DD295834A5 - INSECTICIDES, ACARICIDES AND NEMATICIDES BASED ON ARYLPYRROLES AND METHOD FOR THE PRODUCTION THEREOF - Google Patents

Abstract

The invention relates to novel insecticidal, acaricidal and nematicidal arylpyrrole agents and to a method of combatting insects, mites and nematodes with these agents. The invention also relates to a method of protecting growing plants from insect, mite and nematode attack by applying an insecticidal, acaricidal or nematicidal amount of the novel arylpyrrole compound to these plants or the soil in which they grow. The present invention also relates to a process for producing the arylpyrrole compounds. {Insecticides; acaricides; nematicides; Arylpyrrolmittel; Method; Fighting insects; manufacture; Protection of plants}

Description

N-CH ₂ CH (C ₁ -C ₄ alkoxy) ₂ H

wherein L, M, R and W are as defined above.

Field of application of the invention

The invention relates to novel arylpyrrole compounds which are highly potent insecticidal, acaricidal and nematicidal agents useful in the control of harmful insects, mites and nematodes and for the protection of agricultural crops, both growing and harvested, from infestation by these pests can be used. The invention also relates to processes for the preparation of arylpyrrole compounds.

Explanation of the essence of the invention

The novel arylpyrrole compounds of the present invention have the structural formula shown as Formula I:

(I)

wherein X is F, Cl, Br, I or CF ₃ ; Y is F, Cl, Br, I, CF ₃ or CN; W is CN or NO ₂ and A is H; C ₁ -C ₄ alkyl optionally substituted with one to three halogen atoms, a hydroxy, a C ₁ -C ₄ alkoxy or a C ₁ -C ₄ alkylthio _> a phenyl optionally substituted with C ₁ -C ₃ -A ^ yI or C ₁ -C ₃ -alkoxy or having one to three halogen atoms, a phenoxy optionally substituted with one to three halogen atoms or a benzyloxy optionally substituted with a halo substituent; C, -C ₄ -carbalkoxymethyl; Cj-C ^ alkenyl, optionally substituted with one to three halogen atoms; cyano; Сэ-С ^ АІкупуІ, optionally substituted with a halogen atom; Di (C ₁ -C ₄ alkyl) aminocarbonyl or C ₄ -C ₆ cycloalkylaminocarbonyl; LH ₁ F _{1 is} Cl or Br and M and R are each independently H, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -alkylthio, C ₁ -C -alkylsulfinyl, C ₁ -C -alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF ₃ , R _1, CF ₂ Z, R _2, CO or NR ₃ R ₄ and M and R, when in adjacent positions, together with the carbon atoms to which they are attached, can form a ring, wherein MR represents the following structure:

-OCH ₂ O-, -OCF ₂ O- or

Z is S (O) _n or O; R ₁ is H, F, CHF ₂ , CHFCI or CF ₃ ; R ₂ is C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or NR ₃ R ₄ ; R ₃ is H or C, -C ₃ alkyl; R ₄ is H, C ₁ -C ₃ -alkyl or R ₅ CO; R ₅ is H or dC ₃ alkyl; and π is the integer 0,1 or 2.

The term Ci-Ce-Cycloalkylaminocarbonyl means a C ₄ - to Сб-Cycloalkylaminogruppe, which is bound by the nitrogen atom directly to the carbonyl group.

A preferred group of the inventive novel arylpyrroles is illustrated by the formula II:

(II)

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

Another preferred group of novel arylpyrroles of the invention is represented by Formula III:

(III)

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

Another group of preferred arylpyrroles of the invention is represented by Formula IV:

(IV)

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

Yet another group of preferred arylpyrroles of the invention is represented by Formula V:

wherein A, L, M, R, W, X and Y are as described above; and still other preferred arylpyrroles of the invention are represented by formulas VI and VII:

(VI)

(VII)

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

Preferred arylpyrroles of the formula I according to the invention are those in which A is hydrogen or C 1 -C 4 -alkoxymethyl; W is CN or NO ₂ ; L is hydrogen or F; X and Y are each Cl, Br or CF ₃ ; MH, F, Cl or Br and RF, Cl, Br, CF ₃ or OCF ₃

Preferred compounds of formula II which are particularly effective as insecticides, acaricides and / or nematicides are those in which A is hydrogen or C 1-6 alkoxymethyl; L is hydrogen; M is hydrogen, F, Cl or Br; RF, Cl, Br, CF ₃ or OCF ₃ ; W is CN and X and Y are each independently Cl, Br or CF ₃ .

Other compounds of formula II, which are highly effective as insecticidal, acaricidal and / or nematicidal agents are those in which A is hydrogen or C ₄ alkoxymethyl; L is hydrogen; M is hydrogen, F, Cl or Br; RF, Cl, Br, CF ₃ or OCF ₃ ; W is NO ₂ and X and Y are each independently Cl, Br or CF ₃ .

Illustrative examples of some of the insecticides, acaricidal and nematicidal arylpyrroles of the present invention are:

^ B ^ -Ip-dichloro-ftrifluormethoxyJphenylJpyrrol-S-carbonitrile; ФВгот-б-сЫог-г-Ір-сЫофЬепуОруггоІ-З-сагЬопИхіІ; 5-bromo-4-chloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile; A.S-dichloro ^ -lo-chlorphenylJpyrrol-S-carbonitrile;

2- (p-bromophenyl) -4,5-dichloropyrrole-3-carbonitrile; 4,5-dichloro-2- (a, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitrile; 4,5-dibromo-2- (a, a, a-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-3-carbonitrile; 2,3-dibromo-4-nitro-5-phenylpyrrole; 2- (p-bromophenyl) -4,5-dichloro-3-nitropyrrole; 2,3-dichloro-4-nitro-5- (a, a, a-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-nitropyrrole; 2,3-dichloro-4-nitro-5-phenylpyrrole; 3-Bromo-24; hlor-4-nitro-5- (a, a, a-trifluoro-p-tolyl) pyrrole; 5-СЬІог-2- (3,4-аісЫофИепуІ) -1- (теіЬохутеіНуІ) -4- (иіЛиогтеіНуІ) руггоІ-3-сагЬопіігіІ; 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; S-fp-iTrifluormethoxyJphenyllpyrrol ^^ - 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; S-lp-MethylthiophenyO S ltrifluormethyDpyrrol ^^ - dicarbonitrile; l-allyl ^ -nitro-S-la.a.a-trifluoro-p-tolyD-S-ftrifluormethyllpyrrol ^ -carbonitrile; 4-chloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile; 2- (m-Methanesulfonyl-phenyl) -4- (trifluoromethyl) pyrrole-3-carbonitrile; 2- (3-chloro-4-methylphenyl) -1-methyl-3-nitro-4- (trifluoromethyl) pyrrole; 2-phenylpyrrole-3,4-dicarbonitrile; 5- (p-Ethansulfinylphenyl) -4-nitropyrrole-3-carbonitrile; 2-bromo-5-phenylpyrrole-3,4-dicarbonitrile; 2-chloro-5- (3,5-dichlorophenyl) -4-nitropyrrole-3-carbonitrile; i ^ -nitro-benzyl-S-tp-chlorphenyD ^ -ftrifluormethyDpyrrol-S-carbonitrile; 2-chloro-5- (m-bromophenyl) pyrrole-3-carbonitrile; 2-bromo-1- (p-chlorophenoxy) methyl-5- (p-chlorophenyl) -3-nitropyrrole; 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-24trifluormethyl) pyrrole-34: arbonitril; 5- (2,3-dichlorophenyl) -1-methoxymethyl-3-nitro-2- (trifluormethy!) Pyrrole; 4-chloro-5- (ß-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-34: arbonitril; 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- (a, a, a-trifluoro-p-tolyl) pyrrole-2-carbonitrile; 4-chloro-5- (4-chloro-2-methylphenyl) pyrrole-2,3-dicarbonitrile; 4-bromo-5- (3,4-dibromophenyl) -2-nitropyrrole-3-carbonitrile; 1 - [(1-methoxy) ethyl] -5- (p-chlorophenyl) -4- (trifluoromethyl) pyrrole-2,3-dicarbonitrile; S-lp-lsopropylphenyD ^ ^ -nitro -itrifluormethy ^ pyrrole-S-carbonitrile; 4-chloro-5- (3,4-difluormethylendioxyphenyl) pyrrole-3-carbonitrile; 3-bromo-2- (3-chloro-44: yanophenyl) -4-nitropyrrole; i-KS ^ ^ -Dichlorbenzyloxylmethyll lm-bromphenyDpyrrol ^ carbonitrile; 2- (3,5-dichloro-4-methylphenyl) -4-nitro-3-trifluoromethylpyrrole; 2-phenylpyrrole-3,4-dicarbonitrile; 2- (2-bromo-4-chlorophenyl) -4-nitropyrrole-3-carbonitrile; 2-bromo-5-phenylpyrrole-3,4-dicarbonitrile; S-chloro ^ -O ^ -dibromphenyD-i-methyM-nitropyrrole-S-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-24: arbonitril; 3-bromo-5- (m-bromophenyl) -2-nitropyrrole; S ^ dibromo-ö-O ^ ^ -dichlorphenyllpyrrol carbonitrile; 2- (3-chloro-4-cyanophenyl) -5-nitro-3,4-dichloropyrrole; S-chloro-i-tp-methoxybenzyD-S-OAdifluorphenyD -ltrifluormethyOpyrrol ^ ^ -carbonrtril; 3-bromo-5- (3,5-dibromo-p-tolyl) -2-nitro-4- (trifluoromethyl) pyrrole; 1- (2,3,3-trichloroallyl) -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-BromophenylM-isopropyl-3Abis- (trifluoromethyl) pyrrole-2-arbonitrile; 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; i-Kp-bromophenoxyimethyl-S-im-trifluoromethyl-O-trifluoromethylpyrrole; S-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; 54ni-cyanophenyl) -3- (trifluororriethyl) pyrrc) -1-2-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;

4-Bromo-2- (3,4-dichlorophenyl) 1-nitropyrrole-S-carbonitrile; S-OADibromophenyl O-S-itrifluoromethyl-pyrrole; S-dicarbonitrile; 2- (m-chlorophenyl) -5-nitro-4- (trifluoromethyl) pyrrole-3-carbonitrile; 5-bromo-3- (3,5-dichloro-4-difluoromethoxyphenyl) pyrrole-2-carbonitrile; 2-bromo-4- {2,5-dibromophenyl) -5-nitropyrrole; 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; pyrrole 2-chloro-5-nitro-3- (trifluoromethyl) -4- (m-trifluoromethylphenyl); S-fS-Bromo ^ -chlorphenyD-B-ltrifluormethyDpyrrol ^ -carbonitrile; S-iS-ChloM-fluorphenyD ^ -nitro-S itrifluormethyDpyrrol; 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- (3,4-dichlorophenyl) pyrrole-2,5-dicarbonitrile; 4- (2-bromo-4-methylphenyl) -5-nitropyrrole-2-carbonitrile;

4- (m-bromophenyl) -3-chloro-5-nitropyrrole-2-carbonitrile; S-fp-AcetamidophenylM-ltrifluormethyDpyrrol ^ .S-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-nitropyrrole; i-O ^ -DichlorbenzyO-S-lp-chlorphenyD -ltrifluormethyDpyrrol ^ ^ -carbonitrile; 2-Nitro-3- (p-tetrafluoroethoxyphenyl) -4- (trifluoromethyl) pyrrole; 3- (3-bromo-4-i-propylphenyl) pyrrole-2,4-dicarbonitrile; 4- (p-ethylsulphonylphenyl) -5-nitropyrrole-3-carbonitrile; 5-bromo-1- (2-methoxyethyl) -4- (2,4,6-trichlorophenyl) pyrrole-2,4-dicarbonitrile; 2-chloro-4- (2,3-dichlorophenyl) -5-nitropyrrole-3-carbonitrile; S-tp-FluorphenyD S itrifluormethyDpyrrol ^^ - dicarbonitrile; 4- (p-iodophenyl) -5-nitro-2- (trifluoromethyl) pyrrole-3-carbonitrile; S-ChloM-tp-IN-methylacetamidoJphenylJpyrrol ^ carbonitrile; 5-bromo-4- (o-bromophenyl) -1-propargylpyrrol-2-carbonitrile; 2-8rom-3- (o-bromophenyl) -5-nitropyrrole; 4- (p-chlorophenyl) -3,5-dichloro-1- (2,3,3-trichloroallyl) pyrrole-2-carbonitrile; S-bromo-S-chloM-ip-chlorphenyD ^ -nitropyrrol; 5-Bromo-4- (p- (2,2-dichloro-1,1-difluoroethoxy) phenyl] -3- (trifluoromethyl) pyrrole-2-carbonyl: ril; 2-chloro-3- (2-bromo-4 -ethylthiophenyl) -5-nitro-4- (trifluoromethyl) pyrrole; 3- (3-bromo-4-acetylphenyl) -5- (trifluoromethyl) pyrrole-2-carbonitrile; i-cyano-S-O-dibromophenyl-S-nitro ^ 3-bromo-1-methoxymethyl-4- (m-trifluoromethyl) -5- (trifluoromethyl) pyrrole-2-carbonitrile; 3- (p-chlorophenyl) -4-iodo-5-nitro-2- (trifluoromethyl) -2-trifluoromethylpyrrole; ) pyrrole; 4- (p-bromophenyl) -1 - [(1-ethoxy) ethyl] -3,5-di- (trifluoromethyl) pyrrole-2-carbonitrile;

3- (2-bromo-4-methoxyphenyl) -5-nitro-2,4-di- (trifluoromethyl) pyrrole; S-lp-ChlordifluormethoxyphenyOpyrrol ^ S-dicarbonitrile; 2- (p-lsobutyrylaminophenyl) -5-nitropyrrole-2-carbonitrile; 3-bromo-4- (3,4-dimethoxyphenyl) pyrrole-2,5-dicarbonitrile; ^ Chloro-S-lp-chlorphenyll-i-isopropyloxycarbonylmethyO-S-nitropyrrole ^ -carbonitrile; S f o ^ Bromphenyll -drifluormethyllpyrrol ^ .S-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-trifluoromethylpyrrole; i-methyl ^ -p.S-diltrifluormethyOphenyllpyrrol ^ S-dicarbonitrile; 4- (3,4-dichlorophenyl) -2-nhropyrrol-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-N-methylacetamidophenyl) pyrrole-3-carbonitrile; 2-bromo-4- (3-bromo-4-n-propylphenyl) -3-nitropyrrole; 2,5-dichloro-4- (3,5-dichloro-4-methylthiophenyl) pyrrole-3-carbonitrile; 2,5-dibromo-1- (2,4-dibromphenoxymethyl) -3- (p-chlorophenyl) -4-nitropyrrole; 4- (3-bromo-4-cyanophenyl) -2-chloro-5- (trifluoromethyl) pyrrole-3-carbonitrile; 2-bromo-1-methyl-3-nitro-4- (a, a, a-trifluoro-p-tolyl) pyrrole; 4- (p-chlorophenyl) -1- (n-butyloxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; 4- (3,4-methylenedioxyphenyl) -3-nitro-2- (trifluoromethyl) pyrrole; B-ChloM-iS-chloM-trifluormethoxyphenyD ^ -ftrifluormethyDpyrrol-a-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-lsopropionamidophenyl) -3-nitropyrrole-2-carbonitrile; 5-bromo-4- (2-chloro-4-methylthio) pyrrole-2,3-carbonitrile; S-ChloM-lp-chlorpheriyO-i-hydroxyethyl-S-nitropyrrole ^ -carbonitrile; 4- (3,5-dibromo-4-cyanophenyl) -5- (trifluoromethyl) pyrrole-2,3-carbonitrile; 4- (4-chloro-2-methylphenyl) -1-isopropylthiomethyl-3-nitro-5- (trifluoromethyl) pyrrole-2-carbonitrile; S-bromo ^ ^ -iS -dichlorphenyD-i-fdifluormethyDpyrrol-S-carbonitrile; 2-chloro-3- (m-difluoromethoxyphenyl) -4-nitropyrrole; 1- (2,4-Dibromphenoxymethyl) -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-2-carbonitrile; S-bromo-S-lp-chlorphenyO-i-lisobutyloxymethyDpyrrol-S-carbonitrile; 3- (4-bromo-3-methylphenyl) -5-chloro-4-nitropyrrole-2-carbonitrile; 3- (2-naphthyl) -5- (trifluoromethyl) pyrrole-2,4-carbonitrile; 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- (a, a, a-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; and

4-bromo-5-chloro-2- (p-chlorophenyl) -1-methylpyrrole-3-carbonitrile; S-chloro ^ -O ^ ^ -dichlorphenyD -fluorpyrrol-S-carbonitrile; 2-bromo-5- (p-chlorophenyl) -1- (ethoxymethyl) -4-fluorpyrrol-3-carbonitrile; S-bromo-S-fp-chlorphenyD ^ -fluoM-nitropyrrole.

The a - ^^ - DifC-C ^ alkoxy-ethylaminol-.beta.-cyanostyrenes and .alpha.-nitrostyrene compounds according to the invention are represented by the following structural formula:

= CHU NH-CH ₂ CH (C ₁ -C ₄ alkoxy) ₂

wherein W is CN or NO ₂ ; LH, F, Cl or Br is; M and R are each independently H, C ₁ -C ₄ -alkyl, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -alkylthio, C ₁ -C ₃ -alkylsulfinyl, C ₁ -C 5 -alkylsulfonyl, cyano, F are Cl, Br, I, nitro, CF _3, R ₁ CF ₂ Z, R ₂ CO or NR ₃ R ₄ and M and R, when they are in adjacent positions, together with the carbon atoms to which they are attached , may form a ring, wherein MR represents the structure:

-OCH ₂ O-, -OCF ₂ - or

Z is S (O) _n or O; R ₁ is H, F, CHF ₂ , CHFCI or CF ₃ ; R ₂ is C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or NR ₃ R ₄ ; R ₃ is H or dC ₃ alkyl; R ₄ is H, Сі-Сз-АІкуІ or R ₅ CO; R ₅ is H or C ₁ -C ₃ alkyl and η is the integer 0,1 or 2.

A preferred group of beta (substituted) styrene compounds of the invention has the structure shown above wherein W is CN; LH, Cl or Br is; MH, F, Cl, Br or OCH ₃ ; R, F, Cl, Br, CF ₃ , NO ₂ , OCF ₃ or OCH ₃ , or M and R, when in adjacent positions, together with the carbon atoms to which they are attached, can form a ring wherein MR represents the following structure:

Another preferred group of β- (substituted) styrene compounds of the present invention has the structure shown above wherein W is NO ₂ ; LH, Cl or Br is; MH, F, Cl, Br or OCH ₃ ; R is H, F, Cl, Br, CF _3, NO _2, OCF ₃ or OCH _3, or M and R, when they are in adjacent positions, together with the carbon atoms to which they are attached, may form a ring, wherein MR represents the following structure:

Although the compounds according to the invention are referred to above as β-cyanostyrenes and β-nitrostyrenes, they can also be referred to as dialkyl acetals.

Some of the preferred dialkyl acetal compounds of this invention are (E) - and (Z) - (I) p-chloro-β - [(formylmethyl) amino] cinnamic acid nitrile diethyl acetal; (2) ss - [(formylmethyl) amino] -3,4-dimethoxyzimtsäurenitrildiethylacetal; (3) * Z) -Methyl p- {2-cyano-1 - [(formylmethyl) amino] vinyl} benzoate diethyl acetal; (4) (Z) -beta - [(formylmethyl) amino] -1-naphthalenacrylonitrildiethylacetal; (5) (Z) -β - [(formylmethyl) amino] -p-methylcinnamic acid nitrile diethyl acetal; (6) N- (formylmethyl-p-methyl-a-iminomethylbenzylamine diethyl acetal; (7) N- (formylmethyl) -3,4-dimethoxy-a- (nitromethylene) benzylamine diethyl acetal; (8) N-f-formylmethyl-a-fnitromethylene J ^ - naphthalene-methyl-amine diethyl acetal; (9) methyl-p-ia-ifformylmethoxyamine-nitro-benzoate-p-ldiethylacetal); (10) N- (formylmethyl) -3,4-dimethoxy-α- (nitromethylene) benzylamine dimethyl acetal; (11) (E) - and (Zl-p-chloro-β-KformylmethyDaminolzimtsäurenitrildimethylacetal; (12) β - [(Formylmethyl) amino] -3,4-dimethoxycinnamic acid nitrile dimethylacetal; (13) 3,4-dichloro-β - [( formylmethyl) amino-cinnamic acid nitrile diethyl acetal and (14) p-trifluoromethyl-β - [(formylmethyl) amino] cinnamic acid nitrile diethyl acetal.

The β-cyanostyrenes, also referred to as cinnamonitrile dialkyl acetals, can be prepared by the reaction of a substituted or unsubstituted benzoyl acetonitrile with a г.г-ОіІСг-Сг-аІкоху ^ пуІатіп, in the presence of an aromatic solvent, to give the a- (2, To form 2-di (C ₁ -C ₄ alkoxy) ethylamino) -β-cyano- (substituted) styrene which is then converted to a 2- (substituted phenyl) by reaction of said β-3-cyano (substituted) styrene compound with trifluoroacetic acid ) pyrrole-3-carbonitrile can be converted. Chlorination of the cyanophenyl pyrrole thus prepared with sodium hypochlorite or sulfuryl chloride in an inert solvent affords the insecticidal, acaricidal, and nematicidal 4,5-dichloro-2- (substituted phenyl-pyrrole-S-carbonitrile. Conversion to the pyrrole intermediate can also be achieved by the use of concentrated HCl be carried out at a temperature between about 20 ⁰ C and 4O ⁰ C The reactions may be graphically illustrated as follows.:

Aromalis & hes solvent

CN 0-R ₆

2 and £

Q-R

wherein A is hydrogen, C ₁ -C ₄ alkyl, optionally substituted with a C ₁ -C ₄ alkoxy, a C ₁ -C ₄ alkyl, or one to three halo groups, or phenyl optionally substituted with one or two Ci -C ^ alkyl, C ₁ -C ₄ alkoxy or halogen groups; Сз-С ₄ -АІкепуІ, optionally substituted with one to three halogen groups; or Сз-С ₄ -АІкупуІ; X is Cl or Br; R _{6 is} C ₁ -C ₄ alkyl and L, R and M are as described above.

Certain novel aryl pyrrole compounds of the formula I in which A is hydrogen, W is CN and X, Y, L, M and R are as described above can be prepared by reacting N-formyl-DL-phenylglycine or a substituted N-formylphenylglycine represented by Structural Formula VIII:

xt /

CH

(VIII)

NHCH = O

wherein L is H, F, Cl or Br; R and M are each independently H, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, Сі-Сз alkylthio, C ₁ -C ₃ -AIkV (SuIfinyl, C, -C ₃ alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF _3, R ₁ CF ₂ Z, R ₂ CO or NR ₂ R _4, and M and R, when they are in adjacent positions, together with the carbon atoms to which they are attached are able to form a ring, wherein MR represents the following structure:

OCH ₂ O,

-OCF ₂ O-

or

Z is S (O) _n or O; R ₁ is H, F, CHF ₂ , CHFCI or CF ₃ ; R ₂ is C ₁ -C ₃ alkyl, C, -C ₃ alkoxy or NR ₃ R ₄ ; R ₃ is H or C, -C ₃ alkyl; R ₄ is H, C) -C ₃ alkyl or RsCO; Rg is H or Сг-Сз-АІкуІ; and η is the integer 0,1 or 2; with at least an equivalent amount of a 2-chloroacrylonitrile and two or three equivalents of acetic anhydride. The reaction is carried out at elevated temperature, preferably at about 70 ⁰ C to 100 ⁰ C.

 The reaction can be illustrated as follows:

CO ₂ H

NHCH = O

Cl CH ₂ = C + CN

Rc ₂ O

(VI 1 I)

Conversion of the 2-phenylpyrrole-3-carbonitrile or 2- (substituted phenyl) pyrrole-3-carbonitrile so prepared to the corresponding 4-halo, 5-halo or 4,5-dihalo-2- (substituted phenyl) pyrrole 3-carbonitrile of the formula II can be easily prepared by reacting the above-mentioned 2-phenylpyrrole-3-carbonitrile or 2- (substituted phenyl) pyrrole-3-carbonitrile with at least about one or two equivalents of a sulfuryl halide, bromine or chlorine, in the presence of a solvent such as dioxane, THF, acetic acid or a chlorinated hydrocarbon solvent. For the preparation of a monohalopyrrole-3-carbonitrile, about 1 equivalent of the halogenating agent must be used, while the preparation of a dihalopyrrole-3-carbonitrile requires the use of 2 to 3 equivalents of the halogenating agent. When using sulfuryl chloride or sulfuryl bromide, the reaction is generally carried out at a temperature below about 40 ° C and preferably between about 0 ° C and 30 ° C, while using elemental bromine, the reaction temperature is typically about 30 ° C-40 Other useful halogenating agents that can be used in these reactions include sodium hypochlorite, t-butyl hypochlorite, N-bromosuccinimide, N-iodosuccinimide, and the like.

Br ₈ , Cl ₂ , SQ _a <X> _a

HOPC

The carbonitrile compounds of the formula II according to the invention can also be prepared by the reaction of a substituted or unsubstituted benzoylacetonitrile with a 2,2-di (C ₁ -C ₄ alkoxy) ethylamine in the presence of an aromatic solvent, so that the a- (2,2 Di- (C 1 -C ₄ alkoxy) ethylamino) -β-cyano- (substituted) styrene, which is then converted to the 2- (substituted phenyl) pyrrole-3-carbonitrile of formula II, by reaction of the ß-3-cyano (substituted) styrene compound with trifluoroacetic acid or with concentrated HCl at a temperature between about 20 ⁰ C and 40 ⁰ C. The reactions can be graphically represented as follows:

H ₂ NCH ₂ CH (OC ₂ Hg) ₂

hromaUeches solution

O-R,

ICF ₃ CO ₂ H or HCl

wherein R _{6 is} C 1 -C ₄ alkyl and L, R and M are as described above. In addition, according to the invention, З-ІМгіго-г-рпепуІруггоІ- and 3-nitro-2- (substituted) phenylpyrrolverbindungen of formula II by reacting a-nitroacetophenone or a substituted a-nitroacetophenone with a 2,2-di (Ci-C ₄ - alkoxy) ethylamine. The reaction is generally carried out in the presence of an inert organic solvent, preferably an aromatic solvent, at elevated temperature to give an α- (2,2-di (C 1 -C ₄ alkoxy) ethylamino) -β-nitrostyrene or a substituted a- (2,2-di (C 1 -C ₄ alkoxy) ethylamino) -β-nitrostyrene is formed by treatment with a mineral acid such as hydrochloric or hydrobromic acid in the 3-nitro-2-phenylpyrrole or 3-nitro -2- (substituted) phenylpyrrole of formula II is converted. Reaction of the nitrophenylpyrrole thus prepared with sodium hypochlorite in the presence of an inert organic solvent at a reduced temperature affords the 2,3-dichloro-4-nitro-5-phenyl or -5- (substituted) phenylpyrrole of formula II. The reactions described above can be graphed as follows:

L M-L о

C-CH ₂ NO ₂ + H ₂ NCH ₂ CH (OC ₂ Hg) ₂

N-CH ₂ CH (OC ₂ Hg) ₂ H HCl OrJSrCF ₃ CO ₂ H

(II)

It has surprisingly been found that in addition to the various processes described in the literature for the preparation of substituted and unsubstituted benzoylacetonitriles, it is also possible to prepare these compounds by reacting an appropriately substituted benzoyl halide with an alkali metal hydride and an alkyl cyanoacetate such as t-butyl cyanoacetate to give the corresponding t-butyl (benzoyl or substituted benzoyl cyanoacetate), which can be graphically represented as follows:

C-Cl

NaH + СН _г

CN

Vj> ^ N-C0-C-C0-0C (CH _{3) 3} y \ - / j

^R CN

The cyanoacetate ester so prepared can then be converted to a substituted or unsubstituted benzoylacetonitrile by heating the compound in toluene-containing p-toluenesulfonic acid. The reaction can be graphically illustrated as follows:

CO-C-CO-OC (CH.

CN

PTSfl

toluene

Examples of the t-butyl (benzyl and substituted benzoyl-acetonitriles used in the above reactions are listed in the tables below.

t-Buty! - (benzyl and substituted benzyl cyanoacetates

C-C0-O-C (CH ₃ ) ₃

CN

L M R Melting point, ⁰ C H 3-CI 4-CI 91-94 H H 4-OCF ₃ 81-84 H H 4-Br 113-115 H H 4-CF ₃ 146-147 H H 4-F 98-100 H H 4-CN 127-128 H H 4-CF ₃ CH ₂ O 136-139 H H 4-CH ₃ SO ₂ 127-129 H 3-F 4-F 91-94 H H 4-CH ₃ S 117 to 119.5 H H 4 CHF ₂ CF ₂ O 92-94 3-CI 5-CI 4-CH ₃ O _

Benzoylacetonitrile

С-CH ₂ CN

L M R Melting point, ⁰ C H H 4-CI 128.5 to 129.5 H 3-CI 4-CI 105-107 H H 2-C 153-155 H H 4-OCF ₃ 79 - 81 H H 4-CF ₃ 44-45 H 2-CI 4-CI 66 - 67 H H 3-CI 80 - 83 H H 4-CN 126-128 H H 4-F 78 - 80 H H 4-SO ₂ CH ₃ 129 -132 H 3-F 4-F 74 - 75 H H 3-CF ₃ 58 - 60 H H 4-CH ₃ 103.5 to 106 H H 4-NO ₂ 119-124 3-CI 5-CI 4-OCH3 _

The preparation of N-substituted arylpyrroles of Formula I can be accomplished by the reaction of the appropriately substituted arylpyrrole of Formula I wherein A is hydrogen and L, M, R, W, X and Y are as hereinbefore described, with a suitable alkylating agent and a suitable base, for example a brominated hydroxy-Ci-C ₄ alkyl and potassium t-butoxide, take place. This reaction gives an arylpyrrole with the same substituents as the starting material, but in addition, it is substituted on the nitrogen with Нуагоху-С, -С ₄ -а1ку1. In a similar reaction, cyanogen bromide is used in place of the brominated hydroxy-C 1 -C 4 -alkyl and gives the arylpyrrole of formula I with a carbonitrile substituent on the nitrogen. The reactions can be represented as follows:

1) Br

C ₁ -C ₄ or

alcohol + K ~ 0-t-Bu

2) CNBr

wherein L, M, R, W, X and Y correspond to the above description for formula I and A 1) C-production of г-РпепуІруггоІ-ЗАаісагЬопіиіІ, 2-bromo-5-phenylpyrrole-3,4-dicarbonitri phenyl derivatives can be carried out by reacting fumaronitrile with bromine in the presence of a chloro chloroform at elevated temperature to give bromofumaronitrile, then reacting with ni methylbenzenethioimidate or a substituted derivative thereof in the presence of hexamethylphosphoramide at elevated temperature to give с. Brominating the 3,4-dicarbonitrile thus produced gives 2-bromo-5-phenyl-pyrrole-3,4-c-phenyl derivative, when the substituted N- (trimethylsilyl) is used in the previous reaction, and the reaction can be graphically represented as follows:

C ₄ -AlkOhOl or 2) CN. The and their substituted

N hydrocarbon like

:. The bromofumaronitrile thus prepared

Trimethylsilyl) methyl-5-

: as 2-phenylpyrrole-3,4-dicarbonitrile. icarbonitrile or its substituted ^ -ethyl-5-methylbenzenethioimidate

CN

(-HSr)

br

НМРП / 3 equiv. H ₂ D (-TfIS ₁ -HBr ₁ -CH ₃ SH)

TMS

<чх

The examples which are given below for illustrative purposes are based on the illustrated schemes and are an aid to the preparation of other compounds of the invention which are not specifically described herein. The arylpyrroles of the present invention are effective in the control of insects, mites and nematodes Protection of growing or harvested agricultural crops from infestation by the above mentioned pests

In practice, there are generally about 10 ppm (parts per million) to about 10000 ppm and preferably 100 ppm to about 5000 ppm of the arylpyrrole of formula I, which includes all of the arylpyrrole isomers of formulas II, III, IV, V, VI and VII. dispersed in water or other cheap liquid carrier, effective when applied to the plants, crops or soil in which the crops grow to protect these crops from infestation by insects, mites and / or nematodes These compounds are also useful for protecting turf from infestation by such pests as caterpillars, cereal bugs and the like

The arylpyrroles of the formula I according to the invention are also effective in controlling insects, nematodes and mites when applied to the foliage of plants and / or the soil or water in which the plants grow in an amount sufficient Obviously, larger amounts of the arylpyrroles of formula I can be applied to protect agricultural crops from attack by insects, nematodes and mites, in general However, larger amounts of aphcation are not required and constitute a waste

The arylpyrroles of the present invention may be used alone as effective agents for controlling insects, nematodes and mites, but may be used in combination with other biological chemicals including other insecticides, nematicides and acaricides. For example, the arylpyrroles of the present invention may be used effectively in combination or in combination with phosphates, carbamates, pyrethroids, formamidines, chlorinated hydrocarbons, Halogenbenzoylharnstoffen and the like can be used

The 2-aryl-3-cyano-4,5-dihalopyrroles prepared from the β-cyanostyrene compounds of the invention are effective in controlling insects, mites and nematodes. These compounds are also effective in protecting growing or harvested agricultural crops infestation by said pests In practice, in general, about 10ppm to ЮОООррт and preferably 100ppm to 5000ppm of the halogenated arylpyrrole dispersed in water or other cheap liquid carrier, when applied to the plants, crops or soil in which These cultures grow when grown, effectively protecting these crops from attack by insects, mites and / or nematodes

The above-mentioned halogenated arylpyrroles are also effective in controlling insects, nematodes and mites when applied to foliage of plants and / or the soil or water in which these plants grow. These halogenated arylpyrrole compounds are generally used in an amount sufficient to achieve an amount of drug from about 0.125 kg / ha to about 4.0 kg / ha. Obviously, larger amounts of aphphage of the halogenated arylpyrroles can also be used to protect the cultures from attack by insects, nematodes and mites However, to protect such larger amounts of application are generally not required and are a waste

The above-mentioned arylpyrroles may be advantageously formulated into dry, compacted granules, flowable compositions, granular preparations, net powders, emulsifiable concentrates, dusting agents, dust concentrates, microemulsions and the like, all of which are suitable for application to the soil, water and / or foliage and ensure the required plant protection To such formulations pay the compounds of the invention to which inert pharmacologically acceptable solid or liquid diluents are admixed

For example, netting powders, dusting agents, and dust concentrate formulations according to the present invention may be prepared by milling about 3 to 20 parts by weight in% of the arylpyrrole compound of formula I together with about 3 to 20 parts by weight of solid anionic surfactant. A suitable anionic surfactant is a dioctyl ester of sodium sulfosuccinic acid , especially the surface active agent Aerosol OTB®,

The American Cyanamid Company markets about 60 to 94 parts by weight of a solid solid diluent such as montmorillonite, attapulgite, lime, talc, kaolin, diatomaceous earth, limestone, silicates or the like are also used in such formulations

Compacted granules particularly suitable for application to the soil or water may be prepared by co-grinding the arylpyrrole compound and a solid surfactant at approximately equal parts usually about 3 to 20 parts, with about 60 to 94 parts of gypsum Mixture to small granulated particles having a grain size of about 24/48 mesh or bulk compacted

Other suitable solid surfactants that can be used in the formulations include not only the dioctyl dioctyl ester of sodium sulfosuccinic acid, but also the nonionic block copolymers of ethylene oxide and propylene oxide. Such block copolymers are available from BASF Wyandotte Corporation as Pluronic 10R8®, 17 R8®, 25 R8®, F 38®, F 68®, F77® or F 87® and are particularly effective for the production of compacted granules

In addition to the powder and concentrate formulations described above, wetting powders and flowable materials may also be used since they may be dispersed in water. Preferably, these flowable compositions are applied in situ, with the aqueous compositions being sprayed onto the foliage of the plants to be protected on hatcheries, food bases or habitats of insects and mites to be fought

When solid formulations of the arylpyrroles are to be used in combination treatments with other pesticidal agents, the formulations can be applied as mixtures of the components or sequentially. Likewise, liquid formulations of the arylpyrrole can be mixed or separated in the tank in combination with other pesticidal agents, sequentially in the form of liquid sprays Liquid spray formulations of the compounds of this invention should contain about 0.001 to 0.1 wt.% of the active arylpyrrole. The following examples are given to illustrate the present invention

Exemplary embodiments

example 1

2 phenylpyrrole 3 carbonitrile

CO ₂ H

NHCH = O

Cl

CH ₂ = C-CN

Rc ₂ O

The following procedure is the same in JOC, 43.4273 to 4276 (1978), given Em magnetically stirred mixture of 30.00 g of N-Formylphenylglycin is maintained for a period of IV2 hours at 90 ⁰ C. The clear yellow reaction solution in vacuo The proton NMR spectrum shows that the material partially purified by chromatography on silica gel is a mixture of 73% 2-ппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппп3 3-cyano-5-methylpyrrole The one-time recrystallization from chloroform and the two-fold recrystallization from 1,2-dichloroethane give 1.69 g of an off-white solid which, according to proton NMR, consists of 96% 2-phenylpyrrole-3-carbonitrile, mp 148 ° C-152 ° C Microanalysis (Relative Molecular Mass 168.19) Calculated C-78.55%, H-4.79%, N-16.66% C-78 Determines 52%, H-4.73%, N- 16.54%

Example 2

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

To a magnetically stirred, ice-water-cooled solution of 2.00 g (11.9 mmol) of 2-phenyl-3-cyanopyrrole in 80 mL of methylene chloride is added dropwise 1.90 mL (3.19 g, 23.6 mmol) of sulfuryl chloride via syringe over a period of 5 min In addition, the temperature is maintained between 5 ⁰ C and 1O ⁰ C. At 5 ° C to 10 ° C is stirred for a further 90 min. The reaction mixture is vacuum filtered to remove a precipitated solid (1.28 g), as 5 Chlorine 2 phenylpyrrole 3 carbonitrile, mp 192.5 ° C-195 ° C, identified. The filtrate is diluted with 400 ml of ethyl acetate

washed twice with 200 ml of water, dried (sodium sulfate), treated with charcoal, filtered and then concentrated in vacuo to give (after slurry of the residue with hexane) 0.60 g (yield 21.3%) of a pmk-purple solid is redistilled from 5 ml of hot acetone to give 0.32 g (yield 9%) of 4,5-dichloro-2-phenylpyrrole 3 carbomtril as an orange-brown solid, mp 254 ° C-255 ° C

Max (muli, Nujol) 3165 (broad singlet, below br s), 3120 (singlet, below s), 2245 (s), 1570 (multiple, below m), 1513 (m), 1440 (s), 1252 (m), 1069 (m), 996 (m), 920 (m), 768 (s), 698 (s), 665 (s) cm " ¹

H NMR (DMSO) δ 7.73 (doublet, hereinafter d, J = 6.6Hz, 1.97H, two phenyl protons at C-2.6), 67.52 (triplet, hereinafter t, J = 7.3Hz, 2.04H, two phenyl protons at C-3.5), 67.44 (t, J = 7.3Hz, 1.02H, a phenyl proton at C-4)

C NMR (DMSO) 6137.51, (C-2 pyrrole carbon), 6129.25 (C 4 phenyl carbon), 6129.04 (C-3.5 phenyl carbons), δ 128.37 (C-1 phenyl carbon), 6125 , 88 (C-2,6 phenyl carbons), 6114,32 (either C-5 pyrrole or nitrile carbon), 6114,14 (either C-5 pyrrole or nitrile carbon), δ 110,72 (C-4 pyrrole carbon ), 6 89.78 (C-3 pyrrole carbon)

Microanalysis (relative molecular mass 237.09)

Calculated C-55.72%, H-2.55%, N-11.82%, CI-29.91%

C-55.78%, H-2.59%, N-11.12%, CI-29.74%

Example 3

p-chloro-β - [(formylmethyl) amino] cinnamic acid nitrile, diethyl acetal

- ^ QmLcn * н _;

A magnetically stirred solution of 250.00 g (1 39 mol) ρ of chlorobenzoylacetonitrile, 203 mL (185.95 g, 1.39 mol) of 2,2-diethoxyethylamine and 1300 mL of dried toluene is refluxed for 20 hours. Water is added in a Dean Stark trap ( 23.8 ml, 95.2% theoretical). The hot, cloudy dark brown solution with a large amount of undissolved solids is filtered through diatomaceous earth as a filter aid. After dilution with 200 ml EtOAc, the solution is filtered through a 7 cm × 13.5 cm silica gel column The filtrate is concentrated in vacuo to give 354.38 g (86.4% crude yield) of a clear, dark oil which slowly solidifies. This solid is again uncorked from hot cyclohexane to give 324.26 g (yield 79.1%) of a waxy , orange solid shows the NMR analysis of this product is that it is a 78% (Z) - and 23% (e) -Isomergemisch of p-chloro-ss - [(formylmethyl) amino] zimtsaurenitril, diethyl acetal, mp 60 ° C-72 ° C, The following analytical data are given for another similarly prepared sample

Maxfmull, Nujol) 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). 67.47 (d, J = 8.6Hz, 2.12H, two aromatic protons), 67.37 (d, J = 8.6Hz, 2.12H, two aromatic protons), 65.10 (E) and 64 , 86 (Z) (broad triplet, hereinafter br t, 1.25H, an NH proton), δ 4.69 (Z) and δ 4.60 (E) (t, J = 5.1 Hz, 1, 05H, a methine proton on the acetal carbon), 64.07 (E) and 64.05 (Z) (s, 0.83H, enamine-β-proton), 63.71 (E) and 63.68 (Z) (Quartet , in the following q, J = 7.1 Hz, 2.22 H, two methyl protons of one of the two ethoxy groups), δ3.56 (Z) and δ 3.53 (E) (q, J = 7.1 Hz, 2.22 H, two methylene protons from either ethoxy group), δ 3.18 (t, J = 5.1 Hz, 1.77 H, two methylene protons of the ethylene acetal group), 61.20 (t, J = 7.1 Hz, 4.9 OH, six methyl protons of the two ethoxy groups)

C-NMR (chloroform) 6161.21 (a-enamine carbon), δ 136.29 (Z) and 6134.60 (E) (either C-1 or C-4 of the phenyl ring) 6134.08 (Z) and 6132, 30 (E) (either C-1 or C-4 of the phenyl ring), δ 129.34 (Z) and δ 129.89 (E) (either C-2.6 or C-3.5 of the phenyl ring), δ 128.94 (Z) and δ 128.63 (E) (either C-2,6 or C-3,5 of the phenyl ring), δ 121.19 (Z) and 6119.50 (E) (nitrile carbon), 699 , 43 (Z) and δ 100.63 (E) (β-enamine carbon), 661.88 (Z) and 663.25 (E) (methine carbon of the acetal), 662.64 (Z) and 663.03 (E. (Methylene carbons of ethoxy groups), 646,32 (Z) and 647,33 (E) (ethylenediamine methyl carbon), 615,26 (methyl carbons of ethoxy groups)

Microanalysis (relative molecular mass 294.78)

Calculated C-61.11%, H-6.50%, N-9.51%, CI-12.03%

C-61.25%, H-6.25%, N-9.34%, Cl-12.35%

Example 4 C + \ CF ₃ co ₂ H - * I CN J H \ 4 J 2 (p-chlorophenyl) pyrrole-3-carbonitrile ι Α \ HN г о MU 114th ог •H\ H ^N TU 394.78 гог.бі N f

-Cl

To 108 ml of trifluoroacetic acid, which are stirred at 23 ° C, 54.00 g (0.183 mol) of solid p-chloro-ß - [(formylmethyl) -aminolzimtsäurenitril, diethyl acetal are added over a period of 45min. This addition caused an exothermic reaction to 38 ⁰ C, and after 32 min, a solid began to settle. After the reaction mixture is stirred at room temperature for 30 minutes, it is vacuum filtered and the collected solid is washed first with trifluoroacetic acid, then with an ethyl acetate-hexane mixture and finally with hexane. The yield is 16.83 g (45.4%) of an off-white solid, mp 165 ° C to 166 ° C. The following analytical data come from a similarly prepared sample:

Max (muli, Nujol): 3275 (br, s), 2225 (s), 1502 (s), 1410 (m), 1275 (m), 1200 (m), 1108 (s), 1023 (m), 999 (m), 908 (m), 843 (s), 752 (s), 722 (s), 695 (s), 620 (s) cm " ¹ .

H NMR (acetone): 511.22 (very broad singlet, hereinafter: ν br s, 0.99H, a pyrrole NH proton), 57.82 (d, J = 8.9Hz, 2.46H, two aromatic phenyl protons), 57.51 (d, J = 8.9Hz, 2.46Hz, two aromatic phenyl protons), 57.02 (t, J = 2.6Hz, 1.01Hz, a pyrrole proton at C-5) , 56.58 (t, J = 2.6Hz, 0.77H, a pyrrole proton at C-4).

C-NMR (acetone): 5137.73 (pyrrole C-2), 5134.42 (p-chlorophenyl at C-4), 5129.93 (methine carbons at C-3.5 of the phenyl ring), 5128.07 (methine carbons at C-2,6 of the phenyl ring), 5121.21 (pyrrole at C-5), 5117.93 (nitrile carbon), 5113.78 (pyrrole carbon at C-4), 590.86 (pyrrole carbon at C-3).

Microanalysis (Relative Molecular Weight 202,64):

Calculated: C-65.19%, H-3.48%, N-13.83%, CI-17.50%. Determined: C-64.18%, H-3.52%, N-13.63 %, CI-17.74%

Application of the above process as shown or with the use of concentrated hydrochloric acid instead of trifluoroacetic acid gives the following compounds:

CN

M and / or R

Mp / C

Acid used

4-CI

3,4-di-Cl

2-CI

4-OCF ₃

4-CF ₃

2,4-di-Cl

3-CI

4-CN

4-F

4-SO ₂ CH ₃

3,4-di-F

3-CF ₃

4-COOCH ₃

4-CH ₃

4-NO ₂

165-166

216-221

156-157

143-145

179-180

197-199

150-156

210-212

167-170

221 to 221.5

173 to 175.5

166-168

155.5 to 158

117-137

174-177

conc. HCI, CF ₃ COOH

CF ₃ COOH

CF ₃ COOH

CF ₃ COOH

CF ₃ COOH

CF ₃ COOH

CF ₃ COOH

CF ₃ COOH

conc. HCI

CF ₃ COOH

CF ₃ COOH

CF ₃ COOH

CF ₃ COOH

CF ₃ COOH

CF ₃ COOH

Example 5

4.5 dichloro-1-chloro-phenylpyrrole-S-carbonitrile

CN

2.2 eq SO ₂ Cl ₂ HOfc '

To a mechanically stirred solution of 16.83 g (83.1 mmol) of 2- (p-chlorophenyl) pyrrole-3-carbonitnl in 450 ml of glacial acetic acid are added dropwise at 36 ° C 14.7 ml (24.70 g, 183.0 mmol) of sulfuryl chloride The addition of a slight exothermic reaction to 39 ° C is achieved and after a further 16 minutes the reaction mixture is vacuum filtered. The collected solids are washed first with acetic acid and then with water. This solid melts upon recrystallization from hot ethyl acetate 259 ° C-261 ⁰ C.

Similar procedures were used to prepare other samples of this product and the analytical data for one of these products are given below

Max (muH, Nujol). 3170 (br, s), 3100 (m), 2225 (s), 1500 (m), 1097 (m), 825 (s), 717 (m), 660 (m) cm " ¹

H NMR (DMSO) 67.72 (d, J = 8.6Hz, 2.0OH, two aromatic protons), 57.65 (d, J = 8.6Hz, 2.00H, two aromatic protons)

C-NMR (DMSO). δ 136.01 (pyrrole C-2-carbon), 5133.92 (p-chlorophenyl-C-4-carbon), δ 129.09 (p-chlorophenyl-C-3.5-carbon), 5127.41 (p-chlorophenyl-C-4-carbon), 5127.11 (p-chlorophenyl-C-1-carbon), 5114.49 (nitrile carbon), δ 114.10 (pyrrole C-5-carbon), δ 110 , 92 (Pyrrole C-4 Carbon), δ 90.09 (Pyrrole C-3 Carbon)

Microanalysis (relative molecular mass 271.54)

Calculated C-48.65%, H-1.86%, N-10.32%, CI-39.17%

C-49.22%, H-2.12%, N-9.85%, CI-39.03%

Example 6

4,5-dibromo-2- (a, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitnl

To a stirred mixture of 0.8 g of 2- (a, a, a-t-fluoro-p-tolyl) -pyrrole-3-carbonitrile in 70 ml of chloroform is added 2 ml of bromine. While the mixture is stirred overnight, a white solid precipitates, TLC (ethyl acetate-hexane 1 L) shows a single component, melting point> 230 ° C analysis for Ci ₂ H ₅ Br ₂ F ₃ N ₂

Calculated C-36.55, H-1.27, N-7.11, Br-40.61

C-36.40, H-1.08, N-6.99, Br-40.55

The application of the procedures of Examples 5 and 6 using the appropriately substituted phenylpyrrole-3-carbomtrils instead of 2 (α, α, α-trifluoro-p tolyl) pyrrole-3-carbonitnl the following compounds

\ / R \ X 4-NO ₂ br 4-F Cl 4-F br 4-SO ₂ CH ₃ Cl 4-F Cl 4-F br 4-CI Cl 4-Br br 4-OCF ₃ Cl 4-OCF ₃ br 4-OCF ₃ Cl 4-CN br 4-CN Cl 4-SO ₂ CH ₃ br 4-NO ₂ Cl 4-CI br 3-CF ₃ Cl 4-COCH3 Cl 2,3-CH = CH- Cl 4-CH ₃ Cl 4-CI br 3-CI Cl 4-CI Cl 4-CI br 2-CI br 4-CF ₃ Cl 4-Br Cl 2-CI Cl 4-CI Cl H Cl 4-CI Cl 4-CF ₃ br 4-CI Cl 4-CI br 5-CI Cl 4-CI Cl 5-F Cl

Melting point, ⁰ C

2-CI

2-Br

2-CI

3-F

3-F

3-CI

3-Br

3-CI

H 2-CI

2-CI

3-CI

3-CI

3-CI

4-CI

br

Cl

br

Cl

Cl

br

Cl

br

Cl

br

br

Cl

br

Cl

br

Cl

Cl

Cl

Cl

br

Cl

Cl

br

br

Cl

Cl

Cl

Cl

Cl

Cl

br

br

Cl

Cl

br

Cl

274-277> 220> 220> 230> 230> 220

222-225 231-232

> 230> 240> 230

246-249> 260> 230 251-254 244-247

215-217> 230> 230> 230

273-274> 230> 230> 235> 230> 235 254-255

255-257> 230 262-263 (Zers.)

250-258 (decomp.)> 230> 230 207-210

Example 7

3-nitro-2-phenyl-pyrrole

0 Il

CCH, 'JO,

H ₂ NCH ₂ CH (OEUj

C = CH-NO ₂

Alpha-nitroacetophenone 15.7 g, 0.0345 mol) is taken up in 10 mmol of toluene and 4.6 g (0.0345 mol) of aminoacetaldehyde diethyl acetal are added. The reactants are placed in a 250 ml round bottom flask equipped with a Dean-Stark trap: the trap is filled with 4 Å molecular sieves and the mixture is refluxed for 18 hours. The toluene is removed in vacuo to give 8.36 g of a- (2,2-diethoxyethylamino) -β-nitrostyrene as a brown oil. To this oil is added 50 ml of concentrated HCl. When the piston is pivoted, the oil turns into a yellow suspension. After 10 mm, the solid is filtered, yielding 2.48 g of a yellow solid. Recrystallization from ether / ethyl acetate / hexane gives the product in two fractions, 208g, mp 190 ° C-192 ° C (31%).

Max 1 485 cm ^-1 (NO ₂ ), ¹ H-NMR (CDCl ₃ ZDMSO) 56.73 (m, 2H), 7.46 (m, 5H).

Example 8

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

+ NaOCl

A mixture of 3-nitro-2-phenylpyrrole (1.56 g, 0.0083 mol) in 60 mL dioxane is cooled in an ice bath while 25.9 g (0.0182 mol) of commercial sodium hypochlorite are added dropwise. After the mixture has been stirred for 45 minutes, it is acidified with concentrated HCl. Water and Et ₂ O are added. The layers are separated and the upper organic layer is washed with H ₂ O, dried over anhydrous MgSO ₄ and concentrated in vacuo to give 2.21 g of a yellow solid. Purification by chromatography using silica gel eluting hexane is eluted with increasing ratios of ethyl acetate / results after driving 0.77 g of a yellow solid (96%), mp 190 to 190.5 ⁰ C

Analysis for C ₁₀ H ₆ N ₂ O ₂ Cl ₂ :

Calculated: C-46.72; H-2.35; N-10.90 Determined: C-46.96; H, 2.86; N-10.02

Following the procedure of Examples 7 and 8, but using the appropriately substituted a-nitroacetophenone and 2,2-di (C ₁ -C ₄ alkoxy) ethylamine, the substituted a- (2,2-di (C ₁ -C ₄ alkoxy) ethylamino) -β-nitrostyrene, which is then converted to 3-nitro-2- (substituted) phenylpyrrole by treatment with HCl, HBr or CF ₃ CO ₂ H. The reaction of the substituted phenylpyrroles thus formed with sodium hypochlorite in dioxane affords the chloro analogs, while the reaction of the substituted phenylpyrrole with bromine in chloroform gives the bromo analogs.

L M R X Y Melting point, ⁰ C H H H Cl Cl 190-190.5 H 4-CI H Cl Cl 214 -215 H 4-CI H br br 203 -204 (Zers.) H H H br br 148.5 to 149 3-CI 4-CI C Cl Cl 219-220 (Zers.) H 4-Br H Cl Cl 222 -223 (Zers.) H H 4-CF ₃ Cl Cl 166-168

Example 9 4,5-Dichloro-2- (3,4-dichlorophenyl) -1-methylpyrrole-3-carbonitrile

Cl

Cl

MeI

K0C _<CH3> 3

In a 100 ml flask, 2g4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile in 60 ml of dry THF gives a clear, brown solution. With stirring, 1 equivalent of KOtBu is added, giving a clear solution after a few minutes. With a syringe, 1 equivalent of MeI is added, and the solution is heated at reflux for 4 hours, then stirred at room temperature overnight. The following day, 50 ml H ₂ O are added and the mixture is extracted with 4x50 ml CHCl ₃ . The organic phases are taken together, dried with MgSO ₄ and concentrated. The resulting white solid is purified by flash chromatography on silica gel using 50:50 EtOAc / hexane as the eluent. This gives 1.80 g of a white solid

 Yield = 86%, melting point = 154 ° C-156 ° C.

By the method described above, but using the appropriately substituted phenylpyrrole-3-carbonitrile or 3-nitro-2- (substituted) phenylpyrrole instead of 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile the following compounds were prepared.

Mp., ° C

CH ₃ H C ₂ H ₅ OCH ₂ H C ₂ H ₅ H CH ₃ H CH ₃ H C ₆ H ₅ -CH ₂ H С6П5- Сп2 H CH ₂ = CH-CH ₂ H СгІ2 ⁼⁼ С-Сгі2 H CH- С-С Нг H CH ₃ SCHi H C (CHa) ₃ H CH ₃ H CH3SC2H5 H о C ₂ Hf-OC-CH ₂ H C ₂ H ₅ -OCH ₂ H CH ₃ H CH ₃ H C ₂ H ₆ OCH ₂ H CH ₃ H C ^ H ₅ -CH ₂ H C ₂ H ₅ OCH ₂ H HIGH ₂ CH ₂ H NC H C ₆ H ₅ CH ₂ OCH ₂ H Cl 0-CH ₂ H IC = C-CH ₂ H CH ₃ H C ₂ H ₆ OCH ₂ H C ₂ H ₅ -OCH ₂ H C ₂ H ₆ -OCH ₂ H C ₆ H ₆ -CH ₂ H CH ₃ H CN H C ₂ H ₆ -OCH ₂ H C ₂ H ₅ -OCH ₂ H C ₂ H ₆ OCH ₂ H

3-СІ

3-СІ

3-СІ

3-СІ

3-СІ

3-СІ

3-СІ

3-СІ

3-Ct

3-СІ

3-СІ

3-СІ

3-СІ

3-СІ

3-СІ

3-СІ

3-СІ

4-Cf

4-СІ

4-СІ

4-СІ

4-CF ₃

4-CF ₃

4-СІ

4-СІ

4-СІ

4-СІ

4-СІ

4-CF ₃

4-CF ₃

4-СІ

4-СІ

4-CF ₃

4-OCH ₃

4-СІ

4-OCF ₃

4-OCF ₃

4-OCF ₃

4-СІ

4-СІ

4-СІ

4-СІ

4-СІ

4-СІ

4-СІ

4-СІ

4-СІ

4-СІ

4-СІ

4-С1

4-CF ₃

4-CF ₃

4-CF ₃

4-СІ

Example 10

1-benzyl-4,5-dibromo-2- (a, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitrile

Cl Cl Cl Cl Br Br Cl Cl Cl Cl

Cl Cl Cl Cl Cl

Cl

Cl

br

br

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

br

br

Cl

br

br

br

Cl

br

br

Cl 152-153 - Cl 128-130 143-145 Cl 137-138 251-252 Cl 154-156 88-89 br 145-146 118-120 br 145-147 115-116 Cl 95-96 126-129 Cl 69-70 91-92 Cl 118-120 Cl 147-148 104-105 Cl 81-82 Cl 197-201 Cl 99-100 138-139 Cl 74-75 104-105 Cl 118-120 76-77 Cl 99-100 80-81 br 112-115 br 197-201 Cl 46-47 Cl 72-73 Cl oil Cl Cl Cl Cl Cl Cl CF ₃ CF ₃ Cl br br br Cl CF ₃ CF ₃ CF ₃

In a 1 OO ml flask, 1.5 g of 4,5-dibromo-2- (a, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitrile are mixed with 50 ml of dry THF, resulting in a clear, Dark solution gives 1 equivalent of KOtBu added under stirring After a few minutes the solution becomes clear Benzyl bromide (0.65 g) is added by syringe The mixture is heated under reflux overnight The following day, the thin layer chromatography (50/50 EtOAc / hexane) in that both the starting material and the product are present. The procedure is as follows 50 ml of water are added and the mixture is extracted with 4 × 50 ml of CHCl _3. The organic phases are taken together and washed with 4 × 50 ml of 10% aqueous NaOH The organic phase is dried with MgSO ₄ and driven off. This gives a brown solid which is crystallized from EtOAc / hexane. Yield = 0.75 g = 40.7%, melting point = 145 ° C.-147 ° C., decomposition

Example 11

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

Cl у / CN if -Cl с л ' \ \ 1 г N OC ₂ \ \ с

+ K 0 C <CH ₃ ) ₃ + ClCH ₂ OC ₂ H ₅ Cl

A sample of 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitnl (1.0g, 0.003mol) is dissolved in 10ml dry tetrahydrofuran. This solution is added potassium t-butoxide (0.37g, 0.0033 mol) followed by chloromethyl ethyl ether (0.312 g, 0.0033 mol). The mixture is stirred for about one hour at room temperature and then poured into a large volume of water to precipitate the product. The white solid is collected and dried to give 1.0g (91%) product with a melting point of 128 ° C-130 ° C

Example 12

4 СЫог-З-суапо-гЧр-сЫогрпепуоруггоо

♦ Z NaOCl

dioxane

A magnetically stirred, 20 ⁰ C warm solution of 17,87g (88,2mmol, 1.00 equiv) of 2- (p-СЫогргіепуІІ З-суапоруггоІ in 800ml dioxane was added dropwise 250,15g (13,13g be real, 176,4mmol, 2 equiv.) 5.25% by mass bleach added over a period of 30 mm. After the reaction solution has been stirred for another 30 mm at room temperature, it is poured into 2 200 ml of water. The resulting mixture is vacuum filtered to remove a small amount of a black solid Filtrate is acidified to pH 2 with concentrated HCl to give a brown solid. This solid is vacuum filtered and the collected solids are washed with water to give 22.41 g of a brown solid. This solid is washed with 100 mL of 5% treated aqueous sodium hydroxide to dissolve the mass of the material, leaving a small amount of undissolved black solid This black solid, gelo in 100 ml of ethyl acetate, is washed with 75 ml each time of 5% aqueous NaOH, water and saturated aqueous NaCl. The ethyl acetate layer is dried (MgSO ₄ ), treated with charcoal, filtered and then rotary evaporated in vacuo, yielding 1 ιOg (5, 3% yield) of an orange-brown solid. This solid is recrystallized from an ethyl acetate-chloroform mixture to give 0.51 g (2.4% yield) of an off-white solid which is 4-chloro-3-cyano-2 (ρ-chlorophenyl) pyrrole Melting point 251 ° C-253.5 ° C.

Example 13

Preparation of 5-8rom-2- (3,4-dichlorophenyl) pyrrole-3-carbonitnl

qr

0 ι oxanes

Cl Cl

A sample of 2- (3,4-dichlorophenyl) pyrrole-3-carbonitnl (2.0 g 0.008 mol) is dissolved by heating to 40 ° C-50 ° C in 100 mL dioxane. The solution is then cooled to 30 ° C and it is Bromine (1.3g 0.008mol) added. After the solution has been stirred for one hour at room temperature, it is poured into water and a gray solid (2.2g, 88%) is collected. Melting point is 233 ° C-236 ° C , Decomposition

Similarly, 5-bromo-2- (3,4-dichloro) -3-nitropyrrole can be prepared starting from 2- (3,4-dichlorophenyl) -3-nitropyrrole

Example 14

Preparation of 5-Bromo-4-chloro-2 (3,4-dichlorophenyl) pyrrole-3-carbomtrile

+ (CH ₃ ) ₃ COCl

A sample of 5-bromo-2- (3,4-dichlorophenyl) pyrrole-3-carbonitnl (0.158 g, 0.005 mol) is dissolved in tetrahydrofuran (5 mL). An equivalent amount of t-butyl hypochlorite is added and the solution is transferred Night stirring The solution is poured into water and the precipitate (0.052 g, 30%) is collected. Melting point is> 275 ° C. Similarly, 2-bromo-3-chloro-5- (3,4-dichlorophenyl) 4-nitropyrrole, starting from 2-bromo-5- (3,4-dichlorophenyl) -4-nitropyrrole

Example 15

Production of Б-Вгот ^ -спІог-г-Ір-сЫогргіепупруггоІ-З-сагЬопИпІ

Cl

CN

Br,

CHCl ₃

br

ki.

A magnetically stirred, 22 ⁰ C warm solution of 0.17 g (0.67 mmol, 1.00 equivalents) of 4-chloro-2 (p-chlorophenyl) pyrrole 3-carbonitnl in 100 ml of chloroform is a solution dropwise over a period of 30min of 0.20 ml (0.62 g, 3.88 mmol, 5.79 equivalents) of bromine added in 5 ml of chloroform. No exothermic reaction is induced by the addition. After the clear, red reaction solution has been stirred at room temperature for four hours, it becomes in vacuo This solid is slurried with a hexane-methylene chloride mixture to yield 0.23 g of a gray-white, fluffy solid, mp 262 ° C-263 ° C, on vacuum filtration, decomposition

Example 16

Preparation of o-Chloro-fp-chlorophenyl-pyrrole-S-carbonitnl

+ Br-

CHCl.

To a magnetically stirred, 45 ⁰ C warm solution of 1.00 g (4.22 mmol, 1.00 equivalents) of 5-chloro-2 (p-chlorophenyl) pyrrole-3-carbonitnl in 300 ml of chloroform is added dropwise over a period of 30 min, a solution of 0 40ml (1.24g, 7.76 mmol, 1.84 equiv.) Of bromine added in 25 ml of chloroform. The addition does not cause an exothermic reaction and towards the end of the addition a small amount of solid begins to settle. After the reaction mixture is stirred at room temperature for 19½ hours It is evaporated in vacuo to give 1.49 g of an orange-white solid. This solid is slurried in my hexane / methylene chloride mixture to give, on vacuum filtration, 1.33 g (100% yield) of a fluffy white solid, mp 250 ° C-258 ° C, decomposition

Example 17

Preparation of o-chloro-fp-chlorophenyl-pyrrole-S-carbonitrile

+ SO ₂ Cl ₂

HORC

To a 35 ° C, magnetically stirred solution of 2.40 g (11.8 mmol, 1.00 equivalents) of 2- (p-chlorophenyl) pyrrole-3-carbonitrile and 65 mL of glacial acetic acid is added dropwise via syringe over a period of 5 min 0.75 ml (1.26 g, 9.34 mmol, 0.79 equivalents) of sulfuryl chloride. About 5 minutes after completion of the addition, a solid substance is precipitated from the reaction solution. After the reaction mixture is stirred at room temperature for 45 min, it is filtered and the collected solid is washed well with cold acetic acid to give 2.08 g (74% crude yield) of a greyish white solid. This solid is recrystallized from 75 ml of hot acetic acid to give 1.63 g (58% yield) of 97 mass% pure. Melting point of the product 258.5 ⁰ C to 261 ⁰ C.

Example 18

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

K0C (CII ₃ > 3 t CH ₃ I

Cl

CH

In a 100 ml flask, 2.0 g of 2- (3,4-dichlorophenyl) -pyrrole-3-carbonitrile are dissolved in 50 ml of dry THF and 1 equivalent of potassium t-butoxide is added. This results in a slightly cloudy solution. Subsequently, one equivalent of methyl iodide is added to the mixture with the pipette. This leads to a slight whitening of the color. A drying tube is attached to the flask and stirred at ambient temperature overnight.

The next morning there is a slight light rainfall in the flask. Then 50 ml of water are added and the solution becomes clear before a solid precipitates out of the solution. This solid is filtered from the solution and compared to the starting material by thin layer chromatography (25% ethyl acetate / hexane). This shows a new single spot, which moves faster than the starting material. There is dried overnight in a Vakuumtrockenschrankbei 50 ⁰ C. The product yield is 1.31 g or 62%, the product has a melting point of 140 ° C-142 ° C.

Example 19

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

Cl CN

CH

Cl

In a 50 ml round bottom flask, 0.5 g of 2- (3-4-dichlorophenyl) -1-methylpyrrole-3-carbonitrile are mixed with 35 ml of glacial acetic acid. The mixture is gently heated with a heat gun to dissolve all pyrrole.

To this clear solution, add 2 equivalents of sufluryl chloride with the pipette. The solution is stirred at room temperature for 12 hours.

After 12 hours, the solution is poured into 50 ml of water, resulting in a white precipitate. This is filtered off and dried in a vacuum oven at 50 ° C for 3 hours.

The resulting solid is identical to the product of Example 9 after thin layer chromatography (25% ethyl acetate / hexane) and infrared analysis. The product yield is 0.36g (56%).

Example 20

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

Cl

CN

+ BrCl CHOH +

L-Bu

Cl

CN

A stirred mixture of 2.0g (6.5mmol) of 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile and 0.88g (7.8mmol) of potassium tert -butoxide dissolved in 50ml 0.89 g (7.7 mmol) of bromoethanol are added to the reaction mixture. The mixture is stirred under reflux for 12 hours, cooled, diluted with 50 ml of water and extracted several times with chloroform

The combined chloroform extracts are dried over magnesium sulfate and concentrated in vacuo to leave a solid which upon heating and dissolving in ethyl acetate on cooling predominantly precipitates starting pyrrole. Concentration of the mother liquor and recrystallization of the residual solid from 20% ethyl acetate in hexane gives 0.31 g of a white solid, mp 143 ° C-145 ° C, IR 5077A analysis for C ₁₆ H ₂₃ NO ₄ :

Calculated C-44.57, H-2.29, N-8.00, CI-40.57

Determined (Agm 33139). C-44.77, H-2.29, N-8.06, CI-40.14

Example 21

Preparation of 4-S-dichloro-P ^ -dichlorophenyl-pyrrole-1-dicarbonitrate

Cl

CN

CNBr + K ⁺ t-Bu (T.

Cl

CN

Potassium t-butoxide (617mg, 55mmol) is added portionwise to a solution of S-cyano-o-dichloro-O-di-dichlorophenyl (1.52g, 5mmol) in anhydrous THF (20ml).

After 30mm, add a solution of cyanogen bromide (583mg, 5.5mmol) in THF (1mL). The reaction mixture is stored at room temperature overnight. The solvent is removed in a rotary evaporator. The residue is treated with water and extracted with ethyl acetate. The organic layer is washed with water and saturated sodium chloride and dried (MgSO ₄₎ the e-indampfung and crystallization of the residue from ethyl acetate affords white crystals article (1,07g), mp 250.5 ⁰ C to 252 ⁰ O C, IR ( Nujol) 2255, 2245cm ^-1 (CN); ¹² C NMR (DMSO-de) 102.7 (N-CN), 113.7 (3-CN), mass spectrum 331.9 (M + 1).

Analysis for C ₁₂ H ₃ CP ₄ N ₃ (330.99)

Calculated C-43.54, H-0.91, N-12.70; CI 42.85

Finds C-43.62, H-0.93, Ν-Ί2.63, C) -41.95

Example 22

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

CN

Cl

Cl

To a stirred mixture of 1.91 g (5.5 mmol) of 4,5-dichloro-2- (3,4-dichlorophenyl) -1- (2-propynyl) pyrrole-3-carbonitrile in 500 ml of methanol is added 69 ml of 10% aqueous Sodium hydroxide and then added 0.70 g (2.7 mmol) of iodine. The mixture is stirred for 12 hours and then acidified and diluted with 200 ml of water. The precipitated solids are collected and recrystallized from methanol to give 0.51 g of white crystals, mp 115 ° C-116 ° C. This reaction is also applicable to the conversion of all substituted N-alkynylarylpyrroles of formulas III, IV, V, VI or VII of the invention into N-substituted 3-iodo-2-propynyl-aryl-pyrroles of the invention.

Example 23

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

N-I

THF

N-iodosuccinimide (5.7 g, 0.0254 mol) is slowly added to a solution of 2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile (3.0 g, 0.0127 mol) in 100 mL of THF. The reaction is stirred for several hours at 25 ° C until thin layer chromatography (silica gel: ether: petroleum ether: acetic acid in the ratio 100: 100: 1) indicates the completion.

The mixture is evaporated in vacuo leaving a residue containing pyrrole and succinimide. The crude solid is dissolved in 500 ml of ether and shaken with 5x400 ml of water to remove the succinimide. The ether is dried over Na ₂ SO ₄ and evaporated in vacuo leaving 2.0 g (32.3%) of a gray-brown solid with e ^; A melting point of> 230 ° C (gives off purple vapors).

Example 24

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

CN - / + TMS

jjlO mo 17. nBu ₄ N ⁺ F THF / 16hr / RT

A solution of acrylonitrile (0.65 mL, 0.01 mol) and N- (trimethylsilyl) methyl S-methylbenzenedioimidate (2.4 g, 0.01 mol) in THF (100 mL) is added in an ice-acetone bath -5 ⁰ C cooled. Under nitrogen purge, a solution of tetrabutylammonium fluoride (1.0 mL of a 1 N solution in THF) and THF (20 mL) is added dropwise over a period of 30 min. The solution is stirred at -5 ° C for a further 30 min and then allowed to warm slowly to ambient temperature. It is stirred for a further 18 hours, then the solvent is removed under reduced pressure. The residue is partitioned between ether / water and the water layer extracted with fresh ether. The combined organic layer is washed with water and then with saturated sodium chloride. The solution is dried over MgSO ₄ , and the

Cooling of the filtrate causes the precipitation of an off-white solid (1.2 g, 70% theoretical yield) whose spectral properties are identical to those of the material described by Tsuge (J. Org. Chem. 52, 2523

Melting point = 95 ° C-97 ° C.

Calculated for C "H ₁₀ N ₂ : C-77.65; H, 5.88; N-16.47

Determined: C-77.55; H-5.83; N-16.39

Example 25

Preparation of 2-phenylpyrrole-4-carbonitrile

DDQ / DME / pyr 16 hr / RT

NH

Under a nitrogen purge, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.23 g, 0.001 mol) and 2-phenyl-1-pyrroline-4-carbonitrile (0.17 g, 0.001 mol) in 1,2-dimethoxyethane (13ml), forming a clear, orange solution. In a single portion of pyridine (0.08 ml, 0.001 mol) is added, resulting in a slight exothermic reaction (to about 28 ⁰ C) and the immediate formation of a green / gray precipitate. The suspension is stirred at room temperature for 18 hours during which time most of the solvent evaporates; the brownish, semi-solid residue is partitioned between ether and a semisaturated solution of sodium carbonate. The red-brown, aqueous layer is extracted twice with ether, and the combined ether layer is washed with fresh water and then with saturated sodium chloride. After drying with MgSO ₄ , the solvent is removed under reduced pressure to give a white, semi-solid. This material is recrystallized from ethylene dichloride (DARCO treatment) to give lavender crystals (0.1 g).

An identical product is obtained directly in a single step by condensation of α-chloroacrylonitrile and N- (trimethylsilyl) methyl S-methylbenzenethioimidate using tetrabutylammonium fluoride catalysis (analogous to the preparation of 2-phenyl-1-pyrroline-4-carbonitrile as described above). , Melting point 155 ° C-158 ⁰ C.

Calculated for Ci ₁ H ₈ N ₂ : C-78.57; H, 4.76; N-16.67

Determined: C-78.65; H-4.70; N-16.43

Example 26

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

Br ₂ / CHCl ₃

NH

Under a nitrogen purge, a solution of bromine (0.6 mL, 0.012 mol) in CHCl ₃ (5 mL) is added dropwise over 20 min to a stirred solution of 2-phenylpyrrole-4-carbonitrile (0.84 g, 0.05 mol). in CHCl ₃ (20 ml). The resulting solution is stirred at room temperature for 18 hours, then the solvent is removed under reduced pressure to give a solid which is recrystallised from C ₂ H ₄ Cl ₂ (DARCO treatment) to give the desired end product (0, 6g), melting point 239 ° C-242 ° C. Calculated for C, iH ₆ Br ₂ N ₂ : C-40.49; H-1.84; Br 49.08; N-8.59 Determined: C-39.88; H-1.87; Br 48.81; N-8.48.

2,4-Dibromo-5- (p-chlorophenyl) pyrrole-3-carbonitrile, melting point 270 ° C-272 ° C (decomposition) is also prepared by the method described in Examples 24, 25 and 26.

Example 27

3 ', 4'-dichloro-3- (1,3-dioxolan-2-yl) propiophenone

BrM ₉

THF

rl.

To a rapidly stirred mixture of magnesium turnings (0.64g, 26mmol) in 10ml tetrahydrofuran at a temperature of 25 ° C in a 100ml 3-neck round bottom flask equipped with thermometer, 60ml addition funnel and nitrogen inlet is added dropwise 2- (2-bromoethyl) - 1,3-dioxolane (4.7 g, 26 mmol) in 40 mL tetrahydrofuran. The additional rate is adjusted so that the reaction temperature is kept below 50 ⁰ C. The reaction mixture is then stirred at 25 ^° C. for one hour. 120 ml of tetrahydrofuran are mixed under a nitrogen blanket with potassium 3,4-dichlorobenzoate (5.0 g, 22 mmol). The Grignard solution is then rapidly decanted from the unreacted magnesium turnings and added dropwise to the rapidly stirred potassium benzoate suspension. The reaction is then stirred at 25 ° C for a further 24 hours. 50 ml of diethyl ether and 15 ml of 3N hydrochloric acid are added to the reaction mixture, and the layers are separated. The organic layer is washed with saturated aqueous sodium bicarbonate until neutral, then washed with 10 ml of brine. Drying over sodium sulfate and rotary evaporation gives a beige, semi-solid, which is chromatographed on silica gel using 3: 1 hexane and ethyl acetate as the eluent to give the ketoacetal (4.3 g, 60%) in the form of a white solid, mp 115 ° C-117 ^O C.

Example 28

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

HO ₂ C-COgH H ₂ OzETOH / *

CHO

To 30 ml of 0.2 M oxalic acid (prepared by dissolving 0.9 g of oxalic acid dihydrate in 30 ml of water) and 5 ml of ethanol are added 10 g (26 mmol) of 3 ', 4'-dichloro-3- (1,3-dioxolane-2 -yl) propiophenone. The mixture is refluxed for one hour, then allowed to cool. Most of the ethanol is removed by rotary evaporation, and together with 20 ml of saturated aqueous sodium bicarbonate, 100 ml of diethyl ether are added. The layers are separated and the organic phase is dried over magnesium sulfate. Rotary evaporation gives a viscous yellow oil which is chromatographed on silica gel using 3: 1 hexane-ethyl acetate to give the ketoaldehyde (6.3 g, 75%) as a white solid.

Example 29 Preparation of 2- (3,4-dichlorophenyl) pyrrole O NH ₄ ORC 0 r ^ ^ CHO ETOH Δ

Cl

To a suspension of 3- (3,4-dichlorobenzoyl) propionaldehyde (6g, 26mmol) in 60ml absolute ethanol is added ammonium acetate (4g, 52mmol). The reaction is refluxed for 20 minutes, then allowed to cool. Most of the ethanol is removed by rotary evaporation and 200 ml of 1: 1 dichloromethane-diethyl ether are added along with 50 ml of water. The layers are separated and the organic phase is dried over sodium sulfate. Rotary evaporation gives a dark brown oil which is chromatographed on silica gel using 3: 1 hexane-ethyl acetate as the eluant to give the pyrrole (4.6 g, 83%) as a tan solid, mp 49 ° C -51 ⁰ C.

Example 30

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

Df1F / PCCL ₃

OHC H

2) Naoflc

To 10 ml of dimethylformamide, which are stirred under nitrogen in a 50 ml round bottom flask, are added dropwise 0.6 ml (6.5 mmol) of phosphorus oxychloride by syringe. The solution heats up and turns pale yellow. It is stirred for 20 minutes before adding portionwise 2- (3,4-dichlorophenyl) pyrrole (1 g, 4.7 mmol). The resulting beige suspension is stirred for 30 minutes before being heated to 50 ^° C. in the course of 40 minutes. To the cooled reaction, a solution of sodium acetate (10g, 122mmol) in 15ml of water is added followed by stirring for 20min. From the reaction mixture, a beige precipitate is filtered off and air dried for 20 hours to give the substantially pure aldehyde (1.1 g, 95%), mp> 200 ^° C.

Example 31

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

H ₂ N-OSO ₃ H

EtOH / HPO

To a suspension of 5- (3,4-dichlorophenyl) pyrrole-2-carboxaldehyde (1.5 g, 6.2 mmol) in 20 ml of water and 20 ml of ethanol is added hydroxylamine-O-sulfonic acid (0.7 g, 6.2 mmol The reaction is refluxed for one hour, during which time a gray precipitate appears. After allowing the reaction to cool, is filtered to maintaining the substantially pure nitrile (1.5 g, 99%) as a gray solid, mp 170 ° C-171 ⁰ C.

Example 32

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

NBS

THF

To a solution of o-O-dichloro-phenylpyrrole-carbonitrile (0.5 g, 2.1 mmol) in 20 mL of tetrahydrofuran is added N-bromosuccinimide (0.8 g, 4.2 mmol) in portions under nitrogen. The reaction is stirred at 25 ° C for 30 minutes before adding 10 ml of water and 40 ml of diethyl ether. The layers are separated and the organic layer is dried over sodium sulfate. The rotary evaporation is followed by chromatography on silica gel with hexane-ethyl acetate in the ratio 3 1 as the eluent to give the dibromopyrrole (0.5 g, 60%) in the form of a brown solid, melting point> 250 ⁰ C.

Example 33

Preparation of 4-phenylpyrrole-3-carbonitnl

A mixture of 5.0 g (39 mmol) of cinnamonitrile and 7.6 g (39 mmol) of (p-tolylsulfonyl) methyl isocyanide in 35 ml of DMSO and 65 ml of ether over a period of 20 min, a suspension of 1.86 g of a 60% Olsuspension of sodium hydride ( 1.11 g, 46 mmol) in 80 ml of ether.

The reaction mixture is kept under nitrogen for one hour and then diluted with ether and water. The ether layer is separated, dried over magnesium sulfate and concentrated in vacuo. The resulting oil is applied to silica gel

chromatographed using 1: 1 chloroform-ethyl acetate as eluent to give 2.5 g of cream-colored solid. Recrystallization from ether-hexane gives 1.15 g of product, m.p .: 123 ° C-125 ° C, NMR M 86-1077

Lit. Tet Letters 5337 (1972) Melting point 128 ° C-129 ° C

Example 34

Preparation of 2,5-dichloro-phenylpyrrole-S-carbonitrile

+ SO ₂ Cl ₂

Cl

To a stirred mixture of 0.66 g (3.9 mmol) of 4-phenylpyrrole-3-carbonitnl in 20 mL of dry THF cooled to 6 ° C with an ice-water bath was added 0.66 mL of sulfuryl chloride via syringe over a period of 4 minutes (1.11 g, 8.2 mmol) The mixture is held at 5 ° C-10 ° C for an additional 45 minutes and then stirred for an additional 30 minutes to remove the ice bath. The reaction mixture is then poured into 80 mL of ethyl acetate and 40 mL of water The organic phase is separated, washed with water and dried over sodium sulfate Filtration through a short column of silica gel, spooling with ethyl acetate and concentration of the combined filtrates in vacuo gives 0.95 g of a dark solid. Recrystallization from chloroform gives 0.42 g of grayish white Crystals, mp 195 ° C-196 ° C (decomp.) Analysis for CnH ₆ Cl ₂ N ₂

Calculated C-55.72, H-2.55, N-11.82, CI-29.91

Determines C-55.66, H-2.65, N-11.69 CI-29 97

Following the procedures of Examples 33 and 34, the following analogs are prepared. For the synthesis of 2,6-dibromo-4- (p-chlorophenyl) pyrrole 3-carbonitnl, the procedure of Example 33 is followed employing bromine in dioxane instead of sulfuryl chloride and tetrahydrofuran

Melting point, ° C

4CH ₃

Cl Cl 237-240 (decomposition)

Cl Cl 103-206

Br Br> 245

Example 35

Ethyl 4- (p-chlorophenoxy-pyrrole-3-carboxylate

so,

Cl

To a mixture of 5 63 g of a 60% sodium hydride oil suspension in 200 ml of dry ether under nitrogen is added via an additional funnel a mixture of 23.5 g (122 mmol) of ethyl p-chlorocinnamate and 19.4 g (122 mmol) (p Tolylsulfonyl) methyl isocyanide in solution in 180 ml of ether and 80 ml of dimethylsulfonide added The additional time is about 20min, and it results in a gentle refluxing of the mixture After stirring for a further 10 min, the mixture is diluted with 100 ml of water The mixture is extracted four times with ether then dried over magnesium sulfate and then in

Concentrated vacuum The resulting solid is recrystallized from ethylenedichlorite to give 7.8 g of crystals, mp 137 ^O C-138 ° C.

Analysis for C ₁₃ H ₁₂ CINO ₂ .

Calculated. C-62.53, H-4.81, N-5.61, CI-14.23

Determined. C-61,31, H-5,12, N-4,32, Cl-14,57

Concentration of the stock liquor for crystallization yields additional crude ester, which is fed to the saponification step

Example 36

Preparation of 3- (p-chlorophenyl) pyrrole

♦ N.OH

H, 0

A mixture of 22.0 g of crude EthyM-lp-chlorophenyl-S-carboxylate from the recrystallization stock and the recrystallized product from the previous step is stirred under reflux with 150 ml of 10% aqueous sodium hydroxide for 2.5 hours. The mixture is cooled, extracted with ether and acidified to give a precipitate which weighs 11.6 g after collection and drying.

A mixture of 10.5 g of the acid in 100 ml of β-ethanol is heated under reflux for three hours. After cooling, the mixture is poured over 400 ml of ice, and the resulting mixture is extracted 4 times with chloroform. The chloroform solution is concentrated after drying over magnesium sulfate and the treatment with activated charcoal in vacuo, leaving a brown solid remains

Chromatography on silica gel using ethyl acetate and hexane in a ratio of 1 1 yields 4.0 g of a white solid, mp 117 ° C-118 ^O C

Example 37

Preparation of S-fp-chlorophenylpyrrolecarboxaldehyde

+ (COCl) ₂ + <CH ₃ ) ₂ NCH ι

'CHO

To a mixture of 0.86 g (12 mmol) of dimethylformamide in 10 mL of ethylene dichloride, kept under nitrogen and cooled in an ice bath, is added 1.49 g (12 mmol) of oxalyl chloride in 10 mL of ethylene dichloride over a period of 25 minutes. The ice bath is removed, The mixture is stirred for a further 15 minutes and cooled again in an ice bath. To this mixture is added 1.5 g (8.5 mmol) of 3- (p-chlorophenyl) pyrrole in 25 ml of ethylene dichloride over a period of 20 minutes. The ice bath is removed and after a further 30 minutes' stirring, the mixture is poured into 50 ml of ice water and water 6ml 50% sodium hydroxide poured The resulting mixture is extracted with ether and with chloroform, and the combined organic mixture is dried over magnesium sulfate and concentrated in vacuo. Purification of the resulting solid by chromatography on silica gel using 1: 1 ethyl acetate: hexane gives 0.63 g of an off- white solid which is used directly for conversion to 3- (p-chlorophenyl) pyrrole-2-carbonitrile.

Example 38

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

H ₂ NOSO ₃ H

CH = O

CN

A mixture of 0.63 g (3.1 mmol) of 3- (p-chlorophenyl) pyrrole-2-carboxaldehyde in 10 mM water is stirred and ice-cooled while 0.52 g (4.6 mmol) of hydroxylamine'-O-sulfonic acid are slowly added 1OmI of water are added. After the addition, the cooling bath is removed and the mixture is heated for 25 minutes. Upon cooling, the resulting solid is collected, and NMR shows that it is a mixture of the product and the starting aldehyde. This mixture is reacted in the same manner with an additional amount of 0.49 g (4.2 mmol) of hydroxylamine-0-sulfonic acid in a total of 30 ml of water. The mixture is kept at 60 ^° C. to 70 ^° C. for 2 hours. The mixture is cooled and the resulting solids are collected and purified by chromatography on silica gel using 1: 1 ethyl acetate and hexane to give 0.40 g of a pink solid, mp 114 ° C

Example 39

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

br

CN

CN

To a mixture of 0.40 g (2.0 mmol) of 3- (p-chlorophenylpyrrole) -2-carbonitrile in 25 ml of chloroform is added 0.63 g (4.0 mmol) of bromine. After 20 minutes, the precipitate which forms is collected and recrystallised from ethyl acetate, giving 0.21 g of pink crystals, melting point> 25O ⁰ C.

Analysis for C ₁₁ H ₅ Br ₂ CIN:

Calculated: C-36.62; H-1.39; Br 44.38; CI 9.85; N-7,77 Determined: C-36.92; H-1.32; Br 44.62; CI 9.88; N-7.50

Example 40

Preparation of ethyl S-bromo ^ -lp-chlorophenyl-pyrrole-S-carboxylate

C-OC ₂ H ₅

N-Br

COOC ₂ H ₅

br

Ethyl 4- (p -chlorophenyl) pyrrole-3-carboxylate (1.6 g, 0.0064 mmol) is dissolved in tetrahydrofuran (40 mL). At 25 ° C-28 ° C, N-bromosuccinimide (1.14 g, 0.0064 mmol) is added in small portions. After completion of the addition, the solution is stirred overnight at room temperature. The solution is concentrated in vacuo and the solid residue is partitioned between water and ether. The ether layer is separated and dried over magnesium sulfate. The work-up of the ether extract gives 1.9 g

(90%) of a white solid, which is purified by stirring with a 20/80 mixture of ethyl acetate and hexane. The insoluble solid (1.3 g, 62%) is collected and has a melting point of 161 ° C-164 ° C.

Analysis for C ₁₃ H ₁₁ BrCINO ₂ :

Calculated: C-47.50; H, 3.34; N-4.26; Br 24.33; CI-10.80 Determined: C-47.39; H-3.38; N-4.12; Br 24.29; Cl 10.77.

COOH

Example 41

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

COOC ₂ H ₅

+ 107. NaOH

Ethyl S-bromo-1- p -chlorophenyl-pyrrole-S-carboxylate (15 g, 0.045 mmol) is added to 200 mL of 10% sodium hydroxide and the slurry is heated to reflux. After everything has apparently dissolved, the mixture is refluxed for a further 40 minutes. The mixture is cooled, filtered and the filtrate acidified. The white precipitate (8.0g, 58%) is collected and dried. The solid has a melting point of> 205 ° C, and NMR (d ₆ -DMSO) had a pyrrole proton at 7.52 (d). The mass spectrum is also consistent with that of a monobrominated compound.

Example 42

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

COOH

H ₂ NCH ₂ CH ₂ OH

ö-bromo ^ -FP-chlorphenyOpyrrol-S-carboxylic acid (8.0 g, 0,026mmol) is added to aminoethanol (24 mL), and the slurry is slowly C-120 ⁰ C heated to 110 ° and held at this temperature for one hour , The solution is cooled and poured into water and extracted with ether. The ether extract has a larger, fast moving spot and a slower moving, smaller component on thin layer chromatography (75/25 hexane / ethyl acetate). Working up of the ether gives a dark solid (4.0 g, 56%) which is 2-bromo-3- (p-chlorophenyl) pyrrole and which is used directly for the preparation of 5-bromo-4- (p -chlorophenyl) pyrrole-2-carbonitrile is used.

Example 43

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

+ ClSO ₂ NCO +

OMF

br

br

A freshly prepared sample of 2-bromo-3- (p-chlorophenyl) pyrrole (4.0 g, 0.015 mmol) is dissolved in dry dimethoxyethane (25 mL). Then, chlorosulfonyl isocyanate (3,08g, 0.022 mmol) is added while the temperature is maintained below 25 ⁰ C.

After the solution has been stirred overnight, it is treated with dimethylformamide (6 ml) and stirred for 3 hours. Finally, the solution is poured into water, precipitating a brown solid (3.8 g, 90%).

Dry column chromatography (80/20 hexane / ethyl acetate) gives 1.4 g (33%) of white solid having a melting point of 202 ° C-204 ° C.

Analysis for C ₁₁ H ₆ BrCIN ₂ :

Calculated: C-46.90; H-2.13; N-9.95; Cl 12.61; Br-28.39 Measured: C-47.20; H-2.09; N-9.80; Cl 12.36; Br 27.42

Example 44

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

Br

Dioxane

A sample of S-bromo ^ -fp-chlorophenylpyrrole ^ carbonitrile (2.2 g, 0.078 mol) is dissolved in 30 ml of dry dioxane. The solution is heated with bromine (1.3 g, 0.008 mol) in dioxane (20 ml) and then stirred overnight at room temperature. The

The reaction mixture is poured into water to give a tan solid (2.6 g, 92%). A portion of this (1.6 g) is purified by flash chromatography using 75/25 hexane / ethyl acetate to give 0.8 g gray solid with a melting point of 191 ° C-194 ° C is formed

Analysis for C ₁₁ H ₅ Br ₂ CIN ₂

Calculated C - 36.61, H - 1.38, N - 7.76, Cl - 9.84, Br - 44 3

Determines 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

+ NaH -I

Sodium hydride (2.66 g of a 60% suspension in O1) is spooled with dry ether (66 mmol) and suspended in 150 mL of dry ether. To this mixture, over a period of 15 min, is added a mixture of 12.0 g (5.5 mmol) 3, Add 4-dichloro-β-nitrostyrene and 10.8 g (5.5 mmol) of (p-tolylsulfonyl) methyl isocyanide in 50 mL of DMSO and 15 mL of ether. The mixture is stirred for 1.5 h and then diluted with 150-20 mL of water and additional ether The resulting 10.6 g of crude product are purified by chromatography on silica gel using a mixture of chloroform and ethyl acetate in the ratio 4 1 From chloroform-ethyl acetate-hexane, a solid fraction of 7.2 g is recrystallized and gives 3.0 g of yellow solid, mp 187 ° C-188 ° C (decomp.) Analysis for C ₁₀ H ₆ Cl ₂ N ₂ O ₂

Calculated C - 46.72, H - 2.35, N - 10.90 Determines C - 46.96, H - 2.60, N - 9.77

Example 46

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

O ₂ N

+ SO ₃ Cl.

Cl

A mixture of 3- (3,4-dichlorophenyl) -4-nitropyrrole (2.5 g, 9.7 mmol) warmed to about 40 ° C in 200 ml of chloroform becomes 2.95 g of sulfuryl chloride over one minute (22 mmol) was added. After 1 hour, dilute the mixture with 100 mL of saturated sodium bicarbonate solution and 300 mL of ether. Concentrate the organic layer and dry over magnesium sulfate. Concentrate in vacuo to give a brown solid which is chromatographed on silica gel using chloroform and ethyl acetate in the ratio of 4: 1 be from a chloroform organe-colored solid Fraktiorrwieder is crystallized and then rechromatographed on silica gel, again with chloroform and ethyl acetate in a ratio of 4 1 are used, resulting in 0.36 g yellow solid, mp 193 ° C-194 ⁰ C.

By the methods of Examples 45 and 46 also 2,5-dichloro-3-nitro-4-phenylpyrrole, mp 193 ⁰ C to 194 ° C (decomposition) is prepared

Example 47

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

+ CLS0 ₂ NC0 + <CH _{3) 2} NCH0

DRIF

A sample г-р-СЫогрЬепуІ-З-уупоруггоІ, prepared according to the method of Example 4 (3, Og, 0.01 S mol), is dissolved in 50 ml of dry dimethoxyethane. To this solution is added chlorosulfonyl isocyanate (3.39 g, 0.024 mol). The additive is exothermic and requires some cooling. After being stirred for 3 hours at room temperature, dimethylformamide (6-7 ml) is added and the solution is stirred for a further 4 hours. Then the solution is poured into water, precipitating a white solid (3.4g, 100%). A sample (1.0 g) is purified by dissolving in ethyl acetate and then passing the solution through a silica gel filled eO-ml trap filter funner. The filtrate is concentrated to give 0.7 g of a white solid, mp 235 ° C-240 ° C.

Following the procedure of Example 47, the following analogs are prepared:

CN

Melting point, ° C

3-CI

4-CI

4-OCF ₃

4-CF ₃

> 225 185-190 180-185

Example 48

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

Dioxane

A sample of 5- (p-chlorophenyl) pyrrole-2,3-dicarbonitrile (1.0g, 0.004mol) is dissolved in 20ml dioxane followed by a solution of bromine (0.8g, 0.005mol) in dioxane (10ml). added. The solution is stirred for several hours at room temperature and then poured into water to precipitate a white solid (1.2 g, 100%). The solid has a melting point of> 225 ° C and the mass spectrum of a sample gives a pattern consistent with the desired structure.

Following the procedure in Example 48 above, the following additional compounds are prepared:

CN

N L \) L H 4-CI 4-OCF ₃ R 4-CF ₃ Melting point, ⁰ C 3-CI > 250 H 218-223 H 239-241

Example 49

Preparation of Bromofumaronitrile

CN

(-HBr)

Under a nitrogen purge, fumaronitrile (15.6 g, 0.2 mol) in CHCl ₃ (150 mL) is heated to reflux to give a clear solution. Over a period of 30 minutes, a bromine solution (5.3 ml, 0.2 mol) in CHCl ₃ (25 ml) is added dropwise resulting in slow decolorization and release of acidic fumes (pH test paper). The solution is refluxed for a further 90 minutes during which time most of the color disappears. The solution is cooled and the solvent is removed under reduced pressure leaving an amber oil (approximately theoretical mass for bromofumaronitrile). The oil is subjected to a ball-ball distillation (0.2 mmHg) keeping the temperature below 120 ^° C. (above this point a rapid decomposition of the material occurs). A semi-solid substance is obtained which slowly forms a waxy, amber solid, melting point 43 ° C-47 ° C. Analysis for C ₄ HBrN:

Calculated: C - 30.57; H - 0.64; N - 17,83 Determined: C - 29,13; H - 0.75; N - 16.94

Example 50

Preparation of 2-phenylpyrrole-3,4-dicarbonitrile

TMS

HMPfl / 3 equiv.H ₂ 0 (-TMS ₅ -HBr, -CH ₃ SH)

Under a nitrogen purge, a solution of bromofumaronitrile (4.7 g, 0.03 mol) and N- (trimethylsilyl) methyl S-methylbenzenethioimidate (7.1 g, 0.03 mol) in hexamethylphosphoramide (HMPA) (35 mL) is stirred at room temperature , In a single portion, add water (1.6 mol) (0.09 mol) to which HMPA (10 ml) was added. The solution exotherms almost immediately, with the temperature rapidly reaching 100 ^° C. before the reaction subsides. The resulting dark red solution is stirred at ambient temperature for 20 hours. When the reaction mixture is poured onto an ice-water mixture, a gummy material is slowly obtained which becomes an unobtrusive, beige solid. This material is collected by filtration, washed with cold water and dried on the filter. After further drying (vacuum oven, 60 ⁰ C), the material is recrystallized twice from C ₂ H ₄ Cl ₂ (DARCO treatment) and gives a white powder, melting point 197 ° C-200 ° C.

Analysis for CuHtN ₃ :

Calculated. C - 74.61; H - 3.63; N - 21,76 Determines C - 74.45, H - 3.84, N - 21.61

Example 51

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

CN

Вг _г / СНС1 ₃

NH

Under a nitrogen purge, 2-phenylpyrrole-3,4-dicarbonitrile (1.4 g, 0.0075 mol) CHCl ₃ (35 mL) is added, with most of the solid dissolving. Over a period of 20 minutes, a solution of bromine (0.4 ml, 0.008 mol) in CHCl ₃ (5 ml) is added dropwise. Initially, the coloration decreases rapidly, but as soon as a new, rubbery solid begins to settle, the color is retained. After the mixture has been stirred for 30 mm at ambient temperature, it is refluxed to give a much less noticeable solid. After refluxing for 90 minutes, the reaction mixture is cooled and an aliquot removed and analyzed (high pressure liquid chromatography) to reveal that about 60% of the starting material is still present. In a single portion, fresh bromine (0.2 ml, 0.004 mol) is added and boiled under reflux for a further 45 min, whereupon an aliquot shows that 10% of the starting material remains. Another fresh portion of bromine (0.2 ml, 0.004 mol) is added to the reflux-boiling suspension, and the reflux is continued for a further 30 min. The suspension is cooled and stirred at room temperature for 18 hours. The solvent is removed under reduced pressure to give a greenish solid, which is extracted with hot CHCl ₃ leaving a dark residue. The extract is DARCO treated and hot filtered. The clear, yellow filtrate begins rapidly to deposit a white precipitate. After cooling to -10 ⁰ C, the white solid is collected by filtration, mp 225 ° C-258 ° C. Analysis for C ₁₂ H ₆ BrN ₃ :

Calculated: C - 52.94; H - 2.21; N - 15,44, Br - 29,41. C - 51.64; H - 2.35; N - 14.91; Br - 28.69

Example 52

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

+ ENT, +

2- (3,4-Dichlorophenyl) pyrrole-3-carbonitnl (3.0 g, 0.013 mol) is added to acetic anhydride (50 mL) and 90% nitric acid (0.6 mL) with a very weak exothermic reaction. The mixture is slowly warmed to 30 ⁰ C and then kept at 30 ⁰ C to 33 ° C until everything has gone into solution. Gradually, a new solid is precipitated. The mixture is stirred for 2 to 3 hours at room temperature and then poured into water and ice to decompose the acetic anhydride. After being stirred for one hour, the mixture is filtered and the solid (2.9 g, 82%) is collected and dried. A portion (1.5 g) is purified by column chromatography on silica gel using hexane and ethyl acetate are used in a ratio of 75/25, and one obtains 0.7 g of yellow solid with a melting point of 228 ° C-231 ° C Analysis for C ₁₁ H ₅ Cl ₂ N ₃ O ₂ :

Calculated: C - 46.80; H - 1.77; N - 14,89, CI - 25,17 Determined: C - 46,50; H - 1.96; N - 14.27; Cl - 24,30

Starting from 2 (p-chlorophenyl) pyrrole-3-carbonitnl, 2- (p-chlorophenyl) -5-mtropyrrol-3-carbomtril is obtained by the same procedure. Melting point 201 ° C-206 ° C Similarly, 2- (p -Trifluoromethylphenyl) pyrrole-3-carbomtril 2- (p-Tnfluoromethylphenyl) -5-nitropyrrole 3-carbonitrile by the method described above This compound has a melting point of 164 ° C-165.5 ° C.

Example 53

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

Dissolve 2- (3,4-dichlorophenyl) -5-nitropyrrole-3-carbonitnl (0.5g, 0.0017mol) in dry dioxane (10ml). To this solution is added bromine (0.28g, 0.0017mol in dioxane After the solution has been stirred overnight, it is poured into water to precipitate a tan dye (0.54 g, 88%). Recrystallization from acetonitrile (5 mL) gives 0.26 g of tan solid with a melting point from 195 ° C to 200 ° C

Analysis for C ₁₁ H ₄ BrCl ₂ N ₃ O ₂

Calculated C - 36.57, H - 1.10, N - 11.63, Br - 22.13, Cl - 19.67. Determined C - 36.46, H - 1.29, N - 11.50, Br - 21.63, Cl - 19.28

By the method of Example 53, but starting from 2- (p-chlorophenyl) -5-nitropyrrole-3-carbonitnl, there are obtained 4 Bromo 2 (p-chlorophenyl) -5-nitropyrrole 3-carbonitrile, melting point 180 ° C-185 ° C

Example 54

S-fSADichlorphenylM-mtropyrrol ^ carbonitrile

яс _г о

To a suspension of 5- (3,4-dichlorophenyl) pyrrole-2-carbomtril (1.2 g, 5.1 mmol) in 25 ml acetic anhydride is strength at 30 ⁰ C under nitrogen was added dropwise 90% nitric acid (0.3 mL, 5.1 mmol) is added. An exothermic reaction proceeds to 45 ^° C. and a green solution is formed. After the reaction solution has been stirred for 2 hours, it is poured into 50 ml of water and vigorously stirred for 5 minutes. The resulting beige precipitate The product is filtered off and dissolved in a minimal amount of acetone. Chromatography over silica gel using 3: 1 hexane and ethyl acetate as eluent gives the nitropyrrole (1.2 g, 84%) as an off-white solid, mp> 200 ^° C.

Example 55

S-bromo-ö-O ^ ^ -dichlorphenyD -nitropyrrol ^ -carbonitnl

A solution of o-P 1 -dichlorophenyl M-nitropyrrole-1-carbomtrile (0.6 g, 2.1 mmol) in 10 mL dioxane is added dropwise at 25 ° C under nitrogen to a solution of bromine (0.3 g, 2.1 mmol). added in 5 ml of dioxane The reaction mixture is stirred overnight The addition of 50 ml of water causes the precipitation of a yellow solid which is collected and dried in a vacuum oven (50mmHg, 45 ⁰ C), creating a light yellow solid, melting point> 200 ⁰ C.

Example 56

4- (p-chlorophenyl) -2- (trifluoromethyl) -2-oxazohn-5-one

In one portion is trifluoroacetic anhydride (1.8 ml, 0,012mol) of powdered 2- (p-chlorophenyl) added glycm (11.4g, 0 06 mol), causing an immediate exotherm to about 40 ⁰ C, whereby on the surface the solid forms a yellow color, when the mixture is slowly heated to 70 ⁰ C, a major portion of the solid dissolves to an orange / bernstemfarbenen oil on the whole solid dissolves on in approximately 2 hours, then for a further hour is heated the Solvent is removed under reduced pressure on a rotary evaporator. Toluene is added twice and removed under reduced pressure, but the odor of trifluoroacetic acid is still detectable. This yellow, semi-solid (yield, theoretical, purity> 90% by high pressure liquid chromatography) is the above Compound and is used without further purification in the next step

-42- 294 834

Example 57

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

4- (p-Chlorophenyl) -2- (t -fluoromethyl) -2-oxazolin-5-one (2.5 g, 0.01 mol) is dissolved in nitromethane (50 mL). In a single portion, the solution 2-chloroacrylonitrile (8 , 0ml, 0.10mol), and the resulting solution is stirred under a nitrogen atmosphere for 18 hours under reflux. Cooling of the red-brown solution to -5 ° C in an ice-acetone bath causes the formation of a precipitate, which is collected by filtration and washed with a small portion of cold nitromethane the resulting tan solid is crystallized from hot ethylene dichloride again to afford the product as white crystals (1.8g, 56% theory), melting point 238 ° C-241 ⁰ C (decomposition) sub- Using the corresponding arylglycine in the procedure of Example 55 and using the method of this example, the following 2-aryl-5- (trifluoromethyl) -pyrrole-3-carbonitnl was prepared

R L Melting point, ⁰ C H H 215-218 H 4 CH ₃ 191-193 H 4-OCH ₃ 168-180 (decomposition) 3-CI 4-CI 245-246 (decomposition) H 4-CF ₃ 218-219

Example 58

Preparation of 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitnl Under a nitrogen purge, a suspension of 2- (p-chlorophenyl) -5- (t-fluoromethyl) pyrrole-3-carbonitrile (1 , 6g, 0.005 mole) (in acetic acid 25 ml) was heated, with all of the material at about 6O ⁰ C to a clear solution dissolves a solution of bromine (0.8 mL, 0.015 mol) (in 10 mL acetic acid) is in the course of The solution is refluxed for 6 hours, then stirred at room temperature for 18 hours. High pressure liquid chromatography of the reaction mixture shows about 80% conversion to the product. The mixture is heated to reflux, and further bromine (0.5 ml, 0.01 mol) in acetic acid (5 ml) is added dropwise. After refluxing for a further 3 hours, the aliquot shows more than 95% conversion to the product. The reaction is cooled and the solvent is evaporated to below atmospheric Removed pressure on a rotary evaporator to give a dark gray solid. To the mixture is added toluene and removed under reduced pressure, but the acetic acid odor remains. All material is dissolved in hot toluene (75 ml) to a crude solution and this solution is washed with DARCO filter treated and filtered The light pink solution settles on cooling to ambient temperature a white solid After cooling in the freezer, the solid is collected by filtration, washed with hexanes and dried on the filter Further drying at 45 ° C in a vacuum oven gives the product (1.2 g, about 60% theoretical), mp 247 ° C-250 ° C (decomposition)

Calculated C - 41.20, H - 1.43 N - 8.01, br - 22.89, Cl - 10 16 ρ _ 16.31 determined C - 41.27, H - 1.48 N - 8,10, br - 22.92, Cl - 10 16 F - 16.03

By brominating the corresponding 2-aryl-5- (trifluoromethyl) pyrrole-3-carbonitrile obtained by the method of Example 57, the following additional examples were prepared according to the recipe described above

R L Melting point, ⁰ C H H 235-238 H 4CH ₃ 244-245 3-CI 4cl 218-223 H 4-CF ₃ 225-226

Example 59

Preparation of 2- (4-chlorophenyl) -5-trifluoromethylpyrrole-3,4-dicarbonitrile

V! г

N Ξ?

CH ₃ NO ₂ / / 18hr

Cl

N = 5

Trifluoroacetic anhydride (3.1 mL, 0.022 mol) is added in a single portion to (4-chlorophenyl) glycine (2.0 g, 0.011 mol), causing immediate yellowing and some reflux. The mixture is slowly heated to reflux, dissolving all of the material to a yellow-orange solution which is heated for a further 2 hours. The reaction mixture is cooled and the solvent removed under reduced pressure. Toluene is added twice and removed under reduced pressure, giving a very thick oil (V _C o - 1800 cm ^-1 ). This residue is dissolved in CH ₃ NC> 2 (40 ml) (some insoluble substances) and bromofumaronitrile (2.7 g, 0.0018 mol) is added in a single portion. The resulting solution is refluxed for 18 hours to give a dark red solution. The solvent is removed under reduced pressure and the dark residue is dissolved in CH ₂ Cl ₂ , with some insolubles being removed by filtration. The material is fractionated by flash column chromatography (silica gel, 3% 2-PrOH in CH ₂ Cl ₂ ) and appropriate fractions are removed. Evaporation of a fraction yields the desired compound as a yellow solid which is recrystallized from CH ₃ CN (DARCO treatment) to give a pale yellow solid (0.2 g). Melting point 238 ° C-241 ⁰ C (some decomposition).

Example 60

p-chloro-.beta .- [formylmethyl) amino] cinnamonitrile, diethyl acetal

-IgNCHGCH (OE t:

to 1uene -H ₂ O

A magnetically stirred solution of 250.0 g (1.39 mol) of p-chlorobenzoylacetonitrile, 203 mL (185.9 g, 1.39 mol) of 2,2-diethoxyethylamine and 1,300 mL of dried toluene is refluxed for 20 hours. In a Dean-Stark trap, water is collected (23.8ml, 95.2% theoretical). The hot, cloudy, dark brown solution with a large amount of undissolved solids is filtered through diatomaceous earth filter aid. After dilution with 200 ml EtOAc, the solution is filtered through a silica gel column of 7 cm χ 13.5 cm. The filtrate is concentrated in vacuo to give 354.3 g of a clear, dark oil (86.4% crude yield), which slowly solidifies. This solid is recrystallized from hot cyclohexane to give 324.2 g of a waxy orange solid (yield 79.1%). The NMR of this product shows that it consists of an isomeric mixture of 78% (Z) and 23% (El-p-chloro-β-formylmethylaminocinnamic acid nitrile, diethyl acetal, mp 60 ° C-72 ° C Sample, the following analytical data were determined:

Max. (MulLNujol): 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): 5.7.47 (d, J = 8.6Hz, 2.12 H, two aromatic protons), 5.7.37 (d, J = 8.6Hz, 2.12 H, two aromatic Protons), δ 5,10 (E) & 5 4,86 (Z) (br t, 1,25 H, an NH proton), 5 4,69 (Z) & δ 4,60 (E) (t , J = 5.1 Hz, 1.05 H, a methine proton on the acetal carbon), δ 4.07 (E) and 5. 4.05 (Z) (s, 0.83 H, enamine-β-proton), δ 3.71 (E) undo 3.68 (Z) (q, J = 7.1 Hz, 2.22 H, two methylene protons from either ethoxy group), δ 3.56 (Z) and δ 3.53 ( E) (q, J = 7.1 Hz, 2.22 H, two methylene protons from one of the two ethoxy groups), 5.31 (t, J = 5.1 Hz, 1.77 H, two methyl protons of the ethylene acetal group) , δ 1.20 (t, J = 7.1 Hz, 4.90 H, six methyl protons of the two ethoxy groups).

C-IMMR (chloroform): 5161.21 (a-enamine carbon), δ 136.29 (Z) and δ 134.60 (E) (either C-1 or C-4 of the phenyl ring), δ 134.08 (Z ) and δ 132.30 (E) (either C-1 or C-4 of the phenyl ring), δ 129.34 (Z) and δ 129.89 (E) (either C-2.6 or C-3.5 phenyl ring), δ 128.94 (Z) and 5128.63 (E) (either C-2,6 or C-3,5 of the phenyl ring), δ 121.19 (Z) and δ 119.50 (E) (Nitrile carbon), 599.43 (Z) and 5100.63 (E) (β-enamine carbon, 561.88 (Z) and 563.25 (E) (methine carbon of the acetal),

δ62.64 (Ζ) and 563.03 (E) (methylene carbons of ethoxy groups), 546.32 (Z) and 547.33 (E) (methylene carbon of ethylamine group), δ 15.26 (methyl carbons of ethoxy groups).

Microanalysis (Relative Molecular Weight 294.78):

Calculated: C - 61.11%; H - 6.50%; N - 9.51%; Cl - 12.03% Determined: C - 61.25% H - 6.25%; N - 9.34%; Cl - 12.35%

Following the procedure described above but using the corresponding benzoylacetoylacetonitrile instead of the p-chlorobenzoylacetonitrile and / or the corresponding 2,2-di (C 1 -C ₄ -alkoxy) ethylamine instead of 2,2-diethoxethylamine, the following compounds are obtained:

V / Λ

CO-CH ₂ CN + H ₂ NCH ₂ CH (C ₁ -C ₄ alkoxy) ₂

toluene -H ₂ O

N-CH ₂ CH (C ₁ -C ₄ alkoxy) ₂

(C ₁ -C ₄ -alkoxy) ₂

Melting point, ° C

H H H

P-CH ₃

т-ОСНз

P-CH ₃ OCO

P-OCH ₃

(OC ₂ H ₅ J ₂ (OC ₂ H ₅ J ₂ (OC ₂ H ₅ I ₂

68-73

59-69

red-orange,

semisolid material

Mp-CI Example 61 \/ H у H H P-CH ₃ H H m-Cl p-Cl H H P-OCF ₃ H H P-CF ₃ 2- (p-chlorophenyl) pyrrole-3-carbonitrile

(OC ₂ Hs) ₂

(OCH ₃ ) ₂ (OCH ₃ ) ₂ (OC ₂ H ₅ I ₂ (OC ₂ Hs) ₂ (OC ₂ Hs) ₂

62-70

+ CF ₃ CO ₂ H

To 108 ml of trifluoroacetic acid, which are stirred at 23 ° C, 54.00 g (0.183 mol) of solid p-chloro-ß- [(formylmethyl) amino] cinnamonitrile, diethyl acetal are added over a period of 45 minutes. This addition caused an exothermic reaction to 38 ⁰ C, and after 32 min, a solid material began to precipitate. After the reaction mixture is stirred at room temperature for 30 minutes, it is vacuum filtered and the collected solid is washed first with trifluoroacetic acid, then with an ethyl acetate-hexane mixture and finally with hexane. The yield is 16.83 g (45.4%) of an off-white solid, mp 165 ° C-166 ° C. The following analytical data are from a similarly prepared sample.

Max (muli, Nujol): 3275 (br s), 2225 (s), 1502 (s), 1410 (m), 1275 (m), 1200 (m), 1108 (s), 1023 (m), 999 ( m), 908 (m), 843 (s), 752 (s), 722 (s), 695 (s), 620 (s) cm \

H-NMR (acetone): 511.22 (vbr s, 0.99H, a pyrrole NH proton), δ7.82 (d, J = 8.9Hz, 2.46H, two aromatic phenyl protons), 57, 51 (d, J = 8.9Hz, 2.46H, two aromatic phenyl protons), 57.02 (t, J = 2.6Hz, 1.01H, a pyrrole proton at C-5), 66.58 (t, J = 2.6Hz, 0.77H, a pyrrole proton at C-4).

C-NMR (acetone): δ 137.73 (pyrrole C-2), δ 134.42 (p-chlorophenyl at C-4), δ 129.93 (methine carbons at C-3.5 of the phenyl ring), 6128, 07 (methine carbons at C-2,6 of the phenyl ring), δ 121.21 (pyrrole at C-5), 6117.93 (nitrile carbon), δ 113.78 (pyrocarbon at C-4), 690.86 (pyrrole carbon at C-3).

Microanalysis (Relative Molecular Weight 202,64):

Calculated: C - 65.19%; H - 3.48%; N - 13.83%; Cl - 17.50% Determined: C - 64.18%; H - 3.52%; N - 13.63%; Cl - 17.74%

Using the above-described process as illustrated or substituting concentrated hydrochloric acid for the trifluoroacetic acid, the following compounds can be prepared:

M and / or R Melting point, ° C Acid used 4-CI 165-166 conc. HCI, CF ₃ COOH 3,4-di-Cl 216 -221 CF ₃ COOH 2-CI 156-157 CF ₃ COOH 4-OCF ₃ 143 -145 CF ₃ COOH 4-CF ₃ 179-180 CF ₃ COOH 2,4-di-Cl 197-199 CF ₃ COOH 3-CI 150-156 CF ₃ COOH 4-CN 210-212 CF ₃ COOH 4-F 167-170 conc. HCI 4-SO ₂ CH ₃ 221 -221.5 CF ₃ COOH 3,4-di-F 173-175.5 CF ₃ COOH 3-CF ₃ 166-168 CF ₃ COOH 4-COOCH ₃ 155.5 to 158 CF ₃ COOH 4CH ₃ 117 -137 CF ₃ COOH 4-NO ₂ 174-177 CF ₃ COOH

Example 62

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

CN

2.2 eq SO ₂ Cl ₂ HORC *

To a mechanically stirred solution of 16.83 g, 83.1 mmol) of 2- (p-chlorophenyl) pyrrole-3-carbonitrile in 450 ml of glacial acetic acid at 36 ° C dropwise 14.7 ml (24.7 g, 183,0mmb'r> sulfuryl chloride over a period of 18 minutes, the addition causes a slight exotherm to 39 ° C., and after a further 16 minutes, the reaction mixture is vacuum filtered The collected solids are washed first with acetic acid and then with water, which solid melts upon recrystallization hot ethyl acetate at 259 ° C-261 ⁰ C. Using a similar procedure, other samples of this product were prepared and the analytical data of such a product are set forth below.

Max (muH, Nujol): 3170 (br s,) 3100 (m), 2225 (s), 1508 (m), 1097 (m), 825 (s), 717 (m), 660 {m) cm " ¹

H NMR (DMSO): 67.72 (d, J = 8.6Hz, 2.0OH, two aromatic protons), 67.56 (d, J = protons).

8.6Hz, 2.0OH, two aromatic

13 C NMR (DMSO): 6136.01 (pyrrole C-2 carbon), 6133.92 (p-chlorophenyl C-4 carbon), 5129.03 (p-chlorophenyl C-3.5 carbons δ 127.41 <p-chlorophenyl) -C-4-carbon), δ 127.11 (p-chlorophenyl-C-1-carbon), δ 114.49 (nitrile carbon), 6114.10 (Pyrrol-C 5-carbon), 6110.92 (pyrrole C-4 carbon), 690.09 (pyrrole C-3 carbon).

Microanalysis (relative molecular mass 271.54):

Calculated: C - 48.65%; H - 1.86%; N - 10.32%; Cl - 39.17% Determined: C - 49.22%; H - 2.12%; N - S, 85%; Cl - 39.03%

Example 63

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

+ ВГ;

To a stirred mixture of 0.8 g of 2- (a, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitrile in 70 ml of chloroform is added 2 ml of bromine.

The mixture is stirred overnight leaving a white solid which is collected by filtration. Thin-layer chromatography (ethyl acetate: hexane in the ratio 1: 1) indicates a single component, melting point> 230 ^° C.

Analysis for C ₁₂ H ₅ Br ₂ F ₃ N ₂ :

Calculated: C - 36.55; H - 1.27; N-7.11; Br- 40.61 Determined: C - 36.40; H - 1.08; N - 6.99; Br - 40.55 Following the procedure described above, but using the corresponding substituted phenylpyrrole-3-carbonitrile instead of 2- (a, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitrile, the following compounds are obtained:

L M R X Y Melting point, ⁰ C H H 4-NO ₂ br br 274-277 H H 4-F Cl Cl > 220 H H 4-F br br > 220 H H 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-CI 3-CI 4-CI Cl Cl 2-Br 3-Br 4-Br br br H H 4-OCF ₃ Cl Cl 222-225 H H 4-OCF ₃ br br H H 4-OCF ₃ Cl H H H 4-CN br br > 230 H H 4-CN Cl Cl > 240 H H 4-SO ₂ CH ₃ br br > 230 H H 4-NO ₂ Cl Cl 246-249 H 3-CI 4-CI br br > 260 H H 3-CF ₃ Cl Cl > 230 H H 4-COCH ₃ Cl Cl 251-254 H 2,3-CH = CH- Cl Cl 244-247 H H 4-CH ₃ Cl Cl 215-217 H 2-CI 4-CI br br > 230 H H 3-CI Cl Cl > 230 H 2-CI 4-CI Cl Cl > 230 H H 4-CI br br 273-274 H H 2-CI br br > 230 H H 4-CF ₃ Cl Cl > 230 H H 4-Br Cl Cl > 235 H H 2-CI Cl Cl > 230 H 3-CI 4-CI Cl Cl > 235 H H H Cl Cl 254-255

Example 64

α- (2,2-diethoxyethylamino) -β-nitrostyrene and 3-nitro-2-phenylpyrrole

Δ. Γ =

CCH ₂ NO ₁ ♦ HjNCH _t CH <Oet) j

• CH-HO,

NH-CHjCH (OEl) ₁

Alpha-nitroacetophenone (5.7 g, 0.0345 mol) is taken up in 100 ml of toluene and 4.6 g (0.0345 mol) of aminoacetaldehyde diethyl acetal are added. The reactants are placed in a 250 ml round bottom flask equipped with a Dean-Stark trap. The trap is filled with 4A molecular sieves and the mixture is refluxed for 18 hours. The toluene is removed in vacuo to give 8.36 g of a- (2,2-diethoxyethylamino) -β-nitrostyrene as a brown oil. To this oil is added 50 ml of concentrated HCl. When the piston is pivoted, the oil turns into a yellow suspension. After 10 minutes, the solid is filtered off to give 2.48 g of a yellow solid. Recrystallization from ether / ethylacetate / hexane gives the product in two fractions, 2.08 g, melting point 190 ° C-192 ⁰ C (31%).

Max. 1 485 cm ^-1 (NO ₂ ), ¹ H-NMR (CDCl 3 / DMSO) 66.73 (m, 2H), 7.46 (m, 5H).

By the above-described reaction, other β-nitrostyrene compounds can be prepared by using the appropriately substituted α-nitroacetophenone in place of α-nitroacetophenone and / or the corresponding 2,2-di- (C ₁ -C ₄ -alkoxy) ethylamine in place of the aminoacetaldehyde diethyl acetal starts. This creates the following compounds.

CCH ₂ NO ₂ + H ₂ NCH ₂ CH (C ₁ -C ₄ alkoxy) ₂

toluene

N-CH ₂ CH (C ₁ -C ₄ alkoxy> 2H

H H H

p-Cl

P-CH ₃

т-ОСНз

P-CH ₃

R (C ₁ -C ₄ -alkoxy) ₂ P-CH ₃ OCO H P-OCH ₃ (OC ₂ H ₅ ) ₂ (OC ₂ Hs) ₂ (OC ₂ H ₅ I ₂ (OC ₂ H ₅ I ₂ (OCH ₃ ) ₂ (OCH ₃ ) ₂ (OC ₂ H ₅ I ₂ HH P-CF ₃

Example 65

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

+ NaOCl

A mixture of 3-nitro-2-phenylpyrrole (1.56 g, 0.0083 mol) in 60 mL dioxane is cooled in an ice bath while 25.9 g (0.0182 mol) of commercial sodium hypochlorite are added dropwise. After the mixture has been stirred for 45 minutes, it is acidified with concentrated HCl. Water and Et ₂ O are added. The layers are separated and the top organic layer is washed with H ₂ O, dried over anhydrous MgSO ₄ and concentrated in vacuo to give 2.21 g of yellow solid. Purification by chromatography using silica gel and elution with increasing ratios of ethyl acetate and hexane gives after expulsion 0.77 g of yellow solid (36%), m.p. 190 ° C-190.5 ° C

Analysis for C ₁₀ H ₆ N ₂ O ₂ Cl ₂ :

Calculated: C - 46.72; H - 2.35; N - 10,90 Determined: C - 46,96; H - 2.86; N - 10.02

Example 66

Insecticides and akarzide determinations

All experiments are carried out using technical material. All concentrations given refer to the active ingredient. All experiments are carried out at 27 ° C.

Spodoptera eridania, third instar larvae, Southern Armyworm A 7-7cm length of Sieva lima bean is dipped in the test suspension for 3s with stirring and placed under a hood to dry, then the leaf is turned into a 100mm χ 10mm Petri dish containing a damp filter paper on the bottom and ten 3rd instar caterpillars The dish is allowed to stand for 5 days before any observations are made on mortality, reduced food intake or disturbances to normal moulting.

Sodoptera eridania, 7-day rest

The plants treated in the experiment described above are kept in a greenhouse under high intensity lamps for 7 days. These lamps simulate the effect of a bright, sunny June day in New Jersey and are turned on for 14 hours a day. After 7 days, the foliage is sampled and these samples are analyzed as in the experiment described above.

Aphis fabae, various forms, black bean aphid

Pots with single nasturtium plants (Tropaeolum sp.) Of about 5cm in height are infected with about 100-200 aphids one day before the test. Each pot is sprayed over 2 revolutions of a 4 rpm turntable under a hood with the test formulation using a DeVilbiss # 154 atomizer. The spray tip is held at a distance of about 15 cm from the plant and the spray is directed so that the plants and the aphids are completely covered. The sprayed pots are placed on white enamel dishes and left for 2 days, then mortality estimates are made.

Tetranychus urticae (P-resistant strain), common spider mite

Plant of Sieva lima with primary leaves 7-8cm in length are selected and cut back to one plant per pot. From a leaf from the main colony, a small piece is cut and placed on each leaf of the test plants. This happens about 2 hours before treatment to give the mites the opportunity to move over the test plant and lay eggs. The size of the cut piece is varied to obtain about 100 mites per leaf. At the time of treatment, the leaf piece used to transfer the mites is removed and discarded. The mite-infected plants are immersed in the test formulation with stirring for 3 seconds and placed under a hood to dry. The plants remain for two days before assessing the extinction of adult mites using the first leaf. The second leaf remains on the plant for another 5 days before assessing the death of eggs and / or newly hatched nymphs.

Diabrotica undecimpunctata howardi, Southern corn rootworm, third form One cubic centimeter of fine talc is placed in a 30 ml wide mouthed glass vial and the mouthpiece is added by pipette to one milliliter of the appropriate acetone suspension The vessels are exposed to a gentle stream of air until the acetone has evaporated, the dried talcum is loosened, 1 cm ^{3 of} millet seeds are added as food for the insects, and In addition, 25 ml of moist soil are introduced into each tube, the vial is capped and the contents thoroughly mixed on a vortex mixer, then ten third-degree root worms are placed in each vial and the vials are loosely capped to allow air exchange for the larvae The treated vessels are allowed to stand for 6 days, then one Mortality count made. Missing larvae are considered dead because they rapidly decompose and can not be found. The concentrations used in this experiment correspond to about 50 and 10 kg / ha, respectively.

Rating scale:

0 = no effect

1 = 10-25% killing

2 = 26-35% killing

3 = 36-45% killing

4 = 46-55% killing

Table I

5 = 56-65% killing

6 = 66-75% killing

7 = 76-85% killing

8 = 86-99% killing

9 = 100% killing

R = reduced feed intake

connection bean leaf armyworms ppm 7TG. P-resist. SCRW lice 100 mites ppm ppm 4 5 ppm kg / ha 100 1000 8.5 9 300 50 1 2 3 9 9 6 7 4.5-log Chloro-2-phenyl pyrrole-3-carbonitrile 0 9 9 9 0 0 4,5-dichloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile 0 9 0 5.5 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile 0 9 9 9 0 0 4,5-dichloro-2 | p (triflic thoxy) phenylpyrrole-3-carbonitrile 7.5 9 9 9 7.7 4,5-dichloro-2- (o-chlorophenyl) - pyrrole-3-carbonitrile 0 9 9 0 0 2- (p-bromophenyl) -4,5-dichlorpyrrol- 3-carbonitrile 0 9 9 8th 0 4,5-dichloro-2- (a, a, a-trifluoro p-tolyl) pyrrole-3-carbonitrile 0 9 4 9 8th 4,5-dibromo-2- (o-chlorophenyl) - pyrrole-3-carbonitrile 0 9 0 0

bean leaf armyworms ppm 7TG. -49- 295 834 Table I, continued lice 100 connection ppm ppm 4 5 P-resist. SCRW 100 1000 mites 2 3 9 ppm kg / ha 300 50 1 0 9 9 6 7 4,5-dibromo-2- (p-chlorophenyl) - pyrrole-3-carbonitrile 0 9 9 9 0 0 4,5-dibromo-2- (a, a, a-trifluoro p-tolyl) pyrrole-3-carbonitrile 0 9 9 9 9 9 4,5-dichloro-2- (2,4-dichlorphe- nyl) pyrrole-3-carbonitrile 0 9 9 9 0 0 4,5-dibromo-2- (2,4-dichlorphe- 9 9 nyl) pyrrole-3-carbonitrile 0 9 9 9 0 0 4,5-dichloro-2- (m-chlorophenyl) - 0 9 9 9 pyrrole-3-carbonitrile 0 9 9 9 0 0 2,3-dichloro-4-nitro-5-phenylpyrrole 0 9 9 9 0 0 2,3-dichloro-5- (p-chlorophenyl) -4-nitropyrrole 0 9 9 9 7.5 8th 2,3-dibromo-5- (p-chlorophenyl) -4-nitropyrrole 0 9 0 7.5 2,3-dibromo-4-nitro-5-phenyl-pyrrole 8th 9 9 9 0 0 2,3-dichloro-5- (3,4-dichlorophenyl) -4-nitropyrrole 0 0 2- (p-bromophenyl) -4,5-dichloro-3-nitropyrrole 8.3 9 8.5 8th 2,3-dichloro-4-nitro-5- (a, a, a-trifluoro-p-tolyDpyrrol 9 8.3

Example 67

Insecticidal reviews

Heliothis virescens, Tobacco budworm ("Tobacco Budworm"), Third Instance Cotton plant seed leaves are dipped in the test formulation and allowed to dry under a hood When dry, they are each cut into quarters and 10 sections individually placed in 30 ml plastic medicine cups Each cup is placed with a third instar caterpillar and a cardboard placed on top of the cup These cups are kept for 3 days before mortality counts and estimates of cut damage are made.

Empoasca abrupt, adult insects, Western Potato Leafhopper ("Western potato leafhopper") A 5 cm long leaf of a Sieva lima bean is dipped into the test formulation with stirring for 3 seconds and placed under a hood to dry 100mmx10mm, containing wet filter paper on the bottom, about 10 adult leafhoppers are placed in each dish, and these dishes are kept for 3 days before mortality counts are made.

Blattella germanica. Litter test, adult male German cockroaches A 0.1% bait is prepared by adding 1 ml of a 1000 ppm solution of the test compound in acetone with a pipette to 1 g corn flour in a 30 ml wide mouth bottle. The bait is dried by means of a gentle stream of air which is directed into the bottle. The bait is placed in a 473 ml wide mouth Mason jar and ten male cockroaches are added. A sieve lid is placed on the container, and a piece of cotton cloth soaked in 10% honey is placed on top of the sieve lid. Mortality counts are made after 3 days.

Blatella germanica, residual test, adult male German cockroaches One milliliter of a solution of 1000 ppm test material in acetone is slowly added with a pipette over the bottom of a petri dish of 150 mm x 15 mm, so that coverage is as uniform as possible. After the order has dried, 10 adult male cockroaches are placed in each dish and a lid placed. After 3 days, mortality counts are made.

Spodoptera eridania, systemic uptake, third instar larvae, Southern Armyworm ("southern" armyworm)

The compound is formulated as an emulsion containing 0.1 g of the test material, 0.2 g of Emulphor EI-620® emulsifier, 10 ml of acetone and 90 ml of water. This is diluted with ten times the amount of water so that you get a 100 ppm emulsion for the test. Subsequently, if necessary, dilutions are made with ten times the amount of water. Sieva lima bean plants, whose primary leaves are 7 to 8 cm long, are cut off at least 3 cm above the ground to avoid infection with soil bacteria, which causes the stem to decompose during the experiment. The truncated stems are placed in the test emulsion and each stalk is wrapped with a piece of cotton cloth to keep the stalk away from the bottom of the bottle and to restrict the evaporation and volatilization of the compound. The experiment is carried out at 27 ° C for 3 days to allow the compounds to be ingested by the plant. Thereafter, one leaf of the plant is removed and placed in a 100mm x 10mm petri dish containing 10 "Southern" armyworms as described in Test I. Mortality counts in feed damage observations are made after 3 and 5 days.

Empoasca abrupta, adult insects, Western Potato Leafhopper ("Western potato leafhopper"), systemic

admission

The compound is prepared as an emulsion containing 0.1 g of the test material, 0.2 g of Emulphor EL-620® emulsifier, 10 ml of acetone and 90 ml of water. This is diluted with ten times the amount of water to have a 100 ppm emulsion for the test. Further tenfold dilutions with water are made if necessary. Sieva lima bean plants, whose primary leaves are 7 to 8 cm in length, are cut off at least 3 cm above the ground to avoid infection with soil bacteria, which causes stem degradation during the experiment. The truncated stems are placed in the test emulsions, and each stalk is wrapped with a piece of cotton cloth to keep the stalk away from the bottom of the bottle and to restrict the evaporation and volatilization of the compound. The experiment is carried out at 27 ° C for 3 days to allow the compounds to be ingested by the plant. Subsequently, a leaf is removed from the plant and placed in a Petri dish of

100mm x 10mm and tested as above in Test VIII.

The rating scale for the above-described tests is the same as in Example 9.

Table II

connection

leafhopper

ppm 100

TBW ³

ppm 1000

C-S system. Sheet- German rest hop cockroach ppm SAW ppm 1000 100 bait ppm ppm ppm 100 100 1000

4,5-dichloro-2- 0 8th 8th, phenylpyrrole-3- carbonitrile 4,5-dichloro-2- 0 9 (P-chlorophenyl) - 9 pyrrole-3-carbonitrile 4,5-dichloro-2- (3,4-dichloro 0 9 phenyl) pyrrole-3- 9 carbonitrile 4,5-dichloro-2- [P- (trifluoro 9 9 0 methoxy) phenyl pyrrole-3-carbonitrile 4,5-dichloro-2- 0 9 (O-chlorophenyl) - pyrrole-3-carbonitrile 2- (p-bromophenyl) - 0 9 4.5-dichloropyrrole-3- 9 carbonitrile 4,5-dichloro-2- (a, a, a-trifluoro 9 9 0 p-tolyl) pyrrole-3- carbonitrile 4,5-dibromo-2- (o- 0 9 chlorphenyll-pyrrole 3-carbonitrile 4,5-dibromo-2- (p- 0 9 9 chlorophenyl) pyrrole 3-carbonitrile 4,5-dibromo-2- (a, 9 9 9 α, α-trifluoro-p-tolyl) - pyrrole-3-carbonitrile 4,5-dichloro-2- 0 9 (2,4-dichlorophenyl) - 0 pyrrole-3-carbonitrile 4,5-dibromo-2- (2,4-dichlorphe- 0 9 nyl) pyrrole-3 carbonitrile 6 4,5-dichloro-2- 0 9 (M-chlorophenyl) - pyrrole-3-carbonitrile 0 9 8th 2,3-dichloro-4- nitro-5-phenylpyrrole 2,3-dichloro-5- 8.5 9 (P-chlorophenyl) - 4-nitropyrrole

0 0

Table II, continued

connection

leafhopper

ppm 100

TBW ³

ppm 1000

C-S system. Sheet- German rest hop cockroach ppm SAW ppm 1000 100 bait ppm ppm ppm 100 100 1000

2,3-dibromo-5- (p -chlorophenyl) -4-nitropyrrole 2,3-dibromo-4-nitro-5-phenyl-pyrrole

2,3-dichloro-5- (3,4-dichlorophenyl) -4-nitropyrrole 2- (p-bromophenyl) -4,5-dichloro-3-nitropyrrole 2,3-dichloro-4-nitro-5- α, α a-trifluoro-p tolyOpyrrole

8.5

8.5

Example 68

A) Evaluation of test compounds as nematicidal agents

Culture Conservation: Cultures of C. elegans (Bristol strain from J. Lewis) are grown on E. coli turf on NG agar plates at 20 ^° C

held. New cultures are created weekly.

Nematodes for the experiments are washed using Fresh Ascaris Ringers Solution (FARS) from 4 to 5 day old cultures. The worms are further washed with FARS containing gentamycin to reduce bacterial contamination and centrifuged to separate the worms from the wash solution. This procedure is repeated three times. The washed worms are then added to C. briggsae maintenance medium (CbMM) (maintenance medium) of GIBCOa, to which gentamycin (600 units / ml) and mycostatin (0.5 mg / ml) were added.

The trials are then conducted with blends of three compounds, supported by another high-performance screening program, to reduce additional labor and expense on the links.

The compounds are dissolved in acetone and made up to equal volume with equal parts of water. The final test concentration of each compound in the mixture is 150 ppm. The test material is added with a micropipette (25 μΙ) to a single well of a 96-well sterile tissue culture plate (COSTAR) ^b and the solvent is allowed to evaporate. These "treated" plates are either used immediately or in a freezer without obvious

harmful effects on the compounds stored.

A freshly prepared amount (5C ^ g) of C. elegans in CbMM is added with the micropipette to each well treated and to some control wells per plate. The culture plate is incubated at 2O ⁰ C.

Efficacy observations are made under a dissecting microscope at 4.24 and 48 hours after immersion.

Immediately before evaluation of the plate, it is carefully struck to stimulate the movement of the worms. Activity is assessed subjectively, but semi-quantitatively, based on the effects of the drug on the motility of mature nematodes and larvae. The following criteria were used: 8 = no motility, 7 = greatly reduced motility in about 95% of the worms, 6 = reduced motility, 5 = slightly reduced motility, 0 = normal motility, same as in the control groups. Other factors indicative of activity are easily detected, such as death, rigor, contraction, rolling, paralysis, abnormal twitching, decreased worm population after 48h

and other deviations from normal behavior.

Procedure for Caenorhabditis elegans analysis

Inoculate TagO - E. coli NG agar dish with 30-50 C. elegans.

- Incubate at 2O ⁰ C.

Day 4 - Harvest new C. elegans population.

- Wash with antibiotics.

- Transferred to CbMM.

- Transfer C. elegans (25-100 μΙ) to wells provided with active substance. ⁸ '

- Observe activity 4 hours after immersion. Day 5 - Watch activity.

Day 6 - Watch activity.

a) Wells provided with active ingredient can be freshly prepared or previously applied and stored in the freezer.

The data obtained in these experiments are given below in Tab. Ill.

B) Root-knot nematode analysis

Root gazelle nematode (Meloidogyne incognita) populations are kept on Fireball tomatoes in the greenhouse. The egg masses are removed from the infected root surfaces and kept on moistened filter paper for 24 hours so that they can hatch. The larvae hatch and fall into the water under the paper. Larvae for the test are transferred to cell plate wells in which the test compounds are in a concentration of ЗООррт in 3% acetone, about 10 larvae per cell plate well. The infected wells are kept at about 27 ° C, and 24h

after the treatment the mortality is determined.

The data obtained are given below in Tab. Ill.

Table III

C. elegans

150 ppm

L A

root-

nematode

ЗООррт

4,5-Dichloro-2- [p- (trifluoromethoxy) -phenyl-pyrrole-3-carbonitrile 4,5-dichloro-2- (a, a, a-trifluoro-p-tolyl) -pyrrole-3-carbonitrile 4,5 Dibromo-2- (a, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitrile 2,3-dichloro-4-nitro-5-phenylpyrrole 2,3-dichloro-5- (p-chlorophenyl) 4-nitropyrrole 2,3-dichloro-5- (3,4-dichlorophenyl) -4-nitropyrrole 2- (p-bromophenyl) -4,5-dichloro-3-nitropyrrole 2,3-dichloro-4-nitro- 5- (a, a, a-trifluoro-p-tolyl) pyrrole

9 9 0 9 9 9 9

4 5 0 9 9 0 6

Example 69

According to the methods of Examples 59 and 60, compounds of the present invention are evaluated for their activity against a variety of insect species including "leafhopper", "tobacco budworm", "Southern" armyworm and German cockroach The rating system is the same as in the above examples determined data are summarized in the given below Tab. IV.

If two or more experiments were performed on the same test compound, the mean of the results is given. In addition, a - in the table indicates that no test has been performed.

Table IV

connection sheet TBW ³ ppm armyworms ppm 7 days C-S systemic sheet German hop 100 100 SAW hop cockroach 4 6 7 ppm rest ppm ppm ppm ppm 100 ppm 100 1000 0 1000 9 8th 100 9 1000 1 2 3 5 8th 10 2,5-dichloro-4-phenyl- 0 9 - 0 pyrrole-3-carbonitrile 0 6 9 0 0 2,3-dibromo-4-nitro- 0 5-phenyl pyrrole 0 9 2 9 9 - 9 0 4-chloro-2- (p-chlorphe- nyl) pyrrole-3-carbonyl 9 tril 0 9 0 9 9 - 9 0 4,5-dichloro-2- (o-chloro phenyl) pyrrole-3-carbo- 0 9 - 0 nitrile 0 0 9 7 0 5-bromo-2- (p-chlorophenyl) - 0 pyrrole-3-carbonitrile 0 9 9 - 0 4,5-dichloro-2- (3,4 9 9 9 dichlorphenyO-1- (Ethoxymethyl) pyrrole 0 3-carbonitrile 9 9 9 9 9 9 5 7 4,5-dichloro-2- (p-chloro phenyD-1-methylpyrrole 0 0 - 0 3-carbonitrile 0 9 9 - 9 p- (4,5-dichloro-3-cyano- 0 pyrrol-2-yl) methylbenzoate 0 4R8 0 9 9 9 3 0 4,5-dibromo-2- (3,4-di- chlorphenyDpyrrol-3- 0 carbonitrile 0 9 9 9 9 9 0 0 4,5-dichloro-2- (a, a, a- trifluoro-m-tolyOpyr- 0 rol-3-carbonitrile 0 9 9 9 9

Table IV, continued

connection sheet TBW ³ ppm armyworms ppm 7 days C-S systemic Sheet- German he jumps 100 100 SAW hop cockroach 4 6 7 ppm rest ppm ppm ppm ppm 100 ppm 100 1000 1000 100 9 1000 1 2 3 5 8th 10

4,5-Dichloro-2- {3,4-dichlorophenyl-1-ethyl-pyrrole-3-carbonitrile 4,5-dichloro-2- (3,4-difluorophenyl) pyrrole-3-carbonitrile

4,5-Dichloro-2- {3,4-dichlorophenyD-1-methylpyrrole-3-carbonitrile 4,5-Dichloro-2- [p- (methylsulfonyl) phenyl] pyrrole-3-carbonitrile 4,5 Dibromo-1-methyl-2- (a, a, a-tri)

fluoro-p-tolyl) -

pyrrole-3-carbonitrile 4,5-dichloro-2- (p -fluorophenyl) pyrrole-3-carbonitrile 4,5-dibromo-2- (3,4-difluorophenyl) pyrrole-3-carbonitrile

4,5-Dibromo-2- (p-fluorophenyl) pyrrole-3-carbonitrile 4,5-dibromo-2- (p-nitrophenyl) pyrrole-3-carbonitrile 4,5-dichloro-2- (p-nitropheny-o-pyrrole-3 carbonitrile 1-Benzyl-4,5-dibromo-2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile 4,5-dichloro-2- (p-cyanophenyl) pyrrole-3-carbonitrile 4,5-Dibromo-2- [p- (methylsulfonyl) phenyl] pyrrole-3-carbonitrile

4,5-dibromo-2- (p-chlorophenyl) pyrrole-3-carbonitrile 4,5-dichloro-2- (3,4-dichlorophenyl) -1- [2- (methylthio) ethyl] pyrrole-3-carbonitrile 1-methyl-4 , 5-dichloro-2- (3,4-dichlorophenyl) -pyrrole-3-carbonitrile 4,5-dichloro-1-methyl-2- (a, a, a-trifluoro-p-tolyl) -pyrrole-3 carbonitrile

(p-chlorophenyl) pyrrole-3-carbonitrile.

2,3-dichloro-5- (3,4-dichlorophenyl) -1- (ethoxymethyl) -4-nitropyrrole 4-bromo-5-chloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile

1-Benzyl-2,6-dichloro-2- (3,4-dichlorophenyl) -pyrrole-3-carbonitrile

0 9 8th 9 9 9 0 9 9 9 9 9 0 9 9 9 9 9 0 9 9 9 9 9 0 9 6 9 9 4 0 9 7 9 9 9 9 9 9 9 9 9 0 9 8th 9 9 - 0 2 - 9 0 - 0 9 7 9 9

2.5

9 9 8.5 9 9 0 4.5 4.5 0 0 0 0 4.5 9 9 4.5 4.5 9 9 6 0 0 0 5 0 0 0 0 0 0

5.5

Table IV, continued

connection

Sheet- TBW ³ ppm armyworms 7 days C-S systemic Sheet- German hop 100 SAW hop cockroach ppm rest ppm ppm ppm ppm ppm 100 ppm 100 1000 1000 100 100 1000

Ethyl 2,3-dichloro-5- 0 9 4 9 9 7 9 0 0 (3,4-dichlorophenyl) - 4-cyanopyrrole-1-acetate 4,5-dichloro-1- (ethoxy- 9 9 9 9 9 9 9 9 9 methyl) -2- (a, a, a-tri- fluoro-p-tolyOpyrrol-3-carbonitrile 0 9 8.5 9 9 9 5 0 9 3-bromo-5- (3,4-dichloro- phenyl) pyrrole-2,4-dicarbonitrile 4,5-dichloro-2- (3,4 8th 9 9 9 9 9 9 9 9 dichlorophenyl M - (2- propynyl) pyrrole-3-carbonitrile 0 9 3 9 9 9 0 0 0 4,5-dibromo-3- (p-chloro- phenyl) pyrrole-2-carbonitrile 7 9 9 9 9 9 5 .9 7 5- (3,4-dichlorophenyl) - pyrrole-2,4-dicarbonitrile 5-bromo-4-chloro- (3,4- 0 9 9 9 9 9 0 6 9 dichlorophenyl) pyrrole 3-carbonitrile 4,5-dibromo-3- (p-chloro- 0 - - 9 9 0 0 0 9 phenyl) -1-methylpyrrole 2-carbonitrile 0 2 0 9 0 9 0 0 0 г-Вгот-б-ргіепуІруггоІ- 3,4-dicarbonitrile 4-bromo-2-phenyl-5- 0 9 9 9 9 9 9 9 0 (Trifluoromethyl) pyrrole 3-carbonitrile 7 9 0 9 9 9 0 0 0 2- (3,4-dichloro-phenyl) - S-nitro pyrrole-S-carbonitrile 4-bromo-2- {3,4-dichloro- 0 5 0 9 0 3 0 0 0 phenyl) -5-nitropyrrole 3-carbonitrile 0 9 9 9 9 9 0 0 0 2,4-dibromo-5-phenyl- pyrrole-3-carbonitrile 0 9 9 9 9 9 5 7 9 2- (3,4-DichlorphenyO- 4.5-diiodpyrrol-3-carbonitrile 2,3-dibromo-5- (p-chloro- 9 9 9 9 9 9 9 5 9 phenyl) -1- (ethoxyme- thyl) -4-nitro pyrrole 0 4 0 9 8th 0 9 9 3 1-benzyl-2,3-dibromo 5- (p-chlorophenyl) -4-nitropyrrole 0 8th 7 9 9 7 0 4 0 2,3-dibromo-5- (p-chloro- phenyl) -1-methyl-4-nitropyrrole 4,5-dibromo-2- [p {tri- 9 9 9 9 9 9 9 0 0 fluoromethoxy) phenyl] - pyrrole-3-carbonitrile 4,5-dichloro-1 - (ethoxyme- 9 9 9 9 9 9 9 9 9 thyl) -2- [p- (trifluoro methoxy) phenyl] pyrrole-3-carbonitrile 3 9 9 9 9 9 0 0 8th 5- (p-chlorophenyl) pyrrole rol-2,4-dicarbonitrile 1-benzyl-4,5-dichloro-2 9 9 0 9 9 9 9 9 0 [P- (trifluoromethoxy) phe nyljpyrrol-3 <arbonitril 4,5-dichloro-2- (p-chloro 8.5 9 9 9 9 9 9 9 0 phenyl) -I- (ethoxymethyl) - pyrrole-3-carbonitrile

Table IV, continued

connection Sheet- TBW ³ ppm armyworms ppm 7 days C-S systemic Sheet- German hop 100 100 SAW hop cockroach 4 6 7 ppm rest ppm ppm ppm ppm 100 ppm 100 1000 1000 100 9 1000 1 2 3 2 5 9 9 8th 10 4,5-dichloro-2- (3,4 dichlorophenyl) -1- (2- 0 0 7 9 hydroxyethyl) pyrrole-3-carbonitrile 0 9 9 0 0 2- (p-chlorophenyl) -5- 9 nitropyrrole-3-carbonitrile 7 9 9 9 9 9 0 0 4-bromo-2- (p-chlorophenyl) - 5- (trifluoromethyl) pyrrole 0 9 9 9 3-carbonitrile 9 9 9 9 9 4-bromo-2- (p-chlorophenyl CJL 9 9 7 5-nitropyrrole-3-carbonitrile 0 9 9 0 0 3-bromo-5- (p-chlorophenyl) - 3 pyrrole-2,4-dicarbonitrile 6 7 0 9 9 9 0 9 4,5-dichloro-2- (3,4-di- chlorophenyl) pyrrole-1,3- 0 dicarbonitrile 0 9 9 0 9 1 - [(benzyloxy) methyl] - 0 9 9 4,5-dichloro-2- {3,4- dichlorphenyDpyrrol- 9 3-carbonitrile 5 9 0 9 9 9 9 0 4,5-dichloro-2- (2,4 dichloro-5-fluorophenyl) - 0 9 9 0 pyrrole-3-carbonitrile 4 CJL 9 9 9 5- [p- (trifluoromethoxy) - 0 phenyl] pyrrole-2,4-dicarbonitrile 7 7 9 8th 8th 4,5-dichloro-1 - [(p- 0 9 9 chlorphenoxylmethyl] - 2- (3,4-dichlorophenyl) 9 pyrrole-3-carbonitrile 0 8th 9 9 0 4,5-dichloro-2- (3,4 0 9 9 dichlorophenyl) 1- (3- iodo-2-propynyl) pyrrole 9 9 9 0 3-carbonitrile 9 9 9 9 0 5- (3,4-dichlorophenyl) - 9 9 9 0 4-nitropyrrole-2-carbonitrile 9 9 9 0 9 2,4-dibromo-5- (p-chloro- 0 phenyl) pyrrole-3-carbonitrile 0 9 0 9 9 9 9 0 3-bromo-5- [p- (trifluoro- methoxy) phenyl] pyrrole 0 2,4-dicarbonitrile 9 9 0 9 9 9 9 9 3-bromo-5- (3,4-dichloro- phenyl) -4-nitropyrrole-2- 0 carbonitrile 9 6 0 9 9 9 0 0 4-bromo-2- (p-chloro- phenyl) -1-methyl-5- (tri- 0 fluoromethyl) pyrrole-3-carbonitrile 9 9 9 9 9 9 0 9 3,4-dibromo-5- (3,4-di- chlorophenyl) pyrrole-2- 0 carbonitrile 0 9 9 9 9 9 0 9 2- (3,4-dichloro-phenyl) - 5- (trifluoromethyl) pyrrole 0 3-carbonitrile 0 9 9 9 9 9 0 9 5- (trifluoromethyl) -2-a, a, a- trifluoro-p-tolyl) - 0 9 9 0 pyrrole-3-carbonitrile 7 9 9 0 9 2,5-dibromo-4- (p-chloro- 3 9 9 0 phenyl) -pyrrole-34: arbonitril 0 9 9 0 9 S, S-dibromo ^ lp-chloro 0 phenyl) pyrrole-2-carbonitrile 0 9 9 0 0

Table IV, continued

connection Sheet- TBW ³ ppm armyworms ppm 7 days C-S systemic Sheet- German hop 100 100 SAW hop cockroach 4 6 7 ppm rest ppm ppm ppm ppm 100 ppm 100 1000 0 1000 0 0 100 9 1000 1 2 3 5 8th 10 2-p-tolyl-5- (trifluoro 0 methyOpyrrol-3-carbonitrile 0 9 7.5 0 0

5- (trifluoromethyl) -

pyrrole-3-carbonitrile 0 96999 -

4-bromo-2- (p-chlorophenylM- (ethoxymethyl) -5- (trifluoromethyl) pyrrole)

rol-3-carbonitrile 9 99999 00

4-bromo-2- (3,4-dichlorophenyl) -5- (trifluoromethyl

pyrrole-3-carbonitrile 9 99999 00

5- (a, a, a-trifluoro-p-tolyD-

pyrrole-2,4-dicarbonitrile 9 99999 79

1-Methyl-3- (a, a, a-trifluoro-p-tolyO-pyrrole

2,4-dicarbonitrile 0 30900 00

4-bromo-5- (trifluoromethyl) -2- (a, a, a-trifluoro

p-tolyl) pyrrole-3-carbonitrile 9 99999 00

(α, α, α-trifluoro-ptolyl) pyrrole-2,4-dicarbonitrile 4,5-dichloro-2- {a, a, atrifluoro-p-tolyl) pyrrole-1,3-dicarbonitrile 3-bromo 5- (a, a, a-trifluoro-p-tolyl) pyrrole-2,4-dicarbonitrile

Claims (11)

in which mean X is H, F _{1 is} Cl, Br, I or CF ₃ ;
Y is F, Cl, Br, I, CF ₃ or CN;
W is CN or NO ₂ ; A equals H; a C ₁ -C ₄ alkyl, optionally substituted with one to three halogen atoms, a hydroxy, a C ₁ -C ₄ alkoxy or a C 1-6 alkylthio group, a phenyl optionally substituted with a C ₁ -C ₃ Alkyl or a C ₁ -C ₃ alkoxy group or one to three halogen atoms, a phenoxy group optionally substituted with one to three halogen atoms or a benzyloxy group optionally substituted with a halogen substituent; C ₁ -C ₄ -carbalkoxymethyl; Сэ-С ₄ -АІкепуІ, optionally substituted with one to three halogen atoms; a cyano group; a Cy-Q-alkynyl optionally substituted with a halogen atom; a di (C ₁ -C ₄ alkyl) aminocarbonyl or a Q-Ce-cycloalkylaminocarbonyl; L is H, F, Cl or Br and M and R independently of one another are H, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -alkylthio, C ₁ -C ₃ -alkyl-sulfinyl, С-С-alkyl-sulfonyl, cyano, F, Cl, Br, I, nitro, CF ₃ , R ₁ CF ₂ Z, R ₂ CO or NR ₃ R ₄ and M and R when in adjacent positions and with the carbon atoms to which they are attached can form a ring, in which MR represents the following structure -OCH ₂ O-, -OCF ₂ O- or Z is S (O) _n or 0; R ₁ is H, F, CHF ₂ , CHFCI or CF ₃ ; R ₂ is a C ₁ -C ₃ alkyl, an alkoxy group or NR ₃ R ₄ ; R ₃ is H or C ₁ -C ₃ alkyl; R ₄ is H, C ₁ -C ₃ alkyl or R ₅ CO; R ₅ is H or C ₁ -C ₃ alkyl and η is an integer of 0.1 or 2. 2. A compound according to claim 1, wherein mean
A is H or C ₁ -C 4 alkoxymethyl; W is CN or NO ₂ ;
X and Y are each Cl, Br or CF ₃ ;
R is F, CI ₁ Br, CF ₃ or OCF ₃ ;
M is H, F, Cl or Br and
L is H or fluorine. 3. A compound according to claim 1, characterized in that the compound is the following is 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile;
4,5-dichloro-2- (a, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitrile;
2,3-dichloro-4-nitro-5- (a, a, a-trifluoro-p-tolyl) pyrrole;
2,3-dichloro-5- (3,4-dichlorophenyl) -nitropyrrol;
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- (a, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitrile; 4-bromo-2- (p -chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile or 4-bromo-2- (3,4-dichlorophenyl) -5- (trifluoromethyl) pyrrole 3-carbonitrile. 4. A method for controlling insects, nematodes and mites and for protecting growing plants from their infestation, characterized in that an insecticidal, nematicidal or arkarizid effective amount of a compound of formula I with the insects, nematodes and mites, their breeding sites, feed bases or Habitats or applied to the foliage of the plants or the soil or water in which they grow, the compound of formula I having the following structure L
U (I) wherein X is H, F, Cl, Br, I or CF ₃ ; Y is F, Cl, Br, I, CF ₃ or CN; W is CN or NO ₂ and A is H; a Ci-C ₄ alkyl optionally substituted with one to three halogen atoms, one hydroxy, one C ₁ -C ₄ -AIkOXy- or a C ₁ -C ₄ alkylthio group, a phenyl group optionally substituted with a C ₁ -C ₃ -alkyl or a C 1 -5-alkoxy-3-hydrazine or one to three halogen atoms, one phenoxy group, optionally substituted by one to three halogen atoms or one benzyloxy group, optionally substituted by one halogen substituent; ^ -C-carbalkoxy; C ₃ -C ₄ alkenyl, optionally substituted with one to three halogen atoms; a cyano group; a C ₃ -C ₄ alkynyl optionally substituted with a halogen atom; a di-fCr-Q-alkylaminocarbonyl or a C ₄ -C ₆ -cycloalkylaminocarbonyl; L is H, F, Cl or Br and M and R independently of one another are H, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -alkylthio, C ₁ -C ₃ -alkyl-sulfinyl , C ₁ -C ₃ alkylsulfonyl, a cyano group, F, Cl, Br, I, a nitro group, CF ₃ , R ₁ CF ₂ Z, R ₂ CO or NR ₃ R ₄ , and M and R when in side-by-side Are positions and can form a ring with the carbon atoms to which they are attached, in which MR represents the following structure -OCH ₂ O-, -OCF ₂ O- or Z is S (O) _n or 0; R ₁ is H, F, CHF ₂ CHFCI or CF ₃ ; R ₂ is a C ₁ -C ₃ alkyl, a C ₁ -C ₃ alkoxy group or NR ₃ R ₄ ; R ₃ is H or C ₁ -C ₃ alkyl; R ₄ is H, a C ₁ -C ₃ alkyl or R ₆ CO; R ₅ is H or C ₁ -C ₃ -A ^ yI and η is an integer of 0.1 or 2. 5. The method according to claim 4, characterized in that the compound is the following: 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile;
4,5-dichloro-2- (a, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitrile;
2,3-dichloro-4-nitro-5- (a, a, a-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;
S-bromo-SP ^ ^ -dichlorphenlylpyrrol Adicarbonitril;
4,5-dichloro-1- (ethoxymethyl) -2- (a, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitrile; 4-bromo-2- (p -chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile or 4-bromo-2- (3,4-dichlorophenyl) -5- (trifluoromethyl) pyrrole 3-carbonitrile. 6. A method of protecting growing plants from attack by insects, nematodes and mites according to claim 4, characterized in that the compound in an amount of about 0.125 kg / ha to about 4.0 kg / ha of the compound of formula I to the plants or the soil in which they grow is applied. 7. A method of protecting growing plants from infestation by insects, nematodes and mites according to claim 4, characterized in that the compound of formula I in the form of a liquid composition containing between about 10ppm and about 10000ppm compound of formula I, the foliage the plants or the soil or the water in which they grow is applied. -Z-295 834 8. A process for preparing a novel arylpyrrole compound of the formula structure Il wherein W is CN or NO ₂ ; L is H, F, Cl or Br and M and R are each independently is H, C ₁ -C ₃ -alkyl, a Ci-C ₃ -AIkOXy-, Сг Сэ-alkylsulfinyl, Ci-CrAlkylsulfonyl, a cyano group , F, Cl, Br, I, nitro, CF ₃ , R _1, CF ₂ Z, R _2, CO or NR ₃ R ₄ , and M and R when in adjacent positions and together with the carbon atoms to which they are attached are bound to form a ring in which MR represents the following structure -OCH ₂ O-, -OCF ₂ O- or Z is S (O) _n or O, R ₁ is H, F, CHF ₂ , CHFCI or CF ₃ ; R ₂ is a C ₁ -C ₃ alkyl, a C ₁ -C 6 alkoxy group or NH ₃ R ₄ ; R ₃ is H or C ₁ -C ₃ alkyl; R ₄ is H, C ₁ -C ₃ alkyl or R ₅ CO; R ₅ is H or C ₁ -C ₃ alkyl and η is an integer of 0.1 or 2; characterized in that it consists in the reaction of a benzoylacetonitrile or a-nitroacetophenone having the structure -CH ₂ U wherein L, M, R and W are as defined above, with г ^ -ОЧСг-СгАІкохуІешуІатіп at elevated temperature to give an α-2,2-di (C ₁ -C ₄ alkoxy) ethylamino-β-cyanostyrene or a 2,2-di (dC ₄ -alkoxy) ethylamino-β-nitrostyrene to obtain, which has the following structure N-CHpCH (C ₁ -C ₄ alkyl) ₂ H wherein L, M, R and W are as defined above, and the treatment of the thus prepared α-2,2-di (C ₁ -C ₄ -alkoxy) -ethylamino-β-cyanostyrene or α-2,2-di ( C 1 -C ₄ alkoxy) amino-β-nitrostyrene with a mineral or organic acid to obtain the desired arylpyrrole. 9. The method according to claim 10, characterized in that the reaction of 2,2-di- (C ₁ -C ₄ alkoxy) ethylamine with benzoylacetonitrile or a-nitroacetophenone is carried out neat or in the presence of an inert organic solvent. 10. The method according to claim 10, characterized in that the a ^^ - DHCi-C ^ alkoxyjethylaminoß-cyanostyrene or a-2,2-di (C ₁ -C ₄ -BIkOXy) ethylamino-ß-nitrostyrene with hydrogen chloride, hydrogen bromide - or trifluoroacetic acid is treated to produce the arylpyrrole. 11. A process for preparing an α-2,2-di (C ₁ -C ₄ alkoxy) ethylamino-β-cyanostyrene or α-2,2-di (C ₁ -C ₄ alkoxy) ethylamino-β-nitrostyrene, that is represented by the structure ρ - N-CHpCH (C ₁ -C ₄ alkyl); ^R H where W is CN or NO 2; L is H, F, Cl or Br; Each of M and R is independently H, a СС-Сз-АІкуІ, a Ci-C ₃ -alkoxy, Сі-Сз-alkylthio group, a C ₁ -C ₃ alkylsulfinyl, Сг-Сз alkylsulfonyl, a cyano group, F , Cl, Br, I, nitro, CF ₃ , RiCF ₂ Z, R ₂ CO or NR ₃ R ₄ , and M and R, when in adjacent positions, form a ring together with the carbon atoms to which they are attached can, in which MR the following structure represents -OCH ₂ O-, -OCF ₂ P- or Z is S (O) _n or O; R ₁ is H, F, CHF ₂ , CHFCI or CF ₃ ; R ₂ is a C ₁ -C ₃ alkyl, equal to a Сі-Сз alkoxy group or NR ₃ R ₄ ; R ₃ is H or C ₁ -C ₃ alkyl; R ₄ is H, C ₁ -C ₃ alkyl or R ₅ CO; R ₅ is H or C ₁ -C ₃ alkyl and η is an integer of 0.1 or 2, characterized in that it consists of the reaction of a benzoylacetonitrile or an a-nitroacetophenone having the structure C-CH ₂ U wherein L, M, R and W are as defined above, with 2,2-diethoxyethylamine at elevated temperature to form an α- (2,2-di (C 1 -C ₄ alkoxy) ethylamino) -β-cyanostyrene or a To obtain (2,2-di (CHVakoxy) ethylamino-β-nitrostyrene having the following structure N-CHOCH (OC ₁ -C ₄ alkyl> 2
H wherein L, M, R and W are as defined above.
12. Compound of the formula N-CH ₂ CH (C ₁ -C ₄ alkoxy> 2 in which mean W is CN or NO ₂ ; L is H, F _{1 is} Cl or Br; M and R independently of one another are H, СС-Сз-АІкуІ, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -alkylthio, C ₁ -C ₃ -alkylsulfinyl, C ₁ -C ₃ -alkylsulfonyl; a cyano group, F, Cl, Br, I, a nitro group, CF ₃ , R ₁ CF ₂ Z, R ₂ CO or NR ₃ R ₄ and when M and R, when in adjacent positions and with the carbon atoms to the they are bound, can form a ring, in which MR represents the following structure -OCH ₂ O-, -OCF ₂ - or Z is S (O) _n or O; R is equal to H, F, CHF ₂ , CHFCI or CF ₃ ; R ₂ is C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or NR ₃ R ₄ ; R ₃ is H or C ₁ -C ₃ alkyl; R ₄ is H, C ₁ -C ₃ alkyl or R ₅ CO; R ₅ is H or C ₁ -C ₃ alkyl and η is an integer of 0.1 or 2. 13. A compound according to claim 14, characterized in that the compound is the following: (EI-p-chloro-.beta.-tiformylmethyDaminojzimtsäurenitrildiethylacetal; (Zbp-chloro-ß-KformylmethyOaminoIcimtsäurenitrildiethylacetal; ß - [(formylmethyl) amino] -3,4- (Z) -methyl-p- {2-cyano-1 - [(formylmethyl) amino] vinyl} benzoate diethyl acetal; SADichloro-β-formylmethyldiazole-cinnamic acid nitrile diethyl acetal; (Z) -β - [(Formylmethyl) -amino] -p-methylcinnamic acid nitrile diethyl acetal β- [(formylmethyl) amino] -p-trifluoromethoxycinnamic nitrile dimethylacetal; (Ebp-chloro-β-H-butylmethylamino-cinnamic acid nitrile dimethyl acetal; N-i-formylmethyl-O-p-methyl-alnitromethylene-benzylamine diethyl acetal; p-chloro-N-alkylmethyl-diethyl acetal; N-IFormylmethoxy -a-initromethylene-1-naphthenemethylamine-diethylacetal; methyl-p-ia-flurylmethyldimethyl-β-nitrovinylbenzoate-p-diethylacetal) or p-trifluoromethyl-N-iformylmethyl-a-in-tromethylene-1-benzylamine-diethylacetal. 14. A process for preparing a compound represented by the structure N-CH ₂ CH (C ₁ -C ₄ alkoxy> ₂ wherein W is CN or NO ₂ ; L is H, F, Cl or Br; M and R are each independently H, a Ci-C ₃ alkyl, a C ₁ -C ₃ -AIkOXy-, _Ci-C3 alkylthio group, a C ₁ -C ₃ alkylsulfinyl, Сг-Сз alkylsulfonyl, a Cyano group, F, Cl, Br, I, a nitro group, CF ₃ , R ₁ CF ₂ Z, R ₂ CO or NR ₃ R ₄ and M and R, when in adjacent positions and together with the carbon atoms, to the they are bound to form a ring in which MR represents the following structure -OCH ₂ O-, -OCF ₂ O- or Z is S (O) _n or O; R ₁ is H, F, CHF ₂ , CHFCI or CF ₃ ; R ₂ is a C ₁ -C ₃ alkyl, a ^ -Qr alkoxy group or NR ₃ R ₄ ; R ₃ is H or C ₁ -C ₃ alkyl; R ₄ is H, C ₁ -C ₃ alkyl or R ₅ CO; R ₅ is H or C ₁ -C ₃ alkyl and η is an integer of 0.1 or 2, characterized in that it consists in the reaction of a benzoylacetonitrile or an a-nitroacetophenone having the structure C-CH ₂ U wherein L, M, R and W are as defined above, with 2,2-di- (Ci-C4-alkoxy) ethylamine at elevated temperature to obtain a compound having the following structure