AU610915B2

AU610915B2 - Arylpyrrole insecticidal, acaricidal and nematicidal agents and method for the preparation thereof

Info

Publication number: AU610915B2
Application number: AU20117/88A
Authority: AU
Inventors: Dale Gordon Brown; Robert Eugene Diehl; Jack Kenneth Siddens; Donald Perry Wright Jr.
Original assignee: American Cyanamid Co
Current assignee: Wyeth Holdings LLC
Priority date: 1987-07-29
Filing date: 1988-07-28
Publication date: 1991-05-30
Anticipated expiration: 2008-07-28
Also published as: CA1332060C; JPH01104042A; AU2011788A; IE62489B1; SK536088A3; CZ536088A3; HU204971B; IL87222A0; NZ225582A; CZ280795B6; IE882315L; IL87222A; FI883554A; JP2553156B2; SK279269B6; FI91523B; FI91523C; DK422488A; DK173853B1; HUT48797A

Description

1 S F Ref: 66240 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION 6 1 9 1

(ORIGINAL)

FOR OFFICE

USE:

Class Int Class o 0 Complete Specification Lodged: o Accepted: Published: Priority: 0 0 Related Art: Name and Address of Applicant: American Cyanamid Company One Cyanamid Plaza Wayne New Jersey UNITED STATES OF AMERICA Address for Service: Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street 0Sydney, New South Wales, 2000, Australia Complete Specification for the invention entitled: Arylpyrrole Insecticidal, Acaricidal and Nematicidal Agents and Method for the Preparation Thereof The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/3 S30,655-00 0/ 0 P. 0 o 0.

agent ARYLPYROLE INSECTICIDAL ACARICIDAL AND a a o 0 o o

ABSTRACT

This invention is directed to certain novel insecticidal, acaricidal and nematicidal arylpyrrole .agents and a method for controlling insects, acarids oam t and nematodes therewith. The invention also is directa ed to a method for protecting growing plants from insect, acarid and nematode attack by applying to said plants or the soil in which they are growing, an insecticidally, acaricidally or nematicidally effective amount of a novel arylpyrrole compound. The present 0 0 so invention further is directed to a method for the preparation of the arylpyrrole compounds.

I h- -i 1A The present invention is directed to certain novel arylpyrrole compounds that are highly effective insecticidal, acaricidal and nematicidal agents useful for the control of insect, acarid and nematode pests and for protecting agronomic crops, both growing and harvested, against the ravages of said pests. The present invention is also directed to methods for preparing the arylpyrrole compounds.

According to a first embodiment of the invention there is provided a compound having the formula I structure:

L

S- (I)

R

N

wherein X is F, C1, Br, I, or CF 3 Y is F, C1, Br, I, CF 3 or CN; W is CN or NO 2 and A is H; C 1

-C

4 alkyl optionally substituted with from one to three halogen atoms, one hydroxy, one C 1

-C

4 alkoxy or one Cl-C 4 alkylthio, one phenyl optionally substituted with Cl-C3 alkyl or C1-C3 alkoxy or with one to three halogen atoms, one phenoxy optionally substituted with one to three halogen atoms or one benzyloxy optionally substituted with one halogen substituent; C,-C 4 oooo carbalkoxymethyl; C 3

-C

4 alkenyl optionally substituted with from one to .eo. three halogen atoms; cyano; C3-C4 alkynyl optionally substituted with o.0 one halogen atom; di-(C -C 4 alkyl) aminocarbonyl; or C4-C 6 cycloalkylaminocarbonyl; L is H, F, C1 or Br; and M and R are each independently H, C 1

-C

3 alkyl, C 1

-C

3 alkoxy, C 1

-C

3 alkylthio, Cl-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, cyano, F, Ci, Br, I, nitro, CF 3

R

1

CF

2 Z, R 2 CO or NR 3

R

4 and when M and R are on o adjacent positions and taken with the carbon atoms to which they are 2 5 attached they may form a ring in which MR represents the structure: 0

-OCH

2

-OCF

2 0- or S Z is S(O)n or 0; R 1 is H, F, CHF 2 CHFC1, or CF 3

R

2 is CI-C 3 alkyl, CI-C 3 alkoxy, or NR 3

R

4

R

3 is H or C 1

-C

3 alkyl; R 4 is H, C -C 3 alkyl or R 5 CO; R 5 is H or C 1

-C

3 alkyl; and n is an integer of 0, 1 or 2.

KEH/198f 2 According to a second embodiment of the invention there is provided a method for controlling insects, nematodes and acarina comprising: contacting said insects, nematodes and acarina, their breeding grounds, food supply or habitat with an insecticidally, nematicidally and acaricidally effective amount of a compound having the structure: x 1

R

Y

0 0 0 0 .0 0 o 0 o e C) 0 c 0 0 0 0 0 3 00 0 0OB 0 0 3Q 0o wherein X is H, F, C1, Br, I, or CF 3 Y is F, C1, Br, I, CF 3 or CN; W is CN or NO. and A is H; Cl-C4 alkyl optionally substituted with from one to three halogen atoms, one hydroxy, one C 1

-C

4 alkoxy or one C1-C4 alkylthio, one phenyl optionally substituted with CI-C 3 alkyl or CI-C 3 alkoxy or with one to three halogen atoms, one phenoxy optionally substituted with one to three halogen atoms or one benzyloxy optionally substituted with one halogen substituent; C -C 4 carbalkoxymethyl; C 3

-C

4 alkenyl optionally substituted with from one to three halogen atoms; cyano; C 3

-C

4 alkynyl optionally substituted with one halogen atom; di-(C 1

-C

4 alkyl) aminocarbonyl; or C 4

-C

6 cycloalkylaminocarbonyl; L is H, F, C1 or Br; and M and R are each independently H, C 1

-C

3 alkyl, C 1

-C

3 alkoxy, CI-C 3 alkylthio,, C 1

-C

3 alkylsufinyl, C 1

-C

3 alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF 3

RICF

2 Z, R 2 CO or NR 3

R

4 and when M and R are on adjacent positions and taken with the carbon atoms to which they are attached they may form a ring in which MR represents the structure:

-OCH

2 O-, -OCFO-

I

Z is S(O)n or 0; R 1 is H, F, CHF 2 CHFC1, or CF 3

R

2 is C 1

-C

3 alkyl, C -C 3 alkoxy, or NR 3

R

4

R

3 is H or C 1

-C

3 alkyl; R 4 is H,.C 1

-C

3 alkyl, or R 5 CO; R 5 is H or C 1

-C

3 alkyl; and n is an KEH/198f 2A integer of 0, 1 or 2.

According to a third embodiment of the invention there is provided a method for protecting growing plants from attack by insects, nematodes and acarina, comprising applying to the foilage of said plants or to the soil or water in which they are growing, an insecticidally, nematicidally or acaricidally, effective amount of a formula I compound having the structure: wherein X is H, F, C1, Br, I, or CF 3 Y is F, C1, Br, I, CF 3 or CN; N is CN or NO 2 and A is H; C1-C 4 alkyl optionally substituted with from one to three halogen atoms, one hydroxy, one C 1

-C

4 alkoxy or o.ve

C

1

-C

4 alkylthio, one phenyl optionally substituted with C -C 3 alkyl 00 O*o o or C1-C 3 alkoxy or with one to three halogen atoms, one phenoxy 15, optionally substituted with one to three halogen atoms or one benzyloxy 000000 0 optionally substituted with one halogen substituent; C 1

-C

4 carbalkoxyo0ooo0 methyl; C 3

-C

4 alkenyl optionally substituted with from one to three .0oo halogen atoms; cyano; C 3

-C

4 alkynyl optionally substituted with one oooo" halogen; di-(C 1

-C

4 alkyl) aminocarbonyl; or C 4

-C

6 cycloo" o 20 alkylaminocarbonyl; L is H, F, C1 or Br; and M and R are each independently 0 00 H, C 1

-C

3 alkyl, C 1

-C

3 alkoxy, C -C 3 alkylthio, C 1

-C

3 alkylsulfinyl, C 1

-C

3 alkylsulfonyl, cyano, F, C1, Br, I, nitro, CF 3 SR1CF 2 Z, R 2 CO or NR 3

R

4 and when M and R are on adjacent positions "o and taken with the carbon atoms to which they are attached they may form a 0 o250 ring in which MR represents the structure: 0 o o 00 0 0 000 -OCHO- -OCFO- or Z is S(0)n or 0; R 1 is H, F, CHF 2 CHFC1, or CF 3

R

2 is C1-C3 alkyl, C1-C3 alkoxy, or NR 3

R

4

R

3 is H or C1-C3 alkyl; R 4 is H, .C1-C3 alkyl, or R 5 CO; R 5 is H or C 1

I.C

3 alkyl; and n is an integer of 0, 1 or 2.

KEH/198f 2B According to a fourth embodiment of the invention there is provided a method for the preparation of a novel arylpyrrole compound having the structure: x W

L

Y N

M

R

wherein W is CN or NO2; L is H, F, C1 or Br; and M and R are each independently H, C -C3 alkyl, Cl-C3 alkoxy, Cl-C3 alkylthio, Cl-C3 alkylsulfinyl, C -C 3 alkylsulfonyl, cyano, F, C1, Br, I, nitro, CF 3

R

1

CF

2 Z, R 2 CO or NR 3

R

4 and when M and R are on adjacent positions and taken with the carbon atoms to which they are attached they may form a ring in which MR represents the structure: o0 -OCH

-OCF

2 O- or Z is S(O)n or 0; R 1 is H, F, CHF 2 CHFC1, or CF 3

R

2 is Cl-C3 alkyl, Cl-C3 alkoxy, or NR 3

R

4

R

3 is H or C1-C3 alkyl; R 4 o0 is H, C -C3 alkyl, or R 5 CO; R 5 is H or C1-C3 alkyl; and n is an integer of 0, 1 or 2; X and Y are hydrogen; comprising, reacting a benzoylacetonitrile or c-nitroacetophenone having the structure: o L o0 0. C-CH 1 0 0 0

R

wherein L, M, R, and N are as described above with 2,2-di(C 1

-C

4 oo? alkoxy)ethylamine, at an elevated temperature, to yield an ca-[2,2-di(C -C 4 alkoxy)ethylamino]-3-cyanostyrene or a-[2,2-di(C 1

-C

4 alkoxy)ethylamino3-P-nitrostyrene having the structure: KEH/198f 2C N-CHC loy H C 2

CH(

1

-C

4 aloy 2 wherein L, M, R, and W are as described above and treating the thus formed ax-[2,2-di(C 1 -0C 4 alkoxy)ethylaminoJ-p-cyanostyrene or cx-E2,2-di(C 1

C

4 alkoxy)amino)-j3-nitrostyrene with a mineral or organic acid to yield the desired arylpyrrole.

The term C 4 -C 6 cycloalkylamino carbonyl means a C 4 to C 6 cycloalkylamino group attached directly to the carbonyl group through the nitrogen atom.

A preferred group of novel arylpyrroles of the present invention are illustrated by formula II: x a 00 N 0R 000000 6 0 0000 0 0 0 0 0000 00 0 0 00 o oo 0 0 wherein A, L, M, R, W, X and Y are as described above.

0 00 0n 0 a 0 0100 00 0 0 00 0 a G0 0bo 0 0000 KEH /I 98f 4 n I---R ,i

,I

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

(III)

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

Another group of preferred arylpyrroles of the invention are depicted by formula IV: 9 0 09 r Q 0 9 o o 9o9o9 €0 9 0 0 0 O9 0 6 9 9 a n

(IV)

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

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

(V)

wherein A, L, M R, W, X and Y are as described above; 4 and still other preferred arylpyrroles of the invention are depicted by formulas VI and VII: x o x Y R R y N (VI) (VII) o o wherein A, L, M, R, W, X and Y are as described above.

Preferred formula I arylpyrroles of the o'o' invention are those in which A is hydrogen or C -C °o 90 alkoxymethyl; W is CN or NO 2 L is hydrogen or F; X and Y are each Cl, Br or CF 3 M is H, F, Cl or Br; and R is F, Cl, Br, CF 3 or OCF 3 o Preferred formula II compounds which are especially effective as insecticidal, acaricidal and/or nematicidal agents are those in which A is hydrogen or S 20 C-C 4 alkoxymethyl; L is hydrogen; M is hydrogen, F, Cl or Br; R is F, Cl, Br, CF 3 or OCF 3 W is CN and X and Y are each independently Cl, Br or CF 3 0 9 Other formula II compounds that are highly ,0 effective as insecticidal, acaricidal and/or nematicidal agents are those in which A is hydrogen or

C

1

-C

4 alkoxymethyl; L is hydrogen; M is hydrogen, F, Cl or Br; R is F, Cl, Br, CF 3 or OCF 3 W is NO 2 and X and Y are each independently Cl, Br or CF Illustrative of some of the insecticidal, acaricidal and nematicidal arylpyrroles of the present invention are: 4,5-dichloro-2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile; 4,5-dichloro-2-[E-(trifluoromethoxy)phenyl]pyrrole-3carbonitrile; j: 4-bromo-5-chloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile; 5-broxno-4-chloro-2- 4-dichiorophenyl) pyrrole-3-carbonitrile; 4, 5-dichloro-2- (o-chlorophenyl) pyrrole-3-carbonitrile; 2- (R-bromophe.,yl) 5-dichloropyrrolea-3-carbonitrile; 4, 5-dichloro-2- a, a-trif luoro-pD-tolyl) pyrrole-3carbonitrile; 4, 5-dibromo-2- a, a-trif luoro-p-toly!) pyrrole-3-carbonitrile; 4, 5-dibromo-2- (Q-chlorophenyl) pyrrole-3-oarbonitrile; 4, 5-dibromo--2- (p-chlorophenyl)pyrrole-3-carbonitrile; 04, 5-dichloro-2- 4-dichiorophenyl) pyrrole-3-carbonitrile; 4, 5-dibromo-2- 4-dichiorophenyl) pyrrole-3-carbonitrile; a a 2,3-dibromo-4-nitro-5-phenylpyrrole; 2-(P-bromophenyl) 5-dichloro-3-nitropyrrole; 2, 3 -dichloro-4 -nitro- 5 (a,c,-tri f uoro-p-tolyl) 00 20 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-.riitropyrrole; 2-bromo-3-chloro-5- (p-chloropheny1l, -4-nitropyrrole; 2, 3-dibromo-5- (p-chlorophenyl-4-nitropyrrole; 2, 3-dichloro-4-nitro-5-pheiylpyrrole; 3-bromo-2-chloro-4-litro-5- (a,a,a-trifluoro-p-tolyl) pyrrole; 5-Chloro-2- 4-dichiorophenyl) -1-(methoxymethyl) -4- (trifluoromethyl) pyrrole-3-carbonitrile; 5-Bromo-2- (M-fluorophenyl) -3-nitro-4- (triflucromethyl) pyrrole; 2-(p-chlorophenyl) (trifluorornethyl) pyrrole-3-carbonitrile; -6- (m-fluorophenyl) -4-nitro-2- (trifluoromethyl) pyrrole; 4-Bromo-2- (p-chlorophenyl) -1-(ethoxytnethyl) (trifluoromethyl) pyrrole-3-carbonitrile; 4-Chloro-2- 5-dichloro-4-xnethylphenyl) (trifluoromethyl) tyrrole; 2-(2-Bromo-4-chlorophenyi) -l-(2-propynyl) fluoromethyl) pyrrole-3-carbonitrile; 2-(2,5-Difluorophenyl) -3-nitro-4, methyl) pyrrole; o (Trifluoromethoxy)phenyl]pyrrole-2, 4-dicarbonitrile; 0000 5- (p-Dimethylarciinophenyl) -4-nitropyrrole-2-carbo- O 0~ nitrile; 3-Bromo-5- (p-chlorophenyl) pyrrole-2 ,4-dicarbonitrile; 4,-Bromo-2- (p-chllorophenyl) -5-nitropyrrole-3-carbo- 0 0 00 5- (p-Methylthiophenyl) (trifluoromethyl) pyrrole-2, 4dicarbonitrile; 00 fluoromethyl) pyrrole-2 -carbonitrile; 4-Chloro-2- (p-chlorophenyl)pyrrole-3-carbonitrile; 00 2-(M-Methanesulfonylphenyl)-4-(trifluoromethyl)pyrrole 0 04 25 2- (3-chloro-4-methvlpheriyl) -l-methyl-3-nitro-4- (trifluorcmethyl) pyrrole; 2-Phenylpyrrole-3 4-dicarboriitrile; (p-Ethanesulfinylphenyl) -4-ritropyrrole-3-carbonitrile; 2-Bromo-5-phenylpyrrole-3 ,4-dicarbonitrile; 5-dichlorophenyl) -4-nitropyrrole-3carbonitrile; I1-Benzyl-4-nitro-5- (p-chlorophenyl) (trifluoromethyl) pyrrole-3 -carbonitrile; (M-bromophenyl)pyrrole-3-carbonitrile; wherein X is F, Cl, Br, I, or CF 3 Y is F, Cl, Br, I, CF 3 or CN; W is CN or NO 2 and A is H; C 1 -C 4 alkyl optionally substituted with from one "to three halogen /12 -7- 2-Bromo-l- (p-chlorophenoxy) methyl-5- (P-chlorophenyl) -3-nitropyrrole; 2, 4-Dibromo-5-phenylpyrrole-3-carbonitrile; (p-Bromnophenyl) 4-dichloro-3-nitropyrrole; 2-Bromo-5- (3-bromo-4-methylphenyl)-1- (Il-propyloxy) methyl-4- (trifluoromethyl) pyrrole-3-carbonitrile; (p-chlorophenyl) -3-nitro-4- (trifluoroiaethyl) pyrrole; 105-[rn-(Difluoromethoxy) phenyl] (trifluoromethyl) pyrrole-3 -carbonitrile; 0 05- 3-Dichlorophenyl) -l-methoxymethyl-3-nitro-2- 9 r 0(trifluoromethyl) pyrrole; 0" 4-Chloro-5- (p-napthyl) (trifluoromethyl) pyrrole-3- 0 a carbonitrile; 3-Bromo-2- 4-dichlorophenyl) -4-nitro-5- (trifluoroo009 5- (2-Bromo-5-ethylphenyl) 4-bis- (trifluoromethyl) pyrrole-3-carboriitrile; l-Ethyl-2-(p-fluorophenyl)-4-nitro-3,5-bis-(trifluoromethyl) pyrrole; 6-Dichlorophenoxy)methyl] (m-chlorophenyl) o 00 3-Niro-5pyrrole-2 ,3-dicarbonitrile; 000 Nto a,c-tri fluoro-p-tolyl) pyrrol e -2-carbo 00 25 nitrile; (4-chloro-2-methylphenyl) pyrrole-2 ,3dicarbonitrile; 4-dibromophenyl) -2-nitropyrrole-3-carbo- A nitrile; (1-Methoxy) ethyl] (Q-chlorophenyl) (trifluoromethyl) pyrrole-2 ,3-dicarbonitrile; (p-Isopropylphenyl) -2-nitro-4- (trifluorometiTl) pyrrole-3-carbonitrile; 4-difluoromethylenedioxyphenyl) pyrrole- 3-carbonitrie; grounds, food supply or habitat with an -insecticidally, nematicidally and acaricidally effective amount of an arylpyrrole compound as defined in claim 13 or compositions as defined in claims 14 to 16.

18, A method for protecting growing plants from attack by insects, nematodes and acarina, comprising applying to the foilaqe of said plants or -/3 -8 00 00 0 000 0 00 06 0 006Q00 0 0 0006 0 0 0000 00 0 0 00 6 00 o oo 00 6 0 00 0 00 00 6 0 60 00 00 0 00 06 0 0 60 0 00 3-Bromo-2- (3-chloro-4-cyalophel) -4-nitropyrrole; 4-dichlorobenzyloxy)methyl] (m-bromophenyl) pyrrole-4-carbonitrile; 2- 5-Dichloro-4-methylphelyl) -4-nitro-3-triLfluoromethylpyrrole; 2-Phenylpyrrole-3, 4-dicarbonitrile; 2- (2-Bromo-4-chlorophelyl) -4-nitropyrrole-3-carbonitrile; 2-Bromo-5-pheflylpyrrole-3, 4-dicarbonitrile; 1.0 5-Chloro-2- 4-dibromophenyl) -l-methyl-4-nitropyrrole- 3-carbonitrile; 2- (p-Chlorophenyl-5- (trifluoromethyl) pyrrole-3 ,4dicarbonitrile; 2-(o-Bromophenyl) -4-nitro-5- (trifluoromethyl) pyrrole-3carbonitrile; (3-chloro-4-methoxy) pyrrols-2-carbonitrile; 3-Bromo-5- (I-bromophenyl) -2-nitropyrrole; 3, 4-Dibromo-5- (3 ,4-dichlorophelyl) pyrrole-2-carbonitrile; 20 2- (3-Chloro-4-cyalophelyl) -5-nitro-3 ,4-dichloropyrrole; 3-Chloro-l- (p-methoxybenzyl) 4-difluorophenyl) -4- (trifluoro-methyl) pyrrole-2-carboflitrile; 3-Bromo-5- 5-dibromo-p-tolyl) -2-nitro-4- (trifluoromethyl) pyrrole; 3,3-Trichioroally) (R-chlorophenyl) -3-(trifluor- Iomethyl) pyrrole-2-carboflitriL'L- 2- (p-Iodophenyl) -5-nitro-4- (trifluoromethyl) pyrrole; (L-isopropylphenyl) (trifluoromethy)) pyrrole-2-carbonitrile; 3-Bromo-l-methyl-2- (3-f luoro-4-methylphenyl) -2-nitro- 3- (trifluoromethyl) pyrrole; (R-Bromophenyl) -i-isopropyl-3 ,4-bis- (trifluoromethyl) pyrrole-2 -carboriitrile; 2- 4-Dichloro-4-methylthio) -5-nitro-3 ,4-bis- (trifluoromethyl) pyrrole; t

-J

9- 00 00 000000 0 0 0 a 0 00 0 9 0 0 00 (m-Difluoromethoxyphenyl) pyrrole-2, 3-dicarbonitrile; (3-Bromo-4-cyanophenyl) -2-riitropyrrole-3-carbonitrile; (p-bromophenyl) pyrrole-2 ,3dicarbonitrile; 6-dichloro-4-methylthio) -2-nitropyrrole-3carbonitrile; 1-1 (R-Bromophenoxy) methyl 1-5- (M-trifluoromethyl) -4- (trifluoromethyl) pyrrole-2 ,3-dicarbonitrile; 5- (a-Naphtuhyl) -2-nitro-4- (trifluoromethyl) pyrrole-3carbonitrile; (3-bromo-4-trifluoromethylphelyl) pyrrole-2carbonitrile; 3-Chloro-2- 3-dichiorophenyl) 15 5- (m-Cyanophenyl) (trifluoromethyl) pyrrole-2-carbo"nitrile; 2- (3-Bromo-4-isopropoxy) -5-nitro'-3- (trifluoromethyl) pyrrole; (p-Chlorophenyl) pyrrole,-2 ,4-dicarbonitrile; 2- 4-Dichiorophenyl) -5-nitropyrrole-3-carbonitri-e; 4-dichiorophenyl)n orrrole-2 ,4-dicarbonitrile; 4-Bromo-2- 4-dichiorophenyl) -5-nitropyrrole-3carbonitrile; 5- 4-Dibromopheiyl) -3-(trifluoromethyl) pyrrole-2 ,4dicarbonitrile; 2- (m-Chloropheny1) -5-nitro-4- (trifluoromethyl) pyrrole- 3-carboriitrile; 5-Bromo-3- 5-dichloro-4-di-fluoromethoxyphenyl) pyrrole-2-carbonitrile; 2-Bromo '12, 5-dibromophenyl) 2, 3-Dibromo-4- (p-chlorophenyl) 2, 3-Dichlroro-4- 5-difluorophenyl) 5-Bromo-3- (:-chlorophenyl) -l-hydroxyethyl-4- (trifluoromethyl) pyrrole-2-carbonitrile; Ii

I

V

5845/3 2-Chloro-5-nitro-3-(trifluoromethyl) (r-trifluoromethyiphenyl) pyrrole; 3- (3-Bromo-4-chiorophenyl) -5-(trifluoromethyl) pyrrole- 2 -carbonitrile; 53- (3-Chloro-4-fluoropheiyl) -2-nitro-5- (trifluoroinethyl) pyrrole; 4-Bromo-3- (p-chlorophenyl) -l-methylthiomethyl-5- (trifluoromethyl) pyrrole-2-carbonitrile; 0%3- (4-Bromo-3-cyanophenyl) -4-chloro-2-riitro-5- (trifluoromethyl)pyrrole; 4- (p-Chlorophenyl) 3-bis- (trifluoromethyl) pyrrole-2- 0 carboriitrile; 3 -(2,3-Dichlorophenyl) -2-nitro-4,5-bis-(trifluoromethyl) pyrrole; 3- 4-Dichlorophenyl)pyrrole-2 4- (2-Bromo-4-methylphenyl) -5-nitropyrrole-2-c-arbo- 0 nitrile; 3-Bromo-4- 5-dichloro-4-methylthiophenyl) pyrrole- 2, 4-(m-Bromophenyl)-3-chloro-5-nitropyrrole-2-carbonitrile; 3- (R-Acetamidophenyl) (trifluoromethyl) pyrrole-2, dicarbonitrile; 4- (m-Bromopheny1) -5-nitrO-3- (trifluoromethyl) pyrrole-2carbonitrile; 4-Chloro-3- 4-dichiorophenyl) (-propenyl) pyrrole- 2-carbonitrile; 3-Bromo-4- (p-dimethylaminophenyl) 1- 4-Dichlorobanzyl (p-chlorophenyl) (trifluoromethyl) pyrrole-2-carbonitrile; 2-Nitro-3- (p-tetrafluoroethoxyphenyl) (trifluoromethyl) pyrrole; 3- (3-Bromo-4-i-propylphenyl)pyrrole-2 ,4-dicarbonitrile; 4- (p-Ethylsulfonylphenyl) -5-nitropyrrole-3-carbonitrile; (2-methoxyethyl) 6-trichiorophenyl) pyrrole-2 ,4-dicarbonitrile; 2-Chloro-4- 3-dichiorophenyl) -5-nitropyrrole-3carbonitrile; 3- (p-Fluorophenyl) (trifluoromethyl) pyrrole-2, 4dicarbonitrile; 4- (p-Iodophenyl) -5-nitro-2- (trifluoromethyl) pyrrole-3carbonitrile; 5-Chloro-4-[p- (N-methylacetamido) phenyl]pyrrole-2carbonitrile; 5-Bromo-4- (2-bromophenyl) -l-propargylpyrrole-2-carbo- 0~ nitrile; 2-Bromo-3- (Q-bromophenyl) 4-(p-Chlorophenyl) -3,5-dichloro-l-(2,3 ,3-trichloroally) pyrrole-2-carbonitrile; .0 3-Bromo-5-chloro-4- (p-chlorophenyl) -2-nitropyrrole; 5-Bromo-4- 2-dichloro-l, 1-difluoroethoxy) phenyl I (trifluoromethyl) pyrrole-2-carbonitrile; 2-Chloro-3- (2-bromo-4-ethylthiophenyl) -5-nitro-4- (trifluoromethyl)pyrrole; proe 2-carbonitrile; 1-Cyano-3- 4-dibromophenyl) -5-nitro-2- (trifluoromethyl) pyrrole; 3-Bromo-l-methoxymethyl-4-(m-trifluoromethyl)-5-(trifluoromethyl) pyrrole-2-carbonitrile; 3(p-Chlorophenyl) -4-iodo-5-nitro-2- (trifluoromethyl) pyrrole; 4- (p-Bromophenyl) (1-ethoxy) ethyl] 5-di- (trifluoromethyl) pyrrole-2 -carbonitrile; 3- (2-Bromo-4-methoxyphenyl) -5-nitro-2, 4-di- (trifluoromethyl) pyrrole; 3- (p-Chlorodifluoromethoxyphenyl) pyrrole-2 nitrile; 3- (p-Isobutyrylaminophenyl) -5-nitropyrrole-2-carbo- Ks.

-12 nitrile; 3-Bromo-4- 4-dimethoxyphelyl) pyrrole-2 nitrile; 4-Chloro-3- (p-chlorophenyl) -i-aisopropyloxycarbonylmethyl) -5-nitropyrrole-2-carboflitrile; 3- (Q-Bromophenyl) 4- (trifluoromethyl) pyrrole-2, dicarbonitrile; 1- (2-Chioroethyl) 4-dichiorophenyl) (trifluoromethyl) pyrrole-2-carbonitrile; 4- (4-Bromo-3-trifluoromethoxyphelyl) -3-chloropyrrole-2o carbonitrile; A 3-Bromo-4- 4-dichiorophenyl) -1-isopropyl-2-nitropyrrole; 4- (3-Methoxy-4-cyanophenyl) (trifluoromethyl) pyrrole -2 -carbonitrile; o A 1- 4-Dichlorobenzyl) (2-methyl-4-iodophenyl) -2o nitro-3-trifluoromethylpyrrole; 1-Methyl-4-[3 ,5-di (trifluoromethyl) phenyl]pyrrole-2 .3- A dicarbonitrile; A ACA 20 4-(3,4-Dichloropheny)-2-flitropyrrole-3-Garboflitrile; (M-Bromophenyl) 2, 3-dicarbonitrile; 5-Bromo-4- 6-dichloro-4-methalesufilphely)2nitropyrrole-3-carbonitrile; 4-(p-Chlorophenyl) ,2-trifluoroethyl) fluoromethyl) pyrrole-2, 3-dicarbonitrile; 4- 5-Dichiorophenyl) -2-nitro-5- (trifluoromethyl) pyrrole-3-carbonitrile; 2 -Chloro-4 -chloro-4 -N-methylacetamidophenyl) pyrrole-3-carbonitrile; 2-Bromo-4- (3-bromo-4-n-propylphelyl) -3-nitropyrrole; 2, 5-Dichloro-4- 5-dichloro-4-methylthiophelyl) pyrrole-3-carbonitrile; 2, 5-Dibromo-1- 4-dibromophenoxymethyl) (p-chloro-J alkyl, 01-0 3 alkoxy, or NR 3 R 4

R

3 is H or 01-03 alkyl; R 4 is H,.C 1 -C 3 alkyl, or R 5 0CO; R 5 is H or C01-0 3 alkyl; and n is an KEH/198f -13 phenyl-4-nitropyrrole; 4-(3-Bromo-4-cyanophelyl) -2-chloro-5- (trifluoromethyl) pyrrole-3-carbonitrile; 2-Bromo-l-methyl-3-flitro-4- (cr,a,ac-trifluoro-R-tolYl) pyrrole; 4- (R-chlorophenyl) (I-butyloxymethyl) (trifluoromethyl) pyrrole-3-carbonitrile; 4- 4-Methylenedioxyphenyl) -3-nitro-2- (trifluoromethyl) pyrrole; 5-Chloro-4- (3-chloro-4-trifluoromethoxyphelyl) (trifluoromethyl) pyrrole-3-carbonitrile; 2-Bromo-3- 4-dichiorophenyl) -l-ethylthioinethyl-4oo* nitro-5- (trifluoromethyl) pyrrole; 4-R(tetrafluoroethoxy) phenyl] 5-di- (trifluoro methyl) pyrrole-3-carbonitrile; 3-(3-Bromo-4-acetoxyphenyl) 4-dichiorophenoxymethyl) -4-nitro-2 ,5-di- (trifluoromethyl) pyrrole; -(R-Bromophenyl) (2-methoxy) ethyl]pyrrole-2,3dicarbonitrile; 4- (M-Isopropionamidophenyl) -3-ni.tropyrrole-2-carbonitrile 5-Bromo-4- (2-chloro-4-methylthio) pyrrole-2 ,3-dicarbo- 5-Chloro-4-(p-chlorophenyl)-l-hydroxyethyl-3-nitropyrrole-2-carbonitrile; 4- 5-Dibromo-4-cyanophenyl) (tr,.2luoromethyl) I. pyrrole-2, 3-dicarbonitrile; 4- (4-Chloro-2-methylphenyl) -l-isopropylthiomethyl-3nitro-5- (trifluoromethyl) pyrrole-2-carbonitrile; 5-Bromo-4- 4-dichiorophenyl) -1-(difluoromethyl) pyrrole-3 -carbonitrile; 2-Chloro-3- (M-difluoromethoxyphenyl) -4-nitropyrrole; 351- 4-Dibromophenoxymethyl) (M-chlorophenyl) a]lkyl C-C 3 al koxy, or NR R R 3 i s H or C-C 3 Mlkyl R i s H, *C-C 3 al kyl or R CO; R 5 i s H or C, -C al kyl; and n is an integer of 0, 1 or 2.

KEH/198f

I

-14 fluoromethyl) pyrrole-3-carbonitrile; 3- (3-Bromo-4-ethoxy) -4-nitro-2- (trifluoromethyl) pyrrole; 3- 6-Trichiorophenyl) pyrrole-2, 4-dicarbonitrile; 3- (4-Bromo-3-chlorophenyl) -1-(difluoromethyl) -4-nitropyrrole-2-carbonitrile; 5-Bromo-3- (R-chlorophenyl) -1-(isobutyloxymethyl) pyrrole-3-carbonitrile; 3- (4-Bromo-3-methylphenyl) -5-chloro-4-nitropyrrole-2carbonitrile; 3- (2-Naphthyl) (trifluoromethyl) pyrrole-2 ,4-dicarbo- ,nitrile; 3- (3-Cyano-4-methylphenyl) -l-methyl-4-nitro-5- (trit fluoromethyl) pyrrole-2-carbonitrile; 2, 3-dichloro-5- 4-dichiorophenyl) -4-nitropyrrole 2- 5-dibromo-4-methoxyphenyl) 5-dichloropyrrole-3carbonitrile; 00 2,3-dichloro-4-nitro-5-(2,4,6-trifluorophenyl) pyr~role; 0 00 20 4,5-dibromo-2 3,6-trifluorophenyl) -3-carbonitrile 4, 5-dichloro-2-(3, 4-dichiorophenyl) -1-(ethoxymethyl) 6 0 pyrrole-3 -carbonitrile; 4, 5 -dibroino- 1-methyl -2 a, a-tri fluoro-p-tolyl) 6* 6 0 pyrrole-3-carbonitrile; 4, 5-dichloro-2- 4-dichiorophenyl) -1-ethylpyrrole-3carbonitrile; 2, 3-dichloro-4-nitro-5-[p- (trifluoromethoxy) phenyl] pyrrole; 4 4, 5-dichloro-2-[a- (trifluoromethoxy) phenyl]pyrrole-3carbonitrile; 4, 5-dichloro-2- 4-dichiorophenyl) -1-methylpyrrole-3carbonitrile; 2, 3-dichloro-5- (p-chlorophenyl) -1-methyl-4-nitro and pyrrole; N. cL-2,2-di(C -C 4 alkoxy)ethylamino-3-cyalostyree or c-2,2-di(C-C 4 alkoxy)ethylamino-3-itrostYrele having the structure:

L.

KEH/198f 4-bromo-5-chloro-2- (p-chlorophenyl) -l-methylpyrrole-3 carbonitrile.

5-chloro-2- (3 ,4-dichlorophenyl) -4-fluoropyrrole-3carbonitrile 2-bromo-5- (p-chlorophelyl) -1-(ethoxymethyl) -4-fluoropyrrole-3 -carbonitrile (p-chlorophenyl) -2-fluoro-4-nitropyrrole The a-[2,2-di(C 1 -C 4 alkoxy.)ethylamino]-i-cyanostyrene and a-[2,2 -di (C- 4 alkoxy) ethylamino] -P-nitrooftiPnvnir are depicted by the following structural formula: o0 0 0

L

'S 0

C=CHW

I

0. oR NH-CH 2

CH(C

1

-C

4 alkoxy), wherein W is CN or NO 2 L is H, F, Cl, or Br; M and R are eachindependently H, C -C3alyc_3 ko, C 1 -C 3 alkylthio, c 1 -C 3 alkylsulfinyl, C i- C 3 alkylsula, 0fonyl, cyano, F, Cl, Br, I, nitro, CF 3

R

1 CF 2 Z, R 2

CO,

or NR 3R 4and when on adjacent Positions and taken together with the carbon atoms to which they are attached M and R may form a ring in which MR represent the structure: -OCHO01- rr or Zi r0 Z isS(On o 0; is H, F, CHF 2 CHFC1, or CF; R 2 is ClC 3 alkyl, C 1 -C 3 alkoxy, or NR 3 R 4 R 3 is H orc 353 alkyl R 4 isn- C lyo CO sHo KEH/1 981' -16 A preferred group of #-(substituted)styrene compounds of the p..ent-ixwen-t-1ona have the aboveillustrated structure wherein W is CN; L is H, Cl or Br; M is H, F, Cl, Br or OCH 3 R is H, F, Cl, Br, CF V NO 2

OCF

3 or OCH 3 or when on adjacent positions and taken together with the carbon atoms to which they are attached M and R may form a ring in which MR represents 09 the structure: 01 ilustateAnother preferred group of #-(substituted)styenecompounds ef this Invention have the aboveilusrae structure wherein W is NO 2 L is H, Cl or Hr is H, F, Cl, Br or OCH 3 R is H, F, Cl, Br, CF V NO 2 OCF 3 or OCH 3 or when on adjacent positions and 4 taken together with the carbon atoms to which they are attached M and R may form a ring in which MR represents the structure: 0 0 While t~i-1compounds off thae proesent inupntinip are referred to above as R-cyanostyrenes and 6-nitro- 6 styrenes, they may also be named as dialkyl acetals.

.A A (4-3s5 -17 Some of the preferred dialkyl acetal compounds ~-t*--inomt~are and (lR-chloro-fl-[(formylmethyl) amino~cinnamonitrile diethyl acetal; (2)fi-[I(formylmethyl) amino) 4-dimethoxycinnamonitrile diethyl acetal; -methyl p-(2-cyano-l-[ (formylmethyl) amino] vinyl~benzoate diethyl acetal; (formylmetthyl) amino) -1-naphthaleneacrylonitrile diethyl acetal; (formylmethyl)amino]-2-methylcinnamonitrile diethyl. acetal; (formylmethyl) -2-methyl-a- (nitro- 10 methylene)benzylamine diethyl acetal; (7)N-(formylmethyl)- 4-dimethoxy-r- (nitromethylene) benzylamine diethyl acetal; N- (formylmethyl) (nitromethylene) -2-naphthalenemethylamine diethyl acetal; (9)methyl R-ta-[(formylmethyl) amino) -f-nitrovinyl)benzoate p- (diethyl acetal); (lO)N- (formylmethyl) 4-dimethoxy-Q- (nitromethylene) benzylamine dimethyl acetal; (11) and 2-chloro-p- [(formylmethyl)amino]cinnamonitrile dimethyl acetal; dimethyl acetal; (13)3, 4-dichloro-p-[ (formylmethyl) amino]cinnamonitrile diethy. acetal; and (14)R- trifluorornethyl- (formylmethyl) amino~cinnamonitrile diethyl acetal.

The P-cyanostyrenes, also referred to as cinnamonitrile dialkyl acetals, can be prepared by the reaction of a substituted or unsubstituted benzoyl acetoriitrile with a 2,2-di(C -C 4 alkoxy)ethylamine in the presence of an aromatic solvent to form the a-(2,2di (C 1 -C 4 alkoxy) ethylamino) -R-cyano,- (substituted) styrene which then may be converted to a 2-(substituited-phenyl)-

AI,

pyrrole-3-carbonitrile by reaction of said fl-3-cyano- (substituted) styrene compound with trifluoroacetic acid.

Chlorination of the thus prepared cyanophenyl pyrrole with sodium hypochlorite or sulfuryl chloride in an inert solvent yields the insecticidal, acaricidal, and

JIL

4,5-dichloro-2-[p-(trifluoromethoxy)phenyl]pyrrole-3carbonitrile; I i- -I -:i 18 nematicidal 4,5-dichloro-2-(substituted-phenyl)pyrrole- -3-carbonitrile. The conversion to the pyrrole intermediate may also be achieved by substituting concentrated HCl at a temperature between about 20 and 40 0 C. The reactions may be graphically illustrated as follows: o 00 0 9 9 0 9 00 9 99 09 9~

L

0 10 ri R& \-C

H

2

NCH

2

CH(OC

2

H

5 2 omatic Solvent N -/CN

O-R

6 R N L H O-R 6 I and E 4CF 3 COLIH or

HCI

0 00 0 09 NaOC1 or

SOEC]

2 or Br 2

A-I

L

R

H

i 2- (R-chlorophenyl) (trifluoromethyl) pyrrole-3-carbonitile -19 wherein A is hydrogen, C -C 4 alkyl optionally substituted with one C 1 -Ca alkoxy, one C 1

-C

4 alkylthio, from one to I. three halogen groups, or phenyl optionally substituted with one or two C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or halogen groups; C- C 4 alkenyl optionally substituted with from to three halogen groups; or C 3 -C 4 alkynyl; X is Cl or Br; Ri3 C -C 4 alkyl and L, R and M are as described above.

0 000 0 00 000 *0 0 300 0 04 pyrrole-3-carbofitrile; 352-Chloro-5- (M-bromopheflyl) pyrrole-~3-carbofitrile; II 20 .Certain novel arylpyrrole- compounds of formula I, wherein A is hydrogen; W is CN and X, Y, L, M and R are as described above, can be prepared by reacting N-formyl-DVL-phenyl--glycine or a substituted N-formylpheny-lglycine represented by the structure formula VIII: 00 00 0 009 00000~.

0 0 0 000009 9 0 0$194 0 0 0000 00 0 0 00 0 co 0 09 00 0 0 00 0 00 00 0 00 L zC0 2

H

CH

N- NHCH-=0 VI II a 000 00 0 wherein L is H, F, Cl or Br; R and M are each independently H, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, C 1 -C 3 alkylsulfinyl, C 1

C

3 alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF V R 1 CF 2 Z, R 2 CO or NR 3R 4and when on adjacent positions and taken together with the carbon atoms to which they are attached, M and R .nay f orm a ring in which MR represents the structure: -0OCH 2

-OCF

2 0ll r_ 4-Chloro-5-(3,4-difluoromethylenedioxyphenyl)pyrrole- 3-carbonitrile;

B

r :n j I -il- 21 Z is S(0)n or 0; R1 is H, F, CHF 2 CHFC1 or CF3; R2 is C1-C 3 alkyl, C1-C3 alkoxy or NR3R4; R 3 is H or C1-C3 alkyl; R4 is H, C1-C3 alkyl or R5CO; R 5 is H or C1-C3 alkyl and n is an integer of 0, 1 or 2; with at least an equivalent amount of a 2-chloroacrylonitrile and two to three equivalents of acetic anhydride. The reaction is conducted at an elevated temperature, preferably about 700 to 1000C.

The reaction can be illustrated as follows: 09 a 0 001qt( O 0 0111 0 Do a coo 0P I 0 0 000I O O4 0" *a 0 0 000 0 000 0 00 00 0 0 0 0 o 00 C0 2

H

CH

NHCH=0 C1 c 2 0 CH,=C-c N

CN

L

RM

(VIII)

LU

Conversion of the thus prepared 2-phenylpyrrole-3-carbcoitrile or 2-(substituted phenyl)pyrrole-3-carbonitrile to the corresponding formula II, 4-halo, 5-halo or 4,5-dihalo-2-(substituted phenyl)pyrrole-3-carbonitrile, is readily achieved by reaction of the above said 2-phenylpyrrole-3-carbo.Ltrile or 2-(substituted phenyl)pyrrole-3-carbonitrile with at least about 1 or 2 equivalents of a sulfuryl halide, bromine or chlorine, in the presence of a solvent such 30 as dioxane, THF, acetic acid or a chlorinated hydrocarbon solvent. For preparation of a monohalo pyrrole-3carbonitrile uie of about 1 equ.valent of the halogen-, ating agent is required; whereas, preparation of a dihalo pyrrole-3-carbonitrile requires 2 to 3 ii A 2-(3,4-Dichloro-4-methylthio)-5-nitro-3,4-bis-(trifluoromethyl)pyrrole; ia

:F

VS

22 equivalents of said halogenating agent. When sulfuryl chloride or sulfuryl bromide is used the reaction is generally conducted at a temperature below about and preferably between about 0° and 30 0 C, but when elemental bromine is employed, the reaction is usually conducted at about 30-40 C. Other effective halogenating agents that may be employed in these reactions include sodium hypochlorite, t-butylhypochlorite, N-bromosuccinimide, N-iodosuccinimide and the 10 like. The reaction may be illustrated as follows: one 0 0 0 s0 0 0 0 Q o a0 00 0 o

CN

L

N

M

H

R

Br 2 Cle, S0 2

(X)

2 HOfc X CN H

(II)

The formula II carbonitrile compounds of the 0o., present invention may also be prepared from the reac- .0 o tion of a substituted or unsubstituted benzoyl acetoi'trile with a 2,2-di(C1-C4 alkoxy)ethylamine in the presence of an aromatic solvent to form the a-(2,2-di- (C1-C 4 alkoxy)ethylamino)-p-cyano-(substituted)styrene which is then converted to the 2-(substituted-phenyl)pyrrole-3-carbonitrile of formula II by reaction of said p-3-cyano-(substituted)styrene compound with trifluoroacetic acid or with concentrated HC1 at a temperature between about 200 and 40 0 C. The reactions may be graphically illustrated as follows: 5-Bromo-3- (p-chlorophenyl) -l-hydroxyethyl-4- (trifluoromethyl) pyrrole-2-carbonitrile; J~i 23

H

2

NCHPCH(OC

2

H

5 2 r omatic Solvent o 0 0 0 0 j 0 r 04 0 09 m e 0 0 q ~0 M CN O-R 6 NZ O R L H OR

{CF

3

CO

2 H or HC1

L

M

N

H

R

wherein R 6 is C 1 -C 4 alkyl and L, R and M are as described above.

Also in accordance with the present invention formula II 3-nitro-2-phenylpyrrole and 3-nitro-2-(substituted)phenylpyrrole compounds can be prepared by reaction of an a-nitroacetophenone or a substituted anitroacetophenone with a 2,2-di(C 1 -C 4 -alkoxy) ethylamine. The reaction is generally conducted in the presence of an inert organic solvent preferably an aromatic solvent, at an elevated temperature to give an a- 2-di (C 1 -C 4 alkoxy) ethylamino) -p-nitrostyrene or a substituted a-(2,2-di(C C 4 -alkoxy)ethylamino)-p-nitrostyrene that is converted to the formula II 3-nitro-2or 3-nitro-2- (subst-ituted) phenylpyrr-ole by treatment with a mineral acid such as hydrochloric

I

4- (E-Ethylsulfonylphenyl)-5-nitropyrrole-3-carbonitrile; 1k 24 or hydrobromic acid. Reaction of the thus prepared nitrophenylpyrrole with sodium hypochlorite in the presence of an inert organic solvent at a reduced temperature yields the formula II 2,3-dichloro-4-nitro- 5-phenyl or The above reactions may be graphically illustrated as follows: 0 0 p 0 o 0 9 0 0 09 0 O 00 9 0 9 o0 0 0 0 9 0o 0 r 0 0o a 00 0r B O

L

C-CH

2

NO

2

H

2 NCHgCH(OC 2 H6)e 0

N-CH

2 CH(0C 2

H

5 2

H

HC1 or CF 3

CO

2

H

INaOC ClI 1 NO 2 H

R

I I

(II)

In addition to the several methods described in the literature for preparing substituted and unsubstituted benzoyl acetonitriles, surprisingly we have found that these compounds may also be prepared by reacting an appropriately substituted benzoyl halide with an alkali metal hydride and an alkyl cyanoacetate, 3 such as t-butyl cyanoacetate, to yield the nitrile; 3-(P-Isobutyrylaminophenyl)-5-nitropyrrole-2-carbo- 1* VT 0 i 25 corresponding t-butyl(benzoyl or benzoyl)cyanoacetate. These reactions graphically illustrated as follows: substituted may be o o o oo S00 0 0 0000 00 0 0 00 0 0 00 00 R 00 *r 00 L 0 M I I IoC-OC CH3) 3 C-C1 NaH OCH2 CH)

S\CN

A B

L

CO-C-CO-OC(CH R CN

C

The thus formed cyanoacetate ester can then be converted to a substituted or unsubstituted benzoyl acetonitrile by heating the compound in toluene containing p-toluene sulfonic acid. The reaction may be graphically illustrated as follows: 0 00 o 000 o a 0 00 0 o 40 4 00a CO-C-CO-OC(CH3)

PTS

I toluene

CN

L

MO

CN

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

B* t l._r .0 pyrrole-3-carbonitrile; 352, 5-Dibromo-1- 4-dibromophenoxymethyl) -3-(p-chloro- 0 26 t-Butvl(benzvl and Substituted benzvl)cvanoacetates 0~~ 00 o oo, 0 0 0 004900 0 0 o 0 0000 00 0 0 04 0 00 0 00 00 0 0 00 0 00 00 0 0 00 00 0 04~ 0-0-00-00

(OH

3 3 O N

L

H

Hi

H

3 -Cl m 3 -Cl

H

3-F

H

5-Cl

R

4-Cl 4-OCF 3 4-Br 4-CF 3 4-F 4- CN 4-CF 3CH 20 4-CH 3 so 2 4-F 4-CH 3S 4-CHF 2 CF 2 0 4-CH 3 0 0- 91-94 31-84 3.13-115 146-147 98-100 127-128 136-139 127-129 91-94 117-119 92-94 0 00 00 0 0 00 00 0 00 0 00

II-

2-Chloro-3- (r-difluororethoxyphenyl) -4-nitropyrrole; 351-(2 ,4-Dibromophenoxymethyl) (m-chlorophenyl) (trifk 27 Benzovl Acetonitriles 0

CH

2

CN

00 0 0~0 040 o 0 0 004,000 0 0 9000 0000 oo a 0 09 0 #9 4, 00 0 0 0 00 0 00 0 0 0 0 00 00 o U 00* 0 04 *0 00 00 0 o 00 4, *0

L

H

3 -Cl

M

H

3 -Cl

H

2-Cl

H

3-F

H

5-Cl

R

4-Cl 4-Cl 2-Ck 4 -OCF 3 4 -CF 3 4-Cl 3 -Cl 4-CN 4-F 4-SO 2 CH 3 4-F 3 -CF 3 4 -CH 3 4 -NO 2 4 -OCH 3 128.5-129.5 105-107 153-55 79-81 44-45 66-67 80-83 126-128 78-80 129-132 74-7 58-60 103 .5-106 119-124 rA pyrrole; and j; 19 n:I 1; i i~ t

'G

sti C g i f i-i n 28 0 o o 0 0 0 000 0 a o 0 06 0 O 0 a 0 0 00 o 0 046 0 0 00 0e o0 0 Preparation of N-substituted formula I arylpyrroles can be achieved by reaction of the appropriately substituted formula I arylpyrrole, wherein A is hydrogen and L, M, R, W, X and Y are as described above, with an appropriate alkylating agent and a suitable base. For example, a brominated hydroxy-C -C -alkyl and potassium t-butoxide. This reaction provides an arylpyrrole having the same substituents as the starting material, but in addition 10 is substituted on the nitrogen with hydroxy-C 1

-C

4 alkyl. In a similar reaction cyanogen bromide is substituted for the brominated hydroxy C 1

-C

4 alkyl and yields the formula I arylpyrrole with a carbonitrile substituent on the nitrogen. The reactions may be illustrated as follows: 0 40* tj U 0>0 0 0 040 a 04 0 0 00 0 44Q M 1) Br Ci-C 4 alcohol K+O-t-Bu or R 2)CNBr wherein L, M, R, W, X and Y are as described for and A is 1) alcohol or 2) C.

formula I above and A is 1) C1-C 4 alcohol or 2) CN.

r i i: ii; ji

J

1 29 6 0 00 0 ,0 9 0 0 o a 0 0 1o o0 o 0 0 0 0 0 00 0 00 00 0 0 00 S0 00 0 00 000 O 00 0 D 0 Preparation of 2-phenylpyrrole 3,4-dicarbonitrile, 2-bromo-5-phenylpyrrole-3,4-dicarbonitrile and substituted phenyl derivatives thereof can be obtained by reaction of fumaronitrile with bromine in the presence of a chlorinated hydrocarbon such as chloroform at an elevated temperature to yield bromofumaronitrile.

The thus formed bromofumaronitrile is then reacted with or a substituted derivative thereof, in the presence of 10 hexamethylphosphoramide at an elevated temperature to yield the 2-phenylpyrrole-3,4-dicarbonitrile. Bromination of the thus prepared 3,4-dicarbonitrile yields the 2-bromo-5-phenylpyrrole-3,4-dicarbonitrile or the substituted phenyl derivative if the substituted 15 is used in the previous reaction. The reaction may be graphically illustrated as follows:

CN

NC

Br2/CHCI 3

/A

(-HBr)

CN

NC Br NC CN

L

S\ HMPA/3 equiv. H 2 0 N TS (-TMS,-HBr,-CH 3

SH)

R

Bre/CHCI, NC CN

L

Br

N

R

The examples provided by way of illustration below utilize the schemes illustrated above and provide z -35 0~ 00 0 0 000000 0 000000 0 0 000 000 00 S00 0 do 00 a means for preparing other compounds of the invention which are not specifically described herein.

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

In practice generally about 10 ppm to about 10,000 ppm and preferably 100 to about 5000 ppm, of the formula I arylpyrrole, which encompasses all of the arylpyrrole isomers of formulas II, III, IV, V, VI and VII, dispersed in water or other inexpensive liquid carrier is effective when applied to the plants, the crops or the soil in which said crops are growing to 15 protect said crops from attack by insects, acarina and/or nematodes. These compounds are also useful for protecting turf grass from attack by pests such as grubs, chinch bugs and the like.

The formula I arylpyrroles of this invention 20 are also effective for controlling insects, nematodes and acarina, when applied to the foliage of plants and/or to the soil or water in which said plants are growing in sufficient amount to provide a rate of from about 0.125 kg/ha to about 4.0 kg/ha of active ingredient. Obviously higher rates of application of the formula I arylpyrroles may be used to protect crops from attack by insects, nematodes and acarina, however, higher rates of application are generally unnecessary and wasteful.

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

The 2-aryl-3-cyano-4,5-dihalopyrroles prepared from the p-cyaro-styrene compounds eof E th-prr eninvcnticn are effective for controlling insects, acarina and nematodes. These compounds are also effective for protecting growing or harvested crops from attack by the 00 o. above-said pests.

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

The above-said halogenated arylpyrroles are Si" also effective for controlling insects, nematodes and 0Oo acarina, when applied to the foliage of plants and/or to o n 20 the soil or water in which said plants are growing.

These halogenated arylpyrrole compounds are usually St applied in sufficient amount to provide a rate of from about 0.125 kg/ha to about 4.0 kg/ha of active ingredient. Obviously higher rates of application of said halogenated arylpyrroles may be used to protect crops from attack by insects, nematodes and acarina, however, higher rates of application are generally unnecessary and wasteful.

i 4 These halo a a y c o ar usually H

R

II

32 Advantageously, the above-said arylpyrroles may be formulated into dry compacted granules, flowable compositions, granular formulations, wettable powders, emulsifiable concentrates, dusts, dust concentrates, microemulsions and the like, all of which lend themselves to soil, water and/or foliage application and provide the requisite plant protection. Such formulations e. include the compounds of the invention admixed with o inert, pharmacologically- acceptable solid or liquid 0 diluents.

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

5 Compacted granules especially useful for soil A 00 or water application can be prepared by grinding together in about equal parts, usually about 3 to 20 parts, of the arylpyrrole and a solid surfactant, with about 60 to 94 parts of gypsum. Thereafter, the mixture is compacted into small granular particles, about 24/48 mesh or larger.

Other suitable solid surfactants useful in the present formulations include not only the anionic dioctyl ester of sodium sulfosuccinic acid but also nonionic block copolymers of ethylene oxide and propylene oxide. Such block copolymers are marketed by BASF Wyandotte Corporation as Pluronic 10R8®, 17R8®, 25R8®, F38®, F68®, F77® or F87®, and are especially effective for the preparation of compacted granules.

i Ij 33 In addition to the powders and concentrate formulations described hereinabove, wettable powders and flowables may be used because they may be dispersed in water. Preferably, such flowables will be applied at the locus with the aqueous compositions being sprayed on the foliage of plants to be protected. These sprays also may be applied to the breeding ground, food supply or habitat of the insects and acarina sought to be controlled.

I 10 Where solid formulations of the arylpyrroles 0" 1 are to be used in combination treatments with other 0 •Q pesticidal agents, the formulations can be applied as an S, admixture of the components or may be applied o sequentially.

Similarly, liquid formulations of the arylpyrrole in combination with other pesticidal agents may be tank mixed or may be applied separately, sequentially, as liquid sprays. Liquid spray formulations of the compounds of the invention should contain about 0.001% 5 h to 0.1% by weight of the active arylpyrrole.

The following examples are presented as illustrations of the present invention.

o .o 0O 0 1 Siiary liui fomlain of_ Kh 1_1~_ 34 EXAMPLE 1 2-Phenvlpyrrole-3-carbonitrile 2

CH

NHCH=O

CI

I

AC

2 0

CH

2

=C-CN

CN

N

H

0 0 0 09 0 o 00 900 a 0 0 0 900 00 0 0 00 0 0 The following procedure is similar to the method given in JOC, 43, 4273-6 (1978). A magnetically stirred mixture of 30.00g of N-formyl-phenylglycine is heated at 90 C for 1 1/2 hours. The clear yellow reaction solution is concentrated in vacuo to give 42.5g of an oily brownish orange semi-solid. Material partially purified by chromatography on silica gel is shown by the proton NMR spectrum to be a mixture of 73% 2-phenylpyrrole-3-carbonitrile and 27% 2-phenyl-3-cyano5-methylpyrrole. Recrystallization 20 once from chloroform and twice from 1,2-dichloroethane gives 1.69g of an off-white solid which proton NMR shows it to be 96% 2-phenylpyrrole-3-carbonitrile, mp 148-152 C.

Microanalysis (MW 168.19): Calcd.: C, 78.55%; H, 4.79%; N, 16.66% Found: C, 78.52%; H, 4.73%; N, 16.54% I -L i ainaio pyrr.o.Le--dL7LVU~IIt.L.t_ L~tujtj.L.mz,

LI

I

35 EXAMPLE 2 4,5-Dichloro-2-phenvlpvrrole-3-carboiitrile--and chloro-2 -phenvlpvrrole-3 -carbonitrile CN C1

C

N CH 2 Cl1 2 ci N1 1 N C N

N

H

o -0 o 0 .000000 0 0 000 00 00 00 a0 0 00 0 0.

o 0 Q 0 0 00 0 0 U 0 To a magnetically stirred ice-water cooled solution of 2.00g (11.9 mmol,) of 2-phenyl-3-cyanopyrrole in 80 mL of methy'lene chloride is added drop- 15 wise over a period of 5 min., 1.90 mL (3.19 g, 23.6 mmol,) of sulfuryl chloride by means of a syringe.

Throughout the addition the temperature is kept between OC and 10 0 C. Stirring at 5-10 0 C is continued for minutes. The reaction mixture is vacuum filtered to remove a precipitated solid (1.28g) identified as chloro-2-phenylpyrrole-3-carbonitrile, mp 192. 5-1950 C.

The filtrate is diluted with 400 mL of ethyl acetate, washed twice with 200 mL of water, dried (sodium sulfate) treated with charcoal, filtered, and then concentrated in vacuo to give (after slurrying of the residue with hexane) 0.60g (21.3% yield) of a pinkpurple solid. This solid is recrystallized from 5 mL of hot acetone to give 0.32g yield) of -2-phenylpyrrole-3-carbonitrile as an orangish brown solid, mp 254-255 0

C.

Max(mull,Nujol): 3165(br 3120(s), 2245(s), 1570(m), 1513(m), 1440(s), 1252(m), 1069(m), 996(m), 920(m), 768(s), 698(s), 665(s) cm- 36 H-NMR(DMSO): 57.73 J=6.6Hz, 1.97H, two phenyl protons at 67.52 J=7.3Hz, 2.04H, two phenyl protons at 87.44 J=7.3Hz, 1.02H, one phenyl proton at C-4).

C-NI4(DMSO): 6137.51 (C-2 pyrrole carbon), 6129.25 (C-4 phenyl carbon), 6129.04 phenyl carbons), 6128.37 CC-1 phenyl carbon) 6125.88 (C-2,6 phenyl carbons), 00 61.2(ihrC5prol rtentiecro) 0 10 6114.32 (either C-5 pyrrole or the nitrile carbon), 00 9Q 06110.72 C-4 pyrrole carbon), 689.78 (C-3 pyrrole :00: carbon).

Microanalysis (MW 237.09): Calcd.: C, 55.72%; H, 2.55%; N, 11.82%* Cl, 29.91% 00000Found C, 55.78%; H, 2.59%; N, 11.12%.; Cl, 29.74% EXAMPLE 3 00 20 P-Chloro'-,df(fEormylm-,ethyl'~aminolcinnamonitrile, diethyl acetal 0toluene

N

mo0 Cl K._CN H 2 N "CH(C~t)2 C~ I- 0 0 -H20 N C)-

H

A magnetically stirred solution of 250.00 g (1.39 rmol,) of Q-chlorobenzoyiacetonitrile, 203 mL (185.95 g, 1.39 mol) of 2,2-diethoxyetb-,Lamine, and4 1300 mL of dried toluene is heated at refux for hours. Water is collected in a Dean-Stark trap (23.8 mL, 95.2% theory). The hot cloudy dark brown solution with a 'large amount of undissolved solids is *filtered through diatomaceous filter aid. After dilution with

'I

styrene tnat is convertea to tne tormuia ii j-nl-ro-zphenylpyrrole or 3-nitro-2-(substituted)phenylpyrrole by treatment with a mineral acid such as hydrochloric 200 mL of EtOAc, the solution is filtered through a 7cm X 13.5cm column of silica gel. The filtrate is concentrated in vacuo to give 354.38 g (86.4% crude yield) of a clear dark oil which slowly solidifies.

This solid is recrystallized from hot cyclohexane to give 324.26g (79.1% yield) of a waxy orange solid. NMR of this product shows it to be composed of 78% and 23% isomeric mixture of p-chloro-p-[(formylmeth- 0o yl)amino] cinnamonitrile, diethyl acetal, m.p. 60-72 C.

o 10 The following analytical data is for another similarly Sprepared sample.

3% H-NMR(chloroform): 67.47 J=8.6Hz, 2.12H, two 20 Max(mull,Nujol)t: 3325(s)E, 3065(m), 2197(s) 1600(s)25H, one1530(s), 1314(m), 1265(m), 1173(m, 1154(m), 1128(s) 1.05H, one methine proton at the acetal carbon], 84.07 1100(s), l 06(s) 022(s), 939(m), 895(m)ot .844(s) 1 768(m), 730(m) cm- 300 0groups).

o @4 H-NMR(chloroform): 67.47 =8.6Hz, 2.12H), 616two .,romatic protons), 67.37 J=8.6Hz, 2.12H, two S) 20 aromatic proton(s), 65.10(E) 64.86(Z) [br t, one N-H proton], 84.69(Z) [4.60(E) Ct, 1.05H, one methine proton at the acetal carbon], 64.07 0 04S 64.05(Z) 0.83H, enamine P proton], 83.71(E) o 63.68(Z) J=7.lHz, 2.22H, two methylene protons of one of two ethoxy groups], 63.56(Z) 63.53(E) [q, J=7. Hz, 2.22H, two methylene pro6ons of one of two ethoxy groups], 63.18 J=5.1Hz, 1.77H, two methylene protons of the ethyleneacetal group), 1.20 (t, J=7.lHz, 4.90H, six methyl protons of the two ethoxy groups).

C-NMR(chloroform): 161.21 (a-enamine carbon), 6136.29 6134.60(E) [either C-1 or C-4 of the phenyl ring], 6134.08(Z) 6132.30(E) [either or C-4 of the phenyl ring], 129.34(Z) 129.89(E) [either C-2 6 i C~NM~chorofrm) ^11.21(a-namie crbo), 536.9 i'' 514.60E) eithr Cl o C-4of he peny with an alkali metal hydride and an alkyl cyanoacetate, such as t-butyl cyanoacetate, to yield the i 38 or C-3,5 of the phenyl ring], 6128.94(Z) 6128.63(E) [either C-2,6 or C-3,5 of the phenyl ring], 6121.19(Z) 6119.50(E) [-iitrile carbon], 699.43(Z) 6100.63(E) [p-enamine carbon], 661.88(Z) 663.25(E) [methine carbon of the acetal], 662.64(Z) 663.03(E) [methylene carbons of the ethoxy groups], 646.32(Z) 647.33(E) [methylene carbon of the ethyl ai ine group], 615.26 (methyl carbons of the ethoxy groups).

0 44 10 Microanalysis (MW 294.78): 0 Calcd: C, 61.11%; H, 6.50%; N, 9.51%' Cl, 12.03%.

0° Found: C, 61.25%; H, 6.25%; N, 9.34%; Cl, 12.35%.

a I EXAMPLE 4 2(p-Chlorophenyl)-pyrrole-3-carbonitrile 0 0 o

CN

S00 CN CN oO o C C I 0 20 HN 0 0 -H C1 MW 294.78 MW 114.02 MW 202.64 0 To 108 mL of trifluoroacetic acid stirred at 23 C is 0o added 54.00 g (0.183 mol) of solid p-chloro-p-[(formylmethyl)amino]cinnamonitrile, diethyl acetal over a period of 45 minutes. This addition produced an exotherm to 380C and, 32 minutes into the addition, a solid started to precipitate. After stirring at room temperature for 30 minutes, the reaction mixture is vacuum filtered and the collected solid is washed first with trifluoroacetic acid, secondly with an ethyl acetate-hexane mixture, and finally with hexane. The 0% O 0 0 0~t a '0 0 00 0 0 a 0004* V Of 0 o o 4*4 0 00 4 0 4 I .0 #1 0 '04 '00 0 0~ 4 04 0 4 04 '00 4 040 39 yield is 16.83 g of an off-white solid, mp 165-166 0 The following anal. data is from a similarly prepared sample.

Ma(mull, Nujol): 3275(br 2225(s), 1502(s), 1410(m), 1275(m), 1200(m), 1108(s), 1023(m), 999(m), 1 908 843 752 722 695(s) 620(s) cm- H-NMR(acetone): 611.22 (v or s, 0.99H, one pyrrole N-H 10 proton), 67.82 J=8.9Hz, 2.46H, two aromatic phenyl protons), 67.51 J=8.9Hz, 2.46Hz, two aromatic phenyl protons), 67.02 J=2.6Hz, 1.01H, one pyrrole proton at 66.58 J=2.6Hz, 0.77H, one pyrrole proton at C-4).

C -NIAB(acetone): 6137.73 (pyrrole 6134.42 (p-chlorophenyl at 61z~9.93 (methine carbons at C-3,5 of the phenyl ring), 6128.07 (methine carbons at C-2,6 of the phenyl ring), 6121.21 (pyrrole at 20 6117.93 (nitrile carbon), 6113.78 (pyrrole carbon at 690.86 (pyrrole carbon at C-3).

o 0 00 0 0 04 '00 0 .0 00 0 40 Microanalysis (MW 202.64): Calcd.: C, 65.19%; H, 3.48%; N, Found: C, 64.18%; H, 3.52%; N, 13.83%; Cl, 17.50% 13.63%; Cl, 17.74%

I

40 Use of the above procedure as shown or with the substitution of concentrated hydrochloric acid for trifluoroacetic acid affords the following compounds: C.0 0 0 000 00 0 3 0 0 M and/orR 4-Cl 3 ,4-di-Ci 2-Cl 4-OCF 3 4-CF 3 2, 4-di-Ci 3 -Cl 4-CN 4-F 4-So2 CH 3 3 ,4-di-F 3 -CF 3 4 -COOCH 3 4-CH 3 4 -NO 2 mp 0C 165-166 216-221 156-157 143-145 179-180 197-199 150-156 210-212 167-170 221-221.5 173-175.5 166-168 155. 5-158 117-137 17 4-17 7 Acid Used conc. HC1, CF 3COOH CF 3COOHi CF3 C CF 3COOH CF 3COOH- CF 3COOH- CF 3COOH CF 3COOH CF, COOH- CF 3COON CF 3COOHa a 00.0 0 0 00 0 00 Is 0 0 0 0 0

;I

I

i

B

41 EXAMPLE 4.5-Dichloro-2-(o-chloronhenvl nvrrole-3-carbonitrile

CN

N H C1 C1

CN

2.2 eq S0 2 C1g

HO

F

c

N

C

l H C1 o0 0 3 0 000000 oooo o a 00 Q a a 0000 00 0 a oo 0 00 0 00 0 o 00 0 000 0 00 0 08 0 0 0 00 To a mechanically stirred solution of 16.83g (83.1 mmol) of 2-(p-chlorophenyl)pyrrole-3-carbonitrile in 450 mL of glacial acetic acid at 36 C is added dropwise 14.7 mL (24.70 g, 183.0 mmol) of sulfuryl chloride over a period of 18 minutes. The addition produces a slight exotherm to 39 0 C and, after another 16 minutes, the reaction mixture is vacuum filtered.

The collected solids are washed first with acetic acid and then with water. This solid after recrystallization from hot ethyl acetate, melts at 259-261 C. By similar procedures other samples of this product were prepared and the analytical data for one such product is shown below.

Max(mull, Nujol): 3170(br 3100(m) 1 1508(m), 1097(m), 825(s), 717(m), 660(m) cm- 2225(s), H-NMR(DMSO): d7.72 J=8.6Hz, 2.00H, two aromatic protons), 67.56 J=8.6Hz, 2.00H, two aromatic protons).

C-NMR(DMSO): 6136.01 (pyrrole C-2 carbon), 6133.92 (E-chlorophenyl C-4 carbon), 6129.09 (p-chlorophenyl C-3,5 carbons), 127.41 (chlorophenyl C4 carbon), C-3,5 carbons), 5127.41 (o-chlorophenyl C-4 carbon), 42 6127.11 (p-chlorophenyl C-1 carbon) 6114.49 (nitrile carbon), 6114.10 (pyrrole C-5 carboni), 6110.92 (pyrrole C-4 carbon), 690.09 (pyrrole C-3 carbon).

Microanalysis (MW 271.54): Calcd.: C, 48.65%, H, 1r%;N, 10.32%; Cl, 39.17% Found: C, 49.22%; H, 2.12%; N, 9.85%; Cl, 39.03% 00.

a Ot EXAMPLE 6 0 o 0 4 .5-Dibrono-2- (az, a, -trifluoro-po-tolyl) -Pvrrole-3- 0 a0abnirl 0000 .00. 0 o o CN Br CN 0 00 000+ Br 2

P

.0 H CF 3 Br H CF 3 00 ,6 0N- 040 2 To a stirred mixture of 0.8g of 2 -(aca-trifluoro-p-tolyl)pyrrole-3-carbonitrile in 70 mL of chloroform is added 2 mL of bromine. The mixture, on 00stirring ov ,rnight, deposits a white solid which is collected by filtration. Thin layer chromatography (1:1 ethyl acetate-hexane) shows a single component; m.p. >230 0

C.

Anal. Calc'd for C 2

H

5 Br 2 F N 2 C, 36.55; H, 1.27; N, 7.11; Br, 40.61.

A

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

Following the procedures of Examples 5 and 6, but substituting the appropriately substituted phenylpyrrole-3-carbonitrile for 2- (a,c,a-trifluoro-P-tolyl) pyrrole-3-carbonitrile yields the following compoun~ds.

below utilize the schemes illustrated above and provide

I

43 *C N 00 00 a 0

L

H

2 -Cl 2-Br

H

M R H 4 -NO 2 H 4-F H 4-F H 4-SO 2CH3 3-F 23 3-F 4-F 3 -C1 4-Cl 3 -Br 4-Br H 4-OCF 3 H 4-OCF 3 H 4-OCF 3 H 4-CN H 4-CN H 4-SO 2CH3 H 4 -NO 2 3 -Cl 4-Cl H 3 -CF 3 H 4-COCH~ 2, 3-CH=CH-CH=CH- H 4-CH 3 0PO 274 -2 77 >220 >220 >230 >230 >220 222-225 23 1-23 2 Br Br >230 Cl Cl >240 Br Br >230 Cl Cl 246-249 Br Br >260 Cl Cl >230 Cl Cl 251-254 Cl Cl 244-247 Cl Cl 215-217 Br Br >230 2-Cl 4-Cl 0~ 0* 0 other insecticides, nematicides and acaricides. For example, the arylpyrroles of this invention may be used 44 00 0 0 boo 00000b b 0000000 b 0 0 boo 9 00 0 b 0 .0 4 00 0 0 60 00, a 400

L

H

2-Cl

M

H

2-Cl

H

3-Cl

H

3-Cl 3-Cl 4-Cl

R

3 -Cl 4-Cl 4 -Cl 2-Cl 4-CF 3 4-Br 2-Cl 4-Cl

H

4-Cl 4-CF 3 4-Cl 4-Cl 5-Cl 4-Cl 5-F mp C >230 >230 273-274 >230 >230 >235 >230 >235 254-255 255-257 >230 262-263(dec.) 250-258(dec.) >230 >230 207-210 EXAMPLE 7 3-Nitro-2-iohenvl-ovrrole 0 0 0 0 01) 0 N02 CCH2NO2 HENCH2CH(OEt)2 C=CH-NO2 0- 1 CN NH-CH2CH(OEt)p H Alpha-nitro iacetophenone (5.7 g, 0.0345mol) is taken up in 100 mL toluene and 4.6g (0-0345mol) of amino acetaldehyde diethyl acetal is added. The reactants are put into a 250 mL RB flask fitted with a Dean-Stark trap. The trap is filled with 4A molecular sieves and the mixture is heated at reflux for 18 hours. The toluene is removed in vacuo to give 8.36 g of a-(2,2-diethoxyethylamino)-p-nitrostyrene as a

Y"

r 45 brown oil. To this oil is added 50 mL of concentrated HC1. As the flask is swirled the oil turns to a yellow suspension. After 10 minutes the solid is filtered to give 2.48 g of a yellow solid. Recrystallization from ether/ethylacetate/hexane gives the product as two fractions, 2.08 g of m.p. 190-192°C, d 0 0 0 a- 0 9 00 ob 00 4 0( 0 04 ppO~ Max 1485 cm- (NO H-NMR(CDC1 3

/DMSO)

7.46(m.5H).

EXAMPLE 8 2,3-Dichloro-4-nitro-5-phenylpyrrole 66.73(m,2H)

NO

2 N

H

NaOC1 C 1

NO

2 c 1 H 0 *0 ro S00 A mixture of 3-nitro-2-phenylpyrrole (1.56g, 0.0083mol) in 60 mL of dioxane is cooled in an ice bath while 25.9g (.0182mol) of commercial sodium hypochlorite is added dropwise. After stirring for 45 minutes, the mixture is acidified with concentrated HC1. Water and Et 2 0 are added. The layers are separated and the top organic layer is washed with H20, dried over anhydrous MgSO 4 and concentrated in vacuo to give 2.21g of yellow solid. Purification by chromatography using silica gel and eluting with increasing ratios of ethyl acetate/ hexane gives, after stripping, 0.77g of yellow solid m.p. 190-190.50C; Analysis: Calcd. for C10 6N202CC 2 C, 46.72; H, 2.35; N, copolymers of ethylene oxide and propylene oxide. Such block copolymers are marketed by BASF Wyandotte Corporation as Pluronic 10R8®, 17R8®, 25R8®, F38@, F68®, F77® or F87®, and are especially effective for the preparation of compacted granules.

hi

K

:i Il-l-l:: rl--

.Y

~I

46 10.90 C, 46.96; H, 2.86; N, 10.02 Found: Q0 D o 1 @a P 0 0 0 t 0 O 0 0. 00f 0 0OP o o Do 0, 0 00 0 0O 00 0 0 00 0 0 0t '00 Following the procedures of Examples 7 and 8 above but using the appropriately substituted a-nitroacetophenone and 2,2-di(C 1

-C

4 alkoxy)ethylamine yields the substituted a-(2,2-di(C 1

-C

4 alkoxy)ethylamino)-3nitrostyrene which is then converted to 3-nitro-2-(substituted)phenylpyrrole by treatment with HCl, HBr or 10 CF3CO H. Reaction of the thus formed substituted phenylpyrrole with sodium hypochlorite in dioxane yields the chloro analogs; whereas, reaction of the substituted phonylpyrrole with bromine in chloroform yields the bromine analogs.

X

INO

2 0r 0 '0 II 04n

L

H

3-C1

H

M

H

4-C1 4-Cl

H

4-C1 4-Br

H

R

H

C

H

4-CF 3 mp°C 190-190.5 214-215 203-204(dec.) 148.5-149 219-220(dec.) 222-223(dec.) 166-168 47 EXAMPLE 9 4,5-Dichloro-2-(3,4-dichlorophenl)-l-methvl-pyrrole-3carbonitrile C1 CN C1 CN C1

NC

C C Mel KOC(CH 3 3 Cl N C1 i e 0 400 l or1o .0 o In a 100 mL flask, 2 g of 4,5-dichloro-2-(3, 000 4-dichlorophenyl)pyrrole-3-carbonitrile in 60 mL dry STHF gives a clear brown solution. 1 eq of KOtBu is added w/ stirring, this giving a clear solution after a few minutes. 1 eq of Mel is added by syringe and the solution is heated at reflux for 4 hours. It is then left to stir at RT overnight. The following day 50 mL of H20 is added and the mixture extracted with 4 x mL CHC1 3 The organic phases are combined, dried with .o 20 MgSO 4 and concentrated. The resulting white solid is purified by flash chromatography on silica gel, using 50/50 EtOAc/hexane as an eluent. This gives 1.80 g of o" a a white solid.

0 00 o Yield 86% m.p. 154-156 deg. C Following the above procedure but substituting the appropriately substituted phenylpyrrole-3-carbonitrile or 3-nitro-2-(substituted)phenylpyrrole for 4,5-dichloro-2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile yields the compounds shown below.

-48- X~ ON

R

A L m R X Y MPC CH,. H H 4-Cl Cl Cl 152-153 c 2H 5 OCH 2 H 3-Cl 4-C! Cl Cl 128-130 15 c2H5H 3-Cl 4-Cl Cl Cl 137-138

CH

3 H 3-C1 4-Cl Cl CJ. 154-156 33 C H -C H H 4-CF 3. Br *Br 145-147 ooo*C HI -CH H 3-C 4-Cl- Cr C 145-947 0 6 5 2 CH 2=CH-CH 2H 3-Cl 4-Cl Cl Cl 69-70

H

2 L 2 00C=C-CH H 3-Cl 4-Cl Cl cl 1418 2 CH3C-CH 2 H 3-Cl 4-Cl Cl Cl 14-8 C(CH 3 3 H H 4-F3 c CHi H H 4-CF Cl Cl 99-100 o a3 3 0 j 0CH S H H 3-Cl 4-Cl CI, Cl 74-75 00 250 00 '00 0 Cn -uOC;CH H 3-Cl 4-Cl Cl Cl 118-120 30 C 2 H 5 OCH 2 H H 4-CF Cl c Cl 99-100 aCH 3H H 4-OCH 3 Br Br 112-115 3 C2H 5OCH 2 H H4-OCF Cl c Cl 46-47f CH 3 H H 4-OCF 3 CL Cl 72-73 c6 H5-C 2 H H4-OCF 3 Cl Cl oil SC H 5OCH 2 H H 4-Cl Cl Cl -49- A L M R X Y inPOC HOCH 2CH 2 H 3-Cl 4-Cl Cl Cl 143-145 NC H 3-Cl 4-Cl Cl Cl 251-252 C 6H 5CH OCH 2H 3-Cl 4-Cl Cl Cl 88--89 -Cl-COHP-CH 2 H 3-Cl 4--Cl Cl Cl 118-120 IC=C-CH H 3*-Cl 4-Cl Cl Cl 15-1 21111 CHUH H 4-Cl Br CF 126-129 3-.3 CHOCH II H 4-Cl Br CF 91-92 00CH-OCH H 3-Cl 4-Cl Cl Cl 118-120 2 5 2 C H -OCH H H 4-Cl Br Br 104-105 2 5 2 CU6H -CH H H 4-Cl Br Br 81-82 65 2 oCH 3 H H 4-Cl Br Br 197-201 33 2 5 2 N 4-CF BrC CF 104-105 C H-OCH H H 3-C 3r C 0-0 C H-OCH H H 4-CF H CF 75-77 2 5 2 33 C 2H 5OCH 2 H 3-Cl 4-Cl Br CF 3 80-81 0 C) 0 EXAMPLE 1 -Ben zyl- 4, 5-d ibromo 2 aa-tr if luoro -p -to ly 1) ipxrrole-3-carbonitrile B r CN Br

CN

KOC(CH

3 3

C

2 r BrAN~ 'N\I 'a CF 3 Br CF 3 H In a 100 mL flask, 2.5 g of 4,5-dibrrnmo-2cc, 0!-trif luoro-p-tolyl) pyrrole-3 -carjbonitrile is mixed with 50 mL c-y THF to give a clear dark solution.

1 eq of KOtBu is added with stirring. Af ter a f ew minutes the solution clears. Benzyl bromide (0.65 g) is added by syringe. The mixture is heated at reflux overnight. The following day TLC (50/50 EtOAc/hexane) p with a large amount of undissolved solids is filtered through diatomaceous filter aid. After dilution with

I

i t 50 indicates the presence of both starting material and product. The reaction is worked up in the following manner; 50 mL of water is added and the mixture is extracted with 4 x 50 mL CHC1 3 The organic phases are combined and washed with 4 x 50 mL 10% aq. NaOH. The organic phase is dried with MgSO 4 and stripped. This gives a brown solid which is crystallized from EtOAc/ hexane.

Yield 0.75g 40.7% m.p. 145-147 deg.C dec.

EXAMPLE 11 4,5-Dichloro-2-(3,4-dichlorophenvl)-1-(ethoxymethyl)pvrrole-3-carbonitrile o 0 004 0 THF oC CN ooa o Cl CN ooo«o 20 KOCCCHg) C1CHy0CHS C- 1N Cl^ oo o (H 2 OC2H 5 Cl o oc c 0o C1 25 A sample of 4,5-dichloro-2-(3,4-dichlorophen- 0 0O°° yl)pyrrole-3-carbonitrile (l.Og, 0.003 mole) is disa solved in 10 mL of dry tetrahydrofuran. To this soluo 0 tion is added potassium t-butoxide (0.37g, 0.0033 mole) P o followed by chloromethyl ethyl ether (0.312g, 0.0033 mole). The mixture is stirred for about 1 hour at room temperature and then poured into a large volume of 0o" water precipitating the product. The white solid is collected and dried to give 1.0g with m.p. 128- 1300 6134.60(E) [either C-I or C-4 of the phenyl ring], 6134.08(Z) 6132.30(E) [either C-I or C-4 of the phenyl ring], 6129.34(Z) 6129.89(E) [either C-2,6 i t 51 EXAMPLE 12 4-Chloro-3-cyano-2-(p-chlorophenyl)pyrrole CL CN Cl CN CN 2 NaOC C1 'NN dioxane Cl Cl H l oQ 00 o To a magnetically stirred 20 C solution of a. 17.87g (88.2 mmol, 1.00eq) of 2-(p-chlorophenyl)-3cyanopyrrole in 800 mL of dioxane is added dropwide 0" 250.15g (13.13g real, 176.4 mmol, 2.00eq) of 5.25 weight bleach over a period of 30 minutes. After S00<0 stirring at room temperature for a further the reaction solution is poured into 2200 mL of water.

0 The resulting mixture is vacuum filtered to remove a 0o small amount of a black solid. The filtrate is o 20 acidified to pH 2 with concentrated HCI to produce a brown solid. This 'd is vacuum filtered and the oo o collected solids wash. .ch water to give 22.41g of a 0 brown solid. This so. .a is treated with 100 mL of aqueous sodium hydroxide to dissolve the bulk of the material while leaving a small amount of undissolved black solid. This black solid, dissolved into 100 mL of ethyl acetate, is washed with 75 mL each of aqueous NaOH, water, and sat. aqueous NaCl. The ethyl acetate layer is dried (MgSO 4 treated with charcoal, 4 filtered, and then rotary evaporated in vacuo to give 1.10g yield) of an orangish brown solid. This solid is recrystallized from an ethyl acetate chloroform mixture to give 0.51g yield) of an off-white solid of 4-chloro-3-cyano-2- (-chlorophenyl)pyrrole.

135 mp 251-253.5 C.

I I 52 EXAMPLE 13 Preparation of 5-bromo-2- (3,4-dichlorophenvl)pvrrole-3carbonitrile CN CN Bra ioxane Br2 SC1Br 1 C1 C1 A sample of 2-(3,4-dichlorophenyl)pyrrole-3o 15 carbonitrile 0.008 mole) is dissolved in 100 mL co 0 o .of dioxane by warming to 40-50O. Then the solution is a" cooled to 10 0 C an- bromine (1.3g, .008 mole) is added.

After stirring 1 hour at room temperature the solution 000040 is poured into water and a gray solid (2.2g, 88%) is 20 collected. The mp is 233-236 C, decomposition.

r o I similiar fashion one can prepare S 0 0 -bromo-2-(3, -dichloro)-3-nitropyrrcle starting with 2-(3,4-dichlorophenyl)-3-nitropyrrole.

060004 0 44 Q4 4 F i

A

.53 EXAMPLE 14 Preparation of 5-bromo-4-chloro-2- 4-dichlorophenllnvrrole-3 -carbonitrile C1 CN 00 o 0 000 00000, 0 0 0 000000 0 I 000I o 0004 00 1 0 0 0 0 40 0 00 00 0 O 00 00 0 0 00 00 0 0 0 0*0 0 00 00 0 0 00 00 0 V. 00 0 00

CN

Br

N

H

C

(CH

3 3 COCI A sample of 5-bromo-2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile (0.158g, 0.005 mole) is dissolved in tetrahydrofuran (5 mL) An equivalent amount of t-butyl hypochiorite is added and the solution stirred -ernight. The solution is poured into water and the precipitate (0.052g, 30%) is collected. The mp, is >275 0

C.

In a s-Imiliar fashion one can prepare 2-bromo-3-chloro-5- 4-dichlorophenyl) -4-nitropyrrole by starting with 2-bromo-5- 4-dichlorophenyl) -4nitropyrrole.

C0 o 0 EXAMPLE Preparation of 5-bromo-4-chloro-2-(p-chlorophenyl)- N°

N

0.17g (0.67 mmol, 1.00 equivalent) of 4-chloro-2-( chlorophenyl)pyrrole-3-carbonitrile in 00 mL of chloroform is added drowise over a eriod of S0 S equivalent) of bromn1.00 equivalent) of -chloro-form. The chlorophenyl)pyrrole-3-carbonitrile in 100 mL of addition produces no exotherm. After stirring at room 20 temperature for 3 1/4 hours, the clear red reaction solution is evaporated in vacuo to give 0.28g of an off-white solid. This solid is slurried with a hexanemethylene chloride mixture to give on vacuum filtration o 0.23g of an off-white fluffy solid. mp 262-263C; dec.

s' C-NMR(DMSO): 6136.01 (pyrrole C-2 carbon), 6133.92 (p-chlorophenyl C-4 carbon), 6129.09 .(p-chlorophenyl C-3,5 carbons), 6127.41 (p-chlorophenyl C-4 carbon),

I

55 EXAMPLE 16 5-chloro-4-bromo-2- (D-chloroo2henvl) Prep aration of nvrrn1A-3-narhnni 1-t-r *i I ez Brp CHC1 3 Br CN H C1 00 0 000 O 0 0 009000 0 0 0.9*0* 0 4% 0000 00 0 o 00 0 00 0 00 0 0 0 0 00 4% 00 04% 0 0 20 00 o o 0 000 C' 00 00 0 0 00 00 0 0 00 0 00 To a magnetically stirred 45 0 C solution of 1.00g (4.22 mmol., 1.00 equivalent) of 5-chloro-2-(pchlorophenyl)pyrrole-3-carbonitrile in 300 mL of chloroform is added dropwise over a period of minutes, a solution of 0.40 mL (1.24g, 7..76 mmol., 1.84 equivalent) of bromine in 25 mL of chloroform. The addition produces no exotherm and towards the end of the addition, a small amount of a solid starts to precipitate. After stirring at room temperature for 19 1/2 hours the reaction mixture is evaporated in vacuo to give 1.49g of an orangish white solid. This solid is slurried with a hexane-methylene chloride mixture to give on vacuum filtration 1.33g (100% yield) of a fluffy white solid. mp 250-258 0 C, dec.

pyrrole-3-carbonitrile for 2- (a,a,a-trifluoro-p-tolyl) pyrrole-3-carbonitrile yields the following compounds.

-56

EXAMPLE

PreT)aration of 5-chloro-2-(Io-chloro-phenvl),Pvrrole-3carbonitrile

CN

CN S02cip HOAc C 1 C N

XN

C 1 H C I 0 00 00 4, 00 0 000 To a 35 0 C magnetically stirred solution of 2.40g (11.8 mmol., 1.00 equivalent) of 2-(p-chlorophenyl)pyrrole-3-carbonitrile, and 65 mL of glacial acetic acid is added dropwise by syringe 0.75 mL (1.26g, 9.34 mmol., 0.79 equivalent) of sulfuryl chloride over a period of 5 minutes. Approximately 5 minutes after the completion of the addition, a solid precipitated out of the reaction solution. After stirring at room temperature for 45 minutes, the reaction mixture is filtered and the collected solid is wasned well with cold acetic acid to give 2.08g (74% crude yield) of an off-white solid. This solid is recrystallized from 75 mL of hot acetic acid to give 1.63g (58% yield) of 97 wt% pure.

Product mp 258.5-261 0 C.

57 EXAMPLE 18 Preparation of 2-(3,4-dichlorophenvl)-l-methylpyrrole- -3-carbonitrile CN

CN

o Cl KOC(CH 3 3 CHI Cl N N V oe o 10 CH, Sadded. is gives a sligtly cloudy solution. One 0 equivalent of methyl iodide is then added to the a 00 9 o t In a 100 mL flask, 2.0 g of 2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile is dissolved in 50 mL of dry THF and 1 equivalent of potassium t-butoxide is e added. '2his gives a slightly cloudy solution. One equivalent of methyl iodide is then added to the oo« mixture by pipette. This leads to a slight lightening C of the colour. A drying tube is attached to the flask o° 20 and it is left to stir at ambient temperature overnight.

o s The next morning there is a slight light- O coloured precipitate in the flask. 50 mL of water is *o "S then added and the solution becomes clear before a solid precipitates out of the solution. This solid is filtered out of the solution and compared to the starting material by TLC (25% ethyl acetate/hexane).

This indicates a new single spot which is faster moving than the starting material. It is dried in a vacuum oven at 50 deg. C overnight. The product yield is 1.31g or 62% yield and has a melting point of 140-142 0

C.

sieves and the mixture is heated at reflux for 18 hours. The toluene is removed in vacuo to give 8.36 g of a-(2,2-diethoxyethylamino)-p-nitrostyrene as a 58 EXAMPLE 19 Preparation of 4,5-dichloro-2-(3,4-dichlorophenyl)-1methylpvrrole-3-carbonitrile 4 1 0 e 04 0 03 0 00 0a 090 0 00 go, 00 o 0 0 a8 o0 a 0 0 00 0 Of.

CN

C1

CH

3

SO

2 Cla Cl CN C1 i c

CH

3 In a 50 mL round bottom flask, 0.5g of 2-(3, 15 4-dichlorophenyl)-l-methylpyrrole-3-carbonitrile is mixed with 35 mL of glacial acetic acid. The mixture is warmed slightly with a heat gun to dissolve all of the pyrrole.

To this clear solution is added 2 eq. of 20 sulfuryl chloride by pipette. The solution is left to stir at room temperature for 12 hours.

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

The resulting solid is identical by TLC, ethyl acetate/ hexane), and infrared analysis to the product of Example 9. Product yield is 0.36 li~ i 59 EXAMPLE Preparation of 4,5-Dichloro-2-(3,4-dichlorophenyl)-1- (2-hydroxyethyl)-pyrrole-2-carbonitrile *H CI C i 1 C N

C

OH

To a stirred mixture of 2.0 g (6.5 mmol) of 4,5-dichloro-2-(3,4-dichlorophenyl)-pyrrole-3-carboni- 00 .0 trile and 0.88 g (7.8 mmol) of potassium tert-butoxide heated at reflux in 50 mL of dioxane is added 0.98 g (7.8 mmol) of bromoethanol. The mixture is stirred at 0 00 0 0 reflux for 12 hours, cooled, diluted with 50 mL of 0 water, and extracted several times with chloroform.

The combined chloroform extracts are dried over 2 magnesinm sulfate and concentrated in vacuo to leave a solid which, on warming and dissolving in ethyl acetate, deposits on cooling mostly starting pyrrole.

Concentration of the mother liquor and recrystallization of the residual solid from 20% ethyl acetate in hexane gives 0.31 g of a white solid, mp 143-1450C; IR 5077A.

Anal. Calc'd for C16H23NO4; C, 44.57, H, 2.29; N, 8.00; Cl, 40.57.

Found: (Agm 33139): C, 44.77; H, 2.29; N, 8.06; Cl, 40.14.

EXAMPLE 21 Preparation of 4,5-dichloro-2- L3,4-dichlorophenl) pvrrole-1. 3-dicarbonitrile C1 CN Cl1 N1 CNBr K~t-BuO- H C1 0 0 ooo~C1 CN 150

C

15 CN 0 00 00 0 0 00 0:0: 0 Potassium t-butoxide (617 mg., 55 mmol) is added in portions to a solution of 3-cyano-4,5-dichloro 00 -anhydrous THF (20 mL). After 30 minutes, a solution of cyanogen bromide (583 mg, 5.5 mmol) in THF (1 %nL) is 000added. The reaction mixture is stored at room 00 :0 temperature overnight. The solvent is removed. in a rotary evaporator. The residue is treated with water and extracted with ethyl acetate. The organic layer is washed with water and saturated sodium chloride and dried (MgSO 4 Evaporation and crystallization of the residue from ethyl acetate gives i-.-ile crystals (1.07' 0 -1 k mp 250.5-252.0 C; IR (nujol) 2255, 2245 cm (CN); 1 3 C NMR (DMSO-d 6 102.7 113.7 Mass spectrum 331.9 Anal. Calc'd for C 12

H

3 C1 4 (330.99); C, 43.54; H, 4 0.91; N, 12.70; Cl 42.85.

AFound: C, 4362; 0.93, N, 12.63; Cl 41.95.

j ffl I.1 jj~J1.8 1111.25 11111 1.4' -Ili 'ZAXMn nis8OdONW1Nr1HO~aGAV 'id 068L996L 1 zAxMAnjsabdotw I I! a pz~q o Z)AXXMAfl±SSdONW14 rIHejD( 9DoV, d .LHlt 251 I _12 I~ i I

A

61 EXAMPLE 22 Preparation of 4.5-Dichloro-2-(3.4-dichloro henvl)-- (3-iodo-2-propynvl)-pVrrole-'3-carbonitrile +12 NaOH

CH

C.

\2 00 0 00 0 0 0 000040 0 0 o 0 o 0 0 60 0 0 o 0 aa 0 00 h 0or~ 000 C2

C

To a stirred mixture of 1.91 g (5.5 mmol) of 4,5-dichlorso-2-(3,4-dichlorophenyl)-l-(2-propynyl)- 20 pyrrole-3-carbonitrile in 503 mL of methanol is added 69 mL of 10% aqueous sodirm hydroxide and then 0.70 g (2.7 mmol) of iodine. The mixture is stirred for 12 hours and then acidified and diluted with 200 mL of water. The precipitated solids are collected and recrystallized from methanol to afford 0.51 g while crystals, m.p. 11-116C.

This reaction is also applicable to the conversion of any of the formula II, IV, V, VI or VII substituted N-alkynylarylpyrroles of the present 30 invention to N-substituted 3-iodo-2-propynyl arylpyrroles of said invention.

'Y

.3

I

62 EXAMPLE 23 Preparation of 2-(3,4-dichlorophenvl)-4,5-diiodopyrrole-3-carbonitrile 0

N-I

0 00 N-iodosuccinimide (5.7 g, .0254 mol,) is added slowly to a solution of 2-(3,4-dichlorophenyl)- 0 o pyrrole-3-carbonitrile (3.0 g, .0127 mol) in 100 ml of I THF. The reaction is stirred several hours at 25 0

C

20 o"a 0 until thin layer chromatography (silica gel; 100:100:1o ether:petrolium ether:acetic acid) shows completion.

o The mixture is evaporated in vacuo to give a residue containing the pyrrole and succinimide. The crude solid is dissolved in 500 mL of ether and shaken with S25 x 400 mL of water to remove the succinimide. The ether ooo0 o is dried over Na 2

SO

4 and evaporated in vacuo to leave o 2.0 g of a grey-brown solid with mp >230° oo o (loses purple vapors).

o0 t 00oe oaoo 63 EXAMPLE 24 Preparation of 2-phenyl-l-pyrroline-4-carbonitrile

NC

CN N 10 mol7. nBu 4

N+F-

TMS- THF/16hr/RT

S

N

\N

00 Son 10 A solution of acrylonitrile (0.65 mL; 0.01 mol) and N-(trimethylsilyl)methyl-S-methyl-benzenethioco imidate (2.4 g; 0.01 mol) in THF (100 mL) is cooled to 0,r o -5 C in an ice-acetone bath. Under a nitrogen purge, a solution of tetrabutylammonium fluoride (1.0 mL of a 1 N solution in THF) and THF (20 mL) is added dropwise o over 30 minutes The solution is stirred another SOo minutes at -5 C, and then allowed to warm slowly to ambient. Stirring is continued another 18 hours, and then solvent is removed under reduced pressure. The residue is partitioned between ether/water and the water layer extracted with fresh ether. The combined organic layer is washed with water, then saturated oO o sodium chloride. The solution is dried over MgSO 4 and 0 cooling the filtrate causes precipitation of an offwhite solid (1.2 g; 70% theoretical yield) whose spectral characteristics are identical to the material described by Tsuge Org. Chem. 52, 2523 (1987)].

Calcd. for C 1 1

H

10 N2: C, 77.65; H, 5.88; N, 16.47.

Found: C, 77.55; H, 5.83; N, 16.39. mp 95-970C.

i 64 EXAMPLE Preparation of 2-phenvl-pvrrole-4-carbonitrile 0 0 1 0 0 0 j o 0 0 0 0 0 S 00 0 0 00 0 0 0 0 0 0 0 0 00 DDQ/DME/pyr 16 hr/RT NH Under a nitrogen purge 2,3-dichloro-5,6-dicyano-l,4-bonzoquinone (0.23 g; 0.001 mol) and 2-phenyl -l-pyrroline-4-carbonitrile (0.17 g; 0.001 mol) is dissolved in 1,2-dimethoxyethane (13 mL) to form a clear orange solution. Pyridine (0.08 mL; 0,001 mol) is added in a single portion, causing a slight exotherm (to ca. 280C) and an immediate formation of a green/ grey precipitate. The suspension is stirred at room temperature for 18 hours during which time much of the solvent evaporates. The brownish semi-solid residue is partitioned between ether and a half-saturated solution of sodium carbonate. The red-brown aqueous layer is extracted twice with ether and the combined ether layer is washed with fresh water, then saturated sodium chloride. After drying with MgSO 4 solvent is removed under reduced pressure to obtain a white semi-solid.

This material was recrystallized from ethylene dichloride (DARCO treatment) to yield lavender crystals (0.1 g).

The identical product is obtained directly in a single step by condensing a-chloroacrylonitrile and N-(trimethylsilyl)methyl-S-methyl-benzenethioimidate

SIC

L I 65 using tetrabutylammonium fluoride catalysis (analogous to the preparation of 2-phenyl-l-pyrroline-4-carbonitrile described previously).

Calcd. for C 11 H8N 2 C, 78.57, H, 4.76; N, 16.67.

Found: C, 78.65; H, 4.70; N, 16.43. m.p. 155-158 0

C.

0 s 0 0 EXAMPLE 26 10 Preparation of 2,4-dibromo-5-phenvl pyrrole-3-carbonitrile o 0 BrCHC1 SNH Br NH uo a* Under a nitrogen purge, a solution of bromine (0.6 mL; 0.012 mol) in CHC1 (5 mL) is added dropwise 63 over 20 minutes to a stirring solution of 2-phenyl- 00 pyrrole-4-carbonitrile (0.84 0.05 ml) in CHC mL). The resulting solution is stirred 18 hours at C2H C12 (DARCO treatment), yielding the desired final 0 02 4 2 0 product (0.6 m.p. 239-242 C.

Calcd. for C11H6Br2N2: C, 40.49; H, 1.84; Br, 49.08; N, 8.59.

SUnder a nitrogen purge, 39.88; H,a solution of bromine 0o 3 (0.6 mL; 0.012 mol) in CHC1 (5 mL) is added dropwise over 20 minutes to a stirring solution of 2-phenylpyrrole-4-carbonitrile (0.84 g; 0.05 mol) in CHC1 3 mL). The resulting solution is stirred 18 hours at room temperature, then solvent is removed under reduced pressure to obtain a solid which is recrystallized from C2H4Cl 2 (DARCO treatment), yielding the desired final product (0.6 m.p. 239-242°C.

Calcd. for ClIH 6 Br 2

N

2 C, 40.49; H, 1.84; Br, 49.08; N, 8.59.

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

66 By the procedure described in Example 24, and 26, 2,4-dibromo-5-(E-chlorophenyl)pyrrole-3-carbonitrile, m.p. 270-272°C (dec.) is also prepared.

EXAMPLE 27 3',4'-Dichloro-3-(1l3-dioxolan-2-yl)-propiophenone rt.

2 BrM r o0 C1 0 To a rapidly stirring mixture of magnesium equipped with a thermometer, a 60 mL addition funnel, Sand a nitrogen inlet is added dropwise 2-(2-bromoethyl) S2 t1,3-dioxolane (4.7 g, 26 mmol) in 40 mL of tetrahydrofuran. The rate of addition is adjusted so as to maintain the reaction temperature below 50 0 C. The reaction is then allowed to stir for 1 hour at 25 C.

120 mL of tetrahydrofuran is mixed with potassium 3,4dichlorobenzoate (5.0 g, 22 mmol) under a blanket of nitrogen. The Grignard solution is then quickly decanted away from the unreacted magnesium turnings, and added dropwise to the rapidly stirring potassium benzoate suspension. The reaction is then allowed to I- I ii 67 stir for 24 hours at 25 C. Fifty mL of diethyl ether and 15 mL of 3N hydrochloric acid are added to the reaction mixture and the layers separated. The organic layer is washed with saturated aqueous sodium bicarbonate until neutral followed by one washing with 10 mL of brine. Drying over sodium sulfate, and rotary evaporation yields a beige semisolid which is chromatographed over silica gel using 3:1 hexane-ethyl acetate as oeluent to give the keto-acetal (4.3 g, 60%) as a white 10 solid, m.p. 115-117 0

C.

EXAMPLE 28 $fit Preparation of 3-(3,4-dichlorobenzovyl)propionaldehyde 1 0 0 9 0 00 C° HO 2

CCO

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

EXAMPLE 29 Preparation of 2-(3,4-dichlorophenyl)pyrrole o 040 0 CHO ETOH t> Li H -f 0o' To a suspension of 3-(3,4-dichlorobenzoyl) propionaldehyde (6 g, 26 mmol) in 60 mL of absolute °0 ethanol is added ammonium acetate (4 g, 52 mmol). The 20 S0 20 reaction is refluxed for 20 minutes and allowed to cool. Most of the ethanol is rotary evaporated and 200 0o°o° mL of 1:1 dichloromethane-diethyl ether along with 0 0oo o. o mL of water is added. The layers are separated and the o oo organic phase is dried over sodium sulfate. Rotary evaporation yields a dark brown oil which is chromatographed over silica gel using 3:1 hexane-ethyl acetate as eluent to give the pyrrole (4.6 g, 83%) as a light brown solid, m.p. 49-51 0

C.

I

^i i 4 69 EXAMPLE Preparation of 5-(3,4-dichlorophenyl)pyrrole-2-carboxa- Idehyde C1 Cl N) C 1) DMF/PcC1 3

N

6 H C OHC H C1 o. 10 2) NaoAc 0 0 0n'0 To 10 mL of dimethylformamide stirring under 900 nitrogen in a 50 mL round bottom flask is added phosphorus oxychloride (0.6 mL, 6.5 mmol) dropwise via 0, syringe. The solution, warms and becomes light yellow

B

1 in color. It is allowed to stir for 20 minutes before 9 o the portionwise addition of 2-(3,4-dichlorophenyl)pyrrole (1 g, 4.7 mmol). The beige suspension which 0 20 results is allowed to stir for 30 minutes before being heated to 50 0 C for 40 minutes. A.solution of sodium 0 acetate (10 g, 122 mmol) in 15 mL of water is added to the cooled reaction which is then allowed to stir for o 20 minutes. A beige precipitate is filtered off from the reaction mixture and air-dried for 20 hours to give the essentially pure aldehyde (1.1 g, mp 200 0

C.

i 1 1 IlI I IIII 70 EXAMPLE 31 Preparation of 5- 4-dichlorophenvl) pyrrole-2-carbolitrule o0 00 0/ 10 HO N /H 2

N-OSO

3 H N Cl H __CH C1ETO H/H C 0000 00 To a suspension of 5-(3,4-dichlorophenyl)pyr- 000000role-2-carboxaldehyde (1.5 g, 6.2 minol) in 20 mL of water and 20 mL of ethanol, is added hydroxylamine-Osulfonic acid (0.7 g, 6.2 mmiol). The reaction is 0 00 20 refluxed for 1 hour during which time a gray precipitate appears. After being allowed to cool, the reaction is filtered to give essentially pure nitrile 0 g, 99%) as a gray solid, m.p. 170-171 0 71 EXAMPLE 32 Preparation of 3,4-dibromo-5-(3,4-dichlorophenyl)pyrrole-2-carbonitrile' Br Br o 0 C1 C1 H C TH H CI 0 4 NC NC N 0 0 .C1 THF C 0 00 To a solution of 5-(3,4-dichlorophenyl)pyro role-2-carbonitrile (0.5 g, 2.1 mmol) in 20 mL of o tetrahydrofuran under nitrogen is added portionwise "04 N-bromo-succinimide (0.8 g, 4.2 mmol). The reaction is 0o stirred at 25 0 C for 30 minutes before the addition of 20 10 mL of water and 40 mL of diethyl ether. The layers are separated and the organic layer dried over sodium oo sulfate. Rotary evaporation is followed by chromatography over silica gel using 3:1 hexane-ethyl acetate as eluent to afford the dibromopyrrole (0.5 g, 60%) as a brown solid, m.p. 250 0

C.

i 72 EXAMPLE 33 Preparation of 4-phenylpyrrole-3-carbonitrile CN s

NC

CH

3

N

H

To a mixture of 5.0 g (39 mmol) of cinnamonitrile and 7.6 g (39 mmol) of (g-tolylsulfonyl)methylisocyanide in 35 mL of DMSO and 65 mL of ether is added over a 20 minute period of suspension of 1.86 g of a 60% oil S0 suspension of sodium hydride (1.11 g; 46 mmol) in 80 mL of ether. The 0 00000 0 0 reaction mixture is maintained under nitrogen for an hour and then diluted o o~°°100 with ether and water. The ether layer is separated, dried over magnesium o 00 g sulfate, and concentrated in vacuo. The resulting oil is chromatographed on silica gel using 1:1 chloroform ethyl acetate to give 2.5 g of 03 0 0 cream-colored solids. Recrystallization from ether-hexane affords 1.15 g, m.p. 123-125°C; NMR M86-1077.

0 S01'5 The term "NMR M86-1077" designates a nuclear magnetic resonance oo o spectrum of the title compound obtained in 1986 on an EM360L 360 megaherz 0 o0 o NMR spectrometer manufactured by Varian Associates, Inc. of Palo Alto, California. Said spectrum was given the internal log number of 1077.

o Lit.: Tet. Letters 5337 (1972): m.p. 128-129°C.

KEH/198f ;i r 1 73 EXAMPLE 34 Preparation of 2,5-dichloro-4-phenylpyrrole-3carbonitrile NC N~ NC o iT" o 1t o C1 N C1 SH H 6 Q o" To a stirred mixture of 0.66 g (3.9 mmol) of 4-phenylpyrrole-3-carbonitrile in 20 mL of dry THF cooled to 6 0 C with an ice-water bath is added from a syringe 0.66 mL (1.11 g; 8.2 mmol) of sulfuryl chloride over a 4 minute period. The mixture is maintained at 5-10 0 C for an additional 45 minutes and then stirred an Soo 20 additional 30 minutes with the ice bath removed. After the reaction mixture is poured into 80 mL of ethyl acetate and 40 mL of water, the organic phase is separated, washed with water, and dried over sodium 0 sulfate. Filtration through a short column of silica gel, rinsing with ethyl acetate, and concentration of the combined filtrated in vacuo gives 0.95 g of dark solid. Recrystallization from chloroform gives 0.42 g of off-white crystals, m.p. 195-196 C (dec.).

Anal. Calcd for CH11H6C2N2 C, 55.72; H, 2.55; N, 11.82; Cl, 29.91.

Found: C, 55.66; H, 2.65; N, 11.69; Cl, 29.97.

3 l 12 J5 4-J 0.91; N, 12.70; Cl 42.85.

Found: C, 4362; H, 0.93, N, 12.63; Cl 41.95.

w 74 Following the procedures of Examples 33 and 34, the following analogs are prepared. For the synthesis of 2, 6-dibromo-4- (p-chlorophenyl) pyrrole-3carbonitrile, the procedure of Example 33 is followed using bromine in dioxane to replace sulfuryl chloride and tetrahydrofuron.

0 t 00 a 0 9 4-Cl *4-CH 3 4--C1 0. 237-240 (dec.) 103-206 2450 0 04 00 0 00 0 0 0 0 00 9' 1 ;LLI 9~ :I:

M

"A

m 9% 75 EXAMPLE Ethyl 4-(p-chlorophenvl)-pyrrole-3-carboxylate 0 0 0 0 9 0 0 0 0 0 0 CI 0

H

To a mixture of 5.63 g of a 60% sodium 004 o. hydride/oil suspension in 200 mL of dry ether under 15 nitrogen is added from an additional funnel a mixture of 23.5 g (122 mmol) of ethyl E-chlorocinnamate and o"000 19.4 g (122 mmol) of (p-tolylsulfonyl)methyl isocyanide o 00 S.Oo in solution in 180 mL of ether and 80 mL of dimethylsulfonide. The addition time is about 20 minutes and 0, 20 results in gentle refluxing of the mixture. After 0 000 another 10 minutes stirring, the mixture is diluted with 100 mL of water. The mixture is extracted four 0o00 times with ether which is then dried over magnessium a o sulfate followed by concentrated in vacuo. The 25 resulting solid is recrystallized from ethylene dichlorite to give 7.8 g of crystals, m.p. 137-138 0

C.

Anal. Calcd for C 13

H

12 C1NO 2 C, 62.53; H, 4.81; N, 5.61; Cl, 14.23.

Found: C, 61.31, H, 5.12; N, 5.32; C1, 14.57.

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

rx<

I

i I "WOO" 76 EXAMPLE 36 Preparation of 3-(p-chlorophenvl)-pyrrole H O NaOH 09 o 9 2 er #0 0 o At o o 0c 0 o 00* 0 09 2. 00o 10 11

H

A mixture of 22.0 g of crude ethyl 4-(pchlorophenyl)-pyrrole-3-carboxylate from the recrystallization mother liquor and the recrystallized product from the previous step is stirred at reflux with 150 mL of 10% aqueous sodium hydroxide for 2.5 hours. The mixture is cooled, extracted with ether, and acidified to give a precipitate which on collection and drying 20 weighs 11.6 g.

A mixture of 10.5 g of the acid in 100 mL of P-ethanolamine is heated at reflux for three hours.

After cooling, the mixture is poured over 400 mL of ice and the resulting mixture is extracted four times with chloroform. The chloroform solution, after drying over magnesium sulfate and treatment with activated charcoal, is concentrated in vacuo to leave a brown solid.

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

1 77 EXAMPLE 37 Preparation of 3-(p-chlorophenvl)-pyrrole-2-caboxaldehyde C1 0 S+ (COC1) 2

(CH

3 2

NCH-

o a 0 1" 10

H

ac 00a1 o.o n CHO

H

To a mixture of 0.86 g (12 mmol) of dimethyloQ a formamide in 10 mL of ethylene dichloride maintained °o a under nitrogen and cooled in an ice bath is added 1.49 g (12 mmol) of oxalyl chloride in 10 mL of ethylene o dichloride over a period of 25 minutes. The ice bath is removed, the mixture is stirred an additional minutes and recooled in an ice bath. To this mixture 0 a is added 1.5 g (8.5 mmol) of 3-(p-chlorophenyl)-pyrrole 0 a in 25 mL of ethylene dichloride over a 20 minute o 00 25 period. The ice bath is removed and after an additional 30 minutes of stirring, the mixture is poured into 50 mL of ice-water and 6 mL of 50% sodium hydroxide. The resulting mixture is extracted with ether and with chloroform and the combined organic mixture is dried over magnesium sulfate and concentrated in vacuo. Purification of the resulting solid by chromatography on silica gel using 1:1 ethyl acetate hexane gives 0.63 g of off-white solid which is used 3 directly for conversion to 3-(p-chlorophenyl)-pyrrole- 235 2-carbonitrile. i I! 1 N-(trimethylsilyl)methyl-S-methyl-benzenethioimidate i rI r 78 EXAMPLE 38 Preparation of 3-(p-chlorophenyl)-pyrrole-2-carbonitrile .C1

H

2

NOSO

3

H

o tr o 1- #104 0 4.

*a CH=0 S, A mixture of 0.63 g (3.1 mmol) of 3-(p-chlorophenyl)-pyrrole-2-carboxaldehyde in 10 mL of water is stirred and ice-cooled while 0.52 g (4.6 mmol) of o .9 hydroxylamine-O-sulfonic acid in 10 mL of water is :o slowly added. After the addition, the cooling bath is removed and the mixture is heated for 25 minutes. On a 0o0 cooling, the resulting solid is collected and shown, by NMR, to be a mixture of product and starting aldehyde.

This mixture is reacted in the same manner with an O0 40 o 0 4 additional 0.49 g (4.2 mmol) of hydroxylamine-O-sulfonic acid in a total of 30 mL of water. The mixture is 25 heated at 60-70 C for 2 hours. The mixture is cooled and the resulting solids are collected and purified by chromatography or silica gel using 1:1 ethyl acetate hexane to give 0.40 g of pink solid, m.p. 114-115 0

C.

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

I

4 79 EXAMPLE 39 Preparation of 4. 5-Dibromo-3- (p-chlorophenv1 -,pyrrole- 2-carbonitrile 0 00 4 1 Cl1 Br Br N

CN

H C Br 2 0 00 To a mixture 0.40 g (2.0 manol) of 3-(i,-chlorophenylpyrrole)-2-carbonitrile in 25 mL of chloroform is added 0.63 g (4.0 mmuol) of bromine. After minutes, the precipitate which forms is collected and 0 recrystallized from ethyl acetate to give 0.21 g of 0 -0 0 pink crystals, m.p. 2500C.

Anal. Calcd for C 11H 5Br 2CM C, 44.38; Cl, 9.85; N, 7.77.

Found: C, 36.92; H, 1.32; N, 7.50 36.62; H, 1.39; Br, Br, 44.62; C1, 9.88; I~'-LVII -y U--u ~-u l i EXAMPLE Preparation of Ethyl 5-bromo-4-(p-chlorophenyl)pyrrole- 3-carboxylate 0 0 Cl- N-Br THF H II 0 0 040 a «oo 0 Br N 6 00 Qe~'

'-COOCH

o °o 15 0 0* H Ethyl 4-(E-chlorophenyl)pyrrole-3-carboxylate A* (1.6 0.0054 mmol) is dissolved in tetrahydrofuran mL). N-bromosuccinimide (1.14 0.0064 mmol) is added in small portions at 25-28 0 C. After the addition a is complete, the solution is stirred overnight at room a, temperature. The solution is concentrated in vacuo and S'1 25 the solid residue partioned between water and ether.

The ether layer is separated and dried over magnesium sulfate. Work-up of the ether extract leaves 1.9 g of a white solid which is purified by stirring 3 with a mixture of 80/20 hexane/ethyl acetate. The insoluble solid (1.3 g, 62%) is collected and has m.p.

161-164 0

C.

Calcd for C H 1BrClNO: C, 47.50; H, 3.34; N, 4.26; Br, 24.33; C1, 10.80.

i sulfate. Rotary evaporation yields a viscous yellow r t i i 1 f

I

j j ii

I

81 Found: C, 47.39; H, 3.38; N, 4.12; Br, 24.29; C1, 10.77 EXAMPLE 41 Preparation of 5-bromo-4-(p-chlorophenyl)pvrrole-3carboxvlic acid 00 O 00 0 0C 0 400 04 0 0 009 0s 0 *B 00

COOCAH

Cl 0O 2

H

C1 10% NaOH

N

Br

H

COOH

Br N

H

o o00 '00 o 000 S« 0 0 0 U P0 Ethyl 5-bromo-4-(p-chlorophenyl)pyrrole-3- 20 carboxylate (15 0.045 mmol) is added to 200 mL of sodium hydroxide and the slurry heated to reflux.

After everything appears to dissolve the mixture is refluxed an additional 40 minutes. The mixture is cooled, filtered and the filtrate acidified. The white precipitate (8.0 g, 58%) is collected and dried. The solid has m.p. >2050C and an NMR (d 6 -DMSO) which showed a pyrrole proton at 7.52 The mass spectrum is also consistent for a monobrominated compound.

k 82 EXAMPLE 42 Preparation of 2-bromo-3-(p--chlorophenvl)pvrrole

COOH

1CC HNCH, CH0H\ ci_ C1-07

D

10N

N

Br H Br H 000004 oo D 04 5-bromo-4-(p-chlorophenyl)pyrrole-3-carboxylic acid (8.0 0.026 mmol) is added to aminoethanol 0 00 (24 mL) and the slurry slowly warmed to 110-120 C and 0 held at that temperature for 1 hour. The solution is S cooled and poured into water and extracted with ether.

0 The ether extract, by thin layer chromatography (75/25, hexane/ethyl acetate), shows a major fast moving spot and a slower moving minor component. Work-up of the 00 ether leaves a dark solid (4.0 56%) which is 2bromo-3-(p-chlorophenyl)pyrrole and is used immediately to prepare 5-bromo-4-(p-chlorophenyl)pyrrole-2-carbonitrile.

liii I -ill--i- I 00 00 0 000 000000 0 0 00t,0~ *0 o i~ 83 EXAMPLE 43 Preiparation of 5-bromo-4- (P-chlorophenvl) pvrrole-2carbonitril e C1 DME Cl. 10

C'SO

2 NCQ OMF-- BrN BrN CN BH BrH A freshly prepared sample of 2-bromo-3-(Rchlorophenyl)pyrrole (4.0 0.015 mmol) is dissolved in dry dimethoxyethane (25 mL). Then while holding the temperature below 25 0 C, chiorosulfonyl isocyanate (3.08 0.022 mmol) is added. After stirring overnight, the solution is treated with dimethylformamide (6 mL) and stirred f or 3 hours. Finally, the solution is poured into water precipitating a brown solid (3.8 g, Dry column chromatography (80/20 hexane/ethyl acetate) yields 1.4 g of white solid with m.p.

2 02-204 0

C.

0 00 00 0 0 00 0 00 0 00 00 0 0 0 000 0 00 0 0 0 0 00 0 0 Calcd for C 11H 6BrCIN2 Found: C, 47.20; 27.42.

C, 46.90; H, 2.13; N, 9.95; Cl, 12.61; Br, 28.39.

H, 2.09; N, 9.80; C1, 12.36; Br, 84 EXAMPLE 44 Preparation of 3. 5-Dibromo-4-(p-chlorophenvl) pvrrole-2carbonitril1e 00 o 000 000000 0 010 Br N

CN

Br H Di oxane Br 2 B r C 1 N C N Br

H

0 *0 9 0 Ii 0 *0 00 0 4 0* 0 000 0 4* 04 00 A sample of 5-bromo-4-(p-chlorophenyl)pyrrole -2-carbonitrile (2.2 0.0078 mol) is dissolved in mL of dry dioxane. The solution is heated with bromine (1.3 0.008 mol) ii,, dioxane (20 mL) and then stirred overnight at room temperature. The reaction mixture is poured into water precipitating a tan solid (2.6 g., A portion (1.6 g) is purified by flash chromatography using 75/25 hexane/ethyl acetate to give 0.8 g of grey solid with m.p. 191-194 0

C.

Calcd for C 11

H

5 Br 2 C1N 2 C, 36.61; H, 1.38; N, 7.76; Cl, 9.84; Br, 44.3.

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

85 EXAMPLE Preparation of 3-(3.4-dichlorophenvl)-4-nitropyrrole C1

CH

3 N1NCH SO NC NaH o o C Cl i 0 t

H

Sodium hydride (2.66 g of a 60% suspension in oil is rinsed with dry ether; 66 mmol) and suspended in 150 mL of dry ether. To this mixture is added over 20 minutes a mixture of 12.0 g (5.5 mmol) of 3,4-dichloro- O 0 20 -nitrostyrene and 10.8 g (5.5 mmol) of (.-tolylsulfonyl)methyl isocyanide in 50 mL of DMSO and 150 mL of 4 ether. The mixture is stirred for 1.5 hours and then diluted with 150-200 mL of water and additional ether.

00 The ether layer is separated, dried over magnesium sulfate, and concentrated in vacuo. The resulting 10.6 g of crude product is purified by chromatography on silica gel using a 4:1 mixture of chloroform and ethyl acetate. A 7.2 g solid fraction is recrystallized from i chloroform-ethyl acetate-hexane to give 3.0 g of yellow solid, m.p. 187-188°C (dec.).

Anal. Calcd for C 1H6C12N202: C, 46.72; H, 2.35; N, 10.90.

Found: C, 46.96; H, 2.60; N, 9.77 iI 44 3 i KEH/198f 86 EXAMPLE 46 Preparation of 2,5-Dichloro-3-(3,4-dichlorophenyl)-4nitropyrrole o-0+S-C2--- C1 C1 0 N 0 2 N 2 SN C1 N C1 oH H 0 P r o To a mixture of 3-(3,4-dichlorophenyl)-4-nitropyrrole (2.5 g, 9.7 mmol) warmed to about 40 C in 0, 200 mL of chloroform is added over one minute 2.95 g (22 mmol) of sulfuryl chloride. After another hour, Sthe mixture is diluted with 100 mL of saturated sodium 0o0 bicarbonate solution and 300 mL of ether. The organic o. layer is separated and dried over magnesium sulfate.

Concentration, in vacuo, leaves a brown solid which is :oo. chromatographed on silica gel using 4:1 chloroform o, ethyl acetate. An orange solid fraction is recrystal- S 2 O lized from chloroform and then rechromagraphed on silica gel using 4:1 chloroform ethyl acetate to yield 0.36 g of yellow solid, m.p. 193-194°C.

Also prepared by procedure of Examples 45 and 46 above is 2,5-dichloro-3-nitro-4-phenylpyrrole, m.p.

193-194(dec.).

i4 t t 87 EXAMPLE 47 Preparation of -chlorophenvl)pvrrole-2,4-dicarbonitrile

CN

DMF

N +ClSO2 NCO+(CH 3 2

NCHO

H C1

CN

NC

0 c 0 0 00 coooo A sample of 2-p-chlorophenyl-3-cyanopyrrole, 0 0 S this solution is added chlorosulfonyl isocyanate (3.39 g, 0.024 mole), The addition is exothermic and some cooling is necessary. After stirring 3 hours at room temperature, dimethylformamide (6-7 mL) is added and the solution is stirred 4 hours more. The solution is 'o then poured into water precipitating a white solid (3.4 0 g, 100%). A sample (1.0 g) is purified by dissolving in ethyl acetate and then passing the solution through a 60 mL course filter funnel packed with silica gel.

The filtrate is concentrated to yield 0.7 g of a white co solid with m.p. 235-240 0

C.

jo"CN

I

88 Following the procedure of Example 47, the following analogs are prepared: NC 7R

N

H

L

0 0 0 00000 000 ~0 4 0 3-Cl

H

L

4-Cl 4-QCF 3 4 -CF 3 M. ID.

>225C 185-1900 180-185C 0 Oi 00 1 0 Od 0 00 00 4 00 00 0 000 EXAMPLE 48 Prenaration of 3-Bromo-5- (r-chlorophenvl~pvrrole-2 .4dicarbon itril1e 0 0 ioxane +Sr 2

NI

carried on to the saponification step.

89 A sample of 5-(R-chlorophenyl)pyrrole-2,4dicarbonitrile (1.0 g, 0.004 mole) is dissolved in mL of dioxane and a solution of bromine (0.8 g, 0.005 mole) in dioxane (10 mL) is then added thereto. The solution is stirred several hours at room temperature and then poured into water precipitating a white solid (1.2 g, 100%). The solid has a m.p. >2250C and a mass spectrum of a sample gives a pattern consistent with the desired structure.

10 Following the procedure set forth above in 0 0 0 o Example 48, the following additional compounds are o/ prepared: B

CN

2 5 R L 3-C1 4-C1 >250°C H 4-OCF2 218-223 C 6 0 R 'o 2/L r I I I w V

J

90 EXAMPLE 49 Preparation of bromofumaronitrile CN CN -Br 2 /CHC1 3 10i NC (-HBr) NC Br o o 00 t O (5.3g; 0.2 mol) in CHC1 3 (150 m L) is heated to reflux, resulting in a clear solution. A solution of bromine 0 0 time most of the color has been discharged. The coo solution is cooled and solvent is removed under reduced 4 0 o pressure, leaving an amber oil (weight approximately theoretical for bromofumaronitrile). The oil is subjected to bulb-to-bulb distillation (0.2 mm Hg), 0 maintaining the temperature below 120 C (above that point, a rapid decomposition of material occurs). A semi-solid is obtained which slowly forms a waxy, amber solid, m.p. 43-47 0

C.

Calcd for C 4 HBrNj, C, 30.57; H, 0.64; N, 17.83.

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

oy a i d. y directly for conversion to 3-(p-chlorophenyl)-pyrrole- 2-carbonitrile.

i, B ia i i

::L

91 EXAMPLE Preparation of 2-phenyl-pvrrole-3,4-dicarbonitrile

CN

NC 8r NC CN TMS

N

HMPF/3 (-TMS,-HBr,-CH 3

SH)

0o S00o 0 o o 0 oou 2 0000 oo o 0000 00 0 o 00 0 0 o 0 o 00 0 0 0000 Ga 0000D Under a nitrogen purge, a solution of bromo- 20 fumaronitrile (4.7 g; 0.03 mol) and N-(trimethylsilyl) methyl-S-methyl-benzene-thioimidate (7.1 g; 0.03 mol) in hexamethylphosphoramide (HMPA) (35 mL) is stirred at room temperature. In a single portion, water (1.6 mL); 0.09 mol) is added, washed in with HMPA (10 mL). The solution almost immediately begins to exotherm, the temperature rapidly reaching 100 0 C before subsiding.

The resulting dark red solution is allowed to stir at ambient temperature 20 hours. Pouring the reaction mixture onto an ice/water mixture results in a gummy material which slowly yields a discreet beige solid.

This material is collected by filtration and washed with cold water and dried on the filter. After further drying (vacuum oven; 60 the material is twice recrystallized from C2H 4 C1 2 (DARCO treatment) to yield a white powder.

I

92 Calcd for C 12

H

7

N

3 C, 74.61; H, 3.63; N, 21.76.

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

m.p. 197-200 0

C.

EXAMPLE 51 Preparation of 2-bromo-5-phenylpyrrole-3,4-dicarbonitrile 0 SNC CN NC CN /\Br 2 /CHC1 3 1' NH Br NH o a .Under a nitrogen purge, 2-phenyl-pyrrole-3,4dicarbonitrile (1.4 g; 0.0075 mol) is added to CHC 3 0 o 20 mL), much of the solid dissolving. A solution of bromine (0.4 mL; 0.008 mol) in CHC1 3 (5 mL) is added °oa* dropwise over 20 minutes. Initially the color is a, discharged rapidly, but as a new, gummy solid begins to 2' precipitate, the color remains. After stirring minutes at ambient, the mixture is brought to reflux, resulting in a much more discreet solid. After refluxing 90 minutes, the reaction mixture is cooled and an aliquot is removed and analyzed (HPLC), showing ca. starting material still remaining. In a single portion fresh bromine (0.2 mL; 0.004 mol) is added, and refluxing continued another 45 minutes whereupon an aliquot shows 10% starting material remaining. Another fresh portion of bromine (0.2 mL; 0.004 mol) is added to the refluxing suspension and refluxing is continued

K

L 93 o0 0 0 0 0 04 0 0 0 00 0 00 0 0) 0 00 0 a 0 another 30 minutes. The suspension is cooled and stirred 18 hours at room temperature. Solvent is removed under reduced pressure to yield a greenish solid which is extracted with hot CHC1 3 leaving behind S a dark residue. The extract is treated with DARCO and filtered hot. The clear yellow filtrate quickly began to deposit a white precipitate. After cooling to 0 C, the white solid is collected by filtration.

Calcd for C2 H6BrN3: C, 52.94; H, 2.21; N, 15.44; Br, 29.41.

Found: C, 51.64; H, 2.35; N, 14.91; Br, 28.69. m.p. 225-258 C.

EXAMPLE 52 Preparation of 2-(3,4-Dichlorophenvl)-5-nitropyrrole-3carbonitrile 0 00 0 00 0 0£ 00 0 00

CN

N

cil Cl

CN

HNO

3 Acg-- 0 2 N

C

C1 Br, 24.33; C1, 10.80.

t i.o i iP -94 2-(3,4-Dichlorophenyl)pyrrole-3-carbonitrile g, 0.013 mole) is added to acetic anhydride mL) and 90% nitric acid (0.6 ml) with very little exotherm. The mixture is slowly warmed to 300 and is then held at 30-33O until everything goes into solution. Gradually a new solid precipitates. The mixture o is stirred for 2 to 3 hours at room temperature and then poured into water and ice to decompose the acetic o anhydride. After stirring 1 hour the mixture is i0 filtered and the solid (2.9 g, 82%) collected and 10 oo B dried. A portion (1.5 g) is purified by column chromatography on silica gel using 75/25 hexane/ethyl acetate for elution to give 0.7 g of yellow solid with m.p.

0 0, 228-231° o 0 Calcd for C 1 1

H

5 C1 2 N302: C, 46.80; H, 1.77; N, 14.89; o Cl, 25.17 0 Found: C, 46.50; N, 1.96; N, 14.27; Cl, 24.30.

0 By the same procedure, starting with 2-(Ep \o chlorophenyl)pyrrole-3-carbonitrile, 2-(p-chlorophenyl)- -5-nitropyrrole-3-carbonitrile is obtained, m.p.

201-206 0 C. Also, 2-(p-trifluoromethylphenyl)pyrrole-3- 2 carbonitrile gives 2-(D-trifluoromethylphenyl)-5-nitro- pyrrole-3-carbonitrile by the above procedure. This compound has a malting point of 164-165.5°C.

1 EXAMPLE 53 Prelparation of 4-Bromo-2- 4-dichlorophenvi) p~vrrole-3 -carbonitrile d joxane 02 H C1 C 1 01 0 o aonitrile 2 4-isorophenyof ta-nitopsold-witharb- 190000C Calcd for C H BrCl N 0 36.57; H, 1.10; N, 11.63; 11 4 23 2 Br, 22.13; Cl, 19.67.

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

Following the above procedure of Example 53, but starting with 2- (p-chlorophenyl) -5-nitropyrrole-3carbonitrile gives 4-bromo-2- (p-chlorophenyl) pyrrole-3-'carbonitrile, m.p. 180-185 C I (a- 96 EXAMPLE 54 5-(3,4-Dichlorophenyl)-4-nitropyrrole-2-carbonitrile S/ NO 2 Cl C1 SNC* NC N 0 H C1 C 2 0 H C1 E P 0 S4 15 To a suspension of 5-(3,4-dichlorophenyl)pyro00 role-2-carbonitrile (1.2 g, 5.1 mmol) in 25 mL of acetic anhydride at 300 under nitrogen, is added dropwise 90% nitric acid (0.3 mL, 5.1 mmol). The reaction exotherms to 450C and becomes a green solution. After being allowed to stir for 2 hours the oreaction is poured into 50 mL of water and stirred 0 a oO 0 vigorously for 5 minutes. The beige precipitate which o 00 2 0 in Afe ben aloe tosi fo 2hor th (i^ 0 ractin i pored nto50 m ofwatr an strre o oo Ii 0 'C

C

97 EXAMPLE 3-Bromo-5-(3,4-dichlorophenyl)-4-nitropyrrole-2-carbonitrile o. NO a

B

oH C1 H C1 nitropyrrole-2-carbonitrile (0.6 g, 2.1 mmol) in 10 mL "o of dioxane at 25°C, under nitrogen, is added dropwise a solution of bromine (0.3 g, 2.1 mmol) in 5 mL of dioxane. The reaction is allowed to stir overnight.

"o Addition of 50 mL of water causes precipitation of a o o yellow solid which is collected and vacuum oven dried 4 0 0 00 (50 mm Hg, 450C) to afford the brominated pyrrole (0.7 g, 90%) as a light yellow solid, m.p. >2000C.

EXAMPLE 56 4-(p-chlorophenyl)-2-(trifluoromethyl-2-oxazolin-5-one In a single portion, trifluoroacetic anhydride, (1.7 mL; 0.012 mol) is added to powdered 2-(pchlorophenyl)glycine (11.4 g; 0.06 mol), causing an immediate exotherm to about 400C, a yellow color forming on the surface of the solid. As the mixture is slowly heated to 70 0 C, more of the solid dissolves to an orange/amber oil. All the solid dissolved in 3 approximately 2 hours, and heating is continued another ~cll~l,-~ 98 hour. Solvent is removed under reduced pressure on a rotary evaporator. Toluene is twice added and removed under reduced pressure, but the odor of trifluoroacetic acid is still evident. This yellow semi-solid (yield theoretical; purity 90% by HPLC) is the above-identified compound and is used in the next step without further purification.

0 o EXAMPLE 57 0 "0o° 10 Preparation of °w"et pyrrole-3-carbonitrile S4-(p-chlorophenyl)-2-(trifluoromethyl)-2-oxa- (2.5 g; 0.01 mol) is dissolved in nitromethane (50 mL). In a single portion, 2-chloroacrylonitrile (8.0 mL; 0.10 mol) is added to the solution, and the resulting solution is stirred 18 hours at reflux under a nitrogen atmosphere. Cooling the o red/brown solution to -5°C in an ice-acetone bath causes the formation of a precipitate which is collected by filtration and washed with a small portion of 0Do cold nitromethane. The resulting tan solid is m o recrystallized from hot ethylene dichloride yielding the product as white crystals (1.8 g; 56% theory), m.p.

238-241°C (dec.).

By utilizing the appropriate arylglycine in the procedure of Example 55 and following the procedure of this Example, the following yl)pyrrole-3-carbonitrile were prepared:

CN

N R 3 H Found: C, 46.96; H, 2.60; N, 9.77 99 r'V Cy H 4-CH 3 191-193 H 4-OCH 3 168-180(dec.) 3-Cl 4-Cl 245-246(dec.) Under a nitrogen purge, a suspension or 2-(R- R L m.p.°C chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile (1.6 g; 0.005 mol) in acetic acid (25 mL) is heated, all the material dissolving to a clear solution at 15 about 600C. A solution of bromine (0.8 mL; 0.015 mol) in acetic acid (10 mL) is added dropwise over minutes to the refluxing solution. The solution is S*o refluxed 6 hours then allowed to stir 18 hours at room temperature. The HPLC of the reaction mixture shows about 80% conversion to product. The mixture is heated back to reflux and more bromine (0.5 mL; 0.01 mol) in acetic acid (5 mL) is added dropwise. After refluxing another 3 hours, the aliquot shows 95% conversion to product. The reaction is cooled, and solvent removed under reduced pressure on a rotary evaporator to obtain a dark grey solid. Toluene is added to the mixture and removed under reduced pressure, but the odor of acetic acid still remains. The entire material is dissolved in hot toluene (75 mL) to a turbid solution which is treated with DARCO filter and filtered. The light pink solution deposits a white solid upon cooling to ambient. After cooling in the freezer, the solid is collected by filtration, washed with hexanes, and dried on the filter. Further drying in a vacuum oven at 45C C 100 provides the product (1.2 g; app. 60% theoretical); m.p. 247-250 0C(dec.).

Anal. Calcd for C 12H 5BrC1F 3N 2 C, 41.20; H, 1.43; N, 8.01; Br, 22.89; Cl, 10.16; F, 16.31.

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

By brominating the appropriate 10 fluoromethyl)pyrroie-3-carbonitrile, obtained by the procedure of Example 57, according to the above recipe, the following additional examples are prepared: o 0 0 000 0 0 0000 0 0 0 0 000000 0 0 0000 0 0 000e 0 00 04 0 00 00 0 0 00 0 00 00 0 0 0 ago

CF

3 O 00 00 0 0 oO 00 0 0 00 0 00

R

H

3 -Cl

H

L

H

4 -CH 3 4-Cl 4-CF 3 2 35-238 24 4-2 218-223 22 5-22 6

I

-^i 101 EXAMPLE 59 Preparation of 2-(4-chlorophenvl)-5-trifluoromethylyVrrole-3,4-dicarbonitrile 0 2 N OH 0 N H- \Br (CF CO)?0 F S( )N F CHNO 2 hr I hr Cl C1 0 0 0 0oo 20 Trifluoroacetic anhydride (3.1.mL; 0.022 mol) reflux, causing all the material to dissolve to a yellow/orange solution which is heated 2 hours further.

o 0 The reaction mixture is cooled, and solvent removed 000 Co under reduced pressure. Toluene, is twice added and removed under reduced pressure to yield a very thick 0 -1 oil (VCO 1800cm This residue is dissolved (some insolubles) in CH NO (40 mL) and bromofumaronitrile (2.7 g; 0.018 mol) is added in a single portion. The 2o50 resulting solution is heated at reflux 18 hours, yielding a dark red solution. Solvent is removed under reduced pressure and the dark residue is dissolved in 3 CH 2 C1l 2 some insolubles being removed by filtration.

o JU^ -102- The material is fractionated via dry column chromatography (silica gel; 3% 2-PrOH in CH 2 C1 2 and appropriate fractions are taken. Evaporation of one fraction yields the desired compound as a yellow solid which i~s recrys~nallized from CH 3 CN (DARCO treatment) to yield a pale yellow solid (0.2 g) m.p. 238-241 0 C. (some dec).

o a 0920 090 0030

IL

-103 EXAMPLE p-chloro-8-r (for-mylmethvl) aminolcinriamonitrile. diethyl acetal

H

2

NCH

2 CH<OEt) 2 -oun ;I .09

_-H

2 0 C

H

A magnetically stirred solution of 250.Og (1.39 mol,) Of p-chlorobenzoylacetonitrile, 203 mL (185.9g, l.39mo1) o~f 2,2-diethoxyethylamine, and 1300 inL o 44 of dried toluene is heated at refux for 20 hours. Water is collected in a Dean-Stark trap (23.8 mL, 95.2% God theoy The hot cloudy dark brown solution with a large amount of undissolved solids is filtered through diatomaceous filter aid. After dilution with 200 mL of a 00 0 0 Q 9EtOAc, the solution is filtered through a 7cm X 13.5cm 0 0 column of silica gel. The filtrate is concentrated in v-acuo to give 354.3g (86.4% crude yield) of a clear dark oil which slowly solidifias. This solid is recrystallized from hot cyclohexane to give 324.2g (79.1% yield) of a waxy orange solid. NI4R of this product shows it to be composed of 78% and 23% isomeric mixture of p-chloro-p- (formylmethyl) amino~cinnamonitri2 diethyl acetal, m.p. 60-72 0 C. The following analytical data is for another similarly prepared sample.

Max(mull,Nujol): 3325(s), 3065(m), 2197(s), 1600(s), 1530(s), 1314(m), 1265(m), 1173(m), 1154(m), 1128(s), 1100(s), 1060(s), 1022(s), 939(m), 895(m), 844(s), 768(m), 730(m) Cm

-I,

z -104- H-NI4R(chloroform): 57.47 J=8.6Hz, 2.12H, two aromatic protons) 67.37 J=8.6Hz, 2.12H, two aromatic protons) 55.10 84.8 6(Z br t, 1. 25H, one N-H proton), 54.69(Z) 54.60(E) J=5.lHz, 1.05H-, one proton at the acetal carbon), 54.07 54.05(Z) 0.83H, enamine P proton], 63.71(E) 63.68(.Z) J=7.lHz, 2.22H, tw o methylene protons of o one of two ethoxy groups], 63.56(Z) 63.53(E) [q, J=7.lHz, 2.22H, two methylene protons of one of two 10 ethoxy groups), 63.18 J=5.lHz, 1.77H, two methylene protons of the ethyleneacetal group), 61.20 J=7.l1Hz, #fit4-90OH, six methyl protons of the two ethoxy groups).

C-NMP (chloroform): 6161.21 (a-enamine carbon), 6136.29 6134.60(E) [either C-1 or C-4 of the phenyl ring], 5134.08(Z) 6132 30(E) [either C-1 or C-4 of the phenyl ring), 5129.J~4(Z.) 6129.89(E) [either C-2,6 or C-3,5 of 044 the phenyl ring), 6128.94(.Z) 5128.63(j) [either C-2,6 or C-3,5 of the phenyl ring], 5121.19(Z) 6119.50(E) [ni-t.ile carbon), 699.43(Z) 8100.63(j) [fi-enamine carbon), 661.88(Z) 663.25(E) [methine carbon of the acetal), 862.64(.Z) 663.03(E) [methylene carbons of the o ethoxy groups), 646.32(.Z) 647.33(j) [methylene carbon of the ethyl amine group), 615.26 (methyl carbons of the ethoxy groups).

Microanalysis (MW 294.78): Calcd: C, 61.11%; H, 6.50%; N, 9-52V' Cl, 12.03%.

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

Following the above procedure but substituting the appro,"priate benzoylacetoylacetonitrile for p-chlorobenzoylacetonitrile and/or the appropriate 2,2-di(C 1

C

4 alkoxy)ethylamine for 2,2-diethoxyethylamine yields the following compounds: jl) a white powder.

105 t7 -CO-CH 2 CN H 2

NCH

2

CH(C,-C

4 alkoxy) 2 toun

R

L

-H

2 0 y7~~ ~-N 4 44 0 q A4

N-CH

2 CH(Cl-C 4 alkoxy) 2

H

L M (Ct- 4koxy)- 0DO

H

p-CH 3 m-OCH 3 p-CH 3OCO

H

R-OCH 3 :3 (0C 2 H 5 2 (OC 2 H 5 2 (0C 2 H 5 2 (OC 2 H 5 2 (OCH 3 2 (OCH 3 2 (0C 2 H 5 2 (0C 2 H 5 2 (0C 2 H 5 2 68-7 3 59-69 Red orange semi solid 62-7 0 p-Cl

H

p-CH 3

H

p-Cl p-OCF 3 p-CF 3

J

9 L.-LJu I J- L AIL. -n r l u the refluxing suspension and refluxing is continued 106 EXAMPLE 61 2(p-chlorophenvl)-Dvrrole-3-carbonitrile

/CN

C

Cl H

CN

CF

3

CO

2 H H \/C S 0 0 STo 108 mL of trifluoroacetic acid stirred at 23°C is O added 54.00g (0.183mol) of solid p-chloro-p-[(formyl- 4 methyl)amino]cinnamonitrile, diethyl acetal over a 15 period of 45 minutes. This addition produced an exotherm to 38°C and, 32 minutes into the addition, a solid started to precipitate. After stirring at room o0* temperature for 30 minutes, the reaction mixture is 0 0°o0 vacuum filtered and the collected solid is washed first S 20 with trifluoroacetic acid, secondly with an ethyl o o acetate-hexane mixture, and finally with hexane. The yield is 16.83g of an off-white solid, mp *o prepared sample.

5 Max(mull, Nujol): 3275(br 2225(s), 1502(s), 1410(m), 1275(m), 1200(m), 1108(s), 1023(m), 999(m), 908(m), 843(s), 752(s), 722(s), 695(s), 620(s) Cm 1 107 H-NMR(acetone): 511.22 (v br s, 0.99H, one pyrrole N-H proton), 67.82 J=8.9Hz, 2.46H, two aromatic phenyl protons), 67.51 J-8.9Hz, 2.46Hz, two aromatic phenyl protons), 67.02 J=2.6Hz, 1.01H, one pyrrole proton at 56.58 J=2.6Hz, 0.77H, one pyrrole proton at C-4).

C-NMR(acetone): 6137.73 (pyrrole 6134.42 (E-chlorophenyl at 6129.93 (methine carbons at of the phenyl ring), 6128.07 (methine carbons at I 10 C-2,6 of the phenyl ring), 6121.21 (pyrrole at 6117.93 (nitrile carbon), 6113.78 (pyrrole carbon at 690.86 (pyrrole carbon at C-3).

4 4 a 4, Microanalysis (MW 202.64): Calcd.: C, 65.19%; H, 3.48%; N, 13.83%; Cl, 17.50% S 15 Found: C, 64.18%; H, 3.52%; N, 13.63%; Cl, 17.74% Use of the above procedure as shown or with the substitution of concentrated hydrochloric acid for o O0 trifluoroacetic acid affords the following compounds: 0 00 0 0 H 0 00 0 25 M and/or R mDoC Acid Used 4-C1 165-166 conc. HC1, CF 3

COOH

3,4-di-Cl 216-221 CF 3

COOH

2-C1 156-157 CF 3

COOH

4-OCF 3 143-145 CF3COOH 4-CF 3 179-180 CF 3

COOH

2,4-di-Cl 197-199 CF 3

COOH

I

108 3-Cl 4 -CN 4-F 4-SO 2CH3 3, 4-di-F 3 -CF 3 4-COOCH 3 4 -CH 3 4 -NO 2 150-156 210-212 167-170 221-221.5 173-175.5 166-168 155.5-158 117-137 174-177 CF 3COOH CF 3COOH conc. HC1 CF 3COOH

CF

3

COOH

CF 3COOH CF 3COOH CF 3COOH 04 99 9 900 9 9 '9-p 9 9 0 0 900004 9 4 0000 0 0 9000 Oe 0 0 04 0 00 0 00 0 0 0 0 00 0 90 0 0 0 '9 00 9, o 000 EXAMPLE 62 4 .5-Dichloro-2- (P-chlorophenvl) pyrrole-3-carbonitrile C N H C IC 2.2 eq S0 2 C1 2 HO~t 0 99 0 9 9 4 00 00 0 0 00 4 00 To a mechanically stirred solution of 16.83g (83.lmmnol) of 2-(R-chlorophenyl)pyrrole-3-carbonitrile in 450 mL of glacial acetic acid at 36 0 C is added dropwise 14.7 mL (24.70g, 183.Omnol) of sulfuryl chloride over a period of 18 minutes. The addition.

produces a slight exotherm to 390C and, after another 16 minutes, the reaction mixture is vacuum filtered. The collected solids are washed first with acetic acid and then with water. This solid after recrystallization from hot ethyl acetate, melts at 259-261 0 C. By similar procedures other samples of this product were prepared and the analytical data for on~e such product is shown S below.

1 V~ LJ.IJ1LL~~~L±U~JJ~tiy 1) 0J pyrrole-3-carbonitrile, m-p. 180-185 C.

max(mull, INujo1): 3170(br 3100(m), 2225(s), 1508(m), 1097(m), 825(s), 717(m), 660(m) cm-1 H-NM(DMSO): 57.72 J=8.6Hz, 2.OOH, two aromatic protons), 67.56 J=8.6Hz, 2.OOH, two aromatic protons).

C-N!IR(DMSO): 6136.01 (pyrrole C-2 carbon), 6133.92 (p-chlorophenyl C-4 carbon), 6129.09 (R-chlorophenyl carbons), 6127.41 (p-chlorophenyl C-4 carbon), 0 0 Ott6127.11 (R-chlorophenyl C-1 carbon), 6114.49 (nitrile 0o 10 carbon), 6114. 10 (pyrrole C-5 carbon), 6110.92 (pyrrole C-4 carbon) 890.09 (pyrrole C-3 carbon) Microanalysis (MW 271.54): Calcd.: C, 48.65%, H, 1.86%; N, 10.32%; Cl, 39.17% 4 Found: C, 49.22%; H, 2.12%; N, 9.85%; Cl, 39.03% 9 EXAMPLE 63 4. 5-Dibromo-2-(acx~a-trifluoro-tp-tolv1) -pyrrole-3-carbon trile CN Or CN 9~ 09 Bra -F3 Sr H

F

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

>230 0

C.

Anal. Calcsd for C12H5 Br 2

F

3

N

2 C, 36.55; H, 1.27; 7.11; Br, 40.61.

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

110 Following the above procedure but substituting the appropriately substituted phenylpyrrole-3-carbonitrile for 2- (a,cl,-trifluoro--tolyl)pyrrole-3-carbonitrile yields the following compounds.

00 o ooo 00 C.o 0 0 S 0 p0V4 o 1 00*# 00 1 0 I o as o 00 00 0 0 C)0 o PQ 0 00 00 o o*o o oo 0e' 0

S

00 0 0 0 0 0 00

L

H

20

H

2-Cl 2-Br

H

H4

H

3- 3- 3- 3- 3-

H

3-

H

2- 4-NO 2 4-F 4-F 4-SO 2 CH 3 F 4-F F 4-F Cl 4-Cl Br 4-Br 4 -OCF 3 4-OCF 3 4 -OCF 3 4-CN 4-CN 4-SO 2 CH 3 4 -NO 2 Cl 4 -Cl 3-CF 3 4 -COCH 3 2, 3 -CH=CH-CH =CiA 4 -CH 3 Cl 4 -Cl 274-277 >220 >220 >230 >230 >220 222-225 >230 >240 >230 246-249 >260 >230 251-254 244 -24 7 215-217 >230 an orange/amber oil. All the solid dissolved in approximately 2 hours, and heating is continued another

I

Ii ill

L

H

In H

H'

2-Cl

H

3-Cl

H

R

3-Cl 4-Cl 4-Cl 2-Cl 4-CF 3 4 -Br 2-Cl 4-Cl

H

0no >230 >230 273-27 4 >230 >230 >235 >230 >235 2 54-255 o o 0 044

I'

.04604 ''ft '4 014 '4 o 1

U

o 0* 4) 0 04 o 4, o 0~ 4 o 04 0 444 0 04 44 0 O 40 O 00 4 00 EXAMPLE 64 a- 2-diethoxvethvlamino -8-nitrostyrene and 3-nitrom 2-phenylpyrrole

~CCH

2

NO

2 H2NCH 2 CH(0E~zC) 2

-O

NH-CH C H(COE t)

NO

1 H Alpha-nitro acetophenone (5.7g, 0.0345m) is taken up in 100 mL toluene and 4.6g (0.0345m) of amino acetaldehyde diethyl acetal is added. The reactants are put into a 250 mL RB flask fitted with a Dean-Stark trap. The trap is filled with 4A molecular sieves and the mixture is heateO at reflux for 18 hours. The toluene is removed i~n vacuo to give 8 .36g of a-(2,2-diethoxyethylamino)-fl-nitrostyrene as a brown oil. To this oil is added 50 mL of concentrated HCl. 'As the flask is swirled the oil turns to a yellow suspension.

After 10 minutes the solid is filtered to give 2.48g of a yellow solid. Recrystallization from ether/ethylacetate/hexane gives the product as two fractions, 2.08g of m.p. 190-192 0 C, Max 1485 cm- 1(NO 2 H-NMR(CDC 3 /DMSO) 66.73(m,2H), 7.46(m.5H).

112 other P-nitrostyrene compounds can be prepared by the above reaction by substituting the appropriately substituted a-nitro acetophenone for a-nitro acetophenone and/or appropriate 2,2-di(C 1 -C 4 alkoxy)ethylamine for amino acetaldehyde diethyl acetal to give the following compounds .20 2 040 444 OrE 0 4 4 4 4 4 0 4 0 0440 2 444' 44 4 o i 4 o 4~ 00 0 0 00 0 00 02 4 2 24 00 o 2 .0 204 0 20 0 .2 00 00 4 0 00 0 24 0 1 1

-CCH

2

NO

2

H

2

NCH

2

CH(C,-C

4 al koxy )2 to I uene

-CH

2

CH(C

1 -0 4 alkoxy) 2

H

p-CH 3 p-OCH 3 p-CH 3

OCO

H

p--OCH 3 :3 (0C 2 H 5 2 (0C 2

H

5 2 (0C 2 H 5 2 (OC 2 H 5 2 (OCH 3 2 (OCH 3 2 (0C 2 H 5 2 R-Cl

H

R-CH

3

H

R-CF 3 on the filter. Further drying in a vacuum oven at -113 EXAMPLE 2 .3-Dichloro-4-nitro-5-vRhenvlpvrrole- N0 2 C1 NO 2 NaOCI 1 -Z N H- C1 H .4H A mixur of3nto2peylyr 2 0.083m n6 Lo doaei coolntaed in an icgv .2go elatw whi lutin.g withm fcrcosinerctial odiuethypachtate is headed drivsfer Aftrpig stirrig f 45o mntsothe 00.9 nd Ct, ar4ade.96 TH layer; are seartdndte2o 0 ridoe nyru 3 g5adcnetae ~vcu ogv .1 fylo 114 EXAMPLE 66 Insecticide and acaricide evaluations All tests are preformed using technical materials. All concentrations reported herein are in terms of active ingredient. All tests are kept at 27 C.

Spodoptera eridania, 3rd instar larvae, southern armyworm 0 10 A Sieva lima bean leaf expanded to 7-8 cm in length is dipped in the test suspension with agitation for 3 seconds and placed in a hood to dry. The leaf is then placed in a 100x10 mm petri dish containing a damp 15 filter paper on the bottom and ten 3rd instar cater- ,o pillars. The dish is maintained for 5 days before observations are made of mortality, reduced feeding, or a any interference with normal moulting.

0 0 a o O 4 20 Spodoptera eridania, 7-day residual o The plants treated in the above Test are 0 oO 0 O" maintained under high intensity lamps in the greenhouse for 7 days. These lamps duplicate the effects of a o o, bright sunny day in June in New Jersey and are kept on 0 25 for 14 hour day length. After 7 days, the foliage is sampled and assayed as in the above-said Test.

CH

2 C1 2 some insolubles being removed by filtration.

i i 115 Aphis fabae, mixed instar, bean aphid Pots containing single nasturtium plants (Tropaeolum sp.) about 5 cm tall are infested with about 100-200 aphids one day before the test. Each pot is sprayed with the test formulation for 2 revolutions of a 4 rpm turntable in a hood, using a #154 DeVilbiss atomizer. The spray tip is held about 15 cm from the plant and the spray directed so as to give complete coverage of the plants and the aphids. The sprayed pots are set on their sides on white enamel trays and held for 2 days, following which mortality estimates are .tade.

Tetranychus urticae(P-resistar,t strain),2-spotted o spider mite Sieva lima bean plants with primary leaves expaned to 7-8 cm are selected and cut back to one plant per pot. A small piece is cut from a leaf taken o 4 from the main colony and placed on each leaf of the test plants. This is done about 2 hours before treato° 20 ment to allow the mites to move over to the test plant and to lay eggs. The size of the cut piece is varied to obtain about 100 mites per leaf. At the time of the treatment, the piece of leaf used to transfer the mites Sis removed and discarded. The mite-infested plants are S 25 dipped in the test formulation for 3 seconds with agitation and set in the hood to dry. Plants are kept for 2 days before estimates of adult kill are made using the first leaf. The second leaf is kept on the plant for another 5 days before observations are made of the kill of eggs and/or newly emerged nymphs.

1 116 Diabrotic undecimpunctata howardi, 3rd instar southern corn rootworm One cc of fine talc is placed in a 30 ml wide-mouth screw-top glass jar. One ml of the appropriate acetone suspension is pepetted onto the talc so as to provide 1.25 and 0.25 mg of active ingredient per jar. The jars are set under a gentle air flow until the acetone is evaporated. The dried talc is loosened, 1 cc of millet seed is added to serve as food for the ot o 10. insects and 25 ml of moist soil is added to each jar.

c I The jar is capped and the contents thoroughly mixed on a Vortex Mixer. Following this, ten 3rd instar root- Sorms are added to each jar and the jars are loosely Scapped to allow air exchange for the larvae. The treatments are held for 6 days before mortality counts are made. Missing larvae are presumed dead, since they h adecompose rapidly and can not be found. The concentrations used in this test correspond approximately to and 10 kg/ha, respectively.

0o Rating Scale: o' 0 no effect 5 56-65% kill o o 1 10-25% kill 6 66-75% kilZ 2 26-35% kill 7 76-85% kill 3 36-45% kill 8 86-99% kill 4 46-55% kill 9 100% kill R reduced feeding 5 t eatm nts are held for 6 d ys b for mo tali y c unt 0 0 000 0 0 0 0 00 0 0 0 0 0 0 0 000 0 0 0 0~A 00 0 'P 4 0 0 0 00 0 0 0 0 4 0 Table I B3EAN

APHIDS

ppm 100 0

ARMYWORKS

Compound 4, 5-dichloro-2phenylpyrrole- 3 -carbonitrile 4, 5-dichloro-2- (p-chlGrophenyl) p-yrrole-3 carbonitrile 1000 9 ppm 100 8.5 7 days 9 9 P. RES

MITES

ppm 300 0 0

SCRW

kg/ha 0 03 0 -~0 0 0

%D

*00 '00 5.5 ~0T.o6~ .~S0O--r*-oo

K

L.

00 00 000 0 0 00 0 00 0 0 0 0 0 0 0 0 000 000 0 Table I (Cont.)

BEAN

APHIDS

ppm 100 0

ARMYWOPMS

P.RES

MITES

ppm 300 0 Compound 4, 5-dichloro-2- (3 ,4-dichlorophenyl) pyrrole- 3 -carbonitrile 4, 5-dichloro-2- (trifluoromethoxy) phenylpyrrole-3 -carbonitrile 1000 9 ppm 100 9 7 days 9

SCRW

kg/ha 0 7.7 -4 ~0 rrro Cmon1 0 0 iac Ia 0 day 30 00 4,5-dicloro-2-0 9 00 Tabe I(Cot.

4,5-dichloro-2- 0 99 0 0 (0-chioropel chtlropyrrole- 3carbonitrile

F.

000 0 .0 0 0 P.R1ES

MITES

Table I (Cont.)

BEAN

APHIDS

ppm 100 0 ARNYWORN4S ppm 100o 7 days Compound 4 ,5-dibromo-2- (o-chlorophenyl) pyrrole-3 -carbonitrile 4, 5-dibromo-2- (p-chlorophenyl) pyrrole-3-r rbonitrile 1000 9

PPM

300 0 0

SCRW

kg/ha 0 bow a 'a 'a a 'a 00 "a 0 'a ob Table I (Cont.)

BEAN

APHIDS

ppm 100 0

ARIC-TWORMS

P.-RES

MITES

ppm 300 9 Compound 4 ,5-dibromo-2- (alpha, alpha, aipha-trifluorop-tolyl,)pyrrole- 3-carbonitrile 4, 5-dichloro-2- 4-dichiorophenyl) pyrrole- 3-carbonitrile 1000 9 ppm 100 9 9 7 days 9

SCRW

kg/ha 9 dwli 000 0 0 00 000 0 co0o P. RES M4ITES Table I (Cent.) Compound 4, 5-dibromo-2- (2 ,4-dichlorophenyl) pyrrole- 3 -carbonitrile 4 ,5-dichloro-2- (m-chlorophenyl) pyrrole-3 -carbonitrile

BEAN

APHIDS

ppm 100 0 0 1000 9 ppm 100 9 9 7 days 9 9 AP14YWOR14S

PPM

300 0 0

SCRW

kg/ha 0 <~0

M

00 00 0 00 000 0 000 0 0 0 0 00 0 0 0 0 0 4000 0 0 0 00 0 0 9 0 000 0 0 0 0 00 00 0 000 0 0 0 9 0t 4 0 0 0 00 0 0 0 000 000 0 Table I (Cant.)

ARMYWORMS

Compound 2, 3-dichloro-4pyrrole 2, 3-dichloro-5- (p-chlorophenyL) 4 -nitropyrrole 2, 3-dibromo-5- (p-chlorophenyl) 4-nitropyrrole

BEAN

APHIDS

PPM

100 0 0 1000 0 ppm 100 9 7 days 9 9 9

P.R.ES

MITES

ppm 300 0 0

SCRW

kg/ha 50 0 0 0 CD H- rt H0 0) so rt ii I 0 CD 00 00 :7 w 0 :Ij L- I.-

(U

000 0 0 a a a a 4 0 000 00 0 a 0 a 0 a 000 a

A-~

0

A

X

1 g t Jl~ Table I (Cont.) Compound 2, 3-dibromo-4pyrrole 2, 3-dichloro-5- 4-dichlorophenyl) -4nitropyrrole

BEAN

APHIEDS

PPM

100 0 0 PPM 7 1000 100 days 9 9 9 ARMYWOR14S

P.RES

MITES

PPM

300 0 0

SCRW

kg/ha 50 0 0 0- W 0 0 000 0 0 Table I (Cont.)

P.RES

MITES SCWRW 7 ppm kg/ha

BEAN

APHIDS ARMYWORMS pp'm ppm Compound 100 1000 100 days 300 2-(p-bromo- 8 9 9 9 8.5 8 phenyl) dichloro-3nitropyrrole u-I 2,3-dichloro-4- 8.3 9 9 9 9 8.31 (alpha, alpha, alphatrifluoro-ptolyl) pyrrole 126 EXAMPLE 67 Insecticidal evaluations or, o oo 0 0 oa 0o00oo0 o o o 0 0a 0 0 0 0 0 o o 0 50 ou o D e E c oa Heliothis virescens, 3rd instar tobacco budworm Cotton cotyledons are dipped in the test formulation and allowed to dry in a hood. When dry, each is cut into quarters and ten sections placed individually in 30 ml plastic medicine cups containing a 5-7 mm long piece of damp dental wick. One third- 10 instar caterpillar is added to each cup and a cardboard lid placed on the cup. Treatments are maintained for 3 days at before mortality counts and estimates of reduction in feeding damage are made.

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

Blattella germanica, bait test, adult male German cockroach A 0.1% bait is prepared by pipetting 1 ml of a 1000 ppm solution of the test compound in acetone onto 1 gram of cornmeal in a 30 ml wide-mouth bottle.

3 The bait is dried by passing a gentle stream of air into the bottle. The bait is placed in a 1 pint wide-mouth Mason jar and ten adult male cockroaches are added. A screen lid is placed on the jar and a small piece of cotton soaked in 10% honey is put on the top S of the screen lid. Mortality counts are made after 3 days.

t 127 Blattela germanica, residue test, adult male German cockroach One ml of a 1000 ppm acetone solution of the test material is pipetted slowly over the bottom of a 150 x 15 mm petli dish so as to give as uniform coverage as possible. After the deposit has dried, adult male cockroaches are placed in each dish and the a lid is added. Mortality counts are made after 3 days.

.Spodoptera eridania, systemic uptake, 3rd instar larvae, southern armyworm The compound is formulated as an emulsion containing 0.1 gm of the test material, 0.2 gm of Emulphor EL-620® emulsifier, 10 ml of acetone and 90 ml of water. This is diluted 10-fold with water to give a 4 S 100 ppm emulsion for the test. Subsequent °a dilutions are made with water as needed. Sieva lima bean plants, with the primary leaves expanded to a Sao length of 7-8 cm, are cut off at least 3 cm above the soil level to avoid contamination with soil bacteria that will cause decay of the stem during the test. The o, cut stems are placed in the test emulsions and each 3 stem is wrapped with a bit of cotton to hold the stem off the bottom of the bottle and to limit evaporation and volatilization of the compound. The test is maintained for 3 days at 27 C to allow the compounds to be taken up into the plant. Following this, one leaf is removed from the plant and placed in a 100 x 10 mm Spetri dish with 10 southern armyworms as described in Test III. Mortality counts and observations of feeding damage are made 3 and 5 days later.

Empoasca abrupta, Adults, Western Potato Leafhoppers, Systemic Uptake The compound is formulated as an emulsion containing 0.1 gm of the test material, 0.2 gm of 1.1 1.

1.

liii' 068/9Z zAII 1.1 bdouu lg!! 146ji~l 11 40 ZXMAnliSddONW1)I 1OA.Jal50 Id 8 068L99PC I ZAxMAnjS.jbdoUWpIit JG pnqi5g ZAXMAnLSOdONWi)AFIHOJDaOV 'Id t:5

H

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

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

soillevl t avod cntainaton ithsoilbaceri V ta ilcuedcvo h tmdrn h et h o 0 0 004 0 0 *0 S 4 4 0 4 4 444 o 4 4 4 00 08 8 4 0 0 0 4 4 8 000 000 8 Table II

LEAF

HOPPER

ppm 100 100 TBW 3 ppm C-S SYSTEMIC G. COCKROACH

SAW

ppm 100

IE-AF

HOPPER

ppm 100

BAIT

ppm 1000

RES.

ppm 1000 100 -dichloro-2phenylpyrrole- 3carbon itril e 4, 5-dichloro-2- (p-chlorophenyl) pyrrole-3 -carbonitrile

ILAULUT

a a a a a a a a a a a a a a a a a o a a a a Table 11 (Cont.)

-EAF

HOPPER

ppm TBW 3 ppm C-S SYSTEMIC G. COCKROACH

SAW

PPM

100

LEAF

HOPPER

ppm 100

BAIT

ppm

RES.-

1000 nnn 1i nnl i0on 100 4, 5-dicttloro-2- 4-dichiorophenyl) pyrrole- 3-carbon itrile 4, 5-dichloro-2- (trifluoromethoxy) phenylpyrrole-3-carbonitrile 0 9 0 C 0 .0 000 0 0 a 0 0 000 o a 0 0 00 OS 0 40 0 0 0 .0 8 0 0 Table 11 (Cont.)

LEAF

HOPPER

ppm 100 1000 TBW 3 ppm C-S SYSTEMIC G.-COCKROACH

SAW

ppm 'I00

LEAF

HOPPER

ppm 100

BAIT

ppm 1000 RiES.ppm 1000 100 4, 5-dichloro-2- (o-chiorophenyl) pyrrole-3 -carbonitrile 2- (p-bromophenyl) dichioropyrrole- 3 -carbonitrile 004'? 0 00 000 0 0 0 0000 0 0 0 0 0400 0 0 0 0 000 O 4 0 0 00 00 0 0 0 0 9 0 0 a 0 0 0 0 0 400 040 0 Table II (Cont.)

LEAF

HOPPER

ppm 100 n000 TRW 3 ppm C-S SYSTEMIC G.-COCKROACH

SAW

ppm 100

LEAF

HOPPER

ppm 100

BAIT

PPM

1000

RES,

ppm 1000 'inn 4, 5-dichloro-2- (alpha, alpha, alpha-trifluorop-tolyl) pyrrole- 3 -carbonitrile 4, 5-dibromo-2- (o-chiorophenyl) pyrrole-3 -carbonitrile a a a a a a a a a 040 0 ;aa 0 4 a a 4 taq a aa Oa 4 Table TI (Cont.)

LEAF

HOPPER

ppm 100 1000 TBW 3 ppm C-S SYSTEMIC G.-COCKROACH

SAW

ppm 100

TLEAF

HOPPER

ppm 100

BAIT

ppm 1000

RES.

ppm 1000 100 4, 5-dibromo-2- (p-chlorophenyl) pyrrole-3 -carbonitrile 4, 5-dibromo-2- (alpha, alpha, aipha-trifluorop-to lyl) pyrrole- 3 -carbonitrile a o 0 0 0 0 0 00 000 0 0 0 000 0 0 0 a 0 0 0 0 000 0 0 0 00 00 0 0 0 0 a a 0 0 4 0 0 0 0 4 p 0 0 Table II (Cont..)

LEAF

HOPPER

ppm 100 TRW 3 ppm C-S SYSTEMIC G. COCKROACH

SAW

ppm 100

LEAF

HOPPER

ppm 100

BAIT

ppm 1000

RES.

ppm 1000 1000 100

LOOO

4, 5-dichloro-2- 4-dichiorophenyl) pyrrole- 3 -carbonitrile 4, 5-dibromo-2- 4-dichiorophenyl) pyrrole- 3 -carbonitrile

ML

444 0 4 0 Table II (Cont.)

LEAF

HOPPER

ppm 100 1000 TBW 3 ppm C-S SYSTEMHIC COCKRZOACH

SAW

ppm 100

LEAF

,HOPPER

ppm i00

BAIT

ppm i 000

RES.~

ppm 1000n 100 4, 5-dichloro-2- (m-chlorophenyl) pyrrole-3-carbonitrile 2 ,3-dichloro-4pyrrol e 0 9 a a 000 0 0 a a aaa a 4. 00 0 Table II (Cont.)

LEAF

HOPPER

ppm ion 1000 TBW 3 ppm C-S SYSTEMIC G. COCKROACH

SAW

ppm 100

LEAF

HOPPER

ppm 100

BAIET

1000

RES.

ppmn 1000 100 2, 3-dichloro-5- (p-chlorophenyl) 4 -nitropyrrole 2, 3-dibromo-5- (p-chlorophenyl) 4 -nitropyrrole 2, 3-dibromo-4pyrrole 8 8 8888 8 8 8 08 8 8 8 880 8 888 8 8 0 8 888 0 0 8 8 0 88 8 8 8 88 8 8 8 8 8 0 0 888 8 0 8 8 83 08 8 a a 8 8 8 8 8 8 8 8 8 8 8 8 ~8 3 880 8 808 088 0 Table II (Cont.)

LEAF

HOPPER

ppm TBW 3

PPM

C-S SYSTEMIC G. COCKROACH

SAW

ppm

LEAF

HOPPER

ppm

BAIT

ppm 1000

RES.

ppm 1000 1 00 i~o i~o i~o 100 2,3 (3 ,4-dichlorophenyl) -4-nitropyrrole 2- (p-bromophenyl) dichloro-3 nitropyrrole

I

0 0 4000 000 0 0 6 a a a a. 0 co Table II (Cont.)

LEAF

HOPPER

ppm 100 1000

TBW

3 ppm C-S SYSTEMIC G.-COCKROACH

SAW

ppm 100

LEAF

HOPPER

ppm 100

BAIT

ppm 1000

RES.

ppm 1000 100 2, 3-dichloro-4alpha, alphatrifluoro-ptolyl) pyrrole 139 EXAMPLE 68 A) Evaluation of test compounds as nematicidal agents Culture Maintenance: Cultures of C. elegans (Bristol strain from J. Lewis) are maintained on E. coli lawns on NG Agar Plates at 20 0 C. New cultures are established weekly.

Nematodes for testing are washed from 4-5 day old cultures using Fresh Ascaris Ringers Solution a (FARS). The worms are further washed with FARS, con- 0 taining gentamycin, to reduce bacterial contamination 10 and centrifuged to separate worms from wash solution.

This procedure is repeated three times. The washed o. worms are then added to C. briqqsae Maintenance Medium (CbMM), from GIBCOa to which is added gentamycin (600 units/ml) and mycostatin (0.5 mg/ml).

15 5 The tests are then made with mixtures of three 0 04 o*0* compounds, piggy-backed from another high capacity screening program to reduce additional labor and comoo0" pound expenditures.

Compounds are dissolved in acetone and made up to volume with equal parts of water. The final test o o concentration of each compound in the mixture is 150 0° 0 ppm. The test material is micropipetted (25 ul) into a single well of a 96-well sterile tissue culture plate b (COSTAR) and the solvent allowed to evaporate. These "treated" plates are used immediately or stored in a freezer without apparent adverse effects on the compounds.

A freshly prepared volume (50 ug) of C.

3 elegans in CbMM is micropipetted into each treated well and several control wells per plate. Culture plate are incubated at Observations for efficacy are made under a dissecting microscope at 4, 24 and 48 hours post-immersion. Immediately prior to reading the plate, it is .4 140 gently tapped to stimulate the movement of the worms.

Activity is judged subjectively, but semi-quantitatively, based on the drug effects on motility of the adults and larvae. The criteria are as follows: 8 no motility, 7 markedly reduced motility in approximately of worms, 6 reduced motility, 5 slightly reduced motility, 0 normal motility, same as controls. Other factors indicating activity are easily noted such as death, rigor mortis, contraction, coiling, paralysis, 10 abnormal twitching, reduced worm population in 48 hours and other deviation from normal behavior.

PROCEDURE FOR CAENORHABDITIS ELEGANS ASSAY ar o OC a o a a a

C

a a a 8a an p o O* a as Sa a al C 00 Day 0 Day 4 20 .Inoculate E. Coli-NG Agar Dish With 30-50 C.

Elegans .Incubate At 200C.

.Harvest New C. Elegans Population .Wash With Antibiotics .Transfer To CbMM .Add C. Elecans (25-100 UL) To "Medicated" Wellsa .Observe For Activity At 4 Hours Post- Immersion .Observe For Activity .Observe For Activity Day 5 Day 6 a Medicated Wells May Be Prepared Fresh Or Earlier And Stores In Freezer Data obtained in these tests are reported in Table III below.

bysemicj. upyru= The compound is formulated as an emulsion containing 0.1 gm of the test material, 0.2 gm of N -c

II

141 of 0 0 o a 0 0Q 0 8 0 0 o 0o O 04 0 99 4 4 4 09 0 0r 0 Q 0 a B) Root-Knot Nematode Assay Populations of the root-knot nematode (Meloidogyne incognita) are maintained on Fireball tomatoes in the greenhouse. Egg masses are removed from the infested root surfaces and are kept on moistened filter paper for 24 hours to allow them to hatch.

Larvae emerge and drop into the water beneath the paper.

Larvae for test are transferred to cell plate wells containing test compounds at 300 ppm in 3% acetone, 10 about 10 larvae per cell well. Infested wells are held at 27°C and mortality is determined 24 hours after treatment.

Data obtained are reported in Table III below.

I

E

I

-142 Table III C. Ele. Root Knot 150 ppm~ Nematodes.

L A 300 ppm 4,5-dichloro-2-[p- 4 (trifluoromethoxy) phenylpyrrole-3 -carbonitrile 0 0 4,5-dichloro-2-(alpha, 9 9 0 alpha,alpha-trifluorop-tolyl) pyrrole-3carbonitrile 00 K 15 4,5-dibromo-2-(alpha, 9 9 0 alpha, aipha-trifluoroo ~*0p-tolyl)pyrrole-3carbon itril1e 0 04 00 20 2,3-dichloro-4-nitro-5- 0 0 9 0 0 0phenylpyrrole 2,3-dichloro-5-(D-chloro- 9 9 9 phenyl) -4 -nitropyrrole 2,3-dichloro-5-(3,4- 9 9 C) dichiorophenyl) -4nitropyrrole 0 2-(p-bromophenyl)-4,5- 9 9 6 dichloro-3 -nitropyrrole 2,3-dichloro-4-nitro-5- 9 9 alpha, alphatrifluoro-p-tolyl) pyrrole 1 -i

P

4 ml::i

I

143 EXAMPLE 69 oo 0 4 0 09 o B 0 0 0 o a a 0 0 0 01 0 00 (j D O Following the procedures of Examples 59 and compounds of the invention are evaluated against a variety of insect species including: leaf hoppers, tobacco budworm, southern armyworm, and the German cockroach. The rating system is the same system used in the above-said examples. Data obtained are reported in Table IV below. Where two or more tests have been 10 conducted with the same test compound, the results are overaged. also, a in the table indicates no test.

ii i- t c j I i n I a r 00 00 6 0 0 0 0 000 0 0 0 0 0 0 0 0 600 0 0 0 00 00 0 0 00 0 0 0 0 0 0 0 0 0 000 9 000 090 0 Table IV

LEAF

HOPPER

TRW 3 ARMYWORMS CooS SYSTEMIC ppm 100 ppm ppm 100 1000 1.00 7

SAW

ppm inn

LEAF

HOPPER

ppm inn G. COCKROACH

RES.

ppm lonn Compound 2 ,5-dichloro-4phenylpyrrole-3 carbonitrile 2 ,3-dibromo-4pyrrole 4-chloro-2- (pchiorophenyl) pyrro'ie-3 -carbonitrile I1000 davs 0 6 0 9 0 0 9

L

U 0 0 0 040 0 04 000 0 4 0 4 4 0 t 0 004 0 4 44 40 0 04 4 4 0 4 0 0 0 4 0 0 4 4 404 000 4 Table IV (Cont.)

LEAF

HOPPER

TBW 3 ARMYWORMS C-S SYSTEMIC ppm 100 ppm ppm 100 1000 7 100 days

SAW

ppm 100

LEAF

HOPPER

ppmn 100 G. COCKROACH

RES.

ppm 1000 Compound 1000 4,5-dichloro-2-(O- 0 0 chiorophenyl) pyrrole -3 -carbonitrile 5-bromo-2-(P-chloro- 0 9 phenyl) pyrrole-3 carbonitrile 4,5-dichloro-2-(3,4- 9 dichiorophenyl) -1- (ethoxymethyl) pyrrole-3 -carbonitrile 9 .9 .1

I

0000 0 0 00 0 00 000 0 0 0 000 0 0 0 £000 0 0 0 :0 02 a Table IV (Cont.)

M"A

HOPPER

TRW 3 ARMYWORMS C-S SYSTEMIC pm 100 ppm ppm 100 1000 7 100 days

SAW

ppm 100

LEAF

HOPPER

ppm 100

G.-COCKROACH

RES.

ppm 11000 7~ Compound 4, 5-dichloro-2- (Pchiorophenyl) -1methylpyrrole-3 carbonitrile 1000 0 9 0 4R8 -3 -cyanopyrrole-2 yl) methylbenzoate 4,5-dibromo-2-(3,4- 0 9 dichiorophenyl) pyrrole-3 -carbonitrile CCC p a C C 0430 a C C C

C

C a a 43 43, CCC C ~C C C C C C C C C C C a a C C CCC 9& C Table IV (Cont.)

LEAF

HOPPER

TRW 3 ARMYWORMS C-S SYSTEMIC ppm -u unl ppm ppm inn 11 n 7

SAW

ppm 100

LEAF

HOPPER

ppm 100 G. COCKROACH

RES.

ppm 1000 Compound 4, 5-dichloro-2- (alpha, alpha, alphapyrrole-3 -carbonitrile 4, 5-dichloro-2- (3, 4-dichiorophenyl) l-ethylpyrrole-3 carbonitrile 4, 5-dichloro-2- (3, 4-difluorophenyl) pyrro-le-3 -carbonitrile 11 nun 100 daArs 0 fl 000 000 4 S 0 4 0 0 C 4 00 0 0 0 0 0 0 0 0 oaO 4 9 0 S 4* 00 0 0 0 0 S 0 o 0 0 4 0 0 0 4 0 4 000 000 4 Table IV (Cont.)

LEAF

HOPPER

TBW 3

ARMYWORMS

C-S SYSTEMIC ppm 11 fnn ppm Ppm inn i infn 7 i nn A

SAW

Ppm

LEAF

HOPPER

ppm G. COCKROACH

RES.-

ppm Compound 4 ,5-dichloro-2- (3, 4 -dichiorophenyl) -l-Dlethylpyrrole-3 carbonitrile 4, 5-dichloro-2- Ep- (methylsul fonyl) phenyl ]pyrrole-3 carbonitrile 11 nnn 100O 100J~ 4 ,5-dibromo-l-methyl 0 (alpha, alpha, alpha-trifluoro-ptolyl) pyrrole-3carbon itrile

L

U

a a 0 0 0 a 0 000 0 0 0 0 a a a 0 0 0 o 0 0 0 0 0' S 0 0 a a a a 000 0 0 4) 4 00 00 4 0 00 0 4 0 0 0 4 4 4 0 0 0 taO 000 0 Table IV (Cont.)

LEAF

HOPPER

TBW 3 ARMYWOP14S C-S SYSTEMIC ppm 11 nn ppm ppm 'Inn 'Innn 7 'inn Ai 7c

SAW

ppm

LEAF

HOPPER

ppm G. COCKROACH

RES.

ppm Iona Compound 4, 5-dichloro-2- (pfluorophenyl) pyrrole-3 -carbonitrile 4,5-dibromo-2-(3,4difluorophenyl) pyrrole-3 -carbonitrile 4, 5-dibromo-2- (pfluorophenyl) pyrrole-3 -carbon itrile 11 n nn 100 i0o i 9 9 9 4.5 9 -~4

IL

0 0 000 0 0 0 0 0 0 0 0 0 0 0 0 00 0 0 0 0 0 0 4 0 0 00 00 0 0 4 0 0 0 0 0 a 0 0 0 S 80 0 0 0 000 0 000 000 0 Table IV (Cont.)

LEAF

HOPPER

TBW3 ARMYWORMS C-S SYSTEMIC ppm Ppm ppm inn I1000 7 100 days

SAW

ppm 100

LEAF

HOPPER

ppm 100 G. COCKROACH

RES.

ppm 1000 Compound 10 4, 5-dibroino-2- 0 nitrophenyl) pyrrole -3 -carbonitrile 4, 5-dichloro-2- 0 nitrophenyl) pyrrole -3 -carbonitrile 1-benzyl-4, 5-dibromo 9 (alpha, alpha, alpha-trifluoro-ptolyl) pyrrole-3carbonitrile (1 1(100 0 1000 4.5 9

U

M

a a a a p cPa 0 S 0 *q sa 0 0 a a a a 4 a a a sa aco a Table IN (Cont.)

LEAF

HOPPER

TBW 3

ARMIYWORMS

ppm 7 100 1000 100 davs C-S SYSTEMI1C ppm 100 ppm

SAW

ppm 100

LEAF

HOPPER

ppmR 100 G. COCIKROACH

RIES.

ppm 1000 Compound 4, 5-dichloro-2- (pcyanophenyl) pyrrole -3 -carbonitrile 4, 5-dibrorno-2- [p- (methylsulfonyl) phenyl Ipyrrole-3 carbonitrile 4, 5-dibromo-2- (pchiorophenyl) pyrrojle-3 -carbonitrile 1000

AL

K

0 00 000 0 900 0 0 0 0 00 0 0 0 0 o 9 00 0 0 o a o a 0 0 0 000 o 9 0 0 00 90 9 0 0 0 0 4 0 a 0 9 0 0 4 0 000 000 4.

Table IV (Cont.)

LEAF

HOPPER

TBW 3

ARMYWORMS

pm 7 100 1000 100 days C-S SYSTEMIC pinpm ppm

SAW

ppm 100

LEAF

HOPPER

ppmn 100 G. COCKROACH

RES.

ppm 1000 Compound 4, 5-dichloro-2- (3, 4 -dichiorophenyl) (methylthio) ethyl] pyrrole-3carbonitrile 1-methyl-4, dichloro-2- (3,4dichiorophenyl) pyrrole-3 -carbonitrile i finn 100 1000

U

p 6 0 0 00 00 6 0 000 0 0 0 000 0 0 0 O 0 0 0 9 0 00 Table IV (Cont.)

TEAF

HOPPER

TRW 3 ArMYWORMS C-S SYSTEMIC G. COCKROACH ppm ppm ppm io0 1000 7 i00 days

SAW

ppm 100

LEAF

HOPPER

ppm 100t

RES.-

ppm 1000n Compound 4 ,5-dichloro-1methyl-2- (alpha, alpha,alpha-trifluoro-p-tolyl) pyrroiLe-3 -carbonitrile 5-bromo-4-chloro- (R-chlorophenyl) pyrrole-3 -carbonitrile 2, 3-dichloro-5- (3, 4-dichiorophenyl) 1- (ethoxymethyl) -4nitropyrrole 1000 100 iooo 6 00 *0 0 00 004 0 000' 0 0 V CC 0 0 C C 0 C C tot, 0 C te

C

0 0 0 0 000 o 0 0 0 48 00 0 0 0 4 0 4 C 0 C 0 '0 "0 CC C 5 040 000 4 Table IV (Cont.)

LEAF

HOPPER

TBW 3 ARMYWOR14S C-S SYSTEMIC ppm 100 ppm ppm 100 1000 7 100 dlays

SAW

ppm 100

LEAF

HOPPER

ppm 100

G.-COCKROACH

RES.

ppm 1000 Comipound 1000 4 -bromo-5-chloro- 2- (p-chlorophenyl) pyrrole-3 -carbonitrile loro-2- 4-dichiorophenyl) pyrrole-3 carbonitril1e 0 9 9 Ethyl 2,3-dichioro- 0 4-dichiorophenyl) -4-cyanopyrrole-l-acetate 0 0 0 CO 0 0 o 00 0 00 000 0 000 0 0 0000 0 0 0 o 0 00 0 00 0 0 0 a a 0 0 000 0 0 0 4 00 00 0 4 a 0 0 0 a 9 0 0 Table IV (Cont.)

LEAF

HOPPER

TBW

3 ARMYWOPMS C-S SYSTEMIC G.COCKROACH ppm 100 pm ppm 100 1000 7 100 days

SAW

ppm 100

LEAF

HlOPPER ppm i00

RES.

ppm In()( Compound 1000O 4 ,5-dichloro-l- (ethoxymethyl) -2- (alpha, alpha, alpha-trifluorop-tolyl) pyrrole-3carbonitrile (3,4 dichiorophenyl) pyrrole-2, 4-dicarbonitrile 4, 5-dichloro-2- (3, 4-dichlorophenyl) (2-propynyl) pyrrole-3 -carbonitrile 9 0 9 o 0 00 0 0 0 o 00 0 64 800 0 0 0 8 Q 0 0 000 0 0 0 0 8 0 0 00 00 0 a 0 o 8 0 0 2 0 8 000 84 4 0 0 o 0 8 4 0 a 0 0 408 046 4 Table IV (Cant.)

LEAF

HOPPER

TBW 3 ARMYWORM4S C-S SYSTEMIC ppm 11 nnl ppm ppm 7

SAW

ppm

LEAF

HOPPER

ppm ion G. COCKROACH

RES.-

1000

H

0-

OH

(~D

Compound 4, 5-dibromo-3- (pchiorophenyl) pyrrole-2 -carbonitrile 4-dichiorophenyl) pyrrole-2, 4 -dicarbonitrile it fnnn inn 1000 100 davs ion 5-bromo-4 -chioro- 4-dichiorophenyl) pyrrole-3 -carbonitrile 0 9

I

o 0 C 0 0 00 000 0 0 0 000 0 0 0 0 00 a *4 4 40 0 Table IV (Cont.)

LEAF

HOPPER

TBW 3 AR!4YWCRMS C-S SYSTEMIC G.-COCKROACH Compyound 4, 5-dibromo-3- (p-chlorophenyl) -1-methylpyrrole -2 -carbonitrile 2 pyrrole-3, 4-dicarbonitrile 4-bromo-2 -phenyl- (trifluoromethyl) pyrrole-3-carbonitrile ppm 100 Ppm ppm 100 1000 7 100 days

SAW

ppm 100

LEAF

HOPPER

ppm 100

RES.-

ppm loon 1000 o 0 o 000 0 0 o o 0 o 1.0 000 0 0 0 0 00 0 o St 0 0 000 0o~.0q 00 0 4 0 0 0 0 0 0 000 1.

Table IV (Cont.)

LEAF

HOPPER

TBW 3 ARKY!WORMS C-S SYSTEMIC G. COCKROACH ppmR 100 ppm ppm 100 1000 7 100 days

SAW

ppm 100

LEAF

HOPPER

ppm 100

PIES.-

ppm 1000 Compound 2- 4-dichiorophenyl) -5-nitropyrrole-3 -carbonitrile 4-bromo-2- (3,4cichlorophenyl) -3 -carbonitrile 2, 4-dibromo-5phenylpyrrole-3 carbonitrile 1000 Compound 2 phenylpyi carboniti 2, 3-dibrc nitro-5-1 pyrrol e 4-chlorochi orophE pyrroiLe-.

nitrile v-v V 0 4 4 4 C) C 4 0 C 444 4 0 4 4 Table IV (Cont.)

LEAF

HOPPER

TBW 3

ARMYWORNS

7 100 days C-S SYSTEMIC G. COCKROACH ppm ppm ppm 100 100(

SAW

ppm 100

LEAF

HOPPER

ppm 100

RES.-

ppm 1000 Comp~ound i nnn 100 1000 2- (3,4-dichlorophenyl) -4 ,5-diiodopyrrole-3 -carbonitrile 2, 3-dibromo-5- (pchiorophenyl) -1- (ethoxymethyl) -4nitropyrrole 1-benzyl-2 ,3- (pchiorophenyl) -4nitropyrrole Compound 4, chi orophb -3 -carboi -bromo-: phenyl) p, carbonit: 4, dichloro] (ethoxymi role-3 -c 1 0 000 0 0 0 0 0 o 4 a 0 0 0 0 0 00* Table IV (Cont.)

LEAF

HOPPER

TBW 3

ARMYWORMS

7 inni davn C-S SYSTEMIC G. COCKROACI

SAW

ppm inn

IRAF

HOPPER

ppm 100 ppm ppm PPM 100 100c

RES.

ppm I non Compound 1 flflfl 100 1000 2, 3-dibromo-5- (p-chlorophenyl) -l-methyl-4 -nitropyrrole 4, 5-dibromo-2- (trifluoromethoxy) phenyl] pyrrole-3-carbonitrile 4, 5-dichloro-l- (ethoxymethyl) -2- (trifluoromethoxy) phenyl I pyrrole-3-carbonitril1e Compound 4, chioroph methylpy carbonit: R- -3 -cyano] yl) methy.

4 dichioro, pyrrolenitrile C 9 0 9 390 C 50 0 C 0 Table IV (Cont.) ARMYWORMS C-

LEAF

HOPPER

TBW 3 S SYSTEMIC ppm ppm ppm io00 1010 7 100 days

SAW

ppm 100

LEAF

HOPPER

ppm 100 G. COCKROACH

RES.

ppm 1000 Compound (p-chlorophenyl) -pyrrole-2, 4-dicarbonitrile 1-benzyl-4, 5dichloro-2 [p- (tri fluoromethoxy) phenyl ]pyrrole-3 carbonitril e 4, 5-dichloro-2- (p-chlorophenyl) (ethoxymethyl) pyrrole-3-carbonitrile 1000 100 i0oo Comyon (alpha, a trif luor pyrrolenitrile 4 -dichlo 1-ethyip carbon it 4, 4 -di fJuo pyrrolenitrile e 71.

a 0 000 0 0 000 0 0 -0 0 400$0 Table IV (Cont.)

LEAF

HOPPER

TBW 3 ARMYWORM4S 7 C-S SYSTEMIC ppm 11 nn ppm ppm

SAW

ppm ion

LEAF

HOPPER

ppm 100 G. COCKROACH

RES.

ppm 1000 Compound 4, 5-dichloro-2- 4-dichiorophenyl) -1-(2-hydroxyethyl) pyrrole-3carbonitrile 2- (p-chlorophenyl) -5-nitropyrrole-3 carbonitrile 4-bromo-2- (pchiorophenyl) -5- (trifiluoromethyl) pyrrole-3-carbonitrile i fnnn 100 100 100 davs Compon 4, 4 -dichlo: 1-methy: carboniti 4 (methylsi phenyl p, carbon it: 4, (alphi alpha-tr.

tolyl) py carbon it: a a C a o 0 0 aOO C a a a 0,4 Table IV (Cont.)

LEAF

HOPPER

TBW3 ARMYWOP14S C-S SYSTEMIC ppm 100 PPM ppm 100 1000 7 100 days

SAW

ppm 100

LEAF

HOPPER

ppm 100 G. COCKROACH

RES.

ppmR 1000 Cop~ound 4-bromo-2- (pchiorophenyl) -5nitropyrrole-3 carbonitrile (pchiorophenyl) pyrrol-2 ,4-dicarbonitrile 4, 5-dichloro-2- (3, 4-dichiorophenyl) pyrrole-1, 3-dicarbonitrile 1000 Compon f luoroph role-3-c 4, dif luoro role-3-c 4, fluoroph role-3 -c ~r~9sa 00 00 0 0 0 o 0 0 000 0 000 0 0 0 0 0 0 000 0 0 0 0 0 0 0 0 4 00 Qa C 0 0 0 RO 0 0 0 0 C 0 0 4 0 0 0 0 0 0 0 00 0 0 0 0 0 0 0 0 000 000 0 Table IV (Cant.)

LEAF

HOPPER

TBW 3 ARMYWOPR4S C-S SYSTEMIC ppm 100 ppm ppm 7

SAW

ppm

LEAF

HOPPER

ppm G. COCKROACH

RES.-

1000 Compound (benzyloxy) methyl]-4, 5dichloro-2- (3,4dichiorophenyl) pyrrole-3 -carbonitrile 4, 5-dichloro-2- (2, 4 -dichi oro-5 -fluorophenyl) pyrrole-3carbonitrile (trifluoromethoxy) phenyl] pyrrole-2 ,4-dicarbonitrile 1000 100 1000~c 1nf 100f Compound nitrophei -3-carboi nitrophei -3-carboi 1-benzyl.

(alphi alpha-tr.

tolyl) py: carbon it: '4 04 a 4 444 0 440 4 4 4 0 404 0 4 4 4 0000 *0 44 o 0 0 4 4 0 0 400 0 4 4 4 '43 44 0 440 3 3 0 4 04 3 0 a 4 40 4 e 3 4c4 4 4.44 oao a Table IV (Cont.)

LEAF

HOPPER

TBW 3 ARMYWORMS C-S SYSTEMIC ppm 100 ppm ppm 100 1000 7 100 days

SAW

ppm 100

LEAF

HOPPER

ppm 100 G. COCKROACH

RES.

ppm 1000 Compound 4, 5-dichloro-1- [(p-chlorophenoxy) methyl-2- (3,4dichiorophenyl) pyrrole-3 -carbonitrile 4, 5-dichioro-2- 4-dichiorophenyl) -1-(3-iodo- -2 -propynyl) pyrrole -3 -carbonitrile 1000 Cop~ound cyanophe -3 -carbo 4 (methyls pheny1]r carbon it 4, chioropl role-3-(

-IT

o 0 00 0 0 o 00 0 0 9 000 0 enOC C C 0 000 0 a 0 C 0 0 *OS 9 0 0 0 0 0 000 0 0 0 00 00 C 0 0 a C C 0 0 C OSO 000 0 Table IV (Cont.)

LEAF

HOPPER

TBW 3 7 C-S SYSTEMIC

SAW

ppm 100

LEAF

HOPPER

ppm 100 G. COCKROACH

RES.

ppm 1000 ppm ppm ppm Compoud 4-dichiorophenyl) -4-nitropyrrole-2 -carbonitrile 2, 4-dibromo-5- (pchiorophenyl) pyrrole-3 -carbonitrile (trifluoromethoxy) phenyllpyrrole-2 ,4dicarbonitrile I flfl -Lui Compound 4 -dichlo ethyl ]py carbonit 1-methyl dichioro dichioro pyrrolenitrile 0 9 Q

C

990 0 9 0 C 990 0 9 9 C C 000 9 9 0 90 0 0 0 0 a 0 a 0 a a 0 0 Table IV (Cont.)

LEAF

HOPPER

TBW 3 ARMYWORM4S C-S SYSTEMIC Compound (3,4dichiorophanyl) 4 -ritropyrrole- 2 -carbonitrile 4-bromo-2- (pchiorophienyl) -1- (trifluoromethyl) pyrrole-3carbonitrile 3, 4-dibromo-5- (3, 4-dichiorophenyl) pyrrole-2 -carbonitrile

RPM

Ion ppm ppm 100 1000 7 100 davs

SAW

ppm 100

LEAF

HOPPER

ppm 100

G.COCKROACH

RES.-

1000 1000 Compound methyl-2 alpha,al.

fluoro-p pyrrolenitrile (p-ch pyrrolenitrile 2, 3-dich 4-dichia 1- (ethox nitropyr 0 9 9 9 17 1 0 0 0. 0.

0 0 0 00 0 0 4 0 0 000 00 0~ 3 0 0 0 0 0 0.00 000 3 Table IV (Cont.)

LE.AF

HOPPER

TBW 3 ARHYWORMS C-S SYSTEMIC ppm I nnf ppm ppm 7

SAW

ppm

LEAF

HOPPER

ppm 100 G. COCKROACH

RES.-

1000 Compound 2- 4-dichiorophenyl) (trifluoromethyl) pyrrole-3 -carbonitrile (trifluoromethyl) 2- (alpha, alpha, alpha-trifluoro-ptolyl) pyrrole-3carbonitrile 11 flfl 'i nn '1000 100 davs 100 Compound 4 -broino- 2- (p-chl pyrrolenitrile l-benzyl loro-2-( ophenyl) ca rbon it Ethyl 2, (3,4phenyl) pyrroleo 0 o 00 000 0 J 4 004 Table IV (Cont.)

LEAF

HOPPER

TBW 3 ARHYWORMS C-S SYSTEMIC G. COCKROACH ppm 1I00 ppm ppm 100 1000 7 100 davs

SAW

ppm 100

LEAF

HOPPER

ppmT 100

RES.

ppm 1000 Comipound 2, 5-dibromo-4- (pchiorophenyl) pyrrole-3 -carbonitrile 3' 5-dibromo-4- (pchiorophenyl) pyrrole-2 -carbonitrile (trifluoromethyl) pyrrole-3 -carbonitrile 1000 Compound 4, (ethoxyne (alpha, al aipha-tri p-tolyl) p carbonitr 3 dichiorop pyrrole-2 nitrile 4, 4-dichior (2-prc role-3 -ca 7.5 9 4-broino-2-p-tolyl- 0 (trifluoromethyl) pyrrole-3 -carbonitrile 6 0 600

C

6 *06 0 Qeb 0 6 6 66 0 6 6 6 000 60 o 6 6 0 0 0 00 Table IV (Cont.)

LEAF

HOPPER

TBW 3 ARMYWORMS C-S SYSTEKIC G.-COCKROACH ppm 100 ppm ppm 100 1000 7 100 days

SAW

ppm Io0

LEAF

HOPPER

ppm 100

RES.-

ppla 1000 Compound 1000 4-bromo-2- (pchiorophenyl) -1- (e'..hoxymethyl) (trifluoromethyl) pyrrole-3 carbonitrile 4-bromo-2- (3,4dichi-orophenyl) -5- (trifluoromethyl) pyrrole-3 -carbonit.L le Compound 4, chloroph( role-2 -cz 5- (3,4-di phenyl) p) 4 -dicarbc 5-bromo-4 4-didl pyrrole-'nitrile A A C 0 o c. 0 *00 0 4Tabl IV (Cont.) 0JMWOM 0 0to* o 000.

A

0 0

LEAF

HOPPER

TBW 3 S SYSTEMIC ppm ppm ppm 'inn i nnn 7

SAW

PPM

LEAF

HOPPER

ppmR

G.-COCKROACH

RES.

ppm O000 Compound It fnnn -LIJU 100 d-s 100 100 (alpha, alpha, aipha-trifluoro -p-tolyl) pyrrole 4-dicarbonitrile l-methyl-3- (alpha, alpha,alpha-trifluoro-R-tolYl) pyrrole-2, 4-ei~arbonitrile CoMpon 4, (p-chloro -1-methyl -2-carbon 2 pyrrole-3 nitrile 4 -bromo-2 (trif lu pyrrole-3 nitrile 0 3 I 0 0 0 0 9 a a o 9 0 *00 9 0 9 0 o 0 0 9 099 a a 00 *o a a-a 9 0 0 9 9 ,a a09 9

I

Table -TV (Cont.)

LEAF

HOPPER

TBW 3 ARHYWORMS C-S SYSTEMIC ppm 100 pm ppm ion 10no0 7 100 days

SAW

ppm 100

LEAF

HOPPER

ppm 100 G. COCRROACH

RES.-

ppm 1000 Compound (trifluoromethyl) -2- (alpha, alpha, alphatrifluoro-p-tolYl) pyrrole-3 -carbonitrile 3 -bromo-l-methyl- (alpha, alpha, alpha-trifluoro-ptolyl) pyrrole-2, 4dicarbonitrile 1000 Compound 2- 4-di phenyl) -E pyrrole-2nitrile 4 -bromo-2 dichiorol -3 -carbor 2, 4-dibrc phenylpyi carboniti 0 4 0 000 0 a t Table IV (Cont.) ARMYWORMS

C-

000 0

LEAF

HOPPER

TBW 3 S SYSTEMIC ppm 11 nnf PPM PPM 'Inn 'innn 7

SAW

ppmR

LEAF

HOPPER

ppmR G. COCKROACH

RES.

ppm 1000 jcomound 4, 5-dichloro-2- (alpha, alpha, aipha-trifluorop-tolyl) pyrrole-l, 3-dicarbonitrile (alpha, alpha, alpha-trifluoro-p-tolyl) pyrrole-2, 4dicarbonitrile 11 nnn 'i nn da s 100 i0o compound 2- (3,4-di phenyl) -4 pyrrole-3 nitrile 2, 3-dibrc chi orophE (ethoxyme nitropyri l-benzyldibromo-E chiorophE nitropyrit h.

Claims

1. A compound having the structure: formula I 00 0 000 O Od 000p00l 0 0 S 00 o I 4 4 o I F T0 4 0 *4 0 04 00 0 0 00 00 00 0 060 0 06 0o 0 00 0 0u 0 (I) wherein X is F, Cl, Br, I, or CF 3 Y is F, Cl, Br, I, CF3 or CN; W is CN or NO2 and A is H; C1-C4 alkyl optionally substituted with from one to three halogen atoms, one hydroxy, one C1-C4 alkoxy or one C1-4 alkylthio, one phenyl optionally substituted with C1-C3 alkyl or C 1-C3 alkoxy or with one to three halogen atoms, one phenoxy optionally substituted with one to three halogen atoms or one benzyloxy optionally substituted with one halogen substituent; C 1 -C 4 carbalkoxymethyl; C 3 -Cq alkenyl optionally substituted with from one to three halogen atoms; cyano; C 3 -C4 alkynyl optionally substituted with one halogen atom; di-(C 1 -C 4 alkyl) aminocarbonyl; or C 4 -C 6 cycloalkyl-aminocarbonyl; Is is H, F, Cl or Br; and M and R are each independently H, C 1 -C 3 alkyl, 1-C3 A c1 1. d r1 1 (J P X. 0 U A H H- 0 4 P -H I 11 0 104 I L0) d CN I Q. "N W M M' 1 .11 0 1 0 P4 0 ~C OH 0 -4 414 0 *H 4 >1- 0 04 175 alkoxy, C 1 -C 3 alkylthio, C1-C 3 alkylsulfinyl, C 31-3 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 on adjacent positions and taken with the carbon atoms to which they are attached they may form a ring in which MR represents the structure: 00 4 94 bOC 4 04 44 0 o0 0040 o C 0 40c 0 04 001 -OCH 2 O- -OCF O- or Z is S(O)n or 0; R is H, F, CHF2' CHFC1, or CF R2 is C 1 -C 3 alkyl, Cl-C 3 alkoxy, or NR 3 R 4 R 3 is H or C I alkyl; R 4 is H, C1-C3 alkyl, or R 5 CO; R 5 is H or C1-C3 alkyl; and n is an integer of 0, 1 or 2.

2. A compound according to claim 1 wherein A is hydrogen or C -C alkoxymethyl; W is CN or NO 2 X 1 42 and Y are each CF 3 or Br; R !x F, Cl, Br, CF 3 or OCF 3 M is H, F, Cl, or Br; and L is H, or F.

3. A compound according to claim 1, chloro-2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile; 4,5-dichloro-2-(a,a,-trifluoro-R-tolyl)pyrrole-3-carb- onitrile; 2,3-dichloro-4-nitro-5-(a,a, a-trif uoro-p- -tolyl)pyrrole; 2,3-dichloro-5-(3,4-dichlorophenyl)-4- -nitropyrrole; 4-bromo-2-(p-chlorophenyl)-5-(trifluoro- methyl)pyrrole-3-carbonitrile; 3,4-dibromo-5-(3,4- -dichlorophenyl)pyrrole-2-carbonitrile; 2,4-dibromo-5- -(p-chlorophenyl)pyrrole-3-carbonitrile; phenyl)-3-(trifluoromethyl)pyrrole-2,4-dicarbonitrile; OC.L CI 0 P 0 0 P P-l4 rI r 4J 4 1 0 P4 Q ,Q r- r-i 4 1 0 -ri 0 c'i S-4 01 r mHH~ 0 01 rH H >1d 0- PI4 ~dzr 176 00 o 00 0 0 4 0444 01 04 0 6 4 4 0 0 0 O I 0 00O 0a 0 0 000 0 00d 3-bromo-5-(3,4-dichiorophenyl)pyrrole-2,4-dicarboni- trile; 4,5-dichloro-1-(ethoxymethyl)-2-(a,a,a- trifluoro-p-tolyl) pyrrole-3-carbonitrile; 4-bromo- -2-(p-chloro-phenyAt)- l-(ethoxymethyl) oromethyl)pyrrole-3-carbonitrile; and 4-bromo-2- -(3,4-dichlorophenyl)-5-(trifluoromethyl)pyrrole-3- carbonitrile.

4. A method for controlling insects, nematodes and acarina comprising: contacting said insects, nematodes and acarina, their breeding grounds, food supply or habitat with an insecticidally, nematicidally and acaricidally effective amount of a compound having the structure: L x (I) N A wherein X is H, F, Cl, Br, I, or CF 3 Y is F, Cl, Br, If CF3 or CN; W is CN or NO2 and A is H; C -C4 alkyl optionally substituted with from one to three halogen atoms, one hydroxy, one 14 alkoxy or one 14 alkylthio, one phenyl optionally substituted with 13 alkyl or C1-C3 alkoxy or with one to three halogen atoms, one phenoxy optionally substituted with one to I NI 0 0 Q3H 0 O H H- H- 0 *H 0)-H 0 P H r -H r rd P, r H 1 0 n O H 1 4 H 0 t 04o I'H T" Lore O SI 4J >i X N I 0 I P4. 4 -4 4-J H- -P I 0 -H LO 9 4 177 04 00 o 04.4 0 00*000 o 0 0 00 I 0 II 00 I P0 0 0b o oo, e 00 0 90 ou 4 00 0 0 4 1 three halogen atoms or one benzyloxy optionally substituted with one halogen substituent; C carbalkoxymethyl; C 3 C 4 alkenyl optionally substituted with from one to three halogen atoms; cyano; C 3 -C 4 alkynyl optionally substituted with one halogen atom; di-(C 1 -C 4 alkyl) aminocarbonyl; or C4-C6 cycloalkyl-aminocarbonyl; L is H, F, Cl or Br; and M and R are each independently H, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, C 1 -C 3 alkylsulfinyl, C 1 -C 3 alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF 3 R 1 CF 2 Z, R 2 CO or NR 3 R and when M and R are on adjacent positions and taken with the carbon atoms to which they are attached they may form a ring in which MR represents the structure: -OCHO-, -OCF O- I Z is S(O)n or 0; R 1 is H, F, CHF 2 CHFCl, or CF 3 R 2 is C 1 -C 3 alkyl, C 1 -C 3 alkoxy, or NR 3 R 4 R 3 is H or C1- 3 alkyl; R 4 is H, C 1 -C 3 alkyl, or R 5 CO,; R 5 is H orC 1 -C 3 alkyl; and n is an integer of 0, 1 or 2. A method according to claim 4 wherein said compound is: 4,5-dichloro-2-(3,4-dichlorophenyl)pyrrole-3-carbo- nitrile; 4,5-dichloro-2-(a,a,a-trifluoro-p-tolyl)pyrrole-3- carbonitrile; 2,3-dichloro-4-nitro-5-(a,a,a-trifluoro-p-tolyl) pyrrole; O~-4 I4 Q) C 4 r H 0 H- H- U >1 0 -4- a C) *H >i *H 0 -H 0 -H H0r 0 P I 9 4 tO I I M 4 CN~ M 0 178 Co 00 0 000 0000 0 0 0 000000 0 0 #000 0 0 0000 Op I o 0 0 0 *t 00 0 O 00 O 00 00 0 0 00 00 00 o 000 0 00 0 0 0 00 00 0 0 00 0 00 2, 3-dichloro-5-(3 ,4-dichiorophenyl) -4-nitropyrrole; 4-bromo-2-(*p-chloropheiyl) (trifluoromethyl) pyrrole- 3 -carbonitrile; 3, 4-dibromo-5- 4-dichiorophenyl) pyrrole-2-carbo- nitrile; 2, 4-dibromo-5- (p-chlorophenyl) pyrrole-3-carbonitrile;

5- (p-chlorophenyl) pyrrole-2 ,4-dicarbonitrile; 3-bromo-5- 4-dichlorophenyl)p~yrrole-2 ,4-dicarbo- nitrile; 4, 5-dichloro-l- (ethoxymethyl) a,a-trif luoro-p- tolyl) pyrrole-3-carbonitrile; 4-bromo-2- (p-chlorophenyl) -1-(ethoxymethyl) (tri- fluoromethyl) pyrrole-3-carbonitrile; or 4-bromo-2- (3 ,4-dichiorophenyl) (trifluoromethyl) pyrrole-3 -carbonitrile.

6. A method for protecting growing plants from attack by insects, nematodes and acarina, comprising applying to the foliage of said plants or to the soil or water in which they are growing, an insecticidally, nematicidally or acaricidally, effective amount of a formula I compound having the structure: wherein X is H, F, Cl, Br, I, or CF 3 Y is F, Cl, Br, ro I I I c) Wi S>4 0 -r4 I *rH LOP P *Hi 0 ClI 0 U o4 o g 0 4 0 4 H 4 r

08-~ 179 a q 0 0 nO C a. a 0 0 0 sIC 0 V 0 C O a 0 CC 0 OC S00 00 0 01)0 I, CF 3 or CN; W is CN or NO 2 and A is H; C1-C 4 alkyl optionally substituted with from one to three halogen atoms, one hydroxy, one C1-C4 alkoxy or one C1-C4 alkylthio, one phenyl optionally substituted with C 1 -C 3 alkyl or C1-C3 alkoxy or with one to three halogen atoms, one phenoxy optionally substituted with one to three halogen atoms or one benzyloxy optionally substituted with one halogen substituent; C -C 4 carbalkoxymethyl; C 3 -C 4 alkenyl optionally substituted with from one to three halogen atoms; cyano; C 3 -C 4 alkynyl optionally substituted with one halogen; di-(C 1 -C 4 alkyl) aminocarbonyl; or C4-C 6 cycloalkylaminocarbonyl; L is H, F, Cl or Br; and M and R are each independently H, C-C 3 alkyl, C1-C 3 alkoxy, C1-C 3 alkylthio, C1-C3 alkylsulfinyl, C -C 3 alkylsul- fonyl, 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 on adjacent positions and taken with the carbon atoms to which they are attached they may form a ring in which MR represents the structure: o o1 0o 0 00 0 o 004 0 a -OCFO- or N Z is S(0)n or 0; R 1 is H, F, CHF 2 CHFC1, or CF 3 R 2 is C 1 -C 3 alkyl, C 1 -C 3 alkoxy, or NR 3 R 4 R 3 is H or C 1 -C 3 alkyl; R 4 is H, C 1 -C 3 alkyl, or R 5 CO; R 5 is H or C -C3 alkyl; and n is an integer of 0, 1 or 2. 00 04 1 -H Q-a W 0- 4J P 0 4 4 >4g *H X r r- 4J 4) -180- 7. A method according to claim 6 wherein said compound is: 4, 5-dichloro-2- 4-dichiorophenyl) pyrrole-3-car~bo- nitrile; 4, 5-dichloro-2-(z,c,c-trifluoro-p-tolyl)pyrrole-3- carbonitrile; 2, 3 -dichloro-4 -nitro- a-trif luoro-p-tolyl) pyrrole; C, 1 00 2,3-dichloro-5-(3 ,4-dichlorophenyl) -4-nitropyrrole; I 4-bromo-2- (p-chlorophenyl) (trifluoromethyl) pyrrole- 3-carbonitrile; 3, 4-dibromo-5- 4-dichiorophenyl) pyrrole-2-carbo- nitrile; 2, 4-dibromo-5- (p-chlorophenyl) pyrrole-3-carbonitrile; (p-chlorophenyl) pyrrole-2, 4-dicarbonitrile; 04 3-bromo-5-(3,4-dichlorophenyl)pyrrole-2,4-dicarbo- nitrile; 4, 5-dichloro-1- (ethoxymethyl) -2 (a,ca, a-tri fluoro-p- tolyl) pyrrole-3-carbonitrile; 4-bromo-2- (p-chlorophenyl) -1-(ethoxymethyl) (tri- 0 fluoromethyl) pyrrole-3-carbonitrile; or 4-bromo-2- 4-dichiorophenyl) (trifluoroletL hyl) pyrrole-3-carbonitrile. 8. A method according to claim 6 wherein said compound is applied to said plants or the soil in which they are growing, at about 0.125 kg/ha to about kg/ha of said formula I compound.

9. A method according to claim 6 wherein said formula I compound is applied to the foliage of said plants or the soil or water in which they are growing, in the form of a liquid composition containing arl in +J (a ,r-i 0 M SI ,r-I 0 Cq P4 IH P 4 P H 0-3 r- I CI I C r-I 0 (d O i (d u 181 from about 10 ppm to about 10,000 ppm of said formula I compound. A method for the preparation of a novel arylpyrrole compound having the structure: a e e o *0 on Or'a a Q a o 4 a o a t Co .B a o o a oo o cl 0 C C 0 0 -J o o a Sa a V0 0 U 0 0 s wherein W is CN or NO 2 L is H, F, Cl or Br; and M and R are each independently H, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, C 1 -C 3 alkylsulfinyl, C 1 -C 3 alkylsul- fonyl, 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 on adjacent positions and taken with the carbon atoms to which they are attached they may form a ring in which MR represents the structure: -OCHO-, -OCF 2 O- or Z is S(O)n or 0; R 1 is H, F, CHF 2 CHFC1, or CF 3 R 2 is C 1 -C 3 alkyl, C 1 -C 3 alkoxy, or NR 3 R 4 R 3 is H or C1-C 3 alkyl; R 4 is H, C 1 -C 3 alkyl, or R 5 CO; R 5 is H or C -C 3 -182- alkyl; and n is an integer of 0, 1 or 2; comprising, reacting a benzoylacetonitrile -or c-nitroacetophenone having the structure: L 0 0 0 o 0 R 0 t wherein L, M, R, and W are a described above with 2,2- di(C 1 -C 4 alkoxy)ethylamine, at an elevated temperature, to yield an a-[2,2-di(C-C 4 alkoxy)ethylamino]-g-cyano- 0~ 40 styrene or a-[2,2-di(C 1 -C 4 alkoxy)ethylamino]-p-nitro- 00 styrene having the structure: 00a N 0 HCHCa R H-H 2 HC 1 C 4 2--2) wherein L, M, R, and W are as described above and treating the thus formed a-[2,2-di(C 1 -C 4 alkoxy)ethyl- amino]-p-cyanostyrene or a-L2,2-di(C I- C 4 alkoxy) amino]-pntotrn with a. mineral or organic acid to yield the desired arylpyrrole.

11. A method according to Claim 10 wherein the reaction of 2,2-di(C 1 -C 4 alkoxy)ethylamine with 161K, V. r >4 4 0 r 4 g o P- 0 r I 4J) O W I 1 0 0 0o o r I -H( 4d O 1 0 1 0~ 0 WH r -i r- (4-4 183 benzoylacetonitrile or a-nitroacetophenone is conducted neat or in the presence of an inert organic solvent.

12. A method according to claim 10 wherein the a-[2,2-di- (C -C 4 alkoxy)ethylamino]--cyanostyrene or a-[2,2-di(C 1 -C 4 alkoxy)ethylamino]-P-nitrostyrene is treated with hydrochloric, hydrobromic, or trifluoroacetic acid to form the arylpyrrole.

13. An arylpyrrole compound as defined in claim 1 and as herein described with reference to any one of Examples 2, 5, 6, 8 to 12, 14 to 16, 19 to 23, 26, 32, 34, 39, 44, 46, 48, 51, 53, 55, 58, 59, 62, 63 or

14. An insecticidal composition comprising an insecticidally effective amount of a compound of claim 13 together with an insecticidally acceptable carrier, diluent and/or adjuvant. A nematocidal composition comprising a nematocidally effective amount of a compound of claim 13 together with a nematocidally acceptable carrier, diluent and/or adjuvant.

16. An acaricidal composition comprising an acaricidally effective amount of a compound of claim 13 together with an acaricidally acceptable o carrier, diluent and/or adjuvant. °17. A method for controlling insects, nematodes and acarina comprising: contacting said insects, nematodes and acarina, their breeding grounds, food supply or habitat with an insecticidally, nematicidally and 0 0~II cO 0 acaricidally effective amount of an arylpyrrole compound as defined in claim 13 or compositions as defined in claims 14 to 16.

18. A method for protecting growing plants from attack by insects, nematodes and acarina, comprising applying to the foilage of said plants or to the soil or water in which they are growing, an insecticidally, S nematicidally or acaricidally effective amount of an arylpyrrole compound S as defined in claim 13 or compositions as defined in claims 14 to 16.

19. A method for the preparation of an arylpyrrole compound, which method is as defined in claim 10 and substantially as herein described with reference to Examples 3, 4 and 5, Examples 7 and 8, Examples 60, 61 and 62 or Examples 64 and .DATED this FIRST day of FEBRUARY 1991 0 American Cyanamid Company Patent Attorneys for the Applicant SPRUSON FERGUSni _KEH/198f