DK173853B1 - 2,3,4,5-Tetra-substituted pyrroles, process for their preparation, alpha, beta-disubstituted styrenes for use in the practice, and the use of pyrroles as insecticides, acaricides and nematodicides - Google Patents

Description

in DK 173853 B1

The present invention relates to certain novel 2,3,4,5-tetrasubstituted pyrrole compounds which are very effective insecticidal, acaricidal and nematodicidal agents and are useful for controlling harmful insects, mites and nematodes and for protecting agricultural crops, both growing and harvesting, against the destruction of these pests. The present invention also relates to a process for preparing the arylpyrrole compounds.

The novel 2,3,4,5-tetrasubstituted pyrrole compounds of the invention have the formula I:

R

wherein X is F, Cl, Br, I or CF3; Y is F, Cl, Br, I, CF 3 or CN; W is CN or NO3 and A is H; C 2 -C 4 alkyl optionally substituted with from one to three halogen atoms, one hydroxy group, one C 1-4 alkoxy group or one C 1 -C 4 alkylthio group, one phenyl group optionally substituted with C 1 -C 3 alkyl or C 2 C3-alkoxy or with one to three halogen atoms, one phenoxy group optionally substituted with one to three halogen atoms or one benzyloxy group optionally substituted with one halogen substituent; C3-C4 alkenyl optionally substituted with from one to three halogen atoms; cyano; C3-C4 alkynyl optionally substituted with one halogen atom; di- (C 2 -C 4 alkyl) aminocarbonyl; or C4-C8 cycloalkylaminocarbonyl; L is H, F, Cl or Br; and M and R are each H, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 2 -C 3 -2 B 17 alkylthio, C 1 -C 3 alkylsulfinyl, C 1 -C 3 alkylsulfonyl, cyano, F, Cl , Br, I, nitro, CF3, R1CF2Z, R2CO or NR3R4, and when M and R are at adjacent positions, together with the 5 carbonate to which they are attached, they can form a ring in which MRI is the structure: -0CH20-, -0CF2O or Z is S (O) n or 0; R 1 is H, F, CHF 2, CHFC 1 or CF 3; R 2 is C 1 -C 3 alkyl, C 1 -C 3 alkoxy or NR 3 R 4, R 3 is H or alkyl; R 4 is H, C 1 -C 3 alkyl or R 6 CO; R5 is H or ¢ 4-03 alkyl; and n is an integer 0, 1 or 2.

The term "C ^-Cg cycloalkylaminocarbonyl" is a C4-Cg cycloalkylamino group linked directly to the carbonyl group through the nitrogen atom.

A preferred group of novel aryl pyrroles of the present invention is illustrated by the formula II:

R

wherein A, L, M, R, W, X and Y have the above meanings.

Another preferred group of novel aryl pyrols of the invention is represented by the formula III: x y / n (III) 35 wherein A, L, M, R, W, X and Y have the meanings given above.

3 DK 173853 B1

A third group of preferred aryl pyrroles according to the invention are represented by the formula IV: ....

10 wherein A, L, M, R, W, X and Y have the above meanings.

A further group of preferred aryl pyrrols according to the invention are represented by the formula V:. νά: Y 2 N 7 * fl wherein A, L, M, R, W, X and Y have the above meanings, and again other preferred aryl pyrroles of the invention are represented by formulas VI and VII:

, γ H U H

fl (VI) (VII) wherein A, L, M, R, W, X and Y have the meanings given above.

Preferred aryl pyrroles of formula 1 according to the invention are those wherein A is hydrogen or C 1 -C 6 alkoxy-methyl; W is CN or NO2; L is hydrogen or F; X and Y are each C1, Br or CF3; M is H, F, Cl or Br; and R is F, Cl, Br, CF3 or OCF3.

Preferred compounds of formula II which are particularly effective as insecticidal, acaricidal and / or nematodicidal agents are those in which A is hydrogen or C 1 -C 4 alkoxy-methyl; 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 Cl, Br or CF3.

Other compounds of formula II which are highly effective as insecticidal, acaricidal and / or nematodicidal agents are those wherein A is hydrogen or C 1 -C 4 alkoxy-methyl; L is hydrogen; M is hydrogen, F, Cl or Br; R is F, Cl, Br, CF3 or OCF3; W is NO 2 and X and Y are each Cl, Br or CF 3.

Examples of some of the insecticide, acaricide and nematodicidal aryl pyrrols disclosed herein are: 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile; 4,5-dichloro-2 - [p- (trifluoromethoxy) phenyl] pyrrole-3-carbonitrile; 4-bromo-5-chloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile; 5-bromo-4-chloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile; 4,5-dichloro-2- (o-chlorophenyl) pyrrole-3-carbonitrile; 2- (p-bromophenyl) -4,5-dichlorpyrrol-3-carbonitrile; 4,5-dichloro-2- (ot, ot, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile; 4,5-dibromo-2- (ot, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitrile; 4,5-dibromo-2- (o-chlorophenyl) pyrrole-3-carbonitrile; 4,5-dibromo-2- (p-chlorophenyl) pyrrole-3-carbonitrile; 4,5-dichloro-2- (2,4-dichlorophenyl) pyrrole-3-carbonitrile; , 4,5-dibromo-2- (2,4-dichlorophenyl) pyrrole-3-carbonitrile; 2,3-di bromo-4-nitro-5-phenylpyrrole; 2- (p-bromophenyl) -4,5-dichloro-3-nitropyrrole; 2,3-dichloro-4-nitro-5- (a, at, cu-trifluoro-p-tolyl) pyrrole; DK-173853 B1 4.5-dichloro-2- (m-chlorophenyl) pyrrole-3-carbonitrile; 4,5-dichloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile; 4,5-dichloro-2-phenylpyrrole-3-carbonitrile; 2,3-dichloro-5- (p-chlorophenyl) -4-nitropyrrole; 2-bromo-3-chloro-5- (p-chlorophenyl) -4-nitropyrrole; 2,3-dibromo-5- (p-chlorophenyl) -4-nitropyrrole; 2,3-dichloro-4-nitro-5-phenylpyrrole; 3-bromo-2-chloro-4-nitro-5- (a, a, a-trifluoro p -tolyl) pyrrole; 5-chloro-2- (3,4-dichlorophenyl) -1- (methoxymethyl) -4- (trifluoromethyl) pyrrole-3-carbonitrile; 5-bromo-2- (m-fluorophenyl) -3-nitro-4- (trifluoromethyl) pyrrole; 3-bromo-5- (m-fluorophenyl) -4-nitro-2- (trifluoromethyl) pyrrole; 4- bromo-2- (p-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; 4-chloro-2- (3,5-dichloro-4-methylphenyl) -3-nitro-5- (trifluoro methyl) pyrrole; 2- (2-bromo-4-chlorophenyl) -1- (2-propynyl) -4,5-bis (trifluoro-methyl) pyrrole-3-carbonitrile; 2- (2,5-difluorophenyl) -3-nitro-4,5-bis- (trifluoromethyl) pyrrole; 3-bromo-5- (p-chlorophenyl) pyrrole-2,4-dicarbonitrile; 4- bromo-2- (p-chlorophenyl) -5-nitropyrrole-3-carbonitrile; 5- (p-methylthiophenyl) -3- (trifluoromethyl) pyrrole-2,4-dicarbonitrile; 1- allyl-4-nitro-5- [α, α, α -ι-trifluoro-p-tolyl) -3- (trifluoromethyl) pyrrole-2-carbonitrile; 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-bromo-1- (p-chlorophenoxy) methyl-5- (p-chlorophenyl) -3-nitropyrrole; 2,4-dibromo-5-phenylpyrrole-3-carbonitrile; 5- (p-bromophenyl) -2,4-dichloro-3-nitropyrrole; 2- bromo-5- (3-bromo-4-methylphenyl) -1- (n-propyloxy) methyl-4- (trifluoromethyl) pyrrole-3-carbonitrile; 2-bromo-5- (p-chlorophenyl) -3-nitro-4- (trifluoromethyl) pyrrole; 6-Chloro-5- (S-napthyl) -2- (trifluoromethyl) pyrrole-3-carbonitrile; 3- bromo-2- (3,4-dichlorophenyl) -4-nitro-5- (trifluoromethyl) pyrrole; 5- (2-bromo-5-ethylphenyl) -2,4-bis (trifluoromethyl) pyrrole-3-5 carbonitrile; 1- ethyl-2- (p-fluorophenyl) -4-nitro-3,5-bis- (trifluoromethyl) pyrrole; 4-chloro-5- (4-chloro-2-methylphenyl) pyrrole-2,3-dicarbonitrile; 4- bromo-5- (3,4-dibromophenyl) -2-nitropyrrole-3-carbonitrile; 1- ((1-methoxy) ethyl] -5- (p-chlorophenyl) -4- (trifluoromethyl) pyrrole-2,3-dicarbonitrile; 5- (p-isopropylphenyl) -2-nitro-4- (trifluoromethyl) ) pyrrole-3-carbonitrile; 2-bromo-5-phenylpyrrole-3,4-dicarbonitrile; 5-chloro-2- (3,4-dibromophenyl) -1-methyl-4-nitropyrrole-3-carbonitrile; (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3,4-dicarbonitrile; 2- (o-bromophenyl) -4-nitro-5- (trifluoromethyl) pyrrole-3-carbonitrile; dibromo-5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile; 2- (3-chloro-4-cyanophenyl) -5-nitro-3,4-dichloropyrrole; 3-chloro-1- (p-methoxybenzyl) - 5- (3,4-difluorophenyl) -4- (trifluoromethyl) pyrrole-2-carbonitrile; 3-bromo-5- (3,5-dibromo-p-tolyl) -2-nitro-4- (trifluoromethyl) pyrrole; 4-chloro-5- (m-isopropylphenyl) -3- (trifluoromethyl) pyrrole-2-carbonitrile; 5- (p-bromophenyl) -1-isopropyl-3,4-bis (trifluoromethyl) 2- (3,4-dichloro-4-methylthio) -5-nitro-3,4-bis (trifluoromethyl) pyrrole; 4-chloro-1-methoxymethyl-5- (p-bromophenyl) pyrrole-2-carboxytrile; ) pyrrole-2,3-dicarboxylic bonitril; 4-bromo-5- (2,6-dichloro-4-methylthio) -2-nitropyrrole-3-carbonitrile; B1 1- [(p-bromophenoxy) methyl-5- (m-trifluoromethyl) -4- (trifluoromethyl) pyrrole-2,3-dicarbonitrile; 5- (α-naphthyl) -2-nitro-4- (trifluoromethyl) pyrrole-3-carbonitrile; 3-bromo-5- (3,4-dichlorophenyl) pyrrole-2,4-dicarbonitrile; 4- bromo-2- (3,4-dichlorophenyl) -5-nitropyrrole-3-carbonitrile; 5- (3,4-dibromophenyl) -3- (trifluoromethyl) pyrrole-2,4-dicarbonitrile; 2- (m-chlorophenyl) -5-nitro-4- (trifluoromethyl) pyrrole-3-carbonitrile; 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- (trifluoromethyl) pyrrole-2-carbonitrile; 2-chloro-5-nitro-3- (trifluoromethyl) -4- (m-trifluoromethylphenyl) pyrrole; 4-bromo-3- (p-chlorophenyl) -1-methylthiomethyl-5- (trifluoromethyl) pyrrol-2-carbonyl tri1; 3- (4-bromo-3-cyanophenyl) -4-chloro-2-nitro-5- (trifluoromethyl) -2-pyrrole; 3- (2,3-dichlorophenyl) -2-nitro-4,5-bis (trifluoromethyl) pyrrole; 3-bromo-4- (3,5-dichloro-4-methylthiophenyl) pyrrole-2,5-dicarbonitrile; 4- (m-bromophenyl) -3-chloro-5-nitropyrrole-2-carbonitrile; 3- (p-acetamidophenyl) -4- (trifluoromethyl) pyrrole-2,5-dicarbonitrile; 4- (tn-bromophenyl) -5-nitro-3- (trifluoromethyl) pyrrole-2-carbonitrile; 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; 4- (p-chlorophenyl) -3,5-dichloro-1- (2,3,3-trifluoroallyl) pyrrole-2-carbonitrile; 3-bromo-5-chloro-4- (p-chlorophenyl) -2-nitropyrrole; 5-bromo-4 - [p.- (2,2-dichloro-1,1-difluoroethoxy) phenyl] -3- (trifluoromethyl) pyrrole-2-carbonitrile; 2-chloro-3- (2-bromo-4-ethylthiophenyl) -5-nitro-4- (trifluoromethyl) pyrrole; 3-bromo-1-methoxymethyl-4- (m-trifluoromethyl) -5- (trifluoromethyl) pyrrol-2-carbon in triethyl; 3- (p-chlorophenyl) -4-iodo-5-nitro-2- (trifluoromethyl) pyrrole; 4- (p-bromophenyl) -1- [(1-ethoxy) ethyl] -3,5-di- (trifluoromethyl) pyrrole-2-carbonitrile; 3- (2-bromo-4-methoxyphenyl) -5-nitro-2,4-di- (trifluoromethyl) pyrrole; 3-bromo-4- (3,4-dimethoxyphenyl) pyrrole-2,5-dicarbonitrile; 4-chloro-3- (p-chlorophenyl) -1-isopropyloxycarbonylmethyl) -5-nitropyrrole-2-carbonitrile; 3- (o-bromophenyl) -4- (trifluoromethyl) pyrrole-2,5-dicarbonitrile; 4- (m-bromophenyl) -1-carbomethoxymethyl-5-chloropyrrole-2,3-dicarbonitrile; 5-bromo-4- (2,6-dichloro-4-methanesulfonylphenyl) -2-nitropyrro 1 - 3-carbonitrile; 4- (p-chlorophenyl) -1- (2, 2,2 - trifluoroethyl) -5- (trifluoromethyl) pyrrole-2,3-dicarbonitrile; 4- (3,5-dichlorophenyl) -2-nitro-5- (trifluoromethyl) pyrrole-3-carbonitrile; 2,5-dichloro-4- (3,5-dichloro-4-methylthiophenyl) pyrrole-3-carbonitrile; 2,5-dibromo-1- (2,4-dibromophenoxymethyl) -3- (p-chlorophenyl-4-nitropyrrole) 4 - (3-bromo-4-cyanophenyl) -2-chloro-5- (trifluoromethyl) pyrrols carbonyl tril; 5-chloro-4- (3-chloro-4-trifluoromethoxyphenyl) -2- (trifluoromethyl) pyrrole-3-carbonitrile; 2-bromo-3- (3,4-dichlorophenyl) -1-ethylthiomethyl-4-nitro-5- (trifluoromethyl) pyrrole; 4- [p- (tetrafluoroethoxy) phenyl] -2, 5-di- (trifluoromethyl) pyrrole-3-carbonitrile; 1- (3-bromo-4-acetoxyphenyl) -1- (3,4-dichlorophenoxymethyl) -4-nitro-2,5-di (trifluoromethyl) pyrrole; 5-bromo-4- (2-chloro-4-methylthio) pyrrole-2,3-dicarbonitrile; 5-chloro-4- (p-chlorophenyl) -1-hydroxyethyl-3-nitropyrro 1- 2-5 carbonitrile; 4- (3,5-dibromo-4-cyanophenyl) - 5- (trifluoromethyl) pyrrole-2,3-dicarbonitrile; 4- (4-chloro-2-methylphenyl) -1-isopropylthiomethyl-3-nitro-5- (trifluoromethyl) pyrrole-2-carbonitrile; 3- (4-bromo-3-methyl-phenyl) -5-chloro-4-nitropyrrole-2-carbonitrile; 3- (2-naphthyl) -5- (trifluoromethyl) pyrrole-2,4-dicarbonitrile; 3- (3-cyano-4-methylphenyl) -1-methyl-4-nitro-5- (trifluoromethyl) pyrrole-2-carbonitrile; 2,3-dichloro-5- (3,4-dichlorophenyl) -4-nitropyrrole; 2- (3,5-dibromo-4-methoxyphenyl) -4,5-dichloropyrrole-3-carbonitrile; 2,3-dichloro-4-nitro-5- (2,4,6-trifluorophenyl) 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-1-methyl-2- (a, a, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile; 4,5-dichloro-2- (3,4-dichlorophenyl) -1-ethylpyrrole-3-carbonitrile; 2,3-dichloro-4-nitro-5- [p- (trifluoromethoxy) phenyl] pyrrole; 4,5-dichloro-2- [m- (trifluoromethoxy) phenyl] pyrrole-3-carbonitrile; ; 4,5-dichloro-2- (3,4-dichlorophenyl) -1-methylpyrrole-3-carbonitrile; 2,3-dichloro-5- (p-chlorophenyl) -1-methyl-4-nitropyrrole; 4- bromo-5-chloro-2- (3-chlorophenyl) -1-methylpyrrole-3-carbonitrile; 5- chloro-2- (3,4-dichlorophenyl) -4-fluoropyrrole-3-carbonitrile; 2-bromo-5- (β, -chlorophenyl) -1- (ethoxymethyl) -4-fluoropyrrole-3-carbonitrile; and in 3-bromo-5- (p-chlorophenyl) -2-fluoro-4-nitropyrrole.

The process according to the invention is characterized by reacting a benzoylacetonitrile or a-nitroacetophenone having the structure: 5 L 0 //

C-CHgU

10 R

wherein L, M, R and W have the meanings given in claim 1 with a 2,2-di (C 1 -C 4) alkoxy) ethylamine at an elevated temperature to form an or [2,2-di (C C4-alkoxy) ethylamino] -β-cyanostyrene or α- [2,2-di (C1-C4-alkoxy) ethylamino] -β-nitrostyrene of the formula:

L

·

N-CH, CH (C 1 -C 4 alkyl) 2 K H

wherein L, M, R and W have the above meanings and the ot- [2,2-di (C1-C4-alkoxy) ethylamino] -β-cyanostyrene or ot- [2,2-di ( C1-C4 alkoxy) amino] -β-nitrostyrene is treated with a mineral acid or organic acid to give the desired 2,3,4,5-tetrasubstituted pyrrole.

The invention finally relates to the α, β-substituted styrenes formed by the process which are characterized by the following structural formula:

L

n 1 R N- 'NH-CH 2 CH C C 2 -C 4 alkoxy 2 2 wherein W, L, M and R have the above meanings.

A preferred group of β- (substituted) styrene compounds of the invention has the above structure wherein W is CN; L is H, Cl or Br; M is H, F, Cl, Br 5 or OCH 3; R is H, F, Cl, Br, CF3, NO2, OCF3 or OCH3; or M and R at adjacent positions together with the carbon atoms to which they are attached may form a ring in which MRI represents the structure:

Another preferred group of S- (substituted) styrene compounds of the invention has the structure set forth above wherein W is NO 2; L is H, Cl or Br; M is H, F,

Cl, Br or OCH3; R is H, F, Cl, Br, CF3, NO2, OCF3 or OCH3; or M and R, when in adjacent positions, together with the carbon atoms, to which they are attached may form a ring in which MRI represents the structure: -

ISLAND

20

While the compounds of the invention are listed above as β-cyanostyrenes and β-nitrostyrenes, they can also be called dialkyl acetals.

Some of the preferred dialkyl acetal compounds of the invention are (E) - and (Z) - (1) p-chloro-β - [(formylmethyl) amino] cinnamonitrile diethyl acetal; (2) β - [(formylmethyl) amino] -3,4-dimethoxycinnamonitrile diethyl acetal; (3) (Z) - methyl-β- (2-cyano-1- [(formylmethyl) amino] vinyl) benzoate diethyl acetal; (4) (Z) -β- [(formylmethyl) amino] -1-naphthalene-acrylonitrile diethyl acetal; (5) (Z) -β - [(formylmethyl) amino] - p-methylcinnamonitrile diethyl acetal; (6) N- (formylmethyl) -p-methyl-α- (nitromethylene) benzylamine diethyl acetal; (7) N- (formylmethyl) -3,4-dimethoxy-α-nitromethylene) benzylamine diethyl acetal; (8) N- (formylmethyl) -a- (nitromethylene) -2-naphthalene-methylamine diethyl acetal; (9) methyl-p- {α - [(formylmethyl) amino] -β-nitrovinyl} benzoate-β- (diethyl acetal); (10) N- (form-methylmethyl) -3,4-dimethoxy-α- (nitromethylene) benzylamine dimethyl acetal; (11) (E) - and (Z) -p-chloro-β- [(formylmethyl) amino] cinamonitrile dimethyl acetal; (12) β - [(formylmethyl) amino] -3,4-dimethoxycinnamonitrile dimethyl acetal; (13) 3,4-dichloro-β- [(formylmethyl) amino] -cinnamonitrile diethyl acetal; and (14) 2-trifluoromethylmethyl-β- [(formylmethyl) amino] cinnamonitrile diethyl acetal.

The β-cyanostyrenes, also called the cinnamonitrile dialkyl acetals, can be prepared by reacting a substituted or unsubstituted benzoylacetonitrile with a 2,2-di (C 1 -C 4 alkoxy) ethylamine in the presence of an aromatic solvent to form (2) , 2-Di (C1-C6-alkoxy) ethylamino) -β-cyano- (substituted) styrene, which can then be converted to a 2- (substituted-phenyl) -pyrrole-3-carbonitrile by reaction of the S-3-cyano- (substituted) styrene compound with trifluoroacetic acid. Chlorination of the cyanophenyl pyrrole thus prepared with sodium hypochlorite or sulfuryl chloride in an inert solvent gives the insecticide, acaricide and nematodicide 4,5-dichloro-2- (substituted-phenyl) pyrrole-3-carbonitrile. The conversion to the pyrrole intermediate can also be achieved by substituting concentrated HCl at a temperature of between ca. 20 and 40 ° C. The reactions can be graphically illustrated as follows: ♦ H8NCH2CH (OC2H5> 8 rA = / V-cn

V

Aromatic solvent 13 DK 173853 B1 5 L H 0 R6 CF 3 CO 2 H or HCl

, CN X CN

10 NaOCl / NsJV J_ "H X — a. © Tier * x η '$ <ζ * SOjCIg \ _x

ell * r ΒΓ? R

COC (CH3> 3 O-1 15

X

Wherein A is hydrogen, C 1-6 alkyl optionally substituted with one C 1 -C 4 alkoxy group, one C 1 -C 4 alkylthio group, from one to three halogen groups or phenyl optionally substituted with one or two C1-C4 alkyl, C1-C4 alkoxy or halogen groups; C3-C4 alkenyl optionally substituted with from one to three halogen groups; or C3-C4 alkynyl; X is Cl or Br; R 9 is C 3 -C 4 alkyl and L, R and M have the meanings given above.

Certain novel 2,3,4,5-tetrasubstituted pyrrole compounds of formula I wherein A is hydrogen; W is CN, and X, Y, L, M and R have the above meanings, which can be prepared by reacting N-form vi-DL-phenyl-glycine or a substituted N-formylphenylglycine which is represented. by the structural formula VIII:

L CO 2 H

- ciT (VIII) ^ nhch = o

R

wherein L is H, F, Cl or Br; R and M are each H, C1-C3-10 alkyl, C1-3 alkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1- C3 alkylsulfonyl, cyano, F, Cl, Br, I , nitro, CF 3, R 2 CF 2, R 2 CO or NR 3 R 4, and when M and R are at adjacent positions, together with the carbon towers to which they are attached, they can form a ring in which MRI represents the structure: -OCHoO-, -OCFoO- or; Z is s (O) n or O; Rx is H, F, CHF2, CHFC1 or CF3; R 2 is C 1 -C 3 alkyl, C 1 -C 3 alkoxy or NR 3 R 4; R 3 is H or C 1 -C 3 alkyl; R 4 is H, C 1 -C 3 alkyl or R 5 CO; R5 is H or C1-C3 alkyl and n is an integer 0, 1 or 2; with at least one equivalent amount of 2-chloroacrylonitrile and two to three equivalents of acetic anhydride. The reaction is carried out at an elevated temperature, preferably approx. 70 to 100 ° C.

The reaction can be illustrated as follows: 30 CH + CHe = CVCN -S-

NvNHCH = 0

R CN

ri i «* - 35

R

15 DK 173853 B1

The conversion of the thus obtained 2-phenyl-pyrrole-3-carbonitrile or 2- (substituted phenyl) pyrrole-3-carbonitrile to the corresponding 4-halo, 5-halo or 4,5-dihalo-2- (substituted phenyl) ) pyrrol-3-carbo-5-nitrile of formula II is readily obtained by reacting the above-mentioned 2-phenylpyrrole-3-carbonitrile or 2- (substituted phenyl) pyrrole-3-carbonitrile with at least approx. 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 hydrocarbon solvent.

To prepare a monohalo-pyrrole-3-carbonitrile, use of ca. 1 equivalent of halogenating agent; whereas preparation of a dihalo-pyrrole-3-carbonitrile requires 2 to 3 equivalents of the halogenating agent. When sulfuryl chloride or sulfuryl bromide is used, the reaction is generally carried out at a temperature of less than ca. 40 ° C and preferably between ca. 0 and 30 ° C, but when elemental bromine is used, the reaction is usually carried out at ca. 30-40 ° C. Other effective halogenating agents which can be used in these reactions include sodium hypochlorite, t-butyl hypochlorite, N-bromosuccinimide, N-iodosuccinimide and the like. The reaction can be illustrated as follows:

/ N X CN

25 ci * 's ° * <x> * / CiX _L m V - K horc H γ /

R

<ii> 30

The carbonitrile compounds of formula II of the invention may also be prepared from the reaction of a substituted or unsubstituted benzoylacetonitrile with a 2,2-di (C1-C4 alkoxy) ethylamine in the presence of an aromatic solvent to form a- (2.2 -di- (C1-C6 alkoxy) -ethylamino) -β-cyano- (substituted) styrene, which is then converted to 2- (substituted-phenyl) -pyrrole-3-carbonitrile of formula II by reaction of the β-3-cyano- (substituted) styrene compound with trifluoroacetic acid or with concentrated HCl at a temperature of between ca. 20 and 40 ° C. Reactions 5 can be illustrated graphically as follows:

L

+ H2NCH2CH <0CeH5> 2

/ <S = J N-CN

.. Y

organic solvent: γγΐ: ..

15 CF 3 CO 2 H or HCl CH 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

* 'γ Y

2

R

3 wherein R 9 is C 1 -C 4 alkyl and L, R and M have the above 4 meanings.

5

Furthermore, 3-nitro-2-phenylpyrrole and 3-nitro-2-6 (substituted) phenylpyrrole compounds of formula II are prepared by reacting an α-nitroacetophenone or an 8 substituted α-nitroacetophenone with 2,2-di (C C4-alkoxy-9-ethylamine. The reaction is generally carried out in the presence of an inert organic solvent, preferably an 11 aromatic solvent, at an elevated temperature, to form an at- (2,2-di (C1-C4 alkoxy) ethylamino) -β-nitro 13 styrene or a substituted ot-2,2-di (C 2 -C 4 alkoxy) ethyl 14 amino) -β-nitrostyrene which is converted to 3-nitro-2-phenylpyrrole 15

or 3-nitro-2- (substituted) phenylpyrrole of formula II

16 by treatment with a mineral acid such as hydrochloric or hydrobromic acid. The reaction of the thus-prepared nitrophenylpyrrole with sodium hypochlorite in the presence of an inert organic solvent at a reduced temperature gives 2,3-dichloro-4-nitro-5-phenyl- or -5- (substituted) phenylpyrrole of formula II.

The above reactions can be illustrated graphically

the following way: η V Q

y— C-CH 2 NO 2 + H2 MCH 2 CH (OC 2 H 5) 2

L

io Vy ^ -N0 * ._ CH2CH (0CfiH8> 2 | hC1 screens CF3CO2H NO,

15 / - (8 L

H \ -X Cl NOj

In * oci ί «1- * Cl <II)

In addition to the many methods described in the literature for preparing substituted and unsubstituted benzoylacetonitriles, it has surprisingly been found that these compounds can also be prepared by reacting an appropriately substituted benzoyl halide with an alkali metal hydride and an alkyl cyanoacetate such as t-butyl cyanoacetate formation of the corresponding t-butyl (benzoyl or substituted benzoyl) cyanoacetate. These reactions can be illustrated graphically as follows:

LAUGH OUT LOUD

* N * H ♦ • {”8h ° C <CH3> 3 - * CO-C-M-OCCCH,),

R R CN

35 fl B C

18 DK 173853 B1

The cyanoacetate ester thus formed can then be converted to a substituted or unsubstituted benzoylacetonitrile by heating the compound in toluene containing p-toluene sulfonic acid. The reaction can be graphically illustrated as follows: 10 ^ Ay-cn-c-co-occc ^

R CN

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

19 DK 173853 B1 t-Butyl (benzoyl and substituted benzoyl) cvanoacetates

5 L

H. I

fa \\ - C0-C-C0-0C (CH3) 3

CN

in M £ sbe ^ C

15 H 3-Cl 4-Cl 91-94 Η H 4-OCF3 81-84 Η H 4-Br 113-115 Η H 4_CF3 146-147 Η H 4-F '98-100 20 Η H 4-CN 127- 128 Η H 4-CF3CH20 136-139 Η H 4-CH3S02 127-129 H 3-F 4-F 91-94 Η H 4-CH3S 117-119 j5 25 Η H 4-CHF2CF20 92-94 3-Cl 5- C1 4-CH30 30 1 20 DK 173853 B1

Benzovlacetonitriles 5 L o

M

- C - CH 2 CN

10 R

L Μ E anp ° C

15 HH 4-C1 128.5-129.5 H 3-C1 4-C1 105-107 Η H 2 — C 153-55 Η H 4-OCF3 79-81 Η H 4-CF3 44-45 2Q H 2- C1 4-Cl 66-67 Η H 3 — Cl 80-83 Η H 4-CN 126-128 Η H 4-F 78-80 Η H 4-SO2CH3 129-132 25 H 3 — F 4-F 74-75 Η H 3_CF3 58-60 Η H 4 — CH3 10315-106 Η H 4-NO2 119-124 3-Cl 5-Cl 4-OCH3 --- 30 1 21 DK 173853 B1

Preparation of N-substituted aryl pyrrols of formula I can be achieved by reacting the appropriately substituted aryl pyrrole of formula I wherein A is hydrogen and L, M, R, W, X and Y have the meanings given above with an appropriate alkylating agent and a suitable base. Eg. a brominated hydroxy-C1-C4 alkyl and potassium t-butoxide. This reaction provides an arylpyrrole which has the same substituents as the starting material but is additionally substituted on the nitrogen by hydroxyC1-C4 alkyl. In a similar reaction 10, cyanobromide is used in place of brominated hydroxy-C1-C4 alkyl and yields aryl pyrrole of formula I with a carbonitrile substituent on the nitrogen. The reactions can be illustrated as follows: 15 x 'SOr' * '14 \ 15 Br ci "c4 alcoho1 + K + o-t-Bu V H * 7 + or R 2> CNBr 20 U,

'«I: · J

Wherein L, M, R, W, X and Y have the meanings given above for Formula I and A is 1) C1-C4 alcohol or 2) CN.

Preparation of 2-phenylpyrrole-3,4-dicarbonitrile, 2-bromo-5-phenylpyrrole-3,4-dicarbonitrile and substituted phenyl derivatives thereof can be obtained by reacting fumaronitrile with bromine in the presence of a chlorinated hydrocarbon such as chloroform at an elevated temperature to form bromo-fumaronitrile. The bromofumaronitrile thus formed is then reacted with N- (trimethylsilyl) methyl-5-methyl-benzene-thioimidate 35 or a substituted derivative thereof, in the presence of hexa-methylphosphoramide at an elevated temperature to form 2-phenylpyrrole-3 , 4-dicarbonitrilet. Bromination of the thus-obtained 3,4-dicarbonitrile gives 2-bromo-5-phenyl-pyrrole-3,4-dicarbonitrile or the substituted phenylderivate if the substituted N- (trimethylsilyl) methyl-5-methyl-5-yl- -thioimidobenzoate is used in the previous reaction. The reaction can be illustrated graphically as follows:

CN CN

- / jyCHCyA „i <* - HBr> Y

10 NC CN *

sJi n HHPR / 3 H * ° "A _ L

SofV - τη5ΛΛ / ^ Γ «-TMSrHBr.-CHjSH) w ^

R

15 BP | / CHC] | NC CN 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 2

The aryl pyrroles herein are effective in controlling insects, mites and nematodes. The compounds are also 4 effective in protecting growing or harvested crops 5 against attack by the aforementioned pests.

6 In practice, approx. 10 ppm to approx. 10,000 ppm 7 and preferably 100 to approx. 5000 ppm, of the aryl pyrrole of Formula I dispersed in water or other inexpensive liquid 9, effectively, applied to the plants, crop or soil 10 in which the crop grows, to protect crops against attack 11 by insects, mites and / or nematodes. The compounds are also useful for protecting turf grass against infestation of 13 animals, such as larvae, bedbugs and the like.

14

The aryl pyrrols of formula I according to the invention are also effective in controlling insects, nematodes and 16 mites when applied to the leaves of the plants and / or the soil or water in which the plants grow, in sufficient quantity to provide an amount of from ca. 0.12 5 kg / ha to approx.

4.0 kg / ha active ingredient. Obviously, larger amounts of aryl pyrroles of formula I can be applied to protect crops against infestation of insects, nematodes and mites, but the use of larger amounts of application is generally unnecessary and uneconomical.

While the aryl pyrrols of the invention are effective in controlling insects, nematodes and mites when used alone, they can be used in combination with other biological chemicals, including other insecticides, nematodicides and acaricides. Eg. For example, the aryl pyrroles of the invention can be used effectively in conjunction with or in combination with phosphates, carbamates, pyrethroids, formamidines, chlorinated hydrocarbons, halo benzoylureas and the like.

The 2-aryl-3-cyano-4,5-dihalogen pyrrols prepared from the β-cyano-styrene compounds of the invention are effective in controlling insects, mites and nematodes.

These compounds are also effective in protecting growing and harvested crops against attack by the above-mentioned pests.

In practice, approx. 10 ppm to 10,000 ppm and preferably 100 to 5000 ppm, of the halogenated aryl pyrrole dispersed in water or other inexpensive liquid carrier effective when applied to the plants, crops or soil in which the crops grow, to protect the crops against insect infestation, mites and / or nematodes.

The aforementioned halogenated aryl pyrrols are also effective in controlling insects, nematodes and mites when applied to the leaves of the plants and / or the soil or water in which the plants grow. These halogenated arylpyrrole compounds are usually applied in sufficient quantity to provide a concentration of from ca. 0.125 kg / ha to approx. 4.0 kg / ha active ingredient. Obviously, larger uses of the halogenated aryl pyrrols can be used to protect crops from insect, nematode, and mite infestation, but use of larger amounts of application is generally unnecessary and uneconomical.

Advantageously, the aforementioned aryl pyrrols can be transferred into dry compact granules, liquid preparations, granular preparations, moist powders, emulsifiable concentrates, powders, powder concentrates, microemulsions and the like, all used on the soil, in the water and / or on the leaves and provide the necessary plant protection. . Such compositions comprise the compounds of this invention mixed with inert, pharmacologically acceptable solid or liquid diluents.

Eg. For example, moist powders, powders and powder concentrate compositions of the invention can be prepared by grinding approx. 3 to 20% by weight of the arylpyrrole compound of formula I with about 3 to 20% by weight of a 15 solid anionic surfactant. One suitable anionic surfactant is a dioctyl ester of sodium sulfuric acid, in particular "Aerosol 0TB" surfactant from the American Cyanamid Company. Ca. 60 to 94% by weight of an inert solid diluent such as montmorillonite, attapulgite, chalk, talc, kaolin, diatomaceous earth, limestone, silicates or the like are also used in such compositions.

Compressed granules particularly useful for soil or water application can be prepared by grinding for approx. equal parts, usually approx. 3 to 20 parts 25 arylpyrrole and a solid surfactant, with approx. 60 to 94 parts plaster. Then the mixture is compressed into small grained particles, approx. 0.32 / 0.73 mm or greater.

Other suitable solid surfactants useful in the present compositions include not only the anionic dioctyl ester of sodium sulfuric acid, but also non-ionic block copolymers of ethylene oxide and propylene oxide. Such block copolymers are marketed by BASF Wyandotte Corporation as "Pluronic 10R8", "17R8", "25R8", "F38", "F68M," F77 "or" F87 ", and are particularly effective in the production of compressed granules.

In addition to the powders and concentrate compositions described above, moist powders and liquid agents can be used because they can be dispersed in water. Preferably, such liquid agents are used at the site where the aqueous compositions are sprayed onto the leaves of plants to be protected.

5 These pesticides may also be applied to the hatching site, food supply or biotope of the insects and mites to be controlled.

When solid compositions of the aryl pyrrols are to be used in combination with treatments with other pesticidal agents, the compositions may be applied as a mixture of the components or in sequence.

Similarly, liquid preparations of the aryl pyrrole combined with other pesticidal agents may be mixed in container or applied separately, in succession, as liquid spraying agents. Liquid syringes of the compounds of this invention should contain approx. 0.001 to 0.1% by weight of the active aryl pyrrole.

The following Examples are given by way of illustration of the present invention, Examples 1, 3-4, 7, 20 13, 17-18, 24-25, 27-31, 33, 35-38, 40-43, 45, 47 , 49-50, 52, 54, 55-57 and 60 do not concern compounds of the invention, but intermediates.

EXAMPLE 1 2-Phenylpyrrole-3-carbonitrile

CN

COpH Cl _ 5 / = \ / I flc20 \\ /) - CH + chz = c_cn - ^ Sk 7 = \ \ hch = o jf /)

The following procedure is similar to the method disclosed in JOC, 43, 10 4273-6 (1978). A magnetically stirred mixture of 30.0 g of N-formyl-phenylglycine is heated at 90 ° C for 1¾ hours.

The clear yellow reaction solution is concentrated in vacuo to give 42.5 g of an oily brownish-orange semi-solid. The material, which is partially purified by chromatography on silica gel, is shown by proton NMR spectrum to be a mixture of 73% 2-phenylpyrrole-3-carbonitrile and 27% 2-phenyl-3-cyano-5-methylpyrrole. Recrystallization once from chloroform and twice from 1,2-dichloroethane gives 1.69 g of an off-white solid which, by proton NMR, is found to be 20 96% 2-phenylpyrrole-3-carbonitrile, m.p. 152 ° C.

Microanalysis (molecular weight 168.19):

Calculated: C, 78.55%; H, 4.79%; N, 16.66%

Found: C, 78.52%; H, 4.73%; N, 16.54% EXAMPLE 2 4,5-Dichloro-2-phenylpyrrole-3-carbonitrile and 5-chloro-2-phenyl-pyrrole-3-carbonitrile

30 CN CN CN

[f ^ 2eq.S02Cl2 il 1 ^ J ^ j / = \ cHjCij “ci-" V \ / = \

h X \ /) Cl h v ^ x H \ J

35 '-f \ // 27 DK 173853 B1

To a magnetically stirred ice-water-cooled solution of 2.0 g (11.9 mmol) of 2-phenyl-3-cyanopyrrole in 80 ml of methylene chloride is added dropwise over a period of 5 minutes 1.90 ml (3.19 g, 23.6 mmol) of sulfuryl chloride by means of a syringe. During the addition, the temperature is maintained between 5 and 10 ° C. Stirring at 5-10 ° C is continued for 90 minutes. The reaction mixture is vacuum filtered to remove 1.28 g of a precipitated solid, identified as 5-chloro-2-phenylpyrrole-3-carbonitrile, mp: 192, S-195 ° C. The filtrate 10 is diluted with 400 ml of ethyl acetate, washed twice with 200 ml of water, dried (sodium sulfate), treated with carbon, filtered and then concentrated in vacuo to give (after slurrying the residue with hexane) 0.60 g (21.3% yield) of a pink-violet solid. This solid is recrystallized from 5 ml of hot acetone to give 0.32 g (9% yield) of 4,5-dichloro-2-phenylpyrrole-3-carbonitrile as an orange-brown solid, m.p. 255 ° C.

Max (mull, Nujol): 3165 (br s), 3120 (s), 2245 (s), 1570 (m), 20 1513 (m), 1440 (s), 1252 (m), 1069 (m), 996 (m), 920 (m), 768 (s), 698 (s), 665 (s) cm-1.

H-NMR (DMSO): 67.73 (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 25 C-3.5), 57.44 (t, J = 7.3Hz, 1.02H, one phenyl proton at C-4).

C-NMR (DMSO): 6137.51 (C-2 pyrrole carbon), 6129.25 (C-4 phenylcarbon), 6129.04 (C-3.5 phenylcarbon), 6128.37 (C1 phenylcarbon), 6125 , 88 (C-2.6 phenylcarbons), 6114.32 (either the C-5 pyrrole or nitrile carbon), 6114.14 (either the C-5 pyrrole or nitrile carbon), 6110.72 (C-4 pyrrole carbon), 689.78 (C-3 pyrrole carbon).

Microanalysis (molecular weight 237.09): Calculated: 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% Example 3 β-Chloro-β--(formylmethyl) amino) aminol cinnamonitrile, diethyl acetal

A magnetically stirred solution of 250.0 g (1.39 mol) of 10β-chlorobenzoylacetonitrile, 203 ml (185.95 g, 1.39 mol) of 2,2-diethoxyethylamine and 1300 ml of dried toluene is heated at reflux for 20 hours. Water is collected in a Dean-Stark separator (23.8 ml, 95.2% of theory). The warm, cloudy, dark brown solution with a large amount of 15 dissolved solids is filtered through a diatomaceous filter.

After dilution with 200 ml of EtOAc, the solution is filtered through a 7 cm x 13.5 cm column of silica gel. The filtrate is concentrated in vacuo to give 354.38 g (86.4% crude yield) of a clear dark oil which slowly solidifies. This solid is recrystallized from hot cyclohexane to give 324.26 g (79.1% yield) of a waxy orange solid.

NMR of this product shows that it consists of 78% (Z) and 23% (E) isomer mixture of p-chloro-β - [(formylmethyl) amino] -cin-namonitrile, diethyl acetal, mp: 60-72 ° C . The following analytical data are for another similarly prepared sample.

Max (mull, Nu jol): 3325 (s), 3065 (m), 2197 (s), 1600 (s), 1530 (s), 1314 (m), 1265 (m), 1173 (m), 1154 (s) m), 1128 (s), 1100 (s), 1060-30 (s), 1022 (s), 939 (m), 895 (m), 844 (s), 768 (m), 730 (m) cm -1.

H-NMR (chloroform): 57.47 (d, J = 8.6Hz, 2.12H, two aromatic protons), 67.37 (d, J = 8.6Hz, 2.12H, two aromatic protons), δ , 10 (E) & 4.86 (Z) [br t, 1.25H, one NH proton], δ4.69 (Ζ) & 64.60 (E) [t, J = 5.1Hz, 1 , 05H, one methine proton at the acetal carbon], 64.07 (E) & 64.05 (Z) [s, 0.83H, enamine-6 proton], 29.71 (E) & 63 , 68 (Z) [g, J = 7.1Hz, 2.22H, two methylene protons of one of two ethoxy groups], 63.56 (Z) & 63.53 (E), J = 7.1Hz, 2.22H , two methylene protons of one of two ethoxy groups], 63.18 (t, J = 5, 1Hz, 1.77H, two methylene protons of the ethylene acetal group), 61.20 (t, J = 7, 1Hz, 4.90H , six methyl protons of the two ethoxy groups).

C-NMR (chloroform): 6161.21 (α-enamine carbon), 6136.29 (Z) & 6134.60 (E) [either Cl or C-4 of the phenyl ring], 6134.08 (Z) 10 & 6132, (E) [either Cl or C-4 of the phenyl ring], 6129.3-4 (Z) & 6129.89 (E) [either C-2.6 or C-3.5 of the phenyl ring], 6128.94 (Z) & 6128.63 (E) [either C-2.6 or C-3.5 of the phenyl ring], 6121.19 (Z) & 6119.50 (E) [nitrile carbon], 699.43 ( Z) & 6100.63 (E) [β-Enamine Carbon], 661.88 (Z) & 663.25 (E) [Methine Carbon of Acetal], 662.64 (Z) & 663.03 (E) [methylene carbons of the ethoxy groups], 646.32 (Z) & 647.33 (E) [methylene carbon of the ethylamine group], 615.26 (methylcarbons of the ethoxy groups).

Microanalysis (molecular weight 294.78): Calculated: C, 61.11%; H, 6.50%; N, 9.51%; Cl, 12.03%.

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

Following the above procedure but replacing p-chlorobenzoylacetonitrile with the appropriate benzoylacetoylacetonitrile and / or 2,2-diethoxyethylamine with the appropriate 2,2-di (C1-C4-alkoxy) ethylamine gives the following compounds: CO -CHgCN * HgNCHgCH <CX “C4 * Uoxy> e -

High toluene · R-H, O

L

—CN _

N-CH 2 CHtCl 2 C, alkoxy> 2 R R H

30 DK 173853 B1

I »Μ E fCj-C« alkow) ^ sap ° C

Η H fi-CH3OCO <OC2H5) 2 68-73 H fi-CH3 H (° C2H5> 2 59-69 5 H a-OCH3 fi-OCH3 (OC2Hg) 2 red-orange hollow solid H _ _ <OC2H5> 2 62-70 B-Cl Η H (0CH3) 2 ίο h p-ch3 h (och3) 2 H ffi-Cl B-Cl (OC2H5) 2 Η H β-OCF, (OC2Hs) 2 Η H fi-CF33 (OC2 EXAMPLE 4 2- (p-Chlorophenyl) -nyrrole-3-carbonitrile

VCN

C CN

ciOi λ + - ri "20 \ H \ />" C1 amber 294.78, etc. 114.02, rv 202.64

To 108 ml of trifluoroacetic acid stirred at 23 ° C was added 54.0 g (0.183 mol) of solid p-chloro-β- [(formylmethyl) amino] cinnamonitrile, diethyl acetal over 45 minutes. This addition gives an exotherm to 38 ° C and after 32 minutes of addition a solid begins to precipitate. After stirring at room temperature for 30 minutes, the reaction mixture is vacuum filtered and the collected solid is washed first with trifluoroacetic acid, then with an ethyl acetate-hexane mixture and finally with hexane. The yield is 16.83 g (45.4%) of an off-white solid, mp: 165-166 ° C. The following analysis data is from a similarly prepared sample. 1

Max (mull. Nujol): 3275 (br s), 2225 (s), 1502 (s), 1410 (m), 1275 (m), 1200 (m), 1108 (s), 1023 (m), 999 ( m), 908 (m), 843 (s), 317 1753 53 B1 752 (s), 722 (s), 695 (s), 620 (s) cm -1.

H-NMR (acetone): <511.22 (v br s, 0.99H, one pyrrole-NH proton), 67, 82 (d, J = 8.9Hz, 2.46H, two aromatic phenyl protons), δ 67.51 (d, J = 8.9Hz, 2.46H, two aromatic phenyl protons), 67.02 (t, J = 2.6Hz, 1.01H, one pyrrole proton at C-5), 66.58 (t , J = 2.6Hz, 0.77H, one pyrrole proton at C-4).

C-NMR (acetone): 6137.73 (pyrrole C-2), 6134.42 (p-chlorophenyl 10 at C-4), 6129.93 (methinecarbons at C-3.5 in the phenyl ring), 6128.07 ( methane carbons at C-2.6 in the phenyl ring), 6121.21 (pyrrole at C-5), 6117.93 (nitrile carbon), 6113.78 (pyrrole carbon at C-4), 690.86 (pyrrole carbon at C- 3).

Microanalysis (molecular weight 202.64):

Calculated: 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 process as shown 20 or using concentrated hydrochloric acid instead of trifluoroacetic acid gives the following compounds:

CN

25 JL r 1 32 DK 173853 B1 ^ °! L ^ .e- ^ A ^ -r -JL anp ° C Applied acid

4-Cl 165-166 wife. HCl, CF 3 COOH

3.4- di-Cl 216-221 CFgCOOH

2- C1 156-157 CF, COOH

5 3

4-OCF3 143-145 CF3COOH

4-CF3 179-180 CF3COOH

2.4- di-Cl 197-199 CF3C00H

3- Cl 150-156 CF3COOH

4- CN 210-212 CF.COOH

10 3 4-F 167-170 cone. HCl

4 “SO 2 CH 3 221-221, 5 CF 2 COOH

3.4- di-F 173-175.5 CFgCOOH

3- CF3 166-168 CF3COOH

4- COOCH, 155, 5-158 CF ^ COOH

15 3 3

4-CH3 117-137 CF3COOH

4-NO2 174-177 CF3COOH

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

CN C1 CN

β ^ 2.2 eq.SOeCl2 jj ^ 25 / “- \ HOfic '^ Ssv / ~ \ ri H —C1 C1 H v // C1

To a mechanically stirred solution of 16.83 g (83.1 mmol) of 2- (p-chlorophenylpyrrole-3-carbonitrile in 450 ml glacial acetic acid at 36 ° C, drop 14.7 ml (24.70 g, 183.0 sulfuryl chloride over 18 minutes The addition gives a slight exotherm to 39 ° C and after a further 16 minutes the reaction mixture is filtered in vacuo. The collected solids are first washed with acetic acid and then with water. after recrystallization from hot ethyl acetate at 259-261 ° C. By similar procedures other samples of this product are prepared and the analytical data for such a product are shown below.

Max (mull. Nujol): 3170 (br s), 3100 (m), 2225 (s), 1508 (m), 1097 (m), 825 (s), 717 (m), 660 (m) cm first

H-NMR (DMSO): 57.72 (d, J = 8.6Hz, 2.00H, two aromatic protons), 67.56 (d, J = 8.6Hz, 2.00H, two aromatic protons).

C-NMR (DMSO): 6136.01 (pyrrole C-2 carbon), 6133.92 (p-chloro-phenyl C-4 carbon), 6129.09 (p-chlorophenyl C-3.5 carbon), 6127 , 41 (p-chlorophenyl C-4 carbon), 6127.11 (p-chlorophenyl C-carbon), 6114.49 (nitrile carbon), 6114.10 (pyrrole C-5 carbon), 6110.92 (pyrrole C-4 carbon) ), 690.09 (pyrrole C-3 carbon).

15

Microanalysis (molecular weight 271.54):

Calculated: C, 48.65%; H, 1.86%; N, 10.32%; Cl, 39.17%

Pound: C, 49.22%; H, 2.12%; N, 9.85%; Cl, 39.03% EXAMPLE 6 (4,5-Dibromo-2-ia.a.g-trifluoro-p-tolyl) -ovrrol-3-carbonitrile

Br CN

25 ζΧ _ + Br'-► H V> cr3 Br H ^ ~ CF3

To a stirred mixture of 0.8 g of 2- (ex, α, α-trifluoro-p-30-tolyl) pyrrole-3-carbonitrile in 70 ml of chloroform is added 2 ml of bromine. The mixture precipitates by stirring overnight on a white solid which is collected by filtration. Thin layer chromatography (1: 1 ethyl acetate / hexane) shows a single component; mp:> 230 ° C.

35 34 DK 173853 B1

Analysis:

Calcd for C12 H5 Br2 F3 N2: 36.55; H, 1.27; N, 7.11;

Br, 40.61.

Found: C, 36.40; H, 1.08; N, 6.99; 5 Br, 40.55.

Following the procedures of Examples 5 and 6, but using the appropriately substituted phenylpyrrole-3-carbonitrile instead of 2- (a, or, or trifluoro-p-tolyl) pyrrole-3-carbonitrile, the following compounds are obtained.

10 µ / CN

jT \ y — v n 15 N n / '^

L B B 2 X sPB ^ S

Η H 4-N02 Br Br 274-277 20 Η H 4-F Cl Cl> 220 Η H 4-F Br Br> 220 Η H 4-S02CH3 Cl Cl> 230 H 3-F 4-F Cl Cl> 230 H 3-F 4-F Br Br> 220 25 2-Cl 3-Cl 4-C1 Cl Cl 2-Br 3-Br 4-Br Br Br Η H 4-OCF3 Cl Cl 222-225 Η H 4-OCFj Br Br 231-232

Η H 4-OCF3 Cl H

30 Η H 4 — CN Br Br> 230 Η H 4-CN Cl Cl> 240 Η H 4-S02CH3 Br Br> 230 Η H 4-N ° 2 Cl Cl 246-249 H 3-Cl 4-Cl Br Br> 260 35 Η H 3-CF3 Cl Cl> 230 Η H 4-COCH3 Cl Cl 251-254 35 DK 173853 B1

li U E Σ I

H 2,3-CH-CH- Cl Cl 244-247 Η H 4 ~ ch3 Cl C1 215-217 _ H 2-Cl 4-Cl Br Br> 230

ISLAND

Η H 3-Cl Cl Cl> 230 H 2-C1 4-Cl Cl Cl> 230 Η H 4-Cl Br Br 273-274 Η H 2-Cl Br Br> 230 10 Η H 4-CFj Cl Cl> 230 Η H 4-Br Cl Cl> 235 Η H 2-Cl Cl Cl> 230 H 3-Cl 4-Cl Cl Cl> 235 Η Η H Cl Cl 254-255 15 Η H 4-Cl Cl Cl 255-257 Η H 4 -CF3 Br Br> 230 Η H 4-Cl Cl Br 262-263 (decomposition) Η H 4-Cl Br Cl 250-258 (decomposition) H 3-C1 5-Cl Cl Cl> 230 20 H 3-Cl 4- Cl Cl Br> 230 2-Cl 4-Cl 5-F Cl Cl 207-210 EXAMPLE 7 3-Nitro-2-phenylpyrrole

N0Z

/ fVcCHaKO, ♦ HjNCHjCHtOtDj ^ \ - C-CH'NOe - ^ Λ> / = \

30 .... NH-CHeCH (0Et> e Η V Q

> 5.7 g (0.0345 mole) of α-nitroacetophenone is taken up in 100 ml of toluene and 4.6 g (0.0345 mole) of aminoacetaldehyde diethyl acetal is added. The reactants are added to a 250 ml round bottom flask; 1; «36 DK 173853 B1 equipped with a Dean-Stark separator. The separator is filled with 4Å molecular sieves and the mixture is heated under reflux for 18 hours. The toluene is removed in vacuo to give 8.3 6 g of α- (2,2-diethoxyethylamino) -5β-nitrostyrene as a brown oil. To this oil is added 50 ml of concentrated HCl. As the flask swirls around, the oil becomes a yellow suspension. After 10 minutes, the solid is filtered off to give 2.48 g of a yellow solid. Recrystallization from ether / ethyl acetate / hexane gives the product as two fractions, 2.08 g, mp 190-192 ° C (31%).

Max 1485 cm-1 (NO2).

H-NMR (CDCl 3 / DMSO) 56.73 (m, 2H), 7.46 (m, 5H).

Example 8 2.3-Dichloro-4-nitro-5-phenylpyrrole 20 NO2 Cl NO2 f \ + NaOCl -► SAq "

A mixture of 1.56 g (0.0083 mole) of 3-nitro-2-phenyl-pyrrole in 60 ml of dioxane is cooled in an ice bath, while 25.9 g (0.0182 mole) of commercial sodium hypochlorite is added thereto.

After stirring for 45 minutes, the mixture is acidified with concentrated HCl. Water and Et 2 O are added. The layers are separated and the top organic layer is washed with H 2 O, dried with anhydrous MgSO 4 and concentrated in vacuo to give 2.21 g of yellow solid. Purification by chromatography using silica gel and eluting with increasing amounts of ethyl acetate / hexane, after stripping 0.77 g of yellow solid (36%), mp: 190-190.5 ° C; 37 DK 173853 B1

Analysis; Calcd for C10 H6 N2 ° 2c - * - 2: c '46.72, - H, 2.35; N, 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 α-nitro-acetophenone and 2,2-di (C 1 -C 4 alkoxy) ethylamine, the substituted α- (2,2-di (C C4-alkoxy-ethylamino) -S-nitrostyrene, which is then converted to 3-nitro-2- (substituted) phenylpyrrole by treatment with HCl, HBr or CF3CO2H. Reaction of the substituted phenylpyrrole thus obtained with sodium hypochlorite in dioxane gives the chlorine analogs; whereas reaction of the substituted phenylpyrrole with bromine in chloroform gives the bromine analogs.

x N0g --4¾.

25 R

L XX £ XX s & B ° £ Η Cl H Cl Cl 190-190.5 H 4-Cl H Cl Cl 214-215 H 4-Cl H Br Br 203-204 (decomposition) 30 Η Η H Br Br 148.5-149 3-C1 4-C1 C Cl Cl 219-220 (decomposition) H 4-Br H Cl Cl 222-223 (decomposition) Η H 4-CF3 Cl Cl 166-168 38 DK 173853 B1 EXAMPLE 9 4,5-Dichloro-2 - ( 3,4-dichlorohenyl) -1-methyl-pyrrole-3-carbonitrile

5 - C1v, CN

\ _ / Cl _ CN

Cl ♦ n * i ♦ koc <ch3> 3 - * c * 10 In a 100 ml flask, give 2 g of 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile in 60 ml of dry THF a clear brown solution. 1 eq. KOtBu is added with stirring, giving 15 a clear solution after a few minutes. 1 eq. Flour is added by syringe and the solution is heated at reflux for 4 hours. It is then left to stir at room temperature overnight. The following day, 50 ml H 2 O is added and the mixture is extracted with 4 x 50 ml CHCl 3.

The organic phases are combined, dried with MgSC> 4 and concentrated.

The resulting white solid is purified by flash chromatography on silica gel using 50/50 EtOAc / hexane as eluent. This gives 1.80 g of a white solid.

Yield = 86% m.p. : = 154 -156 ° C.

Following the above procedure, but using the appropriately substituted phenylpyrrole-3-carbonitrile or 3-nitro-2- (substituted phenylpyrrole instead of 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile The following compounds are available: 1 39 DK 173853 B1

X CN

5 J \ 10 h L Μ B XX £ gp.Ig CH3 HH 4-Cl Cl Cl 152-153 C2H5OCH2 H 3-Cl 4-Cl Cl Cl 128-130 C2H5 H 3-Cl 4-Cl Cl Cl 137-138 15 CH3 H 3-Cl 4-C1 Cl Cl 154-156 CH3 HH 4-CF3 Br Br 145-146 C6H5-CH2 Η H 4 “cf3 Br Br 145-147 C6H5-CH2 H 3-Cl 4 — Cl Cl Cl 95- 96 CH2 * CH-CH2 H 3-Cl 4-Cl Cl Cl 69-70 2Q CH2-C-CH2 H 3-Cl 4-Cl Cl Cl

Cl CH = C-CH2 η 3-Cl 4-Cl Cl Cl 147-148 CH3SCH2 H 3-Cl 4-Cl Cl Cl C (CH3) 3 HH 4-CF3 Cl Cl 25 CH3 HH 4-CF3 Cl Cl 99-100 CH3SC2H5 H 3-Cl 4-Cl Cl Cl 74-75

ISLAND

C2H5-OC-CH2 H 3-Cl 4-Cl Cl Cl 118-120 C2H5-OCH2 Η H 4-CF3 Cl Cl 99-100 CH ~ HH 4-OCH, Br Br 112-115 30 3 3 CH3 HH 4-Cl Br Br 197-201 C2H5OCH2 Η H 4-OCF3 Cl Cl 46-47 CH3 Η H 4-OCF3 Cl Cl 72-73 C6H5-CH2 Η H 4-OCF3 Cl Cl oil 35 c2h5och2 HH 4-Cl Cl Cl - 40 DK 173853 B1

& LU B X X s BP ° S

HOCH2CH2 H 3 — Cl 4-C1 Cl Cl 143-145 NC H 3-Cl 4-C1 Cl Cl 251-252 C6H5CH2OCH2 H 3-C1 4-C1 Cl Cl 88-89 5 ClO-CH2 H 3-Cl 4- Cl Cl Cl 118-120 IC = C-CH2 H 3-C1 4-C1 Cl Cl 115-116 CH3 HH 4-C1 Br CF3 126-129 C2H5OCH2 Η H 4-C1 Br CF3 91-92 C2H5 ”OCH2 H 3" C1 4 ~ ε1 C1 C1 118 ”120 10 C2H5-OCH2 Η H 4-C1 Br Br 104-105 C6H5-CH2 Η H 4-C1 Br Br 81-82 CH3 Η H 4-C1 Br Br 197-201 CN HH 4 -CF3 Cl Cl 138-139 C2H5-OCH2 Η H 4-CF3 Br CF3 104-105 C2H5-OCH2 Η H 4 ~ CF3 H CF3 76-77 C2H5OCH2 H 3-C1 4-C1 Br CF-, 80-81 EXAMPLE 1-Benzyl-4,5-dibromo-2- (o, oro, -trifluoro-p-tolyl) ovrrol-3-carbonitrile

Br CN

JT \ ♦ B) CtCH,> 3 * <fV-CHjBr -

25 x X 'W.

ISLAND

In a 100 ml flask, mix 1.5 g of 4,5-dibromo-2- (a, at-trifluoro-p-tolyl) pyrrole-3-carbonitrile with 50 ml of dry THF to form a clear dark solution. 1 eq. KOtBu is added with stirring. After a few minutes, the solution becomes clear. 0.65 g of benzyl bromide is added by syringe. The mixture is heated at reflux overnight. The following day, tic (50/50 EtOAc / hexane) shows the presence of both starting material and product. The reaction is worked up as follows: 50 ml of water is added and the mixture is extracted with 4 x 50 ml of CHCl 3. The organic phases are combined and washed with 4 x 50 ml of 10% aqueous NaOH. The organic phase is dried with MgSC> 4 and stripped. This gives a brown solid which crystallizes from EtOAc / hexane.

Yield = 0.75 g = 40.7%

Mp = 145-147 ° C.

EXAMPLE 11 4,5-Dichloro-2- (3,4-dichlorophenyl) -1- (ethoxymethyl) pyrrole-3-carbonitrile

Cl CM

Cl CN \ / V - '/ TUF \ * K0CCCH3> 3 ♦ ClCH80CeM5 -► Cl'Y \ T \ Lci

Cl M / Y ^ V> C1 I \ = <

\ = / CH80CeH5 CI

Cl 20

A sample of 1.0 g (0.003 mol) of 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile is dissolved in 10 ml of dry tetrahydrofuran. To this solution is added 0.37 g (0.0033 mole) of potassium t-butoxide followed by 0.312 g (0.0033 mole) of chloromethylethyl ether. The mixture is stirred for approx. 1 hour at room temperature and then poured into a large volume of water, which precipitates the product. The white solid is collected and dried to give 1.0 g (91%), mp: 128-130 ° C.

EXAMPLE 12 4- Chloro-3-cyano-2- (p-chlorophenyl) pyrrole

To a magnetically stirred 20 ° C solution of 17.87 g (88.2 mmol, 1.00 eq) of 2- (p-chlorophenyl) -3-cyanopyrrole in 800 ml of dioxane, 250.15 g (13.13 g real, 176.4 mmol, 2.00 eq.) 5.25% by weight of bleach over 30 minutes-5 hours. After stirring at room temperature for an additional 30 minutes, the reaction solution is poured into 2200 ml of water. The resulting mixture is vacuum filtered to remove a small amount of black solid. The filtrate is acidified to pH 2 with concentrated HCl to give a brown solid. This solid is vacuum filtered and the collected solids are washed with water to give 22.41 g of a brown solid. This solid is treated with 100 ml of 5% aqueous sodium hydroxide to dissolve the mass of material, leaving a small amount of undissolved black solid. This black solid, dissolved in 100 ml of ethyl acetate, is washed with 75 ml of 5% aqueous NaOH, water and saturated aqueous NaCl, respectively. The ethyl acetate layer is dried (MgSO4), treated with carbon, filtered and then rotary evaporated in vacuo to give 1.10 g (5.3% yield) of an orange-brown solid. This solid is recrystallized from an ethyl acetate-chloroform mixture to give 0.51 g (2.4% yield) of an off-white solid of 4-chloro-3-cyano-2- (p-chlorophenyl) pyrrole. Mp. : 251-253.5 ° C.

EXAMPLE 13

Preparation of 5-bromo-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile CN / CN 30 cL ♦ is «/ χ YV3_C1 βγ" xiVci

Cl C1 35 43 DK 173853 B1

A sample of 2.0 g (0.008 mol) of 2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile is dissolved in 100 ml of dioxane by heating to 40-50 ° C. The solution is then cooled to 30 ° C and 1.3 g (0.008 mole) of bromine is added. After stirring for 1 hour at room temperature, the solution is poured onto water and 2.2 g (88%) of a gray solid is collected. Mp. is 233-236 ° C, dec.

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

EXAMPLE 14

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

C C1WCN

+ <ch3> 3coci - *

A sample of 0.158 g (0.005 mole) of 5-bromo-2- (3,4-dichloro-phenyl) -pyrrole-3-carbonitrile is dissolved in bromine. 5 ml of tetrahydrofuran.

An equivalent amount of t-butyl hypochlorite is added and the solution is stirred overnight. The solution is poured into water and 0.052 g (30%) of the precipitate is collected. Mp. is> 275 ° C.

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

EXAMPLE 15

Preparation of 5-chloro-4-chloro-2- (p-chlorophenyl) -nyrrole-3-carbonitrile 44 DK 173853 B1

5 Cl CN cl CN

Vi * Br = CHCl 3 irVyci Br s \ IVci 10 To a magnetically stirred 22 ° C solution of 0.17 g (0.67 mmol, 1.00 equivalent) of 4-chloro-2- (p-chlorophenyl) pyrrole-3 -Carbonitrile in 100 ml of chloroform drops over a 30 minute solution of 0.20 ml (0.62 g, 3.88 mol, 5.79 eq) of bromine in 5 ml of chloroform. The addition gives no exo-term. After stirring at room temperature for 3 1/4 hours, the clear red reaction solution is evaporated in vacuo to give 0.28 g of an off-white solid. This solid is slurried with a hexane-methylene chloride mixture to form by vacuum filtration of 0.23 g of an off-white fluffy solid. Mp: 262-263 ° C; dec.

EXAMPLE 16

Preparation of 5-chloro-4-bromo-2- (p-chlorohenyl) pyrrole-3-carbonitrile 25

CN B \ _ / N

Cf \ * βΓΖ CHCl₂

C 1 C 1 H

30 \ = /

To a magnetically stirred 45 ° C solution of 1.00 g (4.22 mmol, 1.00 eq.) Of 5-chloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile in 300 ml of chloroform is dropped over 30 minutes. to a solution of 0.40 ml (1.24 g, 7.76 mmol, 1.84 eq) of bromine in 25 ml of chloroform. The addition gives no exotherm, and towards the end of the addition a small amount of a solid begins to precipitate. After stirring at room temperature for 19M hours, the reaction mixture is evaporated in vacuo to give 1.49 g of an orange-white solid. This solid is slurried with a hexane / methylene chloride mixture to give, by vacuum filtration, 1.33 g (100% yield) of a fluffy white solid, m.p. : 250-258 ° C, dec.

Example 17 Preparation of 5-chloro-2- (n-chlorophenyl) pyrrole-3-carbonitrile

CN

ft A + S0BC12 "'> 15 h vy« c ^ rvv-

To a 35 ° C magnetically stirred solution of 2.40 g (11.8 mmol, 1.00 eq) of 2- (p-chlorophenyl) pyrrole-3-carbonitrile 20 and 65 ml glacial acetic acid, drop by 0.75 ml syringe ( 1.26 g, 9.34 mmol, 0.70 eq) of sulfuryl chloride over 5 minutes. Ca. Five minutes after completion of the addition, a solid precipitates from the reaction solution. After stirring at room temperature for 45 minutes, the reaction mixture is filtered and the collected solid is washed thoroughly with cold acetic acid to give 2.08 g (74% crude yield) of an off-white solid. This solid is recrystallized from 75 ml of hot acetic acid to give 1.63 g (58% yield) 97% by weight pure. The product has mp: 258.5-261 ° C.

EXAMPLE 18

Preparation of 2- (3,4-dichlorophenyl) -1-methylloverrol-3-carbonitrile DK 173853 B1 46

CN CN

In a 100 ml flask, dissolve 2.0 g of 2- (3,4-dichlorophenyl) -pyrrole-3-carbon in triplicate in 50 ml. ml of dry THF and 1 equivalent of potassium t-butoxide are added. This gives a slightly cloudy solution. One equivalent of methyl iodide is then added to the mixture by means of a pipette. This results in a slight brightening of the color. A drying tube is connected to the flask and allowed to stir at ambient temperature overnight.

20 The next morning there is a light, light colored precipitate in the flask. 50 ml of water is then added and the solution becomes clear before a solid precipitates from the solution. This solid is filtered out of the solution and compared with the starting material by tic (25% ethyl acetate / hexane). This one shows a new single spot that moves faster than the starting material. It is dried in a vacuum oven at 50 ° C overnight. The product yield is 1.31 g or 62% yield and the product has a melting point of 140-142 ° C. EXAMPLE 19

Preparation of 4,5-dichloro-2- (3,4-dichlorophenyl) -1-methylpyrrole-3-carbonitrile 47 DK 173853 B1

5 CN clwCN

Γ- / π ♦ S02C12 -►

In a 50 ml round bottom flask, 0.5 g of 2- (3,4-dichloro-phenyl) -1-methylpyrrole-3-carbonitrile is mixed with 35 ml of glacial acetic acid. The mixture is lightly heated with a hot syringe to dissolve all the pyrrole.

15 To this clear solution add 2 eq. sulfuryl chloride by pipette. The solution is allowed to stir at room temperature for 12 hours.

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

The resulting solid is identical with tic (25% ethyl acetate / hexane) and infrared analysis with the product of Example 9. The product yield is 0.36 (56%).

EXAMPLE 20

Preparation of 4,5-dichloro-2- (3,4-dichlorophenyl) -1- (2-hydroxyethyl) -pyrrole-2-carbonitrile C1-6 BrClCHOH + -►

'• WCC

OH

48 DK 173853 B1

To a stirred mixture of 2.0 g (6.5 τητηοΐ) 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile and 0.88 g (7.8 mmol) of potassium -t-butoxide heated under reflux in 50 ml of dioxane is added 0.98 g (7.8 mmol) of bromethanol. The mixture is stirred under reflux for 12 hours, cooled, diluted with 50 ml of water and extracted several times with chloroform.

The combined chloroform extracts are dried over magnesium sulfate and concentrated in vacuo to give a solid which, after heating and dissolving in ethyl acetate on cooling 10, mostly precipitates starting pyrrole. Concentration of the mother liquor and recrystallization of the residual solid from 20% ethyl acetate in hexane gives 0.31 g of a white solid, m.p .: 143-145 ° C; IR 5077A.

Analysis:

Calcd for C 16 H 23 NO 4; C, 44.57 H, 2.29; N, 8.00; Cl, 40.57. Found. (Agm 33139): C, 44.77; H, 2.29; N, 8.06; 8.06;

Cl, 40.14.

EXAMPLE 21

Preparation of 4,5-dichloro-2- (3,4-dichlorohenyl) pyrrole-1,3-dicarbonitrile - "w".

ciA «» - · + * n-Bu0 '—i H "

CN

617 mg (55 mmol) of potassium t-butoxide are added portionwise to a solution of 1.52 g (5 mmol) of 3-cyano-4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole in 20 ml of anhydrous THF. After 30 minutes, a solution of 583 mg (5.5 mmol) of cyanobromide in 1 ml of THF 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 and extracted with ethyl acetate. The organic layer is washed with water and saturated sodium chloride and dried (MgSC4). Evaporation and crystallization of the residue from ethyl acetate give 1.07 g of white crystals; mp: 250.5-252.0 ° C; IR (nujol) 2255, 2245 cm -1 (CN); 13 C-NMR (DMSO-d6) 102.7 (N-10 CN), 113.7 (3-CN); Mass spectrum 331.9 (M + 1) .

Analysis:

Calcd for C12 H3 Cl4 N3 (330.99); C, 43.54; H, 0.91; N, 12.70;

Cl, 42.85.

Found: C, 43.62; H, 0.93, N, 12.63; Cl, 41.95.

EXAMPLE 22

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

Cl__.CN

+ i * + NaDH — i

* v Cl CN

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 give 0.51 g of white crystals, mp: 50 DK 173853 B1 115-116 ° C.

This reaction can also be used to convert all substituted N-alkynylaryl pyrrols of formulas III, IV, V, VI or VII of the invention to N-substituted 5 3-iodo-2-propynyl-aryl pyrrols according to the invention.

EXAMPLE 23

Preparation of 2- (3,4-dichlorophenyl) -4,5-diiodo-pyrrole-3-carbonitrile 10.7 g (0.0254 mol) N-iodosuccinimide is slowly added to a solution of 3.0 g (0.0127 mol ) 2- (3,4-Dichlorophenyl) -pyrrole-3-carbonitrile in 100 ml of THF. The reaction is stirred for several hours at 25 ° C until thin layer chromatography 25 (silica gel; 100: 100: 1 ether: petroleum ether: acetic acid) shows that it is complete. The mixture is evaporated in vacuo to give a residue containing the pyrrole and the sucinimide. The crude solid is dissolved in 500 ml of ether and shaken with 5 x 400 ml of water to remove the succinimide.

The ether is dried over Na 2 SO 4 and evaporated in vacuo to give 2.0 g (32.3%) of a gray-brown solid, m.p. :> 230 ° C (violet vapors).

EXAMPLE 24

Preparation of 2-phenyl-1-pyrroline-4-carbonitrile 51

NC

5 / CN / * v J I) 10 »o IX nBu4N + F„) V

= / + TflS- ^ YY --- ► / \

[N— THF / 16hr / RT

i N

A solution of 0.65 ml (0.01 mole) of acrylonitrile and 2.4 g (0.01 mole) of N- (trimethylsilyl) methyl-S-methyl-thioimido-benzoate in 100 ml of THF is cooled to -5 ° C. in an ice-acetone bath. During a nitrogen purification stream, a solution of tetra-butylammonium fluoride (1.0 ml of a 1 N solution in THF) and 15 ml of THF are dropped over 30 minutes thereafter. The solution is stirred for a further 30 minutes at -5 ° C and then allowed to warm slowly to ambient temperature. Stirring is continued for an additional 18 hours and then the solvent is removed under reduced pressure. The residue is partitioned between ether / water and the aqueous layer is extracted with fresh ether. The combined organic layer is washed with water and then with saturated sodium chloride. The solution is dried with MgSO4 and cooling of the filtrate causes the precipitation of 1.2 g (70% of theoretical yield) of greyish white solid, the spectral characteristics of which are identical to that of Tsuge [J. Org. Chem. 52, 2523 (1987)].

Calcd for C 11 H 10 N 2: C, 77.65; H, 5.88; N, 16.47.

Found: C, 77.55; H, 5.83; N, 16.39.

mp: = 95-97 ° C.

EXAMPLE 25

Preparation of 2-phenylpyrrole-4-carbonitrile NC NC 2 DDQ / OME / pyr N 16 hours / room temp. 10 During a nitrogen purification stream, 0.23 g (0.001 mol) of 2,3-dichloro-5 are dissolved. , 6-dicyano-1,4-benzoguinone and 0.17 g (0.001 mol) of 2-phenyl-1-pyrroline-4-carbonitrile in 13 ml of 1,2-dimethoxy-ethane to give a clear orange solution. 08 ml (0.001 mol) of pyridine is added in a single portion, causing a slight exotherm (to about 28 ° C) and immediate formation of a green / gray precipitate. The suspension is stirred at room temperature for 18 hours, during which time 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 and then with saturated sodium chloride. MgSC> 4, the solvent is removed under reduced pressure to form a white semi-solid, this material is recrystallized 25 from ethylene dichloride (DARCO treatment) to form 0.1 g of lavender colored crystals.

The identical product is obtained directly in a single step by condensing chloroacrylonitrile and N- (trimethylsilyl) methyl-5-methyl-thioimidobenzoate using 30 tetrabutylammonium fluoride catalysis (analogous to the preparation of 2-phenyl-1-pyrroline-4 carbonitrile, as previously described).

Calcd for C; i: i.HgH2: C, 78.57; H, 4.76; N, 16.67.

Found: C, 78.65; H, 4.70; N, 16.43.

Mp: 155-158 ° C.

EXAMPLE 26

Preparation of 2,4-dibromo-5-phenylpyrrole-3-carbonitrile 53 NC 17 Br53 / Br2 / CHCl3 HH \\ Λ; During a nitrogen purification stream, a solution of 0.6 ml (0.012 mol) of bromine in 5 ml of CHCl 3 is added dropwise over 20 minutes to a stirred solution of 0.84 g (0.05 mol) 2-phenylpyrrole-4-carbonitrile in 20 ml of CHCl3. The resulting solution is stirred for 18 hours at room temperature and then the solvent is removed under reduced pressure to give a solid which is recrystallized from C 2 H 4 Cl 2 (DARCO treatment) to give 0.6 g of the desired final product, m.p. : = 239-242 ° C. Calcd for C 11 H 5 Br 2 N 2: c, 40.49; H, 1.84; Br, 49.08; N, 8.59.

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

In the process described in Examples 24, 25 and 26, 2,4-dibromo-5- (p-chlorophenyl) pyrrole-3-carbonitrile, mp: 270-272 ° C (decomposition) is also prepared.

EXAMPLE 27 3'.41-Dichloro-3- (1,3-dioxolan-2-yl) propiophenone

Cl CO 2 K / ΰ — 1 THF

♦ Brtlg ·

χΖ-α J

54 DK 173853 B1

To a rapidly stirred mixture of 0.64 g (26 mmol) of magnesium turning chips in 10 ml of tetrahydrofuran at 25 ° C in a 100 ml three-necked round bottom flask equipped with a thermometer, a 60 ml addition funnel and a nitrogen inlet, drop 4.7 g (26 5 mmol) 2- (2-bromomethyl) -1,3-dioxolane in 40 ml of tetrahydrofuran. The addition rate is adjusted in such a way that the reaction temperature is kept below 50 ° C. The reaction is then stirred for 1 hour at 25 ° C. 120 ml of tetrahydrofuran are mixed with 5.0 g (22 mmol) of potassium 3,4-dichlorobenzoate, under protection of nitrogen. The Grignard solution is then rapidly decanted from the unreacted magnesium turnings and added dropwise to the rapidly stirred potassium benzoate suspension. The reaction mixture is then stirred for 24 hours at 25 ° C. 50 ml of diethyl ether and 15 ml of 3N hydrochloric acid are added to the reaction mixture, 15 and the layers are separated. The organic layer is washed with saturated aqueous sodium bicarbonate until neutral, followed by one wash with 10 ml of brine. Drying with sodium sulfate and evaporation on a rotary evaporator gives an off-white semi-solid which is chromatographed over silica gel using 3: 1 hexane: ethyl acetate as eluent to give 4.3 g (60%) of keto-acetal as a white barrel, m.p .: 115-117 ° C.

EXAMPLE 28 Preparation of 3- (3,4-Dichlorobenzoyl) propionaldehyde 0 1 ° L

C1-8H08C-C0gH

30 ° C

Cl 10 g (26 mmol) of 3 ', 4'-dichloro-3- (1,3-dioxolan-2-yl) -propiophenone is added to 30 ml of 0.2 M oxalic acid (obtained 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 separated by rotation for steaming and 100 ml of diethyl ether is added together with 20 ml of saturated aqueous sodium bicarbonate. The layers 5 are separated and the organic phase is dried with magnesium sulfate. Rotary evaporation gives a viscous yellow oil which is chromatographed over silica gel using 3: 1 hexamethyl acetate to give 6.3 g (75%) of keto-aldehyde as a white solid.

EXAMPLE 29

Preparation of 2- (3,4-Dichlorophenyl) Nyrrole 0 15 in II NH 4 QRC

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

EXAMPLE 30

Preparation of 5- (3,4-Dichlorophenyl) pyrrole-2-carboxaldehyde 5 ΓΛ C1 rp \ _ / cl X> 0f1F / PcC13 H - Cl - 0HC H V ^^ Cl 2) NaoPc 10

To 10 ml of dimethylformamide stirred under nitrogen in a 50 ml round bottom flask drop 0.6 ml (6.5 mmol) of phosphorus oxychloride via syringe. The solution gets warm and turns a pale yellow color. It is stirred for 20 minutes before the 15 portion addition of 1 g (4.7 mmol) of 2- (3,4-dichlorophenyl) pyrrole. The resulting off-white suspension is stirred for 30 minutes before being heated to 50 ° C for 40 minutes. A solution of 10 g (122 mmol) of sodium acetate in 15 ml of water is added to the cooled reaction mixture, which is then stirred for 20 minutes. An off-white precipitate is filtered off from the reaction mixture and air dried for 20 hours to give 1.1 g (95%) of a substantially pure aldehyde, m.p. :> 200 ° C.

EXAMPLE 31

Preparation of 5- (3,4-dichloromethenyl) pyrrole-2-carbonitrile OH - <> YYC1 30 H CTOH / H

To a suspension of 1.5 g (6.2 mmol) of 5- (3,4-dichloro-phenyl) pyrrole-2-carboxaldehyde in 20 ml of water and 20 ml of ethanol was added 0.7 g (6.2 mmol) hydroxyl amine-O-sulphonic acid. The reaction mixture is refluxed for 1 hour, during which time a gray precipitate appears. After being cooled, the reaction mixture is filtered to give 1.5 g (99%) of substantially pure nitrile as a gray solid, mp: 170-171 ° C.

EXAMPLE 32

Preparation of 3,4-dibromo-5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile 10 Br 15

To a solution of 0.5 g (2.1 mmol) of 5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile in 20 ml of tetrahydrofuran under nitrogen is added portionwise 0.8 g (4.2 mmol) of N-bromine. succinimide. The reaction mixture is stirred at 25 ° C for 30 minutes before adding 10 ml of water and 40 ml of diethyl ether. The layers are separated and the organic layer is dried with sodium sulfate. Rotary evaporation is followed by chromatography over silica gel using 3: 1 hexane: ethyl acetate as eluent to give 0.5 g (60%) of dibromopyrrole as a brown solid, mp:> 250 ° C.

EXAMPLE 33

Preparation of 4-phenylloverrol-3-carbonitrile cr * '£ Γ ~~ ί CHj

V ° J

H

58 DK 173853 B1

To a mixture of 5.0 g (39 mmol) of cinnamonitrile and 7.6 g (39 mmol) of (p-tolylsulfonyl) methyl isocyanide in 35 ml of DMSO and 65 ml of ether, a suspension of 1.86 g of a 60% oil suspension of 1.11 g (46 mmol) of sodium hydride in 80 ml of ether. The reaction mixture is kept under nitrogen for one hour and then diluted with ether and water. The ether layer is separated, dried over magnesium sulfate and concentrated in vacuo. The resulting oil is chromatographed on silica gel using 1: 1 chloroform: ethyl acetate 10 to give 2.5 g of cream colored solids. Recrystallization from ether / hexane gives 1.15 g, mp: 123-125 ° C; NMR M86-1077.

Lit .: Tet. Letters 5337 (1972): mp: 128-129 ° C.

EXAMPLE 34

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

20 \ yjD

+ SOgClg + C1E Cl

H H

25

To a stirred mixture of 0.66 g (3.9 mmol) of 4-phenyl-pyrrole-3-carbonitrile in 20 ml of dry THF is cooled to 6 ° C with an ice-water bath, 0.66 ml is added via syringe ( 1.1 g (8.2 mmol) of sulfuryl chloride over 4 minutes. The mixture is kept at 5-10 ° C for an additional 45 minutes and then stirred for an additional 30 minutes 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 35 water and dried with sodium sulfate. Filtration through a short column of silica gel, rinsing with ethyl acetate and concentration of the combined filtrate in vacuo yields 0.95 g of dark solid. Recrystallization from chloroform gives 0.42 g of greyish white crystals, mp: 195-196 ° C (dec.).

Analysis:

Calcd for CnHgCl2N2: C, 55.72; H, 2.55; N, 11.82;

Cl, 29.91.

Found: C, 55.66; H, 2.65; N, 11.69;

Cl, 29.97.

Following the procedures of Examples 33 and 34, the following analogous compounds 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 instead of sulfuryl chloride and tetrahydrofuran.

'ΥίΡ "

Y N X

20 H

X X Y on

Λ m.p. C

4-C1 Cl Cl 237-240 (decomposition) 4-CH * Cl Cl. .3 „103-206 25 4 — Cl Br.

> 245 °

Ethyl 4- (p-chlorohenyl) -pyrr-oi ^ cr

To a mixture of 5, g3 9 60% sodium hydride / oil suspension in 200 ml dry ether under nitrogen is added from a dropping funnel a mixture of 23.5 g (122 mmol) 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 sulfoxide. The addition time is approx. 20 minutes and result in gentle reflux of the mixture. After a further 10 minutes of stirring, the mixture is diluted with 100 ml of water. The mixture is extracted four times with ether, which is then dried with magnesium sulfate and then concentrated in vacuo. The resulting solid is recrystallized from ethylene dichloride to give 7.8 g of crystals, mp 137-138 ° C.

Analysis:

Calcd for C 13 H 12 ClNO 2: c, 62.53; H, 4.81; N, 5.61;

Cl, 14.23.

Found: C, 61.31; H, 5.12; N, 5.32;

Cl, 14.57.

Concentration of the mother liquor for the crystallization provides additional crude ester which is transferred to the saponification step.

EXAMPLE 36 30 "

A mixture of 22.0 g of crude ethyl 4- (p-chlorophenyl) pyrrole-3-carboxylate from the mother liquor from the recrystallization and the recrystallized product of the previous step is stirred under reflux with 150 ml of 10% 9 sodium hydroxide for 2 hours. 5 hours. The mixture is cooled, extracted with ether and acidified to give a precipitate which, after collection and drying, weighs 11.6 g.

A mixture of 10.5 of the acid in 100 ml of S-ethanolamine is heated under reflux for three hours. After cooling 5, the mixture is poured over 400 ml of ice and the resulting mixture is extracted four times with chloroform. The chloroform solution is concentrated in vacuo after drying with magnesium sulfate and activated carbon treatment to give a brown solid. Chromatography on silica gel using 1: 1 ethyl acetate trhexane gives 4.0 g of a white solid, m.p. : 117-118 ° C.

EXAMPLE 37

Preparation of 3- (p-Chlorophenyl) -pyrrole-2-carboxaldehyde 15. C 1-6 - tf + CC0Cl) e ♦ <CHa> eNCH -

H

20 Cl c / \ n / ^ cho

H

To a mixture of 0.86 g (12 mmol) of dimethylformamide in 10 ml of ethylene dichloride kept under nitrogen and cooled in an ice bath, add 1.49 g (12 mmol) of oxalyl chloride in 10 ml of ethylene dichloride over 25 minutes. The ice bath is removed, the mixture is stirred for another 15 minutes and re-cooled in an ice bath. To this mixture is added 1.5 g (8.5 mmol) of 3- (p-chlorophenyl) pyrrole in 25 ml of ethylene dichloride over 20 minutes. The ice bath is removed and after a further 30 minutes of stirring, the mixture is poured onto 50 ml of ice water and 6 ml of 5% sodium hydroxide. The resulting mixture is extracted with ether 35 and with chloroform, and the combined organic mixture is dried over magnesium sulfate and concentrated in vacuo. Purification 62 DK 173853 B1 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 to convert to 3- (p-chlorophenyl) pyrrole-2 carbonitrile.

EXAMPLE 38

Preparation of 3- (p-chlorophenyl) pyrrole-2-carbonitrile [f + HgNOSO 3 H -►

15 K CN

A mixture of 0.63 g (3.1 mmol) of 3- (p-chlorophenyl) pyrrole-2-carboxaldehyde in 10 ml of water is stirred and ice-cooled while 0.52 g (4.6 mmol) of hydroxylamine-O sulphonic acid in 10 ml of water is added slowly. After the addition, the cooling bath is removed and the mixture is heated for 25 minutes. After cooling, the resulting solid is collected, which, by NMR, turns out to be a mixture of product and starting s aldehyde.

This mixture is similarly reacted with an additional 0.49 g (4.2 mmol) of hydroxylamine-O-sulfonic 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 chromatograph on silica gel using 1: 1 ethyl acetate-30: hexane to give 0.40 g of pink solid, mp: 114-115 ° C.

EXAMPLE 39

Preparation of 4,5-dibromo-3- (n-chlorophenyl) -pyrrole-2-carbonitrile 5 / Cl 2 / Cl + Br 2 - * 11 µl

10 H CN Br H CN

To a mixture of 0.40 g (2.0 mmol) of 3- (p-chlorophenyl-pyrrole) -2-carbonitrile in 25 ml of chloroform is added 0.63 g (4.0 mmol) of bromine. After 20 minutes, the precipitate formed is collected and recrystallized from ethyl acetate to give 0.21 g of pink crystals, mp:> 250 ° C.

Analysis.

Calcd for C 11 H 5 Br 2 ClN: 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.

EXAMPLE 40

Preparation of ethyl 5-bromo-4- (p-chlorophenyl) pyrrole-3-carboxylate 0 O-n 30 No. Tf

H II

o.-v. COOCpH- ciOri

Br N - 64 Dissolve 1.6 g (0.0064 mmol) of ethyl 4- (p-chlorophenyl) pyrrole-3-carboxylate in 40 ml of tetrahydrofuran. 1.14 g (0.0064 mmol) of N-bromosuccinimide are 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 is partitioned between water and ether. The ether layer is separated and dried with magnesium sulfate. Work up the ether extract gives 1.9 g (90%) of a white solid which is purified by stirring with a mixture 10 of 80:20 hexane: ethyl acetate. 1.3 g (62%) of insoluble solid is collected and has mp: 161-164 ° C.

Analysis:

Calculated for C H, 3.34; N, 4.26;

Br, 24.33; Cl, 10.80.

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

Br, 24.29; Cl, 10.77.

EXAMPLE 41

Preparation of 5-bromo-4- (p-chlorophenyl) pyrrole-3-carboxylic acid 20 r λ .COOC, «, / ΓΛ / c °° C1_w ~ ir (C1 * wivi N— '/ ly * n * oh - *

Br η βΓ 25 g (0.045 mmol) of 5-bromo-4- (p-chlorophenyl) pyrrole-3-carboxylate is added to 200 ml of 10% sodium hydroxide and the slurry is heated to reflux. to dissolve, the mixture is refluxed for an additional 40 minutes. The mixture is cooled, filtered and the filtrate acidified. 8.0 g (58%) of white precipitate is collected and dried. The solid has mp:> 205 ° C and an NMR- ( dg-DMSO), which shows a pyrrole proton at 7.52 (d), the mass spectrum also corresponds to a monobromerated compound.

EXAMPLE 42

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

5 / T ~ \ / C00H

«-V V-7r / cK Jhn \ \ = / // U H8NCH2CH20H / ^ 3

Br 5 - Br 2 10 8.0 g (0.026 mmol) of 5-bromo-4- (p-chlorophenyl) pyrrole-3-carboxylic acid are added to 24 ml of amino ethanol and the slurry is slowly heated to 110-120 ° C and maintained at The temperature is cooled and poured into water and extracted with ether 15. The ether extract shows at tcl (75:25, hexane ethyl acetate) shows a larger fast moving spot and a slower moving smaller component. 0 g (56%) of a dark solid which is 2-bromo-3- (p-chlorophenyl) pyrrole-2-carbonitrile.

EXAMPLE 43

Preparation of 5-bromo-4- (p-chlorophenyl) pyrrole-2-carbonitrile "-" O ~ jQ> * c'sotHCO. Dm · 0-.

Br H H

30

A freshly prepared sample of 4.0 g (0.015 mmol) of 2-bromo-3- (p-chlorophenyl) pyrrole is dissolved in 25 ml of dry dimethoxyethane. Then, 3.08 g (0.022 mol) of chlorosulfonyl isocyanate are added while keeping the temperature below 25 ° C. After stirring overnight, the solution is treated with 6 ml of dimethylformamide and stirred for 3 hours. Finally, the solution is poured onto water, which precipitates 3.8 g (90%) of a brown solid. Column chromatography (80:20 hexane: ethyl acetate) gives 1.4 g (33%) of white solid, mp: 202-204 ° C.

Analysis:

Calcd for C CHgBrCl:: 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.

EXAMPLE 44

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

. "- O-JV * · '-" -O-tC

20

A sample of 2.2 g (0.0078 mol) of 5-bromo-4- (p-chlorophenyl) pyrrole-2-carbonitrile is dissolved in 30 ml of dry dioxane. The solution is heated with 1.3 g (0.008 mole) of bromine in 20 ml of dioxane and then stirred overnight at room temperature.

The reaction mixture is poured onto water to precipitate 2.6 g (92%) of colored solid. One portion of 1.6 g is purified by flash chromatography using 75:25 hexane: ethyl acetate to give 0.8 g of gray solid, mp: 191-194 ° C.

Analysis: Calculated for C 11 H 5 Br 2 ClN 2: C, 36.61; H, 1.38; N, 7.76;

Cl, 9.84; Br, 44.3.

Found: C, 37.46; H, 1.25; N, 7.41;

Cl, 9.53; Br, 42.99.

EXAMPLE 45

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

H

2.66 g (60% suspension in oil is rinsed with dry ether; 66 mmol) sodium hydride is suspended in 150 ml of dry ether. To this mixture, a mixture of 12.0 g (5.5 mmol) of 3,4-dichloro-S-nitrostyrene and 10.8 g (5.5 mmol) of (p-tolylsulfonyl) methyl isocyanide in 15 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: -25 ethyl acetate. A 7.2 g solid fraction is recrystallized from chloroform: ethyl acetate: hexane to give 3.0 g of yellow solid, mp: 187-188 ° C (dec.).

Analysis:

Calculated for C C ^HggC ^^C C: C, 46.72; H, 2.35; N, 10.90.

Found: C, 46.96; H, 2.60; N, 9.77.

68 DK 173853 B1 EXAMPLE 46

Preparation of 2,5-dichloro-3- (3,4-dichlorophenyl) -4-nitro-pyrrole.Cl / Cl ° ήjOCi ° N N .. + so2cie ► cr ^ ci

10 H H

To a mixture of 2.5 g (9.7 mmol) of 3- (3,4-dichloro-phenyl) -4-nitropyrrole heated to ca. 40 ° C in 200 ml of chloroform is added over one minute to 2.95 g (22 mmol) of sulfuryl chloride. After an additional 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 with magnesium sulfate. Concentration, in vacuo, gives a brown solid which is chromatographed on silica gel using 4: 1 chloroform: ethyl acetate. An orange solid fraction is recrystallized from chloroform and then chromatographed on silica gel using 4: 1 chloroform: ethyl acetate to give 0.36 g of a yellow solid, mp: 193-194 ° C.

The process of Examples 45 and 46 above 25 also produces 2,5-dichloro-3-nitro-4-phenylpyrrole, mp: 193-194 ° C (dec.).

69 DK 173853 B1 EXAMPLE · 47

Preparation of 5- (p-chlorohenyl) -nyrrole-2,4-dicarbonitrile CN

5 I onr + C1SO2NCO + (CH3) 2NCHO -

CN

-vix. J

A sample of 3.0 g (0.015 mol) of 2-p-chlorophenyl-3-cyano-pyrrole prepared by the procedure of Example 4 is dissolved in 50 ml of dry dimethoxyethane. To this solution is added 3.39 g (0.024 mol) of chlorosulfonyl isocyanate. The addition is exothermic and some cooling is required. After stirring for 3 hours at room temperature, 6-7 ml of dimethyl formamide, 20 and the solution are stirred for a further 4 hours. The solution is then poured onto water, which precipitates 3.4 g (100%) of white solid. A sample of 1.0 g is purified by dissolving in ethyl acetate and then passing the solution through a 60 ml filter funnel packed with silica gel. The filtrate is concentrated to give 0.7 g of a white solid, mp: 235-240 ° C.

Following the procedure of Example 47, the following analogous compounds are prepared.

CN

3 ° / ΝΎ ^ τΒ E I, suju.

35

3-Cl 4-C1> 22S ° C

H 4-OCF₂ 185-190 ° C

H <_crj 180-18 SeC

EXAMPLE 48

Preparation of 3-Bromo-5- (p-chlorophenyl) pyrrole-2,4-dicar-bonitrile 5β · · ·, · Vtk ,, ·· - Λχκ »· 10

A sample of 1.0 g (0.004 mol) of 5- (p-chlorophenyl) pyrrole-2,4-dicarbonitrile is dissolved in 20 ml of dioxane and a solution of 0.8 g (0.005 mol) of bromine in 10 ml of dioxane is added. thereafter. The solution is stirred for several hours at room temperature and then poured into water, which precipitates 1.2 g (100%) of a white solid. The solid has a m.p. > 225 ° C, and a 20 mass spectrum of a sample yields a pattern corresponding to the desired structure.

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

CN

25 ΒΓ \ __ τ //

30 H L

B i

a-ci> 250 ° C

35 ° C 4-OCF 3 218-223 ° C

H λ CF 239-241 ° C

H 4 CF3 71 DK 173853 B1 EXAMPLE 49

Preparation of bromofumaronitrile

5 CN CN

- / Brg / CHC13 / ^ NC <“HBr> NC Br 10

Under a nitrogen purge stream, 15.6 g (0.2 mole) of fumaronitrile in 150 ml of CHCl 3 is heated to reflux to give a clear solution. A solution of 5.3 ml (0.2 mole) of bromine in 25 ml of CHCl 3 is added dropwise over 30 minutes to give a slow decolouration, releasing acidic (pH test paper) vapors. The solution is refluxed for a further 90 minutes, during which time the color has disappeared. The solution is cooled and the solvent removed under reduced pressure to give an amber oil (weight 20 approximately theoretical for bromofumaronitrile). The oil is subjected to flask-to-flask distillation (0.2 mm Hg), keeping the temperature below 120 ° C (above this point there is a rapid decomposition of the material). A semi-solid is obtained which slowly forms a waxy amber solid, mp: 43-47 ° C.

Analysis:

Calcd for C 4 H BrN 2: C, 30.57; H, 0.64; N, 17.83.

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

EXAMPLE 50

Preparation of 2-phenyl-pyrrole-3,4-dicarbonitrile 5 CN \ + T "SAN ^ Qn NC Br N> - / 10

NC CN

\ HMPfi / 3 equiv. H * 0 NH (Ti - 2 - V <-TMS, -HBr, -CH3SH)

Under a nitrogen purification stream, a solution of 4.7 g (0.03 mole) of bromfumaronitrile and 7.1 g (0.03 mole) of N- (trimethylsilyl) methyl-S-methylthioimidobenzoate in 35 ml of hexamethylphosphoramide (HMPA) is stirred. ) at room temperature. In a single portion add 1.6 ml (0.09 mol) of water and wash with 10 ml HMPA. The solution begins to exotherm almost immediately, with the temperature rapidly reaching 100 ° C before quenching.

The resulting dark red solution is stirred at ambient temperature for 20 hours. By pouring the reaction mixture onto an ice / water mixture, a rubbery material is obtained which quickly turns into a discrete greyish white 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 recrystallized two times from C 2 H 4 Cl 2 (DARCO treatment) to form a white powder.

73 DK 173853 B1

Analysis:

Calcd for C 12 H 7 N 3: C 7 74 61; H, 3.63; N, 21.76.

Found: C, 74.45; H, 3.84; N, 21.61.

mp: 197-200 ° C.

EXAMPLE 51

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

io NC CN NC CN

/ Ml Bre / CHC13

NH | j ** Bf ^ NH J

15

Under a nitrogen purification stream, 1.4 g (0.0075 mole) of 2-phenyl-pyrrole-3,4-dicarbonitrile is added to 35 ml of CHCl 3 as much of the solid dissolves. A solution of 0.4 ml (0.008 mol) of bromine in 5 ml of CHCl 3 is added dropwise over 20 minutes. At first, the color disappears quickly, but as a new rubbery solid precipitates, the color remains.

After stirring for 30 minutes at ambient temperature, the mixture is refluxed to give a much more discrete solid. After refluxing for 90 minutes, the reaction mixture is cooled and an aliquot removed and analyzed (HPLC), showing that approximately 60% starting material. In a single portion 0.2 ml (0.004 30 moles) of fresh bromine is added and the reflux is continued for a further 45 minutes, after which an aliquot shows that 10% starting material is left. Another fresh portion of 0.2 ml (0.004 mol) of bromine is added to the refluxing suspension and the refluxing is continued for another 30 minutes. The suspension is cooled and stirred for 18 hours at room temperature. The solvent is removed under reduced pressure to give a greenish solid, which is extracted with hot CHCl 3, leaving a dark residue. The extract is treated with DARCO and filtered hot. The clear yellow filtrate quickly begins to precipitate a white precipitate. After cooling to -10 ° C, the white solid is collected by filtration.

Analysis:

Calcd for C12 H6 BrN3: 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.

mp: = 225-258 ° C.

EXAMPLE 52

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

CN CH

/ T \ * HN ° a * fice ° - *

C1 Cl 3.0 g (0.013 mol) of 2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile is added to 50 ml of acetic anhydride and 0.6 ml of 90% nitric acid with very little exotherm. The mixture is slowly heated to 30 ° C and then kept at 30-33 ° C until everything dissolves. Gradually a new solid precipitates. The mixture is stirred for 2-3 hours at room temperature and then poured into water and ice to decompose the acetic anhydride.

After stirring for 1 hour, the mixture is filtered and 2.9 g (82%) of solid are collected and dried. Part (1.5 g) is purified by column chromatography on silica gel using 75:25 hexane: ethyl acetate to elute to give 0.7 g of a yellow solid, mp: 228-231 ° C.

35 75 DK 173853 B1

Analysis:

Calcd for cnH5Cl3C> 2: C, 46.80; H, 1.77; N, 14.89;

Cl, 25.17.

Found: C, 46.50; N, 1.96; N, 14.27; 5 Cl, 24.30.

By the same procedure, starting from 2- (p-chlorophenyl) pyrrole-3-carbonitrile, 2- (p-chlorophenyl) -5-nitropyrrole-3-carbonitrile is obtained, snip: 201-206 ° C. Also 2- (p-trifluoromethylphenyl) pyrrole-3-carbonitrile gives 2- (p-trifluoro-methylphenyl) -5-nitropyrrole-3-carbonitrile by the above process. This compound has a melting point of 164-165.5 ° C.

EXAMPLE 53 Preparation of 4-bromo-2- (3,4-dichlorophenyl) -5-nitro-pyrrole-3-carbonitrile CN \ / dioxane \ - / tt + Br2 -► U \ 20 2 h ycl h 'xc 1

C1 Cl 0.5 g (0.0017 mol) of 2- (3,4-dichlorophenyl) -5-nitropyrrole-3-carbonitrile is dissolved in 10 ml of dry dioxane. To this solution is added 0.28 g (0.0017 mole) of bromine in dioxane. After stirring overnight, the solution is poured into water, which precipitates 0.54 g (88%) of a tan solid. Recrystallization from 5 ml of acetonitrile gives 0.26 g of a brownish yellow solid, mp: 195-200 ° C.

Analysis:

Calcd. For CnH4BrCl2N3C> 2: C, 3 6.57, - 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.

76 DK 173853 B1

Following the above procedure of Example 53, but starting with 2- (p-chlorophenyl) -5-nitropyrrole-3-carbonitrile, 4-bromo-2- (p-chlorophenyl) -5-nitropyrrole-3-carboxylic acid is obtained. bonitrile, mp: 180-185 ° C.

EXAMPLE 54 5- (3,4-Dichlorophenyl) -4-nitropyrrole-2-carbonitrile 10

Cl / NO8 HNOa

H flC20 H

15

To a suspension of 1.2 g (5.1 mmol) of 5- (3,4-dichloro-phenyl) pyrrole-2-carbonitrile in 25 ml of acetic anhydride at 20 ° C under nitrogen, drop 0.3 ml (5.1 mmol) 90% nitric acid. The reaction exotherms to 45 ° C to form a green solution. After stirring for 2 hours, the reaction mixture is poured into 50 ml of water and stirred vigorously for 5 minutes.

The resulting beige precipitate is filtered off and dissolved in a minimum amount of acetone. Chromatography over silica gel using 3: 1 hexane.-ethyl acetate gives 1.2 g (84%) of nitropyrrole as an off-white solid, mp:> 200 ° C.

EXAMPLE 55 3-Bromo-5- (3,4-dichloroahenyl) -4-nitropyrrole-2-carbonitrile - NOg C1

H - Cl H

77 DK 173853 B1

To a suspension of 0.6 g (2.1 mmol) of 5- (3,4-dichloro-phenyl) -4-nitropyrrole-2-carbonitrile in 10 ml of dioxane at 25 ° C, under nitrogen, a solution of 0 , 3 g (2.1 mmol) of bromine in 5 ml of dioxane. The reaction mixture is stirred overnight.

Addition of 50 ml of water causes the precipitation of a yellow solid which is collected and dried in a vacuum oven (50 mm Hg, 45 ° C) to give 0.7 g (90%) of brominated pyrrole as a light yellow solid, m.p. :> 200 ° C.

EXAMPLE 56 4- (p-chlorophenyl) -2- (trifluoromethyl) -2-oxazolin-5-one In a single portion, 1.7 ml (0.012 mol) of trifluoroacetic anhydride are added to 11.4 g (0.06 mol ) powdered 2- (p-chlorophenyl) glycine, causing an immediate exotherm to approx. 40 ° C, forming a yellow color on the surface of the solid. As the mixture slowly warms to 70 ° C, more of the solid dissolves to an orange / amber oil. All the solid dissolves in approx. 2 hours and heating is continued for another hour.

The solvent is removed under reduced pressure on a rotary evaporator. Toluene is added twice and removed under reduced pressure, but the smell of trifluoroacetic acid is still evident.

This yellow semi-solid (yield theoretical; purity> 90% by HPLC) is the above compound and is used in the next step without further purification.

EXAMPLE 57

Preparation of 2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrols carbonitrile 2.5 g (0.01 mole) of 4- (p-chlorophenyl) -2- (trifluoromethyl) -2-oxazolin-5-one dissolve in 50 ml of nitromethane. In a single portion, 8.0 ml (0.10 mol) of 2-chloroacrylonitrile is added to the solution and the resulting solution is stirred for 18 hours under reflux under a nitrogen atmosphere. Cooling 35 of the red / brown solution to -5 ° C in an ice-acetone bath causes the formation of a precipitate which is collected by filtration and washed with a small amount of cold nitromethane. The resulting brownish yellow solid is recrystallized from hot ethylene dichloride to give the product as 1.8 g (56% of theory) of white crystals, m.p. : 238-241 ° C (dec.).

Using appropriate arylglycine in the method of Example 55 and following the procedure of this example, the following 2-aryl-5- (trifluoromethyl) pyrrole-3-carbonitriles are prepared:

10 j CN

15 BL mp ° c Η H 215-218 H 4-CH3 191-193 20 H 4-OCH3 168-180 (decomposition) 3-Cl 4-Cl 245-246 (decomposition) H 4-CF3 218-219 EXAMPLE 58

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

During a nitrogen purification stream, a suspension of 1.6 g (0.005 mol) of 2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile is heated in 25 ml of acetic acid, dissolving all the material to a clear solution. at about. 60 ° C. A solution of 0.8 ml (0.015 mole) of bromine in 10 ml of acetic acid is added dropwise over 15 minutes to the refluxing solution. The solution 35 is refluxed for 6 hours and then stirred for 18 hours at room temperature. HPLC of the reaction mixture shows approx. 80% 79 DK 173853 B1 conversion to product. The mixture is heated back to reflux and 0.5 ml (0.01 mole) more bromine in 5 ml of acetic acid is added thereto. After refluxing for an additional 3 hours, the aliquot shows> 95% conversion to product. The reaction mixture is cooled and the solvent removed under reduced pressure on a rotary evaporator to form a dark gray solid. Toluene is added to the mixture and removed under reduced pressure, but the smell of acetic acid is still there.

The whole material is dissolved in 75 ml of hot toluene to a cloudy solution which is treated with DARCO filter and filtered. The pink solution precipitates a white solid after cooling to ambient temperature. 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 gives 1.2 g (about 60% theoretical yield) of product; mp: 247-250 ° C (dec.).

Analysis:

Calcd for C12 H5 BrClF3 N2: 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 bromination of the appropriate 2-aryl-5- (trifluoro-methyl) pyrrole-3-carbonitrile, obtained by the method of Example 57, according to the above method, the following 25 additional examples are prepared:

B \ / CN

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35 Η H 235-238 H 4-CH3 244-245 3-Cl 4-Cl 218-223 H 4-CF3 225-226 80 DK 173853 B1 EXAMPLE 59

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

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Cl 3.1 ml (0.022 mol) of trifluoroacetic anhydride is added in a single portion to 2.0 g (0.011 mol) of (4-chlorophenyl) -20 glycine to give an instant yellow color and some reflux. The mixture is slowly heated to reflux, causing the entire material to dissolve to a yellow / orange solution which is heated for an additional 2 hours. The reaction mixture is cooled and the solvent removed under reduced pressure. Toluene is added twice and removed under reduced pressure to form a very thick oil (uco = 1800 cm -1). The residue is dissolved (some insoluble constituents) in 40 ml of CH 3 NO 2 and 2.7 g (0.018 mole) of bromofumaronitrile are added in a single portion. The resulting solution is heated at reflux for 18 hours to give a dark red solution. The solvent is removed under reduced pressure and the dark residue is dissolved in CH 2 Cl 2, removing some insoluble components by filtration.

The material is fractionated by dry column chromatography (silica gel; 3% 2-PrOH in CH 2 Cl 2). 9 appropriate fractions are taken. Evaporation of one fraction gives the desired compound as a yellow solid which is recrystallized from CH 3 CN (DARCO treatment) to give 0.2 g of a light yellow solid, mp .: = 238-241 ° C (any decomposition).

EXAMPLE 60 g- (2,2-Diethoxyethylamino) -fe-nitrostyrene and 3-nitro-2-phenyl-nyrrole JT1 ♦ TANCH ^ MCOCt », - / - C-CM-1.0, - 5.7 g (0.0345 mole) of α-nitroacetophenone is taken up in 100 ml of toluene and 4.6 g (0.0345 mole) of aminoacetaldehyde diethyl acetal is added. The reactants are fed to a 250 ml round bottom flask equipped with a Dean-Stark funnel. The funnel is filled with 4Å molecular sieves and the mixture is heated under reflux for 18 hours. The toluene is removed in vacuo to give 8.36 g of α- (2,2-diethoxyethylamino) -β-nitrostyrene as a brown oil.

20 To this oil is added 50 ml of concentrated HCl. As the flask is swirled, the oil becomes a yellow suspension. After 10 minutes, the solid is filtered off to give 2.48 g of a yellow solid. Recrystallization from ether / ethyl acetate / hexane gives the product as two fractions, 2.08 g with 25 mp: 190-192 ° C (31%).

Ma 1485 cm -1 (NO2), H-NMR (CDCl3 / DMSO) 66.73 (m, 2H), 7.46 (m, 5H).

Other β-nitrostyrene preparations may be prepared by the above reaction using the appropriately substituted α-nitroacetophenone in place of α-nitroacetophenone and / or the appropriate 2,2-di (<1-4 alkoxy) ethylamine in place of aminoacetaldehyde. -diethyl acetal to form the following compounds: 82 CH 17 NO 3 B 1? CH 2 NO 2 * HgNCH 2 CH 2 Cl 2 -C * Alkoxy> 2 - toluene

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B-Cl Η H (OCH3) 2 H B “CH3 H (OCH3> 2 Η H B“ CF3 (° C2H5) 2 EXAMPLE 61

Insecticide οσ acaricide reviews

All experiments are carried out using technical materials. All concentrations indicated herein are expressed in 25 active ingredients. All experiments are maintained at 27 ° C.

Spodoptera eridania, 3rd stage larvae, southern army worms.

A Sieva lima bean leaf extended to 7-8 cm in length is dipped into the test suspension with stirring for 3 seconds and placed in a sheath for drying. The leaf is then placed in a 100 x 10 mm Petri dish containing a moist filter paper on the bottom and ten third stage larvae. The dish is stored for 5 days before making observations for mortality, decreased food intake or any disruption of normal skin change.

83 DK 173853 B1

Spodootera eridania. 7 days rest

The plants treated in the above experiments are kept under high intensity lights in the greenhouse for 7 days. These lamps produce the same effects as a bright June 5 sunshine in New Jersey and are kept on for 14 hours a day. After 7 days the leaves are collected and evaluated just as in the above experiments.

Aphis fabae, mixed stages, bed lice

Pots containing single nasturtium plants (Tro-10 paeolum sp.) Ca. 5 cm high is attacked by approx. 100-200 bed lice one day before the trial. Each pot is sprayed with the test preparation for 2 turns on a turntable at 4 rpm. minute turntable in a jacket using a # 154 DeVilbiss nebulizer. The spray tip is held approx. 15 cm from the 15 plant and the spraying agent is designed to provide complete coverage of the plants and beetles. The sprayed pots are placed on the side of white enamel trays and stored for 2 days, after which mortality assessments are made. Tetranvchus urticae (P-resistant strain) 2-spotted spider mite 20 Sieva lima bean plants with primary leaves unfolded to 7-8 cm are selected and cut back to one plant per year. pot. A small piece is cut from a leaf taken from the main colony and placed on each leaf of the test plants.

This is done approx. 2 hours before treatment to allow the mites 25 to move onto the test plant and lay eggs. The size of the cut varies so that there are approx. 100 mites per leaf. At the time of treatment, the piece of leaf used to transfer the mites is removed and discarded. The mite-infested plants are dipped in test preparation 30 for 3 seconds with stirring and put into the sheath for drying. The plants are stored for 2 days before assessing dead adult mites using the first leaf. The second leaf is stored on the plant for a further 5 days before observations of killed eggs and / or recently 35 nymphs have emerged.

84 DK 173853 B1

Diabrotica undecimpunctata howardi, 3rd stage southern May grub rodents.

One cm3 of fine talc is placed in a 30 ml wide-mouthed glass jar with screw cap. One ml of the appropriate acetone suspension is pipetted onto the talc to give 1.25 and 0.25 mg of active ingredient per ml. jar. Place the jars under gentle air flow until the acetone is evaporated. The dried talc is loosened, 1 cm 3 of ground seed is added to serve as food for the insects, and 2 ml of moist soil is added to 10 each pot. The jar is covered and the contents are thoroughly mixed on a Vortex mixer. Then ten third-stage root rodents are added to each jar, and the jars are lightly covered so that the air to the larvae can be replaced. The treatments are done for 6 days before counting mortality. Missing larvae are believed to be dead as they are rapidly degraded and cannot be found. The concentrations used in this experiment correspond to ca. to 50 and 10 kg / ha respectively.

Scale: 20 0 = no effect 5 = 56-65% mortality 1 = 10-25% mortality 6 = 66-75% mortality 2 = 26-35% mortality 7 = 76-85% mortality 3 = 36-45% mortality 8 = 86-99% mortality 25 4 = 46-55% mortality 9 = 10'0% mortality R - reduced food intake 85 DK 173853 B1 in * 3 ·> il ja oo in V ro ti v, tn Q cm ty pi ty>

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Insecticide reviews

Heliothis virescens, 3rd stage tobacco bud worm 5 Cotton mold leaves are dipped into the test preparation and allowed to dry in a cap. When dry, each one is cut into quarters and ten sections are individually placed in 30 ml plastic medicine cups containing a 5-7 mm long piece of damp floss. One third-stage larva is added to each beaker and 10 a cardboard lid is placed on the beaker. Treatments are performed for 3 days before counting mortality and food intake reduction is performed.

Empoasca abrupta. fully grown, western potato-15 cicada.

A Sieva lima bean bath, approx. 5 cm long, dipped in the test specimen for 3 seconds with stirring and placed in a sheath for drying. The sheet is placed in a 100 x 10 mm Petri dish containing a damp filter paper on the bottom.

20 Approx. 10 fully grown cicadas are added to each dish, and the treatments take place for 3 days before counting the mortality.

Blattella cermanica. cooking test, fully grown German 25 cockroach.

A 0.1% brew is prepared by pipetting 1 ml of a 1000 ppm solution of the test compound in acetone onto 1 g of cornmeal in a 30 ml wide mouthed bottle. Dry the food thing by passing a gentle flow of air through the bottle. The food stuff is placed in a ca. ^ liter wide mouth Mason jar, and ten fully grown male cockroaches are added. A screen lid is placed on the jar and a small piece of cotton dipped in 10% honey is placed on top of the screen lid. Mortality counts are made after 3 days.

35 94 DK 173853 B1

Blattela germanica, residual experiment, fully grown German male cockroaches.

One ml of 1000 ppm acetone solution of the test material is pipetted slowly over the bottom of a 150 x 15 mm Petri dish 5 to give as uniform coverage as possible. After the precipitate has dried, 10 fully grown male cockroaches are placed in each bowl and the lid is put on. Mortality counts are made after 3 days.

10 Spodoptera eridania. systemic uptake, 3rd-stage larvae, Southern Army worms.

The compound is formed as an emulsion containing 0.1 g of the test material, 0.2 g of "Emulphor EL-620" emulsifier, 10 ml of acetone and 90 ml of water. This is diluted 15 times with water to form a 100 ppm emulsion for the test. Then dilute 10 times with water, if necessary. Sieva lima bean plants, where the primary leaves are unfolded to a length of 7-8 cm, are cut by at least 3 cm above ground level to avoid contamination with soil bacteria which cause decay of the stem during the experiment.

The cut stems are placed in the test emulsions, and each stem is wrapped in a piece of cotton to keep the stem away from the bottom of the bottle and to limit evaporation and volatility of the compound. The test is carried out for 3 days at 27 ° C so that the compounds can be taken up in the plant. Then, one leaf is removed from the plant and placed in a 100 x 10 mm Petri dish with 10 Southern Army worms, as described in Experiment III. Counting mortality and decreasing food intake observations are made 3 and 5 days 3 o later.

Empoas.ca abrupta. fully grown, western potato cicadas, systemic uptake.

The compound is formed as an emulsion containing 0.1 g of the test material, 0.2 g of "Emulphor EL-620" emulsifier, 10 ml of acetone and 90 ml of water. This is diluted 95 times with water to form a 100 ppm emulsion for the test. Then dilute 10 times with water, as necessary. Sieva lima bean plants, where the primary leaves are unfolded to a length of 7-8 cm, cut 5 by at least 3 cm above ground level to avoid contamination with soil bacteria which cause decay of the stem during the experiment. The cut stalks are placed in the test emulsions, and each stem is placed in the test emulsions, and each stem is wrapped with a bit of cotton to keep the stem away from the bottom of the bottle and to limit evaporation and volatility of the compound. The test is carried out for 3 days at 27 ° C for the compounds to be absorbed into the plant. Then one leaf is removed from the plant and placed in a 100 x 10 mm Petri dish and tested as in Experiment 15 VIII, above.

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

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EXAMPLE 63 A) Assessment of test compounds as nematodic agents Cultivation: Cultures of £. elecans (Bristol strain from J. Lewis) are kept on E. coli lawns on NG agar plates at 5 20 ° C. New cultures are established every week,

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

The experiments are then conducted with mixtures of three compounds taken from another high-capacity screening program to reduce additional work and overall costs.

Compounds are dissolved in acetone and made up with just 20 parts of water. The final test concentration of each compound in the mixture is 150 ppm. The test material is micropipetted (25 μΐ) into a single well in a 96 well sterile tissue culture plate (COSTAR) k and the solvent is allowed to evaporate. These "treated" plates are used immediately or stored in a freezer with no obvious adverse effects on the compounds.

A freshly prepared volume (50 μΐ) of C. eleqans in CbMM is micropipetted into each treated well and several control wells per well. plate. Culture plates are incubated at 20 ° C.

Efficiency observations are made under a dissection microscope at 4, 24 and 48 hours post-immersion. Immediately before releasing the plate, it is lightly tapped to stimulate the movement of the worms. Activity is assessed subjectively, but semi-quantitatively, based on the drug effects on the fully grown and larval motility. The criteria are as follows: 107 DK 173853 B1 8 = no motility 7 = markedly reduced motility for approx. 95% of the worms 6 = reduced motility 5 = slightly reduced motility 5 0 = normal motility, just like the control animals.

Other factors that show activity are easy to see, such as death, rigor mortis, contraction, twisting, paralysis, abnormal throttle, decreased worm resistance of 48 hours and other deviation from normal.

PROCEDURE FOR IMPLEMENTING CAENORHABDITIS ELEGAN TEST

Day 0 E. Celi-NG agar plate seeded at 30-50 C. Elegance.

15 Incubate at 20 ° C.

Day 4 New C. Elecrans stock is harvested.

Wash with antibiotics.

Transfer to CbMM

£ is set. Elegance (25-100 μΐ) for "groomed" 20 recesses3.

Activity is observed at 4 hours post-immersion.

Day 5 Observed for activity.

Day S Activity is observed.

25 aPrepared wells can be prepared immediately or in advance and stored in a refrigerator.

The data obtained in these experiments are given in Table III below.

30 B) Root needle test

Root eel stocks (Meloid oven incognita) are kept on Fireball tomatoes in the greenhouse. Egg masses are removed from the affected root canals and kept on moist filter paper for 35 hours to allow them to hatch. Larvae emerge and fall into the water under the paper. Larvae for test are transferred to cell plate wells containing test compounds at 30 ppm in 3% acetone, approx. 10 larvae per cell recess. Infested wells are maintained at 27 ° C and mortality is determined 24 hours after treatment.

The data obtained are given in Table III below.

109 DK 173853 B1 TABLE III 5 C. Ele. Root needle 150 ppm 300 ppm

L A

4,5-dichloro-2- [p- - 4 (trifluoromethoxy) phenyl] -pyrrole-3-carbonitrile 4,5-dichloro-2- (a, a, a- 9 9 5 15 -trifluoro-p-tolyl) - pyrrole-3-carbonitrile 4,5-dibromo-2- (o, a, a-9,9 O -trifluoro-p-tolyl) pyrrole-3-carbonitrile 2,3-dichloro-4-nitro-5-00 9-phenylpyrrole 2,3-dichloro-5- (p-chloro-999-phenyl) -4-nitropyrrole 2,3-dichloro-5- (3,4-99-dichlorophenyl) -4-nitropyrrole 2- (p-bromophenyl) - 4,5- 9 9 6 -dichloro-3-nitropyrrole 2,3-dichloro-4-nitro-5- 99 (α, α, α-trifluoro-p-tolyl) -pyrrole EXAMPLE 64

Following the procedures of Examples 59 and 60, the compounds of the present invention are assessed in relation to a variety of insect species comprising: cicadas, tobacco budworms, southern army worms and German cockroaches. The rating system is the same system used in the above examples. The dates obtained are given in Table IV below. Where two or more tests are carried out with the same test compound, 10 are averaged and a - in the table indicates that no test has been performed.

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and Hill ro I Η I

Claims (14)

138 2,3,4,5-Tetra-substituted pyrroles, known from the formula I 5 L u Pi-n N 'fi 15 wherein X is F, Cl, Br, I or CF 3; Y is F, Cl, Br, I, CF 3 or CN; 20. is CN or NO2 and A is H; C1-C4 alkyl optionally substituted with from one to three halogen atoms, one hydroxy group, one C1-C4 alkoxy group or one C1-C4 alkylthio group, one phenyl group optionally substituted with C 1 -C 3 alkyl or C 1 -C 3 alkoxy or with one to three halogen atoms, one phenoxy group optionally substituted with one to three halogen atoms, or one benzyloxy group optionally substituted with one halogen substituent; C 1 -C 4 carbalkoxymethyl; C3-C4-alkenyl optionally substituted with from one to three halogen atoms; cyano; C3-C4 alkynyl optionally substituted with one halogen atom; di- (C 2 -C 4 alkyl) aminocarbonyl; or C4-C8 cycloalkylaminocarbonyl; 35. is H, F, Cl or Br; and M and R are each H, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, C 1 -C 3 alkylsulfinyl, C 1 -C 3 alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF3, R3CF2Z, R2CO or NR3R4, and when M and R are attached to neighboring carbon atoms in the phenyl ring, together with the carbon atoms to which they are attached, they can form a ring in which MRI is the structure: -0CH20- , -OCF20- or 10. is S (O) n or 0; Rx is H, F, CHF2, CHFC1 or CF3; R 2 is C 1 -C 3 alkyl, C 1 -C 3 alkoxy or NR 3 R 4; R 3 is H or C 1 -C 3 alkyl; R 4 is H, C 1 -C 3 alkyl or R 5 CO; R 5 is H or C 3 -C 3 alkyl; and n is an integer 0, 1 or 2. A compound according to claim 1, characterized in that A is hydrogen or C 1 -C 4 alkoxymethyl, W is CN or NO 2; X and Y are each Cl, CF 3 or Br; R is F, Cl, Br, CF3 or OCF3; M is H, F, Cl or Br; and L is H or F. A compound according to claim 1, characterized in that it is 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile; 4,5-dichloro-2- (a, ar, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile; 2,3-dichloro-4-nitro-5- (or, a, cu-trifluoro-p-tolyl) pyrrole; 2,3-dichloro-5- (3,4-dichlorophenyl) -4-nitropyr-rol; 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; 3,4-dibromo-5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile; 2,4-dibromo-5- (p-chlorophenyl) pyrrole-3-carbonitrile; 5- (p-chlorophenyl) -3- (trifluoromethyl) pyrrole-2,4-dicarbonitrile; 3-bromo-5- (3,4-dichlorophenyl) pyrrole-2,4-dicarbonitrile; 4,5-dichloro-1- (ethoxymethyl) -2- (a, a, α-trifluoro-p-tolyl) pyrrols' carbonitrile; 4-bromo-2- (p-chloro-phenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; and 4-bromo-2- (3,4- dichlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile. Method for controlling insects, nematodes 140, and mites, characterized in that these insects, nematodes and mites, their breeding sites, food supplies or biotopes are contacted with an insecticidal, nematodicidal or acaricidal effective amount of a compound according to 5 claim 1. Process according to claim 4, characterized in that the compound is: 4.5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile; 4,5-dichloro-2- (a, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitrile; 2,3-dichloro-4-nitro-5- (a, a, a-trifluoro-p-tolyl) pyrrole; 2,3-dichloro-5- (3,4-dichlorophenyl) -4-nitropyrrole; 4- bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; 3,4-dibromo-5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile; 2,4-dibromo-5- (p-chlorophenyl) pyrrole-3-carbonitrile; 5- (p-chlorophenyl) -3- (trifluoromethyl) pyrrole-2,4-dicarbonitrile; 3-bromo-5- (3,4-dichlorophenyl) pyrrole-2,4-dicarbonitrile; 4,5-dichloro-1- (ethoxymethyl) -2- (a, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitrile; 4-bromo-2- (p-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; or 4-bromo-2- (3,4-dichlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile. Method for protecting growing plants 25 from insect, nematode and mite infestation, characterized in that an insecticide, nematodicide or acaricide effective amount of a compound according to claim 1 is applied to the leaves or soil or water in which they grow. . Process according to claim 6, characterized in that the compound is: 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile; 4,5-dichloro-2- (α, α, α-trifluoro-p-tolyl) pyrrole-3-carbonitrile; 2,3-dichloro-4-nitro-5- (α, α, a-trifluoro p -tolyl) pyrrole; 2,3-dichloro-5- (3,4-dichlorophenyl) -4-nitropyrrole; 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; 3,4-dibromo-5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile; 2,4-dibromo-5- (p-chlorophenyl) pyrrole-3-carbonitrile; 5- (p-chlorophenyl) -3- (trifluoromethyl) pyrrole-2,4-dicarbonitrile; 3-bromo-5- (3,4-dichlorophenyl) pyrrole-2,4-dicarbonitrile; 4,5-dichloro-1- (ethoxymethyl) -2- (or, ct, α-trifluoro-p-tolyl) pyrrole -3-carbonitrile; 4-bromo-2- (p-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; or 4-bromo-2- (3,4-dichlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile. Process according to claim 6, characterized in that the compound is applied to the plants or soil in which they grow in amounts of approx. 0.12 5 kg / ha to approx. 4.0 15 kg / ha. Method according to claim 6, characterized in that the compound of formula I is applied to the leaves of the plants or to the soil or water in which they grow, in the form of a liquid composition containing from ca. 10 ppm to approx. 20 10,000 ppm of the compound. Process for the preparation of a 2,3,4,5-tetrasubstituted pyrrole according to claim 1, characterized in that a benzoylacetonitrile or a-nitroacetophenone is reacted with the structure: 25 L o // A \\ - c-CH2U wherein L, M, R and W have the meanings given in claim 1 with a 2,2-di (C1-C4 alkoxy) ethylamine at an elevated temperature to form an α- [2,2-di (C1-C4) -alkoxy) ethylamino] -β-cyanostyrene or α- [2,2-di (C1-C4-alkoxy) ethylamino] -β-nitro-styrene of the formula: "Ar" py "-" N CH 2 CH (OC 2 - alkyl> 2 H 10 wherein L, M, R and W have the meanings given above and the thus obtained α- [2,2-di (C 1 -C 4 alkoxy) ethylamino] -S-cyanostyrene or ct -2,2-di (C1-C4 alkoxy) amino] -β-nitrostyrene is treated with a mineral acid or organic acid to give the desired 2,3,4,5-tetrasubstituted pyrrole. Process according to claim 10, characterized in that the reaction of 2,2-di (alkoxy) ethylamine with benzoylacetonitrile or α-nitroacetophenone is carried out unmixed or in the presence of an inert organic solvent. Process according to claim 10, characterized in that hydrochloric acid, hydrogen bromic acid or trifluoroacetic acid are used as mineral acid. 13. α, β-Disubstituted styrene, characterized by the structural formula: 30 n * - 'U' CH 2 CH <C 1 -C 4 alkoxy) wherein W, L, M and R have the meanings specified in claim 1. The compound of claim 13, characterized in that it is (E) p-chloro-β - [(formylmethyl) amino] - cinnamonitrile diethyl acetal; (Z) p-chloro-β - [(formylmethyl) - 143-amino] -cinnamonitrile-diethyl acetal; free - [(formylmethyl) amino] -3,4-dimethoxycinnamonitrile diethyl acetal; (Z) -methyl-p- (2-cyano-1- [(formylmethyl) amino] vinyl} benzoic acid diethyl acetal; 3,4-dichloro-6- [(formylmethyl) amino] -cinnamonitrile diethyl acetal; (Z) -β- [(formylmethyl) amino] -p-methylcinnamonitrile diethyl acetal; β- [(formylmethyl) amino] -p-trifluoromethoxycin-namonitrile dimethyl acetal; (E) -p-chloro-S - [(formylmethyl) - amino] -cinnamonitrile-dimethyl acetal; N- (formylmethyl) -p-methyl-Qf- (nitromethylene) benzylamine-diethyl acetal; N- (formyl-methyl) -3,4-dimethoxy-α- (nitromethylene) benzylamine-diethyl acetal; p-chloro-N- (formylmethyl) -a- (nitromethylene) benzylamine diethyl acetal; N- (formylmethyl) -or- (nitromethylene) -2-naphthylmethylamine diethyl acetal; methyl p- {o; - [(formylmethyl) ) amino] -β-nitrovinyl} benzoate-β- (diethyl acetal); or p-trifluoromethyl-N- (formylmethyl-α- (nitromethylene)] -benzylamine-diethyl acetal.