Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reexamination Certificate
2001-02-05
2002-04-30
Stockton, Laura L. (Department: 1626)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
C548S334100, C548S349100, C548S348100, C548S350100, C548S353100, C548S347100, C548S354100
Reexamination Certificate
active
06380237
ABSTRACT:
The invention relates to novel diphenylimidazolines, to processes for their preparation and to their use for controlling animal pests.
Hitherto, only few 2,4-diaryl-4,5-dihydroimidazoles, which are optionally substituted at nitrogen and in the aryl radicals, have been known. The parent compound, 2,4-diphenyl-4,5-dihydro-1H-imidazole was synthesized as early as the 19th century (Chem. Ber. 28, 3172 (1895)). Furthermore, Tetrahedron 29, 3137 (1973) describes the N-methoxycarbamate, SU 466231 (cited in C.A. 83:79277) describes the N-cyclohexyl derivative, EP-A 10 852 describes the N-hydroxyethyl derivative and, finally, Synlett 10, 1031 (1995) describes the 2-para-methyl-4-para-methoxy derivative which is substituted in both phenyl rings and the corresponding mono-substituted compounds. Finally, two compounds which are formally derived from the tautomeric 3H-imidazole are described, 5-(3,4-dimethylphenyl)-1-methyl-2-phenyl-4,5-dihydro-1H-imidazole in Pol. Ann. Univ. Mariae Curie-Skiodowska, Sect. D 36, 111 (1981) and 2-hydroxyphenyl-1-methyl-5-phenyl-4,5-dihydro-1H-imidazole in Proc. Indian Acad. Sci., Chem. Sci. 104, 383 (1992). Without concrete examples, diphenylimidazolines are described in other patent applications: BE 695 703; BE 839 503; BE 846 373; DD 155296 (cited in C.A. 98:57781); DOS 25 12 513; DOS 27 38 270; DOS 29 46 085; DOS 32 04 333; DOS 32 11 301; DOS 32 36 598; DOS 36 10 758; DOS 40 17 801; DOS 42 35 590; EP-A 1 468; EP-A1 516 982; EP-A2 617 069; FR-A1 2629092; JP-A 56 90982 (cited in C.A. 96:147323); JP-A 56 90983 (cited in C.A. 96:147322); JP-A 58 152085 (cited in C.A. 100:213975); JP-A 59 116660 (cited in C.A. 102:36786); JP-A2 62 195369 (cited in C.A. 108:167467) JP-A 04 180944 (cited in C.A. 118:23600); U.S. Pat. No. 3,202,674; U.S. Pat. No. 4,066,625; U.S. Pat. No. 4,661,600; WO 93/04045; WO 93/04046; derivatives which are substituted in both phenyl rings are described in DOS 27 01 372 (only methyl or ethyl substituents), DOS 32 17 875 (if the C
6
-C
15
-aryl radical is understood as, for example, tolyl or xylyl), in U.S. Pat. No. 4,389,371 and U.S. Pat. No. 4,452,758 (exclusively alkali metal salts of N-(alkoxy)-alkyl-carboxylic acids) and DOS 27 44 782 and EP-A1 596 326 (specific heterocyclylmethyl substituent).
Hitherto, nothing has been known concerning the use of 2,4-diaryl-4,5-dihydroimidazoles as pesticides.
This invention, accordingly, provides novel diarylimidazolines of the formula (I)
in which
Ar
1
represents the grouping (a)
in which
R
1
represents halogen, alkyl, alkoxy or halogenoalkoxy and
R
2
represents hydrogen, halogen, alkyl or alkoxy,
Ar
2
represents the grouping (b) or (c)
in which
R
3
, R
4
, R
5
and R
6
independently of one another each represent hydrogen, halogen, alkyl, alkoxy, halogenoalkoxy or halogenoalkylthio,
R
7
represents hydrogen, halogen, cyano, alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy or halogenoalkylthio and
Y represents a direct bond, oxygen, methylene, —O—CH
2
— or —CH
2
O— and
R represents cyano, alkoxyalkyl, formyl, alkylcarbonyl, alkoxycarbonyl or —C(X)—NHR
8
in which
X represents oxygen or sulphur and
R
8
represents hydrogen or alkyl.
Here, halogen represents F, Cl, Br and iodine, in particular F, Cl and Br.
The compounds of the formula (I) include N-substituted derivatives of the two tautomeric forms of the cyclic imidate function which forms the basis for the imidazoline. These compounds are 1H-4,5-dihydroimidazoles of the formula (I)
a
and 3H-4,5-dihydroimidazoles of the formula (I)
b
which is intended to be expressed by the dotted line in the formula (I).
The compounds of the formulae (I)
a
and (I)
b
can be present both as mixtures or in the form of the pure isomers and furthermore, depending, inter alia, on the kind of substituents, as geometric and/or optical isomers or isomer mixtures of varying composition. These isomers can, if appropriate, be separated in a customary manner. The invention relates both to the pure isomers and to their mixtures.
Furthermore, it has been found that the novel compounds of the formula (I) are obtained by one of the processes described below.
A) Diphenylimidazolines of the formula (I-a)
in which
Ar
1
and Ar
2
are each as defined above and
R
9
represents C
1
-C
4
-alkyl,
are obtained by condensing &bgr;-chlorocarbamates of the formula (II)
in which
Ar
2
and R
9
are each as defined above
with benzonitriles of the formula (III)
Ar
1
—CN (III),
in which
Ar
1
is as defined above in the presence of sulphuric acid, or
B) diphenylimidazolines of the formula (I-b)
in which
R is as defined above and
R
1-1
represents fluorine, chlorine, alkyl, alkoxy or halogenoalkoxy,
R
2-1
represents hydrogen, fluorine, chlorine, alkyl or alkoxy,
R
5-1
and R
6-1
independently of one another each represent hydrogen, fluorine, chlorine, alkyl, alkoxy, halogenoalkyl or halogenoalkylthio and
R
7-1
represents hydrogen, fluorine, chlorine, cyano, alkyl, alkoxy, alkylthio, halogenoalkyl or halogenoalkylthio
are obtained by coupling halogen compounds of the formula (I-c)
in which
R, R
1-1
, R
2-1
and R
5-1
are each as defined above and
Z represents bromine or iodine
with boronic acids of the formula (IV)
in which
R
6-1
and R
7-1
are each as defined above
in the presence of a catalyst and, if appropriate, in the presence of an acid binder and, if appropriate, in the presence of a diluent, or
C) diphenylimidazolines of the formula (I)
in which
Ar
1
, Ar
2
and R are each as defined above
are obtained by condensing diphenylimidazolines of the formula (V)
which are not substituted at nitrogen and in which
Ar
1
and Ar
2
are each as defined above
with compounds of the formula (VI)
R—X
1
(VI),
in which
R is as defined above and
X
1
represents, depending on the radical R, a suitable leaving group, such as —Cl, —Br, —OSO
2
OR
10
or —OR
10
in which
R
10
represents alkyl or aryl,
if appropriate in the presence of a reaction auxiliary, or
D) diphenylimidazolines of the formula (I-d)
in which
Ar
1
, Ar
2
and X are each as defined above
are obtained by reacting nitrites of the formula (I-e)
in which
Ar
1
and Ar
2
are each as defined above
with water or hydrogen sulphide, if appropriate in the presence of a reaction auxiliary.
Furthermore, it has been found that the compounds of the formula (I) and their biologically active salts are suitable for controlling animal pests, in particular insects, arachnids and nematodes.
The formula (I) provides a general definition of the novel compounds. Preferred substituents or ranges of the radicals listed in the formulae mentioned hereinabove and hereinbelow are illustrated below.
Ar
1
particularly represents the grouping (a)
Ar
2
particularly represents the grouping (b) or (c)
R particularly represents cyano, C
1
-C
4
-alkoxy-C
1
-C
4
-alkyl, C
1
-C
4
-alkylcarbonyl, C
1
-C
4
-alkoxycarbonyl or —C(X)—NHR
8
.
R
1
particularly represents halogen, C
1
-C
3
-alkyl, C
1
-C
3
-alkoxy or C
1
-C
3
-halogenoalkoxy.
R
2
particularly represents hydrogen, halogen, C
1
-C
3
-alkyl or C
1
-C
3
-alkoxy.
R
3
, R
4
, R
5
and R
6
independently of one another each particularly represent hydrogen, halogen, C
1
-C
12
-alkyl or C
1
-C
12
-alkoxy.
R
7
particularly represents hydrogen, halogen, cyano, C
1
-C
6
-alkyl, C
1
-C
6
-alkoxy, C
1
-C
6
-alkylthio, C
1
-C
6
-halogenoalkyl, C
1
-C
4
-halogenoalkoxy or C
1
-C
4
-halogenoalkylthio.
R
8
particularly represents hydrogen or C
1
-C
4
-alkyl.
X particularly represents oxygen or sulphur.
Y particularly represents a direct bond or oxygen.
Here, halogen preferably represents F, Cl, Br and iodine, in particular F, Cl and Br.
Ar
1
particularly preferably represents the grouping (a)
Ar
2
particularly preferably represents the grouping (b-a) or (c-a)
R particularly preferably represents cyano, C
1
-C
3
-alkoxy-C
1
-C
3
-alkyl, C
1
-C
3
-alkylcarbonyl, C
1
-C
2
-alkoxycarbonyl or —C(X)—NHR
8
.
R
1
particularly preferably represents fluorine, chlorine, bromine, iodine, C
1
-C
3
-alkyl
Erdelen Christoph
Graff Alan
Mencke Norbert
Plant Andrew
Turberg Andreas
Bayer Aktiengesellschaft
Gil Joseph C.
Stockton Laura L.
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