Intermediates useful for the synthesis of 1-arylpyrrole...

Details Intermediates useful for the synthesis of 1-arylpyrrole... Intermediates useful for the synthesis of 1-arylpyrrole...

1995-07-12

2001-08-07

Stockton, Laura L. (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C548S541000, C548S544000

Reexamination Certificate

active

06271392

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to new 3-substituted-4-thiopyrroles and to processes for their preparation. The invention also pertains to the application of said compounds to the preparation of pesticides for the use in agriculture for the control of arthropods, especially insects, arachnids, and nematodes.
2. Description of the Related Art
Various substituted pyrrole compounds are known to exhibit a number of different types of activity, including pharmaceutical activity and pesticidal activity. Included among these are the following:
EP 600,157 discloses a method for the chlorination of substituted pyrrole compounds.
Foley,
Tetrahedron Lett
., 1994, 33 (5989-92), is a chemistry article which discloses 3-cyano- or 3-carboethoxypyrroles, which are substituted in the 2-position with either chlorine or alkoxy and in the 5-position with either alkyl or phenyl. There appears to be no disclosed pesticidal activity.
U.S. Pat. No. 5,302,383 and U.S. Pat. No. 5,254,559 disclose 1-(substituted)thioalkylpyrrole compounds for control of insect, acarid, and mollusk pests.
U.S. Pat. No. 5,284,863 discloses 2- or 3-phenylpyrrole compounds for control of phytopathogenic fungi.
EP 557,732 discloses 3-cyano- or 3-nitropyrrole compounds for control of helminth, acarid, and arthropod parasites of warm-blooded animals.
U.S. Pat. No. 5,187,185 discloses 1-arylpyrroles useful as insecticides.
U.S. Pat. No. 5,116,998; U.S. Pat. No. 5,101,042 and U.S. Pat. No. 5,041,556 disclose a process for the preparation of nematicidal, insecticidal, and acaricidal 2-halo-3-substituted pyrrole compounds.
U.S. Pat. No. 5,010,098 discloses 2- or 3-phenylpyrrole compounds for control of insects, acarids, and nematodes.
Abdalla et al.,
J. Heterocyclic Chem
., 1987, 24, 297-301, and Johnson et al.,
J. Heterocyclic Chem
., 1977, 14, 383-5, are chemistry articles which disclose the preparation of 2-amino-3-cyanopyrrole compounds. There appears to be no pesticidal activity.
JP 50105832 discloses substituted pyrrole compounds for use as herbicides.
EP 491,197 discloses the use of 2,3-dicyanopyrroles for the preparation of pyrrole [1,2,-b] [1,2,4]triazole cyan couplers for use in photographic film.
EP 549,866 discloses 2- or 3-phenylpyrrole compounds as insecticides and acaricides.
Berlin et al.,
J. Chem. Soc. Perkin Trans
. 2, 1990, 699-704, is a chemistry article which discloses 3-thiopyrroles. There appears to be no disclosed pesticidal activity.
Cibura et al.,
J. Heterocyclic Chem
., 1985, 22, 1689-91, is a chemistry article which discloses 2- and 3-(trifluoromethylthio)pyrroles. There appears to be no disclosed pesticidal activity.
Haas et al.,
Z. Anorg. Allg. Chem
., 1985, 524, 33-9, and Haas et al.,
Chem. Ber
., 1985, 118, 4588-96, are chemistry articles which disclose tetrakis[trifluoromethyl(thio)]pyrrole compounds. There appears to be no disclosed pesficidal activity.
Harris et al.,
Aust. J. Chem
., 1984, 37, 2479-87, is a chemistry article which discloses 3-thiopyrrole compounds. There appears to be no disclosed pesticidal activity.
JP 55051065 discloses 2-amino-3,4,5-tri(tert-butylthio)pyrrole and its acetamido derivative.
Dorn et al.,
Helv. Chim. Acta
, 1979, 62, 1442-50, is a chemistry article which discloses fungicidal, herbicidal, and insecticidal activity of 2,4-di(perhalomethylthio)pyrrole compounds.
JP 54044669 and JP 54044668 disclose 2,3-di(tert-butylthio)pyrrole compounds.
U.S. Pat. No. 4,112,112 and DE 2629877 disclose 3-thiopyrrole compounds as intermediates to the preparation of pyrrole[2,1-b][3]-benzapines for use as muscle relaxants or tranquilizers.
Haas et al.,
Chem. Ber
., 1977, 110, 67-77, is a chemistry article which discloses 2-, 3-, 4-, and 5-(haloalkylthio)-and-(haloformylthio)pyrroles.
It is thus apparent that the nature and position of substituent groups on substituted pyrroles provide widely different types of biological activity, which type and level of activity is not readily apparent.
SUMMARY OF THE INVENTION
The present invention pertains to novel 3-substituted-4-thiopyrrole intermediates for the preparation of 1-arylpyrrole compounds that are useful for the control of insects, acarids and nematodes.
The compounds, including their isomers, e.g., diastereomers and optical isomers, are compounds of a general formula (I)
wherein:
W is cyano, —CO
2
H, —CO
2
R
3
, —CONH
2
, —CONHR
3
, —CON(R
3
)
2
, —CSNH
2
, —CSNHR
3
, —CSN(R3)2, —COSH, —COSR
3
, —CHO, —CH═NOH, —CH═NOR
3
, or nitro;
R is alkyl, haloalkyl, cyano, —C(NH
2
)(═NH) or an acid addition salt thereof, hydrogen, or
R
1
and R
2
independently represent hydrogen, halogen, alkyl, aryl, heteroaryl, haloalkyl, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, cyano, nitro, NR
11
R
12
, formyl, alkylcarbonyl, haloalkylcarbonyl, hydroxyalkylcarbonyl, —CO
2
H, —CO
2
R
3
, alkylthiocarbonyl, —CONH
2
, —CONHR
3
, —CON(R
3
)
2
, bis(alkoxy)methyl, bis(alkylthio)methyl, (alkoxy)(cyano)methyl, (acyloxy)(cyano)methyl, (phenoxy)(cyano)methyl, (alkoxy)(alkylthio)methyl, (alkylamino)(alkoxy)methyl, (alkoxy)(dialkylamino)methyl, (alkylamino)(alkylamino)methyl, (dialkylamino)(dialkylamino)methyl, (alkoxy)(alkoxycarbonyl)methyl, (alkoxy)(aminocarbonyl)methyl, (alkoxy)(alkylaminocarbonyl)methyl, (alkoxy)(dialkylaminocarbonyl)methyl, alkoxyalkyl, hydroxyalkyl, (haloalkoxy)alkyl, (alkoxy)(haloalkyl)alkyl, cyanoalkyl, halogenated cyanoalkyl, alkoxycarbonylalkyl, aminocarbonylalkyl, monoalkylaminocarbonylalkyl, formylalkyl, dialkylaminocarbonylalkyl, alkoxyalkylcarbonyl, alkylsulfenylalkylcarbonyl, alkylsulfinylalkylcarbonyl, alkylsulfonylalkylcarbonyl, cyanoalkylcarbonyl, alkoxycarbonylalkylcarbonyl, aminocarbonylalkylcarbonyl, monalkylaminocarbonylalkylcarbonyl, dialkylaminocarbonylalkylcarbonyl, —CH═N—O—R
11
, amino(thio)carbonyl, monoalkylamino(thio)carbonyl, dialylamino(thio)carbonyl, or a radical of the formula
wherein:
R
13
is hydrogen, alkyl, or haloalkyl;
Y and Z are O, S, SO, SO
2
, NH, N-alkyl, or N-acyl;
Q is ethylene or propylene optionally substituted with alkyl, haloalkyl, alkoxy, alkoxyalkyl, cyano, hydroxyalkyl, amino, alkylamino, dialkylamino, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, OH or SH;
s is 0 to 3;
R
3
is alkyl, haloalkyl, hydroxyalkyl or alkoxyalkyl;
R
11
and R
12
independently represent H, alkyl, haloalkyl, formyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aminocarbonyl, monoalkylaminocarbonyl, dialkylaminocarbonyl, alkylsulfonyl, haloalkylsulfonyl, alkylsulfinyl, haloalkylsulfinyl, allyl, propargyl, halogen, alkoxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, haloalkoxyalkyl, haloalkylthioalkyl, haloalkylsulfmylalkyl, haloalkylsulfonylalkyl, aminoalkyl, monoalkylaminoalkyl, dialkylaminoalkyl, or alkoxycarbonyl; and
n is 0, 1 or 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the description, the term “alkyl” generally refers to straight- or branched-chain alkyl or cycloalkyl having up to six carbon atoms.
The term “haloalkyl” generally refers to straight- or branched-chain alkyl or cycloalkyl having up to six carbon atoms, bearing one or more halogen which are the same or different.
The term “alkoxy” generally refers to straight- or branched-chain alkoxy having up to six carbon atoms.
The term “haloalkoxy” generally refers to straight- or branched-chain alkoxy having up to six carbon atoms, bearing one or more halogen which are the same or different.
Preferred compounds of formula (I) above are those wherein W is selected from the group consisting of cyano, nitro, —CH═NOH and —CH═NOR
3
, with cyano being most preferred.
A further preferred class of compounds of formula (I) above is that wherein R is selected from the group consisting of alkyl, haloalkyl, cyano, —C(NH
2
)(═NH) or an acid addition salt thereof, and
More preferably, R is selected from the group consisting of haloalkyl, cyano, —C(NH
2
)(═NH) or an acid addition salt thereof, and
with haloal

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