U.S. patent application number 09/772042 was filed with the patent office on 2001-10-11 for annulated azole derivatives useful as microbicidal agents.
Invention is credited to Assmann, Lutz, Elbe, Hans-Ludwig, Stenzel, Klaus, Tiemann, Ralf.
Application Number | 20010029237 09/772042 |
Document ID | / |
Family ID | 7822140 |
Filed Date | 2001-10-11 |
United States Patent
Application |
20010029237 |
Kind Code |
A1 |
Assmann, Lutz ; et
al. |
October 11, 2001 |
Annulated azole derivatives useful as microbicidal agents
Abstract
Novel fused azole derivatives of the formula 1 in which R.sup.1,
R.sup.2, A and G are as defined in the description, and also their
acid addition salts and metal salt complexes, a plurality of
processes for preparing these substances and their use as
microbicides in crop protection and in the protection of
materials.
Inventors: |
Assmann, Lutz; (St.
Peter-Ording, DE) ; Elbe, Hans-Ludwig; (Wuppertal,
DE) ; Tiemann, Ralf; (Leverkusen, DE) ;
Stenzel, Klaus; (Dusseldorf, DE) |
Correspondence
Address: |
BAYER CORPORATION
PATENT DEPARTMENT
100 BAYER ROAD
PITTSBURGH
PA
15205
US
|
Family ID: |
7822140 |
Appl. No.: |
09/772042 |
Filed: |
January 29, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09772042 |
Jan 29, 2001 |
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09380502 |
Sep 3, 1999 |
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6214840 |
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Current U.S.
Class: |
504/129 ;
514/303; 546/118 |
Current CPC
Class: |
A01N 43/90 20130101;
C07F 9/6518 20130101; C07F 9/6506 20130101; C07D 471/04
20130101 |
Class at
Publication: |
504/129 ;
514/303; 546/118 |
International
Class: |
A01N 043/00; A01N
043/00; C07D 471/02 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 4, 1997 |
DE |
197 08 688.8 |
Claims
1. Fused azole derivatives of the formula 82in which R.sup.1 and
R.sup.2 together with the carbon atoms to which they are attached
represent an optionally substituted heterocyclic ring or represent
an optionally substituted benzo-fused heterocyclic ring, G
represents nitrogen or a grouping 83in which R.sup.3 represents
hydrogen, halogen, cyano, nitro, trifluoromethyl, thiocarbamoyl,
thiocyanato or the grouping 84 in which R.sup.4 represents alkyl, A
represents one of the following groupings 85 in which Y represents
oxygen or sulphur, R.sup.5 represents an optionally substituted,
unsaturated heterocyclic radical, and R.sup.6 and R.sup.7
independently of one another represent alkyl, halogenoalkyl,
alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, alkenyl,
halogenoalkenyl, alkenyloxy, alkenylthio, alkinyl, alkinyloxy,
alkinylthio, optionally alkyl-, cycloalkyl- or aryl-substituted
amino, optionally substituted aryl, optionally substituted aryloxy,
optionally substituted arylthio, optionally substituted cycloalkyl,
optionally substituted cycloalkylkoxy, optionally substituted
cycloalkylthio or represents an optionally substituted, saturated
or unsaturated heterocyclic radical, or R.sup.6 and R.sup.7
together with the phosphorus atom to which they are attached
represent an optionally substituted heterocyclic radical, and also
their acid addition salts and metal salt complexes.
2. Process for preparing fused azole derivatives of the formula (I)
according to claim 1 and also their acid addition salts and metal
salt complexes, characterized in that a) azoles of the formula 86in
which R.sup.1, R.sup.2 and G are as defined above are reacted with
halides of the formulaA--X.sup.1 (III)in which A is as defined
above and X.sup.1 represents halogen, if appropriate in the
presence of an acid binder and if appropriate in the presence of a
diluent or b) cyanoimidazoles of the formula 87in which R.sup.1,
R.sup.2 and A are as defined above are reacted with hydrogen
sulphide, if appropriate in the presence of a base and if
appropriate in the presence of a diluent, or c)
thiocarbamoylimidazoles of the formula 88in which R.sup.1, R.sup.2
and A are as defined above are reacted with an alkylating agent of
the formulaR.sup.4--X.sup.2 (IV)in which R.sup.4 is as defined
above and X.sup.2 represents a leaving group, if appropriate in the
presence of an acid binder and if appropriate in the presence of a
diluent, and an acid or a metal salt is added, if appropriate, to
the resulting compounds of the formula (I).
3. Microbicidal compositions, characterized in that they contain at
least one fused azole derivative of the formula (I) according to
claim 1 or an acid addition salt or metal salt complex of a fused
azole derivative of the formula (I), in addition to extenders
and/or surfactants
4. Use of fused azole derivatives of the formula (I) according to
claim 1 or of their acid addition salts or metal salt complexes as
microbicides in crop protection and in the protection of
materials.
5. Method for controlling undesirable microorganisms in crop
protection and in the protection of materials characterized in that
fused azole derivatives of the formula (I) according to claim 11 or
their acid addition salts or metal salt complexes are applied to
the microorganisms and/or their habitat.
6. Process for preparing microbicidal compositions, characterized
in that fused azole derivatives of the formula (I) according to
claim 1 or their acid addition salts or metal salt complexes are
mixed with extenders and/or surfactants.
7. Fused azole derivative according to claim 1 characterized by the
formula 89
8. Fused azole derivative according to claim 1, characterized by
the formula 90
9. Fused azole derivative according to claim 1, characterized by
the formula 91
10. Fused azole derivative according to claim 1, characterized by
the formula 92
Description
[0001] The present invention relates to novel fused azole
derivatives, to a plurality of processes 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 fused azole derivatives
have fungicidal properties (cf. DE-A 195 23 446). Thus, for
example, 1-(3,5-dimethyl-isoxazol-4-sulphonyl)-1H-benzotriazole can
be employed for controlling fungi. The activity of this substance
is good but in some cases unsatisfactory at low application
rates.
[0003] This invention, accordingly, provides novel fused azole
derivatives of the formula 2
[0004] in which
[0005] R.sup.1 and R.sup.2 together with the carbon atoms to which
they are attached represent an optionally substituted heterocyclic
ring or represent an optionally substituted benzo-fused
heterocyclic ring,
[0006] G represents nitrogen or a grouping 3
[0007] in which
[0008] R3 represents hydrogen, halogen, cyano, nitro,
trifluoromethyl, thiocarbamoyl, thiocyanato or the grouping 4
[0009] in which
[0010] R.sup.4 represents alkyl,
[0011] A represents one of the following groupings 5
[0012] in which
[0013] Y represents oxygen or sulphur,
[0014] R5 represents an optionally substituted, unsaturated
heterocyclic radical,
[0015] R6 and R7 independently of one another represent alkyl,
halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio,
halogenoalkylthio, alkenyl, halogenoalkenyl, alkenyloxy,
alkenylthio, alkinyl, alkinyloxy, alkinylthio, optionally alkyl-,
cycloalkyl- or aryl-substituted amino, optionally substituted aryl,
optionally substituted aryloxy, optionally substituted arylthio,
optionally substituted cycloalkyl, optionally substituted
cycloalkyloxy, optionally substituted cycloalkylthio or represents
an optionally substituted, saturated or unsaturated heterocyclic
radical, or
[0016] R6 and R7 together with the phosphorus atom to which they
are attached represent an optionally substituted heterocyclic
radical,
[0017] and also their acid addition salts and metal salt
complexes.
[0018] In the definitions, the saturated or unsaturated hydrocarbon
chains, such as alkyl, alkenyl or alkinyl, are in each case
straight-chain or branched, including in combination with
heteroatoms, such as in alkoxy, alkylthio or alkylamino.
[0019] Furthermore, it has been found that the fused azole
derivatives of the formula (I) and also their acid addition salts
and metal salt complexes are obtained when
[0020] a) azoles of the formula 6
[0021] in which
[0022] R.sup.1, R.sup.2 and G are as defined above
[0023] are reacted with halides of the formula
A--X.sup.1 (III)
[0024] in which
[0025] A is as defined above and
[0026] X.sup.1 represents halogen,
[0027] if appropriate in the presence of an acid binder and if
appropriate in the presence of a diluent,
[0028] or when
[0029] b) cyanoimidazoles of the formula 7
[0030] in which
[0031] R.sup.1, R.sup.2 and A are as defined above
[0032] are reacted with hydrogen sulphide, if appropriate in the
presence of a base and if appropriate in the presence of a diluent,
or when
[0033] c) thiocarbamoylimidazoles of the formula 8
[0034] in which
[0035] R.sup.1, R.sup.2 and A are as defined above
[0036] are reacted with an alkylating agent of the formula
R.sup.4--X.sup.2 (IV)
[0037] in which
[0038] R.sup.4 is as defined above and
[0039] X.sup.2 represents a leaving group,
[0040] if appropriate in the presence of an acid binder and if
appropriate in the presence of a diluent,
[0041] and an acid or a metal salt is added, if appropriate, to the
resulting compounds of the formula (I).
[0042] Finally, it has been found that the fused azole derivatives
of the formula (I) and also their acid addition salts and metal
salt complexes have very good microbicidal properties and can be
employed both in crop protection and in the protection of
materials.
[0043] Surprisingly, the substances according to the invention have
better fungicidal activity than
1-(3,5-dimethyl-isoxazole-4-sulphonyl)-1H-benzot- riazole, which is
an active compound of the prior art having similar constitution and
the same direction of action.
[0044] The formula (I) provides a general definition of the
substances according to the invention.
[0045] R.sup.1 and R.sup.2 together with the carbon atoms to which
they are attached preferably represent a 5- or 6-membered
heterocyclic ring which contains one, two or three identical or
different heteroatoms, such as oxygen, sulphur and/or nitrogen, and
may be mono- to trisubstituted by identical or different
substituents selected from the group consisting of halogen, cyano,
nitro, hydroxyl, amino, formyl, carboxyl, 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,
hydroximinoalkyl 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,
[0046] or
[0047] R.sup.1 and R.sup.2 together with the carbon atoms to which
they are attached preferably represent a benzo-fused 5- or
6-membered heterocyclylic ring which contains one or two identical
or different heteroatoms, such as oxygen, sulphur and/or nitrogen,
and may be mono- to trisubstituted by identical or different
substituents selected from the group consisting of halogen, cyano,
nitro, hydroxyl, amino, formyl, carboxyl, 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,
hydroximinoalkyl 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,
[0048] where, if the heterocyclic ring or the benzo-fused
heterocyclic ring contains more than one oxygen atom, the oxygen
atoms are not adjacent.
[0049] G also preferably represents nitrogen or a grouping 9
[0050] R.sup.3 preferably represents hydrogen, fluorine, chlorine,
bromine, iodine, cyano, nitro, trifluoromethyl, thiocarbamoyl,
thiocyanato or the grouping 10
[0051] R.sup.4 preferably represents alkyl having 1 to 4 carbon
atoms.
[0052] A also preferably represents one of the following groupings:
--SO.sub.2--R.sup.5, 11
[0053] Y also preferably represents oxygen or sulphur.
[0054] R.sup.5 preferably represents an unsaturated heterocyclyl
radical having 5 or 6 ring members and 1 to 3 identical or
different heteroatoms, such as nitrogen, oxygen and/or sulphur,
where each of the heterocyclyl radicals may be mono- or
disubstituted by identical or different substituents selected from
the group consisting of halogen, cyano, nitro, hydroxyl, amino,
formyl, carboxyl, 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, hydroximinoalkyl 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.
[0055] R.sup.6 and R.sup.7 independently of one another preferably
represent 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 identical or different halogen atoms,
straight-chain or branched alkoxy having 1 to 4 carbon atoms,
straight-chain or branched halogenoalkoxy having 1 to 4 carbon
atoms and 1 to 5 identical or different halogen atoms,
straight-chain or branched alkylthio having 1 to 4 carbon atoms,
straight-chain or branched halogenoalkylthio having 1 to 4 carbon
atoms and 1 to 5 identical or different halogen atoms,
straight-chain or branched alkenyl having 2 to 4 carbon atoms,
straight-chain or branched halogenoalkenyl having 2 to 4 carbon
atoms and 1 to 5 identical or different halogen atoms,
straight-chain or branched alkenyloxy having 2 to 4 carbon atoms,
straight-chain or branched alkenylthio having 2 to 4 carbon atoms,
straight-chain or branched alkinyl having 2 to 4 carbon atoms,
straight-chain or branched alkinyloxy having 2 to 4 carbon atoms,
straight-chain or branched alkinylthio having 2 to 4 carbon atoms,
amino which is optionally mono- or disubstituted by identical or
different substituents selected from the group consisting of alkyl
having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms
and phenyl,
[0056] or represent phenyl, phenoxy, phenylamino or phenylthio,
where each of these radicals may be mono- to trisubstituted by
identical or different substituents selected from the group
consisting of fluorine, chlorine, bromine, alkyl having 1 to 4
carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5
fluorine, chlorine and/or bromine atoms, alkoxy having 1 to 4
carbon atoms and halogenoalkoxy having 1 to 4 carbon atoms and 1 to
5 fluorine, chlorine and/or bromine atoms,
[0057] or represent cycloalkyl having 3 to 7 carbon atoms,
cycloalkyloxy having 3 to 7 carbon atoms, cycloalkylthio having 3
to 7 carbon atoms, cycloalkylamino having 3 to 7 carbon atoms,
pyrrolidinyl, piperidinyl or morpholinyl, where each of the
abovementioned radicals may be mono- to trisubstituted by identical
or different substituents selected from the group consisting of
fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms and
halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine,
chlorine and/or bromine atoms,
[0058] or represent a saturated or unsaturated heterocyclyl radical
having 5 or 6 ring members and 1 to 3 identical or different
heteroatoms, such as nitrogen, oxygen and/or sulphur, where each of
these radicals may be mono- or disubstituted by identical or
different substituents selected from the group consisting of
halogen, cyano, nitro, hydroxyl, amino, formyl, carboxyl,
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, hydroximinoalkyl 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, alkyl
carbonyloxy 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.
[0059] R.sup.6 and R.sup.7 furthermore together with the phosphorus
atom to which they are attached preferably represent a 5- or
6-membered heterocyclyl radical which may contain one or two other
identical or different heteroatoms, such as oxygen, sulphur and/or
nitrogen, and may be mono- to trisubstituted by identical or
different substituents selected from the group consisting of
fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms,
alkoxy having 1 to 4 carbon atoms and halogenoalkoxy having 1 to 4
carbon atoms and 1 to 5 fluorine, chlorine and/or bromine
atoms.
[0060] R.sup.1 and R.sup.2 together with the carbon atoms to which
they are attached represent in particular furandiyl, thiophenediyl,
pyrrolediyl, oxazolediyl, thiazolediyl, imidazolediyl,
isoxazolediyl, isothiazolediyl, pyrazolediyl, 1,2,3-oxadiazolediyl,
1,2,3-thiadiazolediyl, 1,2,3-triazolediyl, pyridinediyl,
pyridazinediyl, pyrazinediyl, pyrimidinediyl, 1,2,4-triazinediyl,
indole-2,3-diyl, benzofuran-2,3-diyl, benzothiophene-2,3-diyl,
quinoline-2,3-diyl, quinazoline-2,3-diyl,
benzo[1,4]dioxine-2,3-diyl, benzo[1,4]dithiine-2,3-- diyl,
4H-benzo[1,4]oxazine-2,3-diyl, 4H-benzo[1,4]thiazine-2,3-diyl,
where these radicals may be mono- or disubstituted by identical or
different substituents selected from the group consisting of
fluorine, chlorine, bromine, cyano, nitro, amino, hydroxyl, formyl,
carboxyl, 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, diethylamino, acetyl, propionyl,
acetyloxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyloxy,
ethylsulphonyloxy, hydroxyiminomethyl, hydroxyiminoethyl,
methoxyiminomethyl, ethoxyiminomethyl, methoxyiminoethyl and
ethoxyiminoethyl,
[0061] or
[0062] R.sup.1 and R.sup.2 together represent a radical of the
formula 12
[0063] or 13
[0064] where each of these radicals may be mono- or disubstituted
by methyl.
[0065] G also in particular represents nitrogen or a grouping
14
[0066] R.sup.3 also in particular represents hydrogen, fluorine,
chlorine, bromine, iodine, cyano, nitro, trifluoromethyl,
thiocarbamoyl, thiocyanato or the grouping 15
[0067] R.sup.4 represents in particular methyl or ethyl.
[0068] A also in particular represents one of the following
groupings: --SO.sub.2--R.sup.5, 16
[0069] Y also in particular represents oxygen or sulphur.
[0070] R.sup.5 represents in particular pyrrolyl, furyl, pyrazolyl,
imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl,
oxadiazolyl, thiadiazolyl, 1,2,3-triazinyl, 1,2,4-triazinyl,
1,3,5-triazinyl, pyridyl, pyrimidyl, pyrazinyl or pyridazinyl,
where each of these radicals may be mono- or disubstituted by
identical or different substituents selected from the group
consisting of fluorine, chlorine, bromine, cyano, nitro, amino,
hydroxyl, formyl, carboxyl, 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, diethylamino, acetyl, propionyl,
acetyloxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyloxy,
ethylsulphonyloxy, hydroxyiminomethyl, hydroxyiminoethyl,
methoxyiminomethyl, ethoxyiminomethyl, methoxyiminoethyl and
ethoxyiminoethyl.
[0071] R.sup.6 and R.sup.7 independently of one another represent
in particular methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
trifluoromethyl, trifluoroethyl, methoxy, ethoxy, n- or i-propoxy,
n-, i-, s- or t-butoxy, difluoromethoxy, trifluoromethoxy,
difluorochloromethoxy, trifluoroethoxy, methylthio, ethylthio, n-
or i-propylthio, difluoromethylthio, trifluoromethylthio,
difluorochloromethylthio, allyl, n- or s-butenyl; allyloxy, n- or
s-butenyloxy; altylthio, n- or s-butenylthio; propargyl, n- or
s-butinyl; propargyloxy; propargylthio; amino; methylamino,
ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino;
dimethylamino, diethylamino, di-n- or i-propylamino,
methylethylamino, methyl-n propylamino, methyl-i propylamino,
cyclopropylamino, phenylamino or methyl-phenylamino,
[0072] represent phenyl, phenoxy or phenylthio, where each of these
radicals may be mono- to trisubstituted by identical or different
substituents selected from the group consisting of fluorine,
chlorine, bromine, methyl, ethyl, n- or i-propyl, methoxy, ethoxy,
n- or i-propoxy, trifluoromethyl and trifluoromethoxy; or
[0073] represent cyclopropyl, cyclopentyl, cyclohexyl,
cyclopropyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio,
cyclopentylthio, cyclohexylthio, cyclopropylamino,
cyclopentylamino, cyclohexylamino, 1-pyrrolidinyl, 1-piperidinyl,
and 1-morpholinyl, where each of these radicals may be mono- to
trisubstituted by identical or different substituents selected from
the group consisting of fluorine, chlorine, bromine, methyl, ethyl,
n- or i-propyl and trifluoromethyl, or
[0074] represent pyrrolyl, furyl, thienyl, pyrazolyl, imidazolyl,
thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl,
thiadiazolyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl,
pyridyl, pyrimidyl, pyrazinyl or pyridazinyl, where each of these
radicals may be mono- or disubstituted by identical or different
substituents selected from the group consisting of fluorine,
chlorine, bromine, cyano, nitro, amino, hydroxyl, formyl, carboxyl,
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,
diethylamino, acetyl, propionyl, acetyloxy, methoxycarbonyl,
ethoxycarbonyl, methylsulphonyloxy, ethylsulphonyloxy,
hydroxyiminomethyl, hydroxyiminoethyl, methoxyiminomethyl,
ethoxyiminomethyl, methoxyiminoethyl and ethoxyiminoethyl, or
represent pyrrolidinyl, piperidinyl, morpholinyl or piperazinyl,
each of which is optionally mono- or disubstituted by methyl.
[0075] R.sup.6 and R.sup.7 furthermore together with the phosphorus
atom to which they are attached represent in particular a 5- or
6-membered heterocyclyl radical which may contain one or two other
identical or different heteroatoms, such as oxygen, sulphur and/or
nitrogen, and may be mono- to trisubstituted by identical or
different substituents selected from the group consisting of
methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy,
chlorine and trifluoromethyl.
[0076] The abovementioned general or preferred radical definitions
apply both to the end products of the formula (I) and also
correspondingly to the starting materials or intermediates required
in each case for the preparation.
[0077] Preferred compounds according to the invention are also
addition products of acids and those fused azole derivatives of the
formula (I) in which R.sup.1, R.sup.2, G and A have the meanings
which have been mentioned as being preferred for these
radicals.
[0078] The acids which can be added preferably include hydrohalic
acids, such as, for example, hydrochloric acid and hydrobromic
acid, in particular hydrochloric acid, furthermore phosphoric acid,
sulphuric acid, nitric acid, mono- and bifunctional carboxylic
acids and hydroxycarboxylic 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,
1,5-naphthalenedisulphonic acid, saccharine and thiosaccharine.
[0079] Compounds according to the invention which are also
preferred are addition products of salts of metals of main groups
II to IV and subgroups I and II and IV to VIII of the Periodic
Table of the Elements and those fused azole derivatives of the
formula (I) in which R.sup.1, R.sup.2, G and A have the meanings
which have been mentioned as being preferred for these
radicals.
[0080] Here, particular preference is given to salts of copper,
zinc, manganese, magnesium, tin, iron and nickel. Suitable anions
of these salts are those which are derived from acids which lead to
physiologically tolerable addition products. Acids of this kind
which are particularly preferred in this context are the hydrohalic
acids, such as, for example, hydrochloric acid and hydrobromic
acid, furthermore phosphoric acid, nitric acid and sulphuric
acid.
[0081] Examples of substances according to the invention which may
be mentioned are the fused azole derivatives listed in Tables 1 to
11 below:
1TABLE 1 (I-c) 17 where A represents the following substituents: 18
19 20 21 22 23 24 25 26 27 28 29 30
[0082]
2TABLE 2 (I-d) 31 where A represents the substituents mentioned in
Table 1.
[0083]
3TABLE 3 (I-e) 32 where A represents the substituents mentioned in
Table 1.
[0084]
4TABLE 4 (I-f) 33 where A represents the substituents mentioned in
Table 1.
[0085]
5TABLE 5 (I-g) 34 where A represents the substituents mentioned in
Table 1.
[0086]
6TABLE 6 (I-h) 35 where A represents the substituents mentioned in
Table 1.
[0087]
7TABLE 7 (I-i) 36 where A represents the substituents mentioned in
Table 1.
[0088]
8TABLE 8 (I-j) 37 where A represents the substituents mentioned in
Table 1.
[0089]
9TABLE 9 (I-k) 38 where A represents the substituents mentioned in
Table 1.
[0090]
10TABLE 10 (I-l) 39 where A represents the substituents mentioned
in Table 1.
[0091]
11TABLE 11 (I-m) 40 where A represents the substituents mentioned
in Table 1.
[0092] Using, for example, 2-bromo-1H-imidazo[4,5-b]pyridine and
thiophene-2-sulphonyl chloride as starting materials, the course of
the process (a) according to the invention can be illustrated by
the following equation: 41
[0093] The formula (II) provides a general definition of the azoles
required as starting materials for carrying out the process (a)
according to the invention. In this formula (II), R.sup.1, R.sup.2
and G preferably or in particular have those meanings which have
already been mentioned in conjunction with the description of the
compounds of the formula (I) according to the invention as being
preferred or as being particularly preferred for R.sup.1, R.sup.2
and G.
[0094] The azoles of the formula (II) are known (compare, for
example, Chem. Ber. 85 (1952) 1012, 1020; Arch. Pharm. 290 (1957)
20, 31; Chem. Ber. 60 (1927), 773; and FR-A 2 542 742).
[0095] The formula (III) provides a general definition of the
halides furthermore required as starting materials for carrying out
the process (a) according to the invention. In this formula (III),
A preferably or in particular has those meanings which have already
been mentioned in connection with the description of the compounds
of the formula (I) according to the invention as being preferred or
as being particularly preferred for A. X.sup.1 preferably
represents chlorine.
[0096] The halides of the formula (III) are known or can be
prepared by processes known per se (compare, for example, J.
Heterocyclic Chem. 1981, 997-1006).
[0097] Suitable diluents for carrying out the process (a) according
to the invention are all inert organic solvents. Preferably
utilizable are aliphatic, alicyclic or aromatic hydrocarbons, such
as, for example, petroleum ether, hexane, heptane, cyclohexane,
methylcyclohexane, benzene, toluene, xylene or decalin; halogenated
hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene,
dichloromethane, chloroform, tetrachloromethane, dichloroethane or
trichloroethane; ethers, such as diethyl ether, diisopropyl ether,
methyl t-butyl ether, methyl t-amyl ether, dioxane,
tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or
anisole; ketones, such as acetone, butanone, methyl isobutyl ketone
or cyclohexanone; nitrites, such as acetonitrile, propionitrile, n-
or i-butyronitrile or benzonitrile; amides, such as
N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide,
N-methylpyrrolidone or hexamethylphosphoric triamide; esters such
as methyl acetate, or ethyl acetate; sulphoxides, such as dimethyl
sulphoxide; sulphones, such as sulpholane, or amines, such as
pyridine.
[0098] Suitable acid binders for carrying out the process (a)
according to the invention are all customary inorganic or organic
bases. Preferably utilizable are alkaline earth metal or alkali
metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates
or bicarbonates, such as, for example, sodium hydride, sodium
amide, sodium methoxide, sodium ethoxide, potassium tert-butoxide,
sodium hydroxide, potassium hydroxide, sodium acetate, potassium
acetate, calcium acetate, sodium carbonate, potassium carbonate,
potassium bicarbonate or sodium bicarbonate, furthermore ammonium
compounds, such as ammonium hydroxide, ammonium acetate or ammonium
carbonate, and also tertiary amines, such as trimethylamine,
triethylamine, tributylamine, N,N-dimethylaniline,
N,N-dimethyl-benzylamine, pyridine, N-methylpiperidine,
N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane
(DABCO), diazabicyclononene (DBN) or diazabicycloundecene
(DBU).
[0099] When carrying out the process (a) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. In general, the reaction is carried out at
temperatures between 0.degree. C. and 150.degree. C., preferably at
temperatures between 20.degree. C. and 120.degree. C.
[0100] For carrying out the process (a) according to the invention,
generally from 1 to 15 mol, preferably from 1 to 2 mol, in
particular from 1 to 1.3 mol, of halide of the formula (III) are
employed per mole of azole of the formula (II). Work-up is carried
out by customary methods.
[0101] Using, for example,
1-(thiophene-2-sulphonyl)-1H-imidazo[4,5-b]pyri-
dine-2-carbonitrile as starting material and hydrogen sulphide as
reaction component, the course of the process (b) according to the
invention can be illustrated by the following equation: 42
[0102] The formula (1-a) provides a general definition of the
cyanoimidazoles required as starting materials for carrying out the
process (b) according to the invention. In this formula, R.sup.1,
R.sup.2 and A preferably or in particular have those meanings which
have already been mentioned in connection with the description of
the compounds of the formula (I) according to the invention as
being preferred or as being particularly preferred for R.sup.1,
R.sup.2 and A.
[0103] The cyanoimidazoles of the formula (I-a) are compounds
according to the invention and can be prepared by the process (a)
according to the invention.
[0104] Suitable diluents for carrying out the process (b) according
to the invention are all customary inert organic solvents and also
water. Preferably utilizable are aliphatic, alicyclic or aromatic
hydrocarbons, such as, for example, petroleum ether, hexane,
heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene
or decalin; halogenated hydrocarbons, such as, for example,
chlorobenzene, dichlorobenzene, dichloromethane, chloroform,
tetrachloromethane, dichloroethane or trichloroethane; ethers, such
as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl
t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,
1,2-diethoxyethane or anisole; amides, such as
N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide,
N-methylpyrrolidone or hexamethylphosphoric triamide; esters such
as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl
sulphoxide; sulphones, such as sulpholane; amines, such as
pyridine; alcohols, such as methanol, ethanol, n- or i-propanol,
n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol,
ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether,
diethylene glycol monoethyl ether, mixtures thereof with water or
pure water.
[0105] Suitable bases for carrying out the process (b) according to
the invention are again all customary inorganic or organic acid
binders. Preferably utilizable are alkaline earth metal or alkali
metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates
or bicarbonates, such as, for example, sodium hydride, sodium
amide, sodium methoxide, sodium ethoxide, potassium tert-butoxide,
sodium hydroxide, potassium hydroxide, sodium acetate, potassium
acetate, calcium acetate, sodium carbonate, potassium carbonate,
potassium bicarbonate or sodium bicarbonate, furthermore ammonium
compounds, such as ammonium hydroxide, ammonium acetate or ammonium
carbonate, and also tertiary amines, such as trimethylamine
triethylamine tributylamine, N,N-dimethylaniline,
N,N-dimethyl-benzylamine, pyridine, N-methyl-piperidine,
N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane
(DABCO), diazabicyclononene (DBN) or diazabicycloundecene
(DBU).
[0106] When carrying out the process (b) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. In general, the reaction is carried out at
temperatures between 0.degree. C. and 150.degree. C., preferably at
temperatures between 20.degree. C. and 120.degree. C.
[0107] For carrying out the process (b) according to the invention,
generally from 1 to 1000 mol, preferably from 1 to 50 mol, of
hydrogen sulphide are employed per mole of cyanoimidazole of the
formula (I-a). The practice of the reaction and the work-up are
carried out by customary methods.
[0108] Using, for example, 1
-(thiophene-2-sulphonyl)-1H-imidazo[4,5-b]pyr-
idine-2-thiocarboxamide and iodomethane as starting materials, the
course of the process (c) according to the invention can be
illustrated by the following equation: 43
[0109] The formula (I-b) provides a general definition of the
thiocarbamoyl imidazoles required as starting materials for
carrying out the process (c) according to the invention. In this
formula, R.sup.1, R.sup.2 and A preferably or in particular have
those meanings which have already been mentioned in connection with
the description of the compounds of the formula (I) according to
the invention as being preferred or as being particularly preferred
for R.sup.1, R.sup.2 and A.
[0110] The thiocarbamoyl imidazoles of the formula (I-b) are
compounds according to the invention and can be prepared by the
process (b) according to the invention.
[0111] The formula (IV) provides a general definition of the
alkylating agents furthermore required as starting materials for
carrying out the process (c) according to the invention. In this
formula, R.sup.4 preferably or in particular has those meanings
which have already been mentioned in connection with the
description of the compounds of the formula (I) according to the
invention as being preferred or as being particularly preferred for
R.sup.4. X.sup.2 preferably represents halogen,
methanesulphonyloxy, toluenesulphonyloxy, R.sup.4--O--SO.sub.2--O--
or R.sup.4--O--CO--O--.
[0112] The alkylating agents of the formula (IV) are customary
laboratory chemicals.
[0113] Suitable diluents for carrying out the process (c) according
to the invention are all inert organic solvents. Preferably
utilizable are aliphatic, alicyclic or aromatic hydrocarbons, such
as, for example, petroleum ether, hexane, heptane, cyclohexane,
methylcyclohexane, benzene, toluene, xylene or decalin; halogenated
hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene,
dichloromethane, chloroform, tetrachloromethane, dichloroethane or
trichloroethane; ethers, such as diethyl ether, diisopropyl ether,
methyl t-butyl ether, methyl t-amyl ether, dioxane,
tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or
anisole; ketones, such as acetone, butanone, methyl isobutyl ketone
or cyclohexanone; nitrites, such as acetonitrile, propionitrile, n-
or i-butyronitrile or benzonitrile; amides, such as
N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide,
N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such
as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl
sulphoxide; sulphones, such as sulpholane; or amines, such as
pyridine.
[0114] Suitable acid binders for carrying out the process (c)
according to the invention are all customary inorganic or organic
bases. Preferably utilizable are alkaline earth metal or alkali
metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates
or bicarbonates, such as, for example, sodium hydride, sodium
amide, sodium methoxide, sodium ethoxide, potassium tert-butoxide,
sodium hydroxide, potassium hydroxide, sodium acetate, potassium
acetate, calcium acetate, sodium carbonate, potassium carbonate,
potassium bicarbonate or sodium bicarbonate, furthermore ammonium
compounds, such as ammonium hydroxide, ammonium acetate or ammonium
carbonate, and also tertiary amines, such as trimethylamine,
triethylamine, tributylamine, N,N-dimethylaniline,
N,N-dimethyl-benzylamine, pyridine, N-methylpiperidine,
N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane
(DABCO), diazabicyclononene (DBN) or diazabicycloundecene
(DBU).
[0115] When carrying out the process (c) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. In general, the reaction is carried out at
temperatures between 0.degree. C. and 150.degree. C., preferably at
temperatures between 20.degree. C. and 120.degree. C.
[0116] For carrying out the process (c) according to the invention,
generally from 1 to 10 mol, preferably from 1 to 5 mol, of
alkylating agent of the formula (IV) are employed per mole of
thiocarbamoyl imidazole of the formula (I-b). Work-up is carried
out by customary methods.
[0117] The processes (a), (b) and (c) according to the invention
are generally carried out under atmospheric pressure. However, it
is also possible to operate under elevated or reduced pressure--in
general between 0.1 bar and 10 bar.
[0118] The fused azole derivatives of the formula (I) can be
converted into acid addition salts or metal salt complexes.
[0119] For preparing acid addition salts of the compounds of the
formula (I), preference is given to using those acids which have
already been mentioned in connection with the description of the
acid addition salts according to the invention as being preferred
acids.
[0120] 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, be purified by
washing with an inert organic solvent.
[0121] For preparing metal salt complexes of the compounds of the
formula (I), preference is given to using those salts 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.
[0122] 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 it to compounds of the formula (I). Metal salt
complexes can be isolated in a known manner, for example by
filtering off, and they can be purified, if appropriate, by
recrystallization.
[0123] The compounds according to the invention have potent
microbicidal activity and can be employed for controlling
undesirable microorganisms, such as fungi and bacteria, in crop
protection and in the protection of materials.
[0124] Fungicides are employed in crop protection for controlling
Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,
Ascomycetes, Basidiomycetes and Deuteromycetes.
[0125] Bactericides are employed in crop protection for controlling
Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae,
Corynebacteriaceae and Streptomycetaceae.
[0126] Some pathogens causing fungal and bacterial diseases which
come under the generic names listed above are mentioned as
examples, but not by way of limitation:
[0127] Xanthomonas species, such as, for example, Xanthomonas
campestris pv. oryzae;
[0128] Pseudomonas species, such as, for example, Pseudomonas
syringae pv. lachrymans;
[0129] Erwinia species, such as, for example, Erwinia
amylovora;
[0130] Pythium species, such as, for example, Pythium ultimum;
[0131] Phytophthora species, such as, for example, Phytophthora
infestans;
[0132] Pseudoperonospora species, such as, for example,
Pseudoperonospora humuli or Pseudoperonospora cubensis;
[0133] Plasmopara species, such as, for example, Plasmopara
viticola;
[0134] Bremia species, such as, for example, Bremia lactucae,
[0135] Peronospora species, such as, for example, Peronospora pisi
or P. brassicae;
[0136] Erysiphe species, such as, for example, Erysiphe
graminis;
[0137] Sphaerotheca species, such as, for example, Sphaerotheca
fuliginea;
[0138] Podosphaera species, such as, for example, Podosphaera
leucotricha;
[0139] Venturia species, such as, for example, Venturia
inaequalis;
[0140] Pyrenophora species, such as, for example, Pyrenophora teres
or P. graminea (conidia form: Drechslera, syn:
Helminthosporium);
[0141] Cochliobolus species, such as, for example, Cochliobolus
sativus (conidia form: Drechslera, syn: Helminthosporium);
[0142] Uromyces species, such as, for example, Uromyces
appendiculatus;
[0143] Puccinia species, such as, for example, Puccinia
recondita;
[0144] Sclerotinia species, such as, for example, Sclerotinia
sclerotiorum
[0145] Tilletia species, such as, for example, Tilletia caries;
[0146] Ustilago species, such as, for example, Ustilago nuda or
Ustilago avenae;
[0147] Pellicularia species, such as, for example, Pellicularia
sasakii;
[0148] Pyricularia species, such as, for example, Pyricularia
oryzae;
[0149] Fusarium species, such as, for example, Fusarium
culmorum;
[0150] Botrytis species, such as, for example, Botrytis
cinerea;
[0151] Septoria species, such as, for example, Septoria
nodorum;
[0152] Leptosphaeria species, such as, for example, Leptosphaeria
nodorum;
[0153] Cercospora species, such as, for example, Cercospora
canescens;
[0154] Alternaria species, such as, for example, Alternaria
brassicae; and
[0155] Pseudocercosporella species, such as, for example,
Pseudocercosporella herpotrichoides.
[0156] The fact that the active compounds are well tolerated by
plants at the concentrations required for controlling plant
diseases permits the treatment of aerial parts of plants, of
propagation stock and seeds, and of the soil.
[0157] The active compounds according to the invention can be
employed particularly successfully for controlling diseases in
fruit and vegetable growing and viticulture, such as, for example,
against Phytophthora species.
[0158] The active compounds according to the invention may also be
employed to increase the yield of crops. Moreover, they show
reduced toxicity and are well tolerated by plants.
[0159] Depending on their particular physical and/or chemical
properties, the active compounds can be converted to the customary
formulations, such as solutions, emulsions, suspensions, powders,
foams, pastes, granules, aerosols and microencapsulations in
polymeric substances and in coating compositions for seeds, and ULV
cool and warm fogging formulations.
[0160] These formulations are produced 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 surfactants, that is
emulsifiers and/or dispersants, and/or foam formers. If the
extender used is water, it is also possible to employ for example
organic solvents as auxiliary solvents. Essentially, suitable
liquid solvents are: 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 petroleum fractions, alcohols such as butanol or glycol
and 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, or else
water. Liquefied gaseous extenders or carriers are to be understood
as meaning liquids which are gaseous at standard temperature and
under atmospheric pressure, for example aerosol propellants such as
halogenated hydrocarbons, or else butane, propane, nitrogen and
carbon dioxide. Suitable solid carriers are: for example ground
natural minerals such as kaolins, clays, talc, chalk, quartz,
attapulgite, montmorillonite or diatomaceous earth, and ground
synthetic minerals such as highly disperse silica, alumina and
silicates. Suitable solid carriers for granules are: for example
crushed and fractionated natural rocks such as calcite, marble,
pumice, sepiolite and dolomite, or else synthetic granules of
inorganic and organic meals, and granules of organic material such
as sawdust, coconut shells, maize cobs and tobacco stalks. Suitable
emulsifiers and/or foam formers are: 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, or else protein hydrolysates. Suitable dispersants
are: for example lignin-sulphite waste liquors and
methylcellulose.
[0161] Tackifiers 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, or
else natural phospholipids such as cephalins and lecithins and
synthetic phospholipids can be used in the formulations. Other
possible additives are mineral and vegetable oils.
[0162] It is possible to use colorants 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.
[0163] The formulations generally comprise between 0.1 and 95 per
cent by weight of active compound, preferably between 0.5 and
90%.
[0164] Depending on their particular physical and/or chemical
properties, the active compounds can be converted to the customary
formulations, such as solutions, emulsions, suspensions, powders,
foams, pastes, granules, aerosols and microencapsulations in
polymeric substances and in coating compositions for seeds, and ULV
cool and warm fogging formulations.
[0165] The active compounds according to the invention can be used
as such or in their formulations also mixed with known fungicides,
bactericides, acaricides, nematicides or insecticides in order
thus, for example, to widen the spectrum of action or to prevent
development of resistance. In many cases, synergistic effects are
achieved, i.e. the activity of the mixture exceeds the activity of
the individual components. Examples of co-components in mixtures
are the following compounds:
[0166] Fungicides:
[0167] aldimorph, ampropylfos, ampropylfos potassium, andoprim,
anilazine, azaconazole, azoxystrobin,
[0168] benalaxyl, benodanil, benomyl, benzamacril,
benzamacril-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol,
blasticidin-S, bromuconazole, bupirimate, buthiobate,
[0169] calcium polysulphide, capsimycin, captafol, captan,
carbendazim, carboxin, carvon, quinomethionate, chlobenthiazone,
chlorfenazole, chloroneb, chloropicrin, chlorothalonil,
chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole,
cyprodinil, cyprofuram,
[0170] debacarb, dichlorophen, diclobutrazole, diclofluanid,
diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol,
dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine,
dipyrithione, ditalimfos, dithianon, dodemorph, dodine,
drazoxolon,
[0171] edifenphos, epoxiconazole, etaconazole, ethirimol,
etridiazole,
[0172] famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram,
fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin
acetate, fentin hydroxide, ferbam, ferimzone, fluazinam,
flumetover, fluoromide, fluquinconazole, flurprimidol, flusilazole,
flusulphamide, flutolanil, flutriafol, folpet, fosetyl-aluminium,
fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr,
furcarbonil, furconazole, furconazole-cis, furmecyclox,
[0173] guazatine,
[0174] hexachlorobenzene, hexaconazole, hymexazole,
[0175] imazalil, imibenconazole, iminoctadine, iminoctadine
albesilate, iminoctadine triacetate, iodocarb, ipconazole,
iprobenfos (IBP), iprodione, irumamycin, isoprothiolane,
isovaledione,
[0176] kasugamycin, kresoxim-methyl, copper preparations, such as:
copper hydroxide, copper naphthenate, copper oxychloride, copper
sulphate, copper oxide, oxine-copper and Bordeaux mixture,
[0177] mancopper, mancozeb, maneb, meferimzone, mepanipyrim,
mepronil, metalaxyl, metconazole, methasulphocarb, methfuroxam,
metiram, metomeclam, metsulphovax, mildiomycin, myclobutanil,
myclozolin,
[0178] nickel dimethyldithiocarbamate, nitrothal-isopropyl,
nuarimol,
[0179] ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim,
oxyfenthiin,
[0180] paclobutrazole, pefurazoate, penconazole, pencycuron,
phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim,
probenazole, prochloraz, procymidone, propamocarb,
propanosine-sodium, propiconazole, propineb, pyrazophos, pyrifenox,
pyrimethanil, pyroquilon, pyroxyfur,
[0181] quinconazole, quintozene (PCNB),
[0182] sulphur and sulphur preparations,
[0183] tebuconazole, tecloftalam, tecnazene, tetcyclasis,
tetraconazole, thiabendazole, thicyofen, thifluzamide,
thiophanate-methyl, thiram, tioxymid, tolclofos-methyl,
tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide,
trichlamide, tricyclazole, tridemorph, triflumizole, triforine,
triticonazole,
[0184] uniconazole,
[0185] validamycin A, vinclozolin, viniconazole,
[0186] zarilamide, zineb, ziram and also
[0187] Dagger G,
[0188] OK-8705,
[0189] OK-8801,
[0190]
.alpha.-(1,1-dimethylethyl)-.beta.-(2-phenoxyethyl)-1H-1,2,4-triazo-
le-1-ethanol,
[0191]
.alpha.-(2,4-dichlorophenyl)-.beta.-fluoro-b-propyl-1H-1,2,4-triazo-
le-1-ethanol,
[0192]
.alpha.-(2,4-dichlorophenyl)-.beta.-methoxy-a-methyl-1H-1,2,4-triaz-
ole-1-ethanol,
[0193]
.alpha.-(5-methyl-1,3-dioxan-5-yl)-.beta.-[[4-(trifluoromethyl)-phe-
nyl]-methylene]-1H-1,2,4-triazole-1-ethanol,
[0194]
(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-
-octanone,
[0195] (E)-a-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,
[0196] isopropyl
{2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-
-propyl}-carbamate,
[0197]
1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone-O-(phenyl-
methyl)-oxime,
[0198] 1-(2-methyl-1-naphthalenyl)-1H-pyrrol-2,5-dione,
[0199]
1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,
[0200] 1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,
[0201]
1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,
[0202]
1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,
[0203]
1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazol-
e,
[0204] 1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,
[0205]
2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3--
thiazole-5-carboxanilide,
[0206]
2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopro-
panecarboxamide,
[0207] 2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,
[0208] 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,
[0209]
2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,
[0210] 2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,
[0211]
2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole-
,
[0212]
2-[[6-deoxy-4-O-(4-O-methyl-.beta.-D-glycopyranosyl)-a-D-glucopyran-
osyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,
[0213] 2-aminobutane,
[0214] 2-bromo-2-(bromomethyl)-pentanedinitrile,
[0215]
2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridineca-
rboxamide,
[0216]
2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,
[0217] 2-phenylphenol (OPP),
[0218]
3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,
[0219]
3,5-dichloro-N-[cyano[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,
[0220] 3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,
[0221]
3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,
[0222]
4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sul-
phonamide,
[0223] 4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,
[0224]
8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2--
methaneamine,
[0225] 8-hydroxyquinoline sulphate,
[0226] 9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic
hydrazide,
[0227]
bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophen-
e dicarboxylate,
[0228]
cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,
[0229]
cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethy-
l-morpholine hydrochloride,
[0230] ethyl [(4-chlorophenyl)-azo]-cyanoacetate,
[0231] potassium hydrogen carbonate,
[0232] methanetetrathiol sodium salt,
[0233] methyl
1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-ca-
rboxylate,
[0234] methyl
N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate- ,
[0235] methyl
N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,
[0236]
N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide.
[0237]
N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-ace-
tamide,
[0238]
N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-ace-
tamide,
[0239]
N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,
[0240] N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidine
amine,
[0241] N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidine amine,
[0242]
N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acet-
amide,
[0243] N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide,
[0244]
N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,
[0245]
N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N'-methoxy-methaneimida-
mide,
[0246] N-formyl-N-hydroxy-DL-alanine-sodium salt,
[0247]
O,O-diethyl[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate-
,
[0248] O-methyl S-phenyl phenylpropylphosphoramidothioate,
[0249] S-methyl 1,2,3-benzothiadiazole-7-carbothioate,
[0250] spiro[2H]-1-benzopyran-2,1'(3'H)-isobenzofuran]-3'-one,
[0251] Bactericides:
[0252] bronopol, dichlorophen, nitrapyrin, nickel
dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic
acid, oxytetracyclin, probenazole, streptomycin, tecloftalam,
copper sulphate and other copper preparations.
[0253] Insecticides/Acaricides/Nematicides:
[0254] abamectin, acephate, acrinathrin, alanycarb, aldicarb,
alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos
A, azinphos M, azocyclotin,
[0255] bacillus thuringiensis,
4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-
-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, bendiocarb,
benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC,
brofenprox, bromophos A, bufencarb, buprofezin, butocarboxin,
butylpyridaben,
[0256] cadusafos, carbaryl, carbofuran, carbophenothion,
carbosulphan, cartap, chloethocarb, chlorethoxyfos, chlorfenapyr,
chlorfenvinphos, chlorfluazuron, chlormephos,
N-[(6-chloro-3-pyridinyl)-methyl]-N'-cyano-N-
-methyl-ethaneimidamide, chlorpyrifos, chlorpyrifos M,
cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin,
cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,
[0257] deltamethrin, demeton M, demeton S, demeton S-methyl,
diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos,
dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos,
dioxathion, disulphoton,
[0258] edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion,
ethofenprox, ethoprophos, etrimphos,
[0259] fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,
fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad,
fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam,
fluazuron, flucycloxuron, flucythrinate, flufenoxuron, flufenprox,
fluvalinate, fonophos, formothion, fosthiazate, fubfenprox,
furathiocarb,
[0260] HCH, heptenophos, hexaflumuron, hexythiazox,
[0261] imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb,
isoxathion, ivermectin,
[0262] lambda-cyhalothrin, lufenuron,
[0263] malathion, mecarbam, mevinphos, mesulphenphos, metaldehyde,
methacrifos, methamidophos, methidathion, methiocarb, methomyl,
metolcarb, milbemectin, monocrotophos, moxidectin,
[0264] naled, NC 184, nitenpyram,
[0265] omethoate, oxamyl, oxydemethon M, oxydeprofos,
[0266] parathion A, parathion M, permethrin, phenthoate, phorate,
phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,
pirimiphos A, profenofos, promecarb, propaphos, propoxur,
prothiofos, prothoate, pymetrozin, pyrachlophos, pyridaphenthion,
pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen,
[0267] quinalphos,
[0268] salithion, sebufos, silafluofen, sulphotep, sulprofos,
[0269] tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron,
tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos,
thiafenox, thiodicarb, thiofanox, thiomethon, thionazin,
thuringiensin, tralomethrin, triarathen, triazophos, triazuron,
trichlorfon, triflumuron, trimethacarb,
[0270] vamidothion, XMC, xylylcarb, zetamethrin.
[0271] It is also possible to admix other known active compounds,
such as herbicides, fertilizers and growth-promoting
substances.
[0272] 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 pouring, spraying, atomizing, spreading,
dusting, foaming, brushing on and the like. It is further 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 seed of the plants can also be
treated.
[0273] When using the active compounds according to the invention
as fungicides, the application rates can be varied within a
relatively wide range, depending on the application method. In the
treatment of parts of plants, the active compound application rates
are, in general, between 0.1 and 10,000 g/ha, preferably between 10
and 1000 g/ha. In the treatment of seed, the active compound
application rates are generally between 0.001 and 50 g per kilogram
of seed, preferably between 0.01 and 10 g per kilogram of seed. In
the treatment of the soil, the active compound application rates
are generally between 0.1 and 10,000 g/ha, preferably between 1 and
5000 g/h.
[0274] The preparation and the use of the active compounds
according to the invention is illustrated by the examples
below.
PREPARATION EXAMPLES
Example 1
[0275] 44
[0276] Process (a):
[0277] 0.3 g (10 mmol) of sodium hydride (80% strength suspension
in mineral oil) is added to a solution of 2.5 g (15 mmol) of
1H-imidazo[4,5-b]pyridine in 40 ml of absolute tetrahydrofuran. The
mixture is stirred at 20.degree. C. for 10 minutes. 3.0 g (15 mmol)
of 3,5-dimethylisoxazole-4-sulphonyl chloride are then added, and
the mixture is stirred at 20.degree. C. for another 20 hours. The
reaction mixture is poured into 200 ml of water. The resulting
mixture is extracted twice with 150 ml of diethyl ether each time.
The combined organic phases are dried over sodium sulphate and
concentrated under reduced pressure. The residue is chromatographed
over silica gel using diethyl ether.
[0278] This gives 1.3 g (46% of theory) of
1-(3,5-dimethyl-isoxazole-4-sul- phonyl)-1H-imidazo[4,5-b]pyridine
as a white solid having a melting range of from 77 to 80.degree.
C.
Example 2
[0279] 45
[0280] Process (a):
[0281] 1.4 g (10 mmol) of potassium carbonate are added to a
solution of 1.2 g (10 mMol) of 1H-imidazo[4,5-c]pyridine in 30 ml
of acetonitrile, and the mixture is stirred at 20.degree. C. for 10
minutes. The mixture is then admixed with 1.9 g (10 mmol) of
3,5-dimethylisoxazole-4-sulphonyl chloride and stirred at
20.degree. C. for 20 hours. The reaction mixture is subsequently
poured into 150 ml of water. The resulting mixture is extracted
twice with 70 ml of ethyl acetate each time. The combined organic
phases are dried over sodium sulphate and concentrated under
reduced pressure. The residue is stirred with 20 ml of petroleum
ether and the resulting solid is filtered off and dried.
[0282] This gives 1.6 g (57% of theory) of
1-(3,5-dimethyl-isoxazole-4-sul- phonyl)-1H-imidazo[4,5-c]pyridine
as a yellow solid of melting point 130-135.degree. C.
[0283] The substances listed in Table 12 below are also prepared by
the methods given above.
12TABLE 12 (I-n) 46 Ex. No. 47 R.sup.5 Physical constants 3 48 49
m.p.: 190-195.degree. C. 4 50 51 .sup.lH NMR*: 2.10 5 52 53 .sup.1H
NMR*: 2.43 6 54 55 .sup.lH NMR*: 2.21 7 56 57 .sup.lH NMR*: 2.19 8
58 59 .sup.1H NMR*: 2.30 9 60 61 m.p.: 207.degree. C. .sup.1H NMR*:
2.28 10 62 63 .sup.1H NMR*: 3.01 11 64 65 m.p.: 177.degree. C.
.sup.1H NMR: 2.35 12 66 67 .sup.lH NMR*: 2.56 13 68 69 .sup.1H
NMR*: 2.48 14 70 71 .sup.1H NMR*: 2.89 *The .sup.1H NMR spectra
were recorded in deuterochloroform (CDCl.sub.3) or
hexadeuterodimethylsuiphoxide (DMSO-d.sub.6) using
tetramethylsilane (TMS) as internal standard. The chemical shift is
given as .delta. value in ppm.
USE EXAMPLES
Example A
[0284] Plasmopara Test (grapevine)/protective
[0285] Solvent: 47 parts by weight of acetone
[0286] Emulsifier: 3 parts by weight of alkyl-aryl polyglycol
ether
[0287] To produce a suitable preparation of the 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.
[0288] To test for protective activity, young plants are sprayed
with a preparation of active compound at the stated application
rate. After the spray coating has dried on, the plants are
inoculated with an aqueous spore suspension of Plasmopara viticola
and then remain in an incubation cabin at approximately 20.degree.
C. and 100% relative atmospheric humidity for 1 day. The plants are
then placed in a greenhouse at approximately 21.degree. C. and
approximately 90% atmospheric humidity for 5 days. The plants are
then moistened and placed in an incubation cabin for 1 day.
[0289] Evaluation is carried out 6 days after the inoculation. 0%
means an efficacy which corresponds to that of the control, whereas
an efficacy of 100% means that no infection is observed.
[0290] Active compounds, application rates and test results are
shown in the table below.
13TABLE A Plasmopara Test (grapevine)/protective Application rate
of active Efficacy Active compound compound in g/ha in % According
to the invention: 72 100 93 (1) 73 100 90 (2) 74 100 90 (3) 75 100
74 (6) Known from DE-A 195 23 446: 76 100 49
Example B
[0291] Venturia Test (Apple)/protective
[0292] Solvent: 47 parts by weight of acetone
[0293] Emulsifier: 3 parts by weight of alkyl-aryl polyglycol
ether
[0294] 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.
[0295] To test for protective activity, young plants are sprayed
with the preparation of active compound at the stated application
rate. After the spray coating has dried on, the plants are
inoculated with an aqueous conidia suspension of the causative
organism of apple scab Venturia inaequalis and then remain in an
incubation cabin at approximately 20.degree. C. and 100% relative
atmospheric humidity for 1 day.
[0296] The plants are then placed in a greenhouse at approximately
21.degree. C. and a relative atmospheric humidity of approximately
90%.
[0297] Evaluation is carried out 12 days after the inoculation. 0%
means an efficacy which corresponds to that of the control, whereas
an efficacy of 100% means that no infection is observed.
[0298] Active compounds, application rates and test results are
shown in the table below.
14TABLE B Venturia Test (Apple)/protective Application rate of
active Efficacy Active compound compound in g/ha in % According to
the invention: 77 100 100 (1) 78 100 95 (2) 79 100 92 (3) 80 100 89
Known from DE-A 195 23 446: 81 100 0
* * * * *