspension of 6 g (26 mmol) of 3- (3,4-dichlorobenzoyl) propionaldehyde in 60 ml of absolute ethanol was added 4 g (52 mmol) of ammonium acetate. The reaction mixture was heated to reflux for 20 minutes, then allowed to cool, most of the ethanol was removed by rotary evaporation and 200 ml of a mixture of equal portions of dichloromethane and diethyl ether were added to the residue along with 50 ml of water. The layers were separated, the organic phase was dried over sodium sulfate and evaporated on a rotary evaporator. Chromatography on silica gel using hexane / ethyl acetate (3: 1) as eluent gave 4.6 g (83%) of the desired pyrrole as a brownish solid, mp 49-51 ° C.

Example 30

Preparation of 5- (3,4-dichlorophenyl) pyrrole-2-carbaldehyde

0.6 ml (6.5 mmol) of phosphorus oxychloride was added dropwise to the 10 ml dimethylformamide presented in a 50 ml round bottom flask with stirring under nitrogen. The reaction solution spontaneously warms up and slightly yellows. After stirring for twenty minutes in portions, 1 g (4.7 mmol) of 2- (3,4-dichlorophenyl) pyrrole was added and the resulting beige-colored suspension was stirred for 30 minutes, then heated at 50 ° C for 40 minutes. After cooling, a solution of 10 g (122 mmol) of sodium acetate in 15 ml of water was added to the reaction mixture, and the resulting mixture was stirred for 20 minutes. The precipitated beige precipitate was filtered from the reaction mixture and air dried for 20 hours to give 1.1 g (95%) of the substantially pure desired aldehyde melting above 200 ° C.

Example 31

Preparation of 5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile ci

ci

To a suspension of 1.5 g (6.2 mmol) of 5- (3,4-dichlorophenyl) pyrrole-2-carbaldehyde in 20 mL of water and 20 mL of ethanol was added 0.7 g (6.2 mmol) of hydroxylamine-O- sulfonic acid. The reaction mixture was heated at reflux for 1 hour, whereupon a gray precipitate formed. After cooling, the reaction mixture was filtered to give 1.5 g (99%) of substantially pure nitrile as a gray solid, mp 170-171 ° C.

Example 32

Preparation of 3,4-dibromo-5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile

To a solution of 5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile (0.5 g, 2.1 mmol) in tetrahydrofuran (20 mL) was added N-bromosuccinimide (0.8 g, 4.2 mmol) portionwise under nitrogen. The reaction mixture was stirred at 25 ° C for 30 min, then 10 mL of water and 40 mL of diethyl ether were added. The layers were separated, the organic layer was dried over sodium sulfate and evaporated on a rotary evaporator. The residue was chromatographed on silica gel using hexane / ethyl acetate (3: 1) as eluent. 0.5 g (60%) of the desired dibromopyrrole is obtained in the form of a brown solid which melts above 250 ° C.

Example 33

Preparation of 4-phenylpyrrole-3-carbonitrile

To a mixture of cinnamonitrile (5.0 g, 39 mmol) and (p-tolylsulfonyl) methylisocyanide (7.6 g, 39 mmol) in dimethylsulfoxide (35 mL) and ether (65 mL) was added a suspension of 1.86 g of a 60% oil dispersion of sodium hydride ( 1.11 g (46 mmol) in 80 mL of ether. The reaction mixture was allowed to react under nitrogen for 1 hour, then diluted with ether and water. The ether layer was separated, dried (MgSO4) and concentrated in vacuo. The oily residue is chromatographed on silica gel, eluting with a mixture of equal parts of chloroform and ethyl acetate, to give 2.5 g of a cream-colored solid, which is recrystallized from ether / hexane to give 1.15 g of the desired compound, m.p. C.

References: Tetrahedron Letters 5337 (1972); mp 128-129 ° C.

Example 34

Preparation of 2,5-dichloro-4-phenylpyrrole-3-carbonitrile

To a stirred mixture of 4-phenylpyrrole-3-carbonitrile (0.66 g, 3.9 mmol) and dry tetrahydrofuran (20 ml) was added, while cooling in ice water at 6 ° C, over a period of 4 minutes with a 0.66 ml (1.11) syringe. g (8.2 mol) of sulfuryl chloride. The mixture was cooled to 5-10 ° C for 45 minutes, then the cooling bath was removed and the mixture was stirred for an additional 30 minutes. The reaction mixture is poured into 80 ml of ethyl acetate and 40 ml of water, the organic phase is separated, washed with water, dried over sodium sulphate and filtered through a short column of silica gel, which is washed with ethyl acetate. The combined filtrates were concentrated in vacuo to give 0.95 g of a dark colored solid which, after recrystallization from chloroform, gave 0.42 g of off-white crystals melting at 195-196 ° C with decomposition.

Analysis calculated for: C] [H ₆ C [ ₂ N _2] calculated C 55.72, H 2.55, N 11.82, Cl 29.91; Found: C, 55.66; H, 2.65; N, 11.69; Cl, 29.97.

Following the procedures described in Examples 33 and 34, the following analogs were prepared. For synthesis 2,6-dibromo-421

- (p-chlorophenyl) pyrrole-3-carbonitrile was replaced with bromine in dioxane instead of sulfurochloride and tetrahydrofuran in the procedure of Example 33.

R X Y melting point (* C | 4-C1 Cl Cl 237 - 240 (decomposition) 4-CH Cl Cl 103–206 4-C1 br br > 245

Example 35

Ethyl 4- (p-chlorophenyl) pyrrole-3-carboxylate

Cl

To a mixture of 5.63 g of a 60% suspension of sodium hydride in oil and 200 ml of dry ether under nitrogen is added a solution of a mixture of 23.5 g (122 mmol) of ethyl p-chlorocinamate and 19.4 g (122 mmol) from a dropping funnel. (tolylsulfonyl) methylisocyanide in 180 ml of ether and 80 ml of dimethylsulfoxide. The addition takes about 20 minutes and the mixture spontaneously gently refluxes. After stirring for a further 10 minutes, the reaction mixture was diluted with 100 mL of water and extracted four times with ether. The extract was dried over magnesium sulfate, concentrated in vacuo and the solid residue was recrystallized from ethylene dichloride. 7.8 g of crystalline substance are obtained, m.p. 137-138 ° C.

H, 4.81; N, 5.61; Cl, 14.23. Found: C 61.31, H 5.12, N 5.32, Cl 14.57.

Concentration of the mother liquors from the crystallization yields another crude ester which is used for saponification.

Example 36

Preparation of 3- (p-chlorophenyl) pyrrole

H

quack

A mixture of 22.0 g of crude ethyl 4- (p-chlorophenyl) pyrrole-3-carboxylate from the mother liquors (see the previous example) and the recrystallized product from the previous example is stirred at reflux with 150 ml of 10% for 2.5 hours. aqueous sodium hydroxide. The mixture was cooled, extracted with ether and then acidified to give a precipitate which was collected and dried. It will be obtained

11.6 g of product.

A mixture of 10.5 g of the acid obtained in 100 ml of β-ethanolamine was heated under reflux for 3 hours. After cooling, the reaction mixture was poured onto 400 ml of ice and the resulting mixture was extracted four times with chloroform. The chloroform solution, after drying over magnesium sulphate and clarification with activated carbon, is concentrated in vacuo to a brown solid which is chromatographed on silica gel. By using a mixture of equal parts of ethyl acetate and hexane as the eluent, 4.0 g of a white solid are obtained, m.p. 117-118 ° C.

Example 37

Preparation of 3- (p-chlorophenyl) pyrrole-2-carbaldehyde

To 0.86 g (12 mmol) of dimethylformamide in 10 ml of ethylene dichloride was added, under cooling in ice, under nitrogen for 25 minutes 1.49 g (12 mmol) of oxalyl chloride in 10 ml of ethylene dichloride. The cooling bath was removed, the mixture was stirred for 15 minutes, then re-cooled in ice and 1.5 g (8.5 mmol) of 3- (p-chlorophenyl) pyrrole in 25 ml of ethylene dichloride was added over 20 minutes. The cooling bath was removed and after stirring for another 30 minutes the reaction mixture was poured into 50 ml of ice-water and 6 ml of 50% sodium hydroxide solution. The resulting mixture was extracted with ether and chloroform, the combined organic phases were dried over magnesium sulfate and concentrated in vacuo. The residue is purified by chromatography on silica gel using a mixture of equal parts of ethyl acetate and hexane as eluent. 0.63 g of off-white solid is obtained, which is used directly for conversion to 3- (p-chlorophenyl) pyrrole-2-carbonitrile.

Example 38

Preparation of 3- (p-chlorophenyl) pyrrole-2-carbonitrile

To 0.63 g (3.1 mmol) of 3- (p-chlorophenyl) pyrrole-2-carbaldehyde in 10 ml of water was slowly added 0.52 g (4.6 mmol) of hydroxylamine-O-sulfone under stirring and ice-cooling. of acid in 10 ml of water. After the addition was complete, the cooling bath was removed, the reaction mixture was heated for 25 minutes and then cooled. The precipitated solid product is a mixture of said product and the starting aldehyde according to NMR spectroscopy. This mixture was treated with an additional 0.49 g (4.2 mmol) of hydroxylamine-O-sulfonic acid in a total of 30 mL of water in the same manner. The reaction mixture was heated at 60-70 ° C for 2 h. After cooling, the precipitated solid material was collected and purified by silica gel chromatography eluting with ethyl acetate / hexane. 0.40 g of a pink colored solid is obtained, m.p. 114-115 ° C.

Example 39

Preparation of 4,5-dibromo-3- (p-chlorophenyl) pyrrole-2-carbonitrile

To 0.40 g (2.0 mmol) of 3- (p-chlorophenyl) pyrrole-2-carbonitrile in 25 mL of chloroform was added 0.63 g (4.0 mmol) of bromine. After 20 minutes, the precipitate formed was collected and recrystallized from ethyl acetate. 0.21 g of pink colored crystals with a melting point above 250 ° C are obtained.

H, 1.39; H, 44.38; Cl, 9.85; N, 7.77.

Found: C, 36.92; H, 1.32; Br, 44.62; Cl, 9.88; N, 7.50.

Example 40

Preparation of ethyl 5-bromo-4- (p-chlorophenyl) pyrrole-3-carboxylate

Ethyl 4- (p-chlorophenyl) pyrrole-3-carboxylate (1.6 g, 0.0064 mmol) was dissolved in tetrahydrofuran (40 mL) and 1.14 g (0) was added in small portions at 25-28 ° C. H-bromosuccinimide. After the addition was complete, the reaction solution was stirred at room temperature overnight, then concentrated in vacuo and the solid residue was partitioned between water and ether. The ether layer was separated and dried (MgSO4) to give 1.9 g (90%) of a white solid which was purified by slurrying in hexane / ethyl acetate (80:20) to isolate the insoluble solid to give 1.3 g (90%). 62%) of a solid, m.p. 161-164 ° C.

H, 3.34; N, 4.26; Br, 24.33; C1, 10.80.

found C 47.39, H 3.38, N 4.12, Br 24.29, Cl 10.77.

Example 41

Preparation of 5-bromo-4- (p-chlorophenyl) pyrrole-3-carboxylic acid

Br H

Ethyl 5-bromo-4- (p-chlorophenyl) pyrrole-3-carboxylate (15 g, 0.045 mol) was added to 200 ml of 10% sodium hydroxide and the resulting suspension was heated to reflux. After all solids had dissolved, the reaction mixture was refluxed for a further 40 minutes, then cooled, filtered and the filtrate acidified. The precipitated white precipitate was collected and dried. 8.0 g (58%) of a solid with a melting point above 205 ° C are obtained, the NMR spectrum of which (perdeuterodimethylsulfoxide) contains a signal for a pyrrole proton at δ = 7.52. The mass spectrum also corresponds to the monobrominated product.

SK 279269 Β6

Example 42

Preparation of 2-bromo-3- (p-chlorophenyl) pyrrole

Example 44

HjHCHjOHjOK

Preparation of 3,5-dibromo-4- (p-chlorophenyl) pyrrole-2-carbonitrile

8.0 g (0.026 mol) of 5-bromo-4- (p-chlorophenyl) pyrrole-3-carboxylic acid are introduced into 24 ml of aminoethanol, the resulting suspension is slowly warmed to 110-120 ° C and maintained at this temperature for 1 hour. hour. The reaction solution was cooled, poured into water and extracted with ether. A sample of the ether extract was subjected to thin layer chromatography (hexane-ethyl acetate 75:25). The chromatogram contains a major spot progressing faster and a slower progressing minor spot. After the usual work-up, 4.0 g (56%) of a dark-colored solid, 2-bromo-3- (p-chlorophenyl) pyrrole, was obtained from the ether phase which was used immediately to prepare 5-bromo-4- (p). chlorophenyl) pyrrole-2-carbonitrile.

Example 43

Preparation of 5-bromo-4- (p-chlorophenyl) pyrrole-2-carbonitrile

Freshly prepared 2-bromo-3- (p-chlorophenyl) pyrrole weighing 4.0 g (0.015 mol) was dissolved in 25 ml of dry dimethoxyethane, and 3.08 g (0.022 mol) was added while maintaining the temperature below 25 ° C. chlorosulfonyl isocyanate. The reaction solution was stirred overnight, then 6 ml of dimethylformamide was added thereto, and the mixture was stirred for a further 3 hours. After pouring the solution into water, 3.8 g (90%) of a brown solid precipitated, from which, after chromatography on a silica gel dry column, 1.4 g (33%) of a white solid melting at 202-204 ° C were obtained. Hexane / ethyl acetate (80:20) was used as eluent.

Analysis for C | HgBrCl2 requires C, 46.90; H, 2.13; N, 9.95; Cl, 12.61; Br, 28.39;

Found: C, 47.20; H, 2.09; N, 9.80; Cl, 12.36; Br, 27.42.

Dissolve 2.2 g (0.0078 mol) of 5-bromo-4- (p-chlorophenyl) pyrrole-2-carbonitrile in 30 ml of dry dioxane, heat the solution with a solution of 1.3 g (0.008 mol) of bromine in 20 ml. ml of dioxane and then stirred at room temperature overnight. The reaction mixture was poured into water, whereupon it precipitated

2.6 g (92%) of a yellow-red colored solid material. A 1.6 g portion of this material was purified by flash chromatography using hexane / ethyl acetate (75:25) as eluent. 0.8 g of a gray-colored solid is obtained, m.p. 191-194 ° C.

H, 1.38; N, 7.76; Cl, 9.84; Br, 44.3%.

Found: C, 37.46; H, 1.25; N, 7.41; Cl, 9.53; Br, 42.99.

Example 45

Preparation of 3- (3,4-dichlorophenyl) -4-nitropyrrole

H

2.66 g of a 60% suspension of sodium hydride in oil (66 mmol) was washed with dry ether and the hydride was suspended in 150 ml of dry ether. A mixture of 12.0 g (5.5 mmol) of 3,4-dichloro-p-nitrostyrene and 10.8 g (5.5 mmol) of (p-tolylsulfonyl) methylisocyanide in 50 ml of dimethylsulfoxide and 150 ml of is added to the suspension over 15 minutes. ml ether. The reaction mixture was stirred

The mixture was stirred for 1.5 hours and then diluted with 150-200 mL of water and additional ether. The ether layer was separated and, after drying over magnesium sulfate, concentrated in vacuo. The rest formed

The crude product (10.6 g) was purified by chromatography on silica gel eluting with 4: 1 chloroform: ethyl acetate. A solid product fraction of 7.2 g is obtained which, after recrystallization from a mixture of chloroform, ethyl acetate and hexane, yields 3.0 g of a yellow solid melting at 187 DEG-188 DEG C. with decomposition.

For C10HQCl2N2O2 calculated C 46.72, H 2.35, N 10.90; Found: C, 46.96; H, 2.60; N, 9.77.

Example 46

To a mixture of 3- (3,4-dichlorophenyl) -4-nitropyrrole (2.5 g, 9.7 mmol) with chloroform (200 mL) heated to about 40 ° C was added 2.95 g (22 mmol) over 1 minute. sulíúrychloridu.

After an additional hour, the reaction mixture was diluted with 100 mL of saturated sodium bicarbonate solution and 300 mL of ether, the organic layer was separated, dried over magnesium sulfate and concentrated in vacuo. The brown solid is chromatographed on silica gel using chloroform / ethyl acetate (4: 1) as eluent. The orange-colored solid fraction was first recrystallized from chloroform and then re-chromatographed on silica gel using chloroform / ethyl acetate (4: 1) as eluent. 0.36 g of a yellow solid is obtained, m.p. 193-194 ° C.

2,5-Dichloro-3-nitro-4-phenylpyrrole, melting at 193-194 ° C, was also prepared as described in Examples 45 and 46.

Example 47

Preparation of 5- (p-chlorophenyl) pyrrole-2,4-dicarbonitrile

3.0 g (0.015 mol) of 2- (p-chlorophenyl) -3-cyanopyrrole, prepared as described in Example 4, were dissolved in 50 ml of dry dimethoxyethane, and 3.39 g (0.024 mol) of chlorosulfonyl isocyanate was added. As the exothermic reaction proceeds, the temperature rises and the mixture needs to be cooled somewhat. After stirring at room temperature for 3 hours, 6-7 mL of DMF was added, the solution was stirred for 4 hours, then poured into water to precipitate 3.4 g (100%) of a white solid. A 1.0 g sample of this material was purified by dissolving in ethyl acetate and pouring the solution through a pad of silica gel in a 60 mL filter funnel. Concentration of the filtrate gave 0.7 g of a white solid, mp 235-240 ° C.

Following the procedure of Example 47, the following analogs were prepared.

R L melting point (* C) 3-C1 4-C1 > 255 H 4-OCF3 1B5-190 H 4-CF ₃ 180-185

Example 48

Preparation of 3-bromo-5- (p-chlorophenyl) pyrrole-2,4-dicarbonitrile

of bonitrile was dissolved in 20 mL of dioxane and a solution of 0.8 g (0.005 mol) of bromine in 10 mL of dioxane was added. The reaction solution was stirred at room temperature for several hours and then poured into water to precipitate 1.2 g (100%) of a white solid. This solid material has a melting point above 225 ° C and its mass spectrum is consistent with the desired structure.

The following additional compounds were prepared as described in Example 48.

R L melting point (* c) 3-C1 4-C1 > 250 H 4-OCF ₃ 218-223 H 4-C ^p ₃ 239-241

Example 49

Preparation of bromofumaronitrile

Example 51

Preparation of 2-bromo-5-phenylpyrrole-3,4-dicarbonitrile

Fumaronitrile (15.6 g, 0.2 mol) in chloroform (150 ml) was heated to reflux under nitrogen to form a clear solution, to which a solution of bromine (5.3 ml, 0.2 mol) was added dropwise over 30 minutes. 25 ml of chloroform. With this addition, slow decolouration and release of acid vapors (depending on the pH of the paper) occurs. The reaction solution was stirred for an additional 90 minutes, most of the color disappearing, then cooled and the solvent was evaporated under reduced pressure. An amber oil remains, the weight of which roughly corresponds to the theory calculated for bromofumaronitrile. The oily material is distilled in a bead distillation apparatus at a pressure of 27 Pa while maintaining the temperature below 120 ° C (rapid decomposition of the material above this temperature). A semi-solid residue is obtained, which slowly changes to a waxy amber-colored substance with a melting point of 43-47 ° C.

H, 0.64; N, 17.83. Found: C, 29.13; H, 0.75; N, 16.94.

Example 50

Preparation of 2-phenylpyrrole-3,4-dicarbonitrile

To a solution of 4.7 g (0.03 mol) of bromofumaronitrile and 7.1 g (0.03 mol) of N- (trimethylsilyl) methyl-S-methylbenzenethioimidate in 35 ml of hexamethylphosphoramide under a single atmosphere of stirring at room temperature under nitrogen at room temperature. 1.6 ml (0.09 mol) of water is added, which is washed with 10 ml of hexamethylphosphoramide. An exothermic reaction begins almost immediately in the solution, causing the temperature to rise rapidly to 100 ° C and then drop. The resulting dark red solution was stirred at room temperature for 20 hours and then poured into ice water. A resin material precipitated which slowly turned into a beige-colored solid, which was filtered off and washed on the filter with cold water and dried. After further drying in a vacuum oven at 60 ° C, the product is recrystallized twice from ethylene dichloride with clarification with activated charcoal to give a white powdery solid, m.p. 197-200 ° C.

HC CK

1.4 g (0.0075 mol) of 2-phenylpyrrole-3,4-dicarbonitrile are introduced into 35 ml of chloroform under nitrogen, most of the solid material being dissolved. A solution of 0.4 ml (0.008 mol) of bromine in 5 ml of chloroform was added over 20 minutes. Initially, the color of the mixture disappears rapidly, but as soon as the resinous product begins to precipitate, the coloration persists. The reaction mixture was stirred at room temperature for 30 minutes and then refluxed as the resinous material turned to a solid product. The reaction mixture was heated to reflux for 90 minutes, then cooled, and its sample was analyzed by high performance liquid chromatography, indicating that about 60% of the starting material remained in the mixture. 0.2 ml (0.004 mol) of fresh bromine is added in a single portion and refluxing is continued for a further 45 minutes. After this time, the mixture contains 10% of starting material. An additional 0.2 ml (0.004 mol) of fresh bromine (bromine is added to the refluxing suspension) is added and heating to reflux is continued for 30 minutes. The resulting suspension was cooled, stirred at room temperature for 18 hours, then the solvent was evaporated under reduced pressure. A greenish solid is obtained which, after extraction with hot chloroform, remains a dark colored residue. The extract is clarified with activated carbon and filtered while hot. A white precipitate began to precipitate from the clear yellow filtrate. After cooling to -10 ° C, the white solid product was filtered off.

H, 2.21; N, 15.44; Br, 29.41. found C 51.64, H 2.35, N 14.91, Br 28.69. Mp 225-258 ° C.

Example 52

Preparation of 2- (3,4-dichlorophenyl) -5-nitropyrrole-3-carbonitrile

For C12H7N3: calculated: C, 74.61; H, 3.63; N, 21.76. Found: C, 74.45; H, 3.84; N, 21.61.

SK 279269 Β6

To a mixture of 50 ml of acetic anhydride with 0.6 ml of 90% nitric acid was added 3.0 g (0.013 mol) of 2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile, causing a very slight increase in temperature. The reaction mixture is slowly warmed to 30 ° C and maintained at 30-33 ° C until all solid material has gone into solution. Gradually a new solid product begins to precipitate. The mixture was stirred at room temperature for 2-3 hours and then poured into ice water to decompose acetic anhydride. After stirring for 1 hour, the mixture was filtered and the solid product dried. 2.9 g (82%) of crude product are obtained, of which 1.5 g is purified by chromatography on silica gel, eluting with hexane / ethyl acetate (75:25). 0.7 g of a yellow solid is obtained, m.p. 228-231 ° C.

For C 11 H 5 Cl 2 N 3 O 2 calculated 46.80% C, 1.77% H, 14.89% N, 25.17% C1; Found: C, 46.50; H, 1.96; N, 14.27; Cl, 24.30.

In the same manner 2- (p-chlorophenyl) -5-nitropyrrole-3-carbonitrile, m.p. 201 DEG-206 DEG C., was obtained using 2- (p-chlorophenyl) pyrrole-3-carbonitrile as starting material. Similarly, 2- (p-trifluoromethylphenyl) pyrrole-3-carbonitrile gave 2- (p-trifluoromethylphenyl) -5-nitropyrrole-3-carbonitrile as described above, m.p. 164-165.5 ° C.

Example 53

Preparation of 4-bromo-2- (3,4-dichlorophenyl) -5-nitropyrrole-3-carbonitrile

0.5 g (0.0017 mol) of 2- (3,4-dichlorophenyl) -5-nitropyrrole-3-carbonitrile is dissolved in 10 ml of dry dioxane and to this solution is added a dioxane solution of 0.28 g (0.0017 mol) ) of bromine. The resulting solution was stirred overnight and then poured into water to precipitate 0.54 g (88%) of a red-brown solid which, after recrystallization from 5 ml of acetonitrile, yielded 0.26 g of a red-brown solid, mp 195-200 ° C. C.

Analysis calculated for C 11 H 4 BrCl 2 N 3 O 2: C, 36.57; H, 1.10%; N, 11.63; Br, 22.13; Cl, 19.67;

Found: C, 36.46; H, 1.29; N, 11.50; Br, 21.63; Cl, 19.28.

Following the procedure of Example 53, 2- (p-chlorophenyl) -5-nitropyrrole-3-carbonitrile gave 4-bromo-2- (p-chlorophenyl) -5-nitropyrrole-3-carbonitrile, m.p. 180-185 ° C. .

Example 54

5- (3,4-dichlorophenyl) -4-nitro-pyrrol-2-carbonitrile

Cl

To a suspension of 1.2 g (5.1 mmol) of 5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile in 25 ml of acetic anhydride at 30 ° C under nitrogen is added dropwise 0.3 ml (5.1 mmol) of 90. % nitric acid. As a result of the ongoing exothermic reaction, the temperature rises to 45 ° C and the mixture turns to a green-colored solution. The reaction mixture is stirred for 2 hours, then poured into 50 ml of water and stirred vigorously for 5 minutes. The precipitated beige-colored precipitate was filtered off, dissolved in a minimum volume of acetone and chromatographed on silica gel using hexane / ethyl acetate (3: 1) as eluent. 1.2 g (84%) of the desired nitropyrrole are obtained as an off-white solid, m.p. &gt; 200 ° C.

Example 55 3-Bromo-5- (3,4-dichlorophenyl) -4-nitropyrrole-2-carbonitrile

KO.

To a suspension of 0.6 g (2.1 mmol) of 5- (3,4-dichlorophenyl) -4-nitropyrrole-2-carbonitrile in 10 ml of dioxane at 25 ° C under nitrogen is added dropwise a solution of 0.3 g (2, 1 mmol) of bromine in 5 ml of dioxane. The reaction mixture is stirred overnight, then 50 ml of water are added, whereupon a yellow solid precipitates, which is filtered off and dried in a vacuum oven at 45 [deg.] C. under 50 mm Hg. 0.7 g (90%) of the desired brominated pyrrole is obtained as a yellowish solid with a melting point above 200 ° C.

Example 56 4- (P-chlorophenyl) -2- (trifluoromethyl) -2-oxazolin-5-one

To 11.4 g (0.06 mol) of powdered 2- (p-chlorophenyl) glycine is added in a single portion 1.7 ml (0.012 mol) of trifluoroacetic anhydride, resulting in an immediate temperature rise to about 40 ° C and a yellow color By slowly heating the mixture to 70 ° C, some of the solid material dissolves into orange amber oil, and all solid material dissolves in about 2 hours and heating is continued for 1 hour.

The solvent was evaporated under reduced pressure on a rotary evaporator, toluene was added twice to the residue, which was always evaporated under reduced pressure. Trifluoroacetic acid, however, can still be sensed from the final residue. This yellow semi-solid product,

According to high-performance liquid chromatography, it has a purity of more than 90%. This material is the title compound and is used for the next reaction without further purification.

Example 57

Preparation of 2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile

2.5 g (0.01 mol) of 4- (p-chlorophenyl) -2- (trifluoromethyl) -2-oxazolin-5-one are dissolved in 50 ml of nitromethane and 8.0 ml (0 ml) is added in one portion. (10 mol) of 2-chloroacrylonitrile. The reaction solution was stirred and refluxed under nitrogen for 18 hours, and the resulting red-brown solution was cooled to -5 ° C in an ice / acetone mixture, precipitating a precipitate which was filtered off and washed with a small amount of cold nitromethane. The resulting red-brown solid material, after recrystallization from hot ethylene dichloride, afforded 1.8 g (56% of theory) of the desired product as white crystals melting at 238-241 ° C with decomposition.

Using the appropriate aryl glycine in the reaction described in Example 55 and then following the procedure described in this Example, the following 2-aryl-5- (trifluoromethyl) pyrrole-3-carbonitriles were prepared.

r L melting point (’C)

H H 215-218 H _4-CH3 191-193 H 4-OCH 168-180 (Decomposition) 3-Cl 4-Cl 245-246 (Decomposition) H 4-CF ₃ 218-219

Example 58

Preparation of 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile

A suspension of 1.6 g (0.005 mol) of 2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile in 25 ml of acetic acid was heated until all solid material dissolved at about 60 ° C. A solution of 0.8 ml (0.015 mol) of bromine in 10 ml of acetic acid was added dropwise over 15 minutes to the resulting clear solution. The reaction solution was heated to reflux for 6 hours and then stirred at room temperature for 18 hours. High performance liquid chromatography of the reaction mixture sample indicated about 80% conversion to the desired product. The mixture was again heated to reflux and an additional 0.5 ml (0.01 mol) of bromine in 5 ml of acetic acid was added. After refluxing for 3 hours, the conversion to the desired product is greater than 95%. The reaction mixture was cooled and the solvent was evaporated under reduced pressure on a rotary evaporator. Toluene was added to the dark gray solid, which was then evaporated under reduced pressure. However, the residue is still smelled of acetic acid. The material was dissolved in 75 ml of hot toluene to a cloudy solution, which was clarified with charcoal and filtered. A white solid material precipitated from the pinkish filtrate upon cooling to room temperature. After cooling in the freezer, the solid product is filtered off and, after washing with hexane, dried first on filters and then in a vacuum oven at 45 ° C. 1.2 g (ca. 60% of theory) of the product melting at 247 DEG-250 DEG C. with decomposition are obtained.

For C12H5BrClF3N2 calculated C, 41.20; H, 1.43; N, 8.01; Br, 22.89.

10.15% C1.16.31% F;

found: C 41.27, H 1.48, N 8.10, Br 22.92,

10.16% C1, 16.03% F.

The following additional compounds were prepared by bromination of the corresponding 2-aryl-5- (trifluoromethyl) pyrrole-3-carbonitrile, prepared as described in Example 57, as described above.

melting point (’C)

235-238

H 4 -CH 2

3-Cl 4-Cl

244-245

218-223

4-CFj 225-226

Example 59

Preparation of 2- (4-chlorophenyl) -5- (thifluoromethyl) pyrrole-3,4-dicar-

Trifluoroacetic anhydride (3.1 mL, 0.022 mol) was added in portions, giving an immediate yellow color and, to some extent, refluxing. The mixture was slowly heated to reflux while all solid material dissolved to a yellow-orange solution, which was heated for a further 2 hours. The reaction mixture was cooled and the solvent was evaporated under reduced pressure. Toluene was added twice to the residue, which was always evaporated under reduced pressure

276 Pressure. A very thick oily residue is obtained (cq 1800 cm -1). This residue was dissolved in 40 ml of nitromethane, except for small insolubles, and bromofumaronitrile (2.7 g, 0.018 mol) was added in one portion. The resulting solution was heated to reflux for 18 hours, whereupon it turned dark red. The solvent was evaporated under reduced pressure and the dark colored residue was dissolved in dichloromethane. A small amount of insoluble matter was removed by filtration. The material was fractionated by dry silica gel column chromatography using 3% 2-propanol in dichloromethane as eluent. The eluate is collected in suitable fractions. Evaporation of one fraction yielded the desired product as a yellow solid which, after recrystallization from acetonitrile with decolourising charcoal, gave 0.2 g of a pale yellow solid melting at 238-241 ° C with partial decomposition.

A solution of p-chlorobenzoylacetonitrile (1.39 mol, 250.0 g), 2,2-diethoxyethylamine (203 ml, 185.9 g; 1.39 mol) and dry toluene (1300 ml) was heated under reflux with a magnetic stirrer for 20 hours. condenser, the resulting water being trapped in a Dean-Stark pen (23.8 mL; 95.2% of theory). The hot turbid dark brown solution containing a large amount of undissolved solids is filtered through a pad of diatomaceous earth, the filtrate is diluted with 200 ml of ethyl acetate and again filtered through a silica gel column (7 cm x 13.5 cm). Concentration of the filtrate in vacuo afforded 354.3 g (86.4% yield of crude product) of a clear dark oil which slowly solidified. This solid was recrystallized from hot cyclohexane to give 324.2 g (79.1% yield) of an orange-colored waxy solid. According to NMR spectroscopy, this product was a mixture of 78% (Z) - and 23% (E) -isomers of p-chloro-p - [(formylmethyl) amino] cinnamonitrile diethyl acetal, m.p. 60-72 ° C. The following analytical data are available for another similarly prepared sample.

IR (nujolejy suspension _max : 3325 (s), 3065 (m), 2197 (s), 1600 (s), 1530 (s), 1314 (m), 1265 (m), 1173 (m), 1154 (m)) ), 1128 (s), 1100 (s), 1060 (s), 1022 (s), 939 (m), 895 (m), 844 (s), 768 (m), 730 (m) cm

1 H-NMR (chloroform, δ values): 7.47 (d, J = 8.6 Hz, 2.12H, two aromatic protons), 7.37 (d, J = 8 Hz, 2.12H, two aromatic protons) ), 5.10 (E) and 4.86 (Z) (bt, 1.25H, one NH group proton), 4.69 (Z) and 4.60 (E) (t, J = 5.1 Hz) , 1.05H, one methine proton on acetal carbon), 4.07 (E) and 4.05 (Z) (s, 0.83H, proton in β-position of enamine), 3.71 (E) and 3, 68 (Z) (q, J = 7.1 Hz, 2.22H, two methylene protons of one of the two ethoxy groups), 3.56 (Z) and 3.53 (E) (q, J = T, 1 Hz, 2.22H, two methylene protons of one of the two ethoxy groups), 3.18 (t, J = 5.1 Hz, 1.77H, two methylene protons of the ethylene acetal group), 1.20 (t, J = 7.1 Hz, 4.90H, six methyl protons of two ethoxy groups).

C-NMR (chloroform, δ values): 161.21 (α-enamine carbon), 136.29 (Z) and 134.60 (E) (either C 1 or C 4 of the phenyl ring), 134.08 (Z) and 132.30 (E) (either C 1 or C 4 of the phenyl ring) 129.34 (Z) and 129.89 (R) (either C 2 ₍ 6 or C 35 of the phenyl ring), 128.94 (Z) and 128, 63 (E) (either C2,6 or C3 5 of the phenyl ring), 121.19 (Z) and 119.50 (E) (nitrile carbon), 99.43 (Z) and 100.63 (E) ( β-enamine carbon), 61.88 (Z) and 63.25 (E) (methane of the acetal group), 62.64 (Z) and 63.03 (E) (methylene carbons of ethoxy groups), 46.32 (Z ) and 47.33 (E) (methylene carbon of the ethylamino group), 15.26 (methyl carbons of the ethoxy groups).

Microanalysis (mw): calculated C 61.11, H 6.50, N 9.51, Cl 12.03; Found: C, 61.25; H, 6.25; N, 9.34; Cl, 12.35.

By replacing p-chlorobenzoylacetonitrile with the appropriate benzoylacetonitrile and / or 2,2-diethoxyamine each with the corresponding 2,2-dialkoxyethylamine containing 1-4 carbon atoms in each alkyl moiety, the following compounds are obtained.

R

Alk = alkyl of 1 to 4 carbon atoms

L M R ₂ melting point (* C) H H p-CHjOCO <oc ₂ h ₅ ) ₂ 68-73 H p-CH H <oc ₂ h ₅ > ₂ 59 - 69 H N-OCH p-OCH <oc ₂ h ₅ > ₂ Red-orange semi-solid product H ] (OC ^ lj 62-70 p-Cl H H (OCH ₃ ) ₂ - H p-CH H (OCH) ₂ - H m-Cl p-Cl Cocyijjg - H H p-OCF (OCjHjJg - H H p-CFj (oc ₂ h ₅ ) ₂ -

Example 61

2- (p-chlorophenyl) pyrrole-3-carbonitrile

To 108 ml of trifluoroacetic acid was added with stirring at 23 ° C for 45 minutes 54.00 g (0.183 mol) of solid p-chloro-β - [(formylmethyl) amino] cinnamonitrile diethyl acetal. During the addition, an exothermic reaction occurs and the temperature rises to 38 ° C and 32 minutes after the start of the addition a solid precipitate begins to precipitate. The reaction mixture was stirred at room temperature for 30 minutes and then vacuum filtered. The solid material is washed first with trifluoroacetic acid, then with a mixture of ethyl acetate and hexane and finally with hexane. 16.83 g (45.4%) of an off-white solid are obtained, m.p. 165-166 ° C. The following analytical data were obtained for an analogously prepared sample.

IR (nujolejy suspension _max : 3275 (bs), 2225 (s), 1507 (s), 1410 (m), 1275 (m), 1200 (m), 1108 (s), 1032 (m), 999 (m)) 908 (m), 843 (s), 752 (s), 722 (s), 695 (s), 620 (s) are found.

H-HMR (acetone, δ values): 11.22 (very broad singlet; 0.99 H, one NH group proton in pyrrole), 7.82 (d, J = 8.9 Hz, 2.46 Hz, two aromatic phenyl protons), 7.51 (d, J = 8.9 Hz, 2.46 H; two aromatic phenyl protons), 7.02 (t, J = 2.6 Hz, 1.01 H, one proton per 6.58 (t, J = 2.6 Hz, 0.77H, one proton per C4 pyrrole).

C-NMR (acetone, δ values): 137.73 (C2 pyrrole), 134.42 (p-chlorophenyl to C4), 129.93 (meth carbons at positions 3 and 5 of the phenyl ring), 121.21 (C5 pyrrole) ), 117.93 (nitrile carbon), 113.78 (C4 pyrrole), 90.86 (C3 pyrrole).

Microanalysis (MW 202.64): Calculated: 65.19% C, 3.48% H, 13.83% N, 17.50% Cl; Found: C, 64.18; H, 3.52; N, 13.63. 17.74% Cl.

Using the procedure described above, optionally replacing trifluoroacetic acid with concentrated hydrochloric acid, the following compounds are obtained.

and / or R

(• C)

4-C1

165-16 «horses. HCl, CF3COOH

3,4-Cl

21 «- 221

CFjCOOH

2-C1

156-157

CFjCOOH

4-OCF

143-145

CFjCOOH

H and / or R melting point (• c) the acid used 4-CF ₃ 179-180 CFjCOOH 2,4-di-Cl 197-199 cf ₃ cooh 3-C1 150-156 cf ₃ cooh 4-CN 210-212 cf ₃ cooh 4-F 167-170 horses. ΚΟ1 4-SO ₂ CH ₃ 221 to 221.5 cf ₃ cooh 3,4-OI-F 173 to 175.5 CFjCOOH 3CF ₃ 166-168 CFjCOOH 4-COOCH ₃ 155.5 to 158 cf ₃ cooh 4-CH 117-137 cf ₃ cooh 4-N ° ₂ 174-177 cf ₃ cooh

Example 62

4,5-Dichloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile

To a solution of 2- (p-chlorophenyl) pyrrole-3-carbonitrile (16.83 g, 83.1 mmol) in glacial acetic acid (450 mL) was added dropwise 14.7 mL (24 mL) at -18 ° C while stirring with a mechanical stirrer. 70 g (183.0 mmol) of sulfuryl chloride. During the addition, a slight exothermic reaction is associated with a temperature rise to 39 ° C. After a further 16 minutes, the reaction mixture is filtered under vacuum and the solid material is washed first with acetic acid and then with water. This solid melted after recrystallization from hot ethyl acetate at 259-261 ° C.

Additional samples of this product were prepared by analogous procedures. The following section provides analytical data for one of these products.

IR (nujol suspension) γ _max : 3170 (bs), 3100 (m), 2225 (s), 1508 (m), 1097 (M), 835 (s), 717 (m), 660 (m) cm @ -1 '.

N-NMR (dimethylsulfoxide, δ values): 7.72 (d, J = 8.6 Hz, 2.00 H, two aromatic protons), 7.56 (d, J = 8.6 Hz, 2.00 H) , two aromatic protons).

C-NMR (dimethylsulfoxide, δ values): 136.01 (C2 pyrrole), 133.92 (C4 p-chlorophenyl), 129.09 (carbons at positions 3 and 5 of chlorophenyl), 127.41 (C4 p-chlorophenyl) 127.11 (C1-p-chlorophenyl), 114.49 (nitrile carbon), 114.10 (C5 pyrrole), 110.92 (C4 pyrrole), 90.09 (C3 pyrrole).

Microanalysis (MW 271.54): calculated 48.65% C, 1.86% H, 10.32% N, 39.17% Cl; Found: C, 49.22; H, 2.12; N, 9.85; Cl, 39.03.

Example 63

4,5-Dibromo-2- (a, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitrile

L The R X Y melting point <-C) H H 4-C1 br br 273-274 H H 2-C1 br br > 230 H The 4-CF ₃ Cl Cl > 230 The H 4-Br Cl Cl > 235 H H 2-C1 Cl Cl > 230 H 3-C1 4-C1 Cl Cl > 235 H H H Cl Cl 254-255

To a stirred mixture of 0.8 g of 2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile in 70 mL of chloroform was added 2 mL of bromine. The reaction mixture was stirred overnight to give a white solid which was filtered off. This product, with a melting point above 230 ° C, is a single component according to thin-layer chromatography (a mixture of equal parts of ethyl acetate and hexane).

Analysis for: H5Br _{2 2 2} F3N calculated 36.55% C, 1.27% H, 7.11% N, 40.61% Br; Found: C, 36.40, H, 1.08, N, 6.99, Br.

The following compounds are prepared as described above by substituting 2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile each with an appropriately substituted phenylpyrrole-3-carbonitrile.

x cs

L The R X H H 4-NOJ br H The 4-F Cl H H P-4 br The H 4-SO _? CH, Cl H 3-F 4-yl Cl H 3-F 4-F 2-C1 3-CL 4-C1 2-Br 3-Br 4-Br H H 4-OCF-j H H 4-OCF H H 4-OCF ₃ H H 4-one H H 4-CH The H 4-SO ₂ CH ₃ The H 4-MO ₂ H 3-C1 4-C1 H H 3-CF ₃ H H 4-COCH ₃ H 2,3-CH-CH- H H _4-CH3 H 2-C1 4-C1 H H 3-C1 H 2-01 4-C1

Y melting point

ΒΓ 274-277

Cl> 220

Br > 220

Cl > 230

Cl > 230

br br > 220 Cl Cl br br Cl Cl 222-225 br br Cl H br br > 230 Cl Cl > 240 br br > 230 Cl Cl 246-249 br br > 260 Cl Cl > 230 Cl Cl 251-254 Cl Cl 244-247 Cl Cl 215-217 br br > 230 Cl Cl > 230 Cl Cl > 230

Example 64 α- (2,2-Diethoxyethylamino) -β-nitrostyrene and 3-nitro-2-phenylpyrrole

Δ

KO,

5.7 g (0.0345 mol) of α-nitroacetophenone are taken up in 100 ml of toluene and 4.6 (0.0345 mol) of aminoacetaldehyde diethyl acetal is added to the solution. The reactants were introduced into a 4 L round bottom flask equipped with a Dean-Stark trap. The fence was filled with molecular sieves (4 x 10) (0 m) and the mixture was heated under reflux for 18 hours. Evaporation of the toluene in vacuo afforded 8.36 g of α- (2,2-diethoxyethylamino) -β-nitrostyrene as a brown oil which was taken up in 50 ml of concentrated hydrochloric acid. When the flask was stirred in a circular motion, the oil turned into a yellow suspension. After 10 minutes, the solid material was filtered to give 2.48 g of a yellow solid which, after recrystallization from ether-ethyl acetate-hexane, gave the desired product in two fractions. Yield 2.08 g (31%), m.p. 190-192 ° C.

IR ν max ^{: 1485 cm -1} (NO ₂ ).

H-NMR (CDCl3, dimethylsulfoxide, δ): 6.73 (m, 2H), 7.46 (m, 5H).

Further β-nitrostyrene derivatives can be prepared by the described reaction by replacing α-nitroacetophenone with an appropriately substituted α-nitroacetophenone and / or replacing the aminoacetaldehyde diethyl acetal with an appropriate 2,2-dialkoxyethylamine having 1 to 4 carbon atoms in each alkoxy group. The following compounds are obtained in this way.

R 't ^y K-CH-CH (OAlk) R'

Alk = alkyl of 1 to 4 carbon atoms

L M R (0Xlk) ₂ H H p-OCO-CH hoc ₂ h ₅ ) ₂ H _P-CH3 H (OC ₂ h ₅ ) ₂ H m-OCH p-OCH-j (OC ₂ H ₅ ) ₂ H - _x ] - (00 ^) 2 p-Cl H H (OCH ₃ > ₂ H _p-CH3 H _{(OCH3) 2} H H p-cf ₃

Example 65

2,3-Dichloro-4-nitro-5-phenylpyrrole

To a mixture of 3-nitro-2-phenylpyrrole (1.56 g, 0.0083 mol) and dioxane (60 ml) was added dropwise 25.9 g (0.0182 mol) of commercial sodium hypochlorite under ice-cooling. The reaction mixture was stirred for 45 minutes, then acidified with concentrated hydrochloric acid and water and diethyl ether were added. The layers were separated, the upper organic layer was washed with water and, after drying over anhydrous magnesium sulfate, concentrated in vacuo. 2.21 g of a yellow solid are obtained, which, after purification by chromatography on silica gel using a mixture of ethyl acetate and hexane with an increasing portion of ethyl acetate as eluents, yields 0.77 g (36%) of the resulting solid, m.p.

190.5 ° C.

Analysis Found: ₂ CiQHgN2O2Cl calculated 46.72% C, 2.35% H, 10.90% N; Found: C, 46.96; H, 2.86; N, 10.02.

The following examples illustrate the insecticidal, acaricidal and nematicidal activity of the compounds of the invention.

Example 66

Insecticidal and acaricidal activity tests

All tests are performed using technical quality materials. The concentrations indicated are those of the active ingredient. All tests are performed at 27 ° C.

Test for Spodoptera eridania (3rd instar larvae)

The bean leaves of 7 to 8 cm in length are immersed in the test substance suspension, left under stirring for 3 seconds, and then allowed to dry in a fume hood. The treated leaves are then placed in Petri dishes (100 x 10 mm) having a damp filter paper on the bottom, each containing 10 Spodoptera eridania larvae (3rd instar). After five days, the experiment is evaluated for mortality, reduced feeding and / or any abnormal larval development.

Spodoptera eridania - residual effect (7 days)

Plants treated as described above are maintained in a greenhouse for 7 days under high intensity lamp illumination, which is twice the brightness of a bright sunny day in June in New Jersey, simulating a fourteen hour length of day. After seven days, the leaves of the plants are subjected to the described test.

Aphis fabae

Dishes, each containing a single cappuccino (Tropaeolum sp.) Plant of about 5 cm in height, are infested with about 100 to 200 poppy aphid specimens one day prior to the start of the test. Each dish was then sprayed on a rotary table in a fume hood at a rotating speed of 4 rpm using a DeVilbis atomizer with the test composition. Spraying is carried out within two turns of the stage. The sprayer nozzle is about 15 cm from the plant and the sprayer is aimed at the entire plant and aphids. The treated dishes are placed on the side of the white enamel trays and held in this position for 2 days. Mortality is then evaluated.

Tetranychus urticae (phosphate mite)

One of the monthly bean plants grown in bowls is removed at a time when the primary leaves reach a length of 7 to 8 cm and one is removed from each bowl and the remaining are cut off. Small pieces are cut from the leaves of the infested plant and placed on each leaf of the test plant. This is done 2 hours prior to the treatment so that the mites can disperse around the test plant and lay eggs. The size of the pieces of infested leaves is changed so that each leaf of the test plant has about 100 mites. When the test composition is applied, the pieces of leaf used for infection are removed and discarded. Plants infested with mites are immersed in the test composition under stirring for 3 seconds, then allowed to dry in a fume cupboard and maintained for 2 days, and then adult insect mortality is observed on the first sheet.

The second leaf is left on the plant for an additional 5 days, then the mortality of the eggs and / or the new nymphs is evaluated.

Diabrotica undecimpunctata howardi (3rd instar)

1 cm @ 2 of finely ground talc is introduced into a wide-necked screw-capped glass jar and pipetted with 1 ml of the appropriate acetone suspension of the test substance, each containing 1.25 or 0.25 mg of active ingredient. The flasks were charged with a gentle stream of air until the acetone was evaporated. The dried talc is loosened and 1 cm 3 of millet seeds (as feed for experimental insects) and 25 ml of moist soil are introduced into the container. The vessel is sealed and mixed thoroughly (Vortex stirrer). Diabrotica undecimpunctata howardi (3rd instar) larvae are then introduced into each flask and the flasks are loosely sealed to allow air entry for the larvae. Mortality is evaluated after six days. Missing larvae are considered dead because they decompose rapidly and their remains cannot be found. The active substance concentrations used in this test correspond to about 50 and 10 kg / ha.

The results of the experiment are expressed in numbers and letters and have the following meanings:

No effect

10-25% mortality

26 - 35% mortality

36 - 45% mortality

46 - 55% mortality

56 - 65% mortality

66 - 75% mortality

76 - 85% mortality

86 - 99% mortality

100% mortality

R lower ingestion

The results of the described tests are shown in the following overview.

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test substance Aphis Spodoptera eridania Tetranychus Diabrotica fabae urticae undecimpunctata

100 ppm 1000 ppm 100 ppm 7 days ^ ρρ ^ 50. kg / ha co m

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SK 279269 Β6

Example 67

Insecticidal efficacy tests of Heliothis virescens (3rd instar)

The uterine uterine leaves are immersed in the test composition and allowed to dry in a fume hood. After drying, each leaf is cut into quarters which are individually placed in 30 ml plastic medical bowls containing a 5 to 7 ml long piece of moistened dental swab. One larva (3rd instar) is then placed in each dish and the dish is covered with a cardboard lid. After 3 days, mortality and a decrease in the consumption are found. Empoasca abrupta - adults

A 5 cm long bean leaf is immersed in the test composition for 3 seconds with stirring and then allowed to dry in a fume cupboard. The leaf is placed in a Petri dish (100 x 10 mm) with a wet filter paper placed on the bottom, 10 adults of Empoasca abrupta are placed in each dish and the test is run for 3 days. After this time, mortality was determined.

Blatelle germanica (rus) - adult males (bait test)

1 ml of a 1000 ppm test compound solution was pipetted per 1 g of corn flour presented in a 30 ml wide neck flask to prepare a 0.1% bait composition. The bait is dried by introducing a gentle stream of air into the flask and then placed in a half-liter wide-necked bottle containing 10 adult Russian males. The bottle shall be covered with a lid of netting on which a piece of cotton soaked with 10% honey shall be placed. Mortality was found after three days.

Blatella germanica (rus) - adult males (residual effect test)

Pipette 1 ml of 1000 ppm acetone solution of test substance slowly into the petri dish bottom (150 x 15 mm) so that the bottom of the dish is covered as evenly as possible. After drying of the deposited material, 10 adult Russian males were placed in each dish and the dish was capped. Mortality is calculated after 3 days.

Spodoptera eridania (3rd instar larvae) - systemic efficacy

The test compound is made into an emulsion containing 0.1 g test substance, 0.2 g emulsifier (Emulphor EL-620), 10 ml acetone and 90 ml water. This formulation is diluted with ten times the amount of water to give a 100 ppm emulsion. This emulsion is further diluted 10-fold with water as necessary. Monthly bean plants whose primary leaves have already reached a length of 7 to 8 cm are cut off at least 3 cm above the soil surface to prevent soil bacteria from contaminating the soil during the test. The truncated plants are placed in the test emulsions and coated with a piece of cotton wool which keeps at a certain distance above the bottom of the bottle while preventing evaporation and volatilization of the test substance. This arrangement is kept at 27 ° C for 3 days to allow the plant to receive the active substance, then one leaf is taken from the plant and placed in a Petri dish (100 x 10 mm) with 10 specimens of Spodoptera eridania larvae. After 3 and 5 days, mortality and a detrimental effect on the size of the ingestion are found.

Empoasca abrupta - adults (systemic effect)

The test compound is made into an emulsion consisting of 0.1 g of active ingredient, 0.2 g of emulsifier (Emulphor EL-620), 10 ml of acetone and 90 ml of water. This composition is diluted with ten times the amount of water to give an emulsion with a concentration of 100 ppm. This emulsion is further diluted 10-fold with water as necessary. Monthly bean plants whose primary leaves have already reached a length of 7 to 8 cm are cut off at least 3 cm above the soil surface to prevent soil bacteria from contaminating the soil during the test. The truncated plants are placed in the test emulsions and coated with a piece of cotton wool which keeps at a certain distance above the bottom of the bottle while preventing evaporation and volatilization of the test substance. This arrangement is kept at 27 ° C for 3 days to allow the plant to receive the active substance, then one leaf is taken from the plant and placed in a Petri dish (100 x 10 mm) with 10 specimens of adult Spodoptera eridania. Mortality was found after 3 days.

The results of these tests are expressed using the same scale as in Example 66.

The results obtained are summarized in Table II below.

SK 279269 Β6 ίCQ p 9 P ·

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SK 279269 Β6

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SK 279269 Β6

Example 68

A) Evaluation of test compounds as nematicidal agents

Maintaining culture

Cultures of Caenorhabditis elegans (Bristol strain from J. Lewis) are maintained on Escherichia coli stands on agar plates at 20 ° C. Cultures are renewed weekly.

The nematodes used for the assay are eluted from cultures up to 5 days old using a modified Fresh Ascaris Ringers Solution (FARS). The worms are further washed with gentamicin-containing FARS to suppress bacterial contamination and centrifuged to separate from the wash solution. This procedure is repeated three times. The washed worms are introduced into C. briggsae maintenance medium (C. brigssae Maintenance Medium - CbMM; GIBCO) to which gentamycin (600 units / ml) and mycostatin (0.5 mg / ml) were added.

To save active substances and work, tests are performed with a mixture of three compounds selected on the basis of the results of another high-capacity screening program.

The compounds are dissolved in acetone and the solutions are diluted with equal volumes of water. The final concentration of each compound in the test mixture is 150 ppm. The test material is transferred to a single well in a sterile 96-well tissue culture plate (COSTAR) using a micropipette (25 μΐ) and the solvent allowed to evaporate. The plates thus treated are either used immediately or stored in a freezer without appreciable detriment to the active compounds.

50 g of freshly prepared C. elegans in CbMM was added by micropipette to each well of the drug and to several control wells on each plate and incubated at 20 ° C.

After 4, 24 and 48 hours, the efficiency is evaluated under a scanning microscope. Immediately before reading, it taps slightly into the plate to stimulate worm movement. Activity is assessed subjectively but semiquantitatively based on the effect of the test compound on the mobility of adults and larvae. The evaluation shall be carried out according to the following criteria:

= no movement, = significantly reduced mobility at about 95% worms, = reduced mobility, = slightly reduced mobility, = normal mobility, the same as in the control experiment.

Other factors indicative of efficacy are readily detectable. Examples include death, rigor mortis, contractions, coiling, paralysis, abnormal twitching, reduction of worm populations in 48 hours, and other deviations from normal behavior.

Test procedure for Caenorhabditis elegans day 0 ♦ inoculation of agar plate with E. coli 30 to 50 C. elegans * incubation at 20 ° C day 4 ♦ isolation of new C. elegans population popul antibiotic wash ♦ transfer to CbMM ♦ dosing C elegans (25 to 100 pm) into wells with test substance ³ ) ♦ observation of activity in 4 hours day 5 ♦ observation of activity day 6 ♦ observation of activity

Note: ^(a ) wells with test substance may be prepared either immediately or in advance and stored in a freezer.

The data found in this test are summarized in Table III below.

B) Activity Test against Meloidogyne incognita

Populations of Meloidogyne incognita are kept on greenhouse tomatoes (Fireball). Eggs are taken from the roots of the infested plants and placed on wet filter paper for 24 hours to hatch. The hatched larvae invade the water under the filter paper. For the test, the larvae are transferred to wells in plates containing test compounds deposited as a 3% acetone solution at a concentration of 300 ppm. Approximately 10 larvae are introduced into each well. Mortality was observed after 24 hours, when the infected well plates were kept at 27 ° C.

The data obtained in this test, expressed using the same scale as in the previous examples, are summarized in the following Table III.

T and B III

test substance C. elegans 150 ppn adult larvae Meloidogyne incognita 300 ppm 4,5-Dichloro-2- (p (trifluoromethoxy) phenyl) pyrrole-3-carbonitrile - - 4 4,5-dichloro-2- (a, e, etrlfludr-p-tolyl) pyrrole-3-carbonitrile 9 9 5 4,5-dibrdn 2triťluór-p-tolyl) pyrrole-3-carbonitrile WITH 9 0 2,3-dichloro-4-nitro-5-phenylpyrrole 0 0 9 2,3-dichloro-5- (p-chloro <5rfenyl) 4-nltrapyrcl 9 9 9 2,3-dichl6r-5- (3,4-dichlorophenyl) -4nitropyrol 9 9 0 2- (p-bromophenyl) 4,5-dichloro-3-nitropyrrole 9 9 6 3,3-Amino-4-nitro-5- (α, α, β-trifluoro-p-tolyl) pyrrole 9 9

Example 69

Using the procedures described in Examples 66 and 67, the efficacy of the compounds of the invention is evaluated against various insects, including Empoasca abrupta (EA), Heliothis virescens (HV), Spodoptera eridania (SE) and Blatella germanica (BG). The results are expressed using the same scale as in the previous examples. The results are shown in Table IV below. When two or more assays were performed with the same compound, averages were calculated from the results. A dash indicates that the test has not been performed in this case.

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SK 279269 Β6

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SK 279269 Β6

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Claims (25)

PATENT CLAIMS A method for controlling insects, nematodes and mites, characterized in that the insects, nematodes and mites, the place where they are propagated, their food or natural habitat are contacted with an insecticidally, nematocidally or acaricidally effective amount of an arylpyrrole compound of the general formula ( 1) wherein X represents a hydrogen, fluorine, chlorine, bromine or iodine atom, or a trifluoromethyl group; Y represents a fluorine, chlorine, bromine or iodine atom, a trifluoromethyl group or a cyano group; W is cyano or nitro; A represents a hydrogen atom, a C 1 -C 4 alkyl group optionally substituted by one to three halogen atoms, one hydroxy group, one C 1 -C 4 alkoxy group, or one, an alkylthio group having 1 to 4 carbon atoms, one phenyl group optionally substituted C 1 -C 3 alkyl, C 1 -C 3 alkoxy or C 1 -C 3 halogen, one phenoxy optionally substituted with 1 to 3 halogens or one benzyloxy optionally substituted with one halogen, furthermore represents a C 1 -C 3 alkoxycarbonylmethyl group C 4 -C 4 alkoxy, C 3 -C 4 alkenyl optionally substituted with 1 to 3 halogen atoms, cyano, C 3 -C 4 alkynyl optionally substituted with one halogen atom, dialkylaminocarbonyl containing 1 to 3 alkyl groups in each alkyl moiety 4 carbon atoms or a cycloalkylaminocarbonyl group having 4 to 6 carbon atoms in the cycloalkyl moiety; L is hydrogen, fluorine, chlorine or bromine; and M and R are each independently hydrogen, (C1-C3) alkyl, (C1-C3) alkoxy, (C1-C3) alkylthio, (C1-C3) alkylsulfonyl, (C1-C3) alkylsulfonyl; up to 3 carbon atoms, cyano, fluorine, chlorine, bromine or iodine, nitro, trifluoromethyl, the radical of formula R 1 CF 2 Z, R 2 CO or NR 3 r 4, or M and R, attached at adjacent positions together with the carbon atoms to which they are attached, they may form a ring in which MR represents a residue Z is S (O) _n or oxygen; R1 represents a hydrogen atom, a fluorine atom, a difluoromethyl group, a fluorochloromethyl group or a trifluoromethyl group; R 2 is C 1 -C 3 alkyl, C 1 -C 3 alkoxy or NR 3 R 4; r 3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R 4 represents a hydrogen atom, a C 1 -C 3 alkyl group or the radical R 4 CO; R 5 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms and n is an integer of 0, 1 or 2. 2. A process according to claim 1, wherein the arylpyrrole compounds are those selected from the group consisting of: 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile, 4,5-dichloro-2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile, 2,3-dichloro-4-nitro-5- (α, α, α-trifluoro-p-tolyl) pyrrole, 2,3-dichloro-5- (3,4-dichlorophenyl) -4-nitropyrrole, 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile, 3,4-dibromo-5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile, 2,4-dibromo-5- (p-chlorophenyl) pyrrole-3-carbonitrile, 5- (p-chlorophenyl) pyrrole-2,4-dicarbonitrile, 3-bromo-5- (3,4-dichlorophenyl) pyrrole-2,4-dicarbonitrile, 4,5-dichloro-1- (ethoxymethyl) -2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile, 4-bromo-2- (p-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile and 4-bromo-2- (3,4-dichlorophenyl) -5- (trifluoromethyl) pyrrole- 3-carbonitrile. 3. A method for the protection of growing plants from insect, nematode and mite infestation, characterized in that an insecticidally, nematocidally or acaricidally effective amount of an arylpyrrole compound defined by in claim 1. 4. A process according to claim 3, wherein the arylpyrrole compounds are those selected from the group set forth in claim 2. The method of claim 3, wherein the arylpyrrole compound as defined in claim 1 is applied to the plants or the soil in which the plants grow in an amount of 0.125 to 4.0 kg / ha. A process according to claim 3, wherein the arylpyrrole compound of formula (I) is applied to the leaves of the plants or to the soil or to the water in which they grow, in the form of a liquid composition containing 10 to 10,000 ppm an arylpyrrole compound as defined in claim 1. 7. An insecticidal, acaricidal and nematicidal composition, characterized in that it contains, as active ingredient, an arylpyrrole compound as defined in claim 1. 8. The insecticidal, acaricidal and nematicidal composition of claim 7, wherein the arylpyrrole compound comprises a compound selected from the group set forth in claim 2. Arylpyrrole compounds of formula (I), wherein the individual symbols have the meaning given in claim 1, but X is not a hydrogen atom. Arylpyrrole compounds according to claim 9, wherein A represents a hydrogen atom or a (C 1 -C 4) alkoxymethyl group, W represents a cyano or nitro group, X and Y each represent a chlorine atom, a trifluoromethyl group or a bromine atom; R is fluorine, chlorine or bromine, trifluoromethyl or trifluoromethyloxy SK 279269 nu6 nu; M represents a hydrogen, fluorine, chlorine or bromine atom and L represents a hydrogen or fluorine atom. Arylpyrrole compounds according to claim 9 selected from the group consisting of 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile, 4,5-dichloro-2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile, 2,3-dichloro-4-nitro-5- (α, α, α-trifluoro-p-tolyl) pyrrole, 2,3-dichloro-5- (3,4-dichlorophenyl) -4-nitropyrrole, 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile, 3,4-dibromo-5- (3,4-dichlorophenyl) pyrrole-2-carboritrile, 2,4-dibromo-5- (p-chlorophenyl) pyrrole-3-carbonitrile, 5- (p-chlorophenyl) -3- (trifluoromethyl) pyrrole-2,4-dicarbonitrile, 3-bromo-5- (3,4-dichlorophenyl) pyrrole-2,4-dicarbonitrile, 4,5-dichloro-1- (ethoxymethyl) -2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile, 4-bromo-2- (p-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; and 4-bromo-2- (3,4-dichlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile. A process for the preparation of arylpyrrole compounds of formula (Ia) falling within the scope of compounds of formula (I) according to claim 1 wherein: X represents a hydrogen, chlorine or bromine atom, Y represents a chlorine or bromine atom; A represents a hydrogen atom; W is cyano or nitro; L is hydrogen, fluorine, chlorine or bromine, and M and R are each independently hydrogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, alkylsulfinyl of 1 to 3 carbon atoms, alkylsulphonyl of 1 to 3 carbon atoms, cyano, F, Cl, Br or I, a nitro group, a trifluoromethyl group, a radical of formula R'CF2Z, R ² CO or NR3R4, or F, and R, bound at adjacent positions, together with the carbon atoms to which they are attached, may form a ring in which MR represents a residue Z is S (O) _n or oxygen; R ¹ represents a hydrogen atom, a fluorine atom, a difluoromethyl group, a fluorochloromethyl group or a trifluoromethyl group; R ² is C 1 -C 3 alkyl, C 1 -C 3 alkyl, or _NR3R4; r 3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R 4 represents a hydrogen atom, a C 1 -C 3 alkyl group or the radical R 4 CO; R 3 represents a hydrogen atom or a C 2 -C 3 alkyl group and n is a number of 0, 1 or 2, characterized in that the benzoylacetonitrile or α-nitroacetophenone corresponding to the general formula L M n ___c - ch ₂ w wherein L, M, R, and W are as defined above, reacted at elevated temperature with 2,2-dialkoxyethylamine containing from 1 to 4 carbon atoms in each alkoxy moiety to form α- (2,2-dialkoxyethylamino) -fl -cyanstyrene or α- (2,2-dialkoxyethylamino) -p-nitrostyrene, each containing from 1 to 4 carbon atoms in each alkoxy moiety and corresponding to the general formula L wherein Alk is C 1 -C 4 alkyl and L, M, R, and W are as defined above and treated with a mineral or organic acid to form the desired arylpyrrole. 13. The process of claim 12, wherein the reaction of the 2,2-dialkoxyethylamine having 1 to 4 carbon atoms in each of the alkoxy moieties with benzoylacetonitrile or α-nitroacetophenone is carried out in the absence of a solvent or in the presence of an inert organic solvent. 14. A process according to claim 12, wherein the intermediates are [alpha] - (2,2-dialkoxyethylamino) -p-cyanostyrene or [alpha] - (2,2-dialkoxyethylamino) -P-nitrostyrene, which contain in each alkoxy parts having 1 to 4 carbon atoms each, acting with hydrochloric acid, hydrobromic acid or trifluoroacetic acid. Intermediates for the preparation of arylpyrrole compounds as defined in claim 9, comprising α- (2,2-dialkoxyethylamino) -β-cyanostyrenes and α- (2,2-dialkoxyethylamino) -β-nitrostyrenes of the general formula: Alk represents an alkyl group having 1 to 4 carbon atoms; W is cyano or nitro, L is hydrogen, fluorine, chlorine or bromine; and M and R are each independently hydrogen, (C1-C3) alkyl, (C1-C3) alkoxy, (C1-C3) alkylthio, (C1-C3) alkylsulfinyl, (C1-C3) alkylsulfonyl to 3 carbon atoms, cyano, F, Cl, Br or I, a nitro group, a trifluoromethyl group, a radical of formula R'CF2Z, R ² CO or NR3R4, or F and R attached at adjacent positions together with the carbon atoms to which they are linked, they can form a ring in which MR represents a residue Z is S (O) _n or oxygen; R1 represents a hydrogen atom, a fluorine atom, a difluoromethyl group, a fluorochloromethyl group or a trifluoromethyl group; R ² is C 1 -C 3 alkyl, C 1 -C 3 alkyl, or NR3R4; r 3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; r 4 represents a hydrogen atom, a C 1 -C 3 alkyl group or the radical R 4 CO; r 5 represents a hydrogen atom or a C 1 -C 3 alkyl group and n is a number of 0, 1 or 2. 16. A process according to claim 1, wherein the arylpyrrole compound of formula (I) is a compound of formula (Ia) wherein: X represents a hydrogen, chlorine or bromine atom; Y represents a chlorine or bromine atom; W is cyano or nitro; A represents a hydrogen atom, a C 1 -C 4 alkyl group optionally substituted by one to three halogen atoms, one C 1 -C 4 alkoxy group or one C 1 -C 4 alkylthio group, one phenyl group optionally substituted by a C 1 alkyl group C 3 -C 3 alkoxy, C 1 -C 3 alkoxy or C 1 -C 3 halogen, furthermore C 3 -C 4 alkenyl optionally substituted with 1 to 3 halogen atoms or C 3 -C 4 alkynyl; L is hydrogen, fluorine, chlorine or bromine; and M and R are each independently hydrogen, (C1-C3) alkyl, (C1-C3) alkoxy, (C1-C3) alkylthio, (C1-C3) alkylsulfinyl, (C1-C3) alkylsulfonyl; up to 3 carbon atoms, cyano, fluorine, chlorine, bromine or iodine, nitro, trifluoromethyl, the radical of formula R'CF2Z, R2CO or NR3r4, or M and R, attached at adjacent positions together with the carbon atoms to which they are attached, they may form a ring in which MR represents a residue R ² is C 1 -C 3 alkyl, C 1 -C 3 alkoxy or NR ³ R 4; R ² is H or alkyl having 1 to 3 carbon atoms; R 4 represents a hydrogen atom, a C 1 -C 3 alkyl group or the radical R 4 CO; R 5 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms and n is an integer of 0, 1 or 2. 17. A process according to claim 16, wherein the arylpyrrole compounds are selected from the group consisting of: 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile, 4,5-dichloro-2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile, 2,3-dichloro-4-nitro-5- (α, α, α-trifluoro-p-tolyl) pyrrole; 2.3-dichloro-5- (3,4-dichlorophenyl) -4-nitropyrrole. Process according to Claim 3, characterized in that the arylpyrrole compounds of the formula (I) used are those of the formula (Ia) as defined in claim 16. 19. The method of claim 18 wherein the arylpyrrole compounds used are those selected from the group set forth in claim 17. The method of claim 18, wherein the arylpyrrole compound as defined in claim 16 is applied to the plants or the soil in which the plants grow at a rate of 0.125 to 4.0 kg / ha. 21. An insecticidal, acaricidal and nematicidal composition, characterized in that it contains an arylpyrrole compound as defined in claim 16 as active ingredient. 22. The composition of claim 21, which is in the form of a liquid, wherein the content of the arylpyrrole compound of claim 16 is in the range of 10 to 10,000 ppm. 23. The insecticidal, acaricidal and nematicidal composition of claim 22, wherein the arylpyrrole compound comprises a compound selected from the group set forth in claim 17. Arylpyrrole compounds according to claim 9 of the general formula (Ia), wherein the individual symbols are as defined in claim 16, but X is not hydrogen and when W is nitro and A is methyl then Y is bromo or M and R is different from methoxy. Arylpyrrole compounds according to claim 24 selected from the group consisting of 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile, 4,5-dichloro-2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile and 2,3-dichloro-5- (3,4-dichlorophenyl) -4-nitro-pyrrol. Z is S (O) _n or oxygen; R1 represents a hydrogen atom, a fluorine atom, a difluoromethyl group, a fluorochloromethyl group or a trifluoromethyl group;