Trifluoromethylpyrrolcarboxamides

Details Trifluoromethylpyrrolcarboxamides Trifluoromethylpyrrolcarboxamides

2001-02-09

2002-04-02

Higel, Floyd D. (Department: 1626)

Drug, bio-affecting and body treating compositions

Designated organic active ingredient containing

Having -c-, wherein x is chalcogen, bonded directly to...

C548S537000, C514S423000, C549S059000

Reexamination Certificate

active

06365620

ABSTRACT:

The present invention relates to novel trifluoromethylpyrrolcarboxamides which have microbicidal activity, in particular fungicidal activity. The invention also relates to the preparation of these substances, to agrochemical compositions which comprise at least one of the novel compounds as active ingredient, to the preparation of the compositions mentioned and to the use of the active ingredients or compositions in agriculture and horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.
The trifluoromethylpyrrolcarboxamides of the present invention have the general formula I
wherein
R
1
is hydrogen, halogen, C
1-4
haloalkyl or C
1-4
alkyl,
R
2
is C
1-4
alkyl, C
1-4
haloalkyl, C
1-4
alkoxy-C
1-4
alkyl, cyano, C
1-4
alkylsulfonyl, phenylsulfonyl, di(C
1-4
alkyl)aminosulfonyl, C
1-6
alkylcarbonyl, benzoyl, or substituted phenylsulfonyl or benzoyl, and
A is a group
wherein
R
3
is C
1-6
alkyl, C
1-6
haloalkyl, C
2-6
alkenyl, C
2-6
haloalkenyl, C
2-6
alkinyl, C
1-6
alkoxy, C
1-6
haloalkoxy, C
2-6
alkenyloxy, C
2-6
haloalkenyloxy, C
2
6alkinyloxy, C
3-7
cycloalkyl, C
1-4
alkyl-C
3-7
cycloalkyl, C
4-7
cycloalkenyl, C
1-4
alkyl-C
4-7
cycloalkenyl, C
3-7
cycloalkyloxy, C
1-4
alkyl-C
3-7
cycloalkyloxy, C
5-7
cycloalkenyloxy, C
1-4
alkyl-C
5-7
cycloalkenyloxy, phenyl, naphthyl, phenoxy, naphthyloxy, or substituted phenyl or phenoxy wherein the substitutents are one to three groups independently selected from halogen, C
1-4
alkyl, C
1-4
alkoxy, C
1-4
alkylthio, cyano, C
1-4
alkoxycarbonyl, C
1-4
alkylcarbonyl, C
1-4
haloalkyl, C
1-4
haloalkoxy, methylenedioxy or difluoromethylenedioxy, or phenyl;
R
4
is hydrogen, halogen, C
1-4
alkyl, C
1-4
haloalkyl, C
1-4
alkoxy or C
1-4
haloalkoxy; and
R
5
, R
6
and R
7
independently of each other are C
1-6
alkyl, C
3-7
cycloalkyl or C
3-7
cycloalkyl-C
4
alkyl.
Nicotinic acid amides with fungicidal properties useful in agricultural practice are known from EP-A-0545099. The disclosed compounds for practical purposes do not always satisfy the needs of the modern agriculture.
Surprisingly, it has now been found that the compounds of formula I exhibit improved biological properties which render them more suitable for the practical use in agriculture and horticulture.
Where asymmetrical carbon atoms are present in the compounds of formula I these compounds are in optically active form. The invention relates to the pure isomers, such as enantiomers and diastereomers, as well as to all possible mixtures of isomers, e.g. mixtures of diastereomers, racemates or mixtures of racemates.
Within the present specification alkyl denotes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, tert-pentyl, and neo-pentyl. Non-branched alkyl is preferred. Alkyl as part of other radicals such as alkoxy, alkylthio, haloalkyl, alkylcycloalkyl, alkylcycloalkoxy, alkylcarbonyl, alkylsulfonyl, alkylamino, etc. is understood in an analogous way. Halogen will be understood generally as meaning fluoro, chloro, bromo or iodo. Fluoro, chloro or bromo are preferred meanings. Halogen as part of other radicals such as haloalkyl, haloalkoxy, haloalkenyl, haloalkenyloxy or halophenyl, etc. is understood in an analogous way. Substituents of the substituted phenylsulfonyl and benzoyl may be present mono- to five times and are preferably independently selected from halogen, C
1-4
alkyl, C
1-4
alkoxy, C
1-4
alkylthio, cyano, C
1-4
alkoxycarbonyl, C
1-4
alkylcarbonyl, C
1-4
haloalkyl, C
1-4
haloalkoxy, methylenedioxy or difluoromethylenedioxy, or phenyl. Where phenyl groups as parts of phenyl, phenylsulfonyl, phenoxy and benzoyl are substituted such radicals for example designate 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2,4-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-trifluoromethoxyphenyl, 3-trifluoromethoxyphenyl, 4-trifluoromethoxyphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl 4-tert.butylphenyl, 3,4-dimethylphenyl, 2,4,6-trimethylphenyl, 3-chloro-4-fluorophenyl, 4-chloro-3-fluorophenyl, 4-biphenyl, 3-biphenyl, and the like.
A special subgroup of active ingredients is represented by those compounds of formula I
wherein
R
1
is hydrogen or C
1-4
alkyl,
R
2
is C
1-4
alkyl, and
A is a group
wherein
R
3
C
1-6
alkyl, C
1-6
haloalkyl, C
2-6
alkenyl, C
2-6
haloalkenyl, C
2-6
alkinyl, C
1-6
alkoxy, C
1-6
haloalkoxy, C
2-6
alkenyloxy, C
2-6
haloalkenyloxy, C
2-6
alkinyloxy, C
3-7
cycloalkyl C
1-4
alkyl-C
3-7
cycloalkyl, C
4-7
cycloalkenyl, C
1-4
alkyl-C
4-7
cycloalkenyl, C
3-7
cycloalkyl, C
1-4
alkyl-C
3-7
cycloalkyloxy, C
5-7
cycloalkenyloxy, C
1-4
alkyl-C
5-7
cycloalkenyloxy, phenyl, naphthyl, phenyl substituted by one to three groups independently selected from halogen, C
1-4
alkyl, C
1-4
alkoxy, C
1-4
alkylthio, cyano, C
1-4
alkoxycarbonyl, C
1-4
alkylcarbonyl, C
1-4
haloalkyl, C
1-4
haloalkoxy, methylenedioxy or difluoromethylenedioxy, or phenyl;
R
4
is hydrogen, halogen or C
1-4
alkyl; and
R
5
, R
6
and R
7
independently of each other are C
1-6
alkyl, C
3-7
cycloalkyl or C
3-7
cycloalkyl-C
1-4
alkyl.
Within the group of compounds of formula I those compounds are preferred wherein:
a) R
1
is hydrogen or methyl, or
b) R
2
is methyl, or
c) R
3
is phenyl or phenyl substituted with halogen.
Another preferred subgroup is constituted by the compounds of formula I wherein R
1
is hydrogen or methyl, R
2
is methyl, and R
3
is phenyl or phenyl substituted with halogen.
Preferred individual compounds are:
N-(2-biphenylyl)-1-methyl-4-trifluoromethylpyrrol-3-carboxamide,
N-(4′-chloro-2-biphenylyl)-4-trifluoromethylpyrrol-3-carboxamide,
N-(4′-fluoro-2-biphenylyl)-4-trifluoromethylpyrrol-3-carboxamide,
N-[2-(4-fluorophenyl)-3-thienyl)-4-trifluoromethylpyrrol-3-carboxamide,
N-[2-(4-chlorophenyl)-3-thienyl)-4-trifluoromethylpyrrol-3-carboxamide,
N-(3′,4′-difluoro-2-biphenylyl)-4-trifluoromethylpyrrol-3-carboxamide,
N-(3′-trifluoromethyl-2-biphenylyl)-4-trifluoromethylpyrrol-3-carboxamide, and
N-(4′-chloro-3′-fluoro-2-biphenylyl)-4-trifluoromethylpyrrol-3-carboxamide.
The compounds according to formula I may be prepared according to the following reaction scheme 1.
wherein A, R
1
and R
2
are as defined for formula I, X and Y are leaving groups, alkyl designates a lower alkyl moiety, and aryl stands for phenyl or tolyl.
The leaving groups X and Y preferably designate halogen atoms, but may also stand for moieties of mixed anhydrides, e.g. —O—CO-alkyl, —O—PO(alkyl)
2
, —O—C(═N-alkyl), triazolyl, and the like.
Alternatively the introduction of the radicals R
2
and A may be a different order according to scheme 2.
wherein A, R
1
, R
2
, X and Y are as defined for scheme 1
In special cases of substitution patterns it may be favourable to utilize a protective group at the 1-position of the pyrrol ring in order to avoid side reactions during the amidation reaction at the carbonyl function in 3-position. Suitable protective groups are benzyl and the like. Also introduction and cleaving of the protective group is done by common benzylation and hydrolysation reactions.
The new carboxamides of formula I are preferably obtained by reacting an activated carboxylic acid of formula II with an aromatic amine. Depending on the leaving group Y the reaction is run in the presence of an acid binding agent. Inert solvents are preferably used, but also aqueous solvent mixtures, referred to as Schotten-Baumann conditions, may be employed.
Activation is achieved by reacting the pyrrol carboxylic acid III with an activating agent such acid halide, such as thionyl chloride or oxalyl chloride, to give the corresponding acyl chloride (Y=chlorine) or by any other general coupling activation method known in the literature.
The carboxylic acids of formula III may be prepared from the corresponding esters by hydrolysis using sta

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