LV10773B - Arylpyrrole derivatives, process for preparing thereof, struggle method against insekts, ticks.87 - Google Patents

Abstract

InventedSafeTheSpecifiedNewSilyl Pyrrole Compounds With Insecticide the properties of nematodes and acaricides, as well as the method of controlling insects, parasitic mites and nematodes. The invention relates to a method for the protection of cultivated plants from insects, ticks and nematodes, after which the above-mentioned parts of the surface of the plant, soil or water, in the bark, are treated with an effective amount of arylpyrrole compound, \ t with activity against insects, ticks and nematodes. The invention relates to a bonded ararylpyrrole compound technique.

Description

LV 10773 - ī -

ARYLPYRROLE INSECTICIDAL ACARICIDAL AND NEMĀTICIDAL AĢENTS AND METHODS FOR THE PREPARATION THEREOF

The present invention is directed to certain novel arylpyrrole compounds that are highly effective insecticidal, acaricidal and nematicidal aģents useful for the control of insect, acarid and nematode pests and for protecting agronomic crops, both growing and harvested, against the ravages of said pests. The present invention is also directed to methods for preparing the arylpyrrole compounds.

The novel arylpyrrole compounds of the present invention have the structural formula illus-trated as formula I:

L

wherein X is F, Cl, Br, I, or CF3; Y is F, C1, Br, I, CF3 or CN; W is CN or N02 and A is Η; Cļ-C^ alkyl optionally substituted with from one to three halogen atoms, one hydroxy, one C^-C^ alkoxy or one C]_~C4 alkylthio, one phenyl optionally substituted with Cļ-C 2 alkyl or Cļ-C.^ alkoxy or with one to three halogen atoms, one phenoxy optionally substituted with one to three halogen atoms or one benzyloxy optionally substituted with one halogen substituent; ci“C4 carbalkoxymethyl; C3-C4 alkenyl optionally substituted with from one to three halogen atoms; cyano; C3~C4 alkynyl optionally substituted with one halogen atom; di-(C1~C4 alkyl) aminocarbonyl; or C^-C^ cycloalkylami-nocarbonyl; L is H, F, Cl or Br; and M and R are each independently H, C1“C3 alkyl, alkoxy, Ci-C3 alkylthio, c1“c3 alkylsulfinyl, C1“C3 alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF3, RļCF2Z, R2C0 or NR3R4' and when M and R are on adjacent positions and taken with the carbon atoms to which they are attached they may form a ring in which MR represents the structure: -0CF2ū- or

-ŪCH2ū· Z is S(0)n or 0; R is H, F, CHF2, CHFCl, or CF3; R is 0^2 alkyl, =1-=3 alkoxy, or NR3R4; R3 is H or =1-=3 alkyl; R4 is X n M 1 C3 alkyl, or R5C0; R5 is H or =1-=3 alkyl; and n is an integer of 0, 1 or 2.

The term C.-C, 4 6 a C. to C-4 6 cycloalkylamino carbonyl means cycloalkylamino group attached directly to the carbonyl group through the nitrogen atom. A preferred group of novel arylpyrroles of the present invention are illustrated by formula II:

wherein A, L, M, R, W, X and V are as described above. - 3 - LV 10773

Another preferred group of novel arylpyrroles of this invention are represented by formula III: x

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

Another group of preferred arylpyrroles of the invention are depicted by formula IV:

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

Yet another group of preferred arylpyrroles of this invention are delineated by formula V:

L

wherein A, L, M R, W, X and Y are as described above? 4 and stili other preferred arylpyrroles of the invention are depicted by formulas VI and VII: 4

p < VI > (VII) wherein A, L, M, R, W, X and Y are as described above.

Preferred formula I arylpyrroles of the invention are those in which A is hydrogen or C1“C4 alkoxymethyl; W is CN or N02; L is hydrogen or F; X and Y are each Cl, Br or CF^; M is H, F, C1 or Br; and R is F, Cl, Br, CF3 or OCF3.

Preferred formula II compounds which are

especially effective as insecticidal, acaricidal and/or nematicidal aģents are those in vhich A is hydrogen or C1~C4 alkoxymethyl; L is hydrogen; M is hydrogen, F, Cl or Br; R is F, Cl, Br, CF3 or OCF3; W is CN and X and Y are each independently Cl, Br or CF3.

Other formula II compounds that are highly effective as insecticidal, acaricidal and/or nematicidal aģents are those in vhich A is hydrogen or C1~C4 alkoxymethyl ,· L is hydrogen; M is hydrogen, F, Cl or Br; R is F, Cl, Br, CF3 or OCF3; W is N02 and X and Y are each independently Cl, Br or CF3.

Illustrative of some of the insecticidal, acaricidal and nematicidal arylpyrroles of the present invention are: 4.5- dichloro-2-(3,4-dichlorophenyl)pyrrole-3-carbo- nitrile; 4.5- dichloro-2-[p-(trifluoromethoxy)phenyl]pyrrole-3- carbonitrile; - 5 - LV 10773 4- bromo-5-chloro-2-(p-chlorophenyl)pyrrole-3-carbo- nitrile; 5- bromo-4-chloro-2-(3,4-dichlorophenyl)pyrrole-3-carbo- nitrile; 4.5- dichloro-2-(o-chlorophenyl)pyrrole-3-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-E-tolyl)pyrrole-3-carbo- nitrile; 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-carbo- nitrile; 4.5- dibromo-2-(2,4-dichlorophenyl)pyrrole-3-carbo- nitrile; 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-(E-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-2-chloro-4-nitro-5- (Q,a,a-trifluoro-p-tolyl) - pyrrole; 5-Chloro-2-(3,4-dichlorophenyl)-1-(methoxymethyl)-4-(trifluoromethyl)pyrrole-3-carbonitrile; 5-Bromo-2- (iņ-f luorophenyl) -3-nitro-4- (trifluoromethyl) pyrrole; 2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbo-nitrile; 6 3- Bromo-5- (xņ-fluorophenyl) -4-nitro-2-(trifluoromethyl) pyrrole; 4- Bromo-2-(p-chlorophenyl)-1-(ethoxymethyl)-5-(tri- fluoromethyl)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-ftri-fluoromethyl)pyrrole-3-carbonitrile; 2- (2,5-Difluorophenyl)-3-nitro-4,5-bis-(trifluoro- methyl)pyrrole; 5- [p-(Trifluoromethoxy)phenyl]pyrrole-2,4-dicarbo- nitrile; 5-(p-Dimethylaminophenyl)-4-nitropyrrole-2-carbo-nitrile; 3- Bromo-5-(p-chlorophenyl)pyrrole-2,4-dicarbonitrile; 4- Bromo-2-(p-chlorophenyl)-5-nitropyrrole-3-carbo- nitrile; 5- (p-Methylthiophenyl)-3-(trifluoromethyl)pyrrole-2,4- dicarbonitrile; 1- Allyl-4-nitro-5- (a,a,a-trifluoro-E-tolyl) -3-(tri- fluoromethyl)pyrrole-2-carbonitrile; 4- Chloro-2-(E-chlorophenyl)pyrrole-3-carbonitrile; 2- (:m-Methanesulfonylphenyl) -4- (trifluoromethyl) pyrrole -3-carbonitrile; 2- (3-chloro-4-methylphenyl) -l-methyl-3-nitro-4- (tri-fluoromethyl)pyrrole; 2-Phenylpyrrole-3,4-dicarbonitrile; 5- (p-Ethanesulfinylphenyl)-4-nitropyrrole-3-carbo nitrile ; 2-Bromo-5-phenylpyrrole-3,4-dicarbonitrile; 2-Chloro-5-(3,5-dichlorophenyl)-4-nitropyrrole-3-carbonitrile; 1- Benzyl-4-nitro-5-(p-chlorophenyl)-2-(trifluoromethyl) pyrrole-3-carbonitrile; 2- Chloro-5-(m-bromophenyl)pyrrole-3-carbonitrile; - 7 - 5 10 15 20 25 30 LV 10773 2-Bromo-l-(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- (ņ-propyloxy) methyl-4-(trifluoromethyl)pyrrole-3-carbo-nitrile; 2- Bromo-5-(p-chlorophenyl)-3-nitro-4-(trifluoromethyl) pyrrole; 5-[m-(Difluoromethoxy)phenyl]-2-(trifluoromethyl) pyrrole-3-carbonitrile; 5- (2,3-Dichlorophenyl) -l-meth'oxymethyl-3-nitro-2-(trifluoromethyl)pyrrole; 4- Chloro-5-(0-napthyl)-2-(trifluoromethyl)pyrrole-3- carbonitrile; 3- Bromo-2-(3,4-dichlorophenyl)-4-nitro-5-(trifluoro- methyl)pyrrole; 5- (2-Bromo-5-ethylphenyl)-2,4-bis-(trifluoromethvl) pyrrole-3-carbonitrile; l-Ethyl-2-(p-fluorophenyl)-4-nitro-3,5-bis-(trifluoro-methy1)pyrrole; 1-[(2,6-Dichlorophenoxy)methyl]-5-(m-chlorophenyl) pyrrole-2,3-dicarbonitrile; 3- Nitro-5 (a, a, a-trifluoro-p-tolyl) pyrrole-2-carbo- nitrile; 4- Chloro-5-(4-chloro-2-methylphenyl)pyrrole-2,3- dicarbonitrile; 4- Bromo-5-(3,4-dibromophenyl)-2-nitropyrrole-3-carbo- nitrile; 1-[(l-Methoxy)ethyl]-5-(p-chlorophenyl)-4-(trifluoro-methyl)pyrrole-2,3-dicarbonitrile; 5- (p-Isopropylphenyl)-2-nitro-4-(trifluoromethyl) pyrrole-3-carbonitrile; 4-Chloro-5-(3,4-difluoromethylenedioxyphenyl)pyrrole-3-carbonitrile; 35 8 3-Bromo-2-(3-chloro-4-cyanophenyl)-4-nitropyrrole; 1— [ (3,4-dichlorobenzyloxy)methyl]-2-(nt-broinophenyl) pyrrole-4-carbonitrile; 2- (3,5-Dichloro-4-methylphenyl)-4-nitro-3-trifluoro- methylpyrrole; 2-Phenylpyrrole-3,4-dicarbonitrile; 2-(2-Bromo-4-chlorophenyl)-4-nitropyrrole-3-carbo-nitrile; 2-Bromo-5-phenylpyrrole-3,4-dicarbonitrile; 5-Chloro-2-(3,4-dibromophenyl)-l-methyl-4-nitropyrrole- 3-carbonitrile; 2-(p-Chlorophenyl-5-(trifluoromethyl)pyrrole-3,4-dicarbonitrile; 2- (o-Bromophenyl)-4-nitro-5-(trifluoromethyl)pyrrole-3- carbonitrile; 3- Bromo-5-(3-chloro-4-inethoxy)pyrrole-2-carbonitrile; 3-Bromo-5-(m-bromophenyl)-2-nitropyrrole; 3,4-Dibromo-5- (3,4-dichlorophenyl) pyrrole-2-carbo-nitrile; 2- (3-Chloro-4-cyanophenyl)-5-nitro-3,4-dichloropyrrole; 3- Chloro-l-(p-methoxybenzyl)-5-(3,4-difluorophenyl)-4- (trifluoro-inethyl) pyrrole-2-carbonitrile; 3- Bromo-5-(3,5-dibromo-p-tolyl)-2-nitro-4-(trifluoro- methyl)pyrrole; 1- (2,3,3-Trichloroally)-5-(p-chlorophenyl)-3-(trifluor- omethyl)pyrrole-2-carbonitrile; 2- (p-Iodophenyl)-5-nitro-4-(trifluoromethyl)pyrrole; 4- Chloro-5- (iTt-isopropylphenyl) -3- (trif luoromethyl) pyrrole-2-carbonitrile; 3- Broiao-l-methyl-2- (3-f luoro-4-methylphenyl) -2-nitro- 3-(trifluoromethyl)pyrrole; 5- (p-Bromophenyl)-l-isopropyl-3, 4-bis-(trifluoromethvl) pyrrole-2-carbonitri-le; 2-(3,4-Dichloro-4-methylthio)-5-nitro-3,4-bis-(tri-fluoromethyl)pyrrole; - 9 - LV 10773 5- (m-Difluoromethoxyphenyl)pyrrole-2,3-dicarbonitrile; 5-(3-Bromo-4-cyanophenyl)-2-nitropyrrole-3-carbo-nitrile; 4-Chloro-l-methoxymethyl-5- (p-bromophenyl)pyrrole-2,3-dicarbonitrile; 4- Bromo-5-(2,6-dichloro-4-methylthio) -2-nitropyrrole-3- carbonitrile; 1- [(p-Bromophenoxy)methyl]-5-(m-trifluoromethy1)-4- (trifluoromethyl)pyrrole-2,3-dicarbonitrile; 5- (a-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-nitropvrrole; 5- (m-Cyanophenyl)-3-(trifluoromethyl)pyrrole-2-carbo- nitrile; 2- (3-Bromo-4-isopropoxy)-5-nitro-3-(trifluoromethyl) pyrrole; 5-(p-Chlorophenyl)pyrrole-2,4-dicarbonitrile; 2- (3,4-Dichlorophenyl)-5-nitropyrrole-3-carbonitrile; 3- Bromo-5-(3,4-dichlorophenyl)pyrrole-2,4-dicarbo nitrile ; 4- Bromo-2-(3,4-dichlorophenyl)-5-nitropyrrole-3- carbonitrile; 5- (3,4-Dibromophenyl)-3-(trifluoromethyl)pyrrole-2,4- dicarbonitrile; 2- (ļņ-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)-l-hydroxyethyl-4-(tri- fluoromethyl)pyrrole-2-carbonitrile; 10 2- Chloro-5-nitro-3-(trifluoromethyl)-4-(m-trifluoro- methylphenyl)pyrrole; 3- (3-Bromo-4-chlorophenyl)-5-(trifluoromethyl)pyrrole- 2-carbonitrile; 3- (3-Chloro-4-fluorophenyl)-2-nitro-5-(trifluoromethyl) pyrrole; 4- Bromo-3-(p-chlorophenyl)-l-methylthioniethyl-5- (tri- fluoromethyl)pyrrole-2-carbonitrile; 3- (4-Bromo-3-cyanophenyl)-4-chloro-2-nitro-5-(tri- fluoromethyl)pyrrole; 4- (p-chlorophenyl)-2,3-bis-(trifluoromethyl)pyrrole-2- carbonitrile; 3-(2,3-Dichlorophenyl)-2-nitro-4,5-bis-(trifluoro-methyl)pyrrole; 3- (3,4-Dichlorophenyl)pyrrole-2,5-dicarbonitrile; 4- (2-Bromo-4-methylphenyl)-5-nitropyrrole-2-carbo- nitrile; 3- Bromo-4-(3,5-dichloro-4-methylthiophenyl)pyrrole- 2,5-dicarbonitrile; 4- (xņ-Bromophenyl) -3-chloro-5-nitropyrrole-2-carbo- nitrile; 3- (p-Acetamidophenyl)-4-(trifluoromethyl)pyrrole-2,5- dicarbonitrile; 4- (nļ-Bromophenyl) -5-nitro-3-(trifluoromethyl)pyrrole-2- carbonitrile; 4-Chloro-3-(3,4-dichlorophenyl)-1-(l-propenyl)pyrrole-2-carbonitrile; 3-Bromo-4- (p-dimethylaminophenyl) -5-nitropyrrole; 1- (3,4-Dichlorobenzyl(-3-(p-chlorophenyl)-4-(trifluoro- methyl) pyrrole-2-carbonitrile; 2- Nitro-3-(p-tetrafluoroethoxyphenyl)-4-(trifluoro- methyl)pyrrole; 3- (3-Bromo-4-,i-propylphenyl)pyrrole-2,4-dicarbonitrile; 4- (p-Ethylsulfonylphenyl)-5-nitropyrrole-3-carbo- nitrile; - 11 - LV 10773 5-Bromo-l-(2-methoxyethyl)-4-(2,4,6-trichlorophenyl) pyrrole-2,4-dicarbonitrile; 2- Chloro-4-(2,3-dichlorophenyl)-5-nitropyrrole-3- carbonitrile; 3- (p-Fluorophenyl)-5-(trifluoromethyl)pyrrole-2,4- dicarbonitrile; 4- (p-Iodophenyl)-5-nitro-2-(trifluoromethyl)pyrrole-3- carbonitrile; 5- Chloro-4-[p- (N-methylacetainido) phenyl]pyrrole-2- carbonitrile; 5-Bromo-4-(o-bromophenyl)-l-propargylpyrrole-2-carbo-nitrile; 2- Bromo-3-(o-bromophenyl)-5-nitropyrrole; 4- (p-Chlorophenyl)-3,5-dichloro-l-(2,3,3-trichloroally) pyrrole-2-carbonitrile; 3- Bromo-5-chloro-4-(p-chlorophenyl)-2-nitropyrrole; 5- Bromo-4-[p-(2,2-dichloro-l,1-difluoroethoxy)phenyl] -3-(trifluoromethyl)pyrrole-2-carbonitrile; 2- Chloro-3-(2-bromo-4-ethylthiophenyl)-5-nitro-4-(tri- fluoromethyl)pyrrole; 3- (3-Bromo-4-acetylphenyl)-5-(trifluororoethyl)pyrrole- 2-carbonitrile; 1- Cyano-3-(3,4-dibroraophenyl)-5-nitro-2-(trifluoro- methyl)pyrrole; 3-BroTno-l-methoxymethyl-4- (m-trifluoromethyl) -5- (tri-fluoromethyl)pyrrole-2-carbonitrile; 3- (p-Chlorophenyl)-4-iodo-5-nitro-2-(trifluoromethyl) pyrrole; 4- (p-Bromophenyl)-1-[(l-ethoxy)ethyl]-3,5-di-(trifluor- omethyl)pyrrole-2-carbonitrile; 3-(2-Bromo-4-methoxyphenyl)-5-nitro-2,4-di-(trifluoro-methyl)pyrrole; 3-(p-Chlorodifluoromethoxyphenyl)pyrrple-2,5-dicarbo-nitrile; 2- (p-Isobutyrylaminophenyl)-5-nitropyrrole-2-carbo- 12 nitrile ? 3- Bromo-4-(3,4-dimethoxyphenyl)pyrrole-2,5-dicarbo- nitrile; 4- Chloro-3-(p-chlorophenyl)-l-isopropyloxycarbonyl~ 5 methyl)-5-nitropyrrole-2-carbonitrile; 3-(o-Bromophenyl)4-(trifluoromethyl)pyrrole-2,5-dicarbonitrile; 1-(2-Chloroethyl)-3-(3,4-dichlorophenyl)-4-(trifluoro-methyl)pyrrole-2-carbonitrile; 10 4- (4-Bronto-3- trifluoromethoxyphenyl) -3-chloropyrrole-2- carbonitrile; 3- Bromo-4-(2,4-dichlorophenyl)-l-isopropyl-2-nitro- pyrrole; 4- (3-Hethoxy-4-cyanophenyl)-3-(tri fluoromethyl)pyrrole 15 -2-carbonitrile; 1-(3,4-Dichlorobenzyl)-4-(2-methyl-4-iodophenyl)-2-nitro-3-trifluoromethylpyrrole; 1- Methyl-4-[3,5-di(trifluoromethyl)phenyl]pyrrole-2,3- dicarbonitrile; 20 4-(3,4-Dichlorophenyl)-2-nitropyrrole-3-carbonitrile; 4- (m-Bromophenyl)-l-carbomethoxymethyl-5-chloropyrrole- 2,3-dicarbonitrile; 5- Bromo-4-(2,6-dichloro-4-methanesulfinylphenyl-2- nitropyrrole-3-carbonitrile; 2 5 4 —(p—Chlorophenyl)-1-(2,2,2-trifluoroethyl)-5-(tri- fluoromethyl)pyrrole-2,3-dicarbonitrile; 4-(3,5-Dichlorophenyl)-2-nitro-5-(trifluoromethyl) pyrrole-3-carbonitrile; 2- Chloro-4- (3-chloro-4-N-methylacetainidophenyl) 30 pyrrole-3-carbonitrile; 2-Bromo-4-(3-brorao-4-ņ-propylphenyl)-3-nitro-pyrrole; 2,5-Dichloro-4-(3,5-dichloro-4-methylthiophenyl) pyrrole-3-carbonitrile; 35 2,5-Dibromo-l- (2,4-dibromophenoxyrnethyl) -3- (p-chloro- - 13 - LV 10773 phenyl-4-nitropyrrole; 4-(3-Bromo-4-cyanophenyl)-2-chloro-5-(trifluoromethyl) pyrrole-3-carbonitrile; 2-Bromo-l-methyl-3-nitro-4- (α,α,α-trifluoro-p-tolyl) pyrrole? 4-(p-chlorophenyl)-1-(ņ-butyloxymethyl)-5-(trifluoro-methyl)pyrrole-3-carbonitrile; 4- (3,4-Methylenedioxyphenyl)-3-nitro-2-(trifluoro- methyl)pyrrole; 5- Chloro-4-(3-chloro-4-trifluoromethoxyphenyl)-2-(tri- fluoromethyl)pyrrole-3-carbonitrile; 2- Bromo-3-(3,4-dichlorophenyl)-l-ethylthiomethyl-4- nitro-5-(trifluoromethyl)pyrrole; 4- [p-(tetrafluoroethoxy)phenyl]-2,5-di-(trifluoro xnethyl) pyrrole-3-carbonitrile; 3- (3-Bromo-4-acetoxyphenyl)-1-(3,4-dichlorophenoxy- methyl)-4-nitro-2,5-di-(trifluoromethyl) pyrrole; 4- (p-Bromophenyl)-l-[(2-methoxy)ethyl]pyrrole-2,3- dicarbonitrile; 4- (m-lsopropionamidophenyl)-3-nitropyrrole-2-carbo- nitrile 5- Bromo-4-(2-chloro-4-methylthio)pyrrole-2,3-dicarbo- nitrile; 5-Chloro-4-(p-chlorophenyl)-l-hydroxyethyl-3-nitro-pyrrole-2-carbonitrile; 4-(3,5-Dibromo-4-cyanophenyl)-5-(trifluoromethyl) pyrrole-2,3-dicarbonitrile; 4- (4-Chloro-2-methylphenyl)-l-isopropylthiomethyl-3- nitro-5-(trifluoromethyl)pyrrcle-2-carbo-nitrile ? 5- Bromo-4-(3,4-dichlorophenyl)-1-(difluoromethyl) pyrrole-3-carbonitrile; 2-Chloro-3-(ra-difluoromethoxyphenyl)-4-nitropyrrole; 1- (2,4-Dibromophenoxymethyl) -4- (rņ-chlorophenyl) -5- (tri- 14 fluoromethyl)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-(dif luoromethyl) -4-nitro-pyrrole-2-carbonitrile; 5-Bromo-3- (p-chlorophenyl) -1-(isobutyloxymethyl) pyrrole-3-carbonitrile; 3-(4-Bromo-3-methylphenyl) -5-chloro-4-nitropyrrole-2-carbonitrile; 3- (2-Naphthyl) -5-(trifluoromethyl)pyrrole-2,4-dicarbonitrile; 3- (3-Cyano-4-methylphenyl) -l-methyl-4-nitro-5- (tri-fluoromethyl)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-nitro- pyrrole; 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-l-methyl-2-(a,a,Q-trif luoro-p-tolyl) pyrrole-3-carbonitrile; 4.5- dichloro-2 - (3,4-dichlorophenyl) -l-ethylpyrrole-3- carbonitrile; 2.3- dichloro-4-nitro-5- [p- (trif luororaethoxy) phenyl ] - pyrrole; 4.5- dichloro-2-[iņ- (trif luoromethoxy) phenyl ]pyrrole-3- carbonitrile; 4.5- dichloro-2-(3,4-dichlorophenyl)-l-methylpyrrole-3- carbonitrile; 2.3- dichloro-5-(p-chlorophenyl) -l-methyl-4-nitro pyrrole; and - 15 - LV 10773 4- bromo-5-chloro-2-(p-chlorophenyl)-l-methylpyrrole-3- carbonitrile. 5- chloro-2-(3,4-dichlorophenyl)-4-fluoropyrrole-3- carbonitrile 2- bromo-5-(p-chlorophenyl)-1-(ethoxymethy1)-4-fluoro- pyrrole-3-carbonitrile 3- bromo-5-(p-chlorophenyl)-2-fluoro-4-nitropyrrole

The q-[2,2-di(Cļ-C4 alkoxy) ethylamino)-/?-cyano-styrene and a-[2,2-di(C1~C4 alkoxy) ethylamino]-£-nitro-styrene compounds of this invention are depicted by the following structural formula: fl

\\-C = CHU ^ NH-CH2CH(C1-C4 alkoxy)2 wherein W is CN or NC>2; L is H, F, Cl, or Br; M and R are each independently H, C1~C3 alkyl, alkoxy, alkylthio, C1~C3 alkylsulfinyl, C1~C3 alkylsul-fonyl, cyano, F, Cl, Br, I, nitro, CF3, R^FjZ, R2C0, or NR3R4 and when on adjacent positions and taken together with the carbon atoms to which they are" attached M and R may form a ring in which MR represent the structure:

-och2o-, -ocf2- or Z is S(0)n or 0; is H, F, CHF2, CHFCl, or CF3; R2 is C1~C3 alkyl, C^C.^ alkoxy, or NR3R4; R3 is H or c1_c3 alkyl; R4 is H, alkyl, or R5CO; Rg is H or alkyl; and n is an integer of 0, 1 or 2. 16 A preferred group of £-(substituted)styrene compounds of the present invention have the above-illustrated structure vherein H is CN; L is H( C1 or Br; M is H, F, Cl, Br or OCH3? R is H, F, Cl, Br, CF3, NO^r OCF3 or OCH3; or when on adjacent positions and taken together with the carbon atoms to which they are attached M and R may form a ring in which MR represents the structure:

Another preferred group of jff-(substituted) -styrene compounds of this invention have the above-illustrated structure vherein W is N02; L is H, Cl or Br; M is H, F, Cl, Br or OCH3; R is H, F, Cl, Br, CF3# NO^, OCF3 or OCH3; or vhen on adjacent positions and taken together vith the carbon atoms to vhich they are attached M and R may form a ring in vhich MR represents the structure:

While the compounds of the present invention are referred to above as 0-cyanostyrenes and 0-nitro-styrenes, they may also be named as dialkyl acetals. - 17 -5 10 15 20 25 30 LV 10773

Some of the preferred dialkyl acetal compounds of this invention are (E) and (Z) (l)p-chloro-0-[(formyl-methyl)amino]cinnamonitrile diethyl acetal; (2)0-[(formyl-methyl)amino]-3,4-dimethoxycinnamonitrile diethyl acetal; (3)(Z)-methyl p-{2-cyano-l-[(formylmethyl)amino]-vinyl)benzoate diethyl acetal; (4)(Z)-v9-[(formylmethyl)-amino]-l-naphthaleneacrylonitrile diethyl acetal; (5) (Z)-/?-[ (formylmethyl) amino ]-E~methylcinnamonitrile diethyl acetal; (6)N-(fonnylmethyl)-p-methyl“ct-(nitro-methylene)benzylamine diethyl acetal; (7)N-(formylmethyl)-3,4-dimethoxy-a- (nitromethylene) benzylamine diethyl acetal; (8)N-(formylmethyl) -a- (nitromethylene) -2-naphtha-lenemethylamine diethyl acetal; (9)methyl Ε“{““[(ίοηηγΐ-methyl)amino]-0-nitrovinyl}benzoate p-(diethyl acetal); (10)N-(formylmethyl) -3,4-dimethoxy-a- (nitromethylene)be-nzylamine dimethyl acetal; (11) (E) and (Z) E“Chloro-)9-[(formylmethyl)amino]cinnamonitrile dimethyl acetal; (12) β-[ (formylmethyl) amino] -3,4-dimethoxycinnamonitrile dimethyl acetal; (13) 3,4-dichloro-^-[ (formylmethyl) amino]-cinnamonitrile diethyl acetal; and (14)E-trifluoromethyl--/S-[‘(forroylmethyl) amino] cinnamonitrile diethyl acetal. The £-cyanostyrenes, also referred to as cinnamonitrile dialkyl acetals, can be prepared by the “v _ reaction of a substituted or unsubstituted benzoyl acetonitrile with a 2,2-di(C1~C4 alkoxy)ethylamine in the presence of an aromatic solvent to form the a-(2,2-di (c1“c4 alkoxy) ethylamino) -0-cyano- (substituted) styrene which then may be converted to a 2-(substituted-phenyl)-pyrrole-3-carbonitrile by reaction of said £-3-cyano-(substituted)styrene compound with trifluoroacetic acid. Chlorination of the thus prepared cyanophenyl pyrrole with sodium hypochlorite or sulfuryl chloride in an inert solvent yields the insecticidal, acaricidal, and 35 18 nematicidal 4,5-dichloro-2-(substituted-phenyl) pyrrole--3-carbonitrile. The conversion to the pyrrole inter-mediate may also be achieved by substituting concentrated HC1 at a temperatūre betveen about 20 and 40°C. The reactions may be graphically illustrated as follows: // + H2NCH2CH(0C2H5>2

•CN

flromati c So1ven t

ļ and £

NaOCl or so2c 1 e or BrĒ

- 19 -10 15 20 25 30 LV 10773 vherein A is hydrogen, Cx-C4 alkyl optionally substituted with one C1»c4 alkoxy, one C1«C4 alkylthio, from one to three halogen groups, or phenyl optionally substituted with one or two Cļ-C^ alkyl, C^-C^ al^oxy, or halogen groups; C3-C4 alkenyl optionally substituted with from to three halogen groups; or C3-C4 alkynyl; X is C1 or Br; Rg is C^-C^ alkyl and L, R and M are as described above. 35 20

Certain novel arylpyrrole compounds of formula I, wherein A is hydrogen; W is CN and X, Y, L, M and R are as described above, can be prepared by reacting N-formyl-DIi-phenyl-glycine or a substituted N-formylphenylglycine represented by the structure formula VIII: 10

15 wherein L is H, F, C1 or Br; R and M are each indepen-dently H, Cļ-C3 alkyl, C^-C^ alkoxy, alkylthio, C1~C3 alkylsulfinyl/ C^-C^ alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF3, RļCF2Z, R2C0 or NR3R4 and when on adjacent positions and taken together with the carbon atoms to which they are attached, M and R may form a ring in which MR represents the structure:

- 21 - LV 10773 Z is S(0)n or O; ^ is H, F, CHF2/ CHFCl or CF3? R2 is C^-C^ alkyl, c1“c3 alkoxy or NR3R4; R3 is H or C^-C^ alkyl; R4 is H, C^-Cg alkyl or RgCO; R5 is H or C1“C3 alkyl and n is an integer of 0, 1 or 2; with at least an equivalent amount of a 2-chloroacrylonitrile and two to three equivalents of acetic anhydride. The reaction is conducted at an elevated temperature, preferably about 70° to 100°C.

The reaction can be illustrated as follows:

L

Conversion of the thus prepared 2-phenyl-pyrrole-3-carbonitrile or 2-(substituted phenyl)pyr-role-3-carbonitrile to the corresponding formula II, 4-halo, 5-halo or 4,5-dihalo-2-(substituted phenyl)pyr-role-3-carbonitrile, is readily achieved by reaction of the above said 2-phenylpyrrole-3-carbonitrile or 2-(substituted phenyl)pyrrole-3-carbonitrile with at least about 1 or 2 equivalents of a sulfuryl halide, bromine or chlorine, in the presence of a solvent such as dioxane, THF, acetic acid or a chlorinated hydrocar-bon solvent. For preparation of a monohalo pyrrole-3-carbonitrile use of about 1 equivalent of the halogen-ating aģent is required; whereas, preparation of a dihalo pyrrole-3-carbonitrile reguires 2 to 3 22 eguivalents of said halogenating aģent. When sulfuryl chloride or sulfuryl bromide is used the reaction is generally conducted at a temperature below about 40°C and preferably between about 0° and 30°C, but when elemental bromine is employed, the reaction is usually conducted at about 30-40°C. Other effective halogenating aģents that may be employed in these reactions include sodium hypochlorite, t-butylhypo-chlorite, N-bromosuccinimide, N-iodošuccinimide and the like. The reaction may be illustrated as follows: 22

The formula II carbonitrile compounds of the present invention may also be prepared from the reaction of a substituted or unsubstituted benzoyl aceto-nitrile with a 2,2-di(C^-C4 alkoxy)ethylamine in the presence of an aromatic solvent to form the a-(2,2-di-(C1~C4 alkoxy) ethylamino) -jS-cyano- (substituted) styrene which is then converted to the 2-(substituted-phenyl)-pyrrole-3-carbonitrile of formula II by reaction of said /?-3-cyano- (substituted) styrene compound with tri-fluoroacetic acid or with concentrated HC1 at a temperature between about 20° and 40°C. The reactions may be graphically illustrated as follows: - 23 LV 10773

CFgCOgH or HC1

wherein R- is C,-C. alkyl and L, R and M are as de- o 14. scribed above.

Also in accordance with the present invention formula II 3-nitro-2-phenylpyrrole and 3-nitro-2-(sub-stituted)phenylpyrrole compounds can be prepared by reaction of an α-nitroacetophenone or a substituted a-nitroacetophenone with a 2,2-di (C1-C4-alkoxy) ethyl-amine. The reaction is generally conducted in the presence of an inert organic solvent preferably an aromatic solvent, at an elevated temperature to give an a- (2,2-di (Cļ-C^- alkoxy) ethylamino)-/9-nitrostyrene or a substituted a-(2,2-di(C1-C4~alkoxy)ethylamino)-^-nitro-styrene that is converted to the formula II 3-nitro-2-phenylpyrrole or 3-nitro-2-(substituted)phenylpyrrole by treatment with a mineral acid such as hydrochloric - 24 or hydrobromic acid. Reaction of the thus prepared nitrophenylpyrrole with sodium hypochlorite in the presence of an inert organic solvent at a reduced temperature yields the formula II 2,3-dichloro-4-nitro-5-phenyl or 5-(substituted)phenylpyrrole.

The above reactions may be graphically illustrated as follows:

L

HC1 or CF3C02H

In addition to the several methods described in the literature for preparing substituted and unsub-stituted benzoyl acetonitriles, surprisingly we have found that these compounds may also be prepared by reacting an appropriately substituted benzoyl halide with an alkali mētai hydride and an alkyl cyanoacetate, such as t-butyl cyanoacetate, to yield the > LV 10773 - 25 - corresponding t-butyl(benzoyl or substituted benzoyl) cyanoacetate. These reactions xnay be graphically illustrated as follows:

The thus formed cyanoacetate ester can then be converted to a substituted or unsubstituted benzoyl acetonitrile by heating the compound in toluene con-taining p-toluene sulfonic acid. The reaction may be graphically illustrated as follows:

L

L

M

R

C0-C-C0-0C<CH3>3 CN PTSfl toluene

Π> R IIC1

Examples of the t-butyl(benzyl and substituted benzoyl acetonitriles used in the above reactions are shown in Tables below. 26 •t-Butvl (benzvl and Substituted benzvl') cvanoacetates

L

C0-C-C0-0C(CH3)CN 3 Ļ M R O ΙΠΌ C H 3-C1 4-C1 91-94 H H 4-OCF3 81-84 H H 4-Br 113-115 H H 4-CF3 146-147 H H 4-F 98-100 H H 4-CN 127-128 H H 4-CF3CH20 136-139 H H 4-CH3S02 127-129 H 3-F 4-F 91-94 H H 4-CH3S 117-119", H H 4-CHF2CF20 92-94 3-C1 5-C1 4-CH30 — - 27 - - 27 -LV 10773

Benzovl Acetonitriles

R L M R itioC H H 4-C1 128.5-129.5 H 3-C1 4-C1 105-107 H H 2-C 153-55 H H 4-OCF3 79-81 H H 4-CF3 44-45 H 2-C1 4-C1 66-67 H H 3-C1 80-83 H H 4-CN 126-128 H H 4-F 78-80 " H H 4-S02CH3 129-132 H 3-F 4-F 74-75 H H 3-CF3 58-60 H H 4-CH3 103.5-106 H H 4-N02 119-124 3-C1 5-C1 4-OCH3 — 28

Preparation of N-substituted formula I arylpyrroles can be achieved by reaction of the appropriately substituted formula I arylpyrrole, wherein A is hydrogen and L, M, R, W, X and Y are as described above, with an appropriate alkylating aģent and a suitable base. For example, a brominated hydroxy-Cļ-C4-alkyl and potassium t-butoxide. This reaction provides an arylpyrrole having the same substituents as the starting material, but in addition is substituted on the nitrogen with hydroxy-C1-c4 alkyl. In a similar reaction cyanogen bromide is substituted for the brominated hydroxy c^~c^ alkyl and yields the formula I arylpyrrole with a carbonitrile substituent on the nitrogen. The reactions may be illustrated as follovs:

wherein L, M, R, W, X and Y are as described for formula I above and A is 1) C.-C. alcohol or 2) CN. '14 ' 29 - LV 10773

Preparation of 2-phenylpyrrole 3,4-dicarboni- trile, 2-bromo-5-phenylpyrrole-3,4-dicarbonitrile and substituted phenyl derivatives thereof can be obtained by reaction of fumaronitrile with bromine in the pre-5 sence of a chlorinated hydrocarbon such as chloroform at an elevated temperature to yield bromofumaronitrile. The thus formed bromofumaronitrile is then reacted with N- (trimethylsilyl)methyl-5-methyl-benzene-thioimidate or a substituted derivative thereof, in the presence of 10 hexamethylphosphoramide at an elevated temperature to yield the 2-phenylpyrrole-3,4-dicarbonitrile. Bromi-nation of the thus prepared 3,4-dicarbonitrile yields the 2-bromo-5-phenylpyrrole-3,4-dicarbonitrile or the substituted phenyl derivative if the substituted 15 N- (trimethylsilyl) methyl-5-methyl-benzene-thioimidate is used in the previous reaction. The reaction may be graphically illustrated as follows: 20

CN

CN

NC 25

CN

HHPB/3 equiv. HjO H (-TNS ,-HBr,-CHjSH) R Br,/CHC1

THS

n L R

NC CN

(1 R 30

The examples provided by way of illustration below utilizē the schemes illustrated above and provide 35 -30- a means for preparing other compounds of the invention which are not specifically described herein.

The arylpyrroles of the present invention are effective for controlling insects, acarina and nema-todes. These compounds are also effective for protect-ing growing or harvested crops from attack by the above-said pests.

In practice generally about 10 ppm to about 10,000 ppm and preferably 100 to about 5000 ppm, of the formula I arylpyrrole, which encompasses ali of the arylpyrrole isomers of formulas II, III, IV, V, VI and VII, dispersed in vater or other inexpensive liquid carrier is effective when applied to the plants, the crops or the soil in which said crops are growing to protect said crops from attack by insects, acarina and/or nematodes. These compounds are also useful for protecting turf grass from attack by pests such as grubs, chinch bugs and the like.

The formula I arylpyrroles of this invention are also effective for controlling insects, nematodes and acarina, when applied to the foliage of plants and/or to the soil or water in which said plants are groving in sufficient amount to provide a rāte of from about 0.125 kg/ha to about 4.0 kg/ha of active ingre-dient. Obviously higher rātes of application of the formula I arylpyrroles may be used to protect crops from attack by insects, nematodes and acarina, however, higher rātes of application are generally unnecessary and wasteful.

While the arylpyrroles of this invention are effective for controlling insects, nematodes and acarina when employed alone, they may be used in combination with other biological Chemicals, including other insecticides, nematicides and acaricides. For example, the arylpyrroles of this invention may be used - 31 - LV 10773 effectively in conjunction or combination with phos-phates, carbamates, pyrethroids, formamidines, chlori-nated hydrocarbons, halobenzoylureas and the like.

The 2-aryl-3-cyano-4,5-dihalopyrroles prepared from the £-cyano-styrene compounds of the present invention are effective for controlling insects, acarina and nematodes. These compounds are also effective for protecting growing or harvested crops from attack by the above-said pests. 10 15

In practice generally about 10 ppm to 10,000 ppm and preferably 100 to 5000 ppm, of the halogenated arylpyrrole dispersed in water or other inexpensive liguid carrier is effective when applied to the plants, the crops or the soil in which said crops are growing to protect said crops from attack by insects, acarina and/or nematodes. 20

The above-said halogenated arylpyrroles are also effective for controlling insects, nematodes and acarina, when applied to the foliage of plants and/or to the soil or water in which said plants are growing. 25

These halogenated arylpyrrole compounds are usually applied in sufficient amount to provide a rāte of from about 0.125 kg/ha to about 4.0 kg/ha of active ingre-dient. Obviously higher rātes of application of said halogenated arylpyrroles may be used to protect crops from attack by insects, nematodes and acarina, however, higher rātes of application are generally unnecessary and wasteful. 30 35 32

Advantageously, the above-said arylpyrroles may be formulated into dry compacted granules, flovable compositions, granular formulations, wettable powders, emulsifiable concentrates, dusts, dust concentrates, microemulsions and the like, ali of which lend themselves to soil, water and/or foliage application and provide the requisite plant protection. Such formulations include the compounds of the invention admixed with inert, pharmacologically- acceptable solid or liguid diluents.

For example, wettable powders, dusts and dust concentrate formulations of the invention can be prepared by grinding together about 3% to 20%, by veight, of the formula I arylpyrrole compound, with about 3% to 20% by weight of a solid anionic surfactant. One suitable anionic surfactant is a dioctyl ester of sodium sulfosuc-cinic acid, specifically Aerosol OTB® surfactant marketed by the American Cyanamid Company. About 60% to 94%, by weight, of an inert solid diluent, such as montmorillo-nite, attapulgite, chalk, talc, kaolin, diatomaceous earth, limestone, silicates or the like also is used in such formulations.

Compacted granules especially useful for soil or water application can be prepared by grinding together in about equal parts, usually about 3 to 20 parts, of the arylpyrrole and a solid surfactant, with about 60 to 94 parts of gypsum. Thereafter, the mixture is compacted into small granular pārticies, about 24/48 mesh or larger.

Other suitable solid surfactants useful in the present formulations include not only the anionic dioctyl ester of sodium sulfosuccinic acid but also nonionic block copolymers of ethylene oxide and propy-lene oxide. Such block copolymers are marketed by BASF Wyandotte Corporation as Pluronic 10R8®, 17R8®, 25R8®, F38®, F68®, F7 7® or F87®, and are especially effective for the preparation of compacted granules. - 33 - LV 10773

In addition to the powders and concentrate formulations described hereinabove, vettable powders and flovables may be used because they may be dispersed in vater. Preferably, such flovables will be applied at the ločus vith the aqueous compositions being sprayed on the foliage of plants to be protected. These sprays also may be applied to the breeding ground, food supply or habitat of the insects and acarina sought to be controlled. Vīhere solid formulations of the arylpyrroles are to be used in combination treatments vith other pesticidal aģents, the formulations can be applied as an admixture of the components or may be applied sequentially.

Similarly, liguid formulations of the aryl-pyrrole in combination vith other pesticidal aģents may be tank mixed or may be applied separately, sequentially, as liquid sprays. Liquid spray formulations of the compounds of the invention should contain about 0.001% to 0.1% by veight of the active arylpyrrole.

The following examples are presented as illustrations of the present invention. 34 EXAMPLE 1 2-PhenvlPvrrole-3-carbonitrile

10 The folloving procedure is similar to the method given in JOC, 43, 4273-6 (1978). A magnetically stirred mixture of 30.00g of N-formyl-phenylglycine is heated at 90°C for 1 & 1/2 hours. The clear yellow reaction solution is concentrated iņ vacuo to give 15 42.5g of an oily brownish orange semi-solid. Material partially purified by chromatography on silica gel is shown by the proton NMR spectrum to be a mixture of 73% 2-phenylpyrrole-3-carbonitrile and 27% 2-pheny1-3-cyano5-methylpyrro le. Recrystal1i z ation 20 once from chloroform and twice from 1,2-dichloroethane gives 1.69g of an off-white solid which proton NMR shows it to be 96% 2-phenylpyrrole-3-carbonitrile, mp 148-152°C.

Microanalvsis (MW 168.19): Calcd.: c, 78.55%; H, 4.79%; N, 16.66% Found.: C, 78.52%; H, 4.73%; N, 16.54% 30 35 - 35 - LV 10773 EXAMPLE 2 4,5-Dichloro-2-phenvlpvrrole-3-carbonitrile and 5-chloro-2-phenvlpvrrole-3-carbonitrile

To a magnetically stirred ice-water cooled solution of 2.00g (11.9 mmol,) of 2-phenyl-3-cyano-pyrrole in 80 mL of methylene chloride is added drop-wise over a period of 5 min., 1.90 mL (3.19 g, 23.6 mmol,) of sulfuryl chloride by means of a syringe. Throughout the addition the temperature is ķept between 5°C and 10°C. Stirring at 5-10°c is continued for 90 minūtes. The reaction mixture is vacuum filtered to remove a precipitated solid (1.28g) identified as 5-chloro-2-phenylpyrrole-3-carbonitrile, mp 192.5-195°C. 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 slurrying of the residue with hexane) 0.60g (21.3% yield) of a pink-purple solid. This solid is recrystallized from 5 mL of hot acetone to give 0.32g (9% yield) of 4,5-dichloro -2-phenylpyrrole-3-carbonitrile as an orangish brown solid, mp 254-255°C.

Max(mull,Nujol): 3165(br s), 3120(s), 2245(s), 1570(m), 1513(m), 1440(s), 1252(m), 1069(m), 996(m), 920(m), 768(s), 698(s), 665(s) cm-1. 36 H—NMR(DMSΟ): 57.73 (d, J=6.6Hz, 1.97H, two phenyl protons at C-2,6), 57.52 (t, J=7.3Hz, 2.04H, two phenyl protons at C-3,5), 57.44 (t, J=7.3Hz, 1.02H, one phenyl proton at C-4). C-NMRfDMSO): 5137.51 (C-2 pyrrole carbon), 5129.25 (C-4 phenyl carbon), 5129.04 (C-3,5 phenyl carbons), 5128.37 (C-l phenyl carbon) 5125.88 (C-2,6 phenyl carbons), 5114.32 (either C-5 pyrrole or the nitrile carbon), 5114.14 (either C-5 pyrrole or the nitrile carbon), 5110.72 C-4 pyrrole carbon), 589.78 (C-3 pyrrole carbon).

Microanalvsis (MW 237.09):

Calcd.: C, 55.72%? H, 2.55%; N, 11.82%; Cl, 29.91% Found : C, 55.78%; H, 2.59%; N, 11.12%.; Cl, 29.74% EXĀMPLE 3 p-Chloro-θ-Γ (formvlmethvl)aminolcinnamonitrile. diethvl acetal

A magnetically stirred solution of 250.00 g (1.39 mol,) of p-chlorobenzoylacetonitrile, 203 mL (185.95 g, 1.39 mol) of 2,2-diethoxyethylamine, and 13 00 mL of dried toluene is heated at refux for 20 hours. Water is collected in a Dean-Stark trap (23.8 mL, 95.2% theory). The hot cloudy dark brown solution with a large amount of undissolved solids is filtered through diatomaceous filter aid. After dilution with - 37 - LV 10773 200 mL of EtOAc, the solution is filtered through a 7cm X 13.5cm column of silica gel. The filtrate is concentrated iņ vacuo to give 354.38 g (86.4% crude yield) of a clear dark oil which slowly solidifies. This solid is recrystallized from hot cyclohexane to give 324.26g (79.1% yield) of a waxy orange solid. NMR of this product shows it to be composed of 78% (Z) and 23% (E) isomeric mixture of p-chloro-/9-[ (formylmeth-yl)amino] cinnamonitrile, diethyl acetal, m.p. 60-72°C. The following analytical data is for another similarly prepared sample.

Max(mull,Nujol): 3325(s), 3065(m), 2197(s), 1600(s), 1530 (s) , 1314 (111), 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(chlorof ornO: £7.47 (d, J=8.6Hz, 2.12H, two aromatic protons), £7.37 (d, J=8.6Hz, 2.12H, two aromatic protons), £5.10(E) & £4.86(Z) [br t, 1.25H, one N-H proton], £4.69 (Z) & S4.60(E) [t, J=5.1Hz, 1.05H, one methine proton at the acetal carbon], £4.07 (E) & £4.05(Z) [s, 0.83H, enamine β proton], £3.71(E) & £3.68(Z) [q, J=7.1Hz, 2.22H, two methylene protons of one of two ethoxy groups], £3.56 (Z) & £3.53 (E) [g, J=7.1Hz, 2.22H, two methylene protons of one of two ethoxy groups], £3.18 (t, J=5.1Hz, 1.77H, two methylene protons of the ethyleneacetal group), £1.20 (t, J=7.1Hz, 4.90H, six methyl protons of the two ethoxy groups). C-NMR(chloroform): £161.21 (α-enamine carbon), £136.29 (Z) & £134.60 (E) [either C-l or C-4 of the phenyl ring], £134.08(Z) & £132.30(E) [either C-l or C-4 of the phenyl ring], £129.34(Z) & £129.89(E) [either C-2,6 38 or C-3,5 of the phenyl ring], 5128.94(Z) & 5128.63(E) [either C-2,6 or C-3,5 of the phenyl ring], 5121.19(Z) & 5119.50(E) [nitrile carbon], 599.43(Z) & 5100.63(E) [^-enamine carbon], 561.88(Z) & 563.25(E) [methine carbon of the acetal], 562.64(Z) & 563.03(E) [methylene carbons of the ethoxy groups], 546.32(Z) & 547.33(E) [methylene carbon of the ethyl amine group], 515.26 (methyl carbons of the ethoxy groups).

Microanalvsis (MW 294.78):

Calcd: C, 61.11%; H, 6.50%; N, 9.51%» Cl, 12.03%. Found: C, 61.25%; H, 6.25%; N, 9.34%; Cl, 12.35%. EXAMPLE 4 2 fp-ChlorophenYl)-Pvrrole-3-carbonitrile

To 108 mL of trifluoroacetic acid stirred at 23°C is added 54.00 g (0.183 mol) of solid p-chloro-^-['(formyl-methyl)amino]cinnamonitrile, diethyl acetal over a period of 45 minūtes. This addition produced an exotherm to 38°C and, 32 minūtes into the addition, a solid started to precipitate. After stirring at room temperature for 30 minūtes, the reaction mixture is vacuum filtered and the collected solid is washed first with trifluoroacetic acid, secondly with an ethyl acetate-hexane mixture, and finally with hexane. The - 39 - LV 10773 yield is 16.83 g (45.4%) of an off-white solid, mp 165-166°C. The following anal. data is from a similarly prepared sample.

Maxfmull. Nujol): 3275(br s) , 2225(s) , 1502 (s), 1410(m), 1275(m), 1200im), 1108(s), 1023(m), 999(m), 908(m), 843(s), 752(s), 722(s), 695(s), 620(s) cm-1. H-NMR(acetone): $11.22 (v br s, 0.99H, one pyrrole N-H proton), $7.82 (d, J=8.9Hz, 2.46H, two aromatic phenyl protons), $7.51 (d, J=8.9Hz, 2.46Hz, two aromatic phenyl protons), $7.02 (t, J=2.6Hz, 1.01H, one pyrrole proton at C-5), $6.58 (t, J=2.6Hz, 0.77H, one pyrrole proton at C-4). C-NMR f acetone): $137.73 (pyrrole C-2), $134.42 (E-chlorophenyl at C-4), $129.93 (methine carbons at C-3,5 of the phenyl ring), $128.07 (methine carbons at C-2,6 of the phenyl ring), $121.21 (pyrrole at C-5), $117.93 (nitrile carbon), $113.78 (pyrrole carbon at C-4), $90.86 (pyrrole carbon at c-3).

Microanalvsis (MW 202.64):

Calcd. : C, 65.19%; H, 3.48%; N, 13.83%; Cl, 1-7.50% Found: C, 64.18%; H, 3.52%; N, 13.63%; Cl, 17.74% 40

Use of the above procedure as shown or with the substitution of concentrated hydrochloric acid for trifluoroacetic acid affords the following compounds: M and/or R CN //{ N \/ H \ mo°C / 1 ~\ R Acid Used 4-C1 165-166 conc. HCl 3,4-di-Cl 216-221 cf3cooh 2-Cl 156-157 CF3C00H 4-OCF3 143-145 CF3C00H 4-CF3 179-180 CF3C00H 2,4-di-Cl 197-199 CF3C00H 3-C1 150-156 CF3COOH 4-CN 210-212 CF3COOH 4-F 167-170 conc. HCl 4-S02CH3 221-221.5 CF3C00H 3,4-di-F 173-175.5 CF3COOH 3-CF3 166-168 CF3C00H 4-C00CH3 155.5-158 cf3cooh 4-CH3 117-137 CF3COOH 1 O to < 174-177 cf3cooh

CF3COOH - 41 - LV 10773 EXAMPLE 5 4,5-Dichloro-2- (p-chlorophenvlϊ pvrrole-3-carbonitrile

C1

CN

C1 5 10

To a mechanically stirred solution of 16.83g (83.1 mmol) of 2-(p-chlorophenyl)pyrrole-3-carbonitrile in 450 mL of glacial acetic acid at 3 6°C is added 15 dropwise 14.7 mL (24.70 g, 183.0 mmol) of sulfuryl chloride over a period of 18 minūtes. The addition producēs a slight exotherm to 39°C and, after another 16 minūtes, the reaction mixture is vacuum filtered. The collected solids are washed first with acetic acid 20 and then with water. This solid after recrystalliza- tion from hot ethyl acetate, melts at 259-261°C. By similar procedures other samples of this product were prepared and the analytical data for one such product is shown below. 25

Max(mull, Nujol): 3170(br s) , 3100(m), 2225(s), 1508(m), 1097(m), 825(s), 717(m), 660(m) cm-1. H-NKR(DMSO): d7.72 (d, J=8.6Hz, 2.00H, two aromatic 30 protons), 57.56 (d, J=8.6Hz, 2.00H, two aromatic protons). C-NMRfDMSOĪ: 5136.01 (pyrrole C-2 carbon), 5133.92 (p-chlorophenyl C-4 carbon), 5129.09 (p-chlorophenyl C-3,5 carbons), 5127.41 (p-chlorophenyl C-4 carbon), 42 - £127.11 (E~chlorophenyl C-l carbon), £114.49 (nitrile carbon), £114.10 (pyrrole 05 carbon), £110.92 (pyrrole C—4 carbon), £90.09 (pyrrole 03 carbon).

Microanalvsis (MW 271.54):

Calcd.: C, 48.65%, H, 1.86%; N, 10.32%; Cl, 39.17% Found: C, 49.22%; H, 2.12%; N, 9.85%; Cl, 39.03% EXAMPLE 6 10 4,5-Dibroxno-2-ftt.g.a-trifluoro-p-tolvlĪ -pvrrole-3-carbonitrile 15

20 25

To a stirred mixture of 0.8g of 2-(α,α,ο-tri-fluoro-p-tolyl)pyrrole-3-carbonitrile in 70 mL of chloroform is added 2 mL of bromine. The mixture, on stirring overnight, deposits a white solid which is collected by filtration. Thin layer chromatography (1:1 ethyl acetate-hexane) shows a single component; m.p. >230°C.

Anal. Calc’d for C12Hr 7.11; Br, 40.61. Br2F3N2; c, 36.55; H, 1.27; Found: C, 36.40; H, 1.08; N, 6.99; Br, 40.55.

Following the procedures of Examples 5 and 6, but substituting the appropriately substituted phenyl-pyrrole-3-carbonitrile for 2-(a,a,a-trifluoro-p-tolyl) pyrrole-3-carbonitrile yields the following compounds. -43-: 5 10 15 20 25 30

X. CN

L J \ N H —^ \ R Ļ M R X Y mt>°C H H 4-N02 Br Br 274-277 H H 4-F C1 C1 >220 H H 4-F Br Br >220 H H 4-S02CH3 C1 C1 >230 H 3-F 4-F C1 C1 >230 H 3-F 4-F Br Br >220 2-C1 3-Cl 4-C1 C1 C1 2-Br 3-Br 4-Br Br Br H H 4-OCF3 C1 C1 222-225 H H 4-OCF3 Br Br 231-232 H . H 4-OCF3 C1 H H H 4-CN Br Br >230 H H 4-CN C1 C1 >240 H H 4-S02CH3 Br Br >230 H H 4-N02 C1 C1 246-249 H 3-Cl. 4-C1 Br Br >260 H H 3-CF3 C1 C1 >230 H H 4-COCH3 C1 C1 251-254 H 2,3 -CH=CH- C1 C1 244-247 H H 4-CH C1 C1 215-217 H 2-C1 4-C1 Br Br >230 LV 10773 35 44 Ļ M R X Y mo°C H H 3-Cl C1 C1 >230 H 2-Cl 4-Cl C1 C1 >230 H H 4-Cl Br Br 273-274 H H 2-Cl Br Br >230 H H 4-CF3 C1 C1 >230 H H 4-Br C1 C1 >235 H H 2-Cl C1 C1 >230 H 3-C1 4-Cl C1 C1 >235 H H H C1 C1 254-255 H H 4-Cl C1 C1 255-257 H H 4-CF3 Br Br >230 H H 4-Cl C1 Br 262-263(dec.) H H 4-Cl Br C1 250-258(dec.) H 3-C1 5-C1 C1 C1 >230 H 3-Cl 4-Cl C1 Br >230 2-Cl 4-Cl 5-F C1 C1 207-210 EXAMPLE 7 3-Nitro-2-phenvlpvrrole

ι

Alpha-nitro 'acetophenone (5.7 g, 0.0345mol) is taken up in 100 mL toluene and 4.6g (0.0345mol) of amino acetaldehyde diethyl acetal is added. The reactants are put into a 250 mL RB flask fitted with a Dean-Stark trap. The trap is filled with 4A molecular sieves and the mixture is heated at reflux for 18 hours. The toluene is removed in vacuo to give 8.36 g of a- (2,2-diethoxyethylamino) -/3-nitrostyrene as a LV 10773 - 4 5 - brown oil. To this oil is added 50 mL of concentrated HCl. As the flask is swirled the oil turns to a yellow suspension. After 10 minūtes the solid is filtered to give 2.48 g of a yellow solid. Recrystallization from ether/ethylacetate/hexane gives the product as two fractions, 2.08 g of m.p. 190-192°C, (31%).

Max 1485 cm-1(N02)/ H-NMR(CDCl3/DMSO) *6.73(m,2H), 7.46(m.5H). 10 15 20 EXAMPLE 8 2.3-Dichloro-4-nitro-5-phenvlpvrrole

+ NaOCl

A mixture of 3-nitro-2-phenylpyrrole (1.56g, 0.0083mol) in 60 mL of dioxane is cooled in an ice bath while 25.9g (.0182mol) of commercial sodium hypochlor-ite is added dropwise. After stirring for 45 minūtes, the mixture is acidified with concentrated HCl. Water and Et20 are added. The layers are separated and the top organic layer is washed with H20, dried over anhy-drous MgS04 and concentrated in vacuo to give 2.21g of yellow solid. Purification by chromatography using silica gel and eluting with increasing ratios of ethyl acetate/ hexane gives, after stripping, 0.77g of yellow solid (36%) m.p. 190-190.5°C;

Analysis: Calcd. for C10H6N2C>2Cl2 C, 46.72; H, 2.35; N, 35 46 10.90

Found: C, 46.96; H, 2.86; N, 10.02

Following the procedures of Examples 7 and 8 above but using the appropriately substituted a-nitro-acetophenone and 2,2-di(C1-C4 alkoxy)ethylamine yields the substituted a- (2,2-di(C1“C4 alkoxy)ethylamino)-β-nitrostyrene which is then converted to 3-nitro-2-(substituted) phenylpyrrole by treatment with HC1, HBr or CF^CC^H· Reaction of the thus formed substituted phenylpyrrole with sodium hypochlorite in dioxane yields the chloro analogs; whereas, reaction of the substituted phenylpyrrole with bromine in chloroform yields the bromine analogs.

Ļ M R *1 XI o mo C H H H C1 C1 190-190.5 H 4-C1 H C1 C1 214-215 H 4-C1 H Br Br 203-204(dec.) H H H Br Br 148.5-149 3-C1 4-C1 C C1 C1 219-220(dec.) H 4-Br H C1 C1 222-223(dec.) H H 4-CF3 C1 C1 166-168 - 47 - LV 10773 EXAMPLE 9 4.5-Dichloro-2-f3.4-dichlorophenvl)-l-methvl-pvrrole-3-carbonitrile

In a 100 mL flask, 2 g of 4,5-dichloro-2-(3, 4-dichlorophenyl)pyrrole-3-carbonitrile in 60 mL dry THF gives a clear brown solution. 1 eq of KOtBu is added w/ stirring, this giving a clear solution after a few minūtes. 1 eq of Mel is added by syringe and the solution is heated at reflux for 4 hours. It is then left to stir at RT overnight. The following day 50 mL of HjO is added and the mixture extracted with 4 x 50 mL CHC13· The organic phases are combined, dried with MgS04, and concentrated. The resulting white solid is purified by flash chromatography on silica gel, using 50/50 EtOAc/hexane as an eluent. This gives 1.80 g of a white solid.

Yield = 86%

m.p. = 154-156 deg. C

Following the above procedure but substitut-ing the appropriately substituted phenylpyrrole-3-car-bonitrile or 3-nitro-2-(substituted)phenylpyrrole for 4,5-dichloro-2-(3,4-dichlorophenyl)pyrrole-3-carboni-trile yields the compounds shown below. 48

Α Ļ M R X Y mū°C CH3 H H 4-Cl C1 C1 152-153 C2H5OCH2 H 3-C1 4-C1 C1 C1 128-130 C2H5 H 3-C1 4-Cl C1 C1 137-138 CH3 H 3-C1 4-Cl C1 C1 154-156 CH3 H H 4-CF3 Br Br 145-146 C6H5-CH2 H H. 4-CF3 Br •Br 145-147 C6H5'CH2 H 3-C1 4-Cl C1 C1 95-96 CH,=CH-CH, H 3-C1 4-Cl C1 C1 69-70 CH2=C-CH2 H 3-C1 4-Cl C1 C1 C1 CH=C-CH2 H 3-Cl 4-Cl C1 C1 147-148 ch3sch2 H 3-Cl 4-Cl C1 C1 C(CH3)3 H H 4-CF3 C1 C1 ch3 H H 4-CF3 C1 C1 99-100 CH3SC2H5 H 3-Cl 4-Cl C1 C1 74-75 0 c2h5-oc-ch2 H 3-Cl 4-Cl C1 C1 118-120 C2H5“OCH2 H H 4-CF3 C1 C1 99-100 CH3 H H 4-OCH3 Br Br 112-115 CH3 H H 4-Cl Br Br 197-201 C2H5°CH2 H H 4-OCF3 C1 C1 46-47 CH3 H H 4-OCF3 C1 C1 72-73 C6H5'CH2 H H 4-OCF3 C1 C1 oil C2H5OCH2 H H 4-Cl C1 C1 - - 49 - - 49 -LV 10773 A Ļ M R X Y mD°C hoch,ch9 H 3-C1 4-C1 C1 C1 143-145 NC H 3-C1 4-C1 C1 C1 251-252 C6H5CH2OCH2 H 3-C1 4-Cl C1 C1 88-89 C1 O-CH H 3-C1 4-C1 C1 C1 118-120 H O II o o w SJ 1 H 3-C1 4-Cl C1 C1 115-116 CH3 H H 4-Cl Br CF3 126-129 c2h5och2 H H 4-tl Br CF3 91-92 C2H5-°CH2 H 3-C1 4-Cl C1 C1 118-120 C2h5-°CH2 H H 4-Cl Br Br 104-105 C6H5-CH2 H H 4-Cl Br Br 81-82 CH3 ' H H 4-Cl Br Br 197-201 CN H H 4-CF3 C1 C1 138-139 C2h5-°CH2 H H 4-CF3 Br CF3 104-105 C2H5-°CH2 H H 4-CF3 H CF3 76-77 C2H5OCH2 H 3-C1 4-Cl Br CF3 80-81 EXAMPLE 10 l-Benzvl-4.5-dibromo-2- fa,a.ct-trifluoro-p-tolvl) pvrrole-3-carbonitrile

In a 100 mL flask, 1.5 g of 4,5-dibromo-2-(a/a,a-trifluoro-2-tolyl)pyrrole-3-carbonitrile is xuixed with 50 mL dry THF to give a clear dark solution. 1 eq of KOtBu is added with stirring. After a few minūtes the solution clears. Benzyl bromide (0.65 g) is added by syringe. The mixture is heated at reflux overnight. The following day TLC (50/50 EtOAc/hexane) - .50 indicates the presence of both starting material and product. The reaction is worked up in the following manner; 50 mL of water is added and the mixture is extracted with 4 x 50 mL CHC13· The organic phases are 5 combined and washed with 4 x 50 mL 10% aq. NaOH. The organic phase is dried with MgS04 and stripped. This gives a brown solid which is crystallized from EtOAc/ hexane. 10 Yield = 0.75g = 40.7% m.p. = 145-147 deg.C dec. EXAMPLE 11 4.5-Dichloro-2-(3.4-dichlorophenvl)-1-(ethoxvmethvl)-15 pvrrole-3-carbonitrile 20

ci CN

THF

25 30 A sample of 4,5-dichloro-2-(3,4-dichlorophen-yl)pyrrole-3-carbonitrile (l.Og, 0.003 mole) is dis-solved in 10 mL of dry tetrahydrofuran. To this solu-tion is added potassium t-butoxide (0.37g, 0.0033 mole) followed by chloromethyl ethyl ether (0.312g, 0.0033 mole). The mixture is stirred for about 1 hour at room temperature and then poured into a large volume of water precipitating the product. The white solid is collected and dried to give l.Og (91%) with m.p. 128-130°. 35 - 51 -LV 10773 EXAMPLE 12 4-Chloro-3-cvano-2-(p-chlorophenvl)pvrrole

10 15 20 25 30 .3 5

To a magnetically stirred 20°C solution of 17.87g (88.2 mmol, 1.00eq) of 2-(p-chlorophenyl)-3-cyanopyrrole in 800 mL of dioxane is added dropwide 250.15g (13.13g real, 176.4 mmol, 2.00eg) of 5.25 weight % bleach over a period of 30 minūtes. After stirring at room temperatūre for a further 30.minūtes, the reaction solution is poured into 2200 mL of water. The resulting mixture is vacuum filtered to remove a small amount of a black solid. The filtrate is acidified to pH 2 with concentrated HCl to producē a brown solid. This solid is vacuum filtered and the collected solids washed with water to give 22.41g of a brown solid. This solid is treated with 100 mL of 5% aqueous sodium hydroxide to dissolve the bulJc of the material while leaving a small amount of undissolved black solid. This black solid, dissolved into 100 mL of ethyl acetate, is washed with 7 5 mL each of 5% aqueous NaOH, water, and sat. aqueous NaCl. The ethyl acetate layer is dried (MgSO^), treated with charcoal, filtered, and then rotary evaporated jĻņ vacuo to give 1.10g (5.3% yield) of an orangish brown solid. This solid is recrystallized from an ethyl acetate chloro-form mixture to give 0.51g (2.4% yield) of an off-white solid of 4-Chloro-3-cyano-2-(p-chlorophenyl)pyrrole. mp 251-253.5°C. 52 EXAMPLE 13

Preparation of 5-bromo-2-(3.4-dichlorophenvnpvrrole-3-carbonitrile

A sample of 2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile (2.0g., 0.008 mole) is dissolved in 100 mL of dioxane by warming to 40-50°. Then the solution is cooled to 30°C and bromine (1.3g, .008 mole) is added. After stirring 1 hour at room temperature the solution is poured into water and a gray solid (2.2g, 88%) is collected. The mp is 233-236°C, decomposition.

In a similiar fashion one can prepare 5-bromo-2-(3,4-dichloro)-3-nitropyrrole starting with 2-(3,4-dichlorophenyl)-3-nitropyrrole. LV 10773 - 53 -EXAMPLE 14

Preparation of 5-bromo-4-chloro-2-(3. 4-dichlorophenvl)-pyrrole-3-carbonitrile

A sample of 5-bromo-2-(3,4-dichlorophenyl)-pyrrole-3-carbonitrile (0.158g, 0.005 mole) is dissolved in tetrahydrofuran (5 mL) . An equivalent amount of t-butyl hypochlorite is added and the solution stirred overnight. The solution is poured into water and the precipitate (0.052gf 30%) is collected. The mp is >275°C.

In a similiar fashion one can prepare 2-bromo-3-chloro-5-(3,4-dichlorophenyl)-4-nitropyrrole by starting with 2-bromo-5-(3,4-dichlorophenyl)-4-nitropyrrole. 54 EXAMPLE 15

Preparātiem of 5-bromo-4-chloro-2-fp-chlorophenvH-pvrrole-3-carbonitrile

To a magnetically stirred 22°C solution of 0.17g (0.67 mmol., 1.00 equivalent) of 4-chloro-2-(p-chlorophenyl)pyrrole-3-carbonitrile in Ī00 mL of chloroform is added dropwise over a period of 30 minūtes, a solution of 0.20 mL (0.62g, 3.88 mmol., 5.79 eguivalent) of bromine in 5 mL of chloroform. The addition producēs no exotherm. After stirring at room temperature for 3 1/4 hours, the clear red reaction solution is evaporated īņ vacuo to give 0.28g of an off-white solid. This solid is slurried with a hexane-methylene chloride mixture to give on vacuum filtration 0.23g of an off-white fluffy solid. mp 262-263°C? dec. - 55 - LV 10773 EXAMPLE 16

Preparation of 5-chloro~4-bronio-2-^p-chlorophenyl^ -pyrrole-3-carbonitrile

To a magnetically stirred 45°c solution of l.OOg (4.22 mmol., 1.00 equivalent) of 5-chloro-2-(p-15 chlorophenyl)pyrrole-3-carbonitrile in 300 mL of chloroform is added dropwise over a period of 3 0 minūtes, a solution of 0.40 mL (1.24g, 7.76 mmol., 1.84 eguivalent) of bromine in 25 mL of chloroform. The addition producēs no exotherm and towards the end of 20 the addition, a small amount of a solid starts to precipitate. After stirring at room temperature for 19 1/2 hours the reaction mixture is evaporated iņ vacuo to give 1.49g of an orangish white solid. This solid is slurried with a hexane-methylene chloride mixture to 25 give on vacuum filtration 1.33g (100% yield) of a fluffy white solid. mp 250-258°C, dec. 30 -56 EXAMPLE 17

Preparation of 5“Chloro-2-(p-chlorophenvlĪPvrrole-3-carbonitrile

To a 35°C magnetically stirred solution of 2.40g (11.8 mmol., 1.00 equivalent) of 2-(p-chlorophen-yl)pyrrole-3-carbonitrile/ and 65 mL of glacial acetic acid is added dropwise by syringe 0.75 mL (1.26g, 9.34 mmol., 0.79 equivalent) of sulfuryl chloride over a period of 5 minūtes. Approximately 5 minūtes after the completion of the addition, a solid precipitated out of the reaction solution. After stirring at room tempera-ture for 45 minūtes, the reaction mixture is filtered and the collected solid is vashed well with cold acetic acid to give 2.08g (74% crude yield) of an off-white solid. This solid is recrystallized from 75 mL of hot acetic acid to give 1.63g (58% yield) of 97 wt% pure. Product mp 258.5-261°C. LV 10773 - 57 -EXAMPLE 18

Preparation of 2-f3.4-dichlorophenvl)-l-methvlpvrrole--3-carbonitrile

In a 100 mL flask, 2.0 g of 2-(3,4-dichloro-phenyl)pyrrole-3-carbonitrile is dissolved in 50 mL of dry THF and 1 equivalent of potassium t-butoxide is added. This gives a slightly cloudy solution. One eguivalent of methyl iodide is then added to the mixture by pipette. This leads to a slight lightening of the colour. A drying tube is attached to the flask aiļd it is left to stir at ambient temperature overnight.

The next morning there is a slight light-coloured precipitate in the flask. 50 mL of water is then added and the solution becomes clear before a solid precipitates out of the solution. This solid is filtered out of the solution and compared to the starting material by TLC (25% ethyl acetate/hexane). This indicates a new single spot which is faster moving than the starting material. It is dried in a vacuum oven at 50 deg. C overnight. The product yield is 1.31g or 62% yield and has a melting point of 140-142°C. 58 - EXAMPLE 19

Precaration of 4.5-dichloro-2-(3.4-dichlorophenvl)-l-methvlpvrrole-3-carbonitrile

In a 50 mL round bottom flask, 0.5g of 2-(3, 4-dichlorophenyl) -l-methylpyrrole-3-carbonitrile is mixed with 35 mL of glacial acetic acid. The mixture is warmed slightly with a heat gun to dissolve ali of the pyrrole.

To this clear solution is added 2 eq. of sulfuryl chloride by pipette. The solution is left to stir 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 out and dried in a vacuum oven at 50eC for 3 hours.

The resulting solid is identical by TLC, (25% ethyl acetate/ hexane), and infrared analysis to the product of Example 9. Product yield is 0.36 (56%). - 59 - LV 10773 EXAMPLE 20

Preoaration of 4,5-Dichloro-2-f3.4-dichlorophenvl)-l-f2-hvdroxvethvl) -pvrrole-2-carbonitrile

To a stirred mixture of 2.0 g (6.5 mmol) of 4,5-dichloro-2-(3,4-dichlorophenyl) -pyrrole-3-carboni-trile and 0.88 g (7.8 mmol) of potassium tert-butoxide heated at reflux in 50 mL of dioxane is added 0.98 g (7.8 mmol) of bromoethanol. The mixture is stirred at reflux for 12 hours, cooled, diluted with 50 mL of water, and extracted several times with chloroform. The combined chloroform extracts are, dried over magnesium sulfate and concentrated in vacuo to leave a solid which, on varming and dissolving in ethyl acetate, deposits on cooling mostly starting pyrrole. Concentration of the mother liquor and recrystalliza-tion of the residual solid from 2 0% ethyl acetate in hexane gives 0.31 g of a white solid, mp 143-145°C; IR 5077A.

Anal. Calc'd for CI6H23N04; 8.00; Cl, 40.57. c, 44.57, H, 2.29; N, Found: (Agm 3 3139) : 8.06; Cl, 40. c, 14. 44.77; H, 2.29; N, 5 60 EXAMPLE 21

Preparation of 4,5-dichloro-2-(3.4-dichlorophenvl) pvrrole-1.3-dicarbonitrile

CNBr + K+ t-BuO" 10

15

Potassium t-butoxide (617 mg., 55 mmol) is added in portions to a solution of 3-cyano-4,5-dichloro 2-(3,4-dichlorophenyl)pyrrole (1.52 g, 5 mmol) in 20 anhydrous THF (20 mL). After 30 minūtes, a solution of cyanogen bromide (583 mg, 5.5 mmol) in THF (1 mL) is added. The reaction mixture is stored at room temperature overnight. The solvent is removed in a rotary evaporator. The residue is treated with water 25 and extracted with ethyl acetate. The organic layer is washed with water and saturated sodium chloride and dried (MgS04). Evaporation and crystallization of the residue from ethyl acetate gives while crystals (1.07 g) /· mp 250.5-252.0°C; IR (nujol) 2255, 2245 cm_1 (CN) ; 30 13c NMR (DMSO-dg) 102.7 (N-CN), 113.7 (3-CN); Mass spectrum 331.9 (M+l).

Anal. Calc'd for C12H3CP4N3 (330.99); C, 43.54; H, 0.91; N, 12.70; Cl 42.85.

Found: C, 4362; H, 0.93, N, 12.63; Cl 41.95. LV 10773 - 61 - EXAMPLE 22

Preparātiem of 4.5-Dichloro-2-f3.4-dichlorophenvl)-1-(3-iodo-2-propvnvl1-pvrrole-3-carbonitrile 5 10

+īg + NaūH 15

20 25

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 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 afford 0.51 g while crystals, m.p. 115-116°C. 30

This reaction is also applicable to the conversion of any of the formula III, IV, V, VI or VII substituted N-alkynylarylpyrroles of the present invention to N-substituted 3-iodo-2-propynyl arylpyr-roles of said invention. 35 62 EXAMPLE 23

Preparation of 2-f3.4-dichlorophenvll-4.5-diiodopvr-role-3-carbonitrile

15

N-iodosuccinimide (5.7 g, .0254 mol,) is added slowly to a solution of 2-(3,4-dichlorophenyl)-pyrrole-3-carbonitrile (3.0 g, .0127 mol) in 100 ml of THF. The reaction is stirred several hours at 25°C on , , , until thin layer chromatography (silica gel; 100:100:1- etherrpetrolium ether:acetic acid) shows completion.

The mixture is evaporated is vacuo to give a residue containing the pyrrole and succinimide. The crude solid is dissolved in 500 mL of ether and shaken with 5 25 x 400 mL of water to remove the succinimide. The ether is dried over Na2S04 and evaporated in vacuo to leave 2.0 g (32.3%) of a grey-brown solid with mp >230° (loses purple vapors). 30 35 - 63 - LV 10773 EXAMPLE 24

Preparation of 2-phenvl-l-pvrroline-4-carbonitrile 5

10 15 20 25 A solution of acrylonitrile (0.65 mL; 0.01 mol) and N-(trimethylsilyl)methyl-S-methyl-benzenethio-imidate (2.4 g; 0.01 mol) in THF (100 mL) is cooled to -5°C in an ice-acetone bath. Under a nitrogen purge, a solution of tetrabutylammonium fluoride (1.0 mL of a 1 Ņ solution in THF) and THF (20 mL) is added dropwise over 30 minūtes The solution is stirred another 30 minūtes at -5°C, and then allowed to ,warm slowly to ambient. Stirring is continued another 18 hours, and then 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, then saturated sodium chloride. The solution is dried over MgS04, and cooling the filtrate causes precipitation of -<an off-white solid (1.2 g; 70% theoretical yield) whose spectral characteristics are identical to the material described by Tsuge [J. Org. Chem. 52, 2523 (1987)].

Calcd. for C^H^N^ C, 77.65; H, 5.88; N, 16.47.

Found: C, 77.55; H, 5.83; N, 16.39. mp = 95-97°C. 35 64 EXAMPLE 25

Preparation of 2-phenvl-Pvrrole-4-carbonitrile-

Under a nitrogen purge 2,3-dichloro-5,6-di-cyano-l,4-bonzoquinone (0.23 g; 0.001 mol) and 2-phenyl -l-pyrroline-4-carbonitrile (0.17 g; 0.001 mol) is dissolved in 1,2-dimethoxyethane (13 mL) to form a clear orange solution. Pyridine (0.08 mL; 0,001 mol) is added in a single portion, causing a slight exotherm (to ca. 28°C) and an immediate formation of a green/ grey precipitate. The suspension is stirred at room tempera tūre for 18 hours during which time much of the solvent evaporates. The brownish semi-solid residue is partitioned between ether and a half-saturated solution of sodium carbonate. The red-brown aqueous layer is extracted twice with ether and the combined ether layer is washed with fresh water, then saturated sodium chloride. After drying with MgS04, solvent is removed under reduced pressure to obtain a white semi-solid. This material was . recrystallized from ethylene dichloride (DARCO treatment) to yield lavender crystals (0.1 g).

The identical product is obtained directly in a single step by condensing a-chloroacrylonitrile and N-(trimethylsilyl)methyl-S-methyl-benzenethioimidate 4 - 65 - LV 10773 using tetrabutylammonium fluoride catalysis (analogous to the preparation of 2-phenyl-D-pyrroline-4-carboni-trile described previously) . 5 Calcd. for C, 78.57, H, 4.76; N, 16.67.

Found: C, 78.65; H, 4.70; N, 16.43. m.p. - 155-158°C. EXAMPLE 26 10 Preparation of 2.4-dibromo-5-phenvl pvrrole-3-carbo-nitrile 15 NC NC Br 20

Under a nitrogen purge, a solution of bromine (0.6 mL? 0.012 mol) in CHC13 (5 mL) is added dropvise over 20 minūtes to a stirring solution of 2-phenyl-pyrrole-4-carbonitrile (0.84 g; 0.05 mol) in CHC13 (20 mL). The resulting solution is stirred 18 hours. at room temperature, then solvent is removed under reduced pressure to obtain a solid which is recrystallized from C2H4C12 (DARCO treatment), yielding the desired final product (0.6 g), m.p. = 239-242°C.

Calcd. for CnnH^Br^N_: C, 40.49? H, 1.84; Br, 49.08; XJ. D Z Δ N, 8.59.

Found: C, 39.88; H, 1.87; Br, 48.81; N, 8.48. 5 66

By the procedure described in Example 24, 25 and 26, 2,4-dibromo-5-(p-chlorophenyl)pyrrole-3-carbo- nitrile, m.p. 270-272°C (dec.) is also prepared. EXAMPLE 27 3^41-Dichloro-3-(1.3-dioxolan-2-vl)-propiophenone

To a rapidly stirring mixture of magnesium 20 turnings (0.64 g, 26 mmol) in 10 mL of tetrahydrofuran at 25°C in a 100 mL three-neck round bottom flask equipped with a thermometer, a 60 mL addition funnel, and a nitrogen inlet is added dropwise 2-(2-bromoethyl) -1,3-dioxolane (4.7 g, 26 mmol) in 40 mL of tetrahydro-25 furan. The rāte of addition is adjusted so as to maintain the reaction temperature below 50°C. The reaction is then allowed to stir for 1 hour at 25°C. 120 mL of tetrahydrofuran is mixed with potassium 3,4-dichlorobenzoate (5.0 g, 22 mmol) under a blanket of 30 nitrogen. The Grignard solution is then quickly decanted away from the unreacted magnesium turnings, and added dropwise to the rapidly stirring potassium benzoate suspension. The reaction is then allowed to 35 - 67 - LV 10773 stir for 24 hours at 25°C. Fifty mL of diethyl ether and 15 mL of 3N hydrochloric acid are added to the reaction mixture and the layers separated. The organic layer is washed with saturated aqueous sodium bicarbon-ate until neutral followed by one washing with 10 mL of brine. Drying over sodium sulfate, and rotary evapora-tion yields a beige semisolid which is chromatographed over silica gel using 3:1 hexane~ethyl acetate as eluent to give the keto-acetal (4.3 g, 60%) as a white solid, m.p. 115-117°C. EXAMPLE 28

Preparation of 3-(3.4-dichlorobenzovl)propionaldehvde

Ten grams (26 mmol) of 3 ' , 4 ' -dichloro-3- (1,3-dioxolan-2-yl)-propiophenone is added to 30 mL of 0.2M oxalic acid (made by dissolving 0.9 g of oxalic acid dihydrate in 30 mL of water) and 5 mL of ethanol. The mixture is refluxed for 1 hour and then allowed to cool. Most of the ethanol is rotary evaporated off and 100 mL of diethyl ether is added along with 20 mL of saturated aqueous sodium bicarbonate. The layers are separated and the organic phase is dried over magnesium sulfate. Rotary evaporation yields a viscous yellow 68 oil which is chromatographed over silica gel using 3:1 hexane-ethyl acetate to give the keto-aldehyde (6.3 g, 75%) as a white solid. 5 EXAMPLE 29

Preoaration of 2-C3.4-dichlorophenvl)ovrrole 10 0

To a suspension of 3-(3,4-dichlorobenzoyl) propionaldehyde (6 g, 2 6 mmol) in 60 mL of absolute ethanol is added ammonium acetate (4 g, 52 mmol). The reaction is refluxed for 20 minūtes and allowed to cool. Most of the ethanol is rotary evaporated and 200 mL of 1:1 dichloromethane-diethyl ether along with 50 mL of water is added. The layers are separated and the organic phase is dried over sodium sulfate. Rotary evaporation yields a dark brown oil which is chromatographed over silica gel using 3:1 hexane-ethyl acetate as eluent to give the pyrrole (4.6 g, 83%) as a light brown solid, m.p. 49-51°C. 30 35 LV 10773 - 69 -EXAMPLE 30

Preparation of 5-(3.4-»dichlorophenvl)pvrrole-2-carboxa-ldehvde

2) Naoflc

To 10 mL of dimethylformamide stirring under nitrogen in a 50 mL round bottom flask is added phos-phorus oxychloride (0.6 mL, 6.5 mmol) dropwise via syringe. The solution, warms and becomes light yellow in color. It is allowed to stir for 20 minūtes before the portionwise addition of 2-(3,4-dichlorophenyl)pyr-role (1 g, 4.7 mmol). The beige suspension which results is allowed to stir for 30 minūtes before being heated to 50°C for 40 minūtes. A. solution of sodium acetate (10 g, 122 mmol) in 15 mL of water is added to the cooled reaction which is then alloved to stir for 20 minūtes. A beige precipitate is filtered off from the reaction mixture and air-dried for 20 hours to give the essentially pure aldehyde (1.1 g, 95%), mp > 200°C. 5 70 5 70 10 EXAMPLE 31

Preparation of 5-(3.4-dichlorophenvl)pvrrole-2-carboni-trile

15

To a suspension of 5-(3,4-dichlorophenyl)pyr-role-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 1 hour during which time a gray precipi-tate appears. After being allowed to cool, the reaction is filtered to give essentially pure nitrile (1.5 g, 99%) as a gray solid, m.p. 170-l7l°c. 25 30 35 LV 10773 - 71 -EXAMPLE 32

Preparation of 3.4-dibromo-5-(3.4-dichlorophenvl)Pvr-role-2-carbonitrile

To a solution of 5-(3,4-dichlorophenyl)pyr-role-2-carbonitrile (0.5 g, 2.1 mmol) in 20 mL of tetrahydrofuran under nitrogen is added portionwise N-bromo-succinimide (0.8 g, 4.2 mmol). The reaction is stirred at 25°C for 30 minūtes before the addition of 10. mL of water and 40 mL of diethyl ether. The layers are separated and the organic layer dried over sodium sulfate. Rotary evaporation is followed by chromato-graphy over silica gel using 3:1 hexane-ethyl acetate as eluent to afford the dibromopyrrole (0.5 g,^60%) as a brown solid, m.p. > 250°C. 72 EXAMPLE 33

Preparation of 4-phenvlpvrrole-3-carbonitrile

NC \

H

To a mixture of 5.0 g (39 mmol) of cinnamoni-trile and 7.6 g (39 mmol) of (p-tolylsulfonyl)methyl isocyanide in 35 mL of DMSO and 65 mL of ether is added over a 20 minūte period a suspension of 1.86 g of a 60% oil suspension of sodium hydride (1.11 g; 46 mmol) in 80 mL of ether. The reaction mixture is maintained under nitrogen for an hour and then diluted with ether and water. The ether layer is separated, dried over magnesium sulfate, and concentrated iņ vacuo. The resulting oil is chromatographed on silica gel using 1:1 chloroform ethyl acetate to give 2.5 g of cream-colored solīds. Recrystallization from ether-hexane affords 1.15 g, m.p. 123-125°C; NMR M86-1077.

Lit.: Tet. Letters 5337 (1972): m.p. 128-129°C. LV 10773 - 73 -ΕΧΑΜΡΙιΕ 34

Preparation of 2.5-dichloro-4-phenvlpvrrole-3-carbonitrile

To a stirred mixture of 0.66 g (3.9 mmol) of 4- phenylpyrrole-3-carbonitrile in 20 mL of dry THF cooled to 6°C with an ice-water bath is added from a syringe 0.66 mL (1.11 g; 8.2 mmol) of sulfuryl chloride over a 4 minūte period. The mixture is maintained at 5- 10°C for an additional 45 minūtes and then stirred an additional 30 minūtes with the ice bath removed. After the reaction mixture is 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, rinsing with ethyl acetate, and concentration of the combined filtrated iņ vacuo gives 0.95 g of dark solid. Recrystallization from chloroform gives 0.42 g of off-white crystals, m.p. 195-196°C (dec.).

Anal. Calcd for C^HgCl^: C, 55.72; H, 2.55; N, 11.82; Cl, 29.91.

Found: C, 55.66; H, 2.65; N, 11.69; Cl, 29.97. - •74' -

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-carbonitrile, the procedure of Example 33 is followed using bromine in dioxane to replace sulfuryl chloride and tetrahydrofuron. - •74' -

R R X Y m.D. °C 4-Cl C1 C1 237-240 (dec.) 4-CH3 C1 C1 103-206 4-Cl Br Br > 245° LV 10773 - 75 -EXAMPLE 35

Ethvl 4-(p-chlorophenvll -pvrrole-3—carboxvlate

To a mixture of 5.63 g of a 60% sodium hydride/oil suspension in 200 mL of dry ether under 15 nitrogen is added from an additional funnel a mixture of 23.5 g (122 mmol) of ethyl p-chlorocinnamate and 19.4 g (122 mmol) of (p-tolylsulfonyl)methyl isocyanide in solution in 180 mL of ether and 80 mL of dimethyl-sulfonide. The addition time is about 20 minūtes and 20 results in gentle refluxing of the mixture. After another 10 minūtes stirring, the mixture is diluted with 100 mL of water. The mixture is extracted four times with ether which is then dried over magnessium sulfate followed by concentrated in vacub. The 25 resulting solid is recrystallized from ethylene dich-lorite to give 7.8 g of crystals, m.p. 137-li8°C.

Anal. Calcd for C13H12C1N02: C, 62.53; H, 4.81; N, 5.61; Cl, 14.23. 30 Found: C, 61.31, H, 5.12; N, 5.32; Cl, 14.57.

Concentration of the mother liquor for the crystallization leaves additional crude ester which is carried on to the saponification step. 35 76 EXAMPLE 36

Preoaration of 3-fp-chlorophenvl^-pvrrole

A mixture of 22.0 g of crude ethyl 4-(p-chlorophenyl)-pyrrole-3-carboxylate from the recrystal-lization mother liquor and the recrystallized product from the previous step is stirred at 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 on collection and drying weighs 11.6 g. A mixture of 10.5 g of the acid in 100 mL of £-ethanolamine is heated at reflux for three hours. After cooling, the mixture is poured over 4 00 mL of ice and the resulting mixture is extracted four times with chloroform. The chloroform solution, after drying over magnesium sulfate and treatment with activated char-coal, is concentrated iņ vacuo to leave a brown solid. Chromatography on silica gel using 1:1 ethyl acetate hexane gives 4.0 g of a white solid, m.p. 117-118°C. - 77 - LV 10773 EXĀMPLE 37

Preparation of 3-fp-chlorophenvll -pyrrole-2-caboxal-dehyde

H

To a mixture of 0.86 g (12 mmol) of dimethyl- formamide in 10 mL of ethylene dichloride maintained 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 minūtes. The ice bath is removed, the mixture is stirred an additional 15 minūtes and recooled in an ice bath. To this mixture is added 1.5 g (8.5 mmol) of 3-(p-chlorophenyl)-pyrrole •*1. in 25 mL of ethylene dichloride over a 20 minūte period. The ice bath is removed and after an additional 30 minūtes of stirring, the mixture is poured into 50 mL of ice-water and 6 mL of 50% sodium hydroxide. The resulting mixture is extracted with ether and with chloroform and the combined organic mixture is dried over magnesium sulfate and concentrat-ed iņ vacuo. Purification of the resulting solid by chromatography on silica gel using 1:1 ethyl acetate hexane gives 0.63 g of off-white solid which is used directly for conversion to 3-(p-chlorophenyl)-pyrrole-2-carbonitrile. 78 EXAMPLE 38

Preparation of 3-(p-chlorophenvlī-pvrrole-2-carboni-trile

A mixture of 0.63 g (3.1 nunol) of 3-(p-chlor-ophenyl)-pyrrole-2-carboxaldehyde in 10 mL .of water is stirred and ice-cooled while 0.52 g (4.6 mmol) of hydroxylamine-0-sulfonic acid in 10 mL of water is slowly added. After the addition, the cooling bath is removed and the mixture is heated for 25 minūtes. On cooling, the resulting solid is collected and shown, by NMR, to be a mixture of product and starting aldehyde. This mixture is reacted in the same manner with an additional 0.49 g (4.2 mmol) of hydroxylamine-0-sulfon-ic acid in a total of 30 mL of water. The mixture is heated at 60-70°C for 2 hours. The mixture is cooled and the resulting solids are collected and purified by chromatography or silica gel using 1:1 ethyl acetate hexane to give 0.40 g of pink solid, m.p. 114-115°C. LV 10773 - 79 -EXAMPLE 39

Preparation of 4,5-Dibromo-3-fp-chlorophenvlī-pvrrole-2-carbonitrile 5 10

15

To a mixture 0.40 g (2.0 mmol) of 3-(p-chlor-20 ophenylpyrrole)-2-carbonitrile in 25 mL of chloroform is added 0.63 g (4.0 nunol) of bromine. After 20 minūtes, the precipitate which forms is collected and recrystallized from ethyl acetate to give 0.21 g of pink elstais, m.p. > 250°C. 25

Anal. Calcd for Ci;LH5Br2ClN: C, 36.62; H, 1.39; Br, 44.38; Cl, 9.85; N, 7.77.

Found: C, 36.92; H, 1.32; Br, 44.62; Cl, 9.88; N, 7.50 30 35 80 EXAMPLE 40

Preparation of Ethyl 5-broroo-4-fp-chlorophenyl)pvrrole-3-carboxvlate 0

Ethyl 4-(p-chlorophenyl)pyrrole-3-carboxylate (1.6 g., 0.0064 mmol) is dissolved in tetrahydrofuran (40 mL) . N-bromosuccinimide (1.14 g., 0.0064 mmol) is added in small portions at 25-28°c. After the addition is complete, the solution is stirred overnight at room temperature. The solution is concentrated in vacuo and the solid residue partioned between water and ether. The ether layer is separated and dried over magnesium sulfate. Work-up of the ether extract leaves 1.9 g (90%) of a white solid which is purified by stirring with a mixture of 80/20 hexane/ethyl acetate. The insoluble solid (1.3 g, 62%) is collected and has m.p. 161-164°C.

Calcd for c13Hi;LBrClN02 : C, 47.50; H, 3.34; N, 4.26; Br, 24.33; Cl, 10.80. - 81 - LV 10773

Found: C, 47.39; H, 3.38; N, 4.12; Br, 24.29;

Cl, 10.77 EXAMPLE 41

Preparātion of 5-bromo-4-fp-chlorophenvl)Pvrrole-3-carboxylic acid

Ethyl 5-bromo-4- (p-chlorophenyl) pyrrole-3-carboxylate (15 g., 0.045 mmol) is added to 200 mL of 10% sodium hydroxide and the slurry heated to reflux. After everything appears to dissolve the mixture is refluxed an additional 40 minūtes. The mixture is cooled, filtered and the filtrate acidified. The white precipitate (8.0 g, 58%) is collected and dried. The solid has m.p. >205°C and an NMR (dg-DMSO) which showed a pyrrole proton at 7.52 (d) . The mass spectrum is also consistent for a monobrominated compound. 5 - 82 -EXAMPLE 42

Preoaration of 2-bromo-3-(p-chloroohenvl^ pvrrole

5-bromo-4- (p-chlorophenyl)pyrrole-3-carboxy-lic acid (8.0 g., 0.026 mmol) is added to aminoethanol (24 mL) and the slurry slowly warmed to 110-120°C and held at that temperature for 1 hour. The solution is cooled and poured into water and extracted with ether. The ether extract, by thin layer chromatography (75/25, hexane/ethyl acetate), shows a major fast moving spot and a slower moving minor component. Work-up of the ether leaves a dark solid (4.0 g., 56%) which is 2-bromo-3-(p-chlorophenyl)pyrrole and is used immediately to prepare 5-bromo-4-(p-chlorophenyl) pyrrole-2-carboni-trile. 30 35 LV 10773 - 83 -EXAMPLE 43

Preparation of 5-bromo-4-(p-chlorophenvlīpvrrole-2 carbonitrile

CN 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 while holding the temperature below 25°C, chlorosulfonyl isocyanate (3.08 g.·, 0.022 mmol) is added. After stirring overnight, the solution 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) yields 1.4 g (33%) of white solid with m.p. 202-204°C.

Calcd for C^HgBrClN^: C, 46.90; H, 2.13; N, 9.95; Cl, 12.61; Br, 28.39.

Found: C, 47.20; H, 2.09; N, 9.80; Cl, 12.36; Br, 27.42. 5 84 EXĀMPLE 44

Preparation of 3.5-Dibromo-4-fp-chlorophenvl)pvrrole-2-carbonitrile

A sample of 5-bromo-4-(p-chlorophenyl)pyrrole -2-carbonitrile (2.2 g., 0.0078 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 reaction mixture is poured into water precipitating a tan solid (2.6 g., 92%). A portion (1.6 g) is purified by flash chromato-graphy using 75/25 hexane/ethyl acetate to give 0.8 g of grey solid with m.p. 191-194°C.

Calcd for C1;LH5Br2ClN2: C, 36.61;

Cl, 9.84?

Found: C, 37.46; H, 1.25; N, 30 H, 1.38; N, 7.76; Br, 44.3. 7.41; Cl, 9.53; Br, 42.99. 35 LV 10773 - 85 -EXAMPLE 45

Preparation of 3-(3.4-dichlorophenvH -4-nitropvrrole

Sodium hydride (2.66 g of a 60% suspension in oil is rinsed with dry ether; 66 mmol) and suspended in 150 mL of dry ether. To this mixture is added over 15 minūtes a mixture of 12.0 g (5.5 mmol) of 3,4-dichloro-£-nitrostyrene and 10.8 g (5.5 mmol) of (p-tolylsulfon-yl)methyl isocyanide in 50 mL of DMSO and 150 mL of ether. The mixture is stirred for 1.5 hours and then diluted with 150-200 mL of water and additional ether. The ether layer is separated, dried over magnesium sulfate, and concentrated in vacuo. The resulting 10.6 g of crude product is purified by chromatography on silica gel using a 4:1 mixture of chloroform and ethyl acetate. A 7.2 g solid fraction is recrystallized from chloroform-ethyl acetate-hexane to give 3.0 g of yellow solid, m.p. 187-188°C (dec.).

Anal. Calcd for C1()H6C12N202: C, 46.72; H, 2.35; N, 10.90.

Found: C, 46.96; H, 2.60; N, 9.77 86 EXAMPLE 46

Preparation of 2.5-Dichloro-3-f3.4-dichlorophenvl)-4-nitropvrrole

H

To a mixture of 3-(3,4-dichlorophenyl)-4-ni-tropyrrole (2.5 g, 9.7 nunol) wanned to about 40°C in 200 mL of chloroform is added over one minūte 2.95 g (22 nunol) of sulfuryl chloride. After another hour, the mixture is diluted with 100 mL of saturated sodium bicarbonate solution and 300 mL of ether. The organic layer is separated and dried over magnesium sulfate. Concentration, iņ vacuo. leaves a brown solid which is chromatographed on silica gel using 4:1 chloroform ethyl acetate. An orange solid fraction is recrystal-lized from chloroform and then rechromagraphed on silica gel using 4:1 chloroform ethyl acetate to yield 0.36 g of yellow solid, m.p. 193-194°C.

Also prepared by procedure of Examples 45 and 46 above is 2,5-dichloro-3-nitro-4-phenylpyrrole, m.p. 193-194°C(dec.). LV 10773 - 87 -EXAMPLE 47

Preparation of 5-(p-chlorophenvl^Pvrrole-2.4-dicarbo-nitrile

CN

A sample of 2-p-chlorophenyl-3-cyanopyrrole, prepared by the method of Example 4, (3.0 g, 0.015 mole) is dissolved in 50 mL of dry dimethoxyethane. To this solution is added chlorosulfonyl isocyanate (3.39 g, 0.024 mole). The addition is exothermic and some cooling is necessary. After stirring 3 hours-at room temperature, dimethylformamide (6-7 mL) is added and the solution is stirred 4 hours more. The solution is then poured into water precipitating a white solid (3.4 g, 100%). A sample (1.0 g) is purified by dissolving in ethyl acetate and then passing the solution through a 60 mL course filter funnel packed with silica gel. The filtrate is concentrated to yield 0.7 g of a white solid with m.p. 235-240°C. 88

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

CN

H 4-OCF3 185-190°C

H 4“CF3 180-185°C EXAMPLE 48

Preoaration of 3-Bromo-5-fp-chlorophenvl^pvrrole-2.4-dicarbonitrile

LV 10773 A sample of 5-(p-chlorophenyl)pyrrole-2,4-dicarbonitrile (1.0 g, 0.004 mole) is dissolved in 20 mL of dioxane and a solution of bromine (0.8 g, 0.005 mole) in dioxane (10 mL) is then added thereto. The solution is stirred several hours at room temperature and then poured into water precipitating a white solid (1.2 g, 100%) . The solid has a m.p. >225°C and a mass spectrum of a sample gives a pattem consistent with the desired structure.

Folloving the procedure set forth above in Example 48, the following additional compounds are prepared:

R

L m.o.

3-C1 H H

4-C1 >250°C

4-0CF3 218-223°C

4-CF3 239-241°C 90-- EXAMPLE 49

Preparation of bromofumaronitrile

CN

CN /

NC

Br2/CHC13/^ (-HBr)

NC B r

Under a nitrogen purge, fumaronitrile (15.6 g; 0.2 mol) in CHC13 (150 mL) is heated to reflux, resulting in a clear solution. A solution of bromine (5.3 mL; 0.2 mol) in CHC13 (25 mL) is added dropvise over 30 minūtes, resulting in a slow decolorization and aoidic (pH tēst paper) fumes being released. The solution is refluxed another 90 minūtes, during which time most of the color has been discharged. The solution is cooled and solvent is removed under reduced pressure, leaving an amber oil (weight approximately theoretical for bromofumaronitrile) . The oil is subjected to bulb-to-bulb distillation (0.2 mm Hg), maintaining the temperature below 120°C (above that point, a rapid decomposition of material occurs). A semi-solid is obtained which slowly forms a waxy, amber solid, m.p. - 43-47°C.

Calcd for C4HBrN: C, 30.57; H, 0.64; N, 17.83.

Found: C, 29.13; H, 0.75; N, 16.94. LV 10773 .-91.-EXAMPLE 50

Preparation of 2-phenvl-pyrrole-3,4-dicarbonitrile

Under a nitrogen purge, a solution of bromo-20 fumaronitrile (4.7 g; 0.03 mol) and N-(trimethylsilyl) methyl-S-methyl-benzene-thioimidate (7.1 g; 0.03 mol) in hexamethylphosphoramide (HMPA) (35 mL) is stirred at room temperature. In a single portion, water (1.6 mL) ; 0.09 mol) is added, washed in with HMPA (10 iriL) . The 25 solution almost immediately begins to exotherm, the temperature rapidly reaching 100°C before subsiding. The resulting dark red solution is allowed to stir at ambient temperature 20 hours. Pouring the reaction mixture onto an ice/water mixture results in a gummy material which slowly yields a discreet beige solid. This material is collected by filtration and washed with cold water and dried on the filter. After further drying (vacuum oven; 60°C), the material is twice recrystallized from C2H4C12 (DARCO treatment) to yield a white powder. 35 - 92 - ι

Calcd for C12H?N3 Found C, 74.61; H, 3.63; N, 21.76 C, 74.45; H, 3.84; N, 21.61 m.p. = 197-200°C. EXAMPLE 51

Preparatlon of 2-bromo-5-Phenvlpvrrole-3.4-dicarbon-itrile

NC CN NC CN

Under a nitrogen purge, 2-phenyl-pyrrole-3,4-dicarbonitrile (1.4 g; 0.0075 mol) is added to CHC13 (35 mL) , much of the solid dissolving. A solution of bromine (0.4 mL; 0.008 mol) in CHC13 (5 mL) is added dropwise over 20 minūtes. Initially the color is discharged rapidly, but as a new, gummy solid begins to precipitate, the color remains. After stirring 30 minūtes at ambient, the mixture is brought to reflux, resulting in a much more discreet solid. After reflux-ing 90 minūtes, the reaction mixture is cooled and an aliguot is removed and analyzed (HPLC), showing ca. 60% starting material stili remaining. In a single portion fresh bromine (0.2 mL; 0.004 mol) is added, and reflux-ing continued another 45 minūtes whereupon an aliquot shows 10% starting material remaining. Another fresh portion of bromine (0.2 mL; 0.004 mol) is added to the refluxing suspension and refluxing is continued - 93 - LV 10773 another 30 minūtes. The suspension is cooled and stirred 18 hours at room temperature. Solvent is removed under reduced pressure to yield a greenish solid which is extracted with hot CHC13/ leaving behind a dark residue. The extract is treated with DARCO and filtered hot. The clear yellow filtrate quickly began to deposit a white precipitate. After cooling to -10°C, the white solid is collected by filtration.

10 Calcd for C12H6BrN3: C, 52.94; H, 2.21; N, 15.44; Br 29 .41. Found: C, 51.64? H, 2.35; N, 14.91; Br, 28.69 . m.p . = 225-258°C 15 EXAMPLE 52

Preoaration of 2-(3.4-Dichlorophenvl)-5-nitropvrrole-3-carbonitrile 20

35 94 2-(3, 4-Dichlorophenyl) pyrroļe-3—carbonitrile (3.0 g, 0.013 mole) is added to acetic anhydride (50 mL) and 90% nitric acid (0.6 ml) with very little exotherm. The mixture is slowly warmed to 30° and is 5 then held at 30-33° until everything goes into solu-tion. Gradually a new solid precipitates. 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 stirring 1 hour the mixture is ļQ filtered and the solid (2.9 g, 82%) collected and dried. A portion (1.5 g) is purified by column chroraa-tography on silica gel using 75/25 hexane/ethyl acetate for elution to give 0.7 g of yellow solid with m.p. 228-231°. 15

Calcd for C^I^Cl^C^: C, 46.80; H, 1.77; N, 14.89;

Cl, 25.17

Found: C, 46.50; N, 1.96; N, 14.27; Cl, 24.30. 20

By the same procedure, starting with 2-(p-chlorophenyl)pyrrole-3-carbonitrile, 2-(E~chlorophenyl)--5-nitropyrrole-3-carbonitrile is obtained, m.p. 201-206°C. Also, 2-(p-trifluoromethylphenyl)pyrrole-3-carbonitrile gives 2-(E-trifluoromethylphenyl)-5-nitro-pyrrole-3-carbonitrile by the above procedure. This compound has a melting point of 164-165.5°C. 30 35 LV 10773 - 95 -EXAMPLE 53

Preparation of 4-Bromo-2-(3.4-dichlorophenvll-5-nitro-pvrrole-3-carbonitrile

CN

dioxane

C1 2- (3,4-Dichlorophenyl)-5-nitropyrrole-3-carbonitrile (0.5 g, 0.0017 mol) is dissolved in dry dioxane (10 mL). To this solution is added bromine (0 .'28 g, 0.0017 mole) in dioxane. After stirring overnight, the solution is poured into water precipita-ting a tan solid (0.54 g, 88%). Recrystallization from acetonitrile (5 mL) gives 0.26 g of tan solid with m.p. 195—200°C.

Calcd for C^I^BrCl^C^: C, 36.57; H, 1.10; N, 11.63;

Br, 22.13; Cl, 19.67.

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

Following the above procedure of Example 53, but starting with 2-(p-chlorophenyl)-5-nitropyrrole-3-carbonitrile gives 4-bromo-2-(p-chlorophenyl)-5-nitro-pyrrole-3-carbonitrile, m.p. 180-185°C. 96 EXAMPLE 54 5- (3,4-Dichlorophenvl) -4-nitropvrrole-2-carbonitrile

Το a suspension of 5- (3,4-dichlorophenyl)pyr-role-2-carbonitrile (1.2 g, 5.1 mmol) in 25 mL of acetic anhydride at 30° under nitrogen, is added dropwise 90% nitric acid (0.3 mL, 5.1 mmol). The reaction exotherms to 45°C and becomes a green solu-tion. After being allowed to stir for 2 hours the reaction is poured into 50 mL of water and stirred vigorously for 5 minūtes. The beige precipitate which results is filtered off and dissolved in a minimum amount of acetone. Chromatography over sitica gel using 3:1 hexane-ethyl acetate affords the nitropyrrole (1.2 g, 84%) as an off-white solid, m.p. >200°C. LV 10773 - 97 -EXĀMPLE 55 3-Bromo-5-f 3.4-dichlorophenvl^ -4-nitropvrrole-2-carbon-itrile

15

To a suspension of 5-(3,4-dichlorophenyl)-4-nitropyrrole-2-carbonitrile (0.6 g, 2.1 mmol) in 10 mL of dioxane at 25°C, under nitrogen, is added dropwise a solution of bromine (0.3 g, 2.1 mmol) in 5 mL of dio-20 xane. The reaction is allowed to stir overnight. Addition of 50 mL of water causes precipitation of a yellow solid which is collected and vacuum oven dried (50 mm Hg, 45°C) to afford the brominated pyrrole (0.7 g, 90%) as a light yellow solid, m.p. >200°C. 25 EXĀMPLE 56 4- (p-chlorophenvH -2- (trifluoromethvl-2-oxazolin-5-one In a single portion, trifluoroacetic anhy-dride, (1.7 mL; 0.012 mol) is added to powdered 2-(p-chlorophenyl)glycine (11.4 g; 0.06 mol), causing an immediate exotherm to about 40°C, a yellow color forming on the surface of the solid. As the mixture is slowly heated to 70°C, more of the solid dissolves to an orange/amber oil. Ali the solid dissolved in approximately 2 hours, and heating is continued another 35 98 hour. Solvent is removed under reduced pressure on a rotary evaporator. Toluene is twice added and removed under reduced pressure, but the odor of trifluoroacetic acid is stili evident. This yellow semi-solid (yield theoretical; purity > 90% by HPLC) is the above-identi-fied compound and is used in the next step without further purification. EXAMPLE 57 10 Preparation of 2-(p-chlorophenvl)-5-rtrifluoromethvl) pvrrole-3-carbonitrile 4—(p—chlorophenyl)-2-(trifluoromethyl)-2-oxa-zolin-5-one (2.5 g; 0.01 mol) is dissolved in nitro-methane (50 mL) . In a single portion, 2-chloroacrylo-15 nitrile (8.0 mL; 0.10 mol) is added to the solution, and the resulting solution is stirred 18 hours at reflux under a nitrogen atmosphere. Cooling the red/brown solution to -5°C in an ice-acetone bath causes the formation of a precipitate which is collect-20 ed by filtration and washed with a small portion of cold nitromethane. The resulting tan solid is recrystallized from hot ethylene dichloride yielding the product as white crystals (1.8 g; 56% theory), m.p. 238-241°C (dec.). 25 By utilizing the appropriate arylglycine in the procedure of Example 55 and following the procedure of this Example, the following 2-aryl-5-(trifluorometh-yl)pyrrole-3-carbonitrile were prepared:

- 99 - LV 10773 R Ļ m.o.°C H H 215-218 H 4-CH3 191-193 H 4-0CH3 168-180(dec.) 3-C1 4-C1 245-246(dec.) H 4-^3 218-219 EXAMPLE 58

Preparation of 4-Bromo-2-(p-chlorophenvH-5-ftrifluoro-10 methvl)pvrrole-3-carbonitrile

Under a nitrogen purge, a suspension or 2-(p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile (1.6 g; 0.005 mol) in acetic acid (25 mL) is heated, ali the material dissolving to a clear solution at 15 about 60°C. A solution of bromine (0.8 mL; 0.015 mol) in acetic acid (10 mL) is added dropwise over 15 minūtes to the refluxing solution. The solution is refluxed 6 hours then allowed to stir 18 hours at room temperature. The HPLC of the reaction mixture shows 20 about 80% conversion to product. The mixture is heated back to reflux and more bromine (0.5 mL; 0.01 mol) in acetic acid (5 mL) is added dropwise. After refluxing another 3 hours, the aliquot shows > 95% conversion to product. The reaction is cooled, and solventr removed 25 under reduced pressure on a rotary evaporator to obtain a dark grey solid. Toluene is added to the mixture and removed under reduced pressure, but the odor of acetic acid stili remains. The entire material is dissolved in hot toluene (75 mL) to a turbid solution which is treated with DARCO filter and filtered. The light pink solution deposits a white solid upon cooling to ambient. After cooling in the freezer, the solid is collected by filtration, washed with hexanes, and dried on the filter. Further drying in a vacuum oven at 45°C 35 100 provides the product (1.2 g; app. 60% theoretical); m.p. 247-250°C(dec.).

Anal. Calcd for C12H5BrClF3N2: C, 41.20; H, 1.43; N, 8.01; Br, 22.89; Cl, 10.16; F, 16.31.

Found: C, 41.27; H, 1.48; N, 8.10; Br, 22.92; Cl, 10.16; F, 16.03.

By brominating the appropriate 2-aryl-5-(tri-fluoromethyl)pyrrole-3-carbonitrile, obtained by the procedure of Example 57, according to the above recipe, the following additional examples are prepared;

CF

R H H 3-C1 H

4—CH, 4-C1 4-CF.

R 244-245 218-223 225-226 - 101 - LV 10773 EXAMPLE 59

Preparation of 2-(4-chlorophenvl)-5-trifluoromethvl-pvrrole-3.4-dicarbonitrile

20 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 an immediate yellow color and some refluxing. The mixture is slowly heated to reflux, causing ali the material to dissolve to a yellow/orange solution which is heated 2 hours further. The reaction mixture is cooled, and solvent removed under reduced pressure. Toluene, is twice added and removed under reduced pressure to yield a very thick oil (VCQ = 1800cm ^1) . This residue is dissolved (some insolubles) in CH3N02 (40 mL) and bromofumaronitrile (2.7 g; 0.018 mol) is added in a single portion. The resulting solution is heated at reflux 18 hours, yielding a dark red solution. Solvent is removed under reduced pressure and the dark residue is dissolved in CH2C12, some insolubles being removed by filtration. 35 102 10 15 20 25 30

The material is fractionated via dry column chromato-graphy (silica gel; 3% 2-PrOH in CH2C12), and appropri-ate fractions are taken. Evaporation of one fraction yields the desired compound as a yellow solid which is recrystallized from CH3CN (DARCO treatment) to yield a pale yellow solid (0.2 g) . m.p. = 238-241°C. (some dec). \ 35 103 LV 10773 EXAMPLE 60 p-chloro-jg-Γ (formylmethvl)aminolcinnamonitrile. diethvl acetal C1

A magnetically stirred solution of 250.Og (1.39 mol,) of E-chlorobenzoylacetonitrile, 203 mL (185.9g, 1.39mol) of 2,2-diethoxyethylamine, and 1300 mL of dried toluene is heated at refux for 20 hours. Water is collected in a Dean-Stark trap (23.8 mL, 95.2% theory). The hot cloudy dark brown solution with a large amount of undissolved solids is filtered through diatomaceous filter aid. After dilution with 200 mL of EtOAc, the solution is filtered through a 7cm X 13.5cm column of silica gel. The filtrate is concentrated in vacuo to give 354.3g (86.4% crude yield) of a cLear dark oil vhich slowly solidifies. This solid is recrystal-lized from hot cyclohexane to give 324.2g (79.1% yield) of a waxy orange solid. NMR of this product shows it to be composed of 78% (£) and 23% (|ļ) isomeric mixture of E-chloro-č-[ (form7lmeth7l) amino]cinnamonitrile, diethyl acetal, m.p. 60-72°C. The folloving anal7tical data is for another similarly prepared sample. ūax(mull,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. 104 H-NMRfchloroforml: 57.47 (d, J=8.6Hz, 2.12H, two aromatic protons), 57.37 (d, J=8.6Hz, 2.12H, two aromatic protons), 55.10(2) & 54.86 (2) [br t, 1.25H, one N-H proton], 54.69(2) & 54.60(2) [t, J=5.1Hz, 1.05H, one methine proton at the acetal carbon], 54.07 (E) & 54.05(2.) [s, 0.83H, enamine β proton], 53.71(2) & 53.68(2) [g, J=7.1Hz, 2.22H, two methylene protons of one of two ethoxy groups], 53.56(2) & 53.53(E) [q, J=7.1Hz, 2.22H, two methylene protons of one of two ethoxy groups], 53.18 (t, J=5.1Hz, 1.77H, two methylene protons of the ethyleneacetal group), 51.20 (t, J=7.1Hz, 4.90H, six methyl protons of the two ethoxy groups). ONMRfchloroform^: 5161.21 (α-enamine carbon), 5136.29 (Z) & 5134.60(E) [either C-l or C-4 of the phenyl ring], 5134.08(Z) & 5132.30(E) [either C-l or C-4 of the phenyl ring], 5129.34(2) & 5129.89(2) [either C-2,6 or C-3,5 of the phenyl ring], 5128.94(2) & 5128.63(2) [either C-2,6 or C-3,5 of the phenyl ring], 5121.19(2) & 5119.50(2) [nitrile carbon], 599.43(2) & 5100.63(2) [^-enamine carbon], 561.88(2) & 563.25(2) [methine carbon of the acetal], 562.64(2) & 563.03(2) [methylene carbons of the ethoxy groups], 546.32(2) & 547.33(2) [methylene carbon of the ethyl amine group], 515.26 (methyl carbons of the ethoxy groups).

Microanalvsis (MW 294.78):

Calcd: C, 61.11%; H, 6.50%; N, 9.51%» Cl, 12.03%.

Found: C, 61.25%; H, 6.25%; N, 9.34%; Cl, 12.35%.

Folloving the above procedure but substituting the appropriate benzoylacetoylacetonitrile for p-chloro-benzoylacetonitrile and/or the appropriate 2,2-di(Cļ-C4 alkoxy)ethylamine for 2,2-diethoxyethylamine yields the following compounds: - 105 - LV 10773

C0-CH2CN + HgNCHgCH(C^-C^ alkoxy)2 - to 1uene

Ļ M R (C.—C. alkoxv1 _ mp°C H H E -CH3OCO 14 ' (°C2H5>2 68-73 H e-ch3 H (OC2h5,2 59-69 H 2>-OCH3 E -och3 (0C2H5)2 Red orange semi solid H Vļ (°C2H5)2 62-70 E“C1 H H <och3)2 — H e-ch3 H (och3)2 — H iņ-Cl E”C1 <OC2H5>2 — H H E -OCF3 (°C2H5)2 H H E ’CF3 <OC2H5>2 — 106 EXAMPLE 61 2 fp-chlorophenvl)-pvrrole-3-carbonltrile

Το 108 mL of trifluoroacetic acid stirred at 23°C is added 54.00g (0.183mol) of solid p-chloro-0-[(formyl-methyl)aminoļcinnamonitrile, diethyl acetal over a period of 45 minūtes. This addition produced an exotherm to 38°C and, 32 minūtes into the addition, a solid started to precipitate. After stirring at room temperature for 30 minūtes, the reaction mixture is vacuum filtered and the collected solid is washed first with trifluoroacetic acid, secondly with an ethyl acetate-hexane mixture, and finally with hexane. The yield is 16.83g (45.4%) of an off-white solid, mp 165-166°C. The folloving anal. data is from a similarly prepared sample.

Kax(mull, Nujol): 3275(brs), 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. - 107 - LV 10773 H-NMRfacetone): $11.22 (v br s, 0.99H, one pyrrole N-H proton), $7.82 (d, J«8.9Hz, 2.46H, two aromatic phenyl protons), $7.51 (d, J«8.9Hz, 2.46Hz, two aromatic phenyl protons), $7.02 (t, J«2.6Hz, 1.01H, one pyrrole proton at C-5), $6.58 (t, J*2.6Hz, 0.77H, one pyrrole proton at C-4) . C-NMR(acetone); $137.73 (pyrrole C-2), $134.42 (p-chlorophenyl at C-4), $129.93 (methine carbons at c-3,5 of the phenyl ring), $128.07 (methine carbons at C-2,6 of the phenyl ring), $121.21 (pyrrole at C-5), $117.93 (nitrile carbon), $113.78 (pyrrole carbon at C-4), $90.86 (pyrrole carbon at C-3).

Microanalvsis (MW 202.64):

Calcd.: C, 65.19%,· H, 3.48%; N, 13.83%; Cl, 17.50% Found: C, 64.18%; H, 3.52%; N, 13.63%; Cl, 17.74%

Use of the above procedure as shown or with the substitution of concentrated hydrochloric acid for trifluoroacetic acid affords the following compounds: CN ri _L R M and/or R o_ mp C Acid Used 4-Cl 165-166 conc. HC1, CF3COOH 3,4-di-Cl 216-221 cf3cooh 2-C1 156-157 cf3cooh 4-OCF3 143-145 CF3COOH 4-CF3 179-180 CF3COOH 2,4-di-Cl 197-199 cf3cooh 108 3- C1

4- CN 4-F

4”S°2CH3 3,4-di-F 3- CF3 4- COOCH, 4-CH3 4-N02 150-156 210-212 167-170 221-221.5 173- 175.5 166-168 155.5-158 117-137 174- 177

CF3COOH

GF3COOH conc. HC1

CF3COOH

CF3COOH

CF3COOH

CF3COOH

CF3COOH

CF3COOH ESĀMPLE 62 ' 4,5-Dichloro-2-(p-chlorophenvlĪpvrrole-3-carbonitrile

To a mechanically stirred solution of 16.83g (83.1mmol) of 2-(p-chlorophenyl)pyrrole-3-carbonitrile in 450 mL of glacial acetic acid at 36°C is added dropwise 14.7 mL (24.70g, 183.0mmol) of sulfuryl chloride over a period of 18 minūtes. The addition producēs a slight exotherm to 39°C and, after another 16 minūtes, the reaction mixture is vacuum filtered. The collected solīds are vashed first with acetic acid and then with water. This solid after recrystallization from hot ethyl acetate, melts at 259-261°C. By similar procedures other samples of this product vere prepared and the analytical data. for one such product is shown below. - 109 - LV 10773

Max(mull. Nujol) : 3170(br s), 3100(111), 2225(s)r 1508(m), 1097(m) , 825(s), 717 (m), 660(m) cm”1. H-NMRfDMSOIī «7.72 (d, J=8.6Hz, 2.00H, two aromatic protons), «7.56 (d, J=8.6Hz, 2.00H, two aromatic protons). C-NMRfDMSOI: «136.01 (pyrrole C-2 carbon), «133.92 (p-chlorophenyl C-4 carbon), «129.09 (p-chlorophenyl C-3,5 carbons), «127.41 (p-chlorophenyl C-4 carbon), «127.11 (p-chlorophenyl C-l carbon), «114.49 (nitrile carbon), «114.10 (pyrrole C-5 carbon), «110.92 (pyrrole C-4 carbon), «90.09 (pyrrole C-3 carbon).

Microanalvsis (MW 271.54):

Calcd.: C, 48.65%, H, 1.86%; N, 10.32%; Cl, 39.17% Found: C, 49.22%; H, 2.12%; N, 9.85%; Cl, 39.03% EXAMPLE '63 4.5-Dibromo-2-^o:.Q;.Q:-trifluoro-p-tolvl1 -Pvrrole-3-carbo-nitrile

To a stirred mixture of 0.8g of 2-(a,a,o-tri-fluoro-p-tolyl)pyrrole-3-carbonitrile in 70 mL of chloroform is added 2 mL of bromine. The mixture, on stirring ovemight, deposits a white solid which is collected by filtration. Thin layer chromatography (1:1 ethyl acetate-hexane) shovs a single component; m.p. >230°C.

Anal. Calc'd for C12H.-7.11; Br, 40.61. Br2F3V c, 36.55; H, 1.27; Found: C, 36.40; H, 1.08; N, 6.99; Br, 40.55. 110

Folloving the above procedure but eubstituting the appropriately eubstituted phenylpyrrole-3-carbo-nitrile for 2-(a,a,a-trifluoro-p-tolyl)pyrrole-3-carbo-nitrile yields the folloving compounds.

L M E Σ 2 PJP.-C H H 4-N02 Br Br 274-277 H R 4-F C1 C1 >220 H H 4-F Br Br >220 H H *-*o2cb3 C1 C1 >230 H 3-F 4-F C1 C1 >230 H 3-F 4-F Br Br >220 2-C1 3-Cl 4-C1 C1 Cl 2-Br 3-Br 4-Br Br Br H H 4-OCF, C1 Cl 222-225 3 -» H H 4-OCF3 Br Br H H 4-OCF3 C1 H H H 4-CN Br Br >230 H H 4-CN C1 Cl >240 H H 4-S02CH3 Br Br >230 H H 4-N02 C1 Cl 246-249 H 3-C1 4-C1 Br Br >260 H H 3-CF3 C1 Cl >230 H H 4-COCH3 C1 Cl 251-254 H 2,3 -CH=CH- C1 Cl 244-247 H H 4-CH C1 Cl 215-217 H 2-C1 4-C1 Br Br >230 - 111 - LV 10773 L K E Σ X ļņp°c H H ' 3-Cl C1 C1 >230 H 2-C1 4-Cl C1 C1 >230 H H 4-Cl Br Br 273-274 H K 2-C1 Br Br >230 H H 4-CF3 C1 C1 >230 H H 4-Br C1 C1 >235 H H 2-C1 C1 C1 >230 H 3-Cl 4-Cl C1 C1 >235 H H H C1 C1 254-255 EXAMPLE 64 ct-f2.2-diethoxvethvlamino1-5-nitrostvrene and 3-nitro-2-phenvlpvrrole

Alpha-nitro acetophenone (5.7g, 0.0345m) is taken up in 100 mL toluene and 4.6g (0.0345m) of amino acetaldehyde diethyl acetal is added. The reactants are put into a 250 mL RB flask fitted with a Dean-Stārk trap. The trap is filled with 4A molecular sieves and the mixture is heated at reflux for 18 hours. The toluene is removed iņ vacuo to give 8.36g of a-(2,2-di-ethoxyethylamino)-£-nitrostyrene as a brown oil. To this oil is added 50 mL of concentrated HC1. As the flask is svirled the oil turns to a yellow suspension. After 10 minūtes the solid is filtered to give 2.48g of a yellow solid. Recrystallization from ether/ethyl-acetate/hexane gives the product as two fractions, 2.08g of m.p. 190-192°C, (31%).

Max 1485 cm-1(N02), H-NMR(CDC13/DMS0) i6.73(m,2H), -7.46(111.511) . 112

Other £-nitrostyrene compounds can be prepared by the above reaction by substituting the approprlately substituted α-nitro acetophenone for α-nitro acetophenone and/or appropriate 2,2-di(C^-C^ alkoxy)ethylamine for 5 amino acetaldehyde diethyl acetal to give the folloving compounds 11210

h2nch2chcc1-c4 alkoxy )2 toluene

15 20 25 L ŽS £ ..alkoyy) 2 H H E-CH3OCO (oc2h5)2 H e-ch3 H (oc2h5)2 H m-ocH3 e-och3 (°C285)2 H <OC2H5>2 E“C1 H H (och3)2 H e-ch3 H (och3)2 H H e-cf3 (oc2h5)2 30 35 LV 10773 - 113 -EXAMPLE 65 2,3-Dichloro-4-nitro-5-phenvlpyrrolē

NaOCl

A mixture of 3-nitro-2-phenylpyrrole (1.56g, 0.0083m) in 60 mL of dioxane is cooled in an ice bath while 25.9g (.0182m) of commerclal sodium hypochlorite is added dropvise. After stirring for 45 minūtes, the mixture is acidified with concentrated HC1. Water and Et^O are added. The layers are separated and the top organic layer is vashed with H^O, dried over anhydrous MgS04 and concentrated in vacuo to give 2.21g of yellow solid. Purification by chromatography using silica gel and eluting with increasing ratios of ethyl acetate/ hexane gives, after stripping, 0.77g of yellow solid (36%) ffl.p. 190-190.5°C;

Analvsis: Calcd. for C10H6N2O2Cl2 C, 46.72; H, 2.35; N, 10.90

Found: C, 46.96; H, 2.86; N, 10.02 114 EXAMPLE 66

Insecticide and acaricide evaluations

Ali tests are preformed using technical materiāls. Ali concentrations reported herein are in 5 terms of active ingredient. Ali tests are ķept at 27°C.

Soodoptera eridania. 3rd instar larvae, Southern armyworm 10 A Sieva ļima bean leaf expanded to 7-8 cm in length is dipped in the tēst suspension with agitation for 3 seconds and placed in a hood to dry. The leaf is then placed in a 100x10 mm petri dish containing a damp 15 filter paper on the bottom and ten 3rd instar cater- pillars. The dish is maintained for 5 days before observations are made of mortality, reduced feeding, or any interference with normai moulting. 20 Soodoptera eridania. 7-day residual

The plants treated in the above Tēst are maintained under high intensity lamps in the greenhouse for 7 days. These lamps duplicate the effects of a bright sunny day in June in New Jersey and are ķept on for 14 hour day length. After 7 days, the foliage is sampled and assayed as in the above-said Tēst. 25 - 115 - LV 10773

Aohis fabae. mixed instar, bean aphid

Pots containing single nasturtium plants (Tropaeolum sp.) about 5 cm tall are infested with about 100-200 aphids one day before the tēst. Each pot is sprayed with the tēst formulation for 2 revolutions of a 4 rpm tumtable in a hood, using a #154 DeVilbiss atomizer. The spray tip is held about 15 cm from the plant and the spray directed so as to give complete coverage of the plants and the aphids. The sprayed pots are set on their sides on white enamel trays and held for 2 days, following which mortality estimates are made.

Tetranvchus urticae(P-resistant strain),2-spotted spider mite

Sieva ļima bean plants with primary leaves expaned to 7-8 cm are selected and cut back to one plant per pot. A small piece is cut from a leaf taken from the main colony and placed on each leaf of the tēst plants. This is done about 2 hours before treat-ment to allow the mites to move over to the tēst plant and to lay eggs. The size of the cut piece is varied to obtain about 100 mites per leaf. At the time of the treatment, the piece of leaf used to transfer the mites is removed and discarded. The mite-infested plants are dipped in the tēst formulation for 3 seconds with agitation and Set in the hood to dry. Plants are ķept for 2 days before estimates of adult kill are made using the first leaf. The second leaf is ķept on the plant for another 5 days before observations are made of the kill of eggs and/or newly emerged nymphs. 116 -

Diabrotic undecimpunctata howardi. 3rd instar Southern corn rootworm

One cc of fine talc is placed in a 30 ml wide-mouth screw-top glass jar. One ml of the appro-priate acetone suspension is pepetted onto the talc so as to provide 1.25 and 0.25 mg of active ingredient per jar. The jars are set under a gentle air flow until the acetone is evaporated. The dried talc is loosened, 1 cc of millet seed is added to serve as food for the insects and 25 ml of moist soil is added to each jar. The jar is capped and the contents thoroughly mixed on a Vortex Mixer. Following this, ten 3rd instar root-orms are added to each jar and the jars are loosely capped to allow air exchange for the larvae. The treatments are held for 6 days before mortality counts are made. Missing larvae are presumed dead, since they decompose rapidly and can not be found. The concentra-tions used in this tēst correspond approximately to 50 and 10 kg/ha, respectively.

Rating Scale: 0 = no effect 5 = 56-65% kill 1 = 10-25% kill 6 = 66-75% kill 2 « 26-35% kill 7 = 76-85% kill 3 = 36-45% kill 8 = 86-99% kill 4 = 46-55% kill 9 = 100% kill R - reduced feeding - 117 -LV 10773

I

Μ Μ6 R » S <β XX Ο \ ιη Μ ε ο 04 ο ο η W > >ι (Λ (0 Ό 10 ΙΟ ο σι ΙΟ ε Ο • 04 Ο C0 σι 04 (Η

W Q Η g οοο Η σι σ\ Ε ο 04 ο ο 04 Η Ο I 1 1 ιΗ (Ν 1 φ (Ν >1 1 φ ιΗ 1 C Ο fH •Η ο φ φ 0 Ο 0 0 Λ (Η Ο 0 -Ρ ο 04 1 -Η Η 0 •Η ιΗ 0 η 0 Ό Λ >1 C XX 0 I Ρ C ϋ 04 0 υ 0 Φ Η 0 •Η γΗ XX •Η I—ί ιΗ C Ο Ό >1 0 ΰ XX Ο Ο 04 1 C <0 1 υ 0 XX Ε ΙΟ α) ο ΙΟ I 0 0 0 XX 1 «. 04 >1 (0 Ο <· 04 η 04 ϋ 118 Iw W toB R» £

RJ Λ Ο O \ in tn X β o a O O ft n U > >1 Ol<0 Ό f" σι

Table I (Cont ea &

o o rH σι σ\ ο ο ο Η σ σ β ο ο ο ιη Γ' 1 CN 1 1 α> α> 1 Ο r—( rH 0 U 0 •Η U 0 μ μ 0 γΗ U 4-> rH Λ >1 •Η Ό Λ ϋ Λ C C ϋ •Η #<"*** Ο 3 •Η Ό rH Λ Ο Ό 1 >1 μ Ά 1 C (0 β ΙΓ) Ū) 0 0 % η Λ 1 U «ί* ν— a η

1 1 0 ΓΊ 1 γΗ Λ | ο >1 U 0 S-ι C (C μ Ο α) ϋ 0 3 Λ 1 ιΗ r—1 a η Λ «Η I Ο •Η ίί α> 0) •Η μ X ιΗ ι—1 Ό -μ 0 0 -Η 1 ''— jd μ μ ιη I •μ μ -μ ** a 0) >! •Η 1—1 β a C - 119 -LV 10773 s (Ū Λ o o o ω 0 w \ θ' * in w w g o <n ft o o 00 i & n οι >ι rtJ Ό

ts 0 CJ 0 rH s fc QS S« 3

g o ft O Jl ft H

o o o H σι σ' σι o σι cn

O g O Λ Ο O ft h I I «Η 0 1 η I Μ >1 Λ 1 1 (Μ 1 G Μ •Η 0) I 0 α> <0 Ό ί—! αι 0 <0 u χ υ | 1 Ο ι—1 Λ ο α 1 0 ιη U *»Η ο ft rH ο η g *. ρ 5η rH rH Ό X! >η 1 ο >1 Ρ X (0 c 0 0 α> G) ρ ft •Η 0 p •Η rH ιΗ rH Λ rH Ο C -Η (0 0 Ό Χ3 0 •Η 1 >1 Μ Ο Ό XI ft 1 0 Μ >Η ft C 0 Λ 1 ft 0 ιη >Η -Ρ 'χ—- ω r—1 !η ιη r—i 0 ο >1 •Η 1 XI XI (ΰ « ισ υ sr ft C CM ft υ υ alpha-trifluoro-p-tolyl)pyrrole- 120 I w

Ui wB B» S

Table I (Cont M 55 Q W S« g (0 Λ O * E O 0,0 0 Λ n

Cfl Γ" >1 (0 TJ

E O a o Ά H o o o <n o o cn σι

O E o 0,0 0 Οι rH I I 1 0 t—H 1 O 1 >1 Ά 1 >1 A C\) c P CN c 5-1 1 0) Λ 1 a) «J 0 A υ 0 x: O E a I E a 1 0 0 η o 0 m Ό u P I u ρ 1 C A 0 <D <D A o Ο) <D 0 •H H Ι“Η rH •H rH rH rH o Ό A 0 •H Ό A o Ή a 1 o u 5-1 1 U 5-1 5h E m 1 5H 4-> in 1 U -P 0 ** 0 >1 H a >1 •H u •«a· — a C — a c - 121 -LV 10773

Iw

Table I (Cont w

Q H a

(0 •C \ Cn X o cn o e o CU o & <n 10 Γ' >i <c Ό σι o σι

E o Ā ο oi CU H σι

o o o rH σι σι

ē o CU Ο O CU H o i t o <D 1 1 1 P r-H 0) CN 1 0) ai CN O 0 rH 1 0 rH rH | ia 3 P •P o P 0 •<H 0 XX rH P P p 0 P P E CU <W >1 P o rH P p O r—t •P cu •P rH XX >1 •P Ό P (0 P *·** c Λ υ cu c C XX ·. P rH 0 U •Η ,___. 0 3 M (C l >1 Λ •P Ό rH XX 0 Ό JS to rH P Ό | >1 P CU 1 cu x: 0 (0 1 c 3 E in rH cu P 0 cn *. o O O (0 rH 1 1 CN X 1 U •^r w (0 cu m rr '—' CU cn 122 Iw (0 Λ \ o in e o Λ o O Λ n (0 P' >i σι nJ Ό σι

Table I (Cont

S o a oft H o\ σι οοο ι—1 σι σι

ο 6 ο Cu ο ο a η

I

1 I ρΗ ι Ο I I α) α> CM >1 Λ (Μ 0 γΗ γΗ 1 C VI 1 VI 0 -Η 0 α) (0 Ο Ο νι VI V4 Λ Ο e γΗ VI V» ο a 1 ο χ: >1 •Η Η 0 η Ό Vl ο a C X! Vi I C Λ •Η ο 0 ο α> CD 3 •Η Ό ιΗ Λ •Η ι—Ι ι—1 rH Ο Ό 1 >1 U Ό Λ ο •Η a 1 *3· C ια 1 ϋ VI V Ē ιη α> 0 ιη 1 VI Ρ ο ΓΜ JZ I £ >1 Ή U a η ^3* a C - 123 -LV 10773

Ico co co g B* a

Table I (Cont.)

g ο a Ο ο a η (0 Λ ο O \ un θ' * g o Λ ο O a n w r* >ι σι «s g o a o a h σι ο ο ο σ\ co ir> r- cn σ> σ> in o σ\ σι σι Ο I I 1 I 1 r—i ιΗ ιΗ ιη >Ί φ 1 >1 φ | >1 I C γΗ ιη C ι—1 0 C ο Φ Ο I φ Ο U Ο) U Δ 54 0 Δ 5-ι 0 Δ ο a 54 g a 54 ιΗ a 1 γΗ 0 >1 0 ο >1 TJ Λ Δ α 54 54 a C Ό ιη φ ϋ ο ο Δ ο 0 3 •Η I rH -Η rH 54 •Η rH 5-ι Ο Ό 0 0 Τ3 Δ +J Τ3 Λ -Ρ a 1 U Μ 1 Ό •Η 1 ϋ •Η ε η +J 5-ι η 1 Π η 1 G 0 «. •Η >1 *. a 1 , a 1 υ Μ C a CM ·=τ OJ — •«ί 124 I w

«J Λ \ X o in o o Ē o a o o Λ r> to r* >ι <λ <0 Ό o σι

Table I (Cont.)

β o ft O CTi H d\

O O O rH σι σι w P g ā o

β O D. Ο O Ο. H

I I 1 rH in 1 >1 1 0 | c o <D 0 0) U 0 rH β JG o rH 1 0 0 a (—ļ J3 Ό >H 1 J3 ϋ | C ja in <D O •H .— >1 3 •H | rH •H Ό rH a o Ό 0 0 Ό 1 >1 0 a 1 M U 1 rr C u 6 m +J H r> Q) 4-) 0 •H >1 ** n Λ •H u cm G a CM w a c - 125 - LV 10773 I w

«3 JC o co \ in CJ' X n oo

W M in w w e o • δ P cu o 00 CTi • b a> n 1¾ X

w t" >i 0\ (0 •C c\

Pc0u

0) Ha ĒH

Ē O & O & H o o o σ> cr* Ē O Οι O (0 04 l-t

, 1 1 d) rH 0 in n 0 e | g Ό o •<r O G G u ,—. G >1 3 Λ 1—i o 04 0 1 S*1 iH 0 (¾ a G Λ 0 e ū) 0 •P o | Λ •H o rsī & Ό G 0\ n co

1 (C 1 Λ ω 0 04 1 1 j—i G i—1 «3 0 o 0 (0 Λ 1 G rH 04 o G 1 i—( G >1 ϋ in «3 0 0 •H 1 G .__* Ό o (0 r—i i—1 1 G .c <W >1 r> -P 04 •H r—{ «. •H rH G o CN G fd P -P 126 EXAMPLE 67

Insecticidal evaluations

Heliothis virescens. 3rd instar tobacco budworm

Cotton cotyledons are dipped in the tēst formulation and alloved to dry in a hood. When dry, each is cut into quarters and ten sections placed individually in 30 ml plastic medicine cups containing a 5-7 mm long piece of damp dental wick. One third-instar Caterpillar is added to each cup and a cardboard lid placed on the cup. Treatments are maintained for 3 days at before mortality counts and estimates of reduc-tion in feeding damage are made.

Emooasca abrupta. adults, westem potato leafhopper A sieva ļima bean leaf about 5 cm long is dipped in the tēst formulation for 3 seconds with agitation and placed in a hood to dry. The leaf is placed in a 100x10 mm petri dish containing a moist filter paper on the bottom. About 10 adult leafhoppers are added to each dish and the treatments are ķept for 3 days before mortality counts are made.

Blattella aermanica. bait tēst, adult male1 German cockroach A 0.1% bait is prepared by pipetting 1 ml of a 1000 ppm solution of the tēst compound in acetone onto 1 gram of cornmeal in a 30 ml wide-mouth bottle. The bait is dried by passing a gentle stream of air into the bottle. The bait is placed in a 1 pint wide-mouth Mason jar and ten adult male cockroaches are added. A screen lid is placed on the jar and a small piece of cotton soaked in 10% honey is put on the top of the screen lid. Mortality counts are made after 3 days. - 127 - LV 10773

Blattela germanica. residue tēst, adult male German cockroach

One ml of a 1000 ppm acetone solution of the tēst material is pipetted slowly over the bottom of a 150 x 15 mm petri dish so as to give as uniform coverage as possible. After the deposit has dried, 10 adult male cockroaches are placed in each dish and the lid is added. Mortality counts are made after 3 days.

Spodoptera eridania. systemic uptake, 3rd instar larvae, Southern armyworm

The compound is formulated as an emulsion containing 0.1 gm of the tēst material, 0.2 gm of Emulphor EL-620® emulsifier, 10 ml of acetone and 90 ml of water. This is diluted 10-fold with vater to give a 100 ppm emulsion for the tēst. Subsequent 10-fold dilutions are made with water as needed. Sieva ļima bean plants, with the primary leaves expanded to a length of 7-8 cm, are cut off at least 3 cm above the so-il Ievel to avoid contamination with soil bacteria that will cause decay of the stem during the tēst. The cut stems are placed in the tēst emulsions and each stem is wrapped with a bit of cotton to hold the stem off the bottom of the bottle and to limit evaporation and volatilization of the compound. The tēst is maintained for 3 days at 27°C to allow the compounds to be taken up into the plant. Folloving this, one leaf is removed from the plant and placed in a 100 x 10 mm petri dish with 10 Southern armyworms as described in Tēst III. Mortality counts and observations of feeding damage are made 3 and 5 days later.

Empoasca abrupta. Adults, Western Potato Leafhoppers, Systemic Uptake

The compound is formulated as an emulsion containing 0.1 gm of the tēst material, 0.2 gm of 128

Emulphor EL-620® emulsifier, 10 ml of acetone and 90 ml of water. This is diluted 10-fold with water to give a 100 ppm emulsion for the tēst. Subsequent 10-fold dilutions are made with vater as needed. Sieva ļima bean plants, with the primary leaves expanded to a length of 7-8 cm, are cut off at least 3 cm above the soil Ievel to avoid contamination with soil bacteria that will cause decay of the stem during the tēst. The cut stems are placed in the tēst emulsions and each stem is wrapped with a bit of cotton to hold the stem off the bottom of the bottle and to limit evaporation and volatilization of the compound. The tēst is maintained for 3 days at 27°C to allow the compounds to be taken up into the plant. Following this, one leaf is removed from the plant and placed in a 100 x 10 mm petri dish and tested as in Tēst VIII, above.

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

- 129 - W

oS o ft o 04 H

O r~

Eh HS

o0 o 04 o 04 H

O o

i cu§

0 o & 2 04 H

I o W X W W u % w

0 O 04 o 04 H o σι

Table II

oo H in 00 n i

Ooo H co <x> 0 o 01 O 04 o I 1 CN 1 m 1 rH 1 0 | 1 (M >1 XI 0 <D 1 c u U rH a> 0 a) (Ū 0 0 rH u x: 0 fH •H 0 Of 1 X! u rH 0 n O >. 4J X! u I •H Of Ή O 0 ai φ Ό rH e •rH rH rH rH 1 X 0 Ό X! Ο ·Ή c Λ 1 υ ^ V4 in <d U in 1 >H X> X! (0 cu >i ·Η & 0 «i Of c LV 10773 130 B I 8 • ο w Β ο w a ο 3 a η 00 ĒH ο Η 0 ο < a ο η a η o SYSTEMIC LEAF HOPPER ppm 100 C—S SAW 001 mdd Ο Ο Η o o\ σι cn

Table II (Cont η %

I σ <Λ σ\ σ σι fM 1 (1) 0) es I 1 0 1—f 1—I 1 0 0 P 0 •H 0 p P 0 P P P 0 0 r-H P -P 0 0 1—< XJ •rH 1—( r—ļ Λ 0 a c Λ <H O •H *—* 0 O •H •H TJ i—t Λ •H P Ό I >1 P Ό -P 1 C «3 1 in 0) U in 1 *. n jC l - a s— a co l-i methoxy)phenyl-pyrrole-3-carbo co

oS g 04 o 04 H §

o O 0« o 04 H g - 131 - o o LV 10773

0 O 0* O 0< H

0 O& 0 fti H

O 1 1

Table IX (Cont

0\ e A tt

0 O & O & H

O I I rH 1 0 1 Ο) OJ >1 X5 rH <D 1 c H O 1—( 0 (1) «3 1 u •H u Λ O 1 in M 0 0« 1 0 v >1 +J r-H O n e 'ί Or •H XJ 0 1 0 1 O c u 0 <D α> J*4 0 •H l“H rH ιΗ A iH O Λ Ό A 0 •H >4 rH H 1 υ M & c A <0 in 1 0 +J 0) 0 O ·. 0 >1 •rH 1 A •H 1 •«a* '— 0. c <N α Ό 0

132 • ο W 0 Ο η a ο 2 a η ēh H σι ο o§ s a o a h ο s 1 M W W I u 0 o a o a h 0 o a o a h σι ο t-'

Table IX (Cont. ο ο Η σι ο \ (0

I 0 ο a ο a η σι σι ο

I I 1 0 1 Ο rH I 0 (\ Μ ΐΗ α) 1 >1 XI 1 V 0 ο ιΗ OJ C Ρ 0 (0 3 Ρ •Η 1 β β Μ Χ5 rH Ρ Ρ 0 Λ ϋ 0 a <w >1 Ρ η a 1 ιΗ Η •Η a •Η ο ο η Λ β Μ C Ρ Ρ 1 Ο Ρ rH ο Λ ο β β •Η (0 | >1 XI •Η rH rH ιΗ Ό Λ β Ρ Ό Λ Ο Η 1 a Λ ο β 1 0 Ρ Ρ ιη Μ a μ ϋ ιη 1 Ρ Ρ (0 rH 1 1 *. Ο >1 •Η '— β a η η· —" a C - 133 -w

og o ft o 04 H σι §

oa o04 o 04 H i § w t*w M I u 9w

a o 04 o 04 H σι

0 O & ° 04 H

Table II (Cont

Oo H σ> I 04

0 O 04 O 04 H o\ σι σι CNιο 0 Ορ Λ I >4 C <D Λ 04 Ο Μ Ο Ό Λ I 0 ιη ι ' & •«τ Iο Λ Μ (0 Ο I η Iα> γΗ ΟΡΡ >1 04 0 φ 1 0 «Η φ <Ν •k 0 Ο ιΗ 1 (0 3 Ρ •Η ο Λ rH Ρ Ρ 0 04 <W >4 -Ρ ο 4—1 •Η 04 •Η Ρ (0 Ρ C φ Λ •μ «Η ο rH •Η <0 ι >4 Λ •Η Ό Α 40 Η Ρ 1 04 Λ ο (0 •Ρ lf> Η 04 Ρ υ -Η •k Λί rH 1 ι C «β* —" (0 04 η LV 10773

134 • o E w η o U Ή 04 O < 3 04 H i 8 Eh O « H B O u < 04 O n 04 H o o

SiSTEMIC LEAF HOPPER ppm 100 W £ I < u w ppm 100 o

I

Table II (Cont

o o H σ o

i I CM §l

O o o H σ

I

O o H

O o I I cj I <u 0) I 0 rH rH 0 O 0 •H u O μ μ 0 I—1 μ μ i—1 Λ >1 •rH Λ O 04 c O •H «Ο-Ή o •rH •d rH Λ Ό 1 >1 μ 1 fl· c (0 in 0) 0 V. <N Λ 1 'i· 04 n I 1 1 ο; α) (N 0 rH rH 1 o 0 •Η 0 o ο ο B rH U •μ 0 ,C >1 •rH M ϋ Οι C Λ •Η ο -H Ό rH Λ Ό 1 >1 μ 1 C ιϋ in ** α> 0 •V ΓΜ Λ I >3· >— α η - 135 - w

o Θ Oα o 04 H

oΘ O 04 o 04 H o LV 10773

Table II (Cont.)

I 04 04 g

04 04 5

0 O 04 O 04 H

O σι

£ 0 O < 04 O w 04 H

ooo H

s o 04 O 04 H

I σι C\ co

VO σι o i 1 H 1 O 1 | «N >1 Λ •'T rH 1 c 1 >1 0 <D (0 o C 0 Λ υ u d) 0 04 1 0 X r—1 0 ro rH 04 Λ U | X 1 0 O ο a> υ in 0) •H rH rH rH -H 1 rH Ό Λ Ο -H Ό o 0 1 0 U 0 1 u 0 in 1 U -P n •P 0 0 >1 -H ·. •H >1 •Cf 04 C ΓΊ 0 04

136 W §

8 O

E-i H

o 0 ° a o & H

S

04 O 04 H 0\ CTi o σ

O o

Table II (Cont.)

| £ 04 o a

e a* Cu K §w

0 O 04 O 04 H

0 o 04 O 04 H

O 0\

0 ο in 04 o04 H co o o

VD 00 o I 1 1 iH t—I ir> >1 (2) 1 >4 1 c rH ιη C 0 0) 0 I α) 0 Λ 0 0 Λ 0 04 0 0 04 rH o >1 Ο ο A 0 04 0 Μ O o Ο Λ Ο •0 iH 0 •Η γΗ Ό Λ Ρ V Λ 1 ϋ •Η 1 Ο n 1 C η 1 04 1 *. 04 CM --" Ί· CM --- -nitropyrrole o σι o in oo o - 137 - to

o 0 o Cu O 04 H <n σ

O0 o& 2 04 H ο

0 o& 2 04 H σι σ to (0 to I υ %to

0 O 04 O 04 H σι σ\

Table II (Cont

οοο Η 0 ο 04 Ο 04 Η σ\ σ σι ιο νο σι co ι 1 0 ιο I 0 1 ο 0 Μ •Η 1 tu Μ 0 C 1 10 1 rH 0 rH 1 0 r> O ιΗ Α 0 l 0 Α Ο 1 0 1 0 0 0 •Η 0) 0 0 >1 •Η η iH f—1 Λ 1—1 0 04 Ό I >1 0 1 >1 rH 0 1 c 0 04 C A 0 η <U 0 a> υ -P r> A >4 1 A •rM •H CM w 04 04 CM 04 Ό c LV 10773 138 Ē |8

M

D, A

o o o H σι

Hffi Ej & K i ia

o o o H

O

o o H σι

W X M M I CJ

Table II (Cont. η« ΕΗ ga ο κ £ η ο < a ο μ a Η aa ι a ο ο Η C0 οοο Η ο ο σι σι ι •<r 1 (0 0) 0 £ | 1 rH 34 a «3 a 0 Ο ιΗ xi ι 3-i ιΗ (0 a 0 )-1 Λ 1 ιΗ 3-ι >1 ϋ ιη <0 Ο a •Η ι 3 Ό 0 (0 rH rH 34 Λ <4-1 >1 m •Ρ a •Η rH •Η t—ι u 0 ΓΜ G (0 -μ +j LV 10773 - 139 -EXAMPLE 68 A) Evaluation of tēst compounds as nematicidal aģents Culture Maintenance: Cultures of C. elegans (Bristol strain from J. Lewis) are maintained on E. coli lawns on NG Agar Plates at 20°C. New cultures are established weekly.

Nematodes for testing are vashed from 4-5 day old cultures using Fresh Ascaris Ringers Solution (FARS). The worms are further washed with FARS, con-taining gentamycin/ to reduce bacterial contamination and centrifuged to separate vorms from vash solution. This procedure is repeated three times. The washed worms are then added to c. briggsae Maintenance Medium (CbMM) , from GIBCOa to which is added gentamycin (600 units/ml) and mycostatin (0.5 mg/ml).

The tests are then made with mixtures of three compounds, piggy-backed from another high capacity screening program to reduce additional labor and com-pound expenditures.

Compounds are dissolved in acetone and made up to' volume with equal parts of water. The final tēst concentration of each compound in the mixture is 150 ppm. The tēst material is micropipetted (25 ul) into a single well of a 96-well sterile tissue culture plate (COSTAR)b and the solvent allowed to evaporate. These "treated" plates are used immediately or stored in a freezer without apparent adverse effects on the compounds . A freshly prepared volume (50 ug) of C. elegans in CbMM is micropipetted into each treated well and several control wells per plate. Culture plate are incubated at 20°C.

Observations for efficacy are made under a dissecting microscope at 4, 24 and 48 hours post-immer-sion. Immediately prior to reading the plate, it is 140 gently tapped to stimulate the movement of the worms. Activity is judged subjectively, but semi-quantitative-ly, based on the drug effects on motility of the adults and larvae. The criteria are as follovs: 8 = no 5 motility, 7 = markedly reduced motility in approximately 95% of worms, 6 = reduced motility, 5 = slightly reduced motility, 0 = normai motility, same as Controls. Other factors indicating activity are easily noted such as death, rigor mortis, contraction, coiling, paralysis, 10 abnormal twi.tchi.ng, reduced worm population in 48 hours and other deviation from normai behavior.

PROCEDURE FOR CAENORHABDITIS ELEGĀNS ASSĀY 15 20 25

Day 0 .Inoculate E. Coli-NG Agar Dish With 30-50 C.

Eleoans .Incubate At 20°C.

Day 4 .Harvest New C. Eleoans Population

.Wash With Antibiotics •Transfer To CbMM .Add 0. Eleoans (25-100 UL) To "Medicated" Wellsa .Observe For Activity At 4 Hours Post-Irunersion

Day 5 .Observe For Activity

Day 6 .Observe For Activity

Medicated Viells May Be Prepared Fresh Or Earlier And Stores In Freezer

Data obtained in these tests are reported in Table III below. 35 - 141 - LV 10773 B) Root-Knot Nematode Assav

Populations of the root-knot nematode fMeloidoovne incoanita) are maintained on Fireball tomatoes in the greenhouse. Egg masses are removed from the infested root surfaces and are ķept on moistened filter paper for 24 hours to allow them to hatch. Larvae emerge and drop into the water beneath the paper. Larvae for tēst are transferred to celi plate velis containing tēst compounds at 300 ppm in 3% acetone, about 10 larvae per celi well. Infested wells are held at 27°C and mortality is determined 24 hours after treatment.

Data obtained are reported in Table III below. 142

Table III C. Ele. Root Knot 150 ppm Nemātodes L A 4,5-dichloro-2-[p~ (trifluoromethoxy)phenyl-pyrrole-3-carbonitrile 300 DDM 4 4,5-dichloro-2-(alpha, 9 9 alpha,alpha-trifluoro-p-tolyl)pyrrole-3-carbonitrile 5 4,5-dibromo-2-(alpha, 9 9 alpha,alpha-trifluoro-p-tolyl)pyrrole-3-carbonitrile 0 2,3-dichloro-4-nitro-5- 0 0 phenylpyrrole 9 2,3-dichloro-5-(p-chloro- 9 9 phenyl)-4-nitropyrrole 9 2,3-dichloro-5-(3,4- 9 9 dichlorophenyl)-4-nitropyrrole 0 2-(p-bromophenyl)-4,5- 9 9 dichloro-3-nitropyrrole 2,3-dichloro-4-nitro-5- 9 9 (alpha,alpha,alpha- trif luoro-p-tolyl )pyrrole 6 143 - LV 10773 EXAMPLE 69

Following the procedures of Examples 59 and 60, compounds of the invention are evaluated against a variety of insect species including: leaf hoppers, tobacco budworm, Southern armyworm, and the German cockroach. The rating system is the same system used in the above-said examples. Data obtained are reported in Table IV below. Where two or more tests have been conducted with the same tēst compound, the results are overaged. also, a - in the table indicates no tēst.

144 B o a o a o H o o

S O a o a h B o a o a h o o o σ\ σ>

Table w > •ϋ co

I ο ο Η σ σι σ ο Β ο a ο a η σι σ\ σ η

ο (Ν σι σ | a οκ Β Ο a ο a η ο ο I I η I μ· I 1 r—i I α> >1 ο ι-Η α> I C U Ο r-i ο ω 0 Μ •Η Β Ρ γΗ Μ U 0 a Ό Λ >1 Ρ U 1 e 0 a -Η Λ to 0) ρ Η rH C •Η I ι—1 0 Ό >1 ο Τ5 0 ο 0 1 C Λ 1 Ρ Ρ Β ιη Ο U ΓΟ Ρ Ρ 0 JC (0 •Η >1 υ (Μ a υ <Ν C a 4-chloro-2-(ρ-chlorophenyl)-pyrrole-3-carbo- - 145 - LV 10773 M 8

0 O ft o 04 O pH o r~

SYSTEMIC LEAF HOPPER ppm 100 μ a S O r\. Λ 1 CJ w 04 H o ir>

Table XV (Cont t" «3 Ό σ>

O o H σ> σ\ σ

o o & O 04 H g ο ο Η

n 0 a 04 0 04 M O O o P3 H S I cu Ξ & 0 o ļ_ o 04 O K 04 H

σi σι σ Ο Ο σ ο σ\ σι o o cn <D 1 1 rH 0 •«ί 1 O 0 1 1 01 u 0 1 n rH 0 u i—1 n •— 1 >1 | >1 Φ Λ 1 l — 04 (N 04 I—i 0 Φ CM 1—i .-—* 1 *H 1 rH 1 >1 r—i o rH 0 ΟΙ 0 Φ 0 c >1 u >1 4J 0 rH 0 0) Λ 0 C •H 1 0 •H o Λ 4-> rH <D c CM Ϊ0 0 rH 04 Φ X3 Λ 0 1 04 4-> Λ o 0 U 04 Λ 0 .___. •H o 0 -H O 0 0 i—1 c H o X •d 0 to 0 >1 0 rs rH ο 1 o o 0 c Λ 1 Λ ,0 m rH 1 Λ φ 0 in υ -Ρ •k *: r> Λ CO •rH φ o l in 04 u —" -carbonitrile 146 § to g σ\ o o

O O toxtoto Iu

Table XV (Corrt

Μ m μ

ĒC g o < a o to a H u t*· av g fO o c\ σ>

oo H σι ο σι

Oo 0\ σι σι

οοο θ ο σι σι ο

C0 0S ο σι O o o o H 1 1 1 4J· ai rvj (D s—' 1 1 1 1 -P fO 1 rH n o ω (0 <N 1 1 P iH O 1 rH 1 «·—» Ο) 0 o N (M >4 0 i—1 rH 0) rH P d 1 c }-l >1 0 rH A P ω O Q) 0 C p H υ >4 A E A H 0) p p *H a i—I 0 a Ί3 Λ A >1 -P Ό 0 >4 P o c O a a •H 1 c A Λ ρ p •H 0 rH c in (0 P •H o 0 "d ρ >4 o >4 <L> Ό rH 0 1 0 A A u E 1 A g rH -P P 1 . in O 0 «. A 0) (0 1 n i—1 *H U ϋ E υ P\ 1 X <· pyrrole-3-carbo-nitrile - 147 -w

0 o 0 O cu o H σ I i

S O 04 O 04 H σ\ σν £ Ου w X Ww Iu

0 o 04 O 04 H σι σι cn 0) Η &Η W> 1" (βΌ σι σν σν σν σν σ

I

04 H σ> σν σι σ> σ σι "fen t* I 04

0 O 04 O 04 H σν σ σι LV 10773 (0 «· 1 43 f—1 r> ,.—- I 0 >i 1 ^— ι—t η 1 γΗ rH 0 1 >1 1 (M (0 Ο 43 (Ν C Ο) | ρ Ρ 1 (1) ιΗ 0 (0 1 (0 0 43 0 φ p 43 01 0 Ρ 0 Ρ rH o 0 1 1 ο 0 Ρ •Η iH r—V ο η ιΗ Ρ >1 Μ Ό 43 (0 ρ 1 43 Ο 0 Ρ υ ο 04 Ο) υ rH rH •Η § Η ιο Ρ »Η ι—1 •Η 43 >1 C 0 *0 Λ ιΗ Ο •Η Ό υ 43 0 0 1 0 14-1 Ρ Ρ 1 •Η Ρ Ρ 0 ιη r-H •Η Μ +J ιη Ό 0) Ρ 0 ϋ >1 •Η 1 1 <0 u Ρ 0 C ΤΓ Η υ 4,5-dichloro-2-(3, 4-di fluorophenyl) pyrrole-3-carbo-nitrile - 148 -υ <ο 8 «Ο

0 Ο 04 Ο 04 Η θ ο & ο ft ο Η σι σι σ ιηco σ w fH 10 Μ S 0 Ο ^ I < 04 Ο • ο X Μ 04 Η C Ο υ σι σι σ\ 0) Η a &Η Μ >«JΤ3 σι σ σ σ Ο 0 Ο04 ο 04 Η σι σ η §ΕΗ

σ ο οο οοο Η σ ι σ 0 ο 04 ο 04 Η Ο Ο 1 >4 η 1 X 1 η | 01 1 X ΟΙ rH α> Ι_—J *s η (1) I 1 1 >1 (Η 1 rH I 0 (0 ο Μ (Μ C 0 <Ν >. <υ 1 X 0 1 1 0) 0 1 c rH ι—1 04 0 0) 0 X 0 ω 0 ο 0 0) 1 X 0 ι—( 0) 0 04 >1 ιΗ 0 Ή 0 ιΗ ο <0 rH Ο ιΗ 0 0 04 •Η ο r-4 0 •Η 0 X 0 •Η ι—I 0 rH 0 «Η 0 >1 0 0 ισ •Η 0 0 Ό X 0 >1 X X η 04 X 0 X 0 X C Ό r—1 Λ •Η Ό rH ·—» •Η X 04 X 04 Η 0 ·*Η X X C •Η >1 rH C •Η X 1 ---. C 0 Ό ϋ 0) ο Ό X ο Ό «3 «3 4—1 ο 0 1 •Η Β XI I X C X 1 X >1 X 0 ιη Τ) 0 ιη 0) 0) 0 ιη 1 04 rH 0 0 rH <0 ·. 0 X (0 (Ν rH Ο 0 υ Ί* τΤ 1 ϋ ΊΤ 04 ϋ •=3· 1 (0 X ϋ - 149 - LV 10773 Μ Β Β ο α ο α οΗ ο ο i 1 w * w w Iυ Β ο & ο & Η σ ιη 51· ο μ CΟα φΗ 3 εη η Β Εη S ek Pk οκ £ w Β ο & ο & Η (0> f* «3Ό Ο ο Η Ο Β ο Ο* ο &

ο Ο Ο Η

Ift ν ο Iυ σ σ σι σι σ σ ιη 1# σι σι σι σ σ ο σι σι σ. σ σ ο Ο ο 0 1 1 α) | rH «3· μ ι-Η 01 1 -Η >1 Ή I I μ Ο η α μ 3 μ 1 >1 μ \μ· μ >η ΓΗ α -ιΗ 1 ι-Η •rH 1 ft 1 C ΓΗ >1 C ΓΗ ο rH ο 1 C ο 1 rH 0 >1 Λ 0 0) Α 0 >1 0 c Μ β Α U β C rH ο <0 ο & (0 0 α) Λ Α Ο ο Ο υ μ Λ ο CU 1 Α Ο I Λ α •Η 0 η •Η Ο η •Η ο Ό U I Ό 0 1 Ό μ 1 0 α> 1 rH 0 1 0 ιη 0 ι—1 ιη ΜΗ rH ιη 0 Η Ο •Η 0 ι-Η •*r μ •<3· Ό μ ΜΗ -carbonitrile 150 W2

S o a o a o H σι σι i &c

I

a H σ> ιη μ· νο w * M W Io

Table IV (Cont ļ C3 *w

B ° &4 O ft H W> P' (0 Ό

O B O a o &i H O o H &a

o o o H I ° a o a h ιο σ\ σι νο σι ιη σι σι σ« σι σι σι σι σι σι σι σι o o B O υ φ 1 α) Ε rH 01 1 ι—Η Ο 1 1 Oļ 0 ο μ 01 1 U μ Λ Μ φ 1 Μ φ Η (0 0 1 >1 1—I ΓΊ >. rH Ό Λ μ CM a •Η 1 a •rH 1 a 0 I U ο μ ιη rH 0 ο rH μ U rH μ *. <ϋ ιΗ E >1 •Η 0 >1 •rH -3· V μ 0 C C rH C 0 1 (0 Η μ <1) ο Λ φ Ο rH Λ μ Λ Λ Λ 0 λ Λ >1 a -μ •Η a μ •ιΗ a μ Ν rH I Ό ο <0 Ό ο φ C (0 ια 1 U υ 1 ο υ Φ ---- Λ ιη -μ I ιη -μ ι Λ 1 a •Η η •ιΗ η 1 (Μ rH Ί* C I «3* C I r~i 1 <σ ι η tolyl)pyrrole- - 151 - LV 10773

to B

Ea o H in

0 U

fc 0) H i

w > r·* to V σι σι

og o & o 0« H σι σι σι co n i

I g o a o a h Όi 0 0 §u σι

(N σι

1 ΟΙ 1 0} ιΗ ο Μ VI Ο) 1 a ιΗ I η I 1 a *w<* 1 P >1 <D rH •H P P CM >1 rH 1 >1 0) 1 a •H 1 a •Η (Μ C rH CM c 0 Μ 1 ο 0 <D 1 rH o Μ rH Ρ 0 <1-1 V rH 0 >1 Λ 0 >1 -Η Ε f—1 Ρ •H E c P Γ—1 C C Ο ρ >1 P 0 ω <0 Λ α> 0 νι Μ a P P λ 0 ϋ Λ Λ Λ ιΗ r—i "H Λ a 1 *ιΗ a Ρ •Η >1 ιΗ c •H 0 n σ ο <0 Λ >1 0 Ό P 1 1 G V | Ρ c Λ 1 0 a) ιη π3 1 ιη 0) 0) P ιn iH r—\ *» >1 η ε Λ «3 ·» Λ o Ο 1 η· —· a O U P

152 • w 0 o w a o 3 a o H o 0 o a o a h o M><to W Iu

Table IV (Cont

0 o < a o CO a H wf» «3 fl

oo H o0 Oa o a h

oo H n 0 !S a « a t* o o o r· s Ē a Ξ a 0 o 3 o a o κ a h o> CTi

I

O o o\ σν IT) o co t'' o r- r» O rH •H 1 1 1 >1 A n 0 (N c P 1 rH A 1 <D rH <u 1 m >1 P 0 X! >1 rH d) ir> c <B p a A o t—f *. <u U o o P P •H CM A 1 fH p <D P P 1 a n Ό A 0 £ >1 P rH 0 0 1 0 rH a •H >1 >H P 0) 0) § •H A 1 m c X! 0 0 rH rH 0 Ό 0 (M rH o P rH rH 0 -H D 1 -H 1_1 >1 A d) xi A P P 0 in tj 1 A P 0 ϋ Ό P P 0 *. 1 (—1 P <0 1 •rH •H >1 P O «sr 1 Ο) o rH T3 τί a e - 153 -LV 10773 W 5

0 ° a o o* o H σι σ σ

σι ιο σι Μ S 0 Ο 1 < 04 ο • •Ρ μ 04 Η G O o σ σ 0) Hja (0 M Ό σ σι σ σ

O0 o 04 o 04 H σ σ σ

n§§ &H

o o H I σι σ σ ιη

0 ° 04 O 04 H ιο σ ιη ΓΊ r*H 1 I >3· 1 >1 Γ0 1 1 | o C 1 >—< rH 1 (0 •Η *χ 0 0 0) o 1 >1 rH ιΗ Λ 0 rH Λ 0 A Λ in C >1 1 04 4-) >4 0 rH 04 0 1 0 A 0 rH 1 rH id A O (d 0 A 4J 0 0 <0 (0 0 o υ 0 O 0 04 OJ rH 0 Α Ρ | I o 1 0 O 0 o rH 1 04 1 n -3· rH n rH 0 >1 0 Ό Α (Ν rH 0J I 1 A 1 A 0 X 0 C ο 1 «3 1 0) o o υ a) d) υ f—1 o >1 Ρ •Η rH ο rH rH 0 rH rH •*H A A 04 0 Ό >1 (d u o •H 0 oj o •H υ 4J O 0 1 Α Λ ο 0 0 0 0 0 l •H fl) 0 0 ιη 4-1 α 0 0 -P Λ 0 4J m Ό —· -P 0 *. 0 rH rH >1 1 03 >. •H «X 1 1 •*H υ 0 (0 *0 04 c m 04 c 03 rH c 154 M £

Θ o a o a o H σ\

H ļļ M w x M w I υ i σ\

Table IV (Cont

M

m ĒH s w i

ft H σ> σι M > 10 Ό

o o H

o § o a o ft H i σι σι σ\ ιη ιη σι σ\ σι σι

o o H σ>

o o o H σι σ σι s Ο a Ο ο Ο ο Λ Η ν 1 *_s 1 0 I 0 I γΗ χ γ—1 η 0 >1 I ο X 1 ο U C 0 •Η υ 0) rH ο <U Λ Ό •Η ΐΜ X ι—! X! Vl 1 Ό 0 ϋ X a <0 ιη 1 V ω “Η υ 0 υ *. >ϋ· V rH Ό 1 ν 1 Ί* X •Η 1 ιη 0 η 1 η a Vl η Ό I rH 1 rH ^— Χ> s ο X! α> α) >1 ι rH Η <Ν 3 β ϋ ιΗ ι—i Ν (Ν >1 X 0 ο 1 Ο •Η C 1 C ο r-i 0 Vl a Μ Μ α> Ο α> X >1 g Λ V -Ρ X V X VI X 0 1 1 >1 •Η ι ο a <0 X υ CM a C ιΗ ι—1 ο ο Μ -5-(3,4-dichloro-phenyl)-4-cyano-pyrrole-l-acetate - 155 -LV 10773

W B

§ ° a o a o H o\ σι σι 0 Oa o a h σ> σι s 0 o 1 < a o • A CJ w a H C 0 υ σι ιη σι e 0) H§ M > f» « Ό σι σι σ\ o o σι σι σι o 0 o a o a h σι σι σι ng E-i o o H la σι ιη οο σι σι σι σι 0 o a a

o σι o H 1 0 1 Λ | n IN 1 (0 1 1 o ω 1 υ H -—. u (H ’d* rH Ή 1 rH ·. o 0 V Ό 0 >1 <d P i-l 0) n c 1 u A A rH ι-1 ^— <u Η* o A a <w tx •rH l A *. rH <1> r—1 •H a in a CM Ό Λ e (0 Vl +J 1 o 1 c 0 & A rH •H o k <υ 0) 3 -H X (0 1 >1 C E 0 rH rH 0 Ό o A (0 rH O O rH Ο •Η e 1 A a A O Λ M A U ē in A rH a +J XI υ Α 0 a) (0 1—i I <d 1 H •Η u cd a o m Ό a C co ,5-dichloro-2- (3, -dichlorophenyl) 1-(2-propynyl)pyr ι α> *}· ι k

156 w S g.a σ U h Wi i w X co 0 o a o a h σι νο

Table IV (Cont n

§ &H W i u 0 ο < a ο Μ a Η w > r* a Ό o 0 o a o a h ia

o o o H 0 O a o a h ιη σι σι σ σι σι m σι σι σι σ σι σ σ σ σ α) a ρ •Η ρ 1 (Μ 0) 1 ο C Ψ 1 >1 Ρ 0 | rH Ρ Λ ο | a •Η Ρ αι •Η 0 a ja η C ο rH γΗ 0 Ρ 1 ιΗ ο rH 0 -Ρ ja Ρ Λ 0 >1 Λ ja Ρ •Η ϋ ο Ο £ C Ρ ο Ρ C 1 γΗ 1 0 α> (0 •Η >1 0 Ί3" Λ η Ό Ρ Λ ϋ Ό a Λ 1 υ I ω Λ a 1 | Ρ ο •Η § •Η 0 CN Η ΐΰ β Ό rH 0 Ό μ 1 *» >1 ϋ ο ο 0 1 ο ω C0 C •Η Ρ Ρ Β ιη rH rH ω Τ5 ja Ρ 0 λ ο 1 ja 1 I η >1 U ο Ρ ιη a ιη w a nitrile - 157 - LV 10773 w g

Θ Oa o & o H 0\ Θ o a o a h σι

Μ S ε ο 1 < λ ο « Ρ Ο w a Η C 0 CJ σι

0) H £ &H n> 10 Ό σι σι

o o H σι σι

og o & o 0< H σι σι σι

o o H σι

Ia

o o o H

CM σι

g O a O & H I Ο Λ k 0) rH <0 r—( •—ι α) >1 ϋ 1 >. ο ιΗ C •Η η c Ρ •Η ω Ό 1 α> Ρ Ρ Λ 1 ο Λ >1 -Ρ α «3· ε a a γΗ ι ·. 0 ο rH C ιη η Ό Ρ Ρ >1 0 ι 1 C Λ ο X! Λ 0 Φ α; ρ -Η Η μ Ρ ε ι—1 rH 0 Ό XI Ο) (0 ο Ο ·Η 0 1 ο ε ϋ Ρ Ρ k ε ιη 1 ι Λ k -Ρ ο a Η CM 1 >1 ·Η ο 1 1 04 a c ι rH >1 Cα> & Λ ι ΟΜ I Οεο k Λ I -3· Λ 4-> Οεοk Ο d ι—f <Η Η k -Ρ '—- I ιη ι Ο Λk (C ϋ I η pyrrole-nitrile 158

• θ Ο Μ Λ ο 3 & ο Η o o o

Table IV (Cont. SYSTEMIC LEAF HOPPER 001 mdd C-S SAW ppm 100 Γ

ΙΟ V

o o H o o C\ σ\ o o m o o o «Π σι £ σι σι σι η s

Ο ιη σι σι

θ Ο (¾ ο & Η ο ο

0 0 o 1 0) 0) P P Λ rH rH >—i 1 0 P P S ο •H in iH •H <0 r> c P p 1 Λ c ϋ -— Φ P P o 0 1 I 1 Λ >i •H E -H in n CM & G O ϋ Ό 1 1 1 0 o O P c 1 Ο) <D o p P Λ Λ J3 T* rH r—1 rH E o P P •H 0 >1 o •H 0 rH “H <0 n g r> G p ρ P Λ G U t M — α> P p Λ 0 1 1 0 1 jG >1 •H 1 Ή in n u rsi α c «3· T3 1 1 CM phenylpyrrole- - 159 - LV 10773

w S

0 o a o a o H cn σι η i i 0 o a o a h ιη σι 15 ο u W >* W W I u 0 o a o a h in σι σι 0) Η8 w ► r* λ Ό σι σι σι σ co O 0 O a o a h σι σ σ Ίι o o H i a σι σ σι σ 0 o a o a h σ ι ο 1 ο ι ΟΙ 1 0 •Η ο *·— ι—1 1 u •Η Α 1 1 *—* 0 Ό *4 ιη -—-S rH 1 rH 1 (0 ι ιΗ >1 α) η Α ιη Ο 0 >1 Α ι—1 «· Ο 1 Ē C Α ο (Μ •Η "S* η ο α) <υ >Η 1 Ό •c ι 1 Ιη Α 0 Μ rH c 1 ,__„ 0} α> Λ a >1 >1 >1 2 "i rH ιΗ rH •Η ο X a Ν 0 >1 0 •Η Ό >Η 0 0 C 0 η C VH 1 Ο Α *Η α) 0 (D *Η Α η rH Α 4-> Λ 0 | Α >1 -Η - Α α) •Η ι ο CN3 a a C <Ν Ο —' £ γΗ ι Ί· dibromo-5-(ρ-chlorophenyl)-nitropyrrole i § 160 w g

B o a o Ck o H σι B o a o a h σι

Table IV (Cont.) M JM w W Iu Β ο ·< a ο W a Η w > C- Λ Ό σ> σ σ\ σι σ\ σ\ σι O B o a o a h σ\ σι σι σι σ n

ffl &H

I g ° a o a h oo <η σ

σι σ ο 1 μ I (Μ 1 ιΗ μ r—« 0 I 1 Γ—1 0 1 >1 •Η I 1 rH Λ rH 1 ι—1 XI UD C C ΓΗ 0 >1 μ 1 rH Ο >1 μ 1 0) I 1 Μ G <0 ο >. μ Π (0 0 Χ5 Ο Ο 0) υ μ XI ο α) υ Β a I Ε 3 Λ I ο +J 3 XI I 0 ο rH 0 γ*-Ί a η rH α) rH a η Ό μ U >1 Ρ <4-1 I Λ ε «W .---s 1 C Λ ο X! (1) Λ •Η >1 <υ ω υ >1 -Η >1 0) (1) 3 Η }—i •Ρ rH •Η U X ι-Η rH •Η X μ X rH Γ“{ 0 Ό Λ α) 0 Ό -Ρ 0 0 Η Ό ο -Ρ 0 0 •Η 0 1 Ό Ε P 1 Ν-' χ: μ μ 1 Λ — XI μ μ Β η 1 I P ΙΟ -Ρ μ μ ΙΟ -μ I Η-> μ -μ 0 ·. a rH >1 «. οι α> >1 •Η 0) a ω >1 •Η υ <Ν 1 a 1-· Ε a C 1—> Ε a C 161 LV 10773

w B

s ° (X o 0« o H co ο ο I i i & §

E o CX H σ\ σι μ cou w * W M I u <w

g O R4 2 iX H σ\ σι

Ē 0) H s &H W► t" ΛΌ σι σι σ\

o o H σ\ σι σι

O g 0 & o ft H σι σι σι η Ε

ο σι σι σ\ IIX § g ο (X ο & Η η σι ιη 00 <N >1 1 1 0) X η Q) 1—I 0 1 r—i Ή Λ ω O Μ 1 1 μ ι—( 1 μ μ ιη (X (U 0 0) 0 μ •Η *—ι β μ r—i μ >1 C <3· CSI 0 μ •Η 0 cx 0 1 1 U >η U Ό r—i 1 Λ I—1 0 0 α μ c Λ *—, μ >1 μ 2 ι—» •Η J3 o r—i ί0 Ν ο fH ιΗ C 0 1 >1 0 G ιΗ <Η >1 0 0 C •Μ <ΰ Λ •Η C Λ B Ο) Ό Λ Ο 0) μ O 1 Λ 1 I Η •Ρ £3 (0 U in cu πί Ό IX υ 4,5-dichloro-2-(p-chlorophenyl) -1-(ethoxymethyl) pyrrole-3-carbo-nitrile 162 Μ 0 Ο & Ο a ο γΗ σ I 1 θ ο a ο a η <η σι σ

Μ ίΗ 10 W S 0 O 1 < a o 4-) U W a H σ Cοο δ 0) «Ηa η> t" (0 Ό σι σ Ο ο Η σι σ Ο g Ο a ο a η σ\ σ\ σ ο ο Η ο σ 03 Ε* 0Λa θ ο a ο a η σι σι σ σ ο I .—. 1 Μ η ιΗ η Ό 1 >. I 1 >1 0) C α> OJ 1 Α ι—1 φ /—ι 1 0 1 0 -C 0 o u <Μ Ρ Ο) a ρ αι p o ν-<· Ρ γΗ 0 Ρ ι—1 0 H 1 >1 •Η Ρ >1 -Η »H A Η a ρ Ο a Ρ Ό A υ | 4J rH ο Ρ C O •Η ..—^ ι—1 •Η χ: ρ -Η 9 •H Ό r—1 >1 C ο 4-1 C 0 Ό 1 >1 Α ο ι •Η ο α 1 «ί C 4-1 Α a C X! 0 in Φ (1) Ρ 1 Ρ 0 ·» r» Α >1 (Ū I ιο Λ u '—' a X ϋ CM 1 Ο 4-bromo-2-(ρ-chlorophenyl)-5-(trifluoromethyl)-pyrrole-3-carbo-nitrile 163 - LV 10773 s

S O ft o 04 O H σι «Λ 13ļw * w

Θ O & 2 Q< H η ο sou B 0) Hs

es 04 04 s w

5 O 6 2 04 H W >> (0 Ό

o 0 o 04 o 04 H

Ο ο ο Η ο ο σι σι σι Ο σι σι σι σι σι ιη οο σι σι ο σ« 0 Ο 04 ο ο V0 Ο 04 Η 1 η 1 0 I 1Γ) | >1 0 I 1 η 04 Λ CM | I | <-«* 0 1 04 ιΗ α> Ο 04 ι—1 (C Ο >4 ι—1 ι—i >1 ϋ 0 1 C Ο •r| 1 G •Η ο CM α> 0 0 ιη ω Ό 10 Ό 1 Λ 0 +J I Λ 1 X! C Ο 04 >1 •Η ο 04 «· α) υ ρ 0 ο 04 c 0 Ο ·. γΗ •Η Ο Ο 0 Ο ο ο 0 CM •Η Ό 0 0 0 0 Λ 0 ο I 0 1 0 Λ ιΗ Ρ 0 Λ ΐ“4 γ-Ι Ρ ιη 0 1 λ •Η (0 1 £3 Ο Ή υ μ· υ G Ο η ϋ 0 G Μ* ι 4-dichlorophenyl) pyrrole-l,3-dicar

164w H

e o ft o & o H σ\ οο

Θ O & O Qt H cn W X W W I u

Table XV (Cont n e en

0 O < ft o to & H (0► r* to Ό

o g o Cu O ft H 1 &

Θ O & O Λ H σ\ σι co σι σι σι σι ιη σι σι σι ιη CM I Ο U ο 1 1 W P η •«j· 0 1 rH 1 ,,—, rH Λ CM <(H 0 >1 m >1 Ρ 1 1 rH X 1 w G (0 0 in 0 0) o in 1 ω Ο u 1 Ρ rH rH CNJ Λ 1 0 o Ρ •Η >1 | η rH P >1 Ρ Ό N | o Ο 1 Λ 0 Λ Ρ c r—i P Μ α> <D U rH .—- •Η Ο) rH o Ο ι—f rH •r| Λ rH C 0 <Q >1 rH ι—1 ο •Η Ό υ >1 Ο G N—' .e & Λ Ρ Ρ 1 •Η G Λ Θ l-1 -P υ υ Ρ 4J m Ό ω Ρ 0 1 <u •H •«Η >1 -Η *>. 1 Λ «5 u i—( ε Ό Ό & G Λ 0 σ« σι σι 5-[ρ-(trifluoro-methoxy)pheny1]pyr-role-2,4-dicarbo-nitrile - 165 -LV 10773 w 0 ο Οχ ο Οχ ο Η ο 0 Ο Οχ Ο Οχ Η (Λ ο •μ C Οϋ Μ X Μ W I υ <w 0 ο & Ο Λ Η σ\ σι

<D Η I η> t" (0 Ό σι σ\ σι σι 0 & Ο Οχ Η σι σι οο Η Ο ο Μ 0 ĒC Οχ « Οχ ĒH Ο ο ο α; r- δ g Ρχ 3 Ρχ θ Ο ο Οχ Ο κ Οχ Η 00 σι ο σι ι 1 0 ,— ο 1 Ο ι—1 G 1 »—ι Λ 04 I •Η 1 α> >1 0 1 ο 1 0 Λ G (0 0 U η U Οχ η 0) ϋ U ο — 0 0 Λ | 0 ι-Χ 1 χΗ 0 I Οχ η rH Λ rH Ό Λ 0 04 ο I Α Ο 1 C 0 rH 1 0 0 ο υ Η 3 •Η λ rH 0 ιΗ rH •Η η rH 0 Ό ο >1 γΗ 0 “Η Ό ι >1 0 1 ι Λ Α 0 1 G 0 ΙΛ Οχ 4-1 Ο ο -Ρ ΙΓ> — <D 0 .» 0) •Η ί>1 •Η »*. η A ο χί »--> ε Ό Οχ C "3* 1— Οχ -propynyl)pyrrole 166I Q* σ o σ

Table IV (Cont.)

1 cuoE

I £ 0 ο < a ο Μ a Η r> w > (0 Ό οοΗ ο θ Ο Οι Ο CU Η

O o o o σι σ> <n <n σι σ σ σι σι σ η £

οοο Η σ σι σ ο σ σ

βaa

ο Ο σ ο σ Η φ rH I I r •Η Ή I 1 1 α Ρ Ρ Ρ 0 0 0 >1 -Ρ -Ρ Ρ ρ X I a Η '—' 0 -Ρ Ρ ιη ,—„ C 1 >1 ιΗ •Η <0 I I—ί 0 a X χ: C υ ο >Ί XX 1—J Ο ο 1 1 Ε C Ρ 1 XX •Η ΓΊ 0 ω (0 iri Ρ V 1 1 Ρ XX υ 1 φ C 1 .—^ Φ Φ Λ a 1 0 Ε Β ιΗ r-4 ι—( •Η 0 η Ε 0 0 >1 0 Ή Ό Ρ 1 0 Ρ α ΓΟ C Ρ Ρ I 0 Φ Ρ 0 β φ Ρ -Ρ «ί r—ί γΗ Λ 2 0 1 XX >1 ·Η »» χχ ο 1 ι-Ι υ ιη α a c CN ο Ρ ο <Μ 1 OJ phenyl]pyrrole-dicarbonitrile - 167 - LV 10773 S Ο a ο a ο Η σι σι

Ο Ο a η ο ο ί υ W ίΗ ΜΜ I ϋ 5 Μ 0 ο a ο a η ο ο

Β 0)Η 4 ĒH

Μ > I" Λ V σι σι σι σι σι σι Ο 0 ο a ο a η σι σι σι

Ο ο σι Ēaa § ο ο ο Η ΙΟ σι σι θ ο a ο a η σι σ\ Ο ι ο μ Ο I I Ι3Π I 1 rH γΗ I ιΗ <υ 0) 1 <w <υ >1 ιΗ ιΗ 1 “Η »Η η C 0 •Η a ιΗ Μ 0 α) α) μ μ >1 +J μ ι—ϊ 1 Λ μ +J I C μ •Η ιη a >1 •Η (Ν α) 1 >1 U Ό I 0 a C 1 Λ ΙΛ a μ C ο μ ο ο ο a 1 .ρ—ν» •Η Β e 0 μ Λ β ο I—1 Ι“ί C 0 0 ρΗ 4J μ 0 μ >1 >1 0 α μ Λ •Η <0 μ ο £ Λ Λ 0 Λ U C ϋ Λ ρΗ μ 4J μ 0 1 •Η 1 1 1 Λ (U α) (0 υ η Ό ·<* <Ν 'J· 0 0 0 ϋ 3,4-dibromo-5-(3, 4-dichloropheny1) pyrrole-2-carbo-nitrile 168 co s B O a o a o σι σι ļj U co X co B O a o a h

Table IV (Cont.) co iu £ Β ο < a ο C0 a Η w> X <e Ό σι σι σι σι o B o a o a h σι σι n

S oo HIa σι σι σι σι i ° a a

Ο ο r- Η <u rH iH 1 1 •H X a I M X X 1 1 0 I >1 X 4-) rū 0 n •Η a •H 0) Λ X 1 0 μ B B cu 0 Φ ιΗ X iH 0 o r—i 3 rH <D X Νμι* >1 Λ X ra rH 0 rH Ο 1 XI X O X X -H •Η ιη X «J 3 «3 •H X x Ό Ό 1 I d) O rH Λ X X X B 1 <H α 4-> a •H jļ i O n rH 1 c 0 >1 X 1 X f0 (t3 rH o ο r> e o a> 4-> X X X Β **—· o s rH — I a rH X 0 I X rH o 1 (N rH o «3 υ CM a X in 1 (0 X U - 169 - LV 10773 W 3 I 04

§ ° 04 o 04 H σι w ih w η S S 0 *“«· I < 04 0 • υ Ρ w 04 Η coυ Ēc H i w p- rt Ό σι σι σι

Oo H σ> σι σι

o θ O 04 O 04 H σι σ> ιη ο- <η

oo H η νο I 04

o o o H σι σι σι

g, O4 H 0) -Η α> α) α) rH μ rH rH ιΗ I >1 μ I I •Η I 1 •Η 1 1 •Η ι-Η λ •Η Οι U μ α μ μ -Η μ μ >1 μ C >Ί -μ >1 μ μ >1 μ rH α> Ο 1 04 •Η I α Η -μ ο, •Η Ο Β Λ 41* G 4f G '— ,.—. C μ Ο μ 1 »Η 0 1 ιΗ Ο 1 «Η ο I 01 μ (ΰ Ο >1 Λ 0 >1 Λ ιη >1 Λ 0 ο Β C μ Β C μ 1 £. μ 1 0 I 0 α> ι0 0 (1) π) ιΗ μ <α 03 rH η Ό U λ 0 μ •C ο >1 0) Ό 1 μ I 0) Λ 04 1 Λ Οι 1 rH Β 1 ο -Η § Η ο η •Η ο 03 Ο 0 η ε μ rH 0 Ό μ I ο 1 -μ μ 1 ο μ Ο ο 1 ο α) 1 ο ω I ΟΙ ο Ο) μ s— μ Β ιη ιΗ rH ιη γΗ rH 0 rH Λ 1 μ 0 Λ 0 Λ Ο rH Ο I ιη >1 υ CN 0 μ η υ U 03 <»Η μ I Λ | 1 170 w

g o & o Q< H σ σ M >* W W I υ

Table IV (Cont n § <w W> r» ιβ Ό σι σ

o o H σ\ σ

o g O (¾ o ft H o o H i

o o o H

g O (¾ o H Ό σ> σι σι σ σ σ σ σ Ο Ο θ Ο Ο 1 ιη 1 η I rH 1 Η 1 1 ,— >1 ο 1 « 0) r—i XX Λ 1 *-> rH 0 ιΗ >1 Ρ Ρ CU ι—1 >* Μ Ο φ Ο C φ «5 '— >1 XX 0 Ρ rH ·*— φ β Ο 1 G Ρ Ρ •Η 1 χχ 0 1 Μ Φ α> ιΗ >1 Ρ CM α Ρ η 1 XX β «Μ Λ -Ρ 1 0 ο I ο α •Η -Η Ο Ρ Ρ φ β 0 X Μ (Η G β ο t—( rH ο ρ 0 -Ρ >1 Ο 0 Η <Η Ο Ρ ο XX '—1 XX Λ Ρ XX Η Ρ Λ ιΗ Ρ 1 ρ Ρ Λ υ Ρ Ρ 1 XX (1) ιη α) (0 1 •Η Ρ >1 η- ϋ —' I β ο Η· Λ nitrile - 171 -LV 10773

Μ B S ο ο ft Ο Η ο

σ ο ο ου 0) Η3 μ Μ f» Λ *σ σι ο ο ο Η σι ο

I ο ο ο σι σ>

& Η

σι ο I tu § ο ο ο Η σ ΓΟ Β Ο

ο σ Ο Η ! φ 0 ιΗ Λ •Η (0 Κι α) Κι Λ 1 (0 ν 0 ι—1 +J tu •Η Ο (0 Κι Ο •Η Η Κι γΗ •Η Λ 0 Κι C (0 +> >1 Ό α 3 Κι ο 1 >Η 1 ιΗ γΗ >1 Λ 1 <α Ο (0 «H tu Κι η Λ -Ρ V •Η ιΰ 1 α 1 CM Ό (0 Η α γΗ r-1 01 1 Λ +J >1 •Η <0 I Φ Φ p tu γΗ Ό Λ ο r—1 ιΗ 0 ι—1 η) Ο I •μ (ΰ Κι 0 Ή Ο ιΰ & •μ α) J2 ο Κι Κι Ē α 1 *. ε tu 3 Κι Κ» 0 I ιΗ α (Ν I γΗ ιΗ >1 •μ U ιη Λ I 1 ι—1 (0 1-1 Οι C 172 M Ξ 1 σ\

O

Table IV (Cont.)

§ S ft o ft H B O 0. o ft H w > f» <0 <0

o o H

O

O o\

I

I o o l o o o σι σι a h r>

5 ĒH

σι o 5 6 1¾ §

o o o H σι t"*

B o 0< o Λ H cn o i <o I 1 Λ rH 1 01 1 P, >1 1 rH I 1 M rH r—t o >1 0 Μ -H 1 10 0 Λ jC <0 μ 1 (U μ μ> o μ χ: 0 Ο) γΗ V iH (0 1 (0 0) α 3 rH •Η '·— >1 Λ 01 0 Ε rH γΗ 0 μ 1 Λ α 1 I I (0 ΐμ μ μ) in •μ rH o η rH Ή μ •Η Ό 1 <u <0 μ 1 1 <ο μ >1 C c 0 E o 0) α) 0 Λ μ> Λ 0 3 B O (0 3 rH rH Ε α 1 Λ 0 o μ Λ rH Ο •Η Ο rH (0 ι—1 μ P μ 0 α <*H μ μ μ <0 Λ >τ (0 B Λ 3 rH •H ο μ> Λ '— Λ rH υ 0 1 rH (0 μ >1 -γΗ I 1 rH ο Ή u <· <μ •w μ> α, C η ιη (0 μ) Ό - 173 - LV 10773

TBW ARMYWORMS C-S SYSTEMIC G.COCKROACH

to B 5 O 6 o 04 O rt σι 1|

B O 04 o Οι H

B O 04 O 04 H M > r* ns Ό

o B o 04 o 04 H o o H I 04

B o 04 O 04 H o\ o\ σι σι σι «Η 1 1 0) (0 1 | 0 ο ιΗ Α •Η <Ν 0 ιΗ •Η 04 0 rH 1 «. 0 0 0 rH μ >4 0 ια Ρ 0 μ (0 I rH 1 0 Α ιΗ 0 ·ι-4 (0 Ο *r ο 04 «Η >4 C 1 Λ μ γΗ γΗ •Η 04 0 ιη 04 I (N Α (0 0 Α I rH 0i 1 Β 0 μ γΗ 0 0 (0 1 0) Ρ •Η <0 I >4 « Ε Ο rH 0 η Α <0 rH υ 0 (0 0 0 0 I 04 Α 0 •Η 0 Α 0 0 g ΙΟ ι—1 04 μ Ό Λ 04 Ρ 0 0 <d ιΗ I 1 1 rH rH >4 υ -d* ' ί0 0J η η (0 U-l α dicarbonitrile - 174 - LV 10773 WHAT IS CLAIMED IS?

1. A compound having the formula I structure:

L

fl wherein X is F, Cl, Br, I, or CF3? Y is F, Cl, Br, I, CF3 or CN; W is CN or NC>2 and A is H; alkyl optionally substituted with from one to three halogen atoms, one hydroxy, one c^~c4 alkoxy or one C1“C4 alkylthio, one phenyl optionally substituted with C^-Cj alkyl or C1”C3 alkoxy or with one to three halogen atoms, one phenoxy optionally substituted with one to three halogen atoms or one benzyloxy optionally substituted with one halogen substituent? cj.~C4 carbalkoxymethyl; C3~C4 alkenyl optionally substituted with from one to three halogen atoms? cyano; C3_C4 alkynyl optionally substituted with one halogen atom; di-(C1-C4 alkyl) aminocarbonyl? or C4~cs cycloalkyl-aminocarbonyl? L is H, F, Cl or Br? and M and R are each independently H, alkyl, 175 alkoxy, C1“C3 alkylthio, C^C.^ alkylsulfinyl, ci"C3 alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF3, I^CF^Z, R2CO or NR3R4, and when M and R are on adjacent positions and taken with the carbon atoms to which they are attached they may form a ring in which MR represents the structure: 175

-och2o-, -0CF20- or

Z is S(0)n or 0; Rx is H, F, CHF2, CHFC1, or CF3? R2 is c1'~c3 alkyl/ Cļ-C.^ alkoxy, or NR3R4; R3 is H or alkyl? R4 is H, 0.^-C.j alkyl, or RgCO; Rg is H or C^-C.^ alkyl; and n is an integer of 0, l or 2. 2. A compound according to claim 1 wherein

A is hydrogen or C^-^ alkoxymethyl; W is CN or N02; X and Y are each Cl, CF3, or Br; R if F, Cl, Br, CF3, or OCF-; M is H, F, Cl, or Br; and L is H, or F. 3. A compound according to claim 1, 4,5-di-chloro-2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile; 4,5-dichloro-2- (a,a,a-trifluoro-p-tolyl)pyrrole-3-carb-onitrile; 2,3-dichloro-4-nitro-5-(α,α,α-trifluoro-p--tolyl)pyrrole; 2,3-dichloro-5-(3,4-dichlorophenyl)-4--nitropyrrole; 4-bromo-2-(p-chlorophenyl)-5-(trifluoro-methyl)pyrrole-3-carbonitrile; 3,4-dibromo-5-(3,4--dichlorophenyl)pyrrole-2-carbonitrile; 2,4-dibromo-5--(p-chlorophenyl)pyrrole-3-carbonitrile; 5-(p-chloro-phenyl)-3-(trifluoromethyl)pyrrole-2,4-dicarbonitrile; - 176 - LV 10773 3-bromo-5-(3,4-dichlorophenyl) pyrrole-2,4-dicarboni-trile; 4,5-dichloro-l-(ethoxymethyl)-2-(α,α,α-trifluoro-E-tolyl)pyrrole-3-carbonitrile? 4-bromo--2- (E-chloro-phenyl) -1-(ethoxymethyl) -5-(triflu-oromethyl)pyrrole-3-carbonitrile; and 4-bromo-2-- (3,4-dichlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile. 4. A method for controlling insects, nematodes and acarina comprising: contacting said insects, nematodes and acarina, their breeding grounds, food supply or habitat with an insecticidally, nematicidally and acaricidally effective amount of a compound having the structure:

L

wherein X is H, F, Cl, Br, I, or CF3; Y is F, Cl, Br, I, CF3 or CN; W is CN or NC>2 and A is H; alkyl optionally substituted with from one to three halogen atoms, one hydroxy, one c1’"c4 alkoxy or one c1“c4 alkylthio, one phenyl optionally substituted with alkyl or C1~C3 alkoxy or with one to three halogen atoms, one phenoxy optionally substituted with one to 177 three halogen atoms or one benzyloxy optionally substituted with one halogen substituent; ci“C4 carbalkoxymethyl; C3-C4 alkenyl optionally substituted with from one to three halogen atoms? cyano; C3~C4 alkynyl optionally substituted with one halogen atom; di-fC^-C^ alkyl) aminocarbonyl; or C4~C6 cycloalkyl-aminocarbonyl; L is H, F, C1 or Br; and M and R are each independently H, C^-C3 alkyl, Cx-C3 alkoxy, alkylthio, Cx-C3 alkylsulfinyl, cx“C3 alkylsulfonyl, cyano/ F, Cl, Br, I, nitro, CF3, R^CF^, R2CO or NR3R4, and when M and R are on adjacent positions and taken with the carbon atoms to which they are attached they may form a ring in which MR represents the structure:

-0CH20- , -QCF20- or

Z is S(0)n or 0; R^ is H, F, CHF2, CHFC1, or CF3; R2 is C^-C^ alkyl, C^-C^ alkoxy, or NR3R4; R3 is H or Cļ-C^ alkyl? R4 is H, C^-C3 alkyl, or RgCO; R5 is H or Cļ-C^ alkyl; and n is an integer of 0, l or 2. 5. A method according to claim 4 wherein said compound is: 4.5- dichloro-2-(3,4-dichlorophenyl)pyrrole-3-carbo- nitrile? 4.5- dichloro-2- (a,a,a-trif luoro-p-tolyl) pyrrole-3- carbonitrile; 2,3-dichloro-4-nitro-5- (α,α,α-trifluoro-p-tolyl) pyrrole; - 178 - LV 10773 2.3- dichloro-5-(3,4-dichlorophenyl)-4-nitropyrrole; 4- bromo-2- (E-chlorophenyl) -5- (trifluoromethyl)pyrrole- 3-carbonitrile; 3.4- dibromo-5- (3,4-dichlorophenyl) pyrrole-2-carbo- nitrile ; 2.4- dibromo-5- (β-chloropheny 1) pyrrole-3 -carbonitrile; 5— (p-chlorophenyl)pyrrole-2,4-dicarbonitrile; 3- bromo-5- (3,4-dichlorophenyl) pyrrole-2,4-dicarbo nitrile; 4.5- dichloro-l-(ethoxymethyl) -2-(a,a,a-trifluoro-i>- tolyl)pyrrole-3-carbonitrile; 4- bromo-2- (p-chlorophenyl) -1- (ethoxymethyl) -5- (tri- fluoromethyl) pyrrole-3-carbonitrile; or 4-bromo-2 - (3,4-dichlorophenyl) -5- (trifluoromethyl) pyrrole-3 -carbonitrile. 6. A method for protecting growing plants from attack by insects, nematodes and acarina, comprising applying to the foliage of said plants or to the soil or water in which they are growing; an insecticidally, nematicidally or acaricidally, effective amount of a formula I compound having the structure;

L

wherein X is H, F,

Cl, Br, I, or CF^ī Y is F, Cl, Br, 179 I, CF3 or CN; W is CN or NC>2 and A is H; Cļ-C^ alkyl optionally substituted with from one to three halogen atoms, one hydroxy, one C^-C^ alkoxy or one C^-Cj alkylthio, one phenyl optionally substituted with alkyl or C^-Cj alkoxy or with one to three halogen atoms, one phenoxy optionally substituted with one to three halogen atoms or one benzyloxy optionally substituted with one halogen substituent; ci“C4 carbalkoxymethyl; C3"C4 alkenyl optionally substituted with from one to three halogen atoms; cyano; c3”c4 alkynyl optionally substituted with one halogen; di-(C1~C4 alkyl) aminocarbonyl; or C4~C6 cycloalkylaminocarbonyl; L is H, F, C1 or Br; and M and R are each independently H, C^-Cj alkyl, Cļ-C3 alkoxy, c^-c^ alkylthio, alkylsulfinyl, alkylsul- fonyl, cyano, F, Cl, Br, I, nitro, CF3, R^F^, R2C0 or NR3R4, and when M and R are on adjacent positions and taken with the carbon atoms to which they are attached they may form a ring in which MR represents the structure:

Z is S(0)n or 0; Rx is H, F, CHF2, CHFC1, or CF3; R2 is C^-C^ alkyl, (^-C^ alkoxy, or NR3R4; R3 is H or C^-C^ alkyl; R4 is H, Cļ-C^ alkyl, or RgCO; Rg is H or C^-C.^ alkyl; and n is an integer of 0, 1 or 2. - 180 - LV 10773 7. A method according to claim 6 wherein said compound is: 4.5— dichloro—2-(3,4-dichlorophenyl)pyrrole—3—carbo— nitrile? 4.5- dichloro-2- (α,α,α-trif luoro-]3-tolyl) pyrrole-3- carbonitrile; 2.3- dichloro-4-nitro-5-(a/a,Q-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-carbo- nitrile; 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-dlcarbo- nitrile? 4.5- dichloro-l-(ethoxymethyl)-2-(a,a, a-trifluoro-p- tolyl)pyrrole-3-carbonitrile; 4- broiao-2-(p-chlorophenyl) -l-(ethoxymethyl) -5- (tri- fluoromethyl)pyrrole-3-carbonitrile; or 4-bromo-2-(3,4-dichlorophenyl)-5-(trifluoromethyl) pyrrole-3-carbonitrile. 8. A method according to claim 6 wherein said compound is applied to said plants or the soil in which they are growing, at about 0.125 kg/ha to about 4.0 kg/ha of said formula I compound. 9. A method according to claim 6 wherein said formula I compound is applied to the foliage of said plants or the soil or water in which they are growing, in the form of a liguid composition containing 181 from about 10 ppm to about 10,000 ppm of said formula I compound. 10. A method for the preparation of a novel arylpyrrole compound having the structure:

wherein W. is CN or N02; _L is H, F, C1 or Br; and and R. are each independently Η, C^-C^ alkyl, c1“c3 alkoxy, alkylthio, c1m"c3 alkylsulfinyl/ cļ~c3 alkylsul-fonyl, cyano, F, Cl, Br, I, nitro, CF3, RļCFjZ, R2C0 or NR3R4, and when M and R are on adjacent positions and taken with the carbon atoms to which they are attached they may form a ring in which MR represents the structure:

-0CH20-, -0CF20- or Z is S(0)n or O; Rx is H, F, CHF2, CHFC1, or CF3; R2 is C1-C3 alkyl, C1~C3 alkoxy, or NR3R4; R3 is H or C^-C^ alkyl; R4 is H, C^-C^ alkyl, or RgCO; R5 is H or C^-Cg - 182 - LV 10773 alkyl; and n is an integer of 0, 1 or 2; comprising, reacting a benzoylacetonitrile or a-nitroacetophenone having the structure:

vrtierein L, M, R, and W are as described above with 2,2-di(C1~C4 alkoxy)ethylamine, at an elevated temperatūre, to yield an a-[2,2-di(C1-C4 alkoxy)ethylamino]-/3-cyano-styrene or a-[2,2-di(C1-C4 alkoxy) ethylami.no]-£-nitro-styrene having the structure:

N-CH2CH(C1-C4 alky1)2 H wherein L, M, R, and W are as described above and treating the thus formed a-[2,2-di(Cļ-C4 alkoxy)ethyl-amino]-i0-cyanostyrene or a-[2,2-di (C1~C4 alkoxy)amino]-^-nitrostyrene with a mineral or organic acid to yield the desired arylpyrrole. 11. A method according to claim 10 wherein the reaction of 2,2-di(C1-C4 alkoxy)ethylamine with 183 benzoylacetonitrile or α-nitroacetophenone is conducted neat or in the presence of an inert organic solvent. 12. A method according to claim 10 wherein the a— [2,2—di (C^—alkoxy) ethylamino]-£-cyanostyrene or a—[2,2-di(C^-C^ alkoxy) ethylamino]-£-nitrostyrene is treated with hydrochloric, hydrobromic, or trifluoro-acetic acid to form the arylpyrrole. 13. A process for the preparation of an a-[2,2-di(C^—alkoxy)ethylamino]-j9-cyanostyrene or a-[ 2,2-di (C^-C4 alkoxy) ethylamino] -/9-nitrostyrene repre-sented by the structure:

M

L / u

N-CHpCHCC^H

alky 1) 2 wherein W is CN or NO.; L is H, F, Cl, or Br; M and R are each independently H, ci~C3 alkyl, c1"c3 alkoxy, alkylthio, alkylsulfinyl, C^-C^ alkylsul- fonyl, cyano, F, Cl, Br, I, nitro, CF3, R1CF2Z, R2CO, or NR3R4 and when on adjacent positions and taken together with the carbon atoms to which they are attached M and R may form a ring in which MR represent the structure: - 184 - LV 10773

-OCH20-, -OCFgO- or Z is S(0)n or O; is H, F, CHF2, CHFCl, or CF3; R2 is C^C.^ alkyl, ci“C3 alkoxy, or NR3R4; R3 is H or C^-C^ alkyl? R^ is H, c1“c3 alkyl, or R5CO; R5 is H or Cļ-C^ alkyl; and n is an integer of Ο, 1 or 2; comprising, reacting a benzoylacetonitrile or a-nitroacetophenone having the structure:

wherein L, M, R, and W are as described above with 2,2-diethoxyethylamine, at an elevated temperature, to yield an ο:-(2,2-di (C1~C4 alkoxy) ethylamino) -0-cyanostyrene or a-(2,2-di (C^-C4 alkoxy) ethylamino)-/?-nitrostyrene having the structure:

M

R

\\_/V u

N-CHpCH ( OC·, -Cd a 1 ky 1 ) p H vherein L, M, R, and W are as described above. 185 14. A compound having the structural formula:

185 L

vrtierein W is CN or N02; L is H, Ff Cl, or Br; M and R are each independently H, C1"C3 alkyl, Cļ-C3 alkoxy, alkylthio, C1~C3 alkylsulfinyl, c -c alkylsul-fonyl, cyano, F, Cl, Br, I, nitro, CF3, R1CF2Z, R2CO, or NR3R4 and when on adjacent positions and taken together with the carbon atoms to which they are attached M and R may form a ring in which MR represent the structure:

-och2o-, -OCF2- or Z is S(0)n or 0; R1 is H, F, CHF2, CHFC1, or CF3? R2 is C1~C3 alkyl, C1~C3 alkoxy, or NR3R^; R3 is H or alkyl; R4 is H, C^C.^ alkyl, or RgCO; R5 is H^or Cļ-C3 alkyl; and n is an integer of 0, 1 or 2. 15. A compound according to claim 14 (E) p--chloro-^-[(formylmethyl)amino]cinnamonitrile diethyl acetal; (Z) p-chloro-/9-[ (formylmethyl) amino] -cinnamonitrile diethyl acetal; β-[(formylmethyl)amino]-—3,4-dimethoxycinnamonitrile diethyl acetal; (Z)-methyl p-{2-cyano-l-[(formylmethyl)amino]vinylJbenzoic acid diethyl acetal; 3,4-dichloro-/S [ (formylmethyl) amino]-cinnamonitrile diethyl acetal; (Z)-β-[(formylmethyl)-amino]-p-methylcinnamonitrile diethyl acetal; β- - 186 - LV 10773 -[ (formylmethy1)amino] p-trifluoromethoxycinnamonitrile dimethyl acetal; (E) p-chloro-0“[ (formylmethyl) amino]-cinnamonitirile dimethyl acetal; N-(formylmethyl)-p--methyl-a-(nitromethylene)benzylamine diethyl acetal; N- (formylmethyl) -3,4-dimethoxy-a- (nitromethylene) benzyl-amine diethyl acetal; p-chloro-N-(formylmethyl)-a--(nitromethylene)benzylamine diethyl acetal; N-(formyl-methyl) -o- (nitromethylene) -2-naphthenemethylamine diethyl acetal; methyl p-{a-[(formylmethyl)amino]-β--nitrovinyl)benzoate p-(diethylacetal) ; and p-trifluoro-methyl-N- [ f ormylmethyl-a- (nitromethylene) ] -benzylamine diethyl acetal. 16. A process for the preparation of a compound represented by the structure:

L

wherein W is CN or N02; L is H, F, Cl, or Br;and R are each independently H, c1~c3 alkyl, C^C.^ alkoxy, alkylthio, alkylsulfinyl, C^C.^ alkylsul- fonyl, cyano, F, Cl, Br, I, nitro, CF3, RļCF2Z, R2CO, or NR3R4 and when on adjacent positions and taken together with the carbon atoms to which they are attached M and R may form a ring in which MR represent the structure:

J -0CH20-, -0CF20- or 187 Z is S(0)n or 0; ^ is H, f, CHF2, CHFC1, or CF3; R2 is C^-Cg alkyl, C^-C^ alkoxy, or NR3R4; R3 is H or C^-C^ alkyl; R4 is H, C^-C^ alkyl, or RgCO; Rg is H or Cļ-C.^ alkyl; and n is an integer of 0, 1 or 2; comprising, reacting a benzoylacetonitrile or ο-nitroacetophenone having the structure:

wherein L, M, R, and W are as described above with 2,2-di(C1~C4 alkoxy)ethylamine, at an elevated temperatūre, to give a compound having the structure:

L

vherein L, M, R, and W are as described above. LV 10773

ARYLPYRROLE INSECTICIDAL. ACARICIDAL AND NEMĀTICIDAL AĢENTS AND METHODS FOR THE PREPARATION THEREOF

ĀBSTRACT

This invention is directed to certain novel insecticidal, acaricidal and nematicidal arylpyrrole aģents and a method for controlling insects, acarids and nematodes therevith. The invention also is directed to a method for protecting growing plants from insect, acarid and nematode attack by applying to said plants or the soil in vrhich they are growing, an insecticidally, acaricidally or nematicidally effective amount of a novel arylpyrrole compound. The present invention further is directed to a method -'for the preparation of the arylpyrrole compounds.

Claims (10)

Claims 1. A compound having the structure of the general formula (I) w L X is F, Cl, Br, I or CF-; J Y is F, Cl, Br, I, CF-, or CK; J W is CK or K0o; il A is H; C 1 -C 10 -alkyl, unsubstituted with: 1-3 halogen atoms, one oxo group, one C 1-4 -alkoxy group, one C " -alkylthio group, one phenyl group substituted on its unsubstituted site by C "-, - alkyl or C" -, - 1, which in turn is substituted with 1-3 halogens, one benzyloxy group, which in turn is substituted with 1-3 halogens; C < "-Carbalkoxymethyl | - * t · group; C 1-6 alkenyl substituted in place of 1-3 halogens; di (C1-6alkyl) aminocarbonyl; L is H, F, C1 or Br; M and R are independently of one another H, C < _r > -alkyl, C 1-4 -alkyl-IVIV, C 1-1 -alkylthio, C 1-4 -alkylsulfinyl, < 0 > IJIJ Ilsulfonyl, Oan, F, Cl, Br, I, N, CF 2, V π Vπρ σ r} 2 / y, rr ", · ιτ · η3π4 τ? "+ Vi" in.n t r r, 4i, n. or - itr, at υ «αιπ, if mi u.H h. 3 ι < Γ ο.οαο ui ou oua - vocals, these together with the right carbon atoms to which they are attached can form a straight, in which M and R correspond to the group: or -OCH20-, -OCFOO-? tr? ο · n * 1 * ·% u * p ητxr »ρυτηι * rrp · 4« r * V v / ^ vαχ I χι * n, X 9 vm * o > vm * vx v < a VI * -5 | x and f7 ίη c / r 4 Xj XI * O "* ii d2, ▼ * · r XI * V · rv f R3 and H, respectively. n5 4 ^ tl »^ XI * 11 ΥΛΧ ^ - alkylgroup, C ^ · ^ —alkoxy & pi 9 or gpupa — NR R 9 R ^ ip H 9 9« mm «« Μ in _ r-vn * 11 * 4 7 v * _ ^ —λχλχΙ ^ α * up «a l" " n is an integer B of 0, 1 or 2. 2. A compound as claimed in claim 1 wherein: A is H or C '- alkoxy; W is CN or KO, -; X and Y independently * f C- are Cl, CF, or Br; R is H, F, Cl, Br, CF- or 0CF-; J J J M is H, F, Cl or Br; L is H or F. 2 LV 10773 3 (I) wherein X is F, Cl, Br, I or CF; Y is F, Cl, Br, I, CF, or CN; W is CK or K0o; < 1 A and H; C " -alkyl substituted in the indefinite position by: " l " * t 1 to 3 halogen atoms, one oxo group, one C < An "-alkoxy" * + group, one C < _ * alkylthio group, one phenyl group which in turn is substituted with C < , -alkyl or C ', - | - U 1 -Y-alkoxy or 1-3 halogen atoms, one phenoxy group which in turn is substituted with 1-3 halogens, one benzyloxy group which in turn is substituted with 1-3 halogens; C 'A-carbalkoxymethyl group; C 1-4 alkenyl substituted in place of 1-3 halogens; di (O-alkyl) aminocarbonyl; L is H, F, Cl or Br; M and R independently of one another are H, C ', -alkyl, O *, -alkoxy, C 1-6 alkylthio, C 0 -C 10 alkylsulfinyl, O, -, - alk- | - J I J | " J sulphonyl, oyan, F, Cl, Br, I, nitro, CF ^, group 4 3. The compound of claim 1, namely: 4,5-Dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile, 4,5-dichloro-2- (a, a, a-trifluoroethyl) p-tolyl) pyrrole-3-carbonitrile, 2,3-dihydro-4-nitro-5- (α, α, α-trifluoro-p-tolyl) pyrrole, 2,3-dihydro-4-nitro-5- (3,4-dihydro-p-tolyl) pyrrole; dichlorophenyl) pyrroleB, 4-bromo-2- (p-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile, 3,4-dibromo-5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile, - 2; 4-Dibromo-5- (p-chloro) pyrrole-3-carbomnyl, 5- (p-chlorophenyl) -3-trifluoromethylpyrrole-2,4-dicarbonitrile, 3-bromo-5- (3,4-dinitrofenyl) ) pyrrole-2,4-dicarbonitrile, - 4,5-dichloro-1-ethoxymethyl-2- (a, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile, 4-bromo-2- (p-Chlorophenyl) -1-ethoxymethyl-5-trifluoromethylpyrrole-3-carbonitrile, 4-bromo-2- (3,4-dichlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile. 4. A panacea for insect, mite and nematode differentiation, characterized in that said insects, mites and nematodes, their breeding sites or places of stay are in contact with an effective amount of compound of formula (I) against insects, mites or nematodes 5 wherein: X is F, 01, Br, I or CF2; Y is F, Cl, Br, I, CF, or CN; ΰ W is CK or K02; A is H; C 1-10 -alkyl, unsubstituted, substituted with: 1-3 halogen atoms, one oxo group, one C "-alkoxy-1 * t group, one C 1-10 -alkylthio group, one phenyl group which in turn is undefined replaced by C '-, - alkyl or C' I - > J alkoxy or 1-3 halogen atoms, one phenoxy group which in turn is substituted with 1-3 halogens, one benzyl group which in turn is unsubstituted »5 * ^ 4 · λ rv «* 1 _ Ο m 1 a ^ A A i i j j j j j j j 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 oul oul oul 3 3 3 3 C 1-4 alkenyl substituted in place of 1-3 halogens; di (C 1-4 alkyl) aminocarbonyl; L is H, F, Cl or Br; M and R are independently of one another H, C 1 -C 6 alkyl, C 0 -C 10 alkoxy, C 1 -, - alkylthio, C ", alkylsulfinyl, C < , -alkylsulphonyl, olan, F, Cl, Br, I, nitro, CF- ,, group J) 2nrv and 3 · τ) 4 + _ Ϊλ 1f ·% · * 1ΛT3V n (" 4 ^ x ur j χ χ λ r λ rv > pxc & .tri rv aui uo ^ o AJx < ar ^ uto, they can form with the right carbon atoms to which they are added in which M and R correspond to the group: or -0CHn0-, -OCFoO- cc 1 o < 7 * · », ρ / η ττ ^ i n. ai, v, a, i, v, a, u, v, a, u, u u, and u 11, u u η ^ · π, ίι ~ η - - rn 3n 4., -, 3; "tj -3- < aj.n.xxiļiu.t" < a, '-m_ < 3 — λαγ > λ- > λοα £ 1 u. , va \ iw, ii - 11, I n n iv4i n4; tr η 1 n5nr. tj5 i uM -3 - t3A / VAAiK, lU.ycl, Λ AI '11, U * -3 AAIVAAgl, 3V dll I _Λ_ί, I AI 11V ΛΑI-J6 LV 10773 C <_-3-alkyl; n is integer at 0, 1 or 2. 5. LV 10773 C 1-10 alkyl; n is an integer of 0, 1 or 2. The method of claim 4, wherein one of the compounds is: - 4,5-Dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile , 4,5-Dichloro-2 (', < *, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile, 2,3-dichloro-4-nitro-5- (° *, α, «-trif luor p-tolyl) pyrrole, 2,3-dichloro-4-nitro-5- (3,4-dichlorophenyl) pyrrole, 4-bromo-2- (p-chlorophenyl) -5-trifluoromethylpyrrole-3-carbonitrile, 3.4- dibromo-5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile, 2,4-dibromo-5- (p-chlorophenyl) pyrrole-3-carbonitrile, - 5- (p-chlorophenyl) -3-trifluoromethylpyrrole -2,4-Dicarbonitrile, 3-Bromo-5- (3,4-dinitrophenyl) pyrrole-2,4-dicarbonitrile, 4.5-Dichloro-1-ethoxymethyl-2- (a, af a-trifluoro-p-tolyl) ) pyrrole-3-carbonitrile, 4-bromo-2- (p-chlorophenyl) -1-ethoxymethyl-5-trifluoromethylpyrrole-3-carbonitrile, 4-bromo-2- (3,4-dichlorophenyl) ) -5-trifluoromethylpyrrole-3-carbonitrile. 6. A method for protecting crops from insek L characterized by the fact that the above-ground parts of said plants, the soil or the water in which they grow, infuse insecticide, moth or nematode effective amount of compound of formula (I). 7. A fanamen of claim 6, wherein said compound is: 4.5-Dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonyl, 4.5-dihydro-2- (a, a, α) Trifluoro-p-tolyl) pyrrole-3-carbonyl, 2,3-dichloro-4-nitro-5 (?,?,? - trifluoro-p-tolyl) buyer, 2,3-dichloro-4-nitro-5- (3,4-Dichlorophenyl) pyrrole, β-xuu * iuc uxxpxi 9'-4'-4'-dibromo-5- (3,4-dichlorophenyl) ) pyrrole-2-carbonitrile, 2,4-dihydro-5- (p-chlorophenyl) pyrrole-3-carbonitrile, 5- (p-chlorophenyl) -3-trifluoromethylpyrrole-2,4-dicarbone, t bromo-5- (3,4-dimtrophenyl) pyrrole-4,5-dihydro-1-ethoxymethyl-2, 2,4-dicarbomyl trilium, trifluoro-p-tolyl) pyrrole-3-one V * V Λ NitrileB, 4-bromo-2- (p-chlorophenyl) -1-ethoxymethyl-5-trifluoromethylpyrrole-3-carbonitrileB, 4-bromo-2- (3,4-dichlorophenyl) -5-trifluoromethylpyrrole-3 carbonitrile. 8. The method of claim 6, wherein said compound of formula (I) is applied to said plants or the soil in which they are grown at a dose of from about 0.125 kg / ha to 4.0 kg / ha. 9. A phantom peo 6 of XA lr x P ο o «around said compound of formula (I) being applied to a surface portion of said plant, or to a soil or water which they grow, in a liquid composite form, in the form of a 7-ohm; containing from about 10 to 10,000 parts per million of said compound of formula (I). A process for preparing a novel arylpyrrole compound having a structure of the formula (I). (W is CK or K0n; C-L is H, F, C1 or Br; M and R are independently of one another H, C1-6 alkyl, C0-O-alkoxy , C 1-10 alkylthio, C 1-6 alkylsulfinyl, C 1 -C 6 alkyl 1 '1' J 1 - ylBulfonyl, olan, F, Cl, Br, I, nitro, O, O, J Ti r \ t ntp * rs2 rv OVJ-s / rt3 > 4 i / • itn r fxc o < a m T5 ΙΛ 4 · rs P «VI 1Π uxx rv ο χ lt lt lt oklī oklī χχχ ι ν χ χ oklī oklī they may, together with the right carbon atoms to which they are attached, form a sphere in which M and R correspond to the group: or -OCH ^ O-, -OCF ^ O- 7 i. m x XX * o v dA WJ nu * -5 ~ axrLXX ^ X Lx ^ «a» 1 XX * l nl 1 mm «» λ * kjh -5 "caxrk.xx ^ i * u.pd , HUP ^ 11 ^ * 1 mmi * > eg »« i rn3rj4. N3 * XJ —.and rv, rv XX * AI n5 * ur * x * x * XX ναχ Π * j-Μ ΙΊ1 j ί ί ί ί ^ ^ ^ ^ ^ Λ ι Λ Λ Λ ι ι 1 1 ya ya ya ya v v v v v v 1 1 1, 1 IJ 8 LV 10773 C ^--alkyl; 1 or 2, characterized in that benzoylacetonitrile or «-nitrooetophenone of the general formula f is realized. wherein L, M, R and W are as defined above, with 2,2-di- (C 1 -C 6 alkoxy-ethylamine to give a- [2,2-di- (C "-alkoxy) -ethylamino] -β -olane-styrene or α- [2,2-cLi (C1-6-alkoxy) ethylamino] -fS-nitrostyrene, which is converted into the desired arylpyrrole by mineral acid or organic acid. 11. The method of claim 10, wherein said 2,2-di- (Ο *-alkoxy) ethylamine is reacted with a benzoyl acetonitrile or α-nitrooethophenone in a non-solvent or inert organic solvent. 12. A process as claimed in claim 10, wherein: - [2,2-di (C1-6-alkoxy) ethylamino] - [(3-ol) styrene] or "- [2,2-di (C1-4alkoxy) ) Ethylamino] - N - nitrostyrene is treated with hydrochloric acid, hydrobromic acid or trifluoroacetic acid to give arylpyrrole. 13. Method of a- [2,2-di (β, - alkoxy) ethylamino] -N - (o) styrene or «- [2,2-di (C1-6-alkoxy) ethylamino] - N - nitrostyrene 1 't with the general formula 9 where: π is CK or ROo; L is H, F, C1 or Br; M and R are independently of one another H, C '-, - alkyl, C', -alkyl ', J', O, C-, alkylthio, C '-alkylsulfinyl, C', - alk-, n-ylsulfonyl, oan, F, Cl, Br, I, nitro, CF ,, Tjlpp π · π2ηη! Trr3r > 4 ,, ν, η λ vi ļ n yj, v ru - " ΐιη λ, j ± c utain. jd m and n. auvuac χ / ioauo dw tt l * 4 * λ λ y% λ λ λ! rl γν 4 vvjjxx χ? υotσ rvL / p < ΓΓ χχχχ ννηιχ lt ltΐΐΐΐΐΐ D D D * * * * * * * * * mm mm mm mm mm mm mm mmcc%%%%%%%%%%% »» »· · * * V where M and R correspond to the group: -OCH-, 0-, -OCFoO- or 1o ut? ntrv nii ^ ni ητ * · nt 4 «, χχ · u u u χχ ii ii 9 9 9 9 9 υ χΐ r ,, ,, ,, ,, XX XX XX XX XX XX XX XX XX XX XX XX XX XX XX XX 1 ; 11 ^ ^^ τ »γ > X < > mi 3 ^ 4 ^ 3 4 M TJ 4 U4 ^ -ΛΧΛυΛΟΧ ^ Χ'α ^ Λ, V dX & X * lXyd ~ iVC Λ J Π ΑΧ ji, * * 0 ^ r ^ llri 1 · D * ^ iw XX Π / sT * * * »» «4 T5 3 4 T« XJ * »Λ * vm-o ^ xxvxx ^ x * Lxpta 9 i xi * xx ji ^ * i x-x ū ū x x »ū ū ν χ χ χ χ χ χ υ v v v χ χ χ χ χχ χ 11 1 Λ »ν ^»% Λ · m «« < * p > for the production of silyloetonitrile, characterized in that the vinyl reaction between the benzo or α-nitrooetophenone of formula L \ t 10 LV 10773 in which L, M, R and Ϊ have the meanings already mentioned, and 2,2- < o > (C 1-4 -alkoxy) ethylamine at elevated temperature to give a- [2,2-di (C ") "-Alkoxy) ethylamino] -CH-olanstyrene or i-* α- [2.2-di (C 1-4 alkoxy) ethylamino] -t-nitrostyrene of formula 9 |" * i · L μ WCH2C-w (0C >) 4'aL ^, J2. where L, M, R and W are already mentioned. with a structural formula Λ λ l * t. wherein: YJ is CS or H0o; C L is H, F, C 1 or Br; M and R are independently of one another H, C ', -alkyl, C 1-4, alkyloxy, C', -alkylthio, C '-, - alkylsulfonyl, C', -alk- | · '0 ij ι · “ι5 ilsulfonyl, olan, F, Cl, Br, I, nitro, CF, group JR ^ CFoZ, R2C0, or -liR3R4, and when M and R are adjacent, they are taken together with straight carbon atoms, to which they are attached may form a vertex in which M and R correspond to the group: 11 -OCHnO-, -OCFoO- or τ '^ e / n \ t π 1 i "u r» ntrp buttons i np. tj2 · "XX U XI · 1 OR W, I XX · XX, X ', VXXX'n > V dx UX · o, i XX · Π 1 nwt nn Π «λ * nv« i ^ i ^ Π ^ {{n U ^^ _ T-nixr > ax £, iLXljca - x x η. , η. χχ · x x, I J l * " J ^ ^ Π # · ß 1 ^ nn * Ό ^ 4 m XI Π f »Rr > 4 Γ) 5 / V · T) ^ 4 m XI rrrs 4 U ^ _2 “clX'n " LXC & A * uPtfl       < · 3 ~ ΛΧ4ΥΧΧ £ Α * ΙΧ] -» & lt Λ V dx X OU) Λ XI * XA Veax C? - alkyl; n is an integer of 0, 1 or 2. The compound of Claim 14, namely: (E) -p-Chloro-fS- (formylmethylamino) cinnamic Acid Nitrile Diethyloethal, i * 7 \ t T > 1 / “%« f ^ »» »* > < 1 w ļ 4 1 f μ 4 μ λ 1 ^^ m 5 1 VK V 4 4 x τι * 1 ri / 3 ^ n ^ 4 times let T nv U 1! _LUi'-f · '- \ t «^ 1-11ΙΧΧΐα · 3ϋΧΧΛ1ΐαΐ1 ^ y ΛΛΙΑΟ + ΟΙΥΛΧ ^ Ο ΑΑΧ lii-χχΰ Clxc; 0Xi3U6 1 / U1D (Z} - ['- (xormilm8tilaiiu.no) —3,4-Dimethoxicane + Ecbitrate iA' «4 * 4 1 πλλ ^ λΙ n U.1C 0XX * 1UC ϋ ^ ΧΟl (Z) - (d-(2-cyano-1-formylmethylaminovinyl) benzoic acid methyl ester diethyloetal, (Z) -3,4-dichloro-N- (formylmethylamino) cinnamic acid nitrile diethyloetal, (Z) -phy- (formylmethylamino) -p-methylcinnamic acid nitrile diethyloethal, (Z) -Fi- (formylmethylamino) -p-trifluoromethylcinnamic acid nitrile dimethylacetal, (Z) -p-chloro- [3- (formylmethylamino) cinnamic acid nitrile dimethylacetal, N- (formylmethyl) -p-methyl-α- (nitromethylene) benzylamine diethyloethal K- (formylmethyl) -3,4-dimethoxy -? - (nitromethylene) benzylamine diethyl oetal, p-chloro-N- (formylmethyl) -? - (nitromethylene) benzylamine diethyl oetal, 12 LV 10773 H- (formylmethyl) < * - (Nitromethylene) -2-Naphthylmethylamine diethylacetal B p- (α-formylmethylamino-N-nitpovinylbenzoic acid methyl ether ether-diethyl-ethylB, p-trinoron-R-ethyl-K-fornmethyl-α-nitromethylene-benzylinine) A diethylacetalB. * C IU where: TV is CK or NO2; L is H, F, C1 or Br; M and R are independently of one another H, C 1, C 1-, alkyl, C 1 -, - alkyloxy, C 1 -, - alkylthio, C 1-4 alkylsulphinyl. ; " 0 i-J sulphonyl, oan, F, Cl, Br, I, nitro, CF ^, group rjlnr r r i2 n ~~ 'ττπ3 · η4 · 4 · ^^ V /, .η ι ογ mij, r ,υ, ναι ~ itrv ι, px < = uciiu, jd iu and riii '< _ / u.do i / iariuo ο να Υ' - 'ΓνΧΧ, 0X0 Λ ^, μΑ iAI' ΟΧΛΧΑ 0 · £ Χ0Λ + Α A 0UUixOUi j ^ XC IVLUUOil] 0X0 piCVXC 'note, you can create a vertex in which M and R correspond to the group: -0CH' 0-, -OCFnO- or Cc. * n »7 i-r% c ^ n n * u o ntn? nuc * m *, Λ, no · x x x x ū ū v v «χ 9 9 v v v v v 9 um * n * wixx 'υι νοχ ox * ^ · rt xx * XX CJ η Τ' 1 τί 1 r «T» '1 τ τ Π Τ' 1 st «1rn '/« τνι ^ ηη ττ « ί λ ι λ λ T T T 7 7 7 7 7 t t XX ί ί U U 7 7 XX XX XX XX XX XX XX XX XX * XI j ί JIJ η «ιΐτίι τττ» " τά · tj ^ ίη υ η τΊΐτίι «« ν »t t% ts d5 / see · 4» * υ τ »λϊ T - '' 1_'D '" cXXXVXX ^ XL.Lyd | i XX * XX 9 U * o «aXi XX & I'U.pA V U VU, Λ XX * χχ ναχ I Ί 13 C-O-alkyl; n is an integer of 0, 1, or 2 f J, characterized in that the compound Penzoylacetonitrile or '- nitrooetetophenone of the formula wherein the meanings of L, M, R and V are already mentioned, elevated temperatures of reaction with 2,2-µL- (C * (* -alkoxy) ethylamine to give the desired compound of formula L where L, M, R and W are already mentioned. 14