LT4040B - Arylpyrole insecticidal, acaricidal and nematicidal agents and method for the preparation thereof - Google Patents

Abstract

The invention is directed to some insecticides, acaricide and nematocidal arylpyrolitic and its means and method of fighting against insects, parasite ticks and nematodes. Invention is also directed for growing plant protection against insects, attacks from parasite ticks and nematodes, treating the mentioned plant or the land where it grows by an effective amount of the new arylpyrolitic compound fighting parasite ticks and nematodes. Additionally this invention is directed to the production method of arylpyrolitic compounds.

Description

The present invention is directed to certain novel arylpyrrole compounds which are the most effective insecticidal, acaricidal and nematocidal agents useful in controlling parasitic insects, mites and nematodes, and moreover, the present invention provides the protection of agronomic crops against the harmful effects of said insects, growing and harvesting them. The present invention also encompasses processes for the preparation of arylpyrrole compounds.

The novel aripyrrole compounds of the present invention have the structural formula represented by Formula I:

... L ^W ~ ^{M X} R {D, ^Z N

Y

A wherein X = F, Cl, Br, I or CF; Y = F, Cl, Br, I, CF, or CN; W = CN or NO. and A = H, C -C ₄ -alkyl which may be substituted by one to three halogen atoms, one oxy a C - C ₄ -alkoxy, or a Cj-Cg alkylthio, one phenyl optionally substituted be C 1 -C 1 alkyl or C 1 -C 1 alkoxy or one to 3 halogen atoms or one benzyloxy group having one halogen substituent; C ₁ -C ₄ -carbalkoxymethyl: C 1 -C ₄ -alkenyl which may be substituted with one to three halogen atoms; CIACIA ₃ -C ₄ -alkynyl, which may be one hanogrupe; a logene atom; di- (C _q -C _£ -ai kil) aminocarbon or

C 1 - C 1 - cycloalkylaminocarbonyl;

L = H, F, Cl or Br; and

M and R independently of one another are H, C-C. alkyl, C 1 -C 1 -alkoxy, C-C 1 -alkylthio, C-C.

alkylsulfinyl, C 1 -C 4 -alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF 1, C 1 -C 4 Z, R ₂ CO, or KR, R 1, and if M and R are in adjacent positions together with the carbon atoms to which they are attached, they can form a ring where the MR structure is:

-OCH-.O-, -OCF ₂ - or

Z = S (O), or O; R j = H, F, CHF _Z , CHFCl or CF. R _<; = C, -C, alkyl, C-C, -alkoxyl, or NR.RgR = b or C _: -C, alkyl; Ri = H, C _t -C ₃ -alkyl, or R _CO; R: = F or C _; -C ₃ alkyl and n is an integer equal to 0.1 or 2.

The term C ₄ -C ₆ -cikloalkilaminokarbonilas of C to C _{£ H} -cikloalkilaminogrupė connected directly to karbonilogrupės via a nitrogen atom.

The best group included in the novel arylpyrroles according to the present invention is explained by formula II:

(II) r wherein A, L, M, R, W, X and Y are the same as previously described.

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

M (III) wherein A, L, M, R, W, X and Y have the meanings previously described.

Another group of valuable arylpyrroles according to the invention is represented by Formula IV:

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

Another group of valuable arylpyrroles of the present invention is represented by Formula V:

(V) wherein A, L, M, R, X and Y have the meanings given above and the other arylpyrroles of the present invention are represented by formulas VI and VII:

i {1 'N W

-M

R (VI), i ¹ JL

R / Z ¥ ^X (VII),

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

The most valuable of the invention of formula I arylpyrrole is 5 Dance: A = vandeni1is or C - C ₄ -alkoksimetilas; W = CN or NO; L = hydrogen or F; X and Y, each = Cl,

Br or CF; M = H, F, Cl or Br; and R = F, Cl, Br, CF. or OCF, the most valuable compounds of Formula II, particularly effective as insecticidal acaricidal and / or nematocidal agents, are those in which A = aqueous or C-C _; alkoxylmethyl; L = hydrogen; M = hydrogen, F, Cl or Br, R = F, Cl, Br, CF ₂ or OCF; W = CN and X and Y are each independently Cl, Br or CF _; .

Other compounds of formula II which exhibit increased activity as insecticidal, acaricidal and / or nematicidal agents are as follows: A = hydrogen or C-C, _t 20 alkoxylmethyl; L = hydrogen; M = water, F, Cl or Br, R = F, Cl, Br, CF ₃ or OCF; W = NO ₂ and X and Y are each independently Cl, Br or CF.

Exemplary of many of the insecticidal, acaricidal and nematicidal arylpyrroles of the present invention include:

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

4,5-Dichloro-2- [p- (trifluoromethoxy) phenyl] pyrrole-3-carboxyl nitrile;

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-dichloropyrrole-3-carbonitrile;

4.5-dichloro-2- (α, α, α-trifluoro-p-toluyl) pyrrole-3-carbonitrile;

c

4.5-dibromo-2- (a, a, a-trifluoro-p-toluyl) pyrrole-3-carbonitrile;

4.5-dibromo-2- (o-chlorophenyl) pyrrole-3-carbonitrile;

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

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

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

2.3-dibromo-4-nitro-5-phenylpyrrole;

2- (p-bromophenyl) -4,5-dichloro-3-nitropyrrole;

2.3-dichloro-4-nitro-5- (a, a, a-trifluoro-p-toluyl) -pyrrole;

4.5-dichloro-2- (m-chlorophenyl) pyrrole-3-carbonitrile;

4.5-dichloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile;

4.5-Dichloro-2-phenylpyrrole-3-carbonitrile;

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

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

2.3-dibromo-5- (p-chlorophenyl) -4-nitrophenol;

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

3-bromo-2-chloro-4-nitro-5- (α, α, α-trifluoro-p-toluyl) -pyrrole;

5-chloro-2- (3,4-dichlorophenyl) -1- (methoxymethyl) -4- (trifluoromethyl) pyrrole-3-carbonitrile;

rol;

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

3-Bromo-5- (m-fluorophenyl} -4-nitro-2- (trifluoromethyl) pyrrolo s;

Ί C,

J-J

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

4-chloro-2- (3,5-dichloro-4-methylphenyl) -3-nitro-5- (tri20 fluoromethyl) pyrrole;

2- (2-bromo-4-chlorophenyl) -1- (2-propenyl) -4,5-bis- (trifluoromethyl) pyrrole-3-carbonyl tryl;

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

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

5- (5-dimethylaminophenyl) -4-nitropyrrole-2-carbonitrile;

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

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

5

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

1-allyl-4-nitro-5- (a, a, a-trifluoro-p-toluyl) -3- (trifluoromethyl) pyrrole-3-carbonitrile;

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

2 - [(m-methanesulfonylphenyl) -4-trifluoromethyl] pyrrole-3-carbonitrile;

2- (3-chloro-4-methylphenyl) -1-methyl-3-nitro-4- (trifluoromethyl) pyrrole;

2-phenylpyrrole-3,4-dicarbonitrile;

5- (p-ethanesulfinyl-phenyl) -4- (trifluoromethyl) pyrrole-3-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-chloro-5- (m-bromophenyl) pyrrole-3-carbonitrile;

2-bromo-1- (p-chlorophenoxy) -methyl-5- (p-chlorophenyl) -3-nitropyrrole;

2,4-dibromo-5-phenylpyrrole-3-carbonitrile;

5- (p-bromophenyl) -2,4-dichloro-3-nitropyrrole;

2-bromo-5- (3-bromo-4-methylphenyl) -1- (p-propyloxy) methyl-4- (trifluoromethyl) pyrrole-3-carbonitrile;

2-bromo-5- (p-chlorophenyl) -3-nitro-4- (trifluoromethyl) pyrrolo s;

5- [m- (difluoromethoxy) phenyl] -2- (trifluoromethyl) pyrrole-3-carbonitrile;

5- (2,3-dichlorophenyl) -1-methoxymethyl-3-nitro-2- (trifluoromethyl) pyrrole;

4-chloro-5- (β-naphthyl) -2- (trifluoromethyl) pyrrole-3-carbonitrile;

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

5- (2-bromo-5-ethylphenyl) -2,4-bis- (trifluoromethyl) pyrrole-3-carbonitrile;

1-ethyl-2- (p-fluoromethyl) -4-nitro-3,5-bis- (trifluoromethyl) pyrrole;

1 - [(2,6-dichlorophenoxy) methyl] -5 (m-chlorophenyl) pyrrole-2,3-dicarbonitrile;

3-nitro-5- (a, a, a-trifluoro-p-toluyl) pyrrole-2-carbonitrile;

4-chloro-5- (4-chloro-2-methylphenyl) pyrrole-2,3-dicarbonitrile;

4-bromo-5- (3,4-dibromophenyl) -2-nitropyrrole-3-carbonitrile;

1 - [(1-methoxy) ethyl] -5- (p-chlorophenyl) -4- (trifluoromethyl) pyrrole-2,3-dicarbonitrile;

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

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

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

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

2- (3,5-Dichloro-4-methylphenyl) -4-nitro-3-trifluoromethylpyrrole;

2-phenylpyrrole-3,4-dicarbonitrile;

2- (2-bromo-4-chlorophenyl) -4-nitropyrrole-3-carbonitrile;

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

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

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

2- (o-Bromophenyl) -4-nitro-5- (trifluoromethyl) pyrrole-3-carbonitrile;

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

3-bromo-5- (m-bromophenyl) -2-nitropyrrole;

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

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

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

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

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

1 C 2- (p-1-iodophenyl) -5-nitro-4- (trifluoromethyl) pyrrole;

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

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

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

C

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

5- (m-difluoromethoxyphenyl) pyrrole-2,3-dicarbonitrile;

5- (3-bromo-4-cyanophenyl) -2-nitropyrrole-3-carbonitrile;

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

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

1 - [(p-bromophenoxy) -methyl] -5- (m-trifluoromethyl) -4- (tri35 fluoromethyl) pyrrole-2,3-dicarbonitrile;

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

4-Bromo-5- (3-bromo-4-trifluoromethylphenyl) -pyrrole-2-carbonyl-5-yl;

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

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

2- (3-Bromo-4-isopropoxy) -5-nitro-3- (trifluoromethyl) pyrrole;

1-5 5- (p-chlorophenyl) pyrrole-2,4-dicarbonitrile;

2- (3,4-Dichlorophenyl) -5-nitropyrrole-3-carbonitrile;

3-bromo-5- (3,4-dichlorophenyl) pyrrole-2,4-dixronitrile;

C

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

5- (3,4-Dibromophenyl) -3- (trifluoromethyl) pyrene-2,4-dicarbo [25] nitrile;

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

2-bromo-4- (2,5-dibromophenyl) -5-nitropyrrole;

5-bromo-3- (3,5-dichloro-4-difluoromethoxyphenyl) pyrrole-2-carbonyl tril;

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

2,3-dichloro-4- (3,5-difluorophenyl) -5-nitropyrrole;

5-bromo-3- (p-chlorophenyl) -1-oxyethyl-4- (trifluoromethyl) pyrrole-2-carbonitrile;

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

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

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

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

3- (4-Bromo-3-cyanophenyl) -4-chloro-2-nitro-5- (trifluoromethyl) pyrrole;

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

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

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

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

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

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

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

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

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

3-bromo-4- (p-dimethylaminophenyl) -5-nitropyrrole;

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

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

3- (3-Bromo-4-iso-propyl-phenyl) -pyrrol-2,4-dicarbonitrile;

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

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

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

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

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

5-chloro-4- [p-methylacetamido) phenyl] pyrrole-2-carbonitrile;

5-bromo-4- (o-bromophenyl) -1-propargylpyrrole-2-carbonitrile;

2-bromo-3- (o-bromophenyl) -5-nitropyrrole;

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

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

5-Bromo-4- [p- (2,2-dichloro-1,1-difluoro-oxy) phenyl] -3 (trifluoromethyl) pyrrole-2-carbonitrile;

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

3- (3-bromo-4-acetylphenyl) -5- (trifluoromethyl) pyrrole-2-carbonitrile;

1-cyano-3- (3,4-dibromophenyl) -5-nitro-2- (trifluoromethyl) pyrrole;

3-bromo-2-methoxymethyl-4- (m-trifluoromethyl) -5- (trifluoromethyl) pyrrole-2-carbonitrile;

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

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

3- (2-Bromo-4-methoxyphenyl) -5-nitro-2,4-di (trifluoromethyl) pyrrole;

3- (p-chlorodifluoromethoxyphenyl) pyrrole-2,5-dicarbonitrile;

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

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

4-chloro-3- (p-chlorophenyl) -1-isopropyloxycarbonymethyl) 5-nitropyrrole-2-carbonitrile;

3- (o-Bromophenyl) -4- (trifluoromethyl) pyrrole-2,5-dicarbonitrile;

1- (2-chloroethyl) -3- (3,4-dichlorophenyl) -4- (trifluoromethyl) pyrrole-3-carbonitrile;

4- (4-Bromo-3-trifluoromethoxyphenyl) -3-chloropyrrole-2-carbonitrile;

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

4- (3-methoxy-4-cyanophenyl) -3- (trifluoromethyl) pyrrole-2-carbonitrile;

1- (3,4-Dichlorobenzyl) -4- (2-methyl-4-iodophenyl) -2-nitro-3-trifluoromethylpyrrole;

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

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

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

5-bromo-4- (2,6-dichloro-4-methanesulfinylphenyl) -2-nitropyrrolcarbonitrile;

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

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

2-chloro-4- (3-chloro-4-N-methylacetamidophenyl) pyrrole-3 carbonitrile;

2-bromo-4- (3-bromo-4-n-propylphenyl) -3-nitropyrrole;

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

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

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

2-bromo-1-methyl-3-nitro-4- (a, a, a-trifluoro-p-toluyl) pyrrole;

4- (p-chlorophenyl) -1- (n-butyloxymethyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile;

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

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

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

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

3- (3-Bromo-4-acetoxyphenyl) -1- (3,4-dichlorophenoxyphenyl) 4-nitro-2,5-di- (trifluoromethyl) pyrrole;

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

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

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

5-chloro-4- (p-chlorophenyl) -2-oxyethyl-3-nitropyrrole-2-carbonitrile;

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

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

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

2-chloro-3- (m-difluoromethoxyphenyl) -4-nitropyrrole;

1- (2,4-dibromophenoxymethyl) -4- (m-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile;

3- (3-Bromo-4-ethoxy) -4-nitro-2- (trifluoromethyl) pyrrole;

3- (2,4,6-trichloromethyl) pyrrole-2,4-dicarbonitrile;

3- (4-bromo-3-chlorophenyl) -1- (difluoromethyl) -4-nitropyrrole-2-carbonitrile;

5-bromo-3- (p-chlorophenyl) -1- (isobutyloxymethyl) pyrrole-3 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) -4-nitropyrrole;

4.5-dibromo-2- (2,3,6-trifluorophenyl) -3-carbonyl;

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

4,5-dibromo-1-methyl-2- (a, a, a-trifluoro-p-toluyl) pyrrole-3-carbonitrile;

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

2.3-dichloro-4-nitro-5- (p-trifluoromethoxy) phenylpyrrole;

4.5-Dichloro-2- [m- (trifluoromethoxy) phenyl] -pyrrole-3-carbonitrile;

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

2.3-dichloro-3- (p-chlorophenyl) -1-methyl-4-nitropyrrole;

4-bromo-5-chloro-2- (p-chlorophenyl) -1-methyl-4-nitropyrrole;

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

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

3-bromo-5- (p-chlorophenyl) -2-fluoro-4-nitropyrrole;

a- [2 _f 2-di- (C ₁ -C ₄ alkoxy) ethylamino] -β-cianostirolas a- [2,2-di (C? -C ,, alkoxy) ethylamino] -β-nitrostyrene;

The compounds of the present invention are represented by the following structural formula:

M

NH-CH ₂ - (C 1 -C ₄ alkoxy) ₂ wherein W = CN or NO ₂ ; L = H, F, Cl or Br; M and R are each independently = H, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylsulfinyl, C ₁ -C ₃ alkylsulfonyl, cyano, F, Cl, Br, I nitro, CF ₃ , R, CF ₂ Z, R ₂ CO or NR ₃ R ₄ and if M and R are in adjacent positions and together with the nitrogen atoms to which they are attached may form a ring, where M and R are represented by the following structure:

-OCH ₂ O-, OCF ₂ - or

Z = S (O) _n , or O; R ₃ = H, CHF ₂ , CHFC 1, or CF ₃ ; R ₂ = C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxyl, or NR ₃ R ₄ ; R ₃ = H, or alkyl; R ₄ = H, C ₁ -C ₃ alkyl, or R _S = O; R ₅ = H or alkyl; n integer = 0.1 or 2.

The most valuable group of β- (substituted) styrene compounds of the present invention has the structure explained above, wherein W = CN; L = H, Cl or Br; M = H, F, Cl, Br or OCH ₃ ; R = H, F, Cl, Br, CF ₃ , NO ₂ , OCF ₃ or OCH ₃ ; and if M and R, being in adjacent positions and together with the nitrogen atoms to which they are attached, may form a ring in which M and R are represented by the structure:

Another valuable group of (substituted) styrene compounds of the present invention has the above structure wherein W = NO ₂ ; L = H, Cl or Br; M = H, F, Cl, Br or OCH ₃ ;

R = H, F, Cl, Br, CF ₃ , NO ₂ , OCF ₃ or OCH ₃ ; or in the case where M and R, when in adjacent positions and together with the nitrogen atoms to which they are attached, may form a ring having the following structure:

If the compounds of the present invention are previously mentioned as β-cyanostyrols and β-nitrostyrols, they may also be referred to as dialkyl acetals.

Some of the more valuable dialkyl acetal compounds of the present invention are: (E) and (Z) (1) p-chloro-β - [(formylmethyl) amino] cinnamon nitrile diethyl acetal;

(Z) -β- [formylmethyl) amino) -3,4-dimethoxycinnamone nitrile diethyl acetal;

(3) (Z) -methyl- (2-cyano-1 - [(formylmethyl) amino] -vinylbenzoate diethyl acetal;

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

(5) (Ζ-β - [(Formylmethyl) amino] -p-methylcinnamon nitrile diethylacetal;

(6) N- (formylmethyl) -p-methyl-α- (nitromethylene) benzylaminodiethylacetal;

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

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

(9) methyl p- {α, α - [(formylmethyl) amino] -β-nitrovinyl} benzoate-β- (diethylacetal);

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

(11) (E) and (Z) p -chloro-β- (formylmethyl) amino] cinnamon nitrile dimethyl acetal;

(12) β - [(formylmethyl) amino] -3,4-dimethoxycinnamone nitrile dimethyl acetal;

(13) 3,4-dichloro - [(formylmethyl) amino] cinnamon nitrile diethyl acetal; and (14) p-trifluoromethyl-β- (formylmethyl) amino] cinnamon nitrile diethylacetal.

β-Cyanostyrenes, also mentioned as cinnamon nitrile dialkyl acetals, may be obtained by reaction of substituted or unsubstituted benzoyl acetonitrile with 2,2-di C ₁ -C ₄ alkoxy) ethylamine in the presence of an aromatic solvent to form a- (2,2-di (C) ₁ -C ₄ alkoxy) ethylamino) -cyano (modified) styrene, which then can be converted to 2- (substituted-phenyl) pyrrole-3-carbonitrile by reaction of a compound mentioned in β-cyano-3 (modified) styrene with trifluoroacetic acid. Chlorination of the cyanophenylpyrrole thus prepared with sodium hypochlorate or sulfuryl chloride in an inert solvent affords 4,5-dichloro-2- (substituted-phenyl) pyrrole-3-carbonitrile having insecticidal, acaricidal and nematicidal properties. The conversion to the pyrrole intermediate can also be accomplished by substitution with concentrated hydrochloric acid at about 20 and 40 ° C. The reaction can be graphically explained as follows:

where A = hydrogen, C.-Ci-alkyl substituted with one C _x -C ₄ alkoxy, one C ₁ -C ₄ alkylthio group of from 1 to 3 halo groups, or phenyl substituted with one free or two C ₁ -C ₄ -alkyl , C ₁ -C ₄ -alkoxyl or halogen; C ₃ -C ₄ -alkenyl optionally substituted with 1 to 3 halo groups; or C ₃ -C ₄ -alkynyl; X = C1 or Br; R ₆ = C ₁ -C ₄ alkyl, and L, R and M are as previously described.

Some novel aripyrrole compounds of formula I wherein A = hydrogen; W = CN, and X, Y, L, M and R have the meanings given above, can be prepared by reacting with N-formyl-DL-phenylglycine or substituted N-formylphenylglycine represented by Structural Formula VIII:

L

CO, H (VIII),

NHCH = O wherein L = H, Cl or Br, R and M, each independently, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxyl, C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylsulfinyl, C _1- C ₃ -alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF ₃ , R, CF ₂ Z, R ₂ CO or

NR ₃ R ₄ and provided that M and R, when in adjacent positions and together with the nitrogen atoms to which they are attached, may form a ring having the structure represented by MR:

-OCH ₂ O-, OCF ₂ O- or

Z = S (O) _n , or 0; R 1 H, F, CHF ₂ , CHFC 1, or CF ₃ ; R ₂ =

C _l -C ₃ -alkyl, C ₁ -C _3-alkoxy or NR ₃ R _4; R ₃ = H, or C ₁ -C ₃ alkyl; R ₄ = H, C ₁ -C ₃ alkyl, or R ₅ CO; R ₅ = H or C ₁ -C ₃ -alkyl and integer n = 0, 1 or 2; with at least an equivalent amount of 2-chloroacrylonitrile and 2 to 3 equivalents of acetic anhydride. The reaction is carried out at an elevated temperature, preferably from 70 ° C to 100 ° C.

The reaction can be explained as follows:

CN

L

CO, H

NHCHO

Cl

Thus prepared is 2-phenyl-pyrrole-3-carbonitrile or

Conversion of 2- (substituted phenyl) pyrrole-3-carbonitrile to the corresponding 4-halo, 5-halo or 4,5-dihalo-2- (substituted phenyl) pyrrole, S-carbonitrile according to formula II is readily accomplished by the reaction of 2 -phenylpyrrole-3-carbonitrile or 2- (substituted phenyl) pyrrole-3-carbonitrile with at least 1 or 2 equivalents of sulfuryl halogen, bromide or chloride in the presence of a solvent such as dioxane and tetrahydrofuran, acetic acid or a chlorinated hydrocarbon solvent. Approximately 1 equivalent of a halogenating agent is required to obtain the pyrrole-3-carbonitrile monohalogen; whereas the production of pyrrole-3-carbonitrile requires from 2 to 3 equivalents of the halogenating agent mentioned. In the case of the use of sulfuryl chloride or sulfuryl bromide, the reaction is usually carried out at a temperature below 40 ° C and preferably between 0 ° and 30 ° C. However, with free bromine, the reaction is usually carried out at 30-40 ° C. Other effective halogenation agents that could be used in such reactions include sodium hypochlorite, t-butyl hypochlorite, N-bromosuccinimide, N-iodosuccinimide, and the like. The reaction can be explained as follows:

The carbonitrile compounds of the present invention represented by Formula II may be prepared by reaction of a substituted or unsubstituted benzoylacetonitrile with 2,2-di (C ₁ -C ₄ alkoxy) ethylamine in the presence of an aromatic solvent to give β- [2,2-di ( C ₁ -C ₄ alkoxy) ethylamino] -β-cyano (substituted) styrene, which is then replaced by 2 (substituted-phenyl) pyrrolecarbonitrile of formula II. For this purpose, the aforementioned β-3-cyano (substituted) styrene is used, which is then converted to the 2- (substituted-phenyl) pyrrole carbonitrile of formula II. For this purpose, the reaction of said β-3-cyano (substituted) styrene compound with trifluoroacetic acid or concentrated hydrochloric acid is carried out at a temperature between 20 and 40 ° C.

The reaction is depicted as follows:

M rAV + H.NCH, CH (OC, H.),. (aromatic solvent)

wherein R ₆ = C ₁ -C alkyl _zl earlier values.

L, R and

CN

NH

OR cf ₃ co, f 'OR _ft or HCI

M has specified

In addition, compounds of 3-nitro-2-phenylpyrrole and 3-nitro-2- (substituted) pyrrole can be prepared by reacting nitroacetophenone or substituted nitroacetophenone with 2,2-di (C ₁ -C ₄ alkoxy) according to formula II of the present invention. ethylamine. The reaction is usually carried out in the presence of an inert organic solvent, preferably an aromatic solvent, at elevated temperature. This gives [2,2-di (Cy-C 1-4 alkoxy) ethylamino] -nitrostyrol. It is converted to a 3-nitro-2-phenylpyrrole of formula II or 3-nitro-2- (substituted) phenylpyrrole by treatment with a mineral acid such as hydrochloric acid or hydrobromic acid. Reaction of the thus obtained nitrophenylpyrrole with sodium hypochlorite in an inert organic solvent at reduced temperature affords 2,3-dichloro-4-nitro-5-phenyl or -5- (substituted) phenylpyrrol of formula II.

The above reactions can be explained graphically as follows:

C CH.NO,

H, NCH.CH (OC, H)

S- * 2 ->

NO.

N CH ₂ CH (OC ₂ H ₅ ) ₂ H

NO,

Cl cf, co ₂ f - .... ·>

or HCl

NaOCl k ^CN > Λ ^C1 N lj L ^H ^ R

In addition to several methods described in the literature for the preparation of substituted and unsubstituted benzoylacetonitriles, we have unexpectedly found that such compounds can also be obtained by reacting the appropriately substituted halobenzoyl derivative with an alkali metal hydride and an alkyl cyano acetate such as t-butyl cyano acetate. butyl (benzoyl) -ora- (substituted benzoyl) cyanoacetate. These reactions could be graphically represented as follows:

O

O c OC (CH ₃ ) ₃

C - Cl + NaOH + CH, ^X CN

B

M 1

Ύ Vcochcooc {ch ₃ ^R CN

C

The cyanoacetate ester thus formed can then be converted into the substituted or unsubstituted benzoylacetonitrile by heating the compound in toluene containing p-toluenesulfonic acid. The reaction can be graphically represented as follows:

COCHCOOC (CH ₃ ) ₃

CN

PTSR toluene

O

CH-CH.CN

Examples of 1-butyl (benzoyl) -and- (substituted benzoyl) acetonitrile used in the above reactions are shown in the tables.

Tert-butyl (benzoyl and substituted benzoyl) cyanoacetates:

COCHCOOC (CH ₃ ) ₃

CN

L M R melt t. , ^c C H 3-C1 4-C1 91-94 H H 4-OCF ₃ 81-84 H H 4 -Br 113-115 H H 4-CF ₃ 146-147 H H 4-F 98-100 H H 4-CN 127-128 H H 4-CF ₃ CH ₂ O 136-139 H H 4-CH ₃ SO ₂ 127-129 H 3-F 4-F 91-94 H H 4-CH 3 S 117-119.5 H H 4-CHF ₂ CF ₃ O 92-94 3-C1 5-CI 4-CH3O -

Benzoylacetonitriles:

O

H

C-CH, CN

L M R melt t., C H H 4-C1 128, 5-129.5 H 3-C1 4-C1 105-107 H H 2-Cl 153-55 H H 4-OCF _i 79-81 H H 4-CF ₃ 44-45 H 2-Cl 4-C1 £ 6 - 6 7 H H 3-Cl 80-83 H H 4-CN 126-128 H H 4-F 73-80 H H 4-SO ₂ CH ₃ 129-132 H 3-C1 4-F 74-75 H H 3-CF ₃ 58-60 H H 4-CH3 133.5-106 H H 4-NO ₂ 119-124 3-C1 5-C1 4-OCH3 - Formulas I N-substituted arylpyrenes can to be made Formulas I as needed for substituted arylpyrrole, where A-van- denilis, o L, M, R, W, X, and Y explained above, in response with the right one alkylating agent and suitable base, for example: brominated ox iC ·, -C ₄ alkyl and potassium t-butox

tie. This reaction produces arylpyrrole, which is substituted as in the starting material, but the nitrogen is substituted with an oxy-C _: -C ₄ -alkyl.

In a similar reaction, substitution of brominated oxy-C 1 -C ₄ alkyl with cyanobromide affords arylpyrrole of formula I with a carbonitrile substituent on nitrogen. The reactions could be explained as follows:

1) Br- (C 1 -C 8 -oxyalkyl) ^{+ K 1} -O-Iret.Uu

2) CNBr wherein L, M, W, X and Y have the meanings given in formula I above, and A = 1) C 1 -C 4 alcohol or 2) CN.

2-Phenylpyrrole-3,4-dicarbonitrile, 8-bromo-5-phenylpyrrole-3,4-dicarbonitrile and their phenyl-substituted derivatives can be prepared by reacting fumar nitrile with bromine in the presence of a chlorinated hydrocarbon, such as chloroform, at an elevated temperature to give bromfumaronitrile. The bromfumaronitrile thus formed is further reacted with N- (trimethylsilyl) methyl-5-methyl-benzenethioimidate or a substituted derivative thereof in the presence of hexamethylphosphamide at elevated temperature to give 2-phenyl-pyrrole-3,4-dicarbonitrile. The bromination of the 3,4-dicarbonitrile thus prepared gives 3-bromo-5-phenylpyrrole-3,4-dicarbonitrile or a phenyl-substituted derivative, if a substituted N- (trimethylsilyl) -methylbenzene-thioimidate is used in the previous reaction. The reaction can be graphically explained as follows:

NC

CN

Br _; / CH, C1. Δ (-HBr)

NC

NC CN vol

H

CN

Br

M

R

Based on the above illustrative schemes, the following examples provide methods for the preparation of other compounds of the invention not specifically described herein.

The arylpyrroles of the present invention are effective in the control of insects, parasitic mites and nematodes. These compounds are also effective in protecting crops and their crops against attack by the above insect pests.

In practical conditions, it is generally effective in the range of 100 to 10,000 parts per million, and preferably 100 to 5,000 parts per million, of arylpyrrole comprising all arylpyrrole isomers of formulas II, III, IV, V, VI and VII dispersed in water or other inexpensive liquid carrier , such as crops grown in the field or soil on which the planting material is grown, to protect it from insect pests, parasitic mites and / or nematodes. Such compounds can be used in insect-pest insects such as black larvae, North American wheat bark crayfish and the like.

According to the present invention, arylpyrroles of formula I are also effective in controlling insect pests, nematodes and parasitic mites by treating the foliage of the planting material and / or the soil or water where the material is grown. In addition, the application rate should be sufficient to maintain the active ingredient in the range of 0.125 to 4.0 kg / ha. It is obvious that higher ratios can also be used for the application of formula I arylpyrroles to protect the planting material from attack by insect pests, nematodes and parasitic mites. However, it is not usually necessary to make a larger relationship to avoid unproductive costs. Although arylpyrroles according to the present invention are themselves effective in controlling insect pests, nematodes and parasitic mites, such arylpyrroles can be used in combination with biologically active chemical products including other insecticides, nematocides and acaricides. For example, arylpyrroles according to the present invention can be used effectively or together with phosphates, carbamates, pyrethroids, formamide, chlorinated carbohydrates, halobenzoyl ureas and the like.

2-Aryl-3-cyano-4,5-dihalopyrroles obtained by the present invention from cyano-styrene compounds are effective in controlling insect pests, nematodes and parasitic mites. These compounds are also effective in protecting crop crops and crops against attacks of the previously harmful insects.

In practical conditions, generally effective from 10 to 10,000 m.d. and preferably 100 to 500 m.d. halogenated arylpyrrole dispersed in water or other low-cost liquid carrier for the treatment of planting material, crop crops or soil for cultivation of said crops, protecting them from harmful insects, parasitic mites and / or nematodes.

The above halogenated arylpyrroles are also effective in controlling insect pests, nematodes and parasitic mites, in treating the foliage of the planting material and / or in the water in which the said seedlings are grown. The amount of these halogenated arylpyrroles is usually sufficient to provide a ratio of 0.125 to 4.0 kg of active ingredient per ha. It is clear that higher ratios can also be used to protect crops against insect pests, nematodes and ticks. However, big relationships are usually unnecessary and expensive.

Useful when arylpyrroles mentioned are included in formulas. These include dry compact granules, fluid compositions, granular compositions, wetting powders, emulsifying concentrates, concentrated dusts, microemulsions and the like. All of them can self-treat the soil, water and / or foliage and provide reliable protection for plants. Such formulations include the compounds of the invention in admixture with inert, collectible solid or liquid diluents.

For example, moisturizing powders, dusts, and puffs of the present invention may be formulated together by co-curing 3 to 20% by weight of an arylpyrrole compound of Formula I with 3 to 20% by weight of a solid anionic surfactant that may contain the dioctyl ester of , a surfactant, namely an OTB aerosol manufactured and sold by the American Cyanamid Company. Such formulations contain about 60 to 94% by weight of an inert solid solvent such as montmorillonite, atapulgite, chalk, talc, kaolin, infusible earth, limestone, silicates, and the like.

The granules in compact form are especially used for soil or water treatment and can be prepared by grinding equal parts, typically 3 to 20 parts of arylpyrrole and a solid surfactant, together with 60 to 94 parts of gypsum. The mixture is then solidified to fine granular particles with a degree of comminution of about 24/48 (according to Taylor, strainer # 24/48 corresponds to hole diameters of 0.7-0.3 mm or larger).

Other suitable solid surfactants, including not only the anionic dioctyl ester of sulpho-succinic acid sodium, but also nonionic blocked copolymers of ethylene oxide and propylene oxide, are to be used in existing formulations. Such blocked copolymers are commercially available from BASF Wyadolt Corporation, under the name Pluronin 10R8®, 17R8 *. 25R8®, F38®, F68®, F77® or F87® and are extremely effective in producing compact pellets.

In addition to the powder and concentrate formulations described above, moisturizing powders and water dispersible formulations can be used. Ideally, the fluid compositions should be applied to the subject along with the aqueous compositions sprayed on the foliage of the planting material to be protected. Such spray compositions can be applied at spawning grounds, as well as in the feeding area, and at the locations of the harmful insects and parasitic mites to be destroyed.

Where solid arylpyrrole formulations are to be used in combination treatments with other pesticides, the compositions may be applied in a mixture of components, or may be applied gradually.

Alternatively, the liquid arylpyrrole compositions may be mixed with the other pesticide formulations in the reservoir or may be applied separately in a gradual spray liquid. Liquid formulations of the compounds of the invention that can be sprayed should contain from 0.001 to 0.1% by weight of active arylpyrrole.

The following examples illustrate the invention.

EXAMPLE

2-Phenylpyrrole-3-carbonitrile

CO H

CH

Cl

Δ p

CHy-C CN>

NHCH = O

1.5 hours. concentrated

Another procedure analogous to the method disclosed in 43,42736 (1978). A mixture of 30 g of N-formylphenylglycine was heated to 90 ° C using a magnetic stirrer

Clear yellow reaction solution in vacuo to give 42.5 g of an oily brown-orange semisolid. Part of the material is purified by chromatography on silica gel to give 73% of a mixture of 2-phenyl-pyrrole-3-carbonitrile and 27% of 2-phenyl-cyano-5-methylpyrrole (as determined by proton NMR spectrum). Recrystallization once from chloroform and twice from 1,2-dichloroethane gave 1.69 g of an off-white solid, determined by 96 pyrrole-3-carbonitrile, m.p. t. 148-152 ° C.

2-PhenylMicroanalysis (M. m. 168.19):

Calculated,

% Found:

C, 78.55

C, 78.52

H, 4.79

H, 4.73

N, 16.66

N-16, 54

EXAMPLE

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

eq. SO.Cl, CH.C1,

->

2.00 g (11.9 mmol) of 2-phenyl-3-cyano-pyrrole in 80 ml of a methylene chloride solution are added dropwise via a magnetic stirrer and 5 minutes via syringe. 1.90 mL (3.19 g; 23.6 mmol) of sulfuryl chloride. Temperature is maintained at 5-10 ° C during laying. Stir at 5-10 C for 90 min. The reaction mixture was filtered in vacuo to remove a solid (1.28 g), m.p. t. 192.5-195 C. The filtrate is diluted with 400 mL of ethyl acetate, washed twice with 200 mL of water, dried (sodium sulfate), treated with activated carbon, filtered and then concentrated in vacuo. 0.60 g (21.5% yield) of a pink-purple solid is obtained (after the residue is clouded with hexane). This solid is recrystallized from 5 mL of hot acetone to give 0.32 (9% yield) 4,5-dichloro-2-phenyl-pyrrole-3-carbonitrile-brown.

orange solids, melt t. 254-255 ° C. IR, max (suspension down) : 3165 (wide singlet), 3120 (singlet), 2245 (singlet), 1570 (multiplet),

1513 (multiplet),

1440 (singlet),

1252 (multiplet),

1069 (multiplet),

996 (multiplet),

920 (multiplet),

68 (singlet,

698 (singlet),

665 (singlet) cm ¹ .

δ7.73 (doublet. J = 6.5 Hz;

1.97 H, 2 phenyl protons, at C-2.6), 57.52 (triplet, J = 7.3 Hz);

2.04 H, 2 phenyl protons,

H-NMR (Dimethylsulfoxide):

at C-3.5), 67.44 (triplet, J = 7.3 Hz; 1.02H, 1 phenyl proton at C-5).

C-NMR (dimethylsulfoxide):

0137.51 (C-2 pyrrole carbon), 5129.15 (C-4 phenyl carbon), 5129.04 (C-3.5 phenyl carbon); 5128.37 (Cl phenyl phenyl carbon), 5125.88 (C-2.6 phenyl carbon), 5144.32 (or C-5 pyrrole or nitrile carbon), 5144.14 (or C-5 pyrrole or nitrile carbon), 5110.74 (C-4 pyrrole carbon), 589.78 (C-3 pyrrole carbon).

Microanalysis [M

m. 237.09):

Calculated,

Oh,

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 p-Chloro-β - [(formylmethyl) amino] cinnamon nitrile diethyl acetal

toluene

-H, 0 ci-

NH

A solution of 250.00 g (1.39 mol) of pchlorobenzoylacetonitrile, 203 ml (185.95 g; 1.39 mol) of 2,2-diethoxyethylamine and 1300 ml of pure toluene is stirred under magnetic reflux for 20 hours. The water is collected in a Din-Stark trap (23.8 ml; 95.2% of theory). The hot turbid dark brown solution with a high content of insoluble matter is filtered through a filter aid such as infusion soil. After dilution with 300 ml of ethyl acetate, the solution is filtered through a 7 x 13.5 cm column of silica gel.

The filtrate was concentrated in vacuo to give 354.38 g (86.4% of crude product) as a clear dark, progressively hardening oil. This solid was recrystallized from hot cyclohexane to give 324.26 g (79.1%) of a waxy orange solid.

NMR of this product showed a mixture of 78% (Z) and 23% (E) isomeric p-chloro-O- [formylmethyl) amino] cinnamon nitrile in diethyl acetal, m.p. t. 60-72 ° C.

For another example obtained in a similar manner, the following analytical data were obtained:

IR, max (slope suspension): 3325 (singlet,

3065 (multiplet)

2197 (singlet),

1600 (multiplet),

1530 (singlet),

1314 (multiplet),

1265 (multiplet),

1175 (multiplet),

1154 (multiplet),

1128 (singlet),

1100 (singlet),

1060 (singlet),

1022 (singlet),

939 (multiplet),

895 (multiplet),

844 (singlet),

768 (multiplet),

730 (multiplet), cm

H-NMR (chloroform

67.47 (doublet, J = 8.6 Hz; 2.12H, two aromatic protons), 67.37 (doublet, J = 8.6 Hz, 2.12 H, two aromatic protons), 65.10 (E ) and 64, 86 (Z) / wide triplet; 1.25H, one N-H proton /, 64.69 (Z) and 64.60 (E) (triplet, J = 5.1Hz, 1.05H, one acetal carbon methane proton),

64.07 (E) singlet;

proton /, and 64.05 (Z) /

0.83H, enamine 63.17 (E) and

63.86 (Z) / quartet, J =

7.1 Hz; 2.22H, two methylene protons in one of two ethoxy groups /, 63.56 (Z) and 63.53 (E) / quartet J = 7.1Hz, 2.22H, two methylene protons in one of two ethoxy groups); 63.18 (triplet, J = 5.1 Hz; 1.77H, two methylene protons of the ethylene acetal group); 61.20 (triplet,

C-NMR (chloroform):

J = 7.1Hz; 4.90H; six methylene protons in two ethoxy groups).

6,161,21 α-enamin carbon);

6136.29 (Z) and 6134, 60 (E) (or C-1 or C-4 phenyl ring), 5129.34 (Z) and

5129.89 (E) / or C-2, 6 or C-3.5 phenyl ring /, 5128.94 (Z) and 5128.63 (E) / or C-2, 6 or C-3.5 phenyl ring), 5121.19 (Z) and 5119.50 (E) (nitrile carbon), 599.43 (Z) and 5100.63 (E) methylene carbon; 515.26 (methylene carbon of ethoxy groups).

Microanalysis (M. 94.78)

Calculated,%: C-61.11

Found,%: C-61.25

H, 6.50

N, 3.51

H-6:25

N, 9.34

Cl, 12.03

Cl, 12.35

EXAMPLE

2- (p-Chlorophenyl) -pyrrole-3-carbonitrile, CN

ClH ² O ⁺ CF ₃ CO _; H - '^ ^Z No

H

Cl

To 10 mL of trifluoroacetic acid stirred at 23 ° C for 45 min. 54.00 g (0.183 mol) of solid p-chloro-p - [(formylmethyl) amino] cinnamon nitrile diethyl acetal are added. The exotherm causes the temperature to rise to 38 ° C during this addition and after 32 min. the solid begins to settle from the beginning. After 30 minutes after stirring at room temperature, the reaction mixture is filtered under vacuum and the collected solid is washed first with trifluoroacetic acid followed by ethyl acetate / hexane and finally hexane. Yield: 16.83 g (45.4%) of off-white solid, m.p. t. 165-166 ° C. For example, for analogue production, the following analytical data were obtained:

IR, max (slope suspension): 3275 (broad singlet),

2225 (singlet),

1502 (singlet),

1410 (multiplet),

1275 (multiplet),

1200 (multiplet),

1108 (singlet),

1023 (multiplet),

999 (multiplet),

908 (multiplet),

843 (singlet),

752 (singlet),

695 (singlet),

620 (singlet), cm ¹ .

1 H-NMR (acetone): 611.22 (very broad singlet; 0.66H, 1-pyrrole NH proton), 67.82 (doublet J = 8.9Hz; 2.46H two aromatic phenyl protons), 67.51 ( doublet, J = 8.9Hz; 2.46Hz two aromatic phenyl protons), 67.02 (triplet, J = 2.6Hz; 1.1H, one pyrrole proton at C-5), 66, 58 (triplet, J = 2.6 Hz; 0.77 H, one pyrrole proton at C-4).

6137.73 (pyrrole C-2),

6134.42 (p-chlorophenyl C-4),

C-NMR (acetone):

6129.93 (phenyl ring C-2.6 methine carbon), δ12β, 07 (methyl carbon C-2.6 phenyl ring); 6121.21 (Pyrrole C-5), 5117.93 (Nitrile Carbon), 5113.78 Pyrrole C-4), δ90, 86 (Pyrrole Carbon)

C-3)

Microanalysis (M. m. 102, 64):

Calculated,%: C-65.19 H-3.48

Found,%: C-64.18 H-3.52

N, 13.83 Cl, 17.5

N, 13.63 Cl, 17.74

Using the above procedure, as shown, or replacing concentrated hydrochloric acid with trifluoroacetic acid gave the following compounds:

, CN

N '

H

M and / or

Lyd. t ° C

The acid used

4-C1 165-166 machine.HCI 3,4-di-Cl 216-221 CF ₃ COOH 2-C1 156-157 cf ₃ cooh 4-OCF ₃ 143-145 cf ₃ cooh 4-CF ₃ 179-180 cf ₃ cooh 2,4-di-Cl 197-199 cf ₃ cooh 3-C1 150-156 CF ₃ COOH 4-CN 210-212 CF.COOH

CF ₃ COOH

M and / or Lyd. t ° C The acid used 4-F 167-170 machine.HCI 4-SO.CH, 221-221.5 CF-COOH 3,4-di-F 173-175.5 CF-COOH 3-CF ;, 166-168 CF.COOH 4-COOCH ₃ 155.5-158 CF.COOH 4-CH ₃ 117-137 CF.COOH 4-NO ₂ 174-177 CF.COOH

EXAMPLE

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

2.2 eq. SO, C1,

-...........—----- V

HOAc

Cl / 7

CN

Cl

Cl

The mechanically stirred mixture of 16.83 g (81.3 mmol) of 2- (p-chlorophenyl) pyrrole-3-carbonitrile a solution of 450 ml of glacial acetic acid ⁼ 36 ° C dropwise within 18 min. 14.7 mL (24.70 g, 183.0 mmol) of sulfuryl chloride are added. The addition involves an increase in temperature to 39 ° C due to an exothermic reaction. After 16 additional minutes the reaction mixture was filtered under vacuum. The collected solids are washed first with acetic acid and then with water. This solid, after recrystallization from hot ethyl acetate, has a melting point. t. 259-261 C. Other samples of this product were prepared by similar procedures. The analytical data for one of the samples of the following product are shown below:

IR, max (slope suspension): 3170 (broad singlet), 3100 (multiplet),

2225 (singlet),

1508 (multiplet), 1097 (multiplet), 825 (singlet),

717 (multiplet),

660 (multiplet), cm

H-NMR (Dimethylsulfoxide):

C-NMR (dimethylsulfoxide)

67.72 (doublet, J = 8.6Hz; 2.00H, two aromatic protons), 67.56 (doublet J = 8.6Hz; 2.00H two aromatic protons).

6136.01 (pyrrole C-2 carbon), 6133.92 (p-chlorophenyl C-4 carbon), 6129.09 (p-chlorophenyl C-3.2 carbon), 6127.41 (p-chlorophenyl C-4 carbon) ); 6127.41 (p-chlorophenyl carbon Cl), 6114.10 (nitrile carbon), 6114.10 (pyrrole C-5 carbon), 6110.92 (pyrrole C-4 carbon), 690.09 (pyrrole C-3) coal.

Microanalysis (M.M. 271.54):

Calculated,

Found,

C-48.65 H-1.86 N-10.32 Cl-39.17%

C-49.22 H-2.12 N-9.58 Cl-39.03%

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

Br,

Br. CN

Br N H.

CF.

To a stirred mixture of 0.8 g of 2- (a, a, a-trifluoro-p-toluyl) pyrrole-3-carbonitrile in 70 ml of chloroform was added 2 ml of bromine. After stirring overnight, a white solid is isolated from the mixture which is collected by filtration. Thin layer chromatography showed one component:

(1: 1 ethyl acetate-hexane;

Lyd. t. above 230 ° C.

Analysis C ₁₂ H ₅ Br ₂ F ₃ N ₂

Calculated, %: C-36.95 H, 1:27 N, 7.11 Br-40.61 % Found: C-36.40 H, 08.08 N, 6.99 Br-40.55 According to 5 and 6 examples procedures, one replacing 25th in the right way modified phenylpyrrole -3-carbonitrile 2-

(a, a, a-Trifluoro-p-toluyl) -pyrrole-3-carbonitrile gives the following compounds:

^X y __ ^ CN

V. ' i

L M R X Y Lyd. t., ' ^J C H H 4-NO ₂ Br Br 274-277 H H 4-F Cl Cl > 220 H H 4-F Br Br > 220 H H 4-SO ₂ CH, Cl Cl > 230 H 3-F 4-F Cl Cl > 230 H 3-F 4-F Er Br > 220 2- -Cl 3-C1 4-C1 Cl Cl 2- -Br 3-Br 4-Br Br Br H H 4-OCF _{: <} Cl Cl 222-225 H H 4-0 C F, Br Br 231-232 H H 4-OCF ₃ Cl H H H 4-CN Br Br > 230 H H 4-CN Cl Cl > 240 H H 4-SO ₂ CH _{2 ;} Br Br > 230 H H 4-NO ₂ Cl Cl 246-249 H 3-C1 4-C1 Br Br > 260 H H 3-CF ₃ Cl Cl > 230 H H 4-CO CH _? Cl Cl 251-254 H 2,3-CH = CH- Cl Cl 244-247 H H 4-CH ₃ Cl Cl 215-217 H 2-C1 4-C1 B r Br > 230 H H 3-C1 Cl Cl > 230 H 2-C1 4-C1 Cl Cl > 230 H H 4-C1 Er Br 273-274 H H 2-C1 Br Br > 230 H H 4-CF, Cl Cl > 230

L M R X Y Lyd. t. , 'C H H 4-Br Cl Cl > 235 H H 2-C1 Cl Cl > 230 H 3-Cl 4-CI Cl Cl > 235 H H H Cl Cl 254-255 H H 4-CI Cl Cl 255-257 H H 4-CF ₃ Br Br > 230 H H 4-CI Cl Br 262-263 (s) H H 4-CI Br Cl 250-258 (decay) H 3-Cl 5-C1 Cl Cl > 230 H 3-Cl 4-Cl Cl Br > 230 2-C1 4-CI 5-F Cl Cl 207-210

EXAMPLE

3-Nitro-2-phenylpyrrole

O <YC CH _? NO, · ILNCH.CIKOCJD. ^N0 - _

- CH ₂ CH (OC ₂ H ₅ ) ₂ 'ry ^{2 H}

.......-......... ”VA

H

Alpha-nitroacetophenone (5.7 g, 0.0345 mol) is mixed with 100 ml of toluene and 9.6 g (0.0345 mol) of aminoacetaldehyde diethyl acetal are added. Transfer the reagents to a 250 ml round-bottom flask equipped with a Dino-Stark trap. The trap was filled with 4A molecular mesh and heated under reflux for 18 hours. Removal of toluene in vacuo affords 8.36 g of α- (2,2-diLT 4040 B ethoxyethyleneamino) -β-nitrostyrene (brown oil). Almost 50 ml is added to this oil. hydrochloric acid .. Rotating the flask turns the oil into 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) afforded the product of 2 fractions: 2.08 g m.p. 190-192 ° C (31%).

IR, max: (1485cm ^-1 (NO ₂ ), H-NMR (deuterated chloroform / dimethylsulfoxide) 56.73 (multiplet,

2H): 57.46 (multiplet, 5H).

EXAMPLE

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

A mixture of 3-nitro-2-phenylpyrrole (1. 56g, 0.0083 mol) in dioxane was cooled in an ice bath with 25.9 g (0.0182 mol) of commercially available sodium hypochlorite. After 45 minutes stirring, the mixture is almost acidified. with hydrochloric acid. Water and diethyl ether are added. The layers were separated and the upper organic layer was washed with water, dried over anhydrous magnesium sulfate and concentrated in vacuo to give 2.21 g of a yellow solid.

Purification by chromatography on silica gel eluting with an adsorbent and increasing ethyl acetate / hexane mixture yields, after evaporation, 0.77 g of a yellow solid (36%):

Melting point 190-190.5 ° C;

Analysis: C ₁₀ H, .NO ₂ C ₁₂

% Deducted

% Found

C, 46.72

C-46, 90

H, 2.35; N, 10.90

H, 2.86; N, 10.02

Following the procedures of Examples 7 and 8 above, the use of the appropriately substituted α-nitroacetophenone and 2,2-di- (C 1 -C ₄ ) alkoxy) ethylamine affords the substituted [2,2-di (C ₁ - C, (alkoxy) ethylamino] -β-nitrostyrene which is then converted to 3-nitro-2- (substituted) phenylpyrrole by treatment with hydrochloric acid, hydrobromic acid or CF.COOH. The reaction of the substituted phenylpyrrole thus prepared with sodium hypochlorite in dioxane yields the chloro analogs; while the reaction of the substituted phenylpyrrole with bromine in chloroform yields bromine-containing analogs:

v / NO, vol

L M R X Y Melting point , ° C H H H Cl Cl 190-190.5 H 4-C1 H Cl Cl 214-215 H 4-C1 H Br Br 203-204 (ski1 sample) H H H Br Br 148.5-149 3-C1 4-C1 Cl Cl Cl 219-220 H 4 -Br H Cl Cl 222-223 (decay) H H 4-CFj Cl Cl 166-168

bomtril

H 1 C 1

EXAMPLE

4,5-Dichloro-2- (3,4-dichlorophenyl) -1-methylpyrrole-3-carbC1 CN / 7 + Mel + KOC (CPL) ₃ Λ

Cl N N

To 2 g of 4,5-dichloro-2- (3,4-dichloro-phenyl) pyrrole-3-carbonitrile in dry tetrahydrofuran, which is a clear brown solution, add 1 eq. KO-But (potassium butoxide) and after several minutes a clear solution is obtained. 1 eq. Mel (methyl iodide) was added and the solution was heated to reflux for 4 hours. The solution was then left overnight, stirred at room temperature. The next day, 50 mL of water was added and the mixture was extracted with 4 x 50 mL methylene chloride. The resulting organic phases are combined, dried over magnesium sulfate and concentrated. The resulting solid is purified by flash chromatography on silica gel using 50/50 ethyl acetate / hexane as the adsorbent. This gives l, 80g of white solid. Yield = 86%. Mp = 154-156 ° C.

By the above procedure, the substitution of phenylpyrrole-3-carbonitrile or 3-nitro-2- (substituted) phenylpyrrole with 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile gives the compounds, specify below:

A L M R X Y Melting point , ° C ch ₃ H H 4-C1 Cl Cl 152-153 c ₂ h ₅ och ₂ H 3-C1 4-C1 Cl · Cl 128-130

A L M R X Y Lyd. t. , ^J C C ₂ H ₃ H 3-C1 4-C1 Cl Cl 137-138 ch ₃ H 3-C1 4-C1 Cl Cl 154-156 ch ₃ H H 4-CF ₃ Br Br 145-146 _Cf H ₅ CH ₂ H H 4-CF ₃ Br Br 145-147 _Cf; H ₅ CH ₂ H 3-C1 4-C1 Cl Cl 95-96 ch ₂ = ch-ch ₂ H 3-C1 4-C1 Cl Cl 69-70 ch ₂ = ch-ch ₂ ci H 3-C1 4-C1 Cl Cl 147-148 ch ₃ sch ₂ H 3-C1 4-C1 Cl Cl c (CH ₃ ) ₃ H H 4-CF ;. Cl Cl ch ₃ H H 4-CF ₃ Cl Cl 99-100 ch ₂ sc ₂ h ₅ H 3-Cl 4-C1 Cl Cl 74-75 c ₂ h ₅ och ₂ H 3-C1 4-C1 Cl Cl 118-120 c ₂ h ₅ och ₂ H H 4-CF ₃ Cl Cl 99-100 ch ₃ H H 4-OCH, Br Br 112-115 ch ₃ H H 4-C1 Br Br 197-201 c ₂ h ₅ och ₂ H H 4-OCF, Cl Cl 46-47 ch ₃ H H 4-OCF ₃ Cl Cl 72-73 c ₆ h ₅ ch ₂ H H 4-OCF ₃ Cl Cl oil c ₂ h ₅ och ₂ H H 4-C1 Cl Cl hoch ₂ ch ₂ H 3-C1 4-C1 Cl Cl 143-145 CN H 3-C1 4-C1 Cl Cl 251-252 C _f H ₅ CH ₂ OCH ₂ H 3-C1 4-C1 Cl Cl 88-89 ci-o-ch ₃ H 3-Cl 4-C1 Cl Cl 118-120 J C = C-CH _Z H 3-Cl 4-C1 Cl Cl 115-116 ch ₃ H H 4-C1 Br cf ₃ 126-129 c ₂ h ₅ och ₂ H H 4-C1 Br cf ₃ 91-92 C H OCH H 3-Cl 4-C1 Cl Cl 118-120

A L M R X Y Melting point , ° C C ₂ H ₅ OCH ₂ H H 4-CI Br Br 104-105 ChHrCH ₂ H H 4-CI Br Br 81-82 ch ₃ H H 4-CI Br Br 197-201 CN H H 4-CF ₃ Cl Cl 138-139 C ₂ H ₅ OCH ₂ H H 4-CF ₃ Br cf ₃ 104-105 c ₂ h ₅ och ₂ H H 4-CF ₃ H cf ₃ 76-77 c ₂ h ₅ och ₂ H 3-CI 4-CI Br cf ₃ 80-81

EXAMPLE 1-Benzyl-4,5-dibromo-2- (a, a, a-trifluoro-p-toluyl) pyrrole-2-carbonitrile

In a 100 mL flask, 1.5 g of 4,5-dibromo-2- (et, a, a-trifluoro-p-toluyl) pyrrole-3-carbonitrile is mixed with 50 mL of tetrahydrofuran to give a clear dark solution. While stirring, 1 equivalent of potassium butoxide is added. After a few minutes, the solution becomes clear. Benzyl bromide (0.65g) is added via syringe. The mixture was heated to reflux overnight. The following day, thin layer chromatography (50/50 ethyl acetate / hexane) showed the presence of both starting materials and product. The reaction mixture is treated as follows: 50 ml of water are added and the mixture is extracted with 4 x 50 ml of methylene chloride. The organic phases are mixed and washed with 4x50 ml of 10% aqueous sodium hydroxide solution. The organic phase is dried over anhydrous magnesium. This gives a brown solid, which is removed from ethyl acetate with hexane.

hydroxide sulfate, and the yield was 0.75 g = 40.7%.

Melting point = 145-147 ° C (decomposition)

EXAMPLE

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

+ KOCCCHjh + C1CFL, OC, H ₅

THF —a

Cl CN

M

Cl

Cl 'Cl

N cą

OC, H

A sample of 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile (1.0 g, 0.003 mol) is dissolved in 10 ml of dry tetrahydrofuran. To this solution was added potassium tetrabutoxide (0.37 g, 0.0033 mol) followed by chloromethyl ethyl ether (0.312 g, 0.0033 mol). The mixture is stirred for about 1 hour. at room temperature, then poured into a large volume of water, which precipitated the product into a precipitate. The white solid is collected and dried; 1.0 g (91%), m.p. 128-130 ° C.

EXAMPLE

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

board, 5.25 wt. 30 min. after mixing

To the stirred magnetic stirrer 17.87g (88.2 mmol;

1.00 equivalent) of a solution of 2- (p-chlorophenyl) -3-cyanopyrrole at 20 ° C in 800 ml of droplets of dioxane per minute. 250.15 g (176.4 mmol; 2.00 equivalents) of sodium hypochlorite are added. At room temperature, the reaction solution is poured into 2200 ml of water. The resulting mixture was filtered under vacuum to give a small amount of black solid. The filtrate is almost acidified to pH 2. hydrochloric acid to give a brown solid. This solid is filtered off with suction 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 a 5% aqueous solution of a home hydroxide solution, leaving a small amount of insoluble black solid. This black solid, diluted 100 with 75 ml of ethyl acetate each time, is washed with 5 ml of 5% aqueous sodium hydroxide solution, water and saturated aqueous sodium chloride solution. The ethyl acetate layer was dried (magnesium sulfate), treated with activated carbon, filtered and then evaporated in a vacuum rotary evaporator to give 1.10 g (5.3% yield) of an orange-brown solid. This solid is recrystallized from ethyl acetate with a mixture of chloroform to give 0.51 g (2.5% yield) of an off-white solid, 4-chloro-3cyano- (p-chlorophenyl) pyrrole.

Melting point 251-253 ° C.

EXAMPLE

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

CN

CN

Br, dioxane

Br

Cl

Cl

A sample of 2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile (2.0 g; 0, 008 mol) is dissolved in 100 ml of dioxane by heating to 4050 C. The solution is then cooled to 30 ° C and bromine (1) is added. 3 g, 0.008 mmol). After stirring at room temperature for 1 hour, the solution was poured into water to give a gray solid (2.2 g, 88%).

Melting point 233-236C, decay.

In a similar manner, 5-bromo-2- (3,4-dichloro) -3-nitropyrrole can be prepared starting from 2- (3,4-dichlorophenyl) 3-nitropyrrole.

EXAMPLE

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

CN

(CH,), COCl

A sample of 5-bromo-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile (0.158 g, 0.005 mol) was dissolved in 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 a precipitate is collected (0.052 g, 30%). Melting point above 275 ° C.

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

EXAMPLE

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

Cl CN

To a stirred solution of 0.17 g (0.67 mol; 1.00 equivalent) of 4-chloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile in 22 ° C was added dropwise 100 ml of chloroform dropwise over 30 min. 0.20 ml (0.62 g; 3.88 mol; 5.79 equivalent) of bromine in 5 ml of chloroform are added. When added, exothermic heat is not released. After stirring for 3.25 hours at room temperature, the clear red reaction solution was evaporated in vacuo to give 0.28 g of off-white solid. This solid was triturated with hexane / methylene chloride to give 0.23 g of off-white, fluffy solid after vacuum filtration.

Melting point 262-263 ° C, dec.

EXAMPLE

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

Bl ',

CHC),

Br CN

12 of

Cl N

Cl

To a stirred magnetic stirrer solution of 5-chloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile (1.00 g, 4.22 mmol; 1.00 equivalent) in 300 mL of chloroform was added dropwise over 30 min at 45 ° C. 0.40 mL (1.24 g; 7.76 mmol; 1.84 equivalent) of bromine in 25 mL of chloroform are added. When added, exothermic heat is not released. At the end of the addition, a small amount of solid begins to precipitate. After stirring at room temperature for 19.5 hours, the reaction mixture was evaporated in vacuo to give 1.49 g of an orange-white solid. This solid was triturated in a mixture of hexane and methylene chloride and, after vacuum filtration, 1.33 g (100% yield) of a fluffy white solid.

Melting point 250-258 ° C, dec.

EXAMPLE

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

To a stirred solution of 2.40 g (11.8 mmol; 1.00 equivalent) of 2- (p-chlorophenyl) pyrrole-3-carbonitrile in 65 mL of glacial acetic acid was added dropwise via a syringe dropwise over 5 min. 0.75 mL (1.26 g; 9.35 mmol; 0.79 equivalent) of sulfuryl chloride was added. After about 5 min. upon completion of the addition, a solid precipitates from the reaction solution. After 45 minutes After stirring at room temperature, the reaction mixture is filtered and the collected solid is washed thoroughly with cold acetic acid. 2.08 g (74% yield of crude proLT 4040 B) are obtained in the form of off-white solids. This material was recrystallized from 75 mL of hot acetic acid to give 1.63 g (58% yield) of 97% pure product.

Melting point 258.5-261 ° C.

EXAMPLE

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

CN

CN

J Cl

N + KOC (CH ₃ ) ₃ + CH I

H no

Dissolve 2.0 g of 2- (3,4-dichlorophenyl) pyrrole-4-carbonitrile in 50 ml of dry tetrahydrofuran in a 100 ml flask and add 1 equivalent of potassium t-butylate. A slightly cloudy solution is obtained. Then 1 equivalent of methyl iodide is added by pipette. The color of the mixture lightens slightly. Attach a drying tube to the flask and leave under stirring at ambient temperature overnight.

The next morning, a small amount of slightly colored precipitate appears in the flask. Then 50 ml of water is added and the solution is clarified until a solid precipitates out of solution. This solid is filtered off from the solution and compared to the starting material by thin layer chromatography (25% ethyl acetate / hexane). The aforementioned solid is dried in a vacuum oven at 50 ° C overnight. This gives 1.31 g of product (62% yield).

Melting point 140-142 ° C.

EXAMPLE

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

CN

Cl + SO, C1

Cl

Cl CN> Cl

Mix 0.5 g of 2- (3,4-dichlorophenyl) -1-methylpyrrole-3-carbonitrile with 35 ml of glacial acetic acid in a 1 ml round bottom flask. The mixture is easily heated with a Fen radiator to dissolve all the pyrrole.

Pipette 2 equivalents of sulfuryl chloride into this clear solution. The solution is stirred and left at room temperature for 12 hours. After 12 or. the solution is poured into 50 ml of water to give a white precipitate. They are filtered and dried in a vacuum oven at 50'C for 3 hours.

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

EXAMPLE

Preparation of 4,5-Dichloro-2- (3,4-dichlorophenyl) -1- (2-oxyethyl) pyrrole-2-carbonitrile

Cl CN

Cl CN

Cl

K ⁺ 'O-tret.Bu

Cl

->

Cl

Cl

Cl

OH

To a stirred mixture of 2.0 g (6.5 mmol) of 4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile and 0.88 g (7.8 mmol) of potassium tert-butylate in 50 ml of dioxane was heated to reflux. 0.98 g (7.8 mmol) of bromoethanol are added under a refrigerator, The mixture is refluxed for 12 hours, cooled, diluted with 50 ml of water and extracted several times with chloroform. Concentration of the filtrate and recrystallization of the remaining solid from 20% ethyl acetate in hexane afforded 0.31 g of a white solid, mp 143-145 ° C. C; IR analysis (5077A).

Analysis: <3 _ΐί; Η ₂₃ ΝΟ ₄

Calculated,%: C-44.57 H-2.29

Found,%: C-44.77 H-2.29 (AgM 3313 9).

EXAMPLE

N-8.00 Cl-40.57

N-8.06 Cl-40.14

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

Cl CN

H

CN

Cl

Cl

CNBr

K ⁺ 'O-tret.Bu

CN

Cl

Cl

Potassium t-butylate (617 mg, 55 mmol) was added portionwise to a solution of 3-cyano-4,5-dichloro-2- (3,4-dichlorophenyl) pyrrole (1.52 g, 5 mmol) in anhydrous tetrahydride 4040 B in rofuran ( 20 ml). After 30 minutes a solution of cyanobromide (583 mg, 5.5 mmol) in tetrahydrofuran (1 mL) was added.

The reaction mixture was kept at room temperature overnight. The solvent is removed on a rotary evaporator. The residue is taken up in water and extracted with ethyl acetate. The organic layer was washed with water and a saturated sodium chloride solution, and then dried over magnesium sulfate. Evaporation and crystallization of the residue from ethyl acetate gave white crystals (1.07 g);

Melting point 250.5-252.0 ^c C; infrared spectrum (nuol) 2255.2245 cm (CN);

1 C-NMR (dimethylsulfoxide-d ₆ ) 5102.7 (N-CN); 6113.7 (3-CN); mass spectrum 331.9 (M + 1).

Analysis: C ₁₂ H ₃ C ₁₄ N ₃ (M.M. 330, 99): Calculated%: C-43.54 H-0.91 N, 12.70 Cl, 42.85 % Found: C-43.62 H-0.93 N, 12.63 Cl, 41.95

EXAMPLE

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

Cl CN

CI ^ n ^

C CH

Cl + L + NaOH

Cl

Cl

Cl

To a stirred mixture of 1.19 g (5.5 mmol) of 4,5-dichloro-2- (3,4-dichlorophenyl) -1- (2-propynyl) pyrrole-3-carbonitrile was added 69 ml of 10% aq. of sodium hydrocLT 4040 B solution. Then 0.70 g (2.7 mmol) of iodine. The mixture is stirred for 12 hours, 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. Melting point 115-116 ° C.

This reaction according to the present invention is also suitable for the conversion of any substituted alkynyl arylpyrrole of Formulas III, IV, V, VI or VII to the N-substituted 3-iodo-2-propynyl arylpyrrole of the present invention.

EXAMPLE

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

N-Iodimide of succinic acid (5.7 g, 0.0254 mol) was added slowly to a solution of 2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile (3.0 g, 0.0127 mol) in 100 ml of tetrahydrofuran. The reaction mixture was stirred at 25 ° C for several hours until thin layer chromatography (silica gel, 100: 100: 1 ether: petroleum ether: acetic acid) showed completion. The mixture is evaporated in vacuo to give a residue containing pyrrole and succinic acid imide; the crude solid is dissolved in 500 ml ether and shaken with 50x400 ml water to remove succinic acid imide. The ether layer was dried over sodium sulfate and evaporated in vacuo to leave 2.0 g (32.3%) of a gray-brown solid with m.p. above 230 ° C (purple vapor is leaking).

EXAMPLE

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

INC

TMS -

mol% n-BiuN h 'THF / 16 h / kT ^>

A solution of acrylonitrile (0.65 mL, 0.01 mol) and N- (trimethylsilyl) methyl-S-methylbenzthioimidate (2.4 g, 0.01 mol) in tetrahydrofuran (100 mL) was cooled to minus 5'C acetone in an ice bath . Blow over nitrogen for 30 minutes. a solution of tetrabutylammonium fluoride (1.0 mL IN in tetrahydrofuran) and tetrahydrofuran (20 mL) was added. Solution for another 30 min. stirring minus 5'C, then gradually warming to ambient temperature. Stir for a further 18 hours, then allow to warm to ambient temperature again. After 18 hours, the solvent is removed under reduced pressure. The residue is partitioned between ether and water and the aqueous layer is washed with water followed by a saturated sodium chloride solution. The solution was dried over magnesium sulfate. When the filtrate cooled, an off-white solid precipitated (1.2 g; 70% of theory). The spectral characteristics of this material are identical to those described (J. Org. Chem. 52, 2523 (1987)).

Analysis: C ₁₁ H ₁₀ N ₂

Calculated,%: C-77.65

Found,%: C-77.55

H, 5.88; N, 16.47

H, 5.83; N, 16.39

M.p. = 95 -97 ° C.

EXAMPLE

Preparation of 2-Phenyl-pyrrole-4-carbonitrile

DDQ / DMETpir. 16h / kT>

Under nitrogen purge, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.23 g, 0.001 mol) and 2-phenyl-1-pyrrole-4-carbonitrile (0.17 g, 0.001 mol) were dissolved. 1,2-Dimethoxyethane (13 mL) to give a clear orange solution. A single portion of pyridine (0.08 mL, 0.01 mol) is added, the solution warms slightly (to about 28 ⁼ C) due to the heat of the exothermic reaction, and a greenish-gray precipitate is formed immediately. The suspension is stirred at room temperature for 18 hours, during which time much of the solvent is evaporated. The brown semi-solid residue is partitioned between ether and half-saturated sodium carbonate solution. The red-brown aqueous layer is extracted twice with ether and the combined ether layers are washed with fresh water followed by saturated sodium chloride solution. After drying over magnesium sulfate, the solvent is removed under reduced pressure to give a white semi-solid. This material was recrystallized from ethylene dichloride (DARKO treatments) to give pale violet crystals (0.1 g).

The identical product is obtained directly in Step 1 by condensation of? -Chloroacryl nitrile and N- (trimethylsilyl) -methyl-S-methylbenzentioimidate using tetrabutylammonium fluoride as a catalyst (analogous to the preparation of 2-phenyl-1-pyrrole-4-nitrile as described above).

Analysis: C _{} 1} H _d N ₂

Calculated,%: C-78.57 H-4.76 N-16.67

Found,%: C-78.65 H-4.70 N-16.43

M.p. = 156-158C.

EXAMPLE

Preparation of 2,4-dibromo-5-phenyl-pyrrole-3-carbonitrile

Under nitrogen purge, a solution of bromine (0.6 mL, 0.012 mol) in chloroform (5 mL) was added dropwise over 20 min. is added to a stirred solution of 2-phenyl-pyrrole-4-carbonyl (0.84 g, 0.05 mol) in chloroform (20 mL). The resulting solution was stirred for 18 hours. at room temperature, the solvent is removed under reduced pressure to give a solid which is removed from ethylene dichloride to give the desired product (0.6 g),

Analysis: C _li H ₆ Br ₂ N ₂ substance which will fall over (ACO treatment). M.p. = 239-242 ° C.

Calculated%:

% Found:

C-40.49; H-8.4

C-39.88 H-8.7

Br-49.08 N-8.59

Br, 48.81 N, 8.48

Nitrile, Lyd and the methods set forth in Examples 26 are also obtained according to Examples 24, 25 as follows

Decomposition of 2,4-dibromo-5- (p-chlorophenyl) pyrrole-3-carbot, = 270-272 ° C.

EXAMPLE mas

3 ', 4'-Dichloro-3- (1,3-dioxolan-2-yl) propiophenone gav65 ^C1 CO, K +

To a vigorous stirring mixture of metallic magnesium (0.64 g, 26 mmol) in 10 mL of tetrahydrofuran was added dropwise 2- (2-bromoethyl) in a 100 mL triple-bottomed flask equipped with a thermometer, 60 mL dropping funnel and tube for nitrogen delivery. ) -1,3-Dioxalane (4.7 g, 26 mmol) in 40 mL of tetrahydrofuran. The dropping speed is selected so that the temperature is below 50 ° C. The reaction mixture was then stirred at 25 ° C for 1 hour. 120 ml of tetrahydrofuran are mixed with potassium 3,4-dichlorobenzoate (5.0 g, 22 mmol) under a nitrogen layer. The Grignard solution is then rapidly decanted from unreacted magnesium turnings and added rapidly to a stirred suspension of potassium benzoate. The reaction mixture was 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, and the salts are separated. The organic layer is washed with a saturated aqueous solution of sodium bicarbonate to make the medium neutral, and then washed once with 10 ml of brine. Drying with sodium sulfate and evaporation on a rotary evaporator yields a semi-solid which is chromatographed on silica gel using 3: 1 hexane: ethyl acetate to displace the adsorbed material to give keto-acetal (4.3 g; 60%) as a white solid, m.p. .t. 115-117 ° C.

EXAMPLE

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

O

HO, C-CO, H IO / I t () H

O

Cl

Cl

CHO g (2 6 mmol)

4'-dichloro-3- (1,3-dioxolan-2-yl;

propiophenone is added to 30 ml of 0.2 M acidic acid (obtained by dissolving 0.9 g of acid acid dihydrate in 30 ml of water) and 5 ml of ethanol. Reflux the mixture for one hour, then allow to cool. Much of the ethanol is evaporated on a rotary evaporator; 100 ml of diethyl ether are added followed by 20 ml of saturated sodium bicarbonate. The layers are separated and the organic phase is dried over magnesium sulfate. Evaporation on a rotary evaporator gave a yellow viscous oil which was chromatographed on silica gel using 3: 1 hexane: ethyl acetate to give keto-aldehyde (6.3 g, 73%) as a white solid.

EXAMPLE

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

O

nh ₄ oh EtOH Δ

Cl

Cl

To a suspension of 3- (3,4-dichlorobenzoyl) propionaldehyde (6 g, 26 mmol) in 60 mL of absolute ethanol was added ammonium acetate (4 g, 52 mmol). The reaction mixture was refluxed for 20 min. with reflux and allowed to cool. A large amount of ethanol is evaporated on a rotary evaporator and 200 ml of 1: 1 dichloromethane diethyl ether are added followed by 50 ml of water. The layers are separated and the organic phase is dried over sodium sulfate. Rotary evaporation gave a dark brown oil which was chromatographed on silica gel using 3: 1 hexane-ethyl acetate to remove the adsorbent to afford pyrrole (4.6 g, 83%) as a light brown solid, m.p. 49-51 ° C.

EXAMPLE

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

1) DMF / 'POC1 ₃

2) NaOAc

Cl

Cl

Phosphorus oxychloride (0.6 ml, 6.5 mmol) was added to 10 ml of dimethylformamide, stirred under nitrogen, in a 50 ml round-bottomed flask with a syringe. The solution warms up to light yellow. It is stirred for 20 min until 2- (3,4-dichlorophenyl) pyrrole (1 g; 4.7 mmol) is added in portions.

A light brown suspension was obtained for 30 min followed by heating for 40 min. up to 50Χ. A solution of sodium acetate (10 g, 122 mmol) in 15 mL of water was added to the cooled reaction mixture. The mixture was stirred for 20 min. the light brown precipitate was filtered off from the reaction mixture and air-dried over 20 hours to give a sufficiently pure aldehyde (1.1 g, 95%), m.p. t. above 200 ^J C.

EXAMPLE

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

C,

H.N-OSO.H '------------->

EtOH / H, O

To a suspension of 5- (3,4-dichlorophenyl) pyrrole-2-carboxaldehyde (1.5 g, 6.2 mmol) in 20 mL of water and 20 mL of ethanol was added hydroxylamine-O-sulfonic acid (0.7 g, 6.2 mmol) ). The reaction mixture was refluxed for 1 hour. During this time, a gray precipitate appears. After cooling, the reaction mixture was filtered to give essentially pure nitrile (1.5 g, 99%) as a solid, m.p. t. 170-17VC.

EXAMPLE

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

NC

Cl

Cl

NBS

--------- g

THF

To 5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile (0.5 g;

2.1 mmol) N-bromimide of succinic acid (0.8 g; 20 ml) was added portionwise to 20 ml of tetrahydrofuran.

4.2 mmol). Reaction mixture for 30 min. after stirring at 25 [deg.] C., 10 ml of water and 40 ml of diethyl ether are added. The layers are separated and the organic layer is dried over sodium sulfate. Rotary evaporation with subsequent chromatography on silica gel using hexane-ethyl acetate 3: 1 to remove the adsorbent gave dibromopyrrole (0.5 g, 60%) as a brown solid, m.p. t. above 250 ° C.

EXAMPLE

Preparation of 4-Phenylpyrrole-3-carbonitrile

CN

CN

..

H, C

H

To a mixture of 5 g (39 mmol) of succinic acid nitrole and 7.6 g (39 mmol) of (p-toluenesulfonyl) methyl isocyanide in 35 mL of dimethyl sulfoxide and 65 mL of ether were added over 20 min. a suspension of sodium hydride (1.11 g, 46 mmol) in 80 mL of ether was added. The reaction mixture is kept under nitrogen for 1 hour, then diluted with ether and water. The ether layer was separated, dried over magnesium sulfate and concentrated in vacuo. The resulting oil was chromatographed on silica gel with 1: 1 chloroform-ethyl acetate to give 2.5 g of a cream-colored solid. Recrystallization from ether with hexane gave 1.15 g of a melting point. t. 123-125Χ. References: Tetrahedron Letters, 5337 (1972), vol. t. 128-129 ° C.

EXAMPLE

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

NC + SO, C1 ₂ ^NC , _z . . _v ,., / ΓΛ

H

To a stirred mixture of 0.66 g (3.9 mmol) of 4-phenylpyrrole-3-carbonitrile was added 20 ml of dry tetrahydrofuran, cooled. up to 6 ° C in an ice-bath bath for 4 minutes. 0.66 mL (1.11 g, 8.2 mmol) of sulfuryl chloride was added. Blend for an additional 45 min. Store at 5-10 ° C for a further 30 min. mix by removing bath with ice. The reaction mixture was poured into 80 mL of ethyl acetate and 40 mL of water. The organic phase is separated off, washed and dried over sodium sulfate. Filtration through a short column, rinsing with ethyl acetate, and concentration of the combined filtrates in vacuo afforded 0.95 g of a dark substance. Recrystallization from chloroform gives 0.42 g of off-white crystals, m.p. t. 195-196'C, decay.

Analysis: C _U H ₆ C ₁₂ N ₂

Calculated,%: C-55.72 H-2.55 N-11.82 Cl-29.92

% Found

C-55.66 H-2.65 N-11.69 Cl-29.97

Following the procedures of Examples 33 and 34, other analogs are obtained. Synthesis of 2,6-dibromo-4- (p-chlorophenyl) pyrrole-3-carbonitrile is carried out according to the procedure of Example 33 using bromine in dioxane instead of sulfuryl chloride and tetrahydrofuran.

H

R X Y Lyd. mp, ° C 4-C1 Cl Cl 237-240 (decay) 4-CH ₃ Cl Cl 103-206 4-C1 Br Br > 245

EXAMPLE

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

o

H

To a suspension of 5.63 g of 60% sodium hydride in oil and 200 ml of dry ether under nitrogen was added a mixture of 23.5 g (122 mmol) of p-chlorocinamate and 19.4 g (122 mmol) of p-toluylsulfonyl) methylisocyanide from a drip funnel. ml of ether and 80 ml of dimethylsulfoxide solution. When this addition is complete for 20 minutes, the condensate is slightly dripping from the reflux condenser. After an additional 10 min. After stirring, the mixture is diluted with 100 ml of water. The mixture was extracted with ether 4 times, then dried over magnesium sulfate and then concentrated in vacuo. The resulting solid was recrystallized from ethylene chloride to give 7.8 g of crystals, m.p. t. 137-138 ° C.

Analysis: C ₁₃ H ₁₂ ClNO ₂

Calculated,%: 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 filtrate yields an amount of ester which is diverted to the additional crude soap step.

EXAMPLE

Preparation of 3- (p-Chlorophenyl) pyrrole

Cl

N '

H + NaOH

N '

H

N '

H

The crude ethyl 4- (p-chlorophenyl) pyrrole-3-carboxylate mixture was recrystallized from the filtrate solution and purified after recrystallization from the previous step, refluxed with 150 ml of 10% aqueous sodium hydroxide solution for 2.5 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 g of acid and 100 ml of ethanolamine is heated under reflux for 3 hours. After cooling, the mixture is poured onto 400 ml of ice and the resulting mixture is extracted 4 times with chloroform. The chloroform solution, dried over magnesium sulfate and treated with activated carbon, is concentrated in vacuo to give a brown solid.

Chromatography on silica gel using 1: 1 ethyl acetate-hexane gave 4.0 g of a white solid, m.p. t. 117-118 ° C.

EXAMPLE

Preparation of 3- (p- (Chlorophenyl) pyrrole-2-carboxaldehyde)

O

Cl + (COC1) ₂ + (CFį) ₂ NCH ------>

N CHO H

To a mixture of 0.86 g (12 mmol) of dimethylformamide in 10 mL of dichloroethane, kept under nitrogen and cooled in a bath under ice, was added over 25 min. 1.49 g (12 mmol) of oxalyl chloride in 10 ml of dichloroethane. The bath with ice is removed and the mixture is stirred for an additional 15 min. and re-refrigerated in an ice bath. Add to this mixture within 20 minutes

1.5 g (8.5 mmol) of 3- (p-chlorophenyl) pyrrole in 25 mL of dichloroethane. The bath with ice is removed after an additional 30 minutes. After stirring, the mixture is poured into 50 ml of ice water with 6 ml of 50% sodium hydroxide. The resulting mixture was extracted with ether and chloroform. The combined organic mixture was dried over magnesium sulfate and concentrated in vacuo. Purification of the resulting solid by silica gel chromatography using 1: 1 ethyl acetate: hexane gave 0.63 g of off-white solid. It is used directly for conversion to 3- (pchlorophenyl) -pyrrole-2-carbonitrile.

EXAMPLE

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

Cl + H, NOSO ₃ H->

Cl ^N CHO H

N CN H

0.63 g (3.1 mmol) of 3- (p-chlorophenyl) pyrrole-2-carboxaldehyde in 10 ml, the water mixture was stirred and ice-cooled by the gradual addition of 0.52 g (4.6 mmol) of hydroxyamine-osulphuric acid in 10 ml of water . Once added, the bath with ice is removed and the mixture is heated for 25 min.

The collected solid obtained after cooling, according to NMR, is a mixture of the product and the parent aldehyde.

This mixture was treated in the same manner with an additional amount of 0.49 g (4.2 mmol) of hydroxylamine-O-sulfuric acid in 30 mL of water. The mixture was cooled, the resulting solids collected and purified by silica gel chromatography using 1: 1 ethyl acetate: hexane to give 0.6 g of a pink solid, m.p. t. 114-115 ° C.

EXAMPLE

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

Cl + Br.

N CN H

H

To a mixture of 3- (p-chlorophenylpyrrole) -2-carbonitrile (0.40 g, 2.0 mmol) in 25 mL of chloroform was added 0.63 g (4.0 mmol) of bromine. After 20 minutes the resulting precipitate is collected and recrystallized from ethyl acetate to give 0.21 g of pink crystals, m.p. t. above 250 ^c C.

Analysis: C _n H ₅ Br ₂ ClCN

Calculated,%: 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

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

Cl tl o

o +

N-Br

O

THF o

Cl

Ethyl 4- (p-chlorophenyl) pyrrole-3-carboxylate (1.6 g;

0.00641 mol) was dissolved in tetrahydrofuran (40 mL) and N-succinic acid bromide (1.14 g, 0.064 mol) was 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 ethereal layer is separated and dried over magnesium sulfate. Treatment of the ether extract afforded 1.9 g (90%) of a white solid which was purified by mixing with 80/20 hexane / ethyl acetate. The insoluble solid (1.3 g, 62%) was collected.

Lyd. t. 161-164 ° C.

Analysis: C ₁₃ H _:: BrClNO ₂

Calculated,%: C-47.50 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

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

O yC-OCH \\ ^{2 5}

10% NaOH ->

B, N

Ethyl 5-bromo-4- (p-chlorophenyl) pyrrole-3-carboxylate (0.045 g) is added to 200 ml of 10% sodium hydroxide and the suspension is refluxed. After everything has dissolved, the mixture is heated under reflux for an additional 40 min. The mixture is cooled, filtered and dried. The solid has a melt. t.

above 205 ° C and NMR (d ₆ -dimethylsulfoxide), shows the pyrrole proton at 7.52 md (doublet). The mass spectrum also coincided with that of the monobrominated compound.

EXAMPLE

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

O

Cl

OH

Cl

5-Bromo-4- (p-chlorophenyl) pyrrole-3-carboxylic acid (8.0 g, 0.026 mol) was added to amino ethanol (24 mL) and the suspension was gradually heated to 110-120 ° C and kept at this temperature for one hour. . The solution was cooled, poured into water, and extracted with ether. The ether extract showed the main fast-moving stain and the slower-moving, secondary component, according to TLC (75/25; hexane / ethyl acetate). Treatment with ether gives a dark solid (4.0 g, 56%) which is 2-bromo-3- (p-chlorophenyl) pyrrole, which is used directly for the preparation of 5-bromo-4- (pchlorophenyl) pyrrole-2-carbonitrile. .

EXAMPLE

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

Br ^N oi _H

Cl

A freshly prepared sample of 2-bromo-3- (p-chlorophenyl) pyrrolidone (4.0 g, 0.015 mol) is dissolved in dry dimethoxyethane (25 mL). Chlorosulfonyl isocyanate (3.08 g, 0.022 mol) was then added at a temperature below 25 ° C. After stirring overnight, the solution was treated with dimethylformamide (6 mL) and stirred for 3 h. The solution was then poured into 1 of water to give a brown solid (3.8 g, 90%). Column chromatography (80/20 hexane / ethyl acetate) gave 1.4 g (33%) of a white solid, m.p. t.

202-204 ° C.

Analysis: C _n H ₆ BrCl

Calculated,%: C-46.90 H-2.13N-9.95 Cl-12.61 Br-28.29

Found,%: C-47.20 H-2.09N-9.80 Cl-12.36 Br-27.42

EXAMPLE

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

A sample of 5-bromo-4- (p-chlorophenyl) pyrrole-2-carbonitrile (2.2 g, 0.0078 mol) is dissolved in 30 ml of dry dioxane. The solution was heated with bromine (1.3 g, 0.008 mol) in dioxane (20 mL), then stirred overnight at room temperature. The reaction mixture was poured into water, at which time an orange-brown solid (2.6 g, 92%) precipitated. A portion (1.6 g) was purified by flash chromatography using 75/25 hexane / ethyl acetate to give 0.8 g of a gray solid with m.p. t. 191194 ° C.

Analysis: C ₁₁ H ₅ BrCl ₂ N ₂

Calculated,%: C-36.61 H-1.38

Found,%: C-37.46 H-1.25

N, 7.76; Cl, 9.84

N, 7.41; Cl, 9.53

Br-44.3

Br, 42.99

EXAMPLE

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

Sodium hydride (2.66 g of a 60% oil suspension, rinsed with dry ether; 66 mmol) is suspended in 150 ml of dry ether. Add to this mixture within 15 min. A mixture of 12.0 g (5.5 mmol) of 3,4-dichloro-p-nitrostyrene in 10.8 g (5.5 mmol) of (p-toluenesulfonyl) methyl isocyanide in 50 mL of dimethyl sulfoxide and 150 mL of ether. The mixture is stirred for 1.5 hours, diluted with 150-200 ml water, and ether. The ether layer was separated, dried over magnesium sulfate and concentrated in vacuo. The crude product obtained (10.6 g) is purified by chromatography on silica gel using a 4: 1 mixture of chloroform and ethyl acetate; 7.2 g of a solid fraction are recrystallized from chloroform-ethyl acetate-hexane to give 3.0 g of a yellow solid,

188 ° C, dec.

Analysis: C ₁₀ H ₆ Cl ₂ N ₂ O ₂

Calculated,%: C-46.72; H-2.35. o.

melt t. 187N-10.90

Found,

C, 46.96

H-2.60

N, 9.77

EXAMPLE

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

To a mixture of 3- (3,4-dichlorophenyl) -4-nitropyrrole (2.5 g, 9.7 mmol) in 200 mL of chloroform heated to about 40 ° C was added 2.95 g (22 mmol) of sulfuryl over 1 minute. chloride. After 1 hour, the mixture was diluted with 100 ml of saturated sodium bicarbonate solution and 300 ml of ether. The organic layer was separated and dried over magnesium sulfate. Concentration in vacuo left a brown solid which was chromatographed on silica gel using 4: 1 chloroform-ethyl acetate. The orange solid fraction was recrystallized from chloroform, then re-chromatographed on silica gel using 4: 1 chloroform-ethyl acetate to give 0.36 g of a yellow solid, m.p. t. 193-194 ° C.

2,5-Dichloro-2-nitro-4-phenylpyrrole, m.p. t. 193-194 ° C, dec.

EXAMPLE

Preparation of 5- (p-Chlorophenyl) pyrrole-3,4-dicarbonitrile

A sample of 2-p-chlorophenyl-3-cyanopyrrole (3.0 g, 0.015 mol) prepared according to the procedure of Example 4 is dissolved in ml of dry dimethoxyethane. To this solution was added chlorosulfonyl isocyanate (3.39 g, 0.024 mol). The addition is accompanied by an exothermic reaction and requires some refrigeration. After stirring at room temperature for 3 hours, dimethylformamide (6-7 ml) was added and the solution stirred for an additional 4 hours. The solution is poured into water. a white solid precipitated (3.4 g, 100%). The sample (1.0 g) was purified by dissolving in ethyl acetate and passing the solution through a 60 mL filter pad of silica gel. The filtrate was concentrated to give 0.7 g of a white solid, m.p. t. 235-240 ° C.

According to the procedure of Example 47, other analogs are obtained:

T ',

Vi

CN

N

H

R

R L Lyd. mp, ° C 3-C1 4-C1 > 225 H 4-OCF ₃ 185-190 H 4-CF ₃ 180-185

EXAMPLE

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

Example 5- (p-Chlorophenyl) pyrrole-2,4-dicarbonitrile (1.0 g;

0, 004 mol) is dissolved in 20 ml of dioxane and a solution of bromine (0.8 g; 0.003 mol in dioxane (10 ml)) is added. The solution is stirred for several hours at room temperature and then poured into water, resulting in the precipitation of a white solid (1.2 g, 100%). Solids melts t. above 225 C. The mass spectrum of the sample has an image that coincides with that of the desired structure.

According to the procedure in Example 48 above, other additional compounds are prepared:

CN

NC

--- D

R L Lyd. mp, ° C 3-C1 4-C1 > 250 H 4-OCF ₃ 218-223 H 4-OCF3 239-241

EXAMPLE

Preparation of Bromfumar Nitrile

NC

- /

CN

Br ₂ (CHCl 3) _Δ (-HBr)

NC ·

CN

Br

Under nitrogen purge, fumaronitrile (15.6 g, 0.2 mol) in chloroform (150 mL) was refluxed to give a clear solution. A solution of bromine (5.3 mol; 0.2 mol) in chloroform (25 ml) was added dropwise over 30 min. The solution gradually decolorises and the acid differs (according to pH indicator paper). Reflux the solution for 90 minutes. During this time, much of the color disappears. The solution is cooled and the solvent removed under reduced pressure. An amber oil remains (approximate theoretical weight for bromfumaronitrile).

The oil is redistilled (0.2 mm Hg column) according to the method from ball to ball. The temperature is maintained below 120 ° C (above this temperature the substance decomposes rapidly). The resulting semi-solid is converted to a waxy amber-like solid. t. 43-47 ° C.

Analysis: C ₄ HBrN

Calculated,%: C-30.57

Found,%: C-29.13

H, 0.64

H, 0.67

N, 17.83

N, 16.94

EXAMPLE

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

NC

CN ^S + TMS- _X A

Br N '// Λ

HMPA! 3 equiv. H ₂ O (-TMS, -HBr, -CH ₃ SH) '

NC

A solution of bromfumaronitrile (4.7 g, 0.03 mol) and N- (trimethylsilyl) methyl-S-methylbenzene-thymidate (7.1 g, 0.03 mol) in hexamethylphosphoramide (HMFA) was stirred at room temperature under nitrogen purge. One portion of water (1.6 mL, 0.09 mol) was added, - washed with HMFA (10 mL). The solution warms up almost immediately due to the exothermic reaction. The temperature quickly reaches 100 ° C. The resulting dark red solution was stirred at ambient temperature for 20 hours. The reaction mixture is poured onto a mixture of water and ice. A resinous substance is formed which gradually changes to individual solid particles of a slightly brown color. This material is collected by filtration and rinsed with cold water and dried on a filter. After additional drying (vacuum drying oven dio83), the dichloroethane was burned.

The material is recrystallized twice at 60 ° C (DARCO treatment) to give a white milanalysis: C ₁₂ H ₇ N ₃

Calculated,%: C-74.61

Found,%: C-74.45

H-3.63 N-21.76

H, 3.84; N, 21.61

EXAMPLE

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

NC

Br, / CHCl

---------------- ·,

Under nitrogen purge, 2-phenylpyrrole-3,4-dicarbonitrile (1.4 g, 0.0075 mol) was added to chloroform (35 mL), which dissolved most of the solid. A solution of bromine (0.4 mL, 0.008 mol) in chloroform (5 mL) was added dropwise over 20 min. Initially the color disappears rapidly, but the color remains when the new solid resin type begins to settle. After 30 minutes at room temperature, the mixture is heated to reflux, which results in the formation of a solid consisting of substantially larger individual pieces. In 90 minutes the reflux reaction mixture is cooled and a portion is taken and analyzed by high performance liquid chromatography (HPLC). About 60% of the starting material was found to be unchanged. An additional portion of fresh bromine (0.2 mL, 0.004 mol) was added, refluxing continued for an additional 45 min, after which 10% of the original wood remained in a portion. another portion of fresh bromine (0.2 mL; 0.004 mol) was added to the heated refluxing suspension and refluxing continued for another 30 min. 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 chloroform. The result remains dark matter. The extract is treated by the DARCO method and filtered hot. A clear yellow filtrate begins to separate from a white precipitate. After cooling to minus

At 10 ° C, the white solid was collected by filtration.

Analysis: C ₁₂ H ₆ BrN ₃

Calculated,%: 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

Melting point = 225-258 ° C.

EXAMPLE 52

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

Cl

2- (3,4-Dichlorophenyl) pyrrole-3-carbonitrile (3.0 g, 0.013 mol) was added to a mixture of acetic anhydride (50 mL) and 90% nitric acid (0.6 mL), a very small amount of exothermic heat is emitted. The mixture is heated slowly to 39 ° C, then kept at a temperature of 30-33 ° C until all is in solution. Gradually, a new solid settles. The mixture is stirred for 2 to 3 hours. at room temperature, then poured into water on ice to decompose acetic anhydride. After 1 hour of stirring, the mixture was filtered, the solid collected (2.9 g, 82%) and dried. Removal of the adsorbent from a portion (1.5 g) is purified by column chromatography using 75/25 hexane / ethyl acetate to give 0.7 g of a yellow solid with m.p. 228-231 ° C.

Analysis: C _n H ₅ Cl ₂ N ₃ O ₂

Calculated,%: C-46.80 H-1.77 N-14.89 Cl-25.17

Found,%: C-46.50 H-1.96 N-14.27 Cl-24.30

According to this procedure, 2- (p-chlorophenyl) pyrrole-3-carbonitrile yields 2- (chlorophenyl) -5-nitropyrrole-3-carbonitrile, m.p. Mp 201-206 ° C. Also, 2- (p-trifluoromethylphenyl) pyrrole-3-carbonitrile gives 2- (p-trifluoromethylphenyl) -5-nitropyrrole-3-carbonitrile according to the above procedure. This compound has a melting point of 164-165 ° C.

EXAMPLE

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

2- (3,4-Dichlorophenyl) -5-nitropyrrole-3-carbonitrile (0.5 g, 0.0017 mol) was dissolved in dry dioxane (10 mL). To this solution was added bromine (0.28 g, 0.0017 mol) in dioxane. After stirring overnight, the solution is poured into water and an orange-brown solid (0.54 g,

88%). Recrystallization from acetonitrile (5 mL) afforded 0.26 g of an orange-brown solid with m.p. 195-200 ° C.

Analysis: C ₁₁ H ₄ BrClN ₃ O ₂

Calculated,%: C-36.57 H-1, 10 N-11, 63 Br-2.13 Cl-19.67

Found,%: C-36.46 H-1.29 N-II, 50 Br-1.63 Cl-19.28

According to the procedure of Example 53 above, except for 2- (p-chlorophenyl) -5-nitropyrrole-3-carbonitrile, 4-bromo-2- (p-chlorophenyl) -5-nitropyrrole-3-carbonitrile is obtained, m.p. . 180-185 ° C.

EXAMPLE

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

To a suspension of 5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile (1.2 g, 5.1 mmol) in 25 mL of acetic anhydride at 90 ° C was added 90% nitric acid (0.3 ml; 5.1 mmol). The reaction mixture warms up to 45 ° C due to the exothermic reaction and becomes a green solution. After stirring for 2 hours, the reaction mixture was poured into 50 mL of water and stirred vigorously for 5 min. The resulting light brown precipitate is filtered off and dissolved in a minimum amount of acetone. Chromatography on silica gel using 3: 1 hexane with ethyl acetate afforded nitropyrrole (1.2 g, 84%) as an off-white solid, m.p. above 200 ^c C.

EXAMPLE

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

^Br ^ no ₂

Cl

Cl

Of a suspension of 5- (3,4-dichlorophenyl) -4-nitropyrrole-2-carbonitrile (0.6 g, 2.1 mmol) in 10 mL of dioxane at 25 ° C, a solution of bromine (0.3 g, 2, 1 mmol) in 5 mL of dioxane. The reaction mixture was stirred overnight. Addition of 50 ml of water results in the precipitation of a yellow solid which is collected and dried in a vacuum oven (50 mm Hg column) at 45 ° C to give brominated pyrrole (0.7 g; 90%) as a yellowish solid, m.p. above 200 ° C.

EXAMPLE

Preparation of 4- (p-Chlorophenyl) -2- (trifluoromethyl) -2-oxazolin-5-one

Trifluoroacetic anhydride (1.7 mL; 0.012 mol) was added in one portion to 2- (pchlorophenyl) glycine (11.4 g, 0.06 mol) in powder form; this causes a rapid warm-up to about 40 ° C due to the exothermic reaction and a yellow color appears on the surface of the solid. As the mixture is gradually heated to 70 ° C, most of the solid dissolves to an orange amber oil. All solids dissolve in 2 hours. Heating continues for another 1 hour. The solvent is removed by rotating evaporator under reduced pressure. Toluene is added twice and removed under reduced pressure, but still retains the odor of trifluoroacetic acid. A yellow semi-solid is obtained (theoretical yield); purity by HPLC of more than 90%, indicating the previously identified compound. It is used for the next step without further purification.

EXAMPLE

2- (p-Chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile

4- (p-Chlorophenyl) -2- (trifluoromethyl) -2-oxazolin-5-one (2.5 g, 0.01 mol) was dissolved in nitromethane (50 mL). 2-Chloroacrylonitrile (8.0 mL, 0.10 mol) was added in one portion to the solution and the resulting solution was stirred under reflux for 18 hours under nitrogen. Cooling the red-brown solution to minus 5 ° C in a water bath with acetone causes a precipitate to form which is collected by filtration and washed with a small amount of nitromethane. The resulting orange-brown solid was recrystallized from hot dichloroethane to give the product as white crystals (1.8 g, 56% of theory), m.p. 238-241 ° C (dec.).

Using the appropriate arylglycine according to the procedure of Example 55, other 2-aryl-5- (rifluoromethyl) pyrrolecarbonitriles are prepared:

R L Lyd. mp, ° C H H 215-218 H 4-CH ₃ 191-193

R L Lyd. t. , ° C H 4-OCH3 168-180 (columns) 3-C1 4-C1 245-246 (split) H 4-CF ₃ 218-219

EXAMPLE

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

Under nitrogen purge, a suspension of 2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-5-carbonitrile (1.6 g, 0.005 mol) in acetic acid (25 ml) was heated to 60 ° C until all material was dissolved to give a clear solution. A solution of bromine (0.8 mL; 0.015 mol) in acetic acid (10 mL) over 15 min. drop by drop into a solution heated under reflux. The solution is heated for 6 hours and then stirred at room temperature for 18 hours. High performance gas chromatographic analysis of the reaction mixture showed that about 80% of the reaction product was formed. The mixture was heated again under reflux and a larger amount of bromine (0.5 mL, 0.01 mol) in acetic acid was added dropwise. Continue heating under reflux for 3 hours. A select amount of material showed 95% conversion to product. The reaction mixture is cooled and the solvent removed by reducing the pressure on the rotary evaporator to give a dark gray solid. Toluene is added to the mixture and removed under reduced pressure to leave an acetic acid odor. Dissolve all material in hot toluene (75 mL) to form a cloudy solution which is treated on a DARKO filter and filtered. Upon cooling the pink solution to room temperature, a white solid precipitates. After cooling in the refrigerator, the solid is collected by filtration, washed with hexane and dried on a filter. Additional drying in a vacuum oven at 45 ° C yields the product (1.2 g, approximately 60% of theory). Lyd. t. 247250 ° C (dec.).

Analysis: C ₁₂ H ₅ BrClF ₃ N ₂

Calculated,%: C-41.20 H-1.43 N-8.01 Br-22, 89 Cl-10.16 F-16.31

Found,%: C-41.22 H-1.48 N-8.10 Br-22, 92 Cl-10.16 F-16.03

The bromination of 2-aryl-5- (trifluoromethyl) pyrrole-3-carbonitrile obtained according to procedure 57 gives the following additional compounds:

R L Lyd. mp, ° C H H 235-238 H 4-CH ₃ 244-245 3-C1 4-C1 218-223 H 4-CF3 225-226

EXAMPLE

Preparation of 2- (4-Chlorophenyl) -5-trifluorethyl-pyrrole-1,4-dicarbonitrile

Trifluoroacetic anhydride (3.1 mL, 0.022 mol) was added in one portion to (4-chlorophenyl) glycine (2.0 g, 0.011 mol), and the solution instantly turned yellow and a slight phlegm appeared. The mixture is heated gradually until the fridge is turned on, which causes the whole material to dissolve, forming a yellow-orange solution which is heated for additional 2 hours. The reaction mixture is cooled and the reaction solvent removed under reduced pressure. Toluene was added twice and then removed under reduced pressure to give a viscous oil (O _{; o} = 1800cm ^X ). This residue was dissolved (slightly insoluble material) in nitromethane (40 ml) and bromofumaronitrile (2.7 g, 0.018 mol) was added in one portion. The resulting solution was heated under reflux for 18 hours to give a dark red solution. The solvent is removed under reduced pressure and the dark residue is dissolved in dichloroethane. Some insoluble matter is removed by filtration.

The material is fractionated by column chromatography (silica gel; 3% 2-Pr OH in dichloroethane) and the appropriate fractions selected. Evaporation of one fraction gave the title compound as a yellow solid which upon recrystallization from nitromethane (DARKO treatment) gave a straw colored solid (0.2 g), mp = 238-241 ° C (slight decomposition).

EXAMPLE p-Chloro-β - [(formylmethyl) amino] cinnamon nitrile diethyl acetal

CN + H, NCH, CH (OEt), toluene '-Η, Ο

A solution of p-chlorobenzoylacetonitrile (250.0 g, 1.39 mol), 230 ml (185.9 g; 1.39 mol) of 2,2-diethoxyethylamine and 1300 ml of dried toluene was stirred at reflux for 20 hours with magnetic stirring. Water (23.8 mL; 95.2% of theory) is collected in a Dino-Stark trap. A hot, cloudy dark brown solution with a high content of undissolved material is filtered off using infusion land as an additional measure. After dilution with 200 ml of ethyl acetate, the solution is filtered through a 7 x 13,5 cm silica gel column. The filtrate was concentrated in vacuo to give 354.3 g (86.4% yield of crude material) as a clear dark oil which gradually solidified. This solid was recrystallized from hot cyclohexane to give 324.2 g (79.1% yield) of a waxy orange solid. NMR of this product showed that it is a mixture of p-chloro-β- (formylmethyl) aminocinnamone nitrile diacetate (78%) (Z) and 23% (E), m.p. t. 60-72 ° C. For another example obtained in an analogous manner, the following analytical data were obtained:

IR, Max (slope suspension):

3325 (singlet), 3065 (multiplet) 2197 (singlet), 1600 (multiplet), 1530 (singlet), 1314 (multiplet), 1265 (multiplet), 1173 (multiplet),

1154 (multiplet), 1128 (singlet), 1100 (singlet), 1060 (singlet), 1022 (singlet), 939 (multiplet), 895 (multiplet), 844 (singlet),

768 (multiplet), 730 (multiplet),

-i cm.

H-NMR (chloroform): δ7, 47 (doublet, J = 8.6 Hz; 2, 12H, two aromatic protons), δ7.37 (doublet, J = 8.6 Hz, 2.12 H, two aromatic) protons), δ5.10 (E) and δ4.86 (Ζ) plaLT 4040 B tus triplet; 1.25H, one NH proton /, δ4, 69 (Z) and 54.60 (E) (triplet, J = 5 , lHz l, 05H, one acetal carbon methine proton), 54.07 (E) and 54.05 (Z) / singlet; 0.83H, β-proton of enamine /, 53, 71 (E) and 53.68 (Z) quartet, J = 7.1 Hz; 2.22H, two methylene protons in one of two ethoxy groups, δ 3.18 (triplet, J = 5.1 Hz; 1.77H, two methylene protons in ethylene acetal groups); 51.20 (triplet, J = 7.1Hz; 4.90H; six methylene protons in the two ethoxy groups).

C-NMR (chloroform): 5161.21 (α-enamine carbon); 5,136,29 (Z) and 5,134,00 (E) / (or a C-1 or C-4 phenyl ring); 5,134.08 (Z) and 5,132.30 (E) / or phenyl ring Cl or C-4), 5,129.34 (Z) and 5,129.89 (E) / or phenyl ring C-2,6 or C3, 5), 5128, 94 (Z) and 5128, 63 (E) / or phenyl ring C-2.6 or C-3.5)

5121.19 (Z) and 5119.50 (E) / Nitrile Carbon /, 599.43 (Z) and 5100.63 (E) / Beta Amino Carbon /, 561.88 (Z) and 563.25 (E) Acetal methylene carbon, 62.64 (Z) and / 63.03 (E) / ethoxy methylene carbon /, 546.32 (Z) and 547.33 (E) / ethylamine methylene carbon /, 546.32 (Z) and 547.33 (E) (methylene carbon of ethylamino group), 515.26 (methyl carbon of ethoxy groups).

Microanalysis: (M.M. 294.78):

O. o.

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

In the above procedure, only the appropriately substituted benzoyl acetate nitrile in place of pchlorobenzoyl acetate nitrile and / or 2,2-di- (C 1 -C 4 alkoxy) ethylamine in place of 2,2-diethoxyethylamine gives the following compounds:

iz y COCąCN + H, NCH, CH (C _| -C ₄ alkoxy) _______________ r a ~ ^{0 cn} '= CH ₂ CH (C, -C ₄ alkoxy) ₂

L M R (C 1 -C 6 alkoxy) ₂ Mp. mp, ° C H H p-CH ₃ COO (07K), 68-73 H p-CH ₃ H (OC ₂ H ₅ ) ₂ 59-69 H m-OCH ₃ p-OCH ₃ (OC ₂ K ₅ ) ₂ red-orange H (OC ₂ H ₅ ) ₂ a semi-solid 62-70 p-Cl H H (och ₃ ) ₂ H p-CH ₃ H (OCH ₃ ) ₂ H m-Cl p-Cl (OC ₂ H ₅ ) ₂ H H p-OCF ₃ (OC ₂ H ₅ ) ₂ H H p-cf ₃ (OC ₂ H ₅ ) ₂

EXAMPLE 15

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

CN + CF.CO, H

J '

Cl

To 108 mL of stirred trifluoroacetic acid at 23 ° C over 45 min. 54.00 g (0.183 mol) of solid p-chloro-3 - [(formylmethyl) amino] cinnamon nitrile diethyl acetal are added. This addition raises the temperature to

38 ° C due to exothermic reaction and after 32 min. the deposition of a solid begins during the application. After 30 minutes after stirring at room temperature, the reaction mixture is filtered under vacuum and the collected solid is washed first with trifluoroacetic acid followed by ethyl acetate / hexane. The yield of off-white material was 16.83 g (45.4%). t. 165-166% C. Analytical data for a sample made in a similar manner:

IR, Max (slope suspension):

3275 (broad singlet), 2225 (singlet), 1502 (singlet), 1410 (multiplet),

1275 (multiplet), 1200 (multiplet), 1108 (singlet), 1023 (multiplet),

999 (multiplet), 908 (multiplet),

843 (singlet), 752 (singlet),

695 (singlet), 620 (singlet), cm ¹ .

H-NMR (acetone): 011.22 (considerably broad singlet; 0.99H, 1-pyrrole NH proton), 57.82 (doublet J = 8.9Hz; 2.46H two aromatic phenyl protons), 57.51 (doublet, J = 8.9Hz; 2.46Hz two aromatic phenyl protons), 57.02 triplet, J = 2.6Hz, 1.1H, one pyrrole proton at C-5), 56.58 (triplet, J = 2, 6Hz; 0.77 H, one pyrrole proton at C-4).

C-NMR (acetone): 5137.73 (pyrrole C-2), 5134.42 (p-chlorophenyl C-4), 5129.93 (methylene carbon in the C3.5 phenyl ring), 5128.07 (methylene carbon in the C-) 2.6 in the phenyl ring); 5121.21 (pyrrole C-5), 5117.93 (nitrile carbon), 5113.78 pyrrole carbon C-4), 590.86 (pyrrole carbon C-3).

Microanalysis: (M.M. 202.64):

Calculated,%: C-65.19 H-3.48

Found,%: C-64.18 H-3.52

N, 13.83 Cl, 17.5

N, 13.63 Cl, 17.74

Using the above procedure as shown, 5 replacing almost. hydrochloric acid with trifluoroacetic acid to give the following compounds:

M and / or R Lyd. t., ^c C Use ama acid 4-C1 165-166 machine. HCl, CF3COOH 3,4-di-Cl 216-221 CF ₃ COOH 2-C1 156-157 CF3COOH 4-OCF3 143-145 CF ₃ COOH 4-CF ₃ 179-180 cf ₃ cooh 2,4-di-Cl 197-199 CF3COOH 3-Cl 150-156 CF3COOH 4-CN 210-212 CF ₃ COOH 4-F 167-170 machine. HCl 4-SO ₂ CH ₃ 221-221.5 CF ₃ COOH 3,4-di-F 173-175.5 cf ₃ cooh 3-CF ₃ 166-168 cf ₃ cooh 4-COOCH ₃ 155.5-158 cf ₃ cooh 4-CH ₃ 117-137 cf ₃ cooh 4-NO ₂ 174-177 CF3COOH

EXAMPLE

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

CN CN

To a mechanically stirred solution of 16.83 g (83.1 mmol) of 2- (p-chlorophenyl) pyrrole-3-carbonitrile in 450 ml of glacial acetic acid at 36 ° C was added dropwise over 18 min, 14.7 ml (24.70 g) was added. ; 183.0 mmol) sulfuryl chloride. The addition is accompanied by a slight exothermic rise to 39 ° C. After an additional 16 minutes. the reaction mixture was filtered under vacuum. The collected solids are washed first with acetic acid and then with water. This solid, after recrystallization from hot ethyl acetate, has a melting point. t. 259-261 ° C. Other examples of this product were obtained by analytical procedures. The analytical data for one such product are shown below.

IR, Max (slope suspension): 3170 (broad singlet),

3100 (multiplet), 2225 (singlet), 1508 (multiplet), 1097 (multiplet), 895 (singlet), 717 (multiplet),

660 (multiplet), cm ¹ .

H-NMR (Dimethylsulfoxide): δ7.72 (doublet, J = 8.6 Hz;

2.00 H, two aromatic protons), δ7.56 (doublet J = 8.6 Hz; 2.00 H two aromatic protons).

C-NMR (dimethylsulfoxide): 5136.01 (pyrrole C-2 carbon), 5133, 92 (p-chlorophenyl C-4 carbon), 5129.09 (p-chlorophenyl C-3.5 carbon), 5127, 41 (p-chlorophenyl C-4 carbon), 5127.41 (p-chlorophenyl carbon)

c-1), 5114.49 (nitrile ang- lis), 5114.10 (pyrrol C-5 ang- lis), 5110.92 (pyrrol C-4 ang- lis), 590.09 (pyrrole C-3) ang-

add.

Microanalysis: (M. m. 271.54):

Calculated:% C-48.65 H-1.86 N-10.32 Cl-39.17

Found,%: C-49.22 H-2.12 N-9.58 Cl-39.03

EXAMPLE

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

To a stirred mixture of 0.8 g (a, a, a-trifluoro-p-tolyl) pyrrole-3-carbonitrile in 70 ml of chloroform was added 2 ml of bromine. After stirring overnight, a white solid precipitated out of the mixture, which was collected by filtration. Thin layer chromatography (1: 1 ethyl acetate: hexane) showed the presence of only one component, m.p. t. = 330 ° C.

Analysis: C ₁₂ H ₅ Br ₂ F ₃ N ₂

Calculated%: C-36.55 H, 1:27 N, 7.11 Br-40.61 % Found: C-36.40 H, 08.08 N, 6.99 Br-40.55 According to the above specified procedure, but replacing

substituted in the appropriate manner with phenylpyrrole-3-carbonitrile 2- (a, a, a-trifluoro-p-toluyl (pyrrole-3-carbonitrile) to give the following compounds:

Y

H

L M R X Y Lyd. mp, ° C H H 4-NO ₂ Br Br 274-270 H H 4-F Cl Cl > 220 H H 4-F Br Br > 220 H H 4-SO ₂ CH ₃ Cl Cl > 230 H 3-F 4-F Cl Cl > 230 H 3-F 4-F Br Br > 220 2-Cl 3-C1 4-C1 Cl Cl 2-Br 3-Br 4-Br Br Br H H 4-OCF ₃ Cl Cl 222-225 H H 4-OCF3 Br Br H H 4-OCF3 Cl H H H 4-CN Br Br > 230 H H 4-CN Cl Cl > 240 H H 4-SO ₂ CH ₃ Br Br > 230 H H 4-NO ₂ Cl Cl 246-249 H 3-C1 4-C1 Br Br > 260

100

L M R X Y Lyd. t. , 'C H H 3-CF ₃ Cl Cl > 230 H H 4-COCH3 Cl Cl 251-254 H 2,3-CH = CH- Cl Cl 244-247 H H 4-CH ₃ Cl Cl 215-217 H 2-Cl 4-Cl Br Br > 230 H H 3-Cl Cl Cl > 230 H 2-C1 4-Cl Cl Cl > 230 H H 4-Cl Br Br 273-274 H H 2-C1 Br Br > 230 H H 4-CF ₃ Cl Cl > 230 H H 4-Br Cl Cl > 235 H H 2-C1 Cl Cl > 230 H 3-Cl 4-Cl Cl Cl > 235 H H H Cl Cl 254-255

EXAMPLE Preparation of α- (2,2-Diethoxyethylamino) -β-nitrostyrene and 3-nitro-25-phenylpyrrole

O

C-CH, NO ₂ + H, NCH, CH (OEt), AL

NO,, NO, cz =. /

N HCH ₂ CH (OEt).

Alpha-nitroacetophenone (5.7 g, 0.0345 mol) was dissolved

100 ml of toluene and 4.6 g (0.0345 mol) of aminoacetaldehyde diethyl acetal are added. Reagents are poured i

250 ml round-bottomed flask containing Dino-Stark gauze

101 trays. The trap is filled with 4A molecular grids. The mixture was heated under reflux for 18 hours. The toluene is removed in vacuo to give 8.36 g of a- (2,2-diethoxyethylamino) -β-nitrostyrene as a brown oil. concentrated hydrochloric acid is added to this oil. While stirring the flask, turn the oil into a yellow suspension. After 10 minutes. the solid is filtered off to give 2.48 g of a yellow solid. Recrystallization from ester (ethyl acetate) and hexane gave 2 product fractions: 2.08 g with m.p. t. 190-192 ° C (31%).

IR, Max. 1485 cm ¹ (NO ₂ )

H-NMR (deuterated chloroform / dimethylsulfoxide), 66.73 (multiplet, 2H); 67.46 (multiplet, 5H).

Other nitrostyrene compound can be produced according to the above reaction of the appropriate nitroacetophenone replacing α-mediated nitroacetatofenonu and / aminoacetaldehido appropriate diethyl 2,2-di (C _l -C ₄ alkoxy) ethylamine gives the following compounds:

O

C-CH, NO, + K 1 -CH 2 -CH 2 -C 1 -alkoxy), // no ₂

N HCH, CH (C 1 -C ₄ alkoxy)

L.

toluene>

M

R

L M R (C 1 -C 6 alkoxy) ₂ H H p-CH ₃ OCO (OC ₂ H ₅ ) ₂ H p-CH ₃ H (OC ₂ H ₅ ) ₂ H m-OCH ₃ p-OCH ₃ (OC ₂ H ₅ ) ₂ H J (OC ₂ H ₅ ) ₂ p-Cl H H (OCH ₃ ) ₂ H p-CH ₃ H (OCH ₃ ) ₂ H H p-C (OC ₂ H ₅ ) ₂

102

EXAMPLE

Preparation of 3-Dichloro-4-nitro-5-phenylpyrrole

A mixture of 3-nitro-2-phenylpyrrole (1.56 g; 0.0083 mol) and dioxane (60 mL) was cooled in an ice bath with the addition of 25.9 g (0.0182 mol) of commercial sodium hypochlorite. After 45 minutes the blending mixture is acidified with concentrated hydrochloric acid. Water and diethyl ether are added. The layers are separated and the upper organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated in vacuo to give 2.21 g of a yellow solid. Chromatographic purification using silica gel and a mixture of ethyl acetate and hexane to remove the adsorbent in increasing ratios yielded 0.77 g of a yellow solid (36%), m.p. t. 190-190.5 ° C.

Analysis: C ₁₀ H ₆ N ₂ O ₂ Cl ₂

Calculated,%: C-46.72 H-2.35 N-10.90

Found,%: C-46.96 H-2.86 N-10.02

EXAMPLE

Evaluation of insecticidal and acaricidal activity

All tests shall be prepared in advance using technical materials. All concentrations below are expressed in units of active ingredient. All tests are carried out at 27 ° C.

103

Spodoptera eridania Larvae of the southern shielding mammal at stage 3 of the puppet develop a semicircular bean. The sheet is then placed in a Petri dish 100x10 mm containing moistened filter paper and 10 caterpillars

In the 3rd stage of development. The cup is held for 5 days to observe death, reduced food intake, or any abnormal period.

Spodoptera eridania after 7 days. Plants treated according to the above test are stored in a greenhouse under high intensity lamps. These lamps replicate the effects of a sunny June day in New Jersey, and the day is maintained for 14 hours. After 7 days, the foliage is collected and evaluated according to the above test.

Aphis fabae mixed development stages, bean aphids. Cups containing one plant (about 5 cm) of nasturtium (bropaedum sp) are infected with 100-200 aphids the day before the start of the test. Each cup is sprayed with the test recipe, twice sharply reversing rotation in 4 turns and around the stem. Sprayer De-Vilbis no. 154. The nozzle of the sprayer is kept about 15 cm from the plant and the spray liquid is directed in such a way that both the plants and aphids are fully sprayed. Sprayed cups are placed on white enameled shelves under their walls and stored for two days, after which the degree of killing is determined.

Cetranychus urtical (R-resistant species), 2-spotted spider mite.

Semi-round bean plants with primary leaves spreading up to 7-8 cm, picked and cut

104 so that one pot remains in each pot. A small piece is cut from a leaf taken from the parent colony and placed on each leaf of the test plant. This is done 2 hours ago. pre-treatment to allow the mites to move around the test plant and lay eggs.

resized in this way, for the sheet. Before processing, for tick transmission, infect with ticks, position while stirring

A piece of cut sheet to get about 100 pieces of ticks used is removed and discarded. Plants, 3 sec. immersed in the pilot comir and placed under a hood for drying. Plants are kept for two days for the identification of adult individuals killed using the first leaf. The second leaf is kept on the plant for another 5 days, pending further observations on egg death and / or newly hatched larvae.

Diabrotica undecimpunctata hasardi root worm, southern worm stage 3.

³ cm of finely ground talc is placed in a 30 ml glass bottle with a wide neck and užsisukančiu cap. Pipette 1 ml of a suitable acetone suspension onto the talc so that each vial contains 1.25 and 0.25 mg of the active ingredient. The vials are placed in a stream of progressive air until the acetone evaporates. The dried talc is removed and 1 cm ^{3 of} millet millet for insect feeding is added. Then add 25 g of wet soil to each vial. Cover the vial and mix thoroughly in a Vorteks mixer. Next, 10 root worms at stage 3 of development are placed in each vial and the vials are covered with a cap to allow the larvae to air. The treatment is performed 6 days prior to the counting of the dead individuals. Missing larvae (caterpillars) were considered dead due to their rapid disintegration as they could not be found. Concentrations, nauLT 4040 B

The 105 doses given for this test correspond to 50 and 10 kg / ha, respectively.

Rating scale:

- no operation

- 10-20% killed

- 20-35% killed

- 36-45% killed

4 - 46-55% killed

- 56-65% killed

- 66-75% killed

- 76-85% killed

- 86-99% killed

- 100% mortality R - reduced food intake

106 r03

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TABLE

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107 rd χ:

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co Π3 1-1 m 0 (C G . — 1 • H Ή ω a G m P i-1 M Ή -H (i.e. H C G 1 - 1 • Ή O -P O £ 43 Ή ω G 1-1 G G 03 ω G cn 0 (U O 1-1 G a Π3 -U 44 43 0 '—1 o 1-1 1 i P n 0 G o co (i.e. • H G P G 1 1 44 a -G • G  H '—I 1 o a G a 0 O oo G 0 l o 3 G 1 cn + J G sr G «-H -H i-1 d • H P ω 1 P a o • —I c • H fO • H • I “1 G o 1 c 1-1 i-1 c G 1-1 • «H G sr 1 o -G 1 p Ή a • H 1 sr G C P I c a 1 -H Φ 1 s (D 1-1 r - t i-I .—. a P G p -H • H • H I-1 r-H G O d G G c G -G Ή O l-1 0 Φ Φ O G c l-1 43 d f-1 p 44 P Φ Φ 43 U —- 43 G 1 G P P υ • H 1 U o oo 0 G 1 • H T) P -H (-} 1 l-1 O P TI 1 1 Ό 43 o 43 «—1 1 1 P o 1 υ G U 43 o ·. G sr I P 1 U G sr P • H a 1 P CG 1 -G co c a - H - ' C - 1 1 1 - c 1 i-1 1 1 Csl sr LT) 1 1 UG . G sr Cs] 1 1 1 P sr 1 G 1 1 G G G 1 1 Φ G ε O O O e ε O P O o «—L r-H <—1 o o r-1 ε I-1 G 43 43 43 G G X! o 43 43 U υ υ 43 43 U G υ Ή • H -H • H • H -H • H 43 • H TI T! TI Ό T! Tl T3 1 TI 1 1 1 1 1 1 1 a 1 LG U0 m 00 00 CG CG -— CG k. k. s. o. k. 1 k. CN CN CN CN CN CM CN

108

Evaluation of insecticidal activity

Heliothis virescens 3rd stage of development of tobacco budworm larvae

The cotton seed portion is placed in 1 test composition and left under the hood for drying. Once dried, each is cut into 1 4 parts and 10 sections, each containing 1 30 ml plastic medical cups, 1 piece of moistened toothpick, 5-7 mm long. One cup is placed in each cup at stage 3 of development, and the cups are sealed with cardboard. The treatment is carried out for 3 days before assessing the degree of mortality and determining the degree of forage damage.

Empoasca abrupta adult individuals, western potato leaf bug.

Immerse the Sieva Tima bean leaf about 5 cm long in the test composition for 3 seconds. under stirring and placed under a hood for drying. The leaf is introduced into a petri dish containing a damp liter paper. Approximately 10 individuals of the leaf bug are placed in each cup and maintained for 3 days prior to determining the degree of mortality.

Blattella germanica bait test, adult male cockroach.

0.1% bait is prepared by pipetting 1 ml (1000 ppm) of the test compound solution in acetone and applying this solution to 1 g of corn flour and then placing it in a 30 ml wide-bore bottle. The bait is placed in a 0.6 liter wide-mouthed Madison bottle and 10 adult cockroach males are placed. The bottle is covered with a mesh cap. On the top of the volleyball

A small piece of cotton wool soaked in a 10% honey solution is placed on top of the netting with the 109 parts of the cap inserted in the bottle. After 3 days, death is counted.

Blatella germanica final test, adult male cockroach.

Gradually pipette a volume of 100 ml (1000 m.d.) of the test substance into a 150 x 15 mm bottom of a Petri dish to obtain a coating that is as smooth as possible. Once the spotted material has dried, 10 adult cockroach males are placed in each plate and covered with a lid. After three days, deaths are counted.

Systemic effects of Spadaptera eridania. 3rd stage of caterpillar development. Leukanida monocot south (skydamaris).

The compound is used in a composition in the form of an emulsion containing 0.1 g of the test substance; 0.2 g Emulforius El-620® emulsifier; 10 ml acetone and 90 ml water. It is diluted 10 times with water to give 100 m.d. test emulsion. Then make a 10-fold dilution with water, if necessary. Bean plants Sieva Tima with primary plants 7-8 cm long is cut at least 3 cm above the soil surface. This is done to prevent contamination with soil bacteria that will damage the stem during the test. The cut stems are placed in a test emulsion and each stalk is wrapped with a piece of cotton wool to hold the stalk over the bottom of the bottle and to limit evaporation and volatility of the compound. The test is continued for 3 days at 27 ° C to assimilate the compounds. Then one leaf of the plant is removed from the plant and placed in a Petri dish 100x10 with 10 single-point leukates (skyLT 4040 B

110 damar) as described in Test III. Fatality tests and feed damage monitoring are performed after 3 and 5 days.

Systemic effects of Empoasca abrupta in adult individuals of the western leaf blight

The compound is incorporated into an emulsion formulation containing 0.1 g of the test substance; 0.2 g Emulforius El-620® emulsifier; 10 ml acetone and 90 ml water. It is diluted 10 times with water to give a test emulsion of 100 ppm. Then, if necessary, make up to 10 dilutions with water. Seeds of Sieva Tima beans with primary leaves cut at least 3 cm above the soil at a distance of 7-8 cm. This is done to avoid contamination with soil bacteria, which will damage the stem during the test. The cut stems are placed in test emulsions and each stalk is wrapped with a piece of cotton wool to support the stem over the bottom of the bottle and to limit evaporation and volatility of the compound. The test is performed for 3 days at 27 ° C to assimilate the compounds. Then leaf 1 is removed from the plant and placed in a Petri dish 100x10 and run VIII as above. The rating scale for the above tests as described in Example 9.

EXAMPLE

A) Evaluation of test compounds as nematocidal agents.

Cultures: The culture of C-elegans (a biotype of bristol from J. Lewis) is maintained on E. col. agar plates at 20 ° C. New cultures are described every week.

111

For 4-5 days, the nematodes are washed from cultures using fresh Ascaris Ringers (FARS) solution. The worms are further rinsed with FARS containing gentamicin to reduce bacteriological contamination and centrifuged to separate the rinsing solution from the worms. This procedure is repeated three times. Washed worms are then added to C. Briggal medium to prevent damage (CbMM) to b / BCO, to which gentamicin (600 units / ml) and mycostatin (0.5 mg / ml) are added.

The test is then performed on a mixture of three compounds (piggibacked), different from another application's high throughput, to reduce additional labor costs and compound consumption.

The compounds are dissolved in acetone and diluted with equal volumes of water. For the final test, the concentration of each compound in the mixture is 150 ppm. The test substance is injected into a micropipette (25 ml) into each well of a plate with sterile tissue culture containing 96 wells (CO STAP) b and the solvent allowed to evaporate. Such treated plates are used immediately or stored in the refrigerator to avoid adverse effects on the compound.

A volume of freshly prepared C-elegans CbMM (50 mg) is added via a micropipette to each treated well and several control wells on each plate. The culture plates are incubated at 20 ° C.

Exposure observations are performed with an analytical microscope at 9.24 and 48 hours after immersion. At the start of counting, the plate is carefully beaten to stimulate worm movement. Activity is judged subjectively but also semi-quantitatively based on compound activity for adult mortality and caterpillar mortality. The criteria are as follows: 8-no mobility; 7-Apparently diminished

112 ability to move 95% of worms, 6-reduced motility such as controls; 5-slight decrease in motility; O-Normal agility such as in the control test. Other factors indicating activity are easy to track.

These include paralysis, abnormal seizures, reduced reproductive rate within 48 hours. and other deviations from the normal lifestyle.

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115

Caenorna bottis elegans test procedure day. Inoculation of agar plate at E. Coli-NG 3050'C.

Incubation at 20 ° C.

day. Collection of a new population of C. Elegans.

Antibiotic flushing.

Transfer to CbMM.

Adding C. Elegans (25-100 VL) to saturated wells.

After 4 hours of activity after immersion observation.

day. Activity Tracking.

day. Activity Tracking.

Note: Saturated wells can be made fresh or previously stored in the refrigerator.

The data obtained from these tests are shown in Table III below.

B) Analysis of nematodes in root tubers.

Nematode populations of root tubers (Meloidogyne incognita) are maintained on the Meteor species in the greenhouse. Many eggs are removed from the surface of the infected roots and stored on moistened filter paper for 48 hours to allow them to hatch. Larvae for testing are transferred to wells containing test compounds containing ConcentrateLT 4040 B

116 cations at 300 m.d. About 9% in a 9% acetone solution. The infected wells are stored at 27 ° C. Cloudiness is detected after 24 hours. after processing.

degrees in s

The data obtained are presented in Table 3 below.

117

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118

EXAMPLE

According to the procedures of Examples 59 and 60, the compounds of the invention are evaluated against several insect species: leaf bug, tobacco budworm, southern monocotyledonous leech, and German cockroaches. The scoring system is the same as in the examples above. The resulting data are shown in Table 4 below. In the case of two or more tests on the same test compound, one of the results shall be rejected. The symbol in the table indicates that the test has not been performed.

119

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O o o o o r ~ cn o o O 1 cn o o o o o o O 1 cn Γ 1 LO co o 00 1 1 1 cn cn 1 Cn cn cn cn cn cn cn o cn ΟΊ ΟΊ cn cn cn cn cn cn σι o o CM o o cn cn o CD kO cn cn o cn cn cn 00 fX tr n o o o o o cn o o o

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120

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TABLE (continued) tr

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18. 4,5-Dibromo-2- (p-fluorophenyl) pyrrole-3-carbonite

C \ l

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X • H 1 X 1 o c • H X o c 1 X 0 a 1 4 | X (0 M M (C O i X P m 1 1-1 1 ro X 1-1 1 • H 0 '—1 x M 0 X • H M 1 a  H a , -. CU i-1 a ω -H i-1 (i.e. C • H a " 1-1 0) c '- Ή x 0 1 M o X CM -P M 0 1 • H U M g C • H 4-1 O 0 c • H 44 XI 1 C X! P a -H (U 1 l CN X 1 X 1 CM 1 Lf) CO 1 P Q. | e 0 • tr 1-1 0 1-1 1 0 44 χ: * —1 P x u -H • H - H • H N CU T5 co X co C 1 l 05 d) 1-1 LO io l-1 X Ή Q. • H -P 1 3 o ¹ 44 M 1-1 i-1 cn o t-1 > —1 CN CN

t I

-P • H co 1 1 -P c 1-1 • P 0 o c X M o n H X (U a 44 X 1 (C 1 \ X co 1 — i 1 1 X co 1-1 C 1 o (D 1-1 H 4-1 0 • H 44 CU 1-1 • P , —V. -H CU 1-1 P H O 1-1 c x • P (U 1-1 c x P ω o m X c -H 44 m X o • H 0) pp u e X 1 u a 1 1 a a 1 CM 1 n 1 1 CM (0 CM M 1 , —I 1 O g -H g 1-1 o > 4 O X n X 44 u X  H X • H • P C • P X co X 0 X to 1 03 1 X 1 05 LO 1-1 LO 44 LO »—I <. - H (0 -p sr P N ¹ X 'Tr P CN (O CN CN CN

i

1 <—1 1-1 o P 44 X • P d) cu 1 g o - ' 4-1 X 1 • P 1 CM c a 1 ₍ _ ₁ d) 1 X 44 t-1 44 O 1 O 13th '-1 1-1 , —T X X -H CO u • P C 05 • P 44 d) 1-1 X X X • P 1 1 44 P v a co O -P 05 l-1 • P X a '—1 X c '—- • P u 0 1 a ' P -H X CM - · -P X P 1 1 • P 1 03 44 l-1 ST X O -P 0 1 l-1 X X n to X d) P - 1 u CO g 05 1 i-1 • P 03 1 X CM o X 1-1 , —1 1 1 44 1 • P 1 co 44 • P LO P 44 1 O a -P O rp f-1 'tr • P 1-1 0 X > —1 1 c X P u - P l-1 0 υ • P • P X - P X • P CU X d) X P X 1 - d) 03 1 rP X o g X LO • P • P 1 1 3 X 5-1 co • tr l-I X kO θ'- CM CN CN

122

8. 5-Bromo-4-chloro-2- (p-chlorophenyl) pyrrole-3-carbo <33

CN kO

03

Lf)

Lf) στ lO

CN

03

03

LO kO

03

LO

Lf)

CO co ω

M

X

I

O

1 o 1 G 1 o 1 d) Λ P G p 42 P S P d -P o P d • P (0 0 G G 0 CO a: t — i 1 rp A P A! i • P 'T MP • P d O n G 1 • P Ό 1 -P 1 d) P 1 CM P 1-1 MP '-J -P '-' 1 o P • P 1 1 I-1 P O G d CN 1-1 1 -P 1-1 d) t 1 d 43 4P a l-1 (—L U P o 1-1 - P i-1 -P O d P • P c • P T5 i-1 -— • P c (P c 1 43 1 cn Gh (P M (D U CM G X—, MP M m • p 1 1-1 1-1 P O P co Ό i-1 • P • P O 1-1 o 1 P P G 1-1 a «—1 1 o ¹ 4-) -P d) 43 υ u CN 1! 'P m υ • P 0 1 co e c P • P Tj 1 P - ' • P 0 0 TS 1 co d 0 ω j co 42 l-1 1 rd - rP fuh UO a P 43 O ¹ 1-1 1 Χί 1-1 f o <0 CJ n 0 CM L) P P co -P A • P co M 1 -P P 0 <0 ω 1 1 -H P T ( 4J 1-f -P 1 <n 1 1 LD d o 1 • P G <0 i— ( 1 CN 1 0 1-1 See c U -P 1 1-1 Q. 1 P H 43 o -P d) P o co P 0 -P U 'M' 42 T5 u 0 P 0 1-1 • P 1 1 P 1 G i-1 -P 1 i-1 43 G Lf) ω 1-1 (0 co 1 G d uo cn g υ t 1 (i.e. • P A v i-1 U 1 f υ • H e <—1 N 1 CN 1 • P c-1 ε <-! • P TS 1 0 Ή G m 1 <—1 Ό • P 0 P Ό 1 P P ω 1 (P o 1 G P P 1 m rp 42 -P X} 1-1 • P P uo i-1 X -P uo - P 1 -P 1 o P • P o 1 • P CM -P v G l-1 P ω d o ¹ -P co c ΟΊ o i-1 CN co P ¹ uo CM m co co co co co

I

-P • H

G

O

Λ3

P (Ū

Λί

CN cn «3

P

-P • H c

o

Λ rO

Oh

I m

i r —i o P • H a

36. 4,5-Dibromo-3- (p-chlorophenyl) pyrrole123

OT I · ¹ -! C • H OT 0Λ G • ω c

ω

H z

ω u

v

tP t — t 03 03 03 O O o O o 03 03 O) O i-4 r- LO O o 03 O o o Γ LO 03 <53 LO O O o 03 O o o LO 03 o CO 03 03 O 03 03 03 03 03 03 03 o r- 03 03 03 O 03 03 03 θ ', 03 03 co co 03 03 03 03 03 03 03 03 03 03 03 uo 03 03 1 O 03 O 03 03 03 03 O 03 03 1 CM 03 03 03 03 03 03 'T 00 L O o O O o- O O O 03 o ω 1 o 1 1 (i.e. Cl 43 -P 1 1 0 rp (i.e. 1 C - H 1 0 'tT G • H λ: CM (i.e. G 03 G 1 G G i 1 g 0 1 G (—F • P -P 03 1-1 1 43 i (i.e. • P c H 1 0 ω 03 G o (0 G G 1 c r — f c (i.e. 1 (i.e. G (i.e. 1 d 'T o O -H i-1 1-1 G • P «—1 03 £ 1 G c ct • p 0 1 a • P t • P G H i-1 c c O) o G <—T M i-1 a • H -P  H 1 G 4-) 0 G - P g 4->  H 2 1-1 -P • P G O G • H 1-1 a. c o • P G • P G d G • H S 0 1-1 G c O a d G 1 c 1 43 • P • P 1 43 -d 1 G (U iP C -P UO G O i-1 O 44 1 (i.e. cu o 1 (i.e. • r- | 1 «—1 C \] C G e G g • P G 1 o ι-I • H c -P 1-1 i G l-1 U i-1 1-1 • H G 0 • P • P 03 1 • P 1 CN o g G 1 G c c UO c P. G υ d 'tr 1-1 1 0) 1—} d - • P Ή 44 Q. MP LO 44 o «ΧΤ MP 1 2 G C 03 - H 1 G G ! G LO 1 0 1 c O • P - 0 1 I-1 'tr 1-1 I-1 -P 1-1 1-1 a l-1 1-1 £ • H Q. G o - • P G 1-1 • P G o c 03 U G 1 c d • P c υ G (L) - " 1 H Lf) (D • P c Cl) 1 G MP I Λ 2 1 44 G d) Pd a • P G c --- i-1 1-1 G 1 44 G - G 0 0 1 OT • H • P O 'tr OT 1 O t 1 r-1 1-1 03 (i.e. c c 1-1 Q. (i.e. LO rp Lf) OT 03 2 G 1 1 — I a> d) 43 03 1-1 43 1 (i.e. υ υ m S • P 44 Pd U '-' -P £ U £ 1-1 CM • H 1 (i.e. o c 1 • P 1 G o • P 0 o 1 d i-t c G LO CM ω d CM f) G G co G G r-H 1 j • H 43 • H 1 (i.e. 1 1 • P 43 1 (i.e. G • P • P w * χΓ e c Ή c e £ 1-1 £ c • P 'tr 1-1 • P 2 N (i.e. o -P T! o o O • rd v ω o 0 G Q. • P G 0 c I ^- P 03 c • p 1 4} c G G 03 (i.e. G 43 03 G 1 G d 0 G c LT) C 43 43 G 1-1 43 G 'tr - -P 03 P G P 1 1 o (i.e. 1  1-1 1 • P 1 (i.e. 1 • P • P 1 • 1-1 LO LO G 'tr G CN sr c CM G • o G CM CM G CM c , - ( G i-1 o- 00 03 O T-1 CM 03 'tr UO LO 03 03 03 'CT vr Ό ¹ <tr 'tr <tr 'tr

124

48. 2,3-Dibromo-5- (p-chlorophenyl) -1-methyl-4-nitro-

O O σι O o o O - cn o O cn 00 cn cn cn cn cn Γ o (Ti cn o cn cn o o cn o r- cn cn o cn cn cn r- cn cn cn cn cn cn cn cn cn o cn cn tn (T, cn cn cn cn cn cn cn cn cn Γ cn cn i o cn b o cn o cn 00 cn cn cn cn cn cn cn cn cn LO o ΟΊ cn ro cn o r- cn o 00 1 1 1 ω cn 1-1 a) b <U 1 1 0 ε 1 1-1 -cd ro P P • cd • cd • rd P 1 • H 0 cn 1 cn M 1-1 p c cn b ω b b 1-1 o i-1 (ow 0 ε 0 -cd • cd P 1-1 b 1-1 b - cd 1 G b • cd • cd • cd • cd a) cn CN O (I) P c P P ε b b ε 0 (D b b P 0 1 P P P b —- • cd o b τ-1 fO o -P 1 cn c G d) l b G • cd H P d o i-1 - ' 1 c-d c ω 1-1 b b 1 c-d ro b 1 b 1 • H P • cd c-d • cd 1 • cd LO O CN P it P 1 G i-1 P 1 b 1 b b b d) 0 b —1 (1) • cd 1 —- l-1 M P 0 ε l-1 c sr 1 - H P cn • rd 1 P P  cd o P cn G cn o (i.e. P LO • cd 0 b b b ct d (0 1-1 1-1 0 1 P C a) P 1 1 1-1 b 1 — i b • rd P X. r-d ε co r ~ d CN • cd P • cd c P b «—1 l-1 M • cd b o 1 P o P • cd b • rd • cd - cd • cd m 1 P P b 1— f b P -cd C G c M ro  cd o • cd b • cd G 1 d) cn d) -P o 1 P 1-1 C υ c • rr O LO b (O M - ' b r— | b 0 1 o b 1 P 1-1 P 1 G) 0 1-1 u b P b ro P O • cd o P cn '- P H • cd P -— P - (i.e. 1-1 1-1 P 1-1 (U 1 • cd c P d 1 <0 1 b - cd b -P b 1 f 'd i-1 P (U 1 b CN b CN 1 c u • cd G 0 CN - cd 1 b LO 1 1 1 1 ro d) 1 c 1 (Ό 1 H P 1-1 ro P ro P 1 b P o P «- ( ε b o • H P l o 1 o '—1 P b • rd o • rd 1-1 c O 1 l-1 1-1 l-1 i-1 0 o 1 P l P M G b Φ 1-1 i-1 o b o b P 1-f CN cd CN b cn b O u b b • cd P o P G - rd b 1 b 1 • rd (U • cd b • cd , —Χ O N • cd - H - cd • cd P G ε 1 ε c «—1 P P P • cd 1 c P P P P 1 0 ro 0 0 o 1 (C 1 cn P d ₍ _ _f 1 1 1-1 P P 1 P b p 10 b LO b —- b r - d LO 1-1 LO • cd - ' b 1-1 b P • H Q. 1 o 1 1 • cd • rd b 1 1 o 1 (0 p N ¹ ro b LD <—1 c b d b P oc ΟΊ o '—1 CN ro PT LO co LO LO LO LO LO LO LO LO

125

σ σ ο σ 00 ο ο σ c m ο σ ο ο σ ο ο ο o ο σ σ 00 σ σ ο σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ LO ο σ ο ο ο ο σ σ.

tr σι

LO

C \ l kO O lO r- ~ co 3d P • H ω α /

4-J • ω ω

H s

ω

NT

ι • H 1 1 X tr 1 X 1 4d X • H • H c CN • d X • Η 1 73 X (U CU 1 c • d c co 1 X 73 o c ο tr 1-1 • «d 1 0 X o b 1-1 x • H X CM ΓΊ c X G 1 m c 1 1 1 Thu G Thu i-1 '- Φ * = r m X (U o 1 X 1-1 - 1 X • H c CN 1 <M -H I CM ! Ό -H 1 c 1 X m i-1 1 CU 1 a p 0 1-1 Φ (D 1 i-1 1 sr 0 ω u o S 1 — i o i-1 X 1-1 r-1 Thu 1-1 c H 1-1 c 0 CM  H X 1-1 X • rd H C • d σι -H G 1 C u - H 1 X m X C (U X • <d ι-1 Φ • H C X _f _ _l X - H (D i-1 o X 0 M 73 X 1 i-1 o C 4d • H c G C l -H c -H c o P C X t - t '1-1 0 LD C 0 G Φ X 0 X X • H a i-1 x o 1-1 Φ X c i-1 -H G c x-x X tr X X X c (U OJ C 1 Φ i-1 u 1 c 0 .___ o X υ O X - H • H ₍ _ _i (U '| —1 • H l-1 1 •• d X 1 G c X 1-1 X X m X n 73 c 0 Φ 1 -H 1 1 ω X 0 1 1 (U i-t t-1 x 40 CU lt o 1 i-1 tr X  H X ct < 0) 1 <—1 X X 0 X 1 G υ 0 n £ l — i CM • d φ - c m CU Φ 1 i-1 • —- o M £ _{( _J} •• d 1 X X X 1  H c 1 -P C 1 X 1 1-1 c - u CM w ω -H CM  H 0 l-d CN o o 1 1 1 <t X x 1 C 1 i-1 1 c <-! X x C i-1 o .—. C o 1-1 c • H P • H X 1 - o • r4 1-1 <—T o X o c 0 P, υ e 1 i-1 C • rd  H 1-1 M - d l-1 Φ <-) • <d 0 LD X X N C X t 5d co X X X 1-1 73 G 1 u • r-1 C (D u AA 4d (i.e. υ c u o 1 X g - H C Φ X • r — 1 1 - ' i-1 • H 0 -d c tr • Ή O ω 73 o C 73 m 1 H 73 1-1 73 Ή X co 73 ω c sort of 1 X O 1 1 P < id 1 X l X ΓΩ t 1 o X! ι-1 LT) c _l _ _f 1-1 LO • —1 _ ₍ 4d LO u LO o - l-1 tr 1-1 1 -H x (U 1 X X o 1 • rd • H X c 1 • id X - d m P tr X i-1 u tr c LO C tr X tr X LO G C \ | G co σ o i-1 CN ro tr LO kO LO m kO kO kO kO kO kO kO

126

a O kO CA. O CA. CA. A O o o O O O O O O O a o o O O O O O O σι A A A CA. CA. A A O A A a CA. CA. CA. A A O A A A CA. CA. CA. A A LO Γ- o kO o CA. CA. CA. O A o A kO A CA. CA. CA. A A A

σι σι r- o σι

I

CM. 3-Bromo-5- [p- (trifluoromethoxy) phenyl] pyrrole

i tn o i i

u i

1 i-l b 1-1 • P b CM O M 0 c • P 1 0 (0 i-l 1 o c 1-1 1-1 b • P o b o 0 4-1 1 (X 4-1 i-l b i-l • rd CM 1 (d s • H Ll 1 i-1 Ct 1 b (fl a b <—1 -H 1 b 0 - 0 4-1 tl m 1 M 1 M d) O 1 CO 4-) LO • H 6th 0 1-f 1 H 1 i-l 1-1 0 i-1 t 1-1 0 4-1 S-l o 1 • rd r-d 0 • P * P i-l 4-1 Ή '—1 M a • P 1 d) C 4-1 b 1 a , -. g ω d) • P 1 .—. 1-1 1 4-1 P b ω 1-1 i-1 - H t-1 1 — I i-l -P fO • P  H C 1 -H 0 a «—1 c C CD X—. M 1-1 l • P ω ω 4-1 i — ί 4-1 b uo a P 4-1 4-4 M • p • rd o 1 -— -P M S-l O C C • P 1 • P 0 0 i-1 d) o X r - t CM c 1-1 i-1 Λ 4-1 n 1 • P 1 o b b 0 i-l i-l P X o o • rd 0 nJ 0 I- ( P 1 1 CG X 1-1 b co Pd • P cd a a 1 b 1 - ' P 4-1 Pi ~ - - r-1 CQ u co 1 0 m dJ 1 1 1 • H Q. aj 1 1 uo 1- { (U e co LT -νΓ M co 1-1 a i-1 1 X i-1 M 1 1 1 -P '- • H - o £ u • H o 1-1 ε ε • H 1 H 1 i-l 0 • P i-l 0 0 0 0 C LO 4-J CM • rd P co X 4-1 1 i-l M s-ι 0 1 • H 1 it X) (i.e. 1 i-l 4-1 • p b b X e c oh • P 1-1 C • P • P • P M 0 0 0 i-1 X P O i-l X X ω (U P h i-l rd 1 P co b 4J l-1 1 (13th 1 oh Pi X H b -P X i-l - • P uo i— ( uo l-1 • H 1 (0 1 (D • P 1 Π3 1 0 • H • P X co b £ co P CN b LO 1-1 CM i-l CO P co σι o i-1 CM co 'M ¹ kO CO A r- r- r-

75. 2-p-Toluoyl-5- (trifluoromethyl) pyrrole-3-carbonite127

O ro

CN

07 07 07

07 07 r- o o

O

07

O 07

07

kO 07 07 07 O 07 O 07 07 07 07 07 CO 07 07 O 07 07 07 O 07 o 07

I co i i lo i — I I o -

M i-I

TABLE (cont'd)

• H a • H X ω w 1 (L rd r-1 ε r-1 t-1 CN -H • H • H • H 1 X u P P r-1 (U x 4-1 X 0 e o • H 1 • H p M 4-1 c to c • rd o (D o 1 o X 0 - X X i-1 1 P i-1 P 1-1 X χ-H (U Ή cd • H • H 1 X C X 0 M 1 d) 1 i-1 + J i-1 cn X m 0 • P 1 P 1 X 1 C I-1 0 I-1 1 LO d) 0 1-1 o X 1 u-l p X l-l 1 i-1 P • 1-1 0 - H l-l -H 0 & ♦ H 0 0 r—) TS 0 ω i-1 x 1-1 t r— | 1-1 cd O ω 0  H  H M 1-1 4-1 cd 1 4-1 Q. X • H • H 1 1-1 a d) co d) P P a • H £ - £ X X 1 P 1 P 1 l-l 1 • H CN 4-1 CN 0 CN o a c 1 • H 1 0 1 a o e c e r—) e r-H a X 0 0 0 M 0 M 1-1 P X P • H H • H 6th cd Λ P X P Xi P - X 1 (0 1 4-1 1 X 1 • H vT x N ¹ ΝΓ LO X kO r— CO σ> r ~ r ~ p

X 1 f—) 0 CN P P 1 o • rd r — H a a 0 rp i-i X 1-1 • rd • rd  rd P, P a X 1 1-1 1-1 1 X o • rd a 1 X a P ω 1 l-1 a 0 rd X o a <—1 1 X a 1-1 Ή P 1 - ' ω X P o X 1 rd P X a 1 (N • —1 P • rd 1-1 l-l 1 • rd X C X 0 P 1 0 P a r-1 X a X P l-l • P -H P X X X c a a 1  i-l dl 0 X a i-i £ X a • rd X P P -. T3 a rd 1 0 a 1 1 1-1 a a X X a • rd r— ( 1 1 '- M a X cn 1-1 CN 1 -P OT • rd 1 * rd 1 CN • H cd P 1-1 X 1-1 1 C 1-1 X o d) o P o 1  1 - Vol - P £ P 0 X cn P 1 • rd 1 • rd 1-1 P 1 X LO X i-1 P4 X a 1-1  P 1 1 u X • rd c £ 1-1 £ r-1 • rd • rd X 0 0 • rd 0 • rd T3 Ό dl X P a P a 1 1 £ P X 1-1 X 1-1 Lf) co 1 a 1 o 1 o X ST X cn X ΝΓ , —1

o t-l CN CO co co co co

4. 3-bromo- (a, a, a-trifluoro-p-toluyl) pyrrole

Claims (16)

DEFINITION OF INVENTION A compound having the structural formula (I) wherein X = F, Cl, Br, I or CF _? ; Y = F, Cl, Br, I, CF-, or CN; W = CN or NO ₂ and A = H; C 1 -C 4 alkyl optionally substituted with one to three halogens, one oxo group, one C 1 -C ₄ alkoxy group or one C 1 -C ₄ alkylthio group, one phenyl optionally substituted with C , -C - <alkyl, or C ₁ -C ₂ alkoxy, or one to three halogens, or one benzyloxy substituted with one halogen; C _; -C ₄ -Carbalkoxymethyl: C ₃ -C ₄ -alkenyl which may be substituted with one to three halogen atoms; cyano; C ₃ -C ₄ -alkynyl which may have one halogen atom; di- (C 1 -C ₄ alkyl) aminocarbonyl or C ₄ -C ₈ cycloalkylaminocarbonyl; L = H, F, Cl or Br; and M and R are, independently of one another, H, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylsulfinyl, C ₃ -C ₃ alkylsulfonyl, cyano, F, Cl, Br , I, nitro, CF ₃ , R-.CF ₂ Z, R ₂ CO or NR ₃ R ₄ and, when M and R are in adjacent positions, together with the carbon atoms to which they are attached may form a ring, where the MR structure is: 129 -OCH ₂ O-, -OCF ₂ O- or to; Z = S (O)., Or O; R ₃ = H, F, CHF ₂ , CHFC 1 or CF ₃ ; R ₂ = C 1 -C ₃ alkyl, (C ₁ -C ₄ alkoxyl or NR, R ₄ ; R ₄ = H or C ₁ -C ₃ alkyl; R ₄ = H, C ₁ -C ₃ alkyl or R ₅ CO; R _; = H or C 1 -C ₃ alkyl, and n is an integer equal to 0, 1 or 2. A compound according to claim 1, wherein A in formula (I) is hydrogen or C 1 -C 2 alkoxymethyl; W = CN or NO _Z ; each X and Y = Cl, CF, or Br; R = F, Cl, Br or OCF; M = H, F, Cl or Br; and L = H or F. 3. A compound according to claim 1, which is: 4.5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile; 4.5-dichloro-2- (a, a, a-trifluoro-p-toluyl) pyrrole-3-carbonitrile; 2,3-dichloro-4-nitro-5- (a, a, a -trifluoro-p-toluyl) pyrrole-3-carbonitrile; 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) pyrrol-2,4-dicarbonitrile; 130 3-bromo-5- (3,4-dinitrophenyl) pyrrole-2,4-dicarbonitrile; 4,5-dichloro-1- (ethoxymethyl) -2- (a, a, a -trifluoro-p-toluyl) pyrrole-3-carbonitrile; 4-bromo-2- (p-chlorophenyl) -1- (ethoxyphenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; and 4-Bromo-2- (3,4-dichlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile. Compounds according to claims 1-3, characterized in that they are used for the production of insecticidal, nematocidal and acaricidal plant protection products. 5. A method of controlling insects, nematodes, and mites, comprising treating the specified insects, nematodes, and mites, and their breeding sites or sites, with an effective amount of an insecticidal, nematocidal, and acaricidal compound having the structure represented by Formula (I): wherein X = F, Cl, Br, I or CF ₃ ; Y = F, Cl, Br, I, CF ₃ or CN; W = CN or NO ₂ and A = H, C-C , _; a substituent which may be substituted with one to three halogen atoms, one oxy group, one C ₃ -C ₆ alkyl group or one C 1 -C 2 alkyl alkylthio group, one phenyl optionally substituted with Ci -Cj- alkyl or C _l -C ₃ -alkoxy, or one to three halogen atoms or one benLT 4040 B 131 ziloxy substituted with one halogen; C 1 -C 8 -carbalkoxymethyl: C 1 -C 6 -alkenyl which may be substituted with one to three halogens; cyano; C ₃ -C <1 - alkynyl, which may have one halogen atom; di- (C 1 -C ₄ alkyl) aminocarbonyl or C ₄ -C ₄ cycloalkylaminocarbonyl; L = H, F, Cl or Br; and M and R, independently of one another, are H, C 1 -C ₃ alkyl, Ο ₃ -C ₃ alkoxy, C 1 -C 1 -alkylthio, C _; -C ₃ alkylsulfinyl, C-C ₃ -alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF ₃ , R ₁ CF ₂ Z, R ₂ CO or NR ₃ R ₄ and when M and R are adjacent positions, they may, together with the carbon atoms to which they are attached, form a ring wherein the MRI structure is: - OCH ₂ O-, -OCF ₂ O-, or Z = S (O) _n or O; R 1 H, F, CHF ₂ , CHFCl or CF ₃ ; R ₂ = C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or NR ₃ R ₄ ; R ₃ = H or C _l -C ₃ alkyl; R ₄ = H, C 1 -C 1 alkyl or R ₅ CO; R ₅ = H or C ₁ -C ₃ alkyl; and n is an integer equal to 0, 1 or 2. 6. A process according to claim 5, wherein the compounds are: 4.5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile; 4.5-dichloro-2- (a, a, a -trifluoro-p-toluyl) pyrrole-3-carbonitrile; 2,3-dichloro-4-nitro-5- (?,?,? -Trifluoro-p-toluyl) pyrrole-3-carbonitrile; 132 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-dinitrophenyl) pyrrole-2,4-dicarbonitrile; 4,5-dichloro-1- (ethoxymethyl) -2- (a, a, a-trifluoro-p-toluyl) pyrrole-3-carbonitrile; 4-bromo-2- (p-chlorophenyl) -1- (ethoxyphenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile, and 4-bromo-2- (3,4-dichlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile. 7. A method of protecting a growing crop from attack by insects, nematodes and mites, comprising treating said plants, soil or water where they grow with an effective amount of a compound of formula (I) against insects, nematodes and mites: (I) X 133 wherein X = F, Cl, Br, I or CF-; Y = F, Cl, Br, I, CF, or CN; W = CN or NO ₂ and A = H, C ₁ -C ₄ alkyl which may be substituted with one to three halogen atoms, one oxo group, one C 1 -C ₄ alkoxy group or one C 1 -C ₄ alkyl group. alkylthio, one phenyl optionally substituted with C 1 -C 1 alkyl or C 1 -C 4 alkoxy or with one to three halogens, or one benzyloxy substituted with one halogen; C 1 -C ₄ -carbalkoxymethyl: C ₁ -C ₄ -alkenyl which may be substituted with 1 to 3 halogen atoms; cyano; C ₃ -C ₄ -alkynyl which may have one halogen atom; di (C ₁ -C ₆ -alkyl) aminocarbonyl or C ₄ -C ₈ cycloalkylaminocarbonyl; L = H, F, Cl or Br; and M and R, independently of one another are H, C₁-Cjalkilas C ₁ -C ₃ -alkoxy, C, -C ₃ -alkiltiogrupė C ₁ -C ₃ alkylsulphonylamino inyl, Cj ^ -Cj alkylsulfonyl, cyano, F , Cl, Br, I, nitro group, CF ,, R _: CF ₂ Z, R ₂ CO or NR ₃ R ₄ and, if M and R are in adjacent positions, together with the carbon atoms to which they are attached may to form a ring where the MR structure is;. - OCH ₂ O-, -OCF ₂ O-, or Z = S (O) _n or O; R _x = H, F, CHF ₂ , CHFC 1 or CF ₃ ; R ₂ = C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or NR ₃ R ₄ ; R ₃ = H or C 1 -C 6 alkyl; R ₄ = H, C ₁ -C ₃ alkyl, or R _S = O; R ₅ = H or C 1 -C 6 -alkyl; and n is an integer equal to 0, 1 or 2. 8th 7. A process according to claim 7, wherein said compounds are: 134 4.5-dichloro-2- (3,4-dichlorophenyl) pyrrole-3-carbonitrile; 4.5-dichloro-2- (a, a, a-trifluoro-p-toluyl) pyrrole-3-carbonitrile; 2.3-dichloro-4-nitro-5- (a, a, a-trifluoro-p-toluyl) pyrrole-3-carbonitrile; 2.3-dichloro-5- (3,4-dichlorophenyl) -4-nitropyrrole; 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; 2.4-dibromo-5-p- (chlorophenyl) pyrrole-3-carbonitrile; 3,4-dibromo-5- (3,4-dichlorophenyl) pyrrole-2-carbonitrile; 5- (p-chlorophenyl) -3- (trifluoromethyl) pyrrole-2,4-dicarbonitrile; 3-bromo-5- (3,4-dinitrophenyl) pyrrole-2,4-dicarbonitrile; 4.5-dichloro-1- (ethoxymethyl) -2- (a, a, a-trifluoro-p-toluyl) pyrrole-3-carbonitrile; 4-bromo-2- (p-chlorophenyl) -1- (ethoxyphenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; and 4-Bromo-2- (3,4-dichlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile. 9. The method of claim 7, wherein said plants or the soil in which they are grown are treated from 0.125 kg / ha to 4.0 kg / ha of said compound of formula (I). 135 10. A process according to claim 7, wherein the leaves or soil of said plants, or the yandeni, where said plants are grown, are treated with a liquid composition of said compound of formula (I) containing from 10 to 5 at 10,000 da.s. Of a compound of formula (I). 11. A novel arylpyrrole compound having the structure represented by formula (I): wherein X = F, Cl, Br, I or CF ₃ ; Y = F, Cl, Br, I, CF- <or CN; W = CN or NO ₂ and A = H, C ₁ -C ₄ alkyl which may be substituted with one to three halogens, one oxy group, one C ₁ -C ₄ alkoxy group or one A C 1 -C ₄ -alkyl group, one phenyl optionally substituted with C ₁ -C ₃ alkyl or C _; -C ₃ -alkoxy, either one to three halogens, or one benzyloxy substituted with one halogen; C ₁ -C ₄ -carbalkoxymethyl: C ₃ -C ₄ -alkenyl, substituted as 25 may have one to three halogen atoms; C ₃ -C ₄ -alkynyl which may have one halogen atom; di (C ₁ -C ₄ alkyl) aminocarbonyl or C ₄ -C ₈ cycloalkylaminocarbonyl; 30 L = H, F, Cl or Br; and M and R are, independently of one another, 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 -acylsulfonyl, cyano, F , Cl, 35 Br, I, nitro, CF ₃ , R _X CF ₂ Z, R ₂ CO or NR, R ₄ and, if M and R are in adjacent positions, together with carbon The 136 atoms to which they are attached make a ring where the structure of the MR is: they can with -OCH ₂ O-, -OCF ₂ O- or Z = S (O) _n or O; R ₂ = H, F, CHF ₂ , CHFC 1 or CF ₃ ; R ₂ = C 1 -C 6 -alkyl, C ₂ -C 4 -alkoxyl or NR ₃ R ₄ ; R ₃ = H or C _t C ₃ alkyl or R ₅ CO; R _s = H or C ₁ -C ₃ alkyl; and n is an integer equal to 0, 1 or 2, characterized in that it carries benzoylacetonitrile or α-nitroacetophenone having the structure: where L, M, R and W are as defined above, with a 2,2-di- (C _l -C ₄ alkoxy) ethylamine in the resulting reaction oc .- [2,2-di (C, -C Treatment of _4- alkoxy) ethylamino] -β-cyanostyrol or eth- [2,2-di- (C 1 -C ₄ -alkoxy) ethylamino] -β-nitrostyrene with mineral or organic acid gives the desired product. 12. A process according to claim 11, wherein the reaction between 2,2-di- (C ₁ -C ₄ alkoxy) ethylamine and benzoylacetonitrile or nitroacetophenone is carried out in a solvent-free or inert organic solvent. 13. A process according to claim 11, wherein the α- [2,2-di- (C 1 -C ₄ -alkoxy) ethylamino] -β-cyanostyrol or α- [2,2-di- (C-C ₄₎ (coke) ethanol is treated with hydrochloric, hydrobromic or trifluoroacetic acid to form arylpyrrole. 137 14. α- [2,2-Di- (C 1 -C ₄ alkoxy) ethylamino] -β-cyanostyrene or α- [2,2-di - (C ₁ -C ₄ alkoxy) ethylamino] - β-nitrostyrene having the following structural formula: M W NCH, CH (OC, -C 1 -alkyl), H 'in which CN or NO ₂ ; L = H, F, Cl or I; K and R, independently of one another, are H, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, cyano , F, Cl, Br, I, nitro, CF ₃ , R, CF ₂ Z, R ₂ CO or NR ₃ R ₄ and, if M and R are in adjacent positions, together with the carbon atoms to which they are attached, they may form a ring where M and R correspond to the structure: -OCH ₂ O-, OCF ₂ O- or Z = S (O) _ri or O; R _x = H, F, CHF ₃ , CHFCl or CF ₃ ; R ₂ = C ₁ -C ₃ alkyl, C ₃ -C ₃ alkoxy or NR ₃ R ₄ ; R ₃ = H or C ₁ -C ₃ alkyl; R ₄ = H or C ₁ -C ₃ alkyl or R ₅ CO; R ₅ = H or C ₁ -C ₃ alkyl; and n is an integer equal to 0, 1 or 2, characterized in that it carries benzoylacetonitrile or α-nitroacetophenone of the formula: L II C-CH, W Wherein L, M, R and W have the meanings indicated above, reaction with 2,2-di- (C ₁ -C 4 -alkoxy) ethylamine at higher temperature to form a- [2,2-di- (C 1 - C ₄ -alkoxy) ethylamino] -β-cyanostrol having the structural formula: N CH.CH (OC-C 1 alkyl), H '' wherein L, M, R and W are as defined above. 15. A compound having the structural formula: NCH, CH (OC, -C1-alkyl), H wherein W = CN or NO ₂ ; L = H, F, Cl or I; M and R are independently selected from H, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylsulfinyl, C ₁ -C ₃ alkylsulfonyl, cyano , F, Cl, Br, I, nitro, CF ₃ , R _L CF ₂ Z, R ₂ CO or NR ₃ R ₄ and, if M and R are in adjacent positions, together with the carbon atoms to which they are attached, they may form a ring where M and R correspond to the structure: -OCH ₂ O-, -OCF ₂ O- or Z = S (O) _n or O; R _{1 =} H, F, CHF ₃ , CHFC 1 or CF ₃ ; R ₂ = C j - C ₃ - a 1 ki 1 as C ₁ -C _3-alkoxy or NR ₃ R _4; R ₃ = H or 139 C ₁ -C ₃ alkyl; R ₄ = H, C 1 -C ₅ alkyl or R ₅ CO; R ₅ = H or C 1 -C ₃ alkyl; and n is an integer equal to 0, 1 or 2. 16. The compound of claim 14, which is: (E) -p-chloro-p - [(formylmethyl) amino] cinnamon nitrile diethyl acetal; (Z) -p-chloro-p - [(formylmethyl) amino] -3,4-dimethoxycinnamone nitrile diethyl acetal; β - [(Formylmethyl) amino] vinylbenzoic acid diethyl acetal; 3,4-Dichloro-p - [(formylmethyl) amino] cinnamon nitrile diethyl acetal; (Z) -β - [(formylmethyl) amino] -? - methylcinnamon nitrile diethyl acetal; β - [(formylmethyl) amino] -p-trifluoromethoxycinnamone nitrile dimethyl acetal; (E) -? - chloro-? -? - (formylmethyl) amino] cinnamon nitrile dimethyl acetal; N- (formylmethyl) -p-methyl-α- (nitromethylene) benzylamine diethyl acetal; N-formylmethyl) -3,4-dimethoxy-α- (nitromethylene) benzylamine diethyl acetal; p-chloro-N- (formylmethyl) -a- (nitromethylene) benzylamine diethyl acetal; 140 N- (formylmethyl) -α- (nitromethylene) -2-naphthenomethylamine diethyl acetal; methyl p- {α, α- [formylmethyl) amino] -β-nitrovinyl] benzoate β- (diethyl acetal), and p-trifluoromethyl-N- [formylmethyl-α (nitromethylene)] benzylamine diethyl acetal.