U.S. patent application number 09/767194 was filed with the patent office on 2002-02-28 for benzimidazole derivatives.
Invention is credited to Assmann, Lutz, Kugler, Martin, Marhold, Albrecht, Stenzel, Klaus.
Application Number | 20020026059 09/767194 |
Document ID | / |
Family ID | 7759617 |
Filed Date | 2002-02-28 |
United States Patent
Application |
20020026059 |
Kind Code |
A1 |
Assmann, Lutz ; et
al. |
February 28, 2002 |
Benzimidazole derivatives
Abstract
Novel benzimidazole derivatives of the formula 1 in which
R.sup.1, R.sup.2, X.sup.1,X.sup.2, X.sup.3, X.sup.4 and Y are each
as defined in the description, and acid addition salts and metal
salt complexes thereof, a process for preparing these compounds and
their use as microbicides in crop protection and in the protection
of materials.
Inventors: |
Assmann, Lutz; (Eutin,
DE) ; Marhold, Albrecht; (Leverkusen, DE) ;
Stenzel, Klaus; (Dusseldorf, DE) ; Kugler,
Martin; (Leichlingen, DE) |
Correspondence
Address: |
NORRIS McLAUGHLIN & MARCUS, P.A.
30th FLOOR
220 EAST 42nd STREET
NEW YORK
NY
10017
US
|
Family ID: |
7759617 |
Appl. No.: |
09/767194 |
Filed: |
January 22, 2001 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
09767194 |
Jan 22, 2001 |
|
|
|
09490482 |
Jan 24, 2000 |
|
|
|
6235765 |
|
|
|
|
09490482 |
Jan 24, 2000 |
|
|
|
09227809 |
Jan 11, 1999 |
|
|
|
6080776 |
|
|
|
|
09227809 |
Jan 11, 1999 |
|
|
|
08930767 |
Oct 3, 1997 |
|
|
|
5925663 |
|
|
|
|
08930767 |
Oct 3, 1997 |
|
|
|
PCT/EP96/01435 |
Apr 1, 1996 |
|
|
|
Current U.S.
Class: |
548/309.7 |
Current CPC
Class: |
A01N 43/52 20130101;
C07D 409/12 20130101; A01N 43/90 20130101; A61P 25/22 20180101;
C07D 491/04 20130101; C07D 403/12 20130101; A01N 43/80 20130101;
C07D 413/12 20130101 |
Class at
Publication: |
548/309.7 |
International
Class: |
C07D 235/14 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 13, 1995 |
DE |
195 13 990.9 |
Claims
1. Benzimidazole derivatives of the formula 375in which X.sup.1,
X.sup.2, X.sup.3 and X.sup.4 independently of one another each
represent hydrogen, halogen, cyano, nitro, alkyl, halogenoalkyl,
alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio,
alkylsulphinyl, halogenoalkylsulphinyl, alkylsulphonyl,
halogenoalkylsulphonyl, optionally substituted cycloalkyl,
hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkylcarbonyl,
cycloalkoxycarbonyl, represent 376In which R.sup.3 and R.sup.4
independently of one another each represent hydrogen, alkyl,
halogenoalkyl, alkoxyalkyl, alkylcarbonyl, optionally substituted
aryl, optionally substituted arylcarbonyl, optionally substituted
arylsulphonyl, optionally substituted arylaminocarbonyl or
optionally substituted arylmethylsulphonyl or R.sup.3 and R.sup.4
together with the nitrogen atom that they are attached to represent
an optionally alkyl-substituted heterocyclic ring which may contain
an additional oxygen atom or an alkylimino group, Q represents a
direct bond or a carbonyl group, R.sup.5 represents optionally
substituted aryl or represents optionally substituted heterocyclyl
and Z represents a direct bond, represents CH.sub.2, O, S, SO,
SO.sub.2, CO or an azo group or represents --CO--O-- where the
oxygen atom is linked to the aryl or heterocyclyl radical, or
represents --SO.sub.2--O-- where the sulphur atom is linked to the
aryl or heterocyclyl radical, or represents
--S--CH.sub.2--SO.sub.2-- where the sulphur atom of the thio group
is linked to the aryl or heterocyclyl radical, or X.sup.2 and
X.sup.3 together represent an optionally substituted alkylene chain
having 3 or 4 members wherein one or two (non-adjacent) carbon
atoms may be replaced by oxygen atoms, R.sup.1 represents cyano or
the groupings 377wherein R.sup.6 represents alkyl, halogenoalkyl or
optionally halogen- and/or halogenoalkyl-substituted benzyl,
R.sup.2 represents optionally substituted heterocyclyl and Y
represents a direct bond, represents --CH.sub.2--,
--CH.sub.2--CH.sub.2--, --CO--, --SO.sub.2--, --CO--O-- or
--SO--O-- where in the case of the last two groups the carbon atom
or the sulphur atom is linked to the nitrogen atom of the imidazole
ring, and acid addition salts and metal salt complexes thereof.
2. Benzimidazole derivatives of the formula (I) according to claim
1 in which X.sup.1, X.sup.2, X.sup.3 and X.sup.4 independently of
one another each represent hydrogen, fluorine, chlorine, bromine,
iodine, cyano, nitro, straight-chain or branched alkyl having 1 to
8 carbon atoms, straight-chain or branched halogenoalkyl having 1
to 6 carbon atoms and 1 to 13 identical or different halogen atoms,
straight-chain or branched alkoxy having 1 to 8 carbon atoms,
straight-chain or branched halogenoalkoxy having 1 to 6 carbon
atoms and 1 to 13 identical or different halogen atoms,
straight-chain or branched alkylthio having 1 to 8 carbon atoms,
straight-chain or branched halogenoalkylthio having 1 to 6 carbon
atoms and 1 to 13 identical or different halogen atoms,
straight-chain or branched alkylsulphinyl having 1 to 8 carbon
atoms, straight-chain or branched halogenoalkylsulphonyl having 1
to 6 carbon atoms and 1 to 13 identical or different halogen atoms,
straight-chain or branched alkylsulphonyl having 1 to 8 carbon
atoms, straight-chain or branched halogenoalkylsulphonyl having 1
to 6 carbon atoms and 1 to 13 identical or different halogen atoms,
cycloalkyl having 3 to 6 carbon atoms which is optionally mono- to
pentasubstituted by identical or different substituents from the
group consisting of halogen and alkyl having 1 to 4 carbon atoms,
represent hydroxycarbonyl, alkylcarbonyl having 1 to 6 carbon atoms
in the straight-chain or branched alkyl moiety, alkoxycarbonyl
having 1 to 6 carbon atoms in the straight-chain or branched alkoxy
moiety, cycloalkylcarbonyl having 3 to 6 carbon atoms in the
cycloalkyl moiety, cycloalkoxycarbonyl having 3 to 6 carbon atoms
in the cycloalkyl moiety, represent 378R.sup.3 and R.sup.4
independently of one another each represent hydrogen,
straight-chain or branched alkyl having 1 to 6 carbon atoms,
straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms
and 1 to 13 identical or different halogen atoms, straight-chain or
branched alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy
moiety and 1 to 4 carbon atoms in the alkyl moiety, alkylcarbonyl
having 1 to 6 carbon atoms in the straight-chain or branched alkyl
moiety, aryl having 6 to 10 carbon atoms, arylcarbonyl having 6 to
10 carbon atoms in the aryl moiety, arylsulphonyl having 6 to 10
carbon atoms, arylaminocarbonyl having 6 to 10 carbon atoms in the
aryl moiety or represent arylmethylsulphonyl having 6 to 10 carbon
atoms in the aryl moiety, it being possible for each of the
abovementioned aryl radicals to be mono- to trisubstituted by
identical or different substituents from the group consisting of
halogen, cyano, nitro, alkyl having 1 to 4 carbon atoms, alkoxy
having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms,
halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or
different halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms
and 1 to 5 identical or different halogen atoms, halogenoalkylthio
having 1 to 4 carbon atoms and 1 to 5 identical or different
halogen atoms, alkylsulphinyl having 1 to 4 carbon atoms,
alkylsulphonyl having 1 to 4 carbon atoms, halogenoalkylsulphinyl
having 1 to 4 carbon atoms and 1 to 5 identical or different
halogen atoms and halogenoalkylsulphonyl having 1 to 4 carbon atoms
and 1 to 5 identical or different halogen atoms, and R.sup.3 and
R.sup.4 together with the nitrogen atom that they are attached to
additionally represent a heterocyclic ring having 5 or 6 ring
members which is optionally mono- to trisubstituted by alkyl having
1 to 4 carbon atoms and which may contain an additional oxygen atom
or a C.sub.1-C.sub.4-alkylimino group, Q represents a direct bond
or represents a carbonyl group, R.sup.5 represents aryl having 6 to
10 carbon atoms, it being possible for each of these radicals to be
mono- to trisubstituted by identical or different substituents from
the group consisting of halogen, cyano, nitro, alkyl having 1 to 4
carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1
to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1
to 5 identical or different halogen atoms, halogenoalkoxy having 1
to 4 carbon atoms and 1 to 5 identical or different halogen atoms,
halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 identical
or different halogen atoms, alkylsulphinyl having 1 to 4 carbon
atoms, alkylsulphonyl having 1 to 4 carbon atoms,
halogenoalkylsulphinyl having 1 to 4 carbon atoms and 1 to 5
identical or different halogen atoms and halogenoalkylsulphonyl
having 1 to 4 carbon atoms and 1 to 5 identical or different
halogen atoms, or R.sup.5 represents a saturated or unsaturated
heterocyclyl radical having 5 or 6 ring members and 1 to 3
heteroatoms such as nitrogen, oxygen and/or sulphur, it being
possible for these radicals to be mono- to trisubstituted by
identical or different substituents from the group consisting of
halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4
carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5
identical or different halogen atoms, halogenoalkoxy having 1 to 4
carbon atoms and 1 to 5 identical or different halogen atoms,
alkoxycarbonyl having 1 to 3 carbon atoms in the alkoxy moiety,
cycloalkyl having 3 to 6 carbon atoms, cyano and nitro, Z
represents a direct bond and also represents CH.sub.2, O, S, SO,
SO.sub.2, CO or an azo group, or represents --CO--O--, where the
oxygen atom is linked to the aryl or heterocyclyl radical, or
represents --SO.sub.2--O--, where the sulphur atom is linked to the
aryl or heterocyclyl radical, or represents
--S--CH.sub.2--SO.sub.2--, where the sulphur atom of the thio group
is linked to the aryl or heterocyclyl radical, and furthermore
X.sup.2 and X.sup.3 together also represent an alkylene chain
having 3 or 4 members which is optionally mono- to hexasubstituted
by halogen, alkyl having 1 to 4 carbon atoms and/or halogenoalkyl
having 1 to 4 carbon atoms and 1 to 9 halogen atoms and in which
one or two (non-adjacent) carbon atoms may be replaced by oxygen
atoms, R.sup.1 represents cyano or the groupings 379R.sup.6
represents straight-chain or branched alkyl having 1 to 4 carbon
atoms, straight-chain or branched halogenoalkyl having 1 to 4
carbon atoms and 1 to 9 identical or different halogen atoms or
represents benzyl which is optionally mono- to trisubstituted by
identical or different substituents from the group consisting of
halogen and halogenoalkyl having 1 or 2 carbon atoms and 1 to 5
identical or different halogen atoms, R.sup.2 represents a
saturated or unsaturated, optionally benzo-fused heterocyclyl
radical having 5 or 6 ring members and 1 to 3 heteroatoms such as
nitrogen, oxygen and/or sulphur, it being possible for these
radicals to be mono- to trisubstituted by identical or different
substituents from the group consisting of halogen, cyano, nitro,
hydroxyl, amino, formyl, carboxy, carbamoyl, thiocarbanoyl, alkyl
having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms,
halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or
different halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms
and 1 to 5 identical or different halogen atoms, alkoxycarbonyl
having 1 to 4 carbon atoms in the alkoxy moiety, cycloalkyl having
3 to 6 carbon atoms, halogenoalkylsulphinyl having 1 to 4 carbon
atoms and 1 to 5 identical or different halogen atoms,
halogenoalkylsulphonyl having 1 to 4 carbon atoms and 1 to 5
identical or different halogen atoms, alkylamino having 1 to 4
carbon atoms, hydroxyalkylamino having 1 to 4 carbon atoms,
dialkylamino having 1 to 4 carbon atoms in each alkyl group,
alkylcarbonyl having 1 to 4 carbon atoms in the alkyl moiety,
alkylcarbonylamino having 1 to 4 carbon atoms in the alkyl group,
hydroxyiminoalkyl having 1 to 4 carbon atoms in the alkyl moiety,
alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and
1 to 4 carbon atoms in the alkyl moiety, alkylcarbonyloxy having 1
to 4 carbon atoms in the alkyl moiety and halogenoalkylcarbonyloxy
having 1 to 4 carbon atoms in the halogenoalkyl group and 1 to 5
identical or different halogen atoms, it being possible for the
heterocyclyl radicals to contain oxo groups and Y represents a
direct bond, represents CH.sub.2, CH.sub.2--CH.sub.2, CO, SO.sub.2,
--CO--O-- or --SO--O--, where in the case of the last two groups
the carbon atom or the sulphur atom is linked to the nitrogen atom
of the imidazole ring.
3. Process for preparing benzimidazole derivatives of the formula
(I) according to claim 1 and acid addition salts and metal salt
complexes thereof, characterized in that cyanobenzimidazoles of the
formula 380in which X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are each
as defined above are reacted with halides of the
formulaHal--Y--R.sup.2 (III)in which R.sup.2 and Y are each as
defined above and Hal represents chlorine or bromine, if
appropriate in the presence of an acid binder and if appropriate in
the presence of a diluent, and the resulting benzimidazoles of the
formula 381in which R.sup.2, Y, X.sup.1, X.sup.2, X.sup.3 and
X.sup.4 are each as defined above are, if appropriate, either a)
reacted with hydrogen sulphide in the presence of an acid binder
and in the presence of a diluent or b) reacted with a sulphur
compound of the formulaH--S--R.sup.6 (IV)in which R.sup.6 is as
defined above in the presence of an acid binder and in the presence
of a diluent, and an acid or a metal salt is, if appropriate, added
to the resulting compounds of the formula (I).
4. Microbicidal compositions, characterized by a content of at
least one benzimidazole derivative of the formula (I) according to
claim 1 or an acid addition salt or metal salt complex of a
benzimidazole derivative of the formula (I).
5. Use of benzimidazole derivatives of the formula (I) according to
claim 1 or of acid addition salts or metal salt complexes thereof
as microbicides in crop protection and in the protection of
materials.
6. Process for controlling undesirable microorganisms in crop
protection and in the protection of materials, characterized in
that benzimidazole derivatives of the formula (I) according to
claim 1 or acid addition salts or metal salt complexes thereof are
applied to the microorganisms and/or their habitat.
7. Process for preparing microbicidal compositions, characterized
in that benzimidazole derivatives of the formula (I) according to
claim 1 or acid addition salts or metal salt complexes thereof are
mixed with extenders and/or surface active compounds.
Description
[0001] The present invention relates to novel benzimidazole
derivatives, to a process for their preparation and to their use as
microbicides in crop protection and in the protection of
materials.
[0002] It is already known that certain benzimidazole derivatives
have fungicidal properties (cf. DE-A 4 139 950 and EP-A 0 517 476).
Thus, for example
2-cyano-1-dimethylarninosulphonyl-6,6,7,7-tetrafluoro-[1,4]dioxin-
o[2,3-f]benzimidazole and
2-cyano-6,6-difluoro-1-dimethylaminosulphonyl-[1-
,3]dioxolo[4,5-f]benzimidazole can be used for controlling fungi.
The activity of these compounds is good, but in some cases leaves
something to be desired at low application rates.
[0003] This invention, accordingly, provides novel benzimidazole
derivatives of the formula 2
[0004] in which
[0005] X.sup.1, X.sup.2, X.sup.3 and X.sup.4 independently of one
another each represent hydrogen, halogen, cyano, nitro, alkyl,
halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio,
halogenoalkylthio, alkylsulphinyl, halogenoalkylsulphinyl,
alkylsulphonyl, halogenoalkylsulphonyl, optionally substituted
cycloalkyl, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl,
cycloalkylcarbonyl, cycloalkoxycarbonyl, represent 3
[0006] in which
[0007] R.sup.3 and R.sup.4 independently of one another each
represent hydrogen, alkyl, halogenoalkyl, alkoxyalkyl,
alkylcarbonyl, optionally substituted aryl, optionally substituted
arylcarbonyl, optionally substituted arylsulphonyl, optionally
substituted arylaminocarbonyl or optionally substituted
arylmethylsulphonyl or
[0008] R.sup.3 and R.sup.4 together with the nitrogen atom that
they are attached to represent an optionally alkyl-substituted
heterocyclic ring which may contain an additional oxygen atom or an
aklylimino group,
[0009] Q represents a direct bond or a carbonyl group,
[0010] R.sup.5 represents optionally substituted aryl or represents
optionally substituted heterocyclyl and
[0011] Z represents a direct bond, represents CH.sub.2, O, S, SO,
SO.sub.2, CO or an azo group or
[0012] represents --CO--O--, where the oxygen atom is linked to the
aryl or heterocyclyl radical, or
[0013] represents --SO.sub.2--O--, where the sulphur atom is linked
to the aryl or heterocyclyl radical, or
[0014] represents --S--CH.sub.2--SO.sub.2--, where the sulphur atom
of the thio group is linked to the aryl or heterocyclyl radical,
or
[0015] X.sup.2 and X.sup.3 together represent an optionally
substituted alkylene chain having 3 or 4 members wherein one or two
(non-adjacent) carbon atoms may be replaced by oxygen atoms,
[0016] R.sup.1 represents cyano or the groupings 4
[0017] in which
[0018] R.sup.6 represents alkyl, halogenoalkyl or optionally
halogen- and/or halogenoalkyl-substituted benzyl,
[0019] R.sup.2 represents optionally substituted heterocyclyl
and
[0020] Y represents a direct bond, represents --CH.sub.2--,
--CH.sub.2--CH.sub.2--, --CO--, --SO.sub.2--, --CO--O-- or
--SO--O-- where in the case of the last two groups the carbon atom
or the sulphur atom is linked to the nitrogen atom of the imidazole
ring,
[0021] and acid addition salts and metal salt complexes
thereof.
[0022] Furthermore, it was found that benzimidazole derivatives of
the formula (I) and acid addition salts and metal salt complexes
thereof are obtained when cyanobenzimidazoles of the formula 5
[0023] in which X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are each as
defined above
[0024] are reacted with halides of the formula
Hal--Y--R.sup.2 (III)
[0025] in which
[0026] R.sup.2 and Y are each as defined above and
[0027] Hal represents chlorine or bromine, if appropriate in the
presence of an acid binder and if appropriate in the presence of a
diluent, and the resulting benzimidazoles of the formula 6
[0028] in which
[0029] R.sup.2, Y, X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are each
as defined above
[0030] are, if appropriate, either
[0031] a) reacted with hydrogen sulphide in the presence of an acid
binder and in the presence of a diluent, or
[0032] b) reacted with a sulphur compound of the formula
H--S--R.sup.6 (IV)
[0033] in which
[0034] R.sup.6 is as defined above
[0035] in the presence of an acid binder and in the presence of a
diluent,
[0036] and an acid or a metal salt is, if appropriate, added to the
resulting compounds of the formula (I).
[0037] Finally, it was found that the benzimidazole derivatives of
the formula (1) and acid addition salts and metal salt complexes
thereof have very good microbicidal properties and can be used in
crop protection and in the protection of materials.
[0038] Surprisingly, the compounds according to the invention have
better fungicidal activity than
2-cyano-1-dimethylaminosulphonyl-6,6,7,7-tetrafl-
uoro-[1,4]dioxino-[2,3-f]benzimidazole and
2-cyano-6,6-difluoro-1-dimethyl-
aminosulphonyl-[1,3]-dioxolo[4,5-f]benzimidazole, which are
compounds of the prior art of a similar structure and of the same
direction of action.
[0039] A general definition of the compounds according to the
invention is given by the formula (I).
[0040] X.sup.1, X.sup.2, X.sup.3 and X.sup.4 independently of one
another each preferably represent hydrogen, fluorine, chlorine,
bromine, iodine, cyano, nitro, straight-chain or branched alkyl
having 1 to 8 carbon atoms, straight-chain or branched
halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or
different halogen atoms, straight-chain or branched alkoxy having 1
to 8 carbon atoms, straight-chain or branched halogenoalkoxy having
1 to 6 carbon atoms and 1 to 13 identical or different halogen
atoms, straight-chain or branched alkylthio having 1 to 8 carbon
atoms, straight-chain or branched halogenoalkylthio having 1 to 6
carbon atoms and 1 to 13 identical or different halogen atoms,
straight-chain or branched alkylsulphinyl having 1 to 8 carbon
atoms, straight-chain or branched halogenoalkylsulphinyl having 1
to 6 carbon atoms and 1 to 13 identical or different halogen atoms,
straight-chain or branched alkylsulphonyl having 1 to 8 carbon
atoms, straight-chain or branched halogenoalkylsulphonyl having 1
to 6 carbon atoms and 1 to 13 identical or different halogen atoms,
cycloalkyl having 3 to 6 carbon atoms which is optionally mono- to
pentasubstituted by identical or different substituents from the
group consisting of halogen and alkyl having 1 to 4 carbon atoms,
represent hydroxycarbonyl, alkylcarbonyl having 1 to 6 carbon atoms
in the straight-chain or branched alkyl moiety, alkoxycarbonyl
having 1 to 6 carbon atoms in the straight-chain or branched alkoxy
moiety, cycloalkylcarbonyl having 3 to 6 carbon atoms in the
cycloalkyl moiety, cycloalkoxycarbonyl having 3 to 6 carbon atoms
in the cycloalkyl moiety, represent 7
[0041] R.sup.3 and R.sup.4 independently of one another each
preferably represent hydrogen, straight-chain or branched alkyl
having 1 to 6 carbon atoms, straight-chain or branched
halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or
different halogen atoms, straight-chain or branched alkoxyalkyl
having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon
atoms in the alkyl moiety, alkylcarbonyl having 1 to 6 carbon atoms
in the straight-chain or branched alkyl moiety, aryl having 6 to 10
carbon atoms, arylcarbonyl having 6 to 10 carbon atoms in the aryl
moiety, arylsulphonyl having 6 to 10 carbon atoms,
arylaminocarbonyl having 6 to 10 carbon atoms in the aryl moiety or
represent arylmethylsulphonyl having 6 to 10 carbon atoms in the
aryl moeity, it being possible for each of the abovementioned aryl
radicals to be mono- to trisubstituted by identical or different
substituents from the group consisting of halogen, cyano, nitro,
alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon
atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1
to 4 carbon atoms and 1 to 5 identical or different halogen atoms,
halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical or
different halogen atoms, halogenoalkylthio having 1 to 4 carbon
atoms and 1 to 5 identical or different halogen atoms,
alkylsulphinyl having 1 to 4 carbon atoms, alkylsulphonyl having 1
to 4 carbon atoms, halogenoalkylsulphinyl having 1 to 4 carbon
atoms and 1 to 5 identical or different halogen atoms and
halogenoalkylsulphonyl having 1 to 4 carbon atoms and 1 to 5
identical or different halogen atoms.
[0042] R.sup.3 and R.sup.4 together with the nitrogen atom that
they are attached to additionally preferably represent a
heterocyclic ring having 5 or 6 ring members which is optionally
mono- to trisubstituted by alkyl having 1 to 4 carbon atoms and
which may contain an additional oxygen atom or a
C.sub.1-C.sub.4-alkylimino group.
[0043] Q preferably represents a direct bond or represents a
carbonyl group.
[0044] R.sup.5 preferably represents aryl having 6 to 10 carbon
atoms, it being possible for each of these radicals to be mono- to
trisubstituted by identical or different substituents from the
group consisting of halogen, cyano, nitro, alkyl having 1 to 4
carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1
to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1
to 5 identical or different halogen atoms, halogenoalkoxy having 1
to 4 carbon atoms and 1 to 5 identical or different halogen atoms,
halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 identical
or different halogen atoms, alkylsulphinyl having 1 to 4 carbon
atoms, alkylsulphonyl having 1 to 4 carbon atoms,
halogenoalkylsulphinyl having 1 to 4 carbon atoms and 1 to 5
identical or different halogen atoms and halogenoalkylsulphonyl
having 1 to 4 carbon atoms and 1 to 5 identical or different
halogen atoms, or
[0045] R.sup.5 preferably represents a saturated or unsaturated
heterocyclyl radical having 5 or 6 ring members and 1 to 3
heteroatoms such as nitrogen, oxygen and/or sulphur, it being
possible for these radicals to be mono- to trisubstituted by
identical or different substituents from the group consisting of
halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4
carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5
identical or different halogen atoms, halogenoalkoxy having 1 to 4
carbon atoms and 1 to 5 identical or different halogen atoms,
alkoxycarbonyl having 1 to 3 carbon atoms in the alkoxy moiety,
cycloalkyl having 3 to 6 carbon atoms, cyano and nitro.
[0046] Z preferably represents a direct bond and also represents
CH.sub.2, O, S, SO, SO.sub.2, CO or an azo group, or
[0047] preferably represents --CO--O--, where the oxygen atom is
linked to the aryl or heterocyclyl radical, or
[0048] preferably represents --SO.sub.2--O--, where the sulphur
atom is linked to the aryl or heterocyclyl radical, or
[0049] preferably represents --S--CH.sub.2--SO.sub.2--, where the
sulphur atom of the thio group is linked to the aryl or
heterocyclyl radical.
[0050] X.sup.2 and X.sup.3 together also preferably represent an
alkylene chain having 3 or 4 members which is optionally mono- to
hexasubstituted by halogen, alkyl having 1 to 4 carbon atoms and/or
halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms
and in which one or two (non-adjacent) carbon atoms may be replaced
by oxygen atoms.
[0051] R.sup.1 preferably represents cyano or the groupings 8
[0052] R.sup.6 preferably represents straight-chain or branched
alkyl having 1 to 4 carbon atoms, straight-chain or branched
halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical or
different halogen atoms or represents benzyl which is optionally
mono- to trisubstituted by identical or different substituents from
the group consisting of halogen and halogenoalkyl having 1 or 2
carbon atoms and 1 to 5 identical or different halogen atoms.
[0053] R.sup.2 preferably represents a saturated or unsaturated,
optionally benzo-fused heterocyclyl radical having 5 or 6 ring
members and 1 to 3 heteroatoms such as nitrogen, oxygen and/or
sulphur, it being possible for these radicals to be mono- to
trisubstituted by identical or different substituents from the
group consisting of halogen, cyano, nitro, hydroxyl, amino, formyl,
carboxy, carbamoyl, thiocarbamoyl, alkyl having 1 to 4 carbon
atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 to
4 carbon atoms and 1 to 5 identical or different halogen atoms,
halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical or
different halogen atoms, alkoxycarbonyl having 1 to 4 carbon atoms
in the alkoxy moiety, cycloalkyl having 3 to 6 carbon atoms,
halogenoalkylsulphinyl having 1 to 4 carbon atoms and 1 to 5
identical or different halogen atoms, halogenoalkylsulphonyl having
1 to 4 carbon atoms and 1 to 5 identical or different halogen
atoms, alkylamino having 1 to 4 carbon atoms, hydroxyalkylamino
having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms
in each alkyl group, alkylcarbonyl having 1 to 4 carbon atoms in
the alkyl moiety, alkylcarbonyl amino having 1 to 4 carbon atoms in
the alkyl group, hydroxyiminoalkyl having 1 to 4 carbon atoms in
the alkyl moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the
alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety,
alkylcarbonoxy having 1 to 4 carbon atoms in the alkyl moiety and
halogenoalkylcarbonyloxy having 1 to 4 carbon atoms in the
halogenoalkyl group and 1 to 5 identical or different halogen
atoms,
[0054] it being possible for the heterocyclyl radicals to contain
oxo groups.
[0055] Y preferably represents a direct bond, represents CH.sub.2,
CH.sub.2--CH.sub.2, CO, SO.sub.2, --CO--O-- or --SO--O--, where in
the case of the last two groups the carbon atom or the sulphur atom
is linked to the nitrogen atom of the imidazole ring.
[0056] X.sup.1, X.sup.2, X.sup.3 and X.sup.4 independently of one
another each particularly preferably represent hydrogen, fluorine,
chlorine, bromine, iodine, cyano, nitro, straight-chain or branched
alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 or 2
carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms,
straight-chain or branched alkoxy having 1 to 6 carbon atoms,
halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine,
chlorine and/or bromine atoms, straight-chain or branched alkylthio
having 1 to 6 carbon atoms, halogenoalkylthio having 1 or 2 carbon
atoms and 1 to 5 fluorine, chlorine and/or bromine atoms,
straight-chain or branched alkylsulphinyl having 1 to 6 carbon
atoms, halogenoalkylsulphinyl having 1 or 2 carbon atoms and 1 to 5
fluorine, chlorine and/or bromine atoms, straight-chain or branched
alkylsulphonyl having 1 to 6 carbon atoms, halogenoalkylsulphonyl
having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or
bromine atoms, cycloalkyl having 3 to 6 carbon atoms which is
optionally mono- to trisubstituted by identical or different
substituents from the group consisting of fluorine, chlorine,
bromine, methyl and ethyl, represents hydroxycarbonyl,
alkylcarbonyl having 1 to 4 carbon atoms in the straight-chain or
branched alkyl moiety, alkoxycarbonyl having 1 to 4 carbon atoms in
the straight-chain or branched alkoxy moiety, cycloalkylcarbonyl
having 3 to 6 carbon atoms in the cycloalkyl moiety,
cycloalkoxycarbonyl having 3 to 6 carbon atoms in the cycloalkyl
moiety, represents 9
[0057] R.sup.3 and R.sup.4 independently of one another each
particularly preferably represent hydrogen, straight-chain or
branched alkyl having 1 to 4 carbon atoms, halogenoalkyl having 1
or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine
atoms, straight-chain or branched alkoxyalkyl having 1 to 3 carbon
atoms in the alkoxy moiety and 1 to 3 carbon atoms in the alkyl
moiety, alkylcarbonyl having 1 to 4 carbon atoms in the
straight-chain or branched alkyl moiety, phenyl, phenylcarbonyl,
phenylsulphonyl, phenylaminocarbonyl or phenylmethylsulphonyl, it
being possible for each of the abovementioned phenyl radicals to be
mono- to trisubstituted by identical or different substituents from
the group consisting of fluorine, chlorine, bromine, cyano, nitro,
alkyl having 1 or 2 carbon atoms, alkoxy having 1 or 2 carbon
atoms, alkylthio having 1 or 2 carbon atoms, halogenoalkyl having 1
or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine
atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5
fluorine, chlorine and/or bromine atoms, halogenoalkylthio having 1
or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine
atoms, alkylsulphinyl having 1 or 2 carbon atoms, alkylsulphonyl
having 1 or 2 carbon atoms, halogenoalkylsulphinyl having 1 or 2
carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms and
halogenoalkylsulphonyl having 1 or 2 carbon atoms and 1 to 5
fluorine, chlorine and/or bromine atoms.
[0058] R.sup.3 and R.sup.4 together with the nitrogen atom that
they are attached to additionally particularly preferably represent
a saturated heterocyclic ring having 5 or 6 ring members which is
optionally mono- to trisubstituted by methyl and/or ethyl and in
which one carbon atom of the ring may be replaced by oxygen or
methylimino.
[0059] Q particularly preferably represents a direct bond or a
carbonyl group.
[0060] R.sup.5 particularly preferably represents phenyl which may
be mono- to trisubstituted by identical or different substituents
from the group consisting of fluorine, chlorine, bromine, cyano,
nitro, alkyl having 1 or 2 carbon atoms, alkoxy having 1 or 2
carbon atoms, alkylthio having 1 or 2 carbon atoms, halogenoalkyl
having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or
bromine atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5
fluorine, chlorine and/or bromine atoms, halogenoalkylthio having 1
or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine
atoms, alkylsulphinyl having 1 or 2 carbon atoms, alkylsulphonyl
having 1 or 2 carbon atoms, halogenoalkylsulphinyl having 1 or 2
carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms and
halogenoalkylsulphonyl having 1 or 2 carbon atoms and 1 to 5
fluorine, chlorine and/or bromine atoms, or
[0061] R.sup.5 particularly preferably represents a saturated or
unsaturated heterocyclyl radical having 5 or 6 ring members and 1
to 3 heteroatoms such as nitrogen, oxygen and/or sulphur, it being
possible for these radicals to be mono- to trisubstituted by
identical or different substituents from the group consisting of
fluorine, chlorine, bromine, alkyl having 1 or 2 carbon atoms,
alkoxy having 1 or 2 carbon atoms, halogenoalkyl having 1 or 2
carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms,
halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine,
chlorine and/or bromine atoms, alkoxycarbonyl having 1 or 2 carbon
atoms in the alkoxy moiety, cycloalkyl having 3 to 6 carbon atoms,
cyano and nitro.
[0062] Z particularly preferably represents a direct bond and
CH.sub.2, O, S, SO, SO.sub.2, CO or an azo group, or
[0063] represents --CO--O--, where the oxygen atom is linked to the
phenyl or heterocyclyl radical, or
[0064] represents --SO.sub.2--O--, where the sulphur atom is linked
to the phenyl or heterocyclyl radical, or
[0065] represents --S--CH.sub.2--SO.sub.2--, where the sulphur atom
of the thio group is linked to the phenyl or heterocyclyl
radical.
[0066] X.sup.2 and X.sup.3 together additionally particularly
preferably represent an alkylene chain having 3 or 4 members which
is optionally mono- to hexasubstituted by fluorine, chlorine,
methyl and/or trifluoromethyl and in which one or two
(non-adjacent) carbon atoms may be replaced by oxygen.
[0067] R.sup.1 particularly preferably represents cyano or the
groupings 10
[0068] R.sup.6 particularly preferably represents straight-chain or
branched alkyl having 1 to 4 carbon atoms, straight-chain or
branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 5
fluorine, chlorine and/or bromine atoms or represents benzyl which
is optionally mono- or disubstituted by identical or different
substituents from the group consisting of fluorine, chlorine and
trifluoromethyl.
[0069] R.sup.2 particularly preferably represents a saturated or
unsaturated, optionally benzo-fused heterocyclyl radical having 5
or 6 ring members and 1 to 3 hetero atoms such as nitrogen, oxygen
and/or sulphur, it being possible for these radicals to be mono- to
trisubstituted by identical or different substituents from the
group consisting of fluorine, chlorine, bromine, cyano, nitro,
hydroxyl, amino, formyl, carboxy, carbamoyl, thiocarbamoyl, alkyl
having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms,
halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine,
chlorine and/or bromine atoms, halogenoalkoxy having 1 or 2 carbon
atoms and 1 to 5 fluorine, chlorine and/or bromine atoms,
alkoxycarbonyl having 1 or 2 carbon atoms in the alkoxy moiety,
cycloalkyl having 3 to 6 carbon atoms, halogenoalkylsulphinyl
having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or
bromine atoms, halogenoalkylsulphonyl having 1 or 2 carbon atoms
and 1 to 5 fluorine, chlorine and/or bromine atoms, alkylamino
having 1 or 2 carbon atoms, hydroxyalkyl amino having 1 or 2 carbon
atoms, dialkylamino having 1 to 2 carbon atoms in each alkyl group,
alkylcarbonyl having 1 or 2 carbon atoms in the alkyl moiety,
alkylcarbonylamino having 1 to 3 carbon atoms in the alkyl moiety,
hydroxyiminoalkyl having 1 or 2 carbon atoms in the alkyl moiety,
alkoximinoalkyl having 1 or 2 carbon atoms in the alkoxy moiety and
1 or 2 carbon atoms in the alkyl moiety, alkylcarbonyloxy having 1
or 2 carbon atoms in the alkyl group and halogenoalkylcarbonyloxy
having 1 or 2 carbon atoms in the halogenoalkyl group and 1 to 5
fluorine, chlorine and/or bromine atoms,
[0070] it being possible for the heterocyclyl radicals to contain
one or two oxo groups.
[0071] Y particularly preferably represents a direct bond,
represents CH.sub.2, CH.sub.2--CH.sub.2, CO, SO.sub.2, --CO--O-- or
--SO--O-- where in the case of the last two groups the carbon atom
or the sulphur atom is linked to the nitrogen atom of the imidazole
ring.
[0072] X.sup.1, X.sup.2, X.sup.3 and X.sup.4 independently of one
another each very particularly preferably represent hydrogen,
fluorine, chlorine, bromine, cyano, nitro, represent methyl, ethyl,
n- or i-propyl, n- , i- , s- or t-butyl, methoxy, ethoxy, n- or
i-propoxy, methylthio, ethylthio, n- or i-propylthio,
methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl,
trifluoromethyl, difluoromethoxy, trifluoromethoxy,
difluoromethylthio, trifluoromethylthio, trifluoromethylsulphinyl,
trifluoromethylsulphonyl, acetyl, acetyloxy, methoxycarbonyl,
ethoxycarbonyl, cyclopropyl, cyclohexyl, represent 11
[0073] R.sup.3 and R.sup.4 independently of one another each very
particularly preferably represent hydrogen, methyl, ethyl,
n-propyl, isopropyl or phenyl.
[0074] R.sup.3 and R.sup.4 together with the nitrogen atom that
they are attached to additionally very particularly preferably
represent pyrrolidinyl, piperidinyl, morpholinyl or
4-methyl-piperazinyl.
[0075] Q very particularly preferably represents a direct bond or
represents a carbonyl group.
[0076] R.sup.5 very particularly preferably represents phenyl which
may be mono- to trisubstituted by identical or different
substituents from the group consisting of fluorine, chlorine,
bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n- , i- , s-
or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio,
ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl,
methylsulphonyl, ethylsulphonyl, trifluoromethyl, difluoromethoxy,
trifluoromethoxy, difluoromethylthio, trifluoromethylthio,
difluoromethylsulphinyl and trifluoromethylsulphonyl- , or
[0077] R.sup.5 very particularly preferably represents pyrrolyl,
furyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl,
oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, 1,2,3-triazinyl,
1,2,4-triazinyl, 1,3,5-triazinyl, pyridinyl, pyrimidinyl, pyrazinyl
or pyridazinyl, it being possible for these radicals to be mono- to
trisubstituted by identical or different substituents from the
group consisting of fluorine, chlorine, methyl, methoxy,
trifluoromethyl, trifluoromethoxy and trifluoromethoxy.
[0078] Z very particularly preferably represents a direct bond and
represents CH.sub.2, O, S, SO, SO.sub.2, CO or an azo group, or
[0079] represents --CO--O--, where the oxygen atom is linked to the
phenyl or heterocyclyl radical, or
[0080] represents --SO.sub.2--O--, where the sulphur atom is linked
to the phenyl or heterocyclyl radical, or
[0081] represents --S--CH.sub.2--SO.sub.2--, where the sulphur atom
of the thio group is linked to the phenyl or heterocyclyl
radical.
[0082] X.sup.2 and X.sup.3 together additionally very particularly
preferably represent the groupings
--O--CF.sub.2--O--,--O--CF.sub.2--CHF-- -O--, --O--CHF--CHF--O--,
O--CF.sub.2--CF.sub.2--O--, --O--CF.sub.2--CFCl--O--,
--O--CFCl--CFCl--O--, --O--CF.sub.2--CF.sub.2-- or
--CF.sub.2--CF.sub.2--O--.
[0083] R.sup.1 very particularly preferably represents cyano or the
groupings 12
[0084] R.sup.6 very particularly preferably represents methyl,
ethyl, isopropyl, trichloromethyl, trifluoromethyl or benzyl.
[0085] R.sup.2 very particularly preferably represents pyrrolyl,
furyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl,
oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, 1,2,3-triazinyl,
1,2,4-triazinyl, 1,3,5-triazinyl, pyridinyl, pyrimidinyl,
pyrazinyl, pyridazinyl, benzofuryl, benzothienyl, quinolyl or the
radicals of the formulae 13
[0086] it being possible for these radicals to be mono- to
trisubstituted by identical or different substituents from the
group consisting of fluorine, chlorine, bromine, cyano, nitro,
amino, hydroxyl, formyl, carboxy, carbamoyl, thiocarbamoyl, methyl,
ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n-
or i-propoxy, methylthio, ethylthio, n- or i-propylthio,
methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl,
trifluoromethyl, difluoromethoxy, trifluoromethoxy,
difluoromethylthio, trifluoromethylthio, trifluoromethylsulphinyl
or trifluoromethylsulphonyl, methylamino, ethylamino, n- or
i-propylamino, dimethylamino, diethylanino, acetyl, propionyl,
methylcarbonylamino, acetyloxy, methoxycarbonyl, ethoxycarbonyl,
methylsulphonyloxy, ethylsulphonyloxy, hydroxyiminomethyl,
hydroxyiminoethyl, methoxyiminomethyl, ethoxyiminomethyl,
methoxyiminoethyl and ethoxyiminoethyl.
[0087] Y very particularly preferably represents a direct bond,
represents CH.sub.2, CH.sub.2--CH.sub.2, CO, SO.sub.2, --CO--O--or
--SO--O--, where in the case of the last two groups the carbon atom
or the sulphur atom is linked to the nitrogen of the imidazole
ring.
[0088] Preferred compounds according to the invention are also the
addition products of acids and those benzimidazole derivatives of
the formula (I) in which R.sup.1, R.sup.2, X.sup.1, X.sup.2,
X.sup.3, X.sup.4 and Y each have those meanings which have been
mentioned as being preferred for these radicals.
[0089] The acids which can be subjected to an addition reaction
preferably include hydrohalic acids, such as, for example,
hydrochloric acid and hydrobromic acid, in particular hydrochloric
acid, furthermore phosphoric acid, nitric acid, mono- and
bifunctional carboxylic acids and hydrocarboxylic acids, such as,
for example, acetic acid, maleic acid, succinic acid, fumaric acid,
tartaric acid, citric acid, salicylic acid, sorbic acid and lactic
acid, and also sulphonic acids, such as, for example,
p-toluenesulphonic acid and 1,5-naphthalenedisulphonic acid, and
also saccharin and thio saccharin.
[0090] Other preferred compounds according to the invention are
adducts of salts of metals of main groups II to IV and sub-groups I
and II and IV to VIII of the Periodic Table of the Elements and
those benzimidazole derivatives of the formula (I) in which
R.sup.1, R.sup.2, X.sup.1, X.sup.2, X.sup.3, X.sup.4 and Y each
have those meanings which have been mentioned as being preferred
for these radicals.
[0091] Salts of copper, zinc, manganese, magnesium, tin, iron and
nickel are particularly preferred in this context. Suitable anions
of these salts are those which are derived from acids which lead to
physiologically acceptable adducts. Particularly preferred acids of
this type are, in this context, the hydrohalic acids, such as, for
example, hydrochloric acid and hydrobromic acid, furthermore
phosphoric acid, nitric acid and sulphuric acid.
[0092] Examples of compounds according to the invention which may
be mentioned are the benzimidazole derivatives listed in the tables
below.
1TABLE 1 (I-b) 14 R.sup.1 R.sup.2-Y --CN 15 --CN 16 --CN 17 --CN 18
--CN 19 --CN 20 --CN 21 --CN 22 --CN 23 --CN 24 --CN 25 --CN 26 27
28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49
50
[0093]
2TABLE 2 (I-c) 51 R.sup.1 R.sup.2-Y --CN 52 --CN 53 --CN 54 --CN 55
--CN 56 --CN 57 --CN 58 --CN 59 --CN 60 --CN 61 --CN 62 --CN 63 64
65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
87
[0094]
3TABLE 3 (I-d) 88 R.sup.1 R.sup.2-Y --CN 89 --CN 90 --CN 91 --CN 92
--CN 93 --CN 94 --CN 95 --CN 96 --CN 97 --CN 98 --CN 99 --CN 100
101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117
118 119 120 121 122 123 124
[0095]
4TABLE 4 (I-e) 125 R.sup.1 R.sup.2-Y --CN 126 --CN 127 --CN 128
--CN 129 --CN 130 --CN 131 --CN 132 --CN 133 --CN 134 --CN 135 --CN
136 --CN 137 138 139 140 141 142 143 144 145 146 147 148 149 150
151 152 153 154 155 156 157 158 159 160 161
[0096]
5TABLE 5 (I-f) 162 R.sup.1 R.sup.2-Y --CN 163 --CN 164 --CN 165
--CN 166 --CN 167 --CN 168 --CN 169 --CN 170 --CN 171 --CN 172 --CN
173 --CN 174 175 176 177 178 179 180 181 182 183 184 185 186 187
188 189 190 191 192 193 194 195 196 197 198
[0097]
6TABLE 6 (I-g) 199 R.sup.1 R.sup.2-Y --CN 200 --CN 201 --CN 202
--CN 203 --CN 204 --CN 205 --CN 206 --CN 207 --CN 208 --CN 209 --CN
210 --CN 211 212 213 214 215 216 217 218 219 220 221 222 223 224
225 226 227 228 229 230 231 232 233 234 235
[0098]
7TABLE 7 236 R.sup.1 R.sup.2--Y --CN 237 --CN 238 --CN 239 --CN 240
--CN 241 --CN 242 --CN 243 --CN 244 --CN 245 --CN 246 --CN 247 --CN
248 249 250 251 252 253 254 255 256 257 258 259 260 261 262 263 264
265 266 267 268 269 270 271 272
[0099]
8TABLE 8 273 R.sup.1 R.sup.2--Y --CN 274 --CN 275 --CN 276 --CN 277
--CN 278 --CN 279 --CN 280 --CN 281 --CN 282 --CN 283 --CN 284 --CN
285 286 287 288 289 290 291 292 293 294 295 296 297 298 299 300 301
302 303 304 305 306 307 308 309
[0100] If 2-cyano-6,6-difluoro-[1,3]dioxolo[4,5-f]benzimidazole and
3,5-dimethyl-isoxazolyl-4-sulphonyl chloride are used as starting
materials, the course of the process according to the invention can
be illustrated by the following equation: 310
[0101] If
2-Cyano-6,6-difluoro-3-(3,5-dimethyl-isoxazolyl-4-sulphonyl)-[1,-
3]-dioxolo[4,5-f]benzimidazole is used as starting material and
hydrogen sulphide is used as reaction component, the course of the
process according to the invention can be illustrated by the
following equation: 311
[0102] If
2-cyano-6,6-difluoro-3-(3,5-dimethyl-isoxazole-4-sulphonyl)-[1,3-
]-dioxolo-[4,5-f]benzimidazole is used as starting material and
methyl mercaptan is used as reaction component, the course of the
process according to the invention can be illustrated by the
following equation: 312
[0103] Formula (II) provides a general definition of the
cyano-benzimidazoles required as starting materials for carrying
out the first step of the process according to the invention. In
this formula, X.sup.1, X.sup.2, X.sup.3 and X.sup.4 each have those
meanings which have already been mentioned in connection with the
description of the compounds of the formula (I) according to the
invention for these radicals.
[0104] The cyano-benzimidazoles of the formula (II) are known or
can be prepared by methods known in principle (cf. DE-A 4 139 950,
FR-A 2 572 412, EP-A 0 181 826, EP-A 0 517 476, EP-A 0 549 943 and
EP-A 0 487 286).
[0105] Formula (III) provides a general definition of the halides
further required as starting materials for carrying out the first
step of the process according to the invention. In this formula,
R.sup.2 and Y each have those meanings which have already been
mentioned in connection with the description of the compounds of
the formula (I) according to the invention for these radicals. Hal
represents chlorine or bromine.
[0106] The halides of the formula (III) are known or can be
prepared by known methods.
[0107] Suitable diluents for carrying out the first step of the
process according to the invention are all customary inert organic
solvents. Preference is given to using aliphatic, cycloaliphatic
and aromatic, optionally halogenated hydrocarbons, such as, for
example, benzine, benzene, toluene, xylene, chlorobenzene,
dichlorobenzene, petroleum ether, hexane, cyclohexane,
dichloromethane, chloroform or carbon tetrachloride; furthermore
ethers, such as diethyl ether, diisopropyl ether, dioxane,
tetrahydrofuran or ethylene glycol dimethyl ether or ethylene
glycol diethyl ether, furthermore ketones, such as acetone or
butanone or methyl isobutyl ketone; nitriles such as acetonitrile,
propionitrile or benzonitrile, or esters such as methyl acetate or
ethyl acetate.
[0108] The first step of the process according to the invention is
preferably carried out in the presence of an acid binder. Suitable
acid binders are all customary inorganic or organic bases.
Preference is given to using alkaline earth metal or alkali metal
hydroxides, such as sodium hydroxide, calcium hydroxide, potassium
hydroxide, or else ammonium hydroxide, alkali metal carbonates,
such as sodium carbonate, potassium carbonate, potassium
bicarbonate, sodium bicarbonate, alkali metal or alkaline earth
metal acetates such as sodium acetate, potassium acetate, calcium
acetate, and tertiary amines, such as trimethylamine,
triethylamine, tributylamine, N,N-dimethylaniline, pyridine,
N-methylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane
(DABCO), diazabicyclononene (DBN) or diazabicycloundecene
(DBU).
[0109] When carrying out the first step of the process according to
the invention, the reaction temperatures can be varied within a
relatively wide range. In general, the process is carried out at
temperatures between 0 and 150.degree. C., preferably at
temperatures between 20 and 120.degree. C.
[0110] The first and the second step of the process according to
the invention is generally carried out under atmospheric pressure.
However, it is also possible to work under elevated or reduced
pressure.
[0111] When carrying out the first step of the process according to
the invention, generally 1.0 to 2.0 mol, preferably 1.0 to 1.3 mol,
of a halide of the formula (III) and optionally 1.0 to 2.0 mol,
preferably 1.0 to 1.3 mol, of an acid binder are employed per mole
of a cyano-benzimidazole of the formula (II) in a diluent. Known
processes are employed for carrying out the reaction and for the
work-up and isolation of the reaction products (cf. also the
preparation examples).
[0112] When carrying out the second step (variant a) of the process
according to the invention, preferred acid binders are tertiary
amines such as triethylamine.
[0113] When carrying out the second step of the process according
to the invention (variant a), suitable diluents are all inert polar
organic solvents. Preference is given to using amides, such as
dimethyl formamide, and also ethers, such as diethyl ether or
tetrahydrofuran, and aromatic amines, such as pyridine.
[0114] When carrying out the second step (variant a) of the process
according to the invention, the reaction temperatures can also be
varied within a relatively wide range. In general, this step is
carried out at temperatures between -20.degree. C. and +150.degree.
C., preferably between -10.degree. C. and +80.degree. C.
[0115] When carrying out the second step of the process according
to the invention (variant a), an excess, preferably 2 to 5 mol, of
hydrogen sulphide is employed per 1 mol of the benzimidazole
derivative of the formula (I-a). Work-up is carried out by
conventional methods.
[0116] Formula (IV) provides a general definition of the sulphur
compounds required as reaction components for carrying out the
second step (variant b) of the process according to the invention.
In this formula, R.sup.6 has those meanings already mentioned in
connection with the description of the compounds of the formula (1)
according to the invention for this radical.
[0117] When carrying out the second step (variant b) of the process
according to the invention, preferred acid binders are alkali metal
carbonates such as sodium carbonate or potassium carbonate.
[0118] Suitable diluents for carrying out the second step (variant
b) of the process according to the invention are all customary
polar aprotic solvents. Preference is given to using nitrites such
as acetonitrile.
[0119] When carrying out the second step (variant b) of the process
according to the invention, the reaction temperatures can also be
varied within a relatively wide range. In general, this step is
carried out at temperatures between -20.degree. C. and +150.degree.
C., preferably between -10.degree. C. and +80.degree. C.
[0120] When carrying out the second step of the process according
to the invention (variant b), an excess, preferably 2 to 5 mol, of
the sulphur compound of the formula (IV) is employed per 1 mol of
the benzimidazole derivative of the formula (I-a). Work-up is
carried out by conventional methods.
[0121] The benzimidazole derivatives of the formula (I) can be
converted into acid addition salts or metal salt complexes.
[0122] Suitable acids for the preparation of acid addition salts of
the compounds of the formula (I) are preferably those which have
already been mentioned in connection with the description of the
acid addition salts according to the invention as being preferred
acids.
[0123] The acid addition salts of the compounds of the formula (I)
can be obtained in a simple manner by customary salt formation
methods, for example by dissolving a compound of the formula (I) in
a suitable inert solvent and adding the acid, for example
hydrochloric acid, and they can be isolated in a known manner, for
example by filtering off, and, if appropriate, purified by washing
with an inert organic solvent.
[0124] Suitable salts for the preparation of metal salt complexes
of the compounds of the formula (I) are preferably those of metals
which have already been mentioned in connection with the
description of the metal salt complexes according to the invention
as being preferred metal salts.
[0125] The metal salt complexes of the compounds of the formula (I)
can be obtained in a simple manner by customary processes, for
example by dissolving the metal salt in alcohol, for example
ethanol, and adding the solution to the compounds of the formula
(I). Metal salt complexes can be isolated in a known manner, for
example by filtering off, and, if appropriate, purified by
recrystallization.
[0126] The active compounds according to the invention have a
strong microbicidal activity and can be employed for controlling
undesirable microorganisms, such as fungi and bacteria, in crop
protection and in the protection of materials.
[0127] The undesirable microorganisms include fungi, such as
Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,
Ascomycetes, Basidiomycetes, Deuteromycetes and furthermore
bacteria, such as Pseudomonadaceae, Rhizobiaceae,
Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
[0128] Some causative organisms of fungal and bacterial diseases
which come under the generic names listed above may be mentioned as
examples, but not by way of limitation:
[0129] Xanthomonas species, such as Xanthomonas oryzae;
[0130] Pseudomonas species, such as Pseudomonas lachrymans;
[0131] Erwinia species, such as Erwinia amylovora;
[0132] Pythium species, such as Pythium ultimum;
[0133] Phytophthora species, such as Phytophthora infestans;
[0134] Pseudoperonospora species, such as Pseudoperonospora humuli
or Pseudoperonospora cubensis;
[0135] Plasmopara species, such as Plasmopara viticola;
[0136] Peronospora species, such as Peronospora pisi or P.
brassicae;
[0137] Erysiphe species, such as Erysiphe graminis;
[0138] Sphaerotheca species, such as Sphaerotheca fuliginea;
[0139] Podosphaera species, such as Podosphaera leucotricha;
[0140] Venturia species, such as Venturia inaequalis;
[0141] Pyrenophora species, such as Pyrenophora teres or P.
graminea (conidia form: Drechslera, syn: Helminthosporium);
[0142] Cochliobolus species, such as Cochliobolus sativus (conidia
form: Drechslera, syn: Helminthosporium);
[0143] Uromyces species, such as Uromyces appendiculatus;
[0144] Puccinia species, such as Puccinia recondita;
[0145] Tilletia species, such as Tilletia caries;
[0146] Ustilago species, such as Ustilago nuda or Ustilago
avenae;
[0147] Pellicularia species, such as Pellicularia sasakii;
[0148] Pyricularia species, such as Pyricularia oryzae;
[0149] Fusarium species, such as Fusarium culmorum;
[0150] Botrytis species, such as Botrytis cinerea;
[0151] Septoria species, such as Septoria nodorum;
[0152] Leptosphaeria species, such as Leptosphaeria nodorum;
[0153] Cercospora species, such as Cercospora canescens;
[0154] Alternaria species, such as Alternaria brassicae and
[0155] Pseudocercosporella species, such as Pseudocercosporella
herpotrichoides.
[0156] The good toleration, by plants, of the active compounds, at
the concentrations required for controlling plant diseases, permits
treatment of above-ground parts of plants, of vegetative
propagation stock and seeds, and of the soil.
[0157] The active compounds according to the invention are
particularly suitable for controlling diseases in fruit and
vegetable growing, such as, for example against Venturia species,
or for controlling cereal diseases, such as, for example Erysiphe,
Cochliobolus, Pyrenophora, or Septoria species, or for controlling
rice diseases, such as, for example, against the causative organism
of rice blast (Pyricularia oryzae).
[0158] In materials protection the substances of the invention can
be used to protect industrial materials against infestation and
destruction by undesirable microorganisms.
[0159] The term industrial materials in the present context refers
to nonliving materials which have been prepared for use in
industry. Examples can be industrial materials which are to be
protected by novel active substances against microbial alteration
or destruction, adhesives, sizes, paper and card, textiles,
leather, wood, coating compositions and plastics articles, cooling
lubricants and other materials which can be infested or decomposed
by microorganisms. In the context of the materials to be protected
mention may also be made of parts of production plants, for example
cooling water circuits, which may be adversely affected by
reproduction of microorganisms. Preferred industrial materials in
the context of the present invention are adhesives, sizes, papers
and cards, leather, wood, coating compositions, cooling lubricants
and heat transfer fluids, especially wood.
[0160] Examples of microorganisms which can bring about degradation
or an alteration in the industrial materials are bacteria, fungi,
yeasts, algae and slime organisms. The active substances according
to the invention preferably act against fungi, especially mould
fungi, wood-discolouring and wood-destroying fungi (Basidiomycetes)
and also against slime organisms and algae.
[0161] By way of example, mention may be made of the following
genera:
[0162] Alternaria, such as Alternaria tenuis,
[0163] Aspergillus, such as Aspergillus niger,
[0164] Chaetomium, such as Chaetomium globosum,
[0165] Coniophora, such as Coniophora puetana,
[0166] Lentinus, such as Lentinus tigrinus,
[0167] Penicillium, such as Penicillium glaucum,
[0168] Polyporus, such as Polyporus versicolor,
[0169] Aureobasidium, such as Aureobasidium pullulans,
[0170] Sclerophoma, such as Sclerophoma pityophila,
[0171] Trichoderma, such as Trichoderma viride,
[0172] Escherichia, such as Escherichia coli,
[0173] Pseudomonas, such as Pseudomonas aeruginosa,
[0174] Staphylococcus, such as Staphylococcus aureus.
[0175] In addition, the active compounds according to the invention
are suitable for controlling animal pests, preferably arthropods
and nematodes, in particular insects and arachnids encountered in
agriculture, in forests, in the protection of stored goods and of
materials and in the field of hygiene. They are active against
normally sensitive and resistant species and against all or some
development stages.
[0176] The cyanobenzimidazoles of the formula (II) are also
fungicidally active.
[0177] Depending on their respective physical and/or chemical
properties, the active substances can be converted into customary
formulations, such as solutions, emulsions, suspensions, powders,
foams, pastes, granules, aerosols, very fine capsules in polymeric
substances and in coating compositions for seed, and also ULV
cold-mist and warm-mist formulations.
[0178] These formulations are prepared in a known manner, for
example by mixing the active compounds with extenders, that is,
liquid solvents, liquefied gases under pressure, and/or solid
carriers, optionally with the use of surface-active agents, that
is, emulsifying agents and/or dispersing agents, and/or
foam-forming agents. In the case of the use of water as an
extender, organic solvents such as alcohols can, for example, also
be used as auxiliary solvents. As liquid solvents, there are
suitable in the main: aromatics, such as xylene, toluene or
alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic
hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene
chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins,
for example mineral oil fractions, alcohols, such as butanol or
glycol as well as their ethers and esters, ketones, such as
acetone, methyl ethyl ketone, methyl isobutyl ketone or
cyclohexanone, strongly polar solvents, such as dimethylformamide
and dimethyl sulphoxide, as well as water; by liquefied gaseous
extenders or carriers are meant liquids which are gaseous at
ambient temperature and under atmospheric pressure, for example
aerosol propellants, such as halogenated hydrocarbons such as
butane, propane, nitrogen and carbon dioxide; as solid carriers
there are suitable: for example ground natural minerals, such as
kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite
or diatomaceous earth, and ground synthetic minerals, such as
finely divided silica, alumina and silicates; as solid carriers for
granules there are suitable: for example crushed and fractionated
natural rocks such as calcite, marble, pumice, sepiolite and
dolomite, as well as synthetic granules of inorganic and organic
meals, and granules of organic material such as sawdust, coconut
shells, maize cobs and tobacco stalks; as emulsifying and/or
foam-forming agents there are suitable: for example nonionic and
anionic emulsifiers, such as polyoxyethylene fatty acid esters,
polyoxyethylene fatty alcohol ethers, for example alkylaryl
polyglycol ethers, alkylsulphonates, alkyl sulphates,
arylsulphonates as well as protein hydrolysates; as dispersing
agents there are suitable: for example lignin-sulphite waste
liquors and methylcellulose.
[0179] Adhesives such as carboxymethylcellulose and natural and
synthetic polymers in the form of powders, granules or latices,
such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as
well as natural phospholipids, such as cephalins and lecithins, and
synthetic phospholipids, can be used in the formulations. Other
additives can be mineral and vegetable oils.
[0180] It is possible to use colourants such as inorganic pigments,
for example iron oxide, titanium oxide and Prussian Blue, and
organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and
metal phthalocyanine dyestuffs, and trace nutrients such as salts
of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
[0181] The formulations in general comprise between 0.1 and 95 per
cent by weight of active compound, preferably between 0.5 and
90%.
[0182] The active compounds according to the invention, when used
in crop protection, can be used in the formulations as a mixture
with known fungicides, bactericides, acaricides, nematicides or
insecticides, for example so as to widen the spectrum of action or
to prevent the build up of resistance.
[0183] Suitable components for the mixtures are, for example, the
following substances:
[0184] Fungicides
[0185] 2-aminobutane; 2-anilino4-methyl-6-cyclopropyl-pyrimidine;
2',6'-dibromo-2-methyl4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazol-
e-5-carboxanilide;
2,6-dichloro-N-(4-trifluoromethylbenzyl)benzamide;
(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide;
8-hydroxyquinoline sulphate; methyl
(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidi-
n-4-yloxy]-phenyl}-3-methoxyacrylate; methyl
(E)-methoxyimino[alpha-(o-tol- yloxy)-o-tolyl]acetate;
2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine,
azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl,
bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
calcium polysulphide, captafol, captan, carbendazim, carboxin,
quinomethionate, chloroneb, chloropicrin, chlorothalonil,
chlozolinate, cufraneb, cymoxanil, cypro-conazole, cyprofuram,
dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran,
diethofencarb, difenoconazole, dimethirimol, dimethomorph,
diniconazole, dinocap, diphenylamine, dipyrithion, ditalimfos,
dithianon, dodine, drazoxolon, edifenphos, epoxyconazole,
ethirimol, etridiazole, fenarimol, fenbuconazole, fenfuram,
fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin
acetate, fentin hydroxide, ferbam, ferimzone, fluazinam,
fludioxonil, fluoromide, fluquinconazole, flusilazole,
flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium,
fthalide, fuberidazole, furalaxyl, furmecyclox, guazatine,
hexachlorobenzene, hexaconazole, hymexazol, imazalil,
imibenconazole, iminoctadine, iprobenfos (IBP), iprodione,
isoprothiolane, kasugamycin, copper preparations such as: copper
hydroxide, copper naphthenate, copper oxychloride, copper sulphate,
copper oxide, oxine-copper and Bordeaux mixture, mancopper,
mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole,
methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil,
nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,
ofurace, oxadixyl, oxamocarb, oxycarboxin, pefurazoate,
penconazole, pencycuron, phosdiphen, pimaricin, piperalin,
polyoxin, probenazole, prochloraz, procymidone, propamocarb,
propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil,
pyroquilon, quintozene (PCNB), sulphur and sulphur preparations,
tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole,
thicyofen, thiophanate-methyl, thiram, tolclophos-methyl,
tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamide,
tricyclazole, tridemorph, triflurnizole, triforine, triticonazole,
validamycin A, vinclozolin, zineb, ziram.
[0186] Bactericides
[0187] bronopol, dichlorophen, nitrapyrin, nickel
dimethyldithiocarbamate, kasugarnycin, octhilinone,
furanecarboxylic acid, oxytetracyclin, probenazole, streptomycin,
tecloftalam, copper sulphate and other copper preparations.
[0188] Insecticides/acaricides/nematicides
[0189] abamectin, AC 303 630, acephate, acrinathrin, alanycarb,
aldicarb, alphamethrin, amitraz, avermectin, AZ 60541,
azadirachtin, azinphos A, azinphos M, azocyclotin, Bacillus
thuringiensis, bendiocarb, benfuracarb, bensultap, beta-cyfluthri,
bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin,
butocarboxin, butylpyridaben, cadusafos, carbaryl, carbofuran,
carbophenothion, carbosulfan, cartap, CGA 157 419, CGA 184699,
chloethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron,
chlormephos, chlorpyrifos, chlorpyrifos M, cis-resmethrin,
clocythrin, clofentezine, cyanophos, cycloprothrin, cyfluthrin,
cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin,
demeton-M, demeton-S, demeton-S-methyl, diafenthiuron, diazinon,
dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,
diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,
edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion,
ethofenprox, ethoprophos, etrimphos, fenamiphos, fenazaquin,
fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,
fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion,
fenvalerate, fipronil, fluazinam, flucycloxuron, flucythrinate,
flufenoxuron, flufenprox, fluvalinate, fonophos, fornothion,
fosthiazate, fubfenprox, furathiocarb, HCH, heptenophos,
hexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazophos,
isofenphos, isoprocarb, isoxathion, ivemectin, lambda-cyhalothrin,
lufenuron, malathion, mecarbam, mervinphos, mesulfenfos,
metaldehyde, methacrifos, methamidophos, methidathion, methiocarb,
methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled,
NC 184, NI 25, nitenpyram, omethoate, oxamyl, oxydemethon M,
oxydeprofos, parathion A, parathion M, permethrin, phenthoate,
phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb,
pirimiphos M, pirimiphos A, profenofos, promecarb, propaphos,
propoxur, prothiofos, prothoate, pymetrozin, pyrichlophos,
pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen,
pyriproxifen, quinalphos, RH 5992, salithion, sebufos, silafluofen,
sulfotep, sulprofos, tebufenozid, tebufenpyrad, tebupirimiphos,
teflubenzuron, tefluthrin, temephos, terbam, terbufos,
tetrachlorvinphos, thiafenox, thiodicarb, thiofanox, thiomethon,
thionazin, thuringiensin, tralomethrin, triarathen, triazophos,
triazuron, trichlorfon, triflumuron, trimethacarb, vamidothion,
XMC, xylylcarb, zetamethrin.
[0190] A mixture with other known active compounds, such as
herbicides, or with fertilizers and growth regulators, is also
possible.
[0191] The active compounds can be used as such or in the form of
their formulations or the use forms prepared therefrom, such as
ready-to-use solutions, suspensions, wettable powders, pastes,
soluble powders, dusts and granules. They are used in the customary
manner, for example by watering, spraying, atomizing, scattering,
dusting, foaming, brushing on and the like. It is furthermore
possible to apply the active compounds by the ultra-low volume
method or to inject the active compound formulation or the active
compound itself into the soil. The seeds of the plants can also be
treated.
[0192] In the treatment of parts of plants, the concentrations of
active substance in the use forms can be varied within a relatively
large range: they are in general between 1 and 0.0001% by weight,
preferably between 0.5 and 0.001% by weight.
[0193] In the treatment of seed, amounts of active substance of
from 0.001 to 50 g per kilogram of seed, preferably from 0.01 to 10
g, are generally required.
[0194] In the case of the treatment of soil, active-substance
concentrations of from 0.00001 to 0.1% by weight, preferably from
0.0001 to 0.02% by weight, are required at the site of action.
[0195] The compositions used for protecting industrial materials
comprise the active substances in an amount of in general from 1 to
95%, preferably from 10 to 75%.
[0196] The concentrations in which the novel active substances are
applied depend on the nature and on the incidence of the
microorganisms to be combated and on the composition of the
material to be protected. The optimum amount for use can be
determined by means of test series. In general, the use
concentrations are in the range from 0.001 to 5% by weight,
preferably from 0.05 to 1.0% by weight, based on the material to be
protected.
[0197] The effectiveness and the spectrum of action of the active
substances to be used in materials protection in accordance with
the invention and of the compositions, concentrates or, very
generally, formulations which can be prepared therefrom can be
increased by adding, if desired, further antimicrobially active
compounds, fungicides, bactericides, herbicides, insecticides or
other active substances to increase the spectrum of action or to
achieve particular effects, for example additional protection
against insects. These mixtures may possess a broader spectrum of
action than the compounds according to the invention.
[0198] In many instances, this results in synergistic effects, i.e.
the spectrum of activity of the mixture is superior to the activity
of the individual components. Particularly advantageous mixing
partners are, for example, the following compounds:
[0199] Sulphenamides such as dichlofluanide (Euparene),
tolylfluanide (Methyleuparene), folpet, fluorfolpet;
[0200] Benzimidazoles such as carbendazim (MBC), benomyl,
fuberidazole, thiabendazole or their salts;
[0201] Thiocyanates such as thiocyanatomethylthiobenzothiazole
(TCMTB), methylene bisthiocyanate (MBT);
[0202] Quaternary ammonium compounds such as
benzyldimethyltetradecylammon- ium chloride,
benzyl-dimethyl-dodecyl-ammonium chloride,
dodecyl-dimethyl-ammonium chloride;
[0203] Morpholine derivatives such as
C.sub.11-C.sub.14-4-alkyl-2,6-dimeth- yl-morpholine homologues
(tridemorph), (.+-.)-cis-4-[tert-butylphenyl]-2-m-
ethylpropyl]-2,6-dimethylmorpholine (fenpropimorph), Falimorph;
[0204] Phenols such as o-phenylphenol, tribromophenol,
tetrachlorophenol, pentachlorophenol, 3-methyl-4-chlorophenol,
dichlorophene, chlorophene or their salts;
[0205] Azoles such as triadimefon, triadimenol, bitertanol,
tebucanozole, propiconazole, azaconazole, hexaconazole, prochloraz,
cyproconazole,
1-(2-chlorophenyl)-2-(1-chlorocyclopropyl)-3-(1,2,4-triazol-1-yl)-propan--
2-ol or
1-(2-chlorophenyl)-2-(1,2,4-triazol-1-yl-methyl)-3,3-dimethyl-buta-
n-2-ol.
[0206] Iodopropargyl derivatives such as iodopropargyl
butylcarbamate (IPBC), iodopropargyl chlorophenylfornal,
iodopropargyl phenylcarbamate, iodopropargyl hexylcarbamate,
iodopropargyl cyclohexylcarbamate, iodopropargyloxyethyl
phenylcarbamate;
[0207] Iodine derivatives such as diiodomethyl-p-aryl sulphones,
for example diiodomethyl-p-tolyl sulphone;
[0208] Bromine derivatives such as bromopol;
[0209] Isothiazolines such as N-methylisothiazolin-3-one,
5-chloro-N-methylisothiazolin-3-one,
4,5-dichloro-N-octylisothiazolin-3-o- ne, N-octylisothiazolin-3-one
(octilinone);
[0210] Benzisothiazolinones, cyclopenteneisothazolines;
[0211] Pyridines such as 1-hydroxy-2-pyridinthione (and their Na,
Fe, Mn and Zn salts), tetrachloro4-methylsulphonylpyridine;
[0212] Metal soaps such as the naphthenates, octoactes,
2-ethylhexanoates, oleates, phosphates and benzoates of tin, copper
and zinc, oxides such as TBTO, Cu.sub.2O, CuO, ZnO;
[0213] Organic tin compounds such as tributyltin naphthenate and
tributyltin oxide;
[0214] Dialkyl dithiocarbamates such as the Na and Zn salts of
dialkyldithiocarbamates, tetramethyltiurami disulphide (TMTD);
[0215] Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile
(chlorothalonil) and other microbicides having an activated halogen
group, such as Cl-Ac, MCA, tectamer, bromopol, bromidox;
[0216] Benzothiazoles such as 2-mercaptobenzothiazole; see above
dazomet;
[0217] Quinolines such as 8-hydroxyquinoline;
[0218] Formaldehyde-releasing compounds such as benzyl alcohol
mono(poly)hemiformal, oxazolidines, hexahydro-s-triazines,
N-methylolchloroacetamide;
[0219] Tris-N-(cyclohexyldiazeniumdioxy)-aluminium,
N-(cyclohexyldiazeniumdioxy)-tributyltin or K salts,
bis-(N-cyclohexyl)diazinium-(dioxy-copper or aluminium).
[0220] Preference is given to using the following insecticides:
[0221] Phosphoric esters such as azinphos-ethyl, azinphos-methyl,
1-(4-chlorophenyl)-4-(O- ethyl, S-propyl)phosphoryloxypyrazol
(TIA-230), chlorpyrifos, coumaphos, demeton, demeton--S--methyl,
diazinon, dichlorfos, dimethoate, ethoprophos, etrimfos,
fenitrothion, fention, heptenophos, parathion, parathion-methyl,
phosalone, phoxim, pirimiphos-ethyl, pirimiphos-methyl, profenofos,
prothiofos, sulprofos, triazophos and trichlorphon.
[0222] Carbamates such as aldicarb, bendiocarb, BPMC
(21-methylpropyl)phenyl methylcarbamate), butocarboxim,
butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb,
isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and
thiodicarb.
[0223] Pyrethroids such as allethrin, alphamethrin, bioresmethrin,
byfenthrin (FMC 54800), cycloprothrin, cyfluthrin, decamethrion,
cyhalothrin, cypermethrin, deltamethrin,
alpha-cyano-3-phenyl-2-methylben-
zyl-2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclo-propanecarboxyla-
te, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate,
flumetrin, fluvalinate, permethrin and resmethrin; nitroimino and
nitromethylene compounds such as
1-[(6-chloro-3-pyridinyl)-methyl]-4,5-dihydro-N-nitro-1-
H-imidazol-2-amine (imidachloprid).
[0224] Organosilicon compounds, preferably
dimethyl(phenyl)silylmethyl 3-phenoxybenzyl ethers, such as, for
example, dimethyl-(4-ethoxyphenyl)-s- ilylmethyl 3-phenoxybenzyl
ether, or dimethyl(phenyl)-silylmethyl 2-phenoxy-6-pyridylmethyl
ethers, such as, for example, dimethyl(9-ethoxyphenyl)-silylmethyl
2-phenoxy-6-pyridylmethyl ether, or
(phenyl)[3-(3-phenoxyphenyl)propyl](dimethyl)-silanes, such as, for
example,
(4-ethoxyphenyl)-[3(4-fluoro-3-phenoxyphenyl)-propyl]dimethylsil-
ane.
[0225] Further suitable active compounds are algicides,
molluscicides and active compounds against sea animals which
colonize, for example, ship bottom paints.
[0226] The preparation and the use of the active compounds
according to the invention is illustrated by the examples
below.
PREPARATION EXAMPLES
Example 1
[0227] 313
[0228] At room temperature, a mixture of 3.4 g (15 mmol) of
2-cyano-6,6-difluoro-[1,3]dioxolo[4,5-f]benzimidazole and 80 ml of
absolute tetrahydrofuran is admixed with stirring with 0.45 g (15
mmol) of sodium hydride (80% pure) and then stirred at room
temperature for 10 minutes. 2.9 g (15 mmol) of
3,5-dimethylisoxazolyl4-sulphonyl chloride is then added and the
mixture is stirred at 60.degree. C. for 18 hours. For work-up, the
reaction mixture is poured into 200 ml of water. The resulting
mixture is extracted three times with 80 ml of methylene chloride
each time. The combined organic phases are dried over sodium
sulphate and concentrated under reduced pressure. The remaining
residue is chromatographed over silica gel using diethyl ether as
eluent. In this manner, 1.4 g (24% of theory) of
2-cyano-6,6-difluoro-3-(3,5-dimethyl-iso-
xazolyl-4-sulphonyl)-[1,3]dioxolo[4,5-f]benzimidazole in the form
of a yellow solid of melting point 166 to 170.degree. C. are
obtained.
Example 2
[0229] 314
[0230] At room temperature, a mixture of 0.30 g (10 mmol) of sodium
hydride (80% pure) and 40 ml of absolute tetrahydrofuran is admixed
with stirring with 2.7 g (10 mmol) of
2-cyano-6,6,7,7-tetrafluoro[1,4]-dioxino- [2,3-f]benzimidazole and
then stirred at room temperature for 10 minutes. 2.9 g (15 mmol) of
3,5-dimethylisoxazolyl-4-sulphonyl chloride are then added and the
mixture is stirred at 60.degree. C. for 4 hours. For work-up, the
reaction mixture is poured into 200 ml of water. The resulting
mixture is extracted three times with 80 ml of methylene chloride
each time. The combined organic phases are dried over sodium
sulphate and concentrated under reduced pressure. The remaining
residue is recrystallized from 20 ml of a mixture consisting of
equal amounts of diethyl ether and petroleum ether. In this manner,
1.9 g (44% of theory) of
2-cyano-6,6,7,7-tetrafluoro-3-(3,5-dimethyl-isoxazolyl-4-sulphonyl)-[1-
,4]-dioxino-[2,3-f]benzimidazole in the form of a solid of melting
point 180 to 185.degree. C. are obtained.
Example 3
[0231] 315
[0232] At room temperature, a mixture of 0.30 g (10 mmol) of sodium
hydride (80% pure) and 40 ml of absolute tetrahydrofuran is admixed
with stirring with 2.7 g (10 mmol) of
2-cyano-6,6,7,7-tetrafluoro[1,4]-dioxino- [2,3-f]benzimidazole and
then stirred at room temperature for 10 minutes. 2.2 g (12 mmol) of
thiophene-2-sulphonyl chloride are then added and the mixture is
stirred at 60.degree. for 18 hours. For work-up, the reaction
mixture is poured into 200 ml of water. The resulting precipitate
is filtered off and dissolved in 50 ml of ethyl acetate. The
solution is dried over sodium sulphate and then concentrated under
reduced pressure. The remaining residue is stirred with 20 ml of
petroleum ether. The resulting precipitate is filtered off and
dried. In this manner, 1.9 g (49% of theory) of
2-cyano-6,6,7,7-tetrafluoro-3-(thienyl-2-sulphonyl)-[1-
,4]-dioxino[2,3-f]-benzimidazole in the form of a yellow solid of
melting point 180 to 184.degree. are obtained.
[0233] Using the abovementioned methods, the compounds. of the
formula 316
[0234] listed in Table 9 were also prepared.
9TABLE 9 Ex. Melting No. X.sup.1 X.sup.2 X.sup.3 X.sup.4
--Y--R.sup.2 R.sup.1 point (.degree. C.) 4 Br H CF.sub.3 H 317 --CN
145-149 5 Br H CF.sub.3 H 318 --CN 117-121 6 Br H CF.sub.3 H 319
--CN 217-220 7 H --O--CClF--CClF--O H 320 --CN 115-119 8 H
--O--CF.sub.2--O-- H 321 --CN 166-168 9 H --O--CF.sub.2--O-- H 322
--CN 161-165 10 H --O--CF.sub.2--CF.sub.2--O-- H 323 --CN 155-160
11 H --O--CF.sub.2--CF.sub.2--O-- H 324 --CN 65-68 12 H
--O--CF.sub.2--O-- H 325 --CN 160-164 13 H
--O--CF.sub.2--CF.sub.2--O-- H 326 --CN 178-180 14 H
--O--CF.sub.2--O-- H 327 --CN 171-176 15 H --O--CF.sub.2--O-- H 328
--CN 121-124 16 H --O--CF.sub.2--CF.sub.2--O-- H 329 --CN 220-225
17 H --O--CF.sub.2--CF.sub.2--O-- H 330 --CN >220 18 H
--O--CF.sub.2--O-- H 331 --CN >220 19 H --O--CF.sub.2--O-- H 332
--CN 135-140 20 H --O--CF.sub.2--CF.sub.2--O-- H 333 --CN 124-130
21 H 334 H 335 --CN 180-183 22 Br H CF.sub.3 H 336 --CN 161-164 23
H --OCF.sub.2CF.sub.2O-- H 337 --CN 148-151 24 H --O--CF.sub.2--O--
H 338 --CN 155-158 25 H --O--CF.sub.2--O-- H 339 --CN <220 26 H
--OCF.sub.2--O-- H 340 --CN 203-208 27 H --OCF.sub.2--CHF--O-- H
341 --CN 149-153 28 H --OCF.sub.2--O-- H 342 --CN 138-141 29 H
--OCF.sub.2O-- H 343 --CN 210-215 30 H --O--CF.sub.2CF.sub.2O H 344
--CN 186-190 31 H --OCF.sub.2O-- H 345 --CN 150-154 32 H
--OCF.sub.2CF.sub.2O-- H 346 --CN 210-214
[0235] Use Examples
[0236] In the following use examples, the compounds listed below
were used as comparison substances. 347
[0237]
2-Cyano-1-dimethylaminosulphonyl-6,6,7,7-tetrafluoro-[1,4]dioxino[2-
,3-f]benzimidazole 348
[0238]
2-Cyano-6,6-difluoro-1-dimethylaminosulphonyl-[1,3]dioxolo[4,5-f]be-
nzimidazole
[0239] (Known from EP-A 0 517 476 and DE-A 4 139 950).
Example A
[0240] Venturia test (apple)/protective
[0241] Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3
parts by weight of alkylaryl polyglycol ether
[0242] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvent and emulsifier, and the concentrate is diluted with water
to the desired concentration.
[0243] To test for protective activity, young plants are sprayed
with the preparation of active compound to run-off point. After the
spray coating has dried on, the plants are inoculated with an
aqueous suspension of conidia of the causative organism of apple
scab (Venturia inaequalis) and then remain in an incubation
cupboard at 20.degree. C. and 100% relative atmospheric humidity
for 1 day.
[0244] The plants are then placed in a greenhouse at 20.degree. C.
and a relative atmospheric humidity of about 70%.
[0245] Evaluation is carried out 12 days after the inoculation. 0%
means an efficacy corresponding to that of the control, 100% means
that no infestation is observed.
[0246] In this test, the compounds of Examples 1 to 3 exhibited an
efficacy of more than 50% at an active compound concentration of 10
ppm in the spray liquor, whereas comparison substance (A) showed an
efficacy of 43% and comparison substance (B) showed no
activity.
10TABLE A Venturia test (apple)/protective Efficacy in %, based on
the untreated control, at an active compound Active compounds.
concentration of 10 ppm Known from EP-A 0 517 476 349 43 350 0
According to the invention: 351 81 352 58 353 87
Example B
[0247] Phytophthora test (tomato)/protective
[0248] Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3
parts by weight of alkyl-aryl polyglycol ether
[0249] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvent and emulsifier, and the concentrate is diluted with water
to the desired concentration.
[0250] To test for protective activity, young plants are sprayed
with the preparation of active compound to run-off point. After the
spray coating has dried on, the plants are inoculated with an
aqueous suspension of spores of Phytophthora infestans.
[0251] The plants are placed in an incubation cupboard at 100%
relative atmospheric humidity and about 20.degree. C.
[0252] Evaluation is carried out 3 days after the inoculation. 0%
means an efficacy corresponding to that of the control, whereas an
efficacy of 100% means that no infestation was observed.
[0253] Active compounds, active compound concentrations and test
results are listed in the table below.
11TABLE B Phytophthora test (tomato)/protective Efficacy in %,
based on the untreated control, at an active compound Active
compounds concentration of 100 ppm According to the invention: 354
100 355 97 356 94 357 82 358 64 359 94 360 94 361 94 362 96 363 74
364 97 365 97
Example C
[0254] Plasmopara test (vines)/protective
[0255] Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3
parts by weight of alkyl-aryl polyglycol ether
[0256] To produce a suitable preparation of active compound, 1 part
by weight of active compound is mixed with the stated amounts of
solvent and emulsifier, and the concentrate is diluted with water
to the desired concentration.
[0257] To test for protective activity, young plants are sprayed
with the preparation of active compound to run-off point. After the
spray coating has dried on, the plants are inoculated with an
aqueous suspension of spores of Plasmopara viticola and then remain
in a humidity chamber at 20-22.degree. C. and 100% relative
atmospheric humidity for 1 day. The plants are subsequently placed
in a greenhouse at 21.degree. C. and 90% atmospheric humidity for 5
days. The plants are then moistened and placed in a humidity
chamber for 1 day.
[0258] Evaluation is carried out 6 days after the inoculation. 0%
means an efficacy corresponding to that of the control, whereas an
efficacy of 100% means that no infestation is observed.
[0259] Active compounds, active compound concentrations and test
results are listed in the table below.
12TABLE C Plasmopara test (vines)/protective Efficacy in %, based
on the untreated control, at an active compound Active compounds
concentration of 100 ppm According to the invention: 366 100 367
100 368 80 369 100 370 100 371 74 372 100 373 95 374 100
* * * * *