FUNGICIDAL MIXTURE

MELANGE FONGICIDE

English Abstract

Disclosed is a fungicidal mixture containing the following components: a) a p-
hydroxyaniline derivative of formula (I) in which
R1 is H or optionally substituted alkyl, cycloalkyl, cycloalkenyl,
bicycloalkyl, bicycloalkenyl; R2 and R3 independently of one another
represent halogen, alkyl, alkyl halide, alkoxy, alkoxy halide; Z is H, R4-(CO)-
where R4 is optionally substituted alkyl, alkenyl, cycloalkyl,
cycloalkenyl, aryl, OR5, or NR6R7, R5 and R6 independently of one another
being optionally substituted alkyl, alkenyl, cycloalkyl,
cycloalkenyl, aryl, R7 being H, alkyl; and b) an active substance of formula
(IIA) or (IIB), in which ~ stands for a double or single
bond and the index and substituents have the meanings indicated in the
description, in a synergistically effective quantity. Also disclosed
is the use of said mixture for controlling harmful fungi.

French Abstract

L'invention concerne un mélange fongicide renfermant, en une quantité synergiquement efficace, les composants ci-après: a) un dérivé de p-hydroxy-aniline de formule (I), dans laquelle R<1> = H, alkyle, cycloalkyle, cycloalcényle, bicycloalkyle, bicycloalcényle, chacun de ces radicaux étant éventuellement substitué; R<2>, R<3> désignent, indépendamment l'un de l'autre, un halogène, un alkyle, halogénure d'alkyle, alcoxy, halogénure d'alcoxy; Z = H, R<4>-(CO)-, où R<4> désigne un alkyle, alcényle, cycloalkyle, cycloalcényle, aryle, chacun de ces radicaux étant éventuellement substitué, OR<5>, NR<6>R<7>, où R<5> et R<6> désignent, indépendamment l'un de l'autre, un alkyle, alcényle, cycloalkyle, cycloalcényle, aryle, chacun de ces radicaus étant éventuellement substitué; R<7> = H, alkyle, et b) une matière active de formule (IIA) ou (IIB), dans chacune desquelles <u>....</u> désigne une double liaison ou une liaison simple, et les indices et les substituants ont les significations données dans la description. L'invention concerne également l'utilisation dudit mélange pour lutter contre les champignons parasites.

Claims

29
We claim:
1. A fungicidal mixture comprising
a) a p-hydroxyaniline derivative of the formula I
<IMG>
where the radicals have the following meanings:
R1 is hydrogen, C1-C8-alkyl which can be partially or
fully halogenated and/or can have attached to it one
or two of the following groups: C1-C4-alkoxy,
C1-C4-haloalkoxy, C1-C4-alkylthio, C3-C7-cycloalkyl,
C5-C7-cycloalkenyl, it being possible for the cyclic
groups, in turn, to have attached to them one to
three halogen atoms, C1-C3-alkyl groups and/or
C1-C3-alkoxy groups, and aryl which can be partially
or fully halogenated and/or can have attached to it
one to three of the following substitutents: nitro,
cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy and C1-C4-alkylthio;
C3-C6-cycloalkyl or C3-C6-cycloalkenyl, it being pos-
sible for these radicals to be partially or fully
halogenated and/or to have attached to them one to
five of the following groups: C1-C4-alkyl, C1-C4-
haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and aryl
which can be partially or fully halogenated and/or
can have attached to it one to three of the following
substituents: nitro, cyano, C1-C4-alkyl, C1-C4-halo-
alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and C1-C4-al-
kylthio;
C6-C15-bicycloalkyl or C7-C15-bicycloalkenyl, it being
possible for these radicals to be partially or fully
halogenated and/or to have attached to them one to
five of the following groups: C1-C4-alkyl,
C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and
aryl which can be partially or fully halogenated and/
or can have attached to it one to three of the follo-
wing substituents: nitro, cyano, C1-C4-alkyl,

30
C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and
C1-C4-alkylthio;
R2 and R3 independently of one another are halogen,
C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-
haloalkoxy;
Z is 8 or R4-(CO)- where
R4 is C1-C6-alkyl or C2-C6-alkenyl, it being pos-
sible for these groups to be partially or fully
halogenated and/or to have attached to them one
of the following radicals: C1-C4-alkoxy,
C1-C4-haloalkoxy, C1-C4-alkylthio, C3-C7-cyclo-
alkyl, C5-C7-cycloalkenyl or aryl, it being pos-
sible for the aromatic radicals, in turn, to
have attached to them one to three of the
following groups: nitro, cyano, halogen, C1-C4-
alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-
haloalkoxy and C1-C4-alkylthio;
C3-C7-cycloalkyl or C5-C7-cycloalkenyl, it being
possible for these groups to have attached to
them one to three of the following radicals:
halogen, C1-C4-alkyl, C1-C4-haloalkyl and
C1-C4-alkoxy;
aryl which can be partially or fully halogenated
and/or can have attached to it one to three of
the following radicals: nitro, cyano,
C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy and C1-C4-alkylthio;
OR5 or NR6R7 where
R5 is C1-C6-alkyl or C2-C6-alkenyl, it being
possible for these groups to be partially or
fully halogenated and/or to have attached to
them one of the following radicals:
C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkyl-
thio, C3-C7-cycloalkyl, C5-C7-cycloalkenyl or
aryl, it being possible for the aromatic ra-
dicals, in turn, to have attached to them
one to three of the following groups: nitro,
cyano, halogen, C1-C4-alkyl, C1-C4-haloalkyl,

31
C1-C4-alkoxy, C1-C4-haloalkoxy and C1-C4-al-
kylthio;
C3-C7-cycloalkyl or C5-C7-cycloalkenyl, it
being possible for these groups to have
attached to them one to three of the follow-
ing radicals: halogen, C1-C4-alkyl, C1-C4-
haloalkyl and C1-C4-alkoxy;
aryl, which can be partially or fully halo-
genated and/or can have attached to it one
to three of the following radicals: nitro,
cyano, C1-C4-alkyl, C1-C4-haloalkyl,
C1-C4-alkoxy, C1-C4-haloalkoxy and
C1-C4-alkylthio;
R6 is C1-C6-alkyl or C2-C6-alkenyl, it being
possible for these groups to be partially or
fully halogenated and/or to have attached to
them one of the following radicals:
C1-C4-alkylthio, C3-C7-cycloalkyl,
C5-C7-cycloalkenyl or aryl, it being possi-
ble for the aromatic radicals, in turn, to
have attached to them one to three of the
following groups: nitro, cyano, halogen,
C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy and C1-C4-alkylthio;
C3-C7-cycloalkyl or C5-C7-cycloalkenyl, it
being possible for these groups to have
attached to them one to three of the
following radicals: halogen, C1-C4-alkyl,
C1-C4-haloalkyl and C1-C4-alkoxy;
aryl which can be partially or fully halo-
genated and/or can have attached to it one
to three of the following radicals: nitro,
cyano, C1-C4-alkyl, C1-C4-haloalkyl,
C1-C4-alkoxy, C1-C4-haloalkoxy and C1-C4-
alkylthio; and
R7 is hydrogen or C1-C6-alkyl,
and
b) an active ingredient of the formula IIA or IIB

32
<IMGS>
where ~~is a double or single bond and the index and
the substituents have the following meanings:
R' -C(CO2CH3]=CHOCH3, -C[CO2CH3]=NOCH3,
-C(CONHCH3]=NOCH3, -C[CO2CH3]=CHCH3,
-C[CO2CH3]=CHCH2CH3, -C(COCH3]=NOCH3,
-C[COCH2CH3]=NOCH3, -N(OCH3)-CO2CH3,
-N(CH3)-CO2CH3, -N(CH2CH3)-CO2CH3;
R" is a C-organic radical which is bonded directly or
via an oxy, mercapto, amino or alkylamino group;
together with a group X and the ring Q or T to which
it is bonded is an unsubstituted or substituted bicy-
clic, partially or fully unsaturated system which,
besides carbon ring members, may contain hetero atoms
from the group consisting of oxygen, sulfur and
nitrogen;
Rx -OC[CO2CH3]=CHOCH3, -OC[COCH3]=CHCH3,
-OC[CO2CH3]=CHCH2CH3, -SC(CO2CH3]=CHOCH3,
-SC[CO2CH3]=CHCH3, -SC[CO2CH3]=CHCH2CH3,
-N(CH3)C[CO2CH3]=CHOCH3, -N(CH3)C[CO2CH3]=NOCH3,
-CH2C[CO2CH3]=CHOCH3, -CH2C[CO2CH3]=NOCH3,
-CH2C[CONHCH3]=NOCH3;
Ry is oxygen, sulfur, =CH- or =N-;
n is 0, 1, 2 or 3, it being possible for the radicals X
to be different when n > 1;
X is cyano, nitro, halogen, C1-C4-alkyl, C1-C4-halo-
alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkyl-
thio;
in the event that n > 1, a C3-C5-alkylene, C3-C5-al-
kenylene, oxy-C2-C4-alkylene, oxy-C1-C3-
alkyleneoxy, oxy-C2-C4-alkenylene,
oxy-C2-C4-alkenyleneoxy or butadienediyl group which

33
is bonded to two adjacent C atoms of the phenyl ring,
it being possible for these chains, in turn, to have
attached to them one to three of the following radi-
cals: halogen, C1-C4-alkyl, C1-C4-haloalkyl,
C1-C4-alkoxy, C1-C4-haloalkoxy or C1-C4-alkylthio,
Y is =C- or -N-;
Q is phenyl, pyrrolyl, thienyl, furyl, pyrazolyl,
imidazolyl, oxazolyl, isoxazolyl, thiazolyl, thiadia-
zolyl, triazolyl, pyridinyl, 2-pyridinyl, pyrimidinyl
and triazinyl; and
T is phenyl, oxazolyl, thiazolyl, thiadiazolyl, oxadia-
zolyl, pyridinyl, pyrimidinyl and triazinyl,
in a synergistically active amount.
2. A mixture as claimed in claim 1, wherein, in the compounds I
as set forth in claim 1, Z is hydrogen.
3. A mixture as claimed in claim 2, wherein the compound I as
set forth in claim 1 is a compound from the table which fol-
lows:
<IMG>

34
4. A fungicidal mixture as claimed in any of claims 1 to 3,
wherein the weight ratio of the compound I to the compound
IIA or IIB is 20:1 to 0.05:1.
5. A method of controlling harmful fungi, which comprises treat-
ing the harmful fungi, their environment, or the plants,
seeds, soils, areas, materials or spaces to be kept free from
them, with a compound of the formula I as set forth in claim
1 and a compound of the formula IIA or IIB as set forth in
claim 1.
6. A method as claimed in claim 5, wherein the compound I as set
forth in claim 1 and the compound IIA or IIB, as set forth in
claim 1 are applied simultaneously, namely together or sepa-
rately, or in succession.
7. A method as claimed in claim 5 or 6, wherein the compound I
as set forth in claim 1 is applied in an amount of 0.05 to
1 kg/ha.
8. A method as claimed in any of claims 5 to 7, wherein the com-
pound IIA or IIB as set forth in claim 1 is applied in an
amount of 0.01 to 1 kg/ha.
9. A method of preparation of a fungicidal mixture, which
comprises mixing a compound I as set forth in claim 1
with a compound IIA or IIB as also set forth in claim
1, in a synergistically active amount.

Description

CA 02235039 1998-OS-07
Fungicidal mixture
The present invention relates to a fungicidal mixture comprising
a) a p-hydroxyaniline derivative of the formula I
R3 R2
O
ZO ~ ~ NH-C-R1
where the radicals have the following meanings:
R1 is hydrogen, C1-Cg-alkyl which can be partially or fully
halogenated and/or can have attached to it one or two of
the following groups: C1-C4-alkoxy, C1-C4-haloalkoxy,
C1-C4-alkylthio, C3-C~-cycloalkyl, CS-C7-cycloalkenyl, it
being possible for the cyclic groups, in turn, to have
attached to them one to three halogen atoms, C1-C3-alkyl
groups and/or C1-C3-alkoxy groups, and aryl which can be
partially or fully halogenated and/or can have attached
to it one to three of the following substitutents: nitro,
cyano, C1-Cq-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy and C1-C4-alkylthio;
C3-C6-cycloalkyl or C3-C6-cycloalkenyl, it being possible
for these radicals to be partially or fully halogenated
and/or to have attached to them one to five of the
following groups: C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-al-
koxy, C1-C4-haloalkoxy and aryl which can be partially or
fully halogenated and/or can have attached to it one to
three of the following substituents: nitro, cyano,
C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloal-
koxy and C1-C4-alkylthio;
C6-C15-bicycloalkyl or C~-C15-bicycloalkenyl, it being
possible for these radicals to be partially or fully
halogenated and/or to have attached to them one to five
of the following groups: C1-C4-alkyl, CI-C4-haloalkyl,
C1-C4-alkoxy, C1-C4-haloalkoxy and aryl which can be
partially or fully halogenated and/or can have attached
to it one to three of the following substituents: nitro,
cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy and C1-C4-alkylthio;

CA 02235039 1998-OS-07
2
Rz and R3 independently of one another are halogen,
C1-Cq-alkyl, C1-Cq-haloalkyl, C1-Cq-alkoxy or C1-Cq-halo-
alkoxy;
Z is H or Rq-(CO)- where
Rq is C1-C6-alkyl or CZ-C6-alkenyl, it being possible
for these groups to be partially or fully halogenated
and/or to have attached to them one of the following
radicals: C1-Cq-alkoxy, C1-Cq-haloalkoxy, C1-Cq-alkyl-
thio, C3-C~-cycloalkyl, CS-C~-cycloalkenyl or aryl,
it being possible for the aromatic radicals, in turn,
to have attached to them one to three of the follo-
wing groups: nitro, cyano, halogen, C1-Cq-alkyl,
C1-Cq-haloalkyl, C1-Cq-alkoxy, C1-Cq-haloalkoxy and
C1-Cq-alkylthio;
C3-C7-cycloalkyl or C5-C7-cycloalkenyl, it being pos
sible,for these groups to have attached to them one
to three of the following radicals: halogen,
C1-Cq-alkyl, C1-Cq-haloalkyl and C1-Cq-alkoxy;
aryl which can be partially or fully halogenated and!
or can have attached to it one to three of the
following radicals: vitro, cyano, C1-Cq-alkyl,
C1-Cq-haloalkyl, C1-Cq-alkoxy, C1-Cq-haloalkoxy and
CI-Cq-alkylthio;
OR5 or NR6R7 where
R5 is C1-C6-alkyl or C2-C6-alkenyl, it being pos-
sible for these groups to be partially or fully
halogena~ed and/or to have attached to them one
of the following radicals: C1-Cq-alkoxy,
C1-Cq-haloalkoxy, C1-Cq-alkylthio, C3-C7-cyclo-
alkyl, CS-C7-cycloalkenyl or aryl, it being
possible for the aromatic radicals, in turn, to
have attached to them one to three of the follo-
wing groups: vitro, cyano, halogen, Ci-Cq-alkyl,
C1-Cq-haloalkyl, C1-Cq-alkoxy, C1-Cq-haloalkoxy
and C1-Cq-alkylthio;
C3-C7-cycloalkyl or CS-C7-cycloalkenyl, it being
possible for these groups to have attached to
them one to three of the following radicals:

., CA 02235039 1998-OS-07
3
halogen, C1-C4-alkyl, C1-C4-haloalkyl and
C1-C4-alkoxy;
aryl, which can be partially or fully halo-
genated and/or can have attached to it one to
three of the following radicals: nitro, cyano,
C1-C~-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy and C1-C4-alkylthio;
R6 is C1-C6-alkyl or C2-C6-alkenyl, it being pos-
sible for these groups to be partially or fully
halogenated and/or to have attached to them one
of the following radicals: C1-C4-alkylthio,
C3-C7-cycloalkyl, C5-C~-cycloalkenyl or aryl, it
being possible for the aromatic radicals, in
turn, to have attached to them one to three of
the following groups: nitro, cyano, halogen,
C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy and C1-C4-alkylthio;
ao
C3-C7-cycloalkyl or C5-C7-cycloalkenyl, it being
possible for these groups to have attached to
them one to three of the following radicals:
halogen, C1-C4-alkyl, C1-C4-haloalkyl and
C1-C4-alkoxy;
aryl which can be partially or fully halogenated
and/or can have attached to it one to three of
the following radicals: vitro, cyano,
C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy and C1-C4-alkylthio; and
and
R7 is hydrogen or C1-C6-alkyl,
b) an active ingredient of the formula IIA or IIB
/R. /Rx
Y C
Xn Q , ( Xn T , ~ RY
~R" ~R"
IIA IIB

t CA 02235039 1998-OS-07
a
4
where . is a double or single bond and the index and the
substituents have the following meanings:
R' -C[COyCH3]=CHOCH3, -C[COyCH3]=NOCH3, -C[CONHCH3]=NOCH3,
-C[C02CH3]=CHCH3, -C[COaCH3]=CHCH2CH3, -C[COCH3]=NOCH3,
-C[COCH2CH3]=NOCH3, -N(OCH3)-C02CH3,
-N(CH3)-COyCH3, -N(CHyCH3)-COyCH3;
R" is a C-organic radical which is bonded directly or via an
oxy, mercapto, amino or alkylamino group;
together with a group X and the ring Q or T to which they
are [sic] bonded is an unsubstituted or substituted bicy-
clic, partially or fully unsaturated system which, besi-
des carbon ring members, may contain hetero atoms from
the group consisting of oxygen, sulfur and nitrogen;
RX -OC[COyCHg]=CHOCH3, -OC[COyCH3]=CHCHg,
-OC[C02CH3]=CHCHyCHg, -SC[COyCH3]=CHOCH3,
-SC[C02CH3]=CHCH3, -SC[C02CH3]=CHCH2CH3,
-N(CH3)C[C02CH3]=CHOCH3, -N(CH3)C[C02CH3]=NOCH3,
-CH2C[COgCH3]=CHOCH3, -CH2C[COyCH3]=NOCH3,
-CH2C[CONHCH3]=NOCH3;
Ry is oxygen, sulfur, =CH- or =N-;
n is 0, 1, 2 or 3, it being possible for the radicals X to
be different when n > 1;
X is cyano, nitro, halogen, C~-C4-alkyl, C1-C4-haloalkyl,
C1-C4-alkoxy, Cl-C4-haloalkoxy, C1-C4-alkylthio;
in the event that'n > 1, a C3-C5-alkylene, C3-C5-alkenyl-
ene, oxy-Ca-C4-alkylene, oxy-C1-C3-alkyleneoxy,
oxy-C2-C4-alkenylene, oxy-CZ-C4-alkenyleneoxy or butadie-
nediyl group which is bonded to two adjacent C atoms of.
the phenyl ring, it being possible for these chains, in
turn, to have attached to them one to three of the
following radicals: halogen, C1-C4-alkyl, C1-C4-haloalkyl,
C1-C4-alkoxy, C1-C4-haloalkoxy or C1-C4-alkylthio;
Y =C- or -N-;

CA 02235039 2004-02-24
Q is phenyl, pyrrolyl, thienyl, furyl, pyrazolyl, imida-
zolyl, oxazolyl, isoxazolyl, thiazolyl, thiadiazolyl,
triazolyl, pyridinyl, 2-pyridinyl, pyrimidinyl and tria-
zinyl; and
T is phenyl, oxazolyl, thiazolyl, thiadiazolyl, oxadia-
zolyl, pyridinyl, pyrimidinyl and triazinyl,
in a synergistically active amount.
Compounds of the formula I are disclosed in EP-A 339 418,
EP-A 653 417, EP-A 653 418 and DE-A 195 04 599 and DE-A
195 40 970.
Compounds of the formula I which are preferably suitable for the
mixtures according to the invention are those in Table I.1.
Table I.1: Preferred compounds of the formula I
R3 R2
O
ll
HO ~ ~ NH- C- Rl
130. R3 R2 R1 References*
)
I.1.1 C1 C1 C(CH3)g--- CHy~CH3 (A), (C), (D)
I.1.2 F CH3 C(CH3)2-CH3 (A), (C), (D)
I.1.3 F CH3 C(CH3)2-CH2-Cl (A), (C), (D)
I.1.4 F CH3 C(CH3)2--- CH2~C1 (A) ~ (C),
(D)
I.1.5 C1 CH3 C(CH3)2-CH2CH2CH3 {A), (C), (D)
I.1.6 F CH3 C(CH3)2-CH2CHZCH3 (A), (C), (D)
I.1.7 F CH3 C{CH3)2-CH2Br (A), (C), (D)
I.1.8 C1 C1 C(CH3)2-CH3 (A), (C), (D)
I.1.9 C1 C1 C(CH3)2-CH2Br (A), (C), (D)
I.1.10 C1 CH3 C(CH3)2-CH2C1 (A), (C), (D)
I1.11 C1 CH3 C(CH3)2-CHZBr (A), (C), (D)
I.1.12 C1 CH3 C(CH3)2-CH3 (A), (C), (D)
I.1.13 C1 CH3 C(CH3)2--- CHz~ C1 (A), (C), (D)
I.1.14 C1 CH3 2-CH3-[2.2.1]-heptan-2-yl(B), (C), (D)

CA 02235039 1998-OS-07
6
*) (A) = EP-A 653 417
(B) = EP-A 653 418
(C) = German Patent Application File Ref. No. 195 04 599.8
(D) = German Patent Application File Ref. No. 195 40 970.I_
Especially preferred compounds of the formula I are those of Ta-
ble I.2.
Table I.2: Especially preferred compounds of the formula I
(References and formula as in Table I.1)
No. R3 R2 R1 References
I.2.1 C1 C1 C(CH3)Z-CHyCl (A),(C), (D)
I.2.2 C1 C1 C(CH3)y-CH2CH3 (A),(C), (Dj
I.2.3 Cl C1 C(CH3)y-CHaCHaCH3 (A),(C), (Dj
I.2.4 C1 C1 C(CH3)2-CH2 ~ ~ C1 (A)i(C)r (D)
I.2.5 C1 C1 2-CH3-[2.2.1)-heptan-2-yl (B),(C), (Dj
I.2.6 C1 C1 2-CH3-[2.2.1-hepten-2-yl (B),(C), (D)
I.2.7 C1 C1 1-CH3-cyclohexyl EP-A 418
339
The active ingredients IIA and IIB are described, for example, in
the following publications: EP-A 178 826, EP-A 203 606,
EP-A 203 608, EP-A 206 523, EP-A 212 859, EP-A 226 917,
EP-A 229 974, EP-A 242 070, EP-A 242 081, EP-A 243 012,
EP-A 243 014, EP-A 251 082, EP-A 253 213, EP-A 254 426,
EP-A 256 667, EP-A 260 794, EP-A 260 832, EP-A 26? 734,
EP-A 273 572, EP-A 274 825, EP-A 278 595, EP-A 280 185,
EP-A 291 196, EP-A 299 694, EP-A 307 101, EP-A 307 103,
EP-A 310 954, EP-A 312 221, EP-A 312 243, EP-A 329 011,
EP-A 331 966, EP-A 335 519, EP-A 336 211, EP-A 337 211,
EP-A 341 845, EP-A 350 691, EP-A 354 571, EP-A 363 818,
EP-A 370 629, EP-A 373 775, EP-A 374 811, EP-A 378 308,
EP-A 378 755, EP-A 379 098, EP-A 382 375, EP-A 383 117,
EP-A 384 211, EP-A 385 224, EP-A 385 357, EP-A 386 561,
EP-A 386 681, EP-A 389 901, EP-A 391 451, EP-A 393 428,
EP-A 393 861, EP-A 398 692, EP-A 400 417, EP-A 402 246,
EP-A 405 782, EP-A 407 873, EP-A 409 369, EP-A 414 153,
EP-A 416 746, EP-A 420 091, EP-A 422 597, EP-A 426 460,
EP-A 429 968, EP-A 430 471, EP-A 433 233, EP-A 433 899,
EP-A 439 785, EP-A 459 285, EP-A 460 575, EP-A 463 488,
EP-A 463 513, EP-A 464 381, EP-A 468 684, EP-A 468 695,
EP-A 468 775, EP-A 471 261, EP-A 472 224, EP-A 472 300,
EP-A 474 042, EP-A 475 158, EP-A 477 631, EP-A 480 795,
EP-A 483 851, EP-A 483 985, EP-A 487 409, EP-A 493 711,

CA 02235039 1998-OS-07
7
EP-A 498 188, EP-A 498 396, EP-A 499 823, EP-A 503 436,
EP-A 508 901, EP-A 509 857, EP-A 513 580, EP-A 515 901,
EP-A 517 301, EP-A 528 245, EP-A 532 022, EP-A 532 126,
EP-A 532 127, EP-A 535 980, EP-A 538 097, EP-A 544 587,
EP-A 546 387, EP-A 548 650, EP-A 564 928, EP-A 566 455,
EP-A 567 828, EP-A 571 326, EP-A 579 071, EP-A 579 124,
EP-A 579 908, EP-A 581 095, EP-A 582 902, EP-A 582 925,
EP-A 583 806, EP-A 584 625, EP-A 585 751, EP-A 590 610,
EP-A 596 254, WO-A 90/07,493, WO-A 92/13,830, WO-A 92/18,487,
WO-A 92/18,494, WO-A 92/21,653, WO-A 93/07,116, WO-A 93/08,180,
WO-A 93/08,183, WO-A 93/15,046, WO-A 93/16,986, WO-A 94/00,436,
WO-A 94/05,626, WO-A 94/08,948, WO-A 94/08,968, WO-A 94/10,159,
WO-A 94/11,334, JP-A 02/121,970, JP-A 04/182,461,
JP-A 05/201,946, JP-A 05/201,980, JP-A 05/255,012,
JP-A 05/294,948, JP-A 06/025,133, JP-A 06/025,142,
JP-A 06/056,756, FR-A 2 670 781, GB-A 2 210 041, GB-A 2 218 702,
GB-A 2 238 308, GB-A 2 249 092, GB-A 2 253 624, GB-A 2 255 092,
DE-A 39 05 911, DE Pat. Appl. 43 05 502.8,
DE Pat. Appl. 43 10 143.7, DE Pat. Appl. 43 18 397.2,
DE Pat. Appl. 43 34 709.6, DE Pat. Appl. 44 03 446.6,
DE Pat. Appl. 44 03 447.4, DE Pat. Appl. 44 03 448.2,
DE Pat. Appl. 44 10 424.3, DE Pat. Appl. 44 21 180.5,
DE Pat. Appl. 44 21 182.1, DE Pat. Appl. 44 15 483.6,
DE Pat. Appl. 44 23 615.8 and DE Pat. Appl. 44 23 612.3.
a5
It is an object of the present invention to enhance the fungi-
cidal action of the compounds I by mixing them with suitable
other fungicides.
We have found that this object is achieved and harmful fungi can,
in principle, be controlled more efficiently when a further acti-
ve ingredient of the formula IIA or of the formula IIB is used in
addition to an active ingredient I.
The harmful fungus is controlled more efficiently by using the
combination of the active ingredients I and IIA or IIB according
to the invention since lower rates of application of the indivi-
dual active ingredients are required (synergism).
All compounds of type IIA or IIB mentioned in the publications
mentioned at the outset are suitable for the mixtures according
to the invention.
Compounds IIA and IIB where R" is one of the groups below are es-
pecially important:

CA 02235039 1998-OS-07
8
unsubstituted or substituted aryloxy, unsubstituted or substitu-
ted hetaryloxy, unsubstituted or substituted aryloxymethylene,
unsubstituted or substituted hetaryloxymethylene, unsubstituted
or substituted arylethenylene, unsubstituted or substituted heta-
rylethenylene, or a group
RCCR~C=NOCHZ- or RYON=CR~CRE=NOCHa where the radicals ROC, R~ Ry, RS
and RE in general and in particular have the meanings described in
the following publications: EP-A 370 629, EP-A 414 153, EP-A 426
460, EP-A 460 575, EP-A 463 488, EP-A 472 300, EP-A 498 188,
EP-A 498 396, EP-A 515 901, EP-A 585 751, WO-A 90/07,493,
WO-A 92/13,830, WO-A 92/18,487, WO-A 92/18,494, WO-A 93/15,046,
WO-A 93/16,986, WO-A 94/08,948, WO-A 94/08,968, JP-A 0'5/201,946,
JP-A 05/255,012, JP-A 05/294,948, JP-A 06/025,133,
Jp-A 06/025,142, DE Pat. Appl. 44 03 447.., DE Pat. Appl. 44 03
448.., DE Pat. Appl. 44 21 180.5 and DE Pat. Appl. 44 21 182.1;
especially preferred radicals "unsubstituted or substituted aryl-
oxy, unsubstituted or substituted hetaryloxy" in general and in
particular have the meanings described in the following publica-
tions: EP-A 178 826, EP-A 242 070, EP-A 242 081, EP-A 253 213,
EP-A 254 426, EP-A 256 667, EP-A 260 794, EP-A 280 185, EP-A 307
103, EP-A 341 845, EP-A 382 375, EP-A 393 861, EP-A 398 692,
EP-A 405 782, EP-A 430 471, EP-A 468 684, EP-A 468 695,
EP-A 477 631, EP-A 483 985, EP-A 498 188, EP-A 513 580,
EP-A 515 901, WO-A 93/15,046, WO-A 94/10,159, GB-A 2 253 624,
JP-A 04/182,461 and DE Pat. Appl. 44 23 612.3;
especially preferred radicals "unsubstituted or substituted
aryloxymethylene, unsubstituted or substituted hetaryloxymethy-
lene" in general and in particular have the meanings described in
the following publications: EP-A 178 826, EP-A 226 917, EP-A 253
213, EP-A 254 426, EP-A 27$ 595, EP-A 280 185, EP-A 299 694,
EP-A 335 519, EP-A 350 691, EP-A 363 818, EP-A 373 775,
Ep-A 378 308, EP-A 385 224, EP-A 386 561, EP-A 398 692,
EP-A 400 417, EP-A 407 873, EP-A 472 224, EP-A 477 631,
EP-A 498 188, EP-A 498 396, EP-A 513 580, EP-A 515 901,
EP-A 579 124, WO-A 93/08,180, WO-A 93/15,046, WO-A 94/00,436,
JP-A 04/182,461, DE Appl. No. 43 05 502.., DE Appl. No. 44 10
424.. and DE Pat. Appl. 44 15 483.6;
especially preferred radicals "unsubstituted or substituted aryl-
ethenylene, unsubstituted or substituted hetarylethenylene" in
general and in particular have the meanings described in the fol-
lowing publications: EP-A 178 826, EP-A 203 606, EP-A 253 213,
EP-A 254 426, EP-A 280 185, EP-A 378 755, EP-A 398 692,
EP-A 402 246, EP-A 474 042, EP-A 475 158, EP-A 477 631,

CA 02235039 1998-OS-07
9
EP-A 487 409, EP-A 498 188, EP-A 498 396, EP-A 513 580,
EP-A 515 901, EP-A 528 245, EP-A 544 587, WO-A 93/15,046,
WO-A 94/11,334, FR-A 2 670 781 and DE Pat. Appl. 44 23 615.8;
especially preferred active ingredients of the formula IIA where
R' is -C[COaCH3]=CHOCHg generally and in particular have the mean-
ings of the compounds described in the following publications:
EP-A 178 826, EP-A 203 606, EP-A 226 9I7, EP-A 242 070,
EP-A 242 081, EP-A 256 667, EP-A 260 794, EP-A 278 595,
EP-A 299 694, EP-A 307 103, EP-A 335 519, EP-A 341 845,
EP-A 350 691, EP-A 370 629, EP-A 373 775, EP-A 378 308,
EP-A 378 755, EP-A 382 375, EP-A 385 224, EP-A 386 561,
EP-A 393 861, EP-A 402 246, EP-A 405 782, EP-A 407 873,
EP-A 414 153, EP-A 426 460, EP-A 430 471, EP-A 463 488,
EP-A 468 695, EP-A 472 224, EP-A 474 042, EP-A 475 158,
EP-A 483 985, EP-A 487 409, EP-A 515 901, EP-A 528 245,
EP-A 544 587, WO-A 90/07,493, WO-A 92/18,487, WO-A 92/18,494,
WO-A 93/08,180, WO-A 93/16,986, WO-A 94/00,463, WO-A 94/08,948,
WO-A 94/08,968, WO-A 94/10,159, WO-A 94/11,334, FR-A 2 670 781,
JP-A 06/025,133, DE Appl. No. 44 03 447.., DE Appl. No. 44 10
424.. and DE Pat. Appl. 44 21 180.5;
especially preferred active ingredients of type II where R' is
-C[COaCH3]=NOCH3 generally and in particular have the meanings of
the compounds described in the following publications: EP-A 253
213, EP-A 254 426, EP-A 299 694,
EP-A 363 818, EP-A 378 308, EP-A 385 224, EP-A 386 561,
EP-A 400 417, EP-A 407 873, EP-A 460 575, EP-A 463 488,
EP-A 468 684, EP-A 472 300, EP-A 515 901, WO-A 94/00,436,
WO-A 94/08,948, WO-A 94/10,159, WO-A 94/11,334, JP-A 05/201,946,
JP-A 05/255,012, JP-A 05/294,948, DE Appl. No. 44 03 447..,
DE Appl. No. 44 10 424.. and DE Pat. Appl. 44 21 180.5;
especially preferred active ingredients of type II where R' is
-C[CONHCH3]=NOCH3 generally and in particular have the meanings of
the compounds described in the following publications:
EP-A 398 692, EP-A 463 488, EP-A 477 631, EP-A 515 901,
EP-A 579 124, EP-A 585 751, WO-A 92/13,830, WO-A 93/08,180,
WO-A 94/08,948, WO-A 94/10,159, WO-A 94/11,334, GB-A 2 253 624,
JP-A 04/182,461, JP-A 05/201,946, JP-A 05/255,012,
JP-A 05/294,948, DE Appl. No. 43 05 502.., DE Appl.
No. 44 03 448.., DE Appl. No. 44 10 424.., DE Pat. Appl.
No. 44 23 615.8 and DE Pat. Appl. 44 21 182.1;
especially preferred active ingredients of type II where R' is
-C[COZCH3]=CHCH3 or -C[COZCH3]=CHCH2CH3 generally and in particular
have the meanings of the compounds described in the following

CA 02235039 1998-OS-07
a
10
publications: EP-A 280 185, EP-A 463 488, EP-A 501 901,
EP-A 513 580, EP-A 515 901, DE Appl. No. 44 03 447.., DE Appl.
No. 44 IO 424.., DE Pat. Appl. No. 44 21 180.5 and DE Pat. Appl.
No. 44 15 483.6;
especially preferred active ingredients of type II where R' is
-C[COCH3]=NOCH3 or -C[COCHZCH3]=NOCH3 generally and in particular
have the meanings of the compounds described in EP-A 498 188;
especially preferred active ingredients of type II where R' is
-N(OCH3)C02CH3, -N(CH3)-C02CH3 or -N(CH2CH3)-C02CH3 generally and in
particular have the meanings of the compounds described in the
following publications: EP-A 498 396, WO-A 93/15,046,
JP-A 06/025,142 and DE Pat. Appl. 44 23 612.3;
especially preferred active ingredients of type II where R' is
-OC[COyCH3]=CHOCHg, -OC[COyCH3]=CHCHg, -OC[COyCH3]=CHCHyCH3,
-OC[COCHZCH3]=NOCH3, -SC[COZCH3]=CHOCH3, -SC[COyCH3]=CHCH3,
-SC[C02CH3]=CHCHZCH3, -N(CH3)C[COyCH3]=CHOCH3,
-N(CH3)C[C02CH3]=NOCH3, -CHzC[C02CH3]=CHOCH3, -CH2C[C02CH3]=NOCH3 or
-CH2C[CONHCH3]=NOCH3 generally and in particular have the meanings
of the compounds described in the following publications:
EP-A 212 859, EP-A 331 966, EP-A 383 117, EP-A 384 211,
EP-A 389 901, EP-A 409 369, EP-A 464 381, EP-A 471 261,
EP-A 503 436, EP-A 546 387, EP-A 548 650, EP-A 579 908 and
EP-A 584 625.
Examples of especially suitable active ingredients of type II are
compiled in the tables which follow.
Table II.lA
Compounds of the formula IIA where Q is phenyl, R' is
-C(C02CH3)=CHOCH3, n has a value of 0, R" is unsubstituted or sub-
stituted (het)aryloxymethylene, the unsubstituted or substituted
(het)aryl group having the following meanings:
45

CA 02235039 1998-OS-07
11
No. unsubstituted or substituted Reference
(het)aryl
II.lA-1 2-CH3-CgH4 EP-A 226 917
II.lA-2 2,5-(CH3)y-C6H3 EP-A 226 917
II.lA-3 2-CH3, 4-C[CH3]=NOCH3-C6H3 EP-A 386 561
il.lA-4 2-CH2CHyCH3, 6-CF3-pyrimidin-4-ylEP-A 407 873
II.lA-5 2,4-(CH3)g-C6H3 EP-A 226 917
Table II.1B
Compounds of the formula IIA where R' is -C(C02CHg)=CHOCHg , Q is
phenyl, n has a value of 0, R" is unsubstituted or substituted
(het)aryloxy, the unsubstituted or substituted (het)aryl group
having the following meanings:
No. unsubstituted or substituted Reference
(het)aryl
II.1B-1 C6H5 EP-A 178 826
II.1B-2 6-[2-CN-C6H4-O]-pyrimidin-4-yl EP-A 382 375
9
Table II.1C
Compounds of the formula IIA where R' is -C(C02CH3)=CHOCH3, Q is
phenyl, n has a value of 0, R" is unsubstituted or substituted
(het)arylethenylene, the unsubstituted or substituted (het)aryl
group having the following meanings:
No. unsubstituted or substituted Reference
(het)arpl
Ii.iC-1 1-(2,4-C12-C6H3),,5-CF3-pyrazol-4-ylEP-A 528 245
II.1C-2 1-(4-Cl-C6H4)-pyrazol-4-yl EP-A 378 755
II.1C-3 3-CFg-C6H4 EP-A 203 606
II.1C-4 3-C1-C6H4 EP-A 203 606
II.1C-5 4-C6H5-C6H4 EP-A 203 606
45

CA 02235039 1998-OS-07
12
Table II.1D
Compounds of the formula IIA where Q is phenyl, R' is
-C(COyCH3)=CHOCH3, n has a value of 0, R" is CHaON=CRaR~ , R°' and
R~ having the following meanings:
No. Ra R Reference
II.1D-1 CH3 4-Cl-C6H4 EP-A 370 629
II.1D-2 CH3 3-CF3-C6H4 EP-A 370 629
II.iD-3 CH3 4-OCH2CH3-pyrimidin-2-yl WO-A 92/18,487
Table
II.lE
Compounds of the IIA
formula where
Q
is
phenyl,
R'
is
-C(COzCH3)=CHOCH3, a CH20N=CRYCRB=NORE,

n value RY,
has of
0,
R"
is
Rs having
and the
RE following
meanings:
No. R R R~ Reference
II.lE-1 CH3 CH3 CH3 DE Appl.No. 44 03 447.4
II.lE-2 CH3 CH3 CHyCH3 DE Appl.No. 44 03 447.4
II.lE-3 CH3 C6H5 CH3 DE Appl.No. 44 03 447.4
II.lE-4 CH3 C6H5 CHyCH3 DE Appl.No. 44 03 447.4
II.lE-5 CH3 4-C1-C6H4 CH3 DE Appl.No. 44 21 180.5
II.1E-6 CH3 4-C1-C6H4 CH2CH3 DE Appl.No. 44 21 180.5
Table II.2A
Compounds of the formula IIA where Q is phenyl, R' is
-C(COZCH3)=NOCH3, n has a value of 0, R" is unsubstituted or sub-
stituted (het)aryloxymethylene, the unsubstituted or substituted
(het)aryl group having the following meanings:
No. unsubstituted or substituted Reference
(het)aryl
II.2A-1 2-CH3-C6H4 EP-A 253 213
II.2A-2 2,5-(CH3)2-C6H3 EP-A 400 417
II.2A-3 2,4-(CHg)2-C6H3 EP-A 400 417
II.2A-4 2,3,5-(CH3)3-C6H2 EP-A 400 417
II.2A-5 2-C1, 5-CH3-C6H3 EP-A 400 417
II.2A-6 2-CH3, 4-C[CH3)=NOCH3-C6H3 EP-A 386 561

CA 02235039 1998-OS-07
' 13
Table II.2B
Compounds of the formula IIA where Q is phenyl, R' is
-C(COZCH3)=NOCH3, n has a value of 0, R" is unsubstituted or sub-
s stituted (het)aryloxy, the unsubstituted or substituted (het)aryl
group having the following meanings:
No. unsubstituted or substituted Reference
(het)aryl
II.28-1 CsgS EP-A 253 213
II.2B-2 6-[2-CN-C6H4-O]-pyrimidin-4-yl EP-A 468 684
Table II.2C
Compounds of the formula IIA where Q is phenyl, R' is
-C(C02CH3)=NOCH3, n has a value of 0, R" is CH20N=CRaR~, where Ra
and R~ have the following meanings:
No. R' R Reference
II.2C-1 CH3 4-C1-C6H4 EP-A 463 488
II.2C-2 CH3 3-C1-C6H4 EP-A 463 488
II.2C-3 CH3 4-CF3-C6H4 EP-A 463 488
II.2C-4 CH3 3-CF3-C6H4 EP-A 463 488
II.2C-5 CH3 4-CH3-C6H4 EP-A 463 488
II~2C-6 CH3 4-OCHaCH3-pyrimidin-2-ylEP-A 472 300
I
II.2C-7 CH3 3,5-C12-C6H3 EP-A 463 488
Table II.2D
Compounds of the formula IIA where Q is phenyl, R' is
-C(C02CH3)=NOCHg, n has a value of 0, R" is CH20N=CRYCRb=NORE, whe-
re RY, Ra and RE have the following meanings:
No. Ry R RE Reference
II.2D-1 CH3 CH3 CH3 DE Appl. No. 44 03 447.4
II.2D-2 CH3 CH3 CHZCHg DE Appl. No. 44 03 447.4
II.2D-3 CH3 C6H5 CH3 DE Appl. No. 44 03 447.4
I
II.2D-4 CH3 C6H5 CH2CH3 DE Appl. No. 44 03 447.4

CA 02235039 1998-OS-07
r
14
No. Ry R R Reference
II.2D-5 CH3 4-C1-C6H4 CH3 DE Appl. No. 44 21 180.5
II.2D-6 CH3 4-Cl-C6H4 CHyCH3 DE Appl. No. 44 21 180.5
Table II.3A
Compounds of the formula IIA where Q is phenyl, R' is
-C(CONHCH3)=NOCHg, n has a value of 0, R" is unsubstituted or sub-
stituted (het)aryloxymethylene, the unsubstituted or substituted
(het)aryl group having the following meanings:
No. unsubstituted or substitutedReference
(het)aryl
II.3A-12-CH3-C6H4 EP-A 477 631
II.3A-22,5-(CH3)2-C6H3 EP-A 477 631
iI.3A-32,4-(CH3)2-C6H3 EP-A 477 631
II.3A-42,3,5-(CH3)3-C6H2 EP-A 477 631
II.3A-52-CH3, 4-C[CH3]=NOCH3-C6H3 EP-A 579 124
iI.3A-61-[4-C1-C6H4]-pyrazol-3-yl DE Appl. No. 43 05 502.8
II.3A-71-[2,4-C12-C6H3]-pyrazol-3-ylDE Appl. No. 43 05 502.8
Table II.3B
Compounds of the formula IIA where Q is phenyl, R' is
-C(CONHCH3)=NOCH3, n has a value of 0, R" is unsubstituted or sub-
stituted (het)aryloxy, the unsubstituted or substituted (het)aryl
group having the following meanings:
35No. unsubstituted or substituted Reference
(het)aryl
II.3B-1 C6H5 EP-A 398 692
II.3B-2 6-[2-CN-C6H4-O]-pyrimidin-4-yl GB-A 2 253 624

CA 02235039 1998-OS-07
Table II.3C
Compounds of the formula IIA where Q is phenyl, R' is
-C(CONHCH3)=NOCH3, n has a value of 0, R" is unsubstituted or sub-
s stituted (het)arylethenylene, the unsubstituted or substituted
(het)aryl group having the following meaning:
No. unsubstituted or substi- Reference
tuted (het)aryl
10 II.3C-1 1-[2,4-C12-C6H3], DE Appl. No. 44 23 615.8
5-CF3-pyrazol-4-yl
Table II.3D
Compounds of the formula IIA where Q is phenyl, R' is
-C(CONHCH3)=NOCHg, n has a value of 0, R" is CH20N=CRaR~, where R°~
and R~ have the following meanings:
No. Ra R Reference
II.3D-1 CH3 4-Cl-C6H4 EP-A 463 488
II.3D-2 CH3 3-C1-C6H4 EP-A 463 488
II.3D-3 CH3 4-CF3-C6H4 EP-A 585 751
II.3D-4 CH3 3-CF3-C6Hq EP-A 585 751
I
II.3D-5 CHg 4-CH3-C6H4 EP-A 463 488
II.3D-6 CH3 3,5-C12-C6H3 EP-A 463 488
II.3D-7 CH3 2-OCH2CH3-pyrimidin-2-yl WO-A 92/13,830
Table II.3E '
Compounds of the formula IIA where Q is phenyl, R' is
-C(CONHCH3)=NOCH3 , n has a value of 0, R" is CHaON=CRYCRa=NORE,
where RY, Ra and RE have the following meanings:
No. RY R R Reference
II.3E-1 CH3 CH3 CH3 DE Pat.Appl. 44 21182.1
II.3E-2 CHg CHg CHZCHg DE Pat.Appl. 44 21182.1
II.3E-3 CH3 C6H5 CH3 DE Pat.Appl. 44 21182.1
II.3E-4 CH3 C6H5 CH2CH3 DE Pat.Appl. 44 21182.1
II.3E-5 CH3 4-C1-C6H4 CH3 DE Pat.Appl. 44 21182.1

CA 02235039 1998-OS-07
16
No. RY R RE Reference
II.3E-6 CHg 4-C1-C6Hq CH2CH3 DE Pat. Appl. 44 21 182.1
ii.3E-7 CH3 4-F-C6H4 CH3 DE Pat. Appl. 44 21 182.1
Table II.4A
Compounds of the formula IIA where Q is phenyl, R' is
-C(COZCH3)=CHCH3, n has a value of 0, R" is unsubstituted or sub-
stituted (het)aryloxymethylene, the unsubstituted or substituted
(het)aryl group having the following meanings:
No. unsubstituted or substi- Reference
tuted (het)aryl
II.4A-1 2-CH3-C6H4 EP-A 280 185
II.4A-2 2,5-(CH3)2-C6H3 EP-A 513 580
II.4A-3 2,4-(CH3)2-C6H3 EP-A 513 580
II.4A-4 2,3,5-(CH3)3-C6Hy EP-A 513 580
II.4A-5 2-C1, 5-CH3-C6H3 EP-A 513 580
II.4A-6 2-CHg, 4-C[CH3]=NOCH3-C6H3EP-A 513 580
II.4A-7 1-[4-C1-C6H4]-pyrazol-3-ylDE Pat. Appl. 44 15 483.6
Table II.4B
Compounds of the formula IIA where Q is phenyl, R' is
-C(COgCH3)=CHCH3, n has a value of 0, R" is unsubstituted or sub-
stituted (het)aryloxy, the unsubstituted or substituted (het)aryl
group having the following meaning:
No. unsubstituted or substituted Reference
(het)aryl
II.48-1 C6H5 EP-A 513 580
45

CA 02235039 1998-OS-07
17
Table II.4C
Compounds of the formula IIA where Q is phenyl, R' is
-C(COZCHg)=CHCH3, n has a value of 0, R" is CH20N=CRYCR$=NORE, whe-
y re RY, Ra and RE have the following meanings:
No . RY R RE Re
f
erence
II.4C-1 CH3 CH3 CH3 DE Pat.Appl. 44 21 180.5
II.4C-2 CH3 CH3 CH2CH3 DE Pat.Appl. 44 21 180.5
Ii.4C-3 CH3 C6H5 CH3 DE Pat.Appl. 44 21 180.5
II.4C-4 CH3 C6H5 CH2CH3 DE Pat.Appl. 44 21 180.5
II.4C-5 CH3 4-C1-CgHq CH3 DE Pat.Appl. 44 21 180.5
II.4C-6 CH3 4-C1-C6H4 CH2CH3 DE Pat.Appl. 44 21 180.5
Table II.5A
Compounds of the formula IIA where Q is phenyl, R' is
-C(COZCH3)=CHCH2CH3, n has a value of 0, R" is unsubstituted or
substituted (het)aryloxymethylene, the unsubstituted or substitu-
ted (het)aryl group having the following meanings:
No. unsubstituted or substituted Reference
(het)aryl
II.5A-1 2-CH3-C6Hg EP-A 513 580
II.SA-2 2,5-(CH3)2-C6H3 EP-A 513 580
II.SA-3 2,4-(CH3)2-C6H3 EP-A 513 580
ii.SA-4 2,3,5-(CH3)3-C6H2 EP-A 513 580
'
II.5A-5 2-C1, 5-CH3-C6H3 EP-A 513 580
II.5A-6 2-CH3, 4-C[CH3]=NOCH3-C6H3 EP-A 513 580
Table II.5B
Compounds of the formula IIA where Q is phenyl, R' is
-C(C02CH3)=CHCH2CH3, n has a value of 0, R" is unsubstituted or
substituted (het)aryloxy, the unsubstituted or substituted
(het)aryl group having the following meaning:
No unsubstituted or substituted Reference
.
(het)aryl
II.5B-1 C6H5
EP-A 513 580

CA 02235039 1998-OS-07
18
Table II.5C
Compounds of the formula IIA where Q is phenyl, R' is
-C(C02CH3)=CHCH2CH3, n has a value of 0, R" is CH20N=CRYCR$=NORE,
-'> where RY, R$ and RE have the following meanings
NO. RY R RE Reference
II. SC-1CH3 CH3 CH3 DE Pat. Appl.44 21 180.5
II. SC-2CH3 CH3 CH2CH3 DE Pat. Appl.44 21 180.5
II.5C-3 CH3 C6H5 CH3 DE Pat. Appl.44 21 180.5
II.5C-4 CH3 C6H5 CH2CH3 DE Pat. Appl.44 21 180.5
II. SC-5CH3 4-Cl-C6H4 CH3 DE Pat. Appl.44 21 180.5
II. SC-6CH3 4-C1-C6H4 CH2CH3 DE Pat. Appl.44 21 180.5
Table II.6A
Compounds of the formula IIA where Q is phenyl, R' is
-C(COCH3)=NOCH3, n has a value of 0, R" is unsubstituted or sub-
stituted (het)aryloxymethylene, the unsubstituted or substituted
(het)aryl group having the following meanings:
No. unsubstituted or substituted Reference
(het)aryl
II.6A-1 2-CH3-C6H4 EP-A 498 188
II.6A-2 2,5-(CH3)2-C6H3 EP-A 498 188
II.6A-3 2,4-(CH3)2-C6H3 EP-A 498 188
II.6A-4 2,3,5-(CH3)3-C6H2 EP-A 498 188
II.6A-5 2-CH3, 4-C[CH3]=NOCH3-C6H3 EP-A 498 188
40

CA 02235039 1998-OS-07
19
Table II.6B
Compounds of the formula IIA where Q is phenyl, R' is
-C(COCH3)=NOCH3, n has a value of 0, R" is unsubstituted or sub-
s stituted (het)aryloxy, the unsubstituted or substituted (het)aryl
group having the following meanings:
No. uasubstituted or substituted reference
(het)aryl
II . C6H5 EP-A 498 188
fiB-1
II.6B-26-[2-CN-C6H4-O]-pyrimidin-4-yl EP-A 498 188
Table II.7A
Compounds of the formula IIA where Q is phenyl, R' is
-C(COCH2CH3)=NOCH3, n has a value of 0, R" is unsubstituted or
substituted (het)aryloxymethylene, the unsubstituted or sub-
stituted (het)aryl group having the following meanings:
No. unsubstituted or substituted Reference
(het)aryl
II.7A-1 2-CH3-C6H4 EP-A 498 188
II.7A-2 2,5-(CH3)Z-C6H3 EP-A 498 188
II.7A-3 2,4-(CH3)Z-C6H3 EP-A 498 188
II
II.7A-4 2,3,5-(CH3)3-C6Ha EP-A 498 188
30~II7A-5 I2-CH3, 4-C[CH3]=NOCH3-C6H3 ~EP-A 498 188
Table II.7B
Compounds of the formula IIA where Q is phenyl, R' is
-C(COCHyCH3)=NOCH3, n has a value of 0, R" is unsubstituted or
substituted (het)aryloxy, the unsubstituted or substituted
(het)aryl group having the following meanings:
40No. unsubstituted or substituted Reference
(het)aryl
II.7B-1 C6H5 Ep-A 498 188
II.7B-2 6-[2-CN-C6H4-O]-pyrimidin-4-yl EP-A 498 188

CA 02235039 1998-OS-07
Table II.8A
Compounds of the formula IIA Where Q is phenyl, R' is
-N(OCH3)-COaCH3, n has a value of 0, R" is unsubstituted or sub-
s stituted (het)aryloxymethylene, the unsubstituted or substituted
(het)aryl group having the following meanings:
No. unsubstituted or substituted Reference
(het)aryl
10 II.8A-Z 2-CH3-C6Hg WO-A 93/15,046
II.8A-2 2,5-(CH3)2-C6H3 WO-A 93/15,046
II.8A-3 2,4-(CH3)y-C6Hg WO-A 93/15,046
15 II. BA-4 2,3,5-(CH3)3-C6Hz WO-A 93/15,046
II.8A-5 2-C1, 5-CH3-C6H3 WO-A 93/15,046
II.8A-6 2-CHg, 4-C[CHg]=NOCH3-C6H3 WO-A 93/15,046
II.8A-7 2-CH3, 4-C[CH3]=NOCH2CH3-C6H3 WO-A 93/15,046
20 =I. BA-8 2-CH3, 4-C[CHyCH3]=NOCH3-CgH3 WO-A 93/15,046
II. BA-9 2-CH3, 4-C[CHaCH3]=NOCH2CH3-C6H3 WO-A 93/15,046
II.8A-10 1-[4-C1-C6H4]-pyrazol-3-yl DE Pat. Appl.
44 23 612.3
Table II.8B
Compounds of the formula IIA where Q is phenyl, R' is
-N(OCH3)-COyCH3, n has a value of 0, R" is CH20N=CRaR~, where Ra
and R~ have the following meaning:
No. R' R ~ Reference
~II'8B CH3 I 3,5-C12-C6H3 I WO-A 93/15,046
1 I
When providing the mixtures, it is preferred to employ the pure
active ingredients I and IIA or IIb, with which it is possible to
a~lx further active ingredients against pests (for example
insects, arachnids or nematodes) or harmful fungi, or else herbi-
cidally active ingredients or growth-regulating active ingre-
dients or fertilizers, as required.
The mixtures of the compounds I and IIA or IIB, or the simul-
taneous joint or separate use of the compounds I and IIA or I and
IIB, are distinguished by an outstanding activity against a broad

CA 02235039 1998-OS-07
21
spectrum, in particular of phytopathogenic fungi. Some of them
act systemically (ie. when used in crop protection, they can be
taken up by the treated plant without losing their activity and
may be translocated within the plant) and can therefore also be
employed as foliar- and soil-acting fungicides.
They are especially important for controlling a large number of
fungi on a variety of crop plants such as cotton, vegetables (eg.
cucumbers, beans and cucurbits), barley, grass, oats, coffee,
maize, fruit species, rice, rye, soybeans, grapevines, wheat,
ornamentals, sugar cane, and a variety of seeds.
In particular, they are suitable for controlling the following
phytopathogenic fungi: Erysiphe graminis (powdery mildew) on
cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on cu-
curbits, Podosphaera leucotricha on apples, Puccinia species an
cereals, Rhizoctonia species on cotton, rice and lawns, Ustilago
species on cereals and sugar cane, Venturia inaequalis (scab) on
apples, Helminthosporium species on cereals, Septoria nodorum on
wheat, Botrytis cinera [sic] (gray mold) on strawberries, vegeta-
bles, ornamentals and grapevines, Cercospora arachidicola on pea-
nuts, Pseudocercosporella herpotrichoides on wheat and barley,
Pyricularia oryzae on rice, Phytophthora infestans on potatoes and
tomatoes, Plasmopara viticola on grapevines, Pseudoperonospora
species in hops and cucumbers, Alternaria species on vegetables
and fruit, and Fusarium and Verticillium species.
Moreover, they can be used in the protection of materials (eg.
protection of wood), for example against Paecilomyces variotii.
35
The compounds I and IIA, or I and IIB, can be applied simulta-
neously, namely together or separately, or in succession; in the
case of separate application, the order in which the compounds
are applied generally does not affect the degree of control.
The compounds I and IIA are normally used in a weight ratio of
10:1 to 1:20, preferably 5:1 to 1:3, in particular 3:1 to 1:1
(I:IIA).
The compounds I and IIB are normally used in a weight ratio of
10:1 to 1:20, preferably 5:1 to 1:3, in particular 3:1 to 1:1
(I:IIB).

CA 02235039 1998-OS-07
22
Depending on the nature of the desired effect, the rates of ap-
plication of the mixtures according to the invention are from
0.015 to 10 kg/ha, preferably 0.1 to 7 kg/ha, in particular 0.2
to 3 kg/ha.
The rates of application for the compounds I are from 0.005 to
3 kg/ha, preferably 0.02 to 2 kg/ha, in particular 0.05 to
1 kg/ha.
The rates of application of the compounds IIA are generally from
0.005 to 5 kg/ha, preferably 0.01 to 2 kg/ha, in particular 0.01
to 1 kg/ha.
The rates of application of the compounds IIB are generally from
0.005 to 5 kg/ha, preferably 0.01 to 2 kg/ha, in particular 0.01
to 1 kg/ha.
For the treatment of seed, the mixture is generally applied at
rates of 0.001 to 0.1 g/kg of seed, preferably 0.002 to 0.05 g/kg
of seed, in particular 0.005 to 0.5 g/kg of seed.
If the aim is the control of phytopathogenic harmful fungi, the
compounds I and IIA, or I and IIB, or the mixtures of the com-
pounds I and IIA, or I and IIB, are applied together or separ-
ately by spraying or dusting the seeds, the plants or the soils
before or after the plants are sown or before or after the plants
have germinated.
The fungicidal synergistic mixtures according to the invention or
the compounds I and IIA or I and IIB can be applied for example
in the form of directly sprayable solutions, powders and suspen-
sions or in the form of highly concentrated aqueous, oily or
other suspensions, dispersions, emulsions, oil dispersions,
pastes, dusts, materials for spreading, or granules, and applied
by spraying, atomizing, dusting, spreading or pouring. The use
form depends on the intended purpose; in any case, it should gua-
rantee as fine and uniform a distribution as possible of the mix-
ture according to the invention.
The formulations are prepared in a manner known per se, eg. by
adding solvents and/or carriers. Inert additives such as emulsi-
fiers or dispersants are normally admixed with the formulations.
Suitable surfactants are the alkali, alkaline earth and ammonium
salts of aromatic sulfonic acids, eg. ligno-, phenol-, naph-
thalene- and dibutylnaphthalenesulfonic acid, and of fatty acid,
of alkyl- and alkylarylsulfonates, of alkyl, lauryl ether and

CA 02235039 1998-OS-07
a3
fatty alcohol sulfates, and the salts of sulfated hexa-, hepta-
and octadecanols, or 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, polyoxyethylene octylphenyl ether,
ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol or tri-
butylphenyl polyglycol ether, alkylaryl polyether alcohols, iso-
tridecyl alcohol, fatty alcohol/ethylene oxide condensates, etho-
xylated castor oil, polyoxyethylene alkyl ethers or polyoxypropy-
lene [sic], lauryl alcohol polyglycol ether acetate, sorbitol
esters, lignin-sulfite waste liquors or methylcellulose.
Powders, materials for spreading and dusts can be prepared by
mixing or concomitantly grinding the compounds I and IIA, or I
and IIB, or the mixtures of the compounds I and IIA, or I and
IIB, with a solid carrier.
Granules (eg. coated granules, impregnated granules or homogenous
granules) are normally prepared by binding the active ingredient,
or active ingredients, to a solid carrier. '
Suitable fillers or solid carriers are, for example, mineral
earths such as silica gel, silicas, silica gels [sic], silicates,
talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolo-
mite, 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 and other
solid carriers.
In general, the formulations comprise from 0.1 to 95 $ by weight,
preferably 0.5 to 90 ~ by weight, of one of the compounds IA or
IB, IIA or IIB or of the mixture of the compounds I and IIA, or I
and IIB.
The active ingredients are employed in a purity of from 90 ~ to
100 ~, preferably 95 ~ to 100 ~ (according to 1H NMR or HPLC spec-
trum [sic]).
The compounds I, IIA and IIB, or the mixtures, or the correspon-
ding formulations, are applied by treating the harmful fungi,
their environment, or the materials, plants, seeds, soils, areas
or spaces to be protected against fungal infection, with a fungi-
cidally active amount of the mixture, or of the compounds I and

CA 02235039 1998-OS-07
24
IIA or I and IIB in the case of separate application. Treatment
can be effected before or after infection by the harmful fungi.
The synergistic action of the mixtures according to the invention
was demonstrated by the following experiments:
Use examples
The experiments were carried out with the following compounds to
which the symbols (A), (B), (C) and (D) were assigned for reasons
of clarity:
C1 C1
HO NH- CO- C ( CH3 ) 2-- CH2C1
(A)
Compound I.2.1
C1 C1
HO ~ ~ NH- CO ( g )
CH3
Compound I.2.5
endo : exo = 1 . 1
C1 C1
HO ~ ~ NH- CO ~ ( C )
H3C
Compound I.1.15
CH3
O - CH2 ~ / (D)
H3C0-CSC= N- OCHg
Compound II.2A-1 O

CA 02235039 1998-OS-07
\ N%~N \
O \ ~ O I / (E)
5 CN H3C0-CSC= C- OCH3
O
Compound II.1B-2
H3C0-N * C- C ( CH3 ) * N- O- CH2
(F)
\ H C-N -CSC N OCH3
H O
Compound II.3E-3
95 % of the double bonds denoted by "*" were in the E configura-
tion.
Use example 1
Activity against Botrytis cinerea
Bell pepper seedlings cv. "Neusiedler Ideal Elite" which had 4 to
5 well developed leaves were sprayed to run-off point with aqueous
suspensions comprising 80 % of active ingredient and 20 % of emul-
sifier in the dry matter. After the spray coating had dried on,
the plants were sprayed with a conidia suspension of the fungus
Botrytis cinerea and placed into a chamber with high atmospheric
humidity at 22 to 24~C. After 5 days, the disease on the untreated
control plants had developed to such an extent that the leaf
necroses formed covered most of the leaves.
The visually determined value for the percentage of diseased leaf
area were converted into efficacies as a percentage of the un-
treated control. An efficacy of 0 is the same disease level as in
the untreatd control, an efficacy of 100 is a disease level of
0 %. The expected efficacies for active ingredient combinations
were determined using Colby's formula (S. R. Colby "Calculating
synergistic and antagonistic responses of herbicide
combinations", Weeds 15, pages 20 to 22 (1967)) and compared with
the observed efficacies.
Untreated control: Disease level 100 %

CA 02235039 1998-OS-07
26
Table 1.1: Efficacies of the individual active ingredients
Active Active ingredient con- Efficacy [~ of untreated
ingred- centration in the spray control]
Tent mixture [ppm]
100 84
(A)
40
25
100 80
B
( )
25 65
_ 100 70
(C)
25 35
(D) 25 0
0
(E) 25
(F) 25 0
Table 1.2: Efficacy of the mixture
observed Expected
Active ingre dient efficacy efficacy
mixture
100 ppm (A) + ppm (D); 100 84
25
Mixing ratio 1
4
25 ppm (A) + ppm (D); g2 40
25
Mixing ratio 1
1
100 ppm (A) + ppm (E); gg g4
25
Mixing ratio 1
4
25 ppm (A) + ppm (E); g3 40
25
Mixing ratio 1
1
100 ppm (A) + ppm (F); g8 g4
25
Mixing ratio 1 '
4
25 ppm (A) + ppm (F); gg 40
25
Mixing ratio 1
1
100 ppm (B) + ppm (D); gg gp
25
Mixing ratio 1
4 .
25 ppm (B) + ppm (D); gg 65
25
Mixing ratio 1
1 .
100 ppm (B) + ppm (E); gg gp
25
Mixing ratio 1
4 .
25 ppm (B) + ppm (E); gg 65
25
Mixing ratio 1
1 .
100 ppm (B) + ppm (F); 100 80
25
Mixing ratio 1
4 :
25 ppm (B) + ppm (F); gg 65
25
Mixing ratio 1
1

CA 02235039 1998-OS-07
27
Observed Expected
Active ingredient mixture efficacy efficacy
100 ppm (C) + 25 ppm (D); gg 70
Mixing ratio 4 . 1
25 ppm (C) + 25 ppm (D);
75 35
Mixing ratio 1 . 1
100 ppm (C) + 25 ppm (E); gg 70
Mixing ratio 4 1
25 ppm (C) + 25 ppm (E); 65 35
10Mixing ratio 1 : 1
100 ppm (C) + 25 ppm (F); g8 70
Mixing ratio 4 1
25 ppm (C) + 25 ppm (F); g7 35
Mixing ratio 1 1
Test result: For all mixing ratios, the observed efficacy exceeds
the value calculated beforehand using Colby's formula.
Use example 2
Activity against Botrytis cinerea on bell peppers
Disks of green bell peppers were sprayed to run-off point with
aqueous preparation of active ingredient comprising 80 $ of active
ingredient and 20 ~ of emulsifier in the dry matter. 2 hours
after the spray coating had dried on, the bell pepper disks were
inoculated with a spore suspension of Botrytis cinerea containing
1.7 x 106 spores per ml of a 2 $ strength Biomalz solution. The
inoculated bell pepper disks were subsequently transferred for 4
days into humid chambers at 18~C. The diseased bell pepper disks
were then evaluated visually for botrytis development.
The visually determined values for the percentage of diseased
leaf area were converted into efficacies as a percentage of the
untreated control. An efficacy of 0 is the same disease level as
in the untreatd control, an efficacy of 100 is a disease level of
0 $. The expected efficacies for active ingredient combinations
were determined using Colby's~formula (S. R. Colby "Calculating
synergistic and antagonistic responses of herbicide combina-
tions", Weeds 15, pages 20 to 22 (1967)) and compared with the
observed efficacies.

CA 02235039 1998-OS-07
28
Active Active ingredient con- Efficacy [~ of untreated
ingred- centration in the spray control]
ient mixture [ppm]
(A) 100 20
100 25
(B)
25 10
100 25
(C)
25 30
(D) 25 77
(F) 25 10
Table 2.2: Efficacy of the mixture
Active ingredient mixture observed Expected
efficacy efficacy
100 ppm (A) + 25 ppm (F); 77 48
Mixing ratio 4 . 1
25 ppm (B) + 25 ppm (D);
g0 79
Mixing ratio 1 1
100 ppm (B) + 25 ppm (F); g0 51
Mixing ratio 4 1
25 ppm (B) + 25 ppm (F); 75 42
Mixing ratio 1 . 1
100 ppm (C) + 25 ppm (F); g7 51
Mixing ratio 4 . 1
25 ppm (C) + 25 ppm (F); gg 55
Mixing ratio 1 1
40
Untreated control: Disease level 100 %
Table 2.1: Efficacies of the individual active ingredients
Test result: For all mixing ratios, the observed efficacy exceeds
the value calculated beforehand using Colby's formula.