Note: Descriptions are shown in the official language in which they were submitted.
CA 02323593 2000-09-13
1
FUNGICIDE MIXTURES BASED ON TRIPLE OXIME ETHER
DERIVATIVES AND RESISTANCE INDUCTORS
The present invention relates to fungicidal mixtures for
controlling harmful fungi, comprising
a) phenylacetic acid derivatives of the formula I
R3
4 ~R2~m
R.O.N~ ~N.O
tI)
5
R ~ N R~
I
O, Rs
in which the substituents and the index have the following
meaning:
X is NOCH3, CHOCH3, CHCH3;
Y is O, NR;
R1~ R independently of one another are each hydrogen and
C1-C4-alkyl;
RZ is cyano, nitro, trifluoromethyl, halogen, C1-C4-alkyl
and C1-C4-alkoxy;
m is 0, 1 or 2, where the radicals R2 may be different if
m is 2;
R3 is hydrogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl,
C3-C6-cycloalkyl;
R4, R6 independently of one another are each hydrogen,
are C -C -alk 1 C -C -c cloalk 1 C -C -alken 1
i io Y . s s Y Y . 2 io Y .
Cz-Clo-alkynyl, C1-Clo-alkylcarbonyl,
CZ-Clo-alkenylcarbonyl, C3-Clo-alkynylcarbonyl or
CA 02323593 2000-09-13
la
C1-Clo-alkylsulfonyl, where these radicals may be
partially or fully halogenated or may carry one to
three of the following groups: cyano, vitro, hydroxyl,
mercapto, amino, carboxyl, aminocarbonyl,
aminothiocarbonyl, halogen, C1-C6-alkyl,
0050/48893
CA 02323593 2000-09-13
2
C1-C6-haloalkyl, C1-C6-alkylsulfonyl,
C1-C6-alkylsulfoxyl, C1-C6-alkoxy, C1-C6-haloalkoxy,
C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino,
di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl,
di-C1-C6-alkylaminocarbonyl,
C1-C6-alkylaminothiocarbonyl,
di-C1-C6-alkylaminothiocarbonyl, CZ-C6-alkenyl,
C2-C6-alkenyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy,
heterocyclyl, heterocyclyloxy, benzyl, benzyloxy, aryl,
aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio,
where the cyclic groups for their part may be partially
or fully halogenated or may carry one to three of the
following groups: cyano, vitro, hydroxyl, mercapto,
amino, carboxyl, aminocarbonyl, aminothiocarbonyl,
halogen, C1-C6-alkyl, C1-C6-haloalkyl,
C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl,
C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy,
C1-C6-alkyloxycarbonyl, C1-C6-alkylthio,
C1-C6-alkylamino, di-C1-C6-alkylamino,
C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl,
C1-C6-alkylaminothiocarbonyl,
di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl,
C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy,
arylthio, hetaryl, hetaryloxy, hetarylthio or
C(=NORM)-An-Re;
are aryl, arylcarbonyl, arylsulfonyl, hetaryl, hetaryl-
carbonyl or hetarylsulfonyl, where these radicals may
be partially or fully halogenated or may carry one to
three of the following groups: cyano, vitro, hydroxyl,
mercapto, amino, carboxyl, aminocarbonyl, aminothiocar-
bonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl,
C1-C6-alkylcarbonyl, C1-C6-alkylsulfonyl,
C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy,
C1-C6-haloalkoxy, C1-C6-alkyloxycarbonyl,
C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino,
C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl,
C1-C6-alkylaminothiocarbonyl,
di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl,
C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy,
hetaryl, hetaryloxy or C(=NORM)-An-Re;
RS is hydrogen,
is C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, where the
hydrocarbon radicals of these groups may be partially
or fully halogenated or may carry one to three of the
0050/48893
CA 02323593 2000-09-13
3
following radicals: cyano, vitro, hydroxyl, mercapto,
amino, carboxyl, aminocarbonyl, aminothiocarbonyl,
halogen, C1-C6-alkylaminocarbonyl,
di-C1-C6-alkylaminocarbonyl,
C1-C6-alkylaminothiocarbonyl,
di-C1-C6-alkylaminothiocarbonyl, C1-C6-alkylsulfonyl,
C1-C6-alkylsulfoxyl, C1-C6-alkoxy, C1-C6-haloalkoxy,
C1-C6-alkoxycdrbonyl, C1-C6-alkylthio, C1-C6-alkylamino,
di-C1-C6-alkylamino, CZ-C6-alkenyloxy, C3-C6-cycloalkyl,
C3-C6-cycloalkyloxy, heterocyclyl, heterocyclyloxy,
aryl, aryloxy, aryl-C1-C4-alkoxy, arylthio,
aryl-C1-C4-alkylthio, hetaryl, hetaryloxy,
hetaryl-C1-C4-alkoxy, hetarylthio,
hetaryl-C1-C4-alkylthio, where the cyclic radicals for
their part may be partially or fully halogenated and/or
may carry one to three of the following groups: cyano,
vitro, hydroxyl, mercapto, amino, carboxyl,
aminocarbonyl, aminothiocarbonyl, C1-C6-alkyl,
C1-C6-haloalkyl, C1-C6-alkylsulfonyl,
C1-C6-alkylsulfoxyl, C3C6-cycloalkyl [sic],
C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl,
C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino,
C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl,
C1-C6-alkylaminothiocarbonyl,
di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl,
C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy,
arylthio, hetaryl, hetaryloxy, hetarylthio and
C ( =NORM ) -An-R8 ;
is C3-C6-cycloalkyl, C3-C6-cycloalkenyl, heterocyclyl,
aryl, hetaryl, where the cyclic radicals may be
partially or fully halogenated or may carry one to
three of the following groups: cyano, vitro, hydroxyl,
mercapto, amino, carboxyl, aminocarbonyl,
aminothiocarbonyl, halogen, C1-C6-alkyl,
C1-C6-haloalkyl, C1-C6-alkylsulfonyl,
C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy,
C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio,
C1-C6-alkylamino, di-C1-C6-alkylamino,
C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl,
C1-C6-alkylaminothiocarbonyl,
di-C1-C6-alkylaminothiocarbonyl, CZ-C6-alkenyl,
CZ-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy,
hetaryl and hetaryloxy;
where
CA 02323593 2000-09-13
0050/48893
4
A is oxygen, sulfur or nitrogen and where the nitrogen
carries hydrogen or C1-C6-alkyl;
n is 0 or 1;
R~ is hydrogen or C1-C6-alkyl and
Re is hydrogen or C1-C6-alkyl,
and their salts,
and
b) at least one fungicide selected from fungicides of the
formulae II to III
d S~CH
3
S (II)
NN
~S/O
/N (III)
OCH2CH=CH2
It is an object of the present invention to provide fungicidal
mixtures having good fungicidal activity, in particular against
fungal diseases in rice, exceeding the efficacy of the mixture
components on their own.
we have found that this object is achieved according to the
invention by the mixtures as claimed in claim 1.
The compounds of the formula I are known per se and are described
in the literature (WO 97/15552).
, CA 02323593 2000-09-13
0050/48893
The fungicides of the formulae II to III are also known and
described in the literature. Additionally, they are commercially
available under the trade names given below in brackets:
5 II: EP 313,512, proposed common name: acibenzolar (trade name:
Bion~, from Novartis)
III:common name: probenazole (trade name Oryzamate~, from Meiji
Seika)
Owing to their C=C and C=N double bonds, the preparation of the
compounds I may yield E/Z isomer mixtures which can be separated
into the individual compounds in a customary manner, for example
by crystallization or chromatography.
However,,if the synthesis yields isomer mixtures, a separation is
generally not necessarily required since in some cases the
individual isomers can be converted into one another during the
preparation for use or upon use (for example under the action of
light, acids or bases). Similar conversions may also occur after
use, for example in the treatment of plants in the treated plant
or in the harmful fungus or animal pest to be controlled.
With regard to the C=x double bond, preference is given to the E
isomers of the compounds I (configuration based on the -OCH3 or
the -CH3 group in relation to the -C02R1 group) with respect to
their activity.
with regard to the -C(R3)=NOCHZ- double bond, preference is given
to the cis isomers of the compounds I (configuration based on the
radical R3 in relation to the -OCH2- group) with respect to their
activity.
In the definitions of the compounds I given at the outset,
collective terms were used which generally represent the
following groups:
Halogen: fluorine, chlorine, bromine and iodine;
Alkyl: straight-chain or branched alkyl groups having 1 to 4, 6
or 10 carbon atoms, for example C1-C6=alkyl such as methyl, ethyl,
propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl,
1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl,
3-methylbutyl, 2,2-di-methylpropyl, 1-ethylpropyl, hexyl,
1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,
2-methylpentyl, 3-methylpentyl, 4-methylpentyl,
1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,
CA 02323593 2000-09-13
0050/48893
6
2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl,
1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,
1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and
1-ethyl-2-methylpropyl;
Haloalkyl: straight-chain or branched alkyl groups having 1 to 6
carbon atoms, it being possible for some or all of the hydrogen
atoms in these groups to be replaced by halogen atoms as
mentioned above, for example C1-C2-haloalkyl, such as
chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl,
difluoromethyl, trifluoromethyl, chlorofluoromethyl,
dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl,
2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,
2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,
2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and
pentafluoroethyl;
Cycloalkyl: monocyclic alkyl groups having 3 to 6 carbon ring
members, for example cyclopropyl, cyclobutyl, cyclopentyl and
cyclohexyl;
Alkenyl: straight-chain or branched alkenyl groups having 2 to 6
or 10 carbon atoms and a double bond in any position, for example
C2-C6-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl,
1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl,
1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl,
2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl,
4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,
3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,
3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,
3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl,
1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl,
1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl,
3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl,
2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl,
1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl,
4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl,
3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl,
2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,,
1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,
1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,
1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl,
1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,
2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,
2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,
3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl,
1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl,
CA 02323593 2000-09-13
0050/48893
7
2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,
1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl,
1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;
Alkynyl: straight-chain or branched alkynyl groups having 2 to 10
carbon atoms and a triple bond in any position, for example
CZ-C6-alkynyl, such as ethynyl, 2-propynyl, 2-butynyl, 3-butynyl,
1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl,
1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl,
1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl,
3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,
1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl,
2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl,
1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl,
1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl,
1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and
1-ethyl-1-methyl-2-propynyl;
Heterocyclyl or heterocyclyloxy, heterocyclylthio and
heterocyclylamino: three- to six-membered saturated or partially
unsaturated mono- or polycyclic heterocycles which contain one to
three heteroatoms selected from a group consisting of oxygen,
nitrogen and sulfur and which are attached to the skeleton
directly or (heterocyclyloxy) via an oxygen atom or
(heterocyclylthio) via a sulfur atom or (heterocyclylamino) via a
nitrogen atom, such as, for example, 2-tetrahydrofuranyl,
oxiranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl,
3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl,
3-isoxazoldinyl, 4-isoxazolidinyl, 5-isoxazolidinyl,
3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl,
3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl,
2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl,
4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl,
4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl,
1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl,
1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl,
1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl,
1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl,
2,3-dihydrofur-4-yl, 2,3-dihydrofur-5-yl, 2,5-dihydrofur-2-yl,
2,5-dihydrofur-3-yl, 2,3-dihydrothien-2-yl,
2,3-dihydrothien-3-yl, 2,3-dihydrothien-4-yl,
2,3-dihydrothien-5-yl, 2,5-dihydrothien-2-yl,
2,5-dihydrothien-3-yl, 2,3-dihydropyrrol-2-yl,
2,3-dihydropyrrol-3-yl, 2,3-dihydropyrrol-4-yl,
2,3-dihydropyrrol-5-yl, 2,5-dihydropyrrol-2-yl,
2,5-dihydropyrrol-3-yl, 2,3-dihydroisoxazol-3-yl,
2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl,
. CA 02323593 2000-09-13
0050/48893
8
4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl,
4,5-dihydroisoxazol-5-yl, 2,5-dihydroisothiazol-3-yl,
2,5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol-5-yl,
2,3-dihydroisopyrazol-3-yl, 2,3-dihydroisopyrazol-4-yl,
2,3-dihydroisopyrazol-5-yl, 4,5-dihydroisopyrazol-3-yl,
4,5-dihydroisopyrazol-4-yl, 4,5-dihydroisopyrazol-5-yl,
2,5-dihydroisopyrazol-3-yl, 2,5-dihydroisopyrazol-4-yl,
2,5-dihydroisopyrazol-5-yl, 2,3-dihydrooxazol-3-yl,
2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl,
4,5-dihydrooxazol-3-yl, 4,5-dihydrooxazol-4-yl,
4,5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-3-yl,
2,5-dihydrooxazol-4-yl, 2,5-dihydrooxazol-5-yl,
2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl,
2,3-dihydrothiazol-5-yl, 4,5-dihydrothiazol-2-yl,
4,5-dihydrothiazol-4-yl, 4,5-dihydrothiazol-5-yl,
2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl,
2,5-dihydrothiazol-5-yl, 2,3-dihydroimidazol-2-yl,
2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl,
4,5-dihydroimidazol-2-yl, 4,5-dihydroimidazol-4-yl,
4,5-dihydroimidazol-5-yl, 2,5-dihydroimidazol-2-yl,
2,5-dihydroimidazol-4-yl, 2,5-dihydroimidazol-5-yl,
2-morpholinyl, 3-morpholinyl, 2-piperidinyl, 3-piperidinyl,
4-giperidinyl, 3-tetrahydropyridazinyl, 4-tetrahydropyridazinyl,
2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl,
5-tetrahydropyrimidinyl, 2-tetrahydropyrazinyl,
1,3,5-tetrahydrotriazin-2-yl, 1,2,4-tetrahydrotriazin-3-yl,
1,3-dihydrooxazin-2-yl, 1,3-dithian-2-yl, 2-tetrahydropyranyl,
1,3-dioxolan-2-yl, 3,4,5,6-tetrahydropyridin-2-yl,
4H-1,3-thiazin-2-yl, 4H-3,1-benzothiazin-2-yl,
1,1-dioxo-2,3,4,5-tetrahydrothien-2-yl, 2H-1,4-benzothiazin-3-yl,
2H-1,4-benzoxazin-3-yl, 1,3-dihydrooxazin-2-yl, 1,3-dithian-2-yl;
Aryl or aryloxy, arylthio, arylcarbonyl and arylsulfonyl:
aromatic mono- or polycyclic hydrocarbon radicals which are
attached to the skeleton directly or (aryloxy) via an oxygen atom
(-0-) or (arylthio) a sulfur atom (-S-), (arylcarbonyl) via a
carbonyl group (-CO-) or (arylsulfonyl) via a sulfonyl group
(-S02-), for example phenyl, naphthyl and phenanthrenyl or
phenyloxy, naphthyloxy and phenanthrenyloxy and the corresponding
carbonyl and sulfonyl radicals;
Hetaryl or hetaryloxy, hetarylthio, hetarylcarbonyl and
hetarylsulfonyl: aromatic mono- or polycyclic radicals which,
beside carbon ring members, can additionally contain one to four
nitrogen atoms or one to three nitrogen atoms and one oxygen or
one sulfur atom or one oxygen or one sulfur atom and which are
attached to the skeleton directly or (hetaryloxy) via an oxygen
CA 02323593 2000-09-13
0050/48893
9
atom (-O-) or (hetarylthio) a sulfur atom (-S-),
(hetarylcarbonyl) via a carbonyl group (-CO-) or
(hetarylsulfonyl) via a sulfonyl group (-S02-), for example
- 5-membered heteroaryl, containing one to three nitrogen
atoms: 5-membered heteroaryl groups which, beside carbon
atoms, can contain one to three nitrogen atoms as ring
members, for example 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl,
4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl,
IO 1,2,4-triazol-3-yl and 1,3,4-triazol-2-yl;
- 5-membered heteroaryl, containing one to four nitrogen atoms
or one to three nitrogen atoms and one sulfur or oxygen atom
or one oxygen or one sulfur atom: 5-membered heteroaryl
groups which, beside carbon atoms, can contain one to four
nitrogen atoms or one to three nitrogen atoms and one sulfur
or oxygen atom or one oxygen or sulfur atom as ring members,
for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl,
2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl,
5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl,
3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl,
4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl,
5-thiazolyl, 2-imidazolyl, 4-imidazolyl,
1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl,
1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl,
1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl,
1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl;
- benzo-fused 5-membered heteroaryl, containing one to three
nitrogen atoms or one nitrogen atom and/or one oxygen or
sulfur atom: 5-membered heteroaryl groups which, beside
carbon atoms, can contain one to four nitrogen atoms or one
to three nitrogen atoms and one sulfur or oxygen atom or one
oxygen or one sulfur atom as ring members, and in which two
adjacent carbon ring members or one nitrogen and one adjacent
carbon ring member may be bridged by a buta-1,3-dien-1,4-diyl
group;
- 5-membered heteroaryl bonded via nitrogen and containing one
to four nitrogen atoms, or benzo-fused 5-membered heteroaryl,
bonded via nitrogen and containing one to three nitrogen
atoms: 5-membered heteroaryl groups which, beside carbon
atoms, can contain one to four nitrogen atoms and one to
three nitrogen atoms, respectively, as ring members, and in
which two adjacent carbon ring members or one nitrogen and
one adjacent carbon ring member can be bridged by a
buta-1,3-dien-1,4-diyl group, these rings being attached to
0050/48893
CA 02323593 2000-09-13
the skeleton via one of the nitrogen ring members;
6-membered heteroaryl containing one to three and one to four
30
nitrogen atoms, respectively: 6-membered heteroaryl groups
5 which, beside carbon atoms, can contain one to three and one
to four nitrogen atoms, respectively, as ring members, for
example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl,
4-pyridazinyl, 2-py~imidinyl, 4-pyrimidinyl, 5-pyrimidinyl,
2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl and
10 1,2,4,5-tetrazin-3-yl;
- benzo=fused 6-membered heteroaryl containing one to four
nitrogen atoms: 6-membered heteroaryl groups in which two
adjacent carbon ring members can be bridged by a buta-
15 1,3-dien-1,4-diyl group, for example quinoline, isoquinoline,
quinazoline and quinoxaline,
and the corresponding oxy, thio, carbonyl or sulfonyl groups.
20 Hetarylamino: aromatic mono- or polycyclic radicals which, beside
carbon ring members, can additionally contain one to four
nitrogen atoms or one to three nitrogen atoms and one oxygen or
one sulfur atom and which are attached to the skeleton via a
nitrogen atom.
The specification "partially or fully halogenated" is meant to
express that some or all of the hydrogen atoms in the groups thus
characterized may be replaced by identical or different halogen
atoms as mentioned above.
With respect to their biological activity, preference is given to
compounds of the formula I in which m is 0.
Likewise, preference is given to compounds of the formula I in
which R1 is methyl.
Besides, preference is given to compounds I in which R3 is
hydrogen, cyano, cyclopropyl, methyl, ethyl, 1-methylethyl or CF3.
Moreover, preference is given to compounds I in which R3 is
methyl.
Besides, preference is given to compounds I in which R3 is cyano.
Furthermore, preference is given to compounds I in which R3 is
cyclopropyl.
0050/48893
CA 02323593 2000-09-13
11
Additionally, preference is given to compounds I in which R3 is
CF3.
Additionally, preference is given to compounds I in which R5 is
hydrogen, cyclopropyl, methyl, ethyl, isopropyl, unsubstituted or
substituted aryl or hetaryl.
Moreover, preference is given to compounds I in which RS is
methyl.
Additionally, preference is given to compounds I in which R5 is
ethyl.
Moreover, preference is given to compounds I in which R5 is
isopropyl.
Moreover, preference is given to compounds I in which R5 is
cyclopropyl.
Moreover, preference is given to compounds I in which R5 is CF3.
Additionally, preference is given to compounds I in which R5 is
unsubstituted or substituted aryl or hetaryl.
Additionally, preference is given to compounds I in which R5 is
unsubstituted or substituted pyridyl, pyrimidyl, pyrazinyl,
pyridazinyl or triazinyl.
Additionally, preference is given to compounds I in which RS is
unsubstituted or substituted furyl, thienyl or pyrrolyl.
Additionally, preference is given to compounds I in which R5 is
unsubstituted or substituted oxazolyl, thiazolyl, isoxazolyl,
isothiazolyl, pyrazolyl or imidazolyl.
Additionally, preference is given to compounds I in which R5 is
unsubstituted or substituted oxdiazolyl [sic], thiadiazolyl or
triazolyl.
Moreover, preference is given to compounds I in which RS is phenyl
which is unsubstituted or carries one or two of the following
groups: nitro, cyano, hydroxyl, amino, aminocarbonyl,
aminothiocarbonyl, halogen, C1-C4-alkyl, C1-C4-haloalkyl,
C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylamino,
di-C1-C4-alkylamino, C1-C4-alkylsulfonyl, C1-C4-alkoxycarbonyl,
C1-C4-alkylaminocarbonyl or di-C1-C4-alkylaminocarbonyl.
CA 02323593 2000-09-13
0050/48893
12
Moreover, preference is given to compounds I in which R4 is
hydrogen, C1-C6-alkyl, C2-C6-alkenyl, CZ-C6-alkynyl, allyl,
arylalkyl, hetarylalkyl, aryloxyalkyl, hetaryloxyalkyl, aryl or
hetaryl.
Additionally, preference is given to compounds I in which R4 is
C1-C6-alkyl.
Further preferred compounds I are disclosed in WO 97/15,552.
The compounds I which are contained in the mixtures according to
the invention have outstanding activity against a wide range of
phytopathogenic fungi, in particular against fungi from the
classes of the Ascomycetes, Deuteromycetes, Phycomycetes and
Basidiomycetes.
They are especially important for controlling a large number of
fungi in a variety of crop plants, such as cotton, vegetable
species (for example cucumbers, beans, tomatoes, potatoes and
cucurbits), barley, grass, oats, bananas, coffee, maize, fruit
species, rice, rye, Soya, grapevine, wheat, ornamentals, sugar
cane, and a variety of seeds.
They are particularly suitable for controlling the following
phytopathogenic fungi: Erysiphe graminis (powdery mildew) in
cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in
cucurbits, Podosphaera leucotricha in apples, Uncinula necator in
grapevines, Puccinia species in cereals, Rhizoctonia species in
cotton, rice and lawns, Ustilago species in cereals and sugar
cane, Venturia inaequalis (scab) in apples, Helminthosporium
species in cereals and rice, Septoria nodorum in wheat, Botrytis
cinera [sic] (gray mold) in strawberries, vegetables, ornamentals
and grapevines, Cercospora arachidicola in groundnuts,
Pseudocercosporella herpotrichoides in wheat and barley,
Pyricularia oryzae in rice and lawns, Phytophthora infestans in
potatoes and tomatoes, Plasmopara viticola in grapevines,
Pseudoperonospora species in hops and cucumbers, Alternaria
species in vegetables and fruit, Mycosphaerella species in
bananas and Fusarium and Verticillium species.
The compound II is commercially available as a resistance inducer
(i.e. an active ingredient which immunizes against attack by
diseases), i.e. II has no direct fungicidal activity, but induces
resistance against harmful fungi in the treated plant. Compound
III is known as a fungicide.
0050/48893
CA 02323593 2000-09-13
13
When preparing the mixtures, it is preferred to employ the pure
active ingredients I and II to III, with which further active
ingredients against harmful fungi or other pests, such as
insects, arachnids or nematodes, or else herbicidal or
growth-regulating active ingredients or fertilizers can be
admixed.
The mixtures of the compounds I and at least one compound II to
III can be applied simultaneously, that is together or
separately, and have outstanding activity against a wide range of
phytopathogenic fungi, in particular from the class of the
Ascomycetes, Basidiomycetes, Phycomycetes and Deutervmycetes.
Some of them act systematically and are therefore also suitable
for use as folio and soil-acting fungicides.
They are especially important for controlling a large number of
fungi in a variety of crop plants, such as cotton, vegetable
species (for example cucumbers, beans, tomatoes, potatoes and
cucurbits), barley, grass, oats, bananas, coffee, maize, fruit
species, rice, rye, Soya, grapevine, wheat, ornamentals, sugar
cane, and a variety of seeds.
They are particularly suitable for controlling the following
phytopathogenic fungi: Erysiphe graminis (powdery mildew) in
cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in
cucurbits, Podosphaera leucotricha in apples, Uncinula necator in
grapevines, Puccinia species in cereals, Rhizoctonia species in
cotton, rice and lawns, Ustilago species in cereals and sugar
cane, Venturia inaequalis (scab) in apples, Helminthosporium
species in cereals and rice, Septoria nodorum in wheat, Botrytis
cinera [sic] (gray mold) in strawberries, vegetables, ornamentals
and grapevines, Cercospora arachidicola in groundnuts,
Pseudocercosporella herpotrichoides in wheat and barley,
Pyricularia oryzae in rice and lawns, Phytophthora infestans in
potatoes and tomatoes, Plasmopara viticola in grapevines,
Pseudoperonospora species in hops and cucumbers, Alternaria
species in vegetables and fruit, Mycosphaerella species in
bananas and Fusarium and Verticillium species.
The mixtures according to the invention are particularly
preferably utilizable for controlling Pyricularia oryzae.
The compounds I and at least one of the compounds II to III can
be applied simultaneously, either together or separately, or in
succession, the sequence, in the case of separate application,
generally not having any effect on the control results.
0050/48893
CA 02323593 2000-09-13
14
Depending on the nature of the desired effect, the application
rates of the mixtures according to the invention are, in
particular in agricultural crops, from 0.01 to 8 kg/ha,
preferably from 0.1 to 5 kg/ha, in particular from 0.5 to
3.0 kg/ha.
In the case of the compounds I, the application rates are from
0.01 to 2.5 kg/ha, preferably from 0.05 to 2.5 kg/ha, in
particular from 0.1 to 1.0 kg/ha.
Correspondingly, in the case of the compounds II to III, the
application rates are from 0.001 to 5 kg/ha, preferably from
0.005 to 2 kg/ha, in particular from 0.01 to 1.0 kg/ha.
For seed treatment, the application rates of the mixture are
generally from 0.001 to 250 g/kg of seed, preferably from 0.01 to
100 g/kg, in particular from 0.01 to 50 g/kg.
If phytopathogenic harmful fungi are to be controlled, the
separate or joint application of the compounds I and at least one
of the compounds II to III is effected by spraying or dusting the
seeds, the plants or the soils before or after sowing the plants,
or before or after plant emergence.
The fungicidal synergistic mixtures according to the invention
can be formulated for example in the form of ready-to-spray
solutions, powders and suspensions or in the form of highly
concentrated aqueous, oily or other suspensions, dispersions,
emulsions, oil dispersions, pastes, dusts, materials for
broadcasting or granules, and applied by spraying, atomizing,
dusting, broadcasting or watering. The use form depends on the
intended purpose; in any case, it should ensure as fine and
uniform as possible a distribution of the mixture according to
the invention.
The formulations are prepared in a known manner, for example by
expanding the active ingredient with solvents and/or carriers, if
desired by use of emulsifiers and dispersants. If the diluent
used is water, it is also possible to use other organic solvents
as auxiliary solvents. Suitable auxiliaries are essentially:
solvents, such as aromatics (for example xylene), chlorinated
aromatics (for example chlorobenzenes), paraffins (for example
mineral oil fractions), alcohols (for example methanol, butanol),
ketones (for example cyclohexanone), amines (for example
ethanolamine, dimethylformamide) and water; carriers, such as
ground natural minerals (for example kaolins, clays, talc, chalk)
and ground synthetic minerals (for example finely divided silica
0050/48893
CA 02323593 2000-09-13
gel, silicates); emulsifiers, such as nonionic and anionic
emulsifiers (for example polyoxyethylene fatty alcohol ethers,
alkylsulfonates and arylsulfonates), and dispersants, such as
lignosulfite waste liquors and methylcellulose.
5
Suitable surfactants are the alkali metal salts, alkaline earth
metal salts and ammonium salts of aromatic sulfonic acids, e.g.
ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic
acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl,
10 lauryl ether and fatty alcohol sulfates, and salts of sulfated
hexa-, hepta- and octadecanols, or of fatty alcohol glycol
ethers, condensates of sulfonated naphthalene and its derivatives
with formaldehyde, condensates of naphthalene or of the
naphthalenesulfonic acids with phenol and formaldehyde,
15 polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl-
or nonylphenol, alkylphenol polyglycol ethers, tributylphenyl
polyglycol ethers, alkylaryl polyether alcohols, isotridecyl
alcohol, fatty alcohol ethylene oxide condensates, ethoxylated
castor oil, polyoxyethylene alkyl ethers or polyoxypropylene
[sic], lauryl alcohol polyglycol ether acetate, sorbitol esters,
lignosulfite waste liquors or methylcellulose.
Powders, materials for broadcasting and dusts can be prepared by
mixing or jointly grinding the compounds I and at least one of
the compounds II to III or the mixture of the compounds I and at
least of a compound II to III with a solid carrier.
Granules (eg. coated granules, impregnated granules or
homogeneous granules) are usually prepared by binding the active
ingredient, or active ingredients, to a solid carrier.
Fillers or solid carriers are, for example, mineral earths, such
as silica gel, silicic acids, silica gels [sic], silicates, talc,
kaolin, limestone, lime, chalk, bole, loess, clay, dolomite,
diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium
oxide, ground synthetic materials, and fertilizers, such as
ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas,
and products of vegetable origin, such as cereal meal, tree bark
meal, wood meal and nutshell meal, cellulose powders or other
solid carriers.
The formulations generally comprise 0.1 to 95~ by weight,
preferably 0.5 to 90$ by weight, of one of the compounds I and at
least one of the compounds II to III or of the mixture of the
compounds I and at least one of the compounds II to III. The
active ingredients are employed in a purity of from 90~ to 100,
preferably from 95~ to 1008 (according to NMR or HPLC spectrum
0050/48893
CA 02323593 2000-09-13
16
[sick).
The corresponding formulations are applied by treating the
harmful fungi, their habitat or the plants, seeds, soils, areas,
materials or spaces to be kept free from them with a fungicidally
effective amount of the mixture, or of the compounds I and at
least one of the compounds II to III in the case of separate
application.
Application can be effected before or after infection by the
harmful fungi.
Examples of such preparations comprising the active ingredients
are:
'
I. A solution of 90 parts by weight of the active ingredients
and 10 parts by weight of N-methylpyrrolidone; this
solution is suitable for use in the form of microdrops;
II. A mixture of 20 parts by weight of the active ingredients,
80 parts by weight of xylene, 10 parts by weight of the
adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic
acid N-monoethanolamide, 5 parts by weight of the calcium
salt of dodecylbenzenesulfonate, 5 parts by weight of the
adduct of 40 mol of ethylene oxide and 1 mol of castor oil;
a dispersion is obtained by finely distributing the
solution in water;
III. An aqueous dispersion of 20 parts by weight of the active
ingredients, 40 parts by weight of cyclohexanone, 30 parts
by weight of isobutanol, 20 parts by weight of the adduct
of 40 mol of ethylene oxide and 1 mol of castor oil;
IV. An aqueous dispersion of 20 parts by weight of the active
ingredients, 25 parts by weight of cyclohexanol, 65 parts
by weight of a mineral oil fraction of boiling point 210 to
280~C, and 10 parts by weight of the adduct of 40 mol of
ethylene oxide and 1 mol of castor oil;
V. A mixture, ground in a hammer mill, of 80 parts by weight
of the active ingredients, 3 parts by weight of the sodium
salt of diisobutylnaphthalene-1-sulfonic acid, 10 parts by
weight of the sodium salt of a lignosulfonic acid from a
sulfite waste liquor and 7 parts by weight of pulverulent
silica gel; a spray mixture is-obtained by finely
distributing the mixture in water;
VI. An intimate mixture of 3 parts by weight of the active
ingredients and 97 parts by weight of finely divided
kaolin; this dust comprises 3~ by weight of active
ingredient;
0050/48893
CA 02323593 2000-09-13
17
VII. An intimate mixture of 30 parts by weight of the active
ingredients, 92 parts by weight of pulverulent silica gel
and 8 parts by weight of paraffin oil which had been
sprayed onto the surface of this silica gel; this
formulation imparts good adhesion to the active ingredient;
VIII. A stable aqueous dispersion of 40 parts by weight of the
active ingredients, 10 parts by weight of the sodium salt
of a phenolsulfonic acid/urea/formaldehyde condensate, 2
parts by weight of silica gel and 48 parts by weight of
water; this dispersion may be diluted further;
IX. A stable oily dispersion of 20 parts by weight of the
active ingredients, 2 parts by weight of the calcium salt
of dodecylbenzenesulfonic acid, 8 parts by weight of fatty
alcohol polyglycol ether, 20 parts by weight of the sodium
salt of a phenolsulfonic acid/urea/formaldehyde condensate
and 88 parts by weight of a paraffinic mineral oil.
25
35
45
0050/48893
CA 02323593 2000-09-13
. 18
The synergistic activity of the mixtures according to the
invention can be demonstrated by the following experiments:
The active ingredients, separately or together, are formulated as
a 10% emulsion in a mixture of 63% by weight of cyclohexanone and
27% by weight of emulsifier, and correspondingly diluted with
water to the desired concentration.
Evaluation is carried out by determining the infected leaf areas
in percent. These percentages are converted into efficacies. The
efficacy (W_) is calculated as follows using Abbot's formula:
W = (1 - a)~100/~
a corresponds to the fungal infection of the treated plants in
% and
corresponds to the fungal infection of the untreated
(control) plants in %
An efficacy of 0 means that the infection level of the treated
plants corresponds to that of the untreated control plants; an
efficacy of 100 means that the treated plants were not infected.
The expected efficacies of the mixtures of the active ingredients
were determined using Colby's formula [R. S. Colby, Weeds
20-22 (1967)] and compared with the observed efficacies.
Colby's formula: E = x + y - x~y/100
E expected efficacy, expressed in % of the untreated control,
when using the mixture of the active ingredients A and B at '
the concentrations a and b
. x efficacy, expressed in % of the untreated control, when using
active ingredient A at the concentration a
y efficacy, expressed in % of the untreated control, when using
active ingredient B at the concentration b
Use Example 1 - Activity against Pyricularia oryzae (protective)
Leaves of potted rice seedlings c.v. "Tai-Nong 67" were sprayed
to runoff point with an aqueous preparation of active ingredient
which had been prepared from a stock solution comprising 10% of
active ingredient, 63% of cyclohexanone and 27% of emulsifier.
The following day, the plants were inoculated with an aqueous
spore suspension of Pyricularia oryzae. The test plants were
subsequently placed in climatized chambers at 22 - 24~C and 95-99%
relative atmospheric humidity for 6 days. The extent of the
0050/48893
CA 02323593 2000-09-13
19
development of the disease on the leaves was then determined
visually.
The visually determined values for the percentage of diseased
leaf areas were converted into efficacies as percent of the
untreated control. An efficacy of 0 means the same disease level
as in the untreated control, an efficacy of 100 means 0% disease.
The expected efficacies for active ingredient combinations were
determined using Colby's formula (Colby, S.R. "Calculating
synergistic and antagonistic responses of herbicide
combinations", Weeds, 15, pp. 20-22, 1967) and compared with the
observed efficacies.
The following compound I' was employed as component a):
CH3
H3C.O.N~ ~N.
C O-CH3
2o CH3 ~ N
H C'
3
The test results are shown in Tables 1 and 2 below:
Table 1:
Ex. Active ingredient conc. in ppm Efficacy in ~ of
, the
untreated control
1C none (100 disease) 0
2C Compound I' 2.0 20
0.5 0
3C Compound II 2.0 0
0.5 0
4C Compound III 2.0 0
0.5 0
45
0050/48893
CA 02323593 2000-09-13
Table 2:
Ex. mixture according to Observed Calculated
the efficacy efficacy*
invention (conc. in ppm)
5 5 2 ppm I' + 2 ppm II 40 20
6 0.5 ppm I' + 0.5 ppm 20 0
II
7 2 ppm I' + 2 ppm III 50 20
10 g 0.5 ppm I' + 0.5 ppm 25 0
III
* calculated using Colby's formula
15 The test results show that for all mixing ratios the observed
efficacy is higher than the efficacy which had been calculated
beforehand using Colby's formula.
25
35
45
