AU3331699A

AU3331699A - Fungicidal mixtures based on tris (oxime ether) derivatives and rice fungicides

Info

Publication number: AU3331699A
Application number: AU33316/99A
Authority: AU
Inventors: Eberhard Ammermann; Thomas Grote; Gisela Lorenz; Hubert Sauter; Klaus Schelberger; Siegfried Strathmann
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1998-03-24
Filing date: 1999-03-22
Publication date: 1999-10-18
Anticipated expiration: 2019-03-22
Also published as: JP2002507553A; CO5060425A1; TW521992B; ZA200005908B; EP1065928A1; CN1294489A; JP4458667B2; CA2324464A1; AU737879B2; IL138296A0; KR20010034644A; ID28001A; KR100557367B1; WO1999048368A1; AR014766A1; BR9909002A

Description

UUbU/GUU'i Fungicidal mixtures based on tris(oxime ether) derivatives and rice fungicides 5/ The present invention relates to fungicidal mixtures for controlling harmful fungi, which [lacuna] a) phenylacetic acid derivatives of the formula I 10 4 R(32) M O N N y0(I) 15 5 Y R N R~ R0 20 in which the substituents and t index have the following meaning: X is NOCH 3 , CHOCH 3 or CHCH 3 ; 25 Y is oxygen or NR;

R

1 , R independently of one another are each hydrogen or Ci-C 4 -alkyl; 30 R2 is cyano, nitro, trifluoromethyl, halogen, Ci-C 4 -alkyl or Ci-C 4 -alkoxy; 35 m is 0, 1 or 2, where the radicals R 2 may be different if m is 2; R3 is hydrogen, cyano, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl or

C

3

-C

6 -cycloalkyl; 40

R

4 , R 6 independently of one another are each hydrogen, are Ci-Cio-alkyl,

C

3

-C

6 -cycloalkyl,

C

2 -Cio-alkenyl, 45 C 2 -Cio-alkynyl, Ci-Cio-alkylcarbonyl,

C

2 - Cio-alkenylcarbonyl,

C

3 - Cio-alkynylcarbonyl or Ci-Cio-alkylsulfonyl, where these radicals may be 2 partially or fully halogenated or may carry one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci-C 6 -alkyl, 5 Ci-C 6 -haloalkyl, CI-C 6 -alkylsulfonyl, Ci-C 6 -alkylsulfoxyl, Ci-C 6 -alkoxy, Ci-C 6 -haloalkoxy, Ci-C 6 -alkoxycarbonyl, Ci-C 6 -alkylthio, Ci-C 6 -alkylamino, di-Ci-C 6 -alkylamino, Ci-C 6 -alkylaminocarbonyl, 10 di-Ci-C 6 -alkylaminocarbonyl, Cl-C 6 -alkylaminothiocarbonyl, di-Ci-C 6 -alkylaminothiocarbonyl,

C

2

-C

6 -alkenyl,

C

2

-C

6 -alkenyloxy,

C

3

-C

6 -cycloalkyl,

C

3

-C

6 -cycloalkyloxy, heterocyclyl, heterocyclyloxy, benzyl, benzyloxy, aryl, 15 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, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, 20 halogen, Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C6-alkylsulfonyl, Ci-C 6 -alkylsulfoxyl,

C

3

-C

6 -cycloalkyl, Ci-C 6 -alkoxy, Ci-C 6 -haloalkoxy, Ci-C6-alkyloxycarbonyl, Ci-C 6 -alkylthio, Ci-C 6 -alkylamino, di-Ci-C 6 -alkylamino, 25 Ci-C6-alkylaminocarbonyl, di-Ci-C 6 -alkylaminocarbonyl, Ci-C 6 -alkylaminothiocarbonyl, di-Ci-C 6 -alkylaminothiocarbonyl,

C

2

-C

6 -alkenyl,

C

2

-C

6 -alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, 30 arylthio, hetaryl, hetaryloxy, hetarylthio or

C(=NOR

7 )-An-R 8 ; are aryl, arylcarbonyl, arylsulfonyl, hetaryl, hetaryl carbonyl or hetarylsulfonyl, where these radicals may 35 be partially or fully halogenated or may carry one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocar bonyl, halogen, Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkylcarbonyl, Ci-C 6 -alkylsulfonyl, 40 Ci-C 6 -alkylsulfoxyl,

C

3

-C

6 -cycloalkyl, Ci-C 6 -alkoxy, Ci-C 6 -haloalkoxy, Ci-C 6 -alkyloxycarbonyl, Ci-C 6 -alkylthio, Ci-C 6 -alkylamino, di-Ci-C 6 -alkylamino, Ci-C 6 -alkylaminocarbonyl, di-Ci-C 6 -alkylaminocarbonyl, Ci-C 6 -alkylaminothiocarbonyl, 45 di-Ci-C 6 -alkylaminothiocarbonyl,

C

2

-C

6 -alkenyl, /~\ RA4, 11C r 3

C

2

-C

6 -alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy or C(=NOR 7 )-An-R 8 ; 55 sis hydrogen, 5 is Ci-C 6 -alkyl, C 2

-C

6 -alkenyl, C 2

-C

6 -alkynyl, where the hydrocarbon radicals of these groups may be partially or fully halogenated or may carry one to three of the following radicals: cyano, nitro, hydroxyl, mercapto, 10 amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci-C 6 -alkylaminocarbonyl, di-Ci-C 6 -alkylaminocarbonyl, Ci-C 6 -alkylaminothiocarbonyl, di-Ci-C 6 -alkylaminothiocarbonyl, Ci-C 6 -alkylsulfonyl, 15 Ci-C 6 -alkylsulfoxyl, Ci-C 6 -alkoxy, Ci-C 6 -haloalkoxy, Ci-C6-alkoxycarbonyl, Ci-C 6 -alkylthio, Ci-C 6 -alkylamino, di-Ci-C 6 -alkylamino,

C

2

-C

6 -alkenyloxy, C 3

-C

6 -cycloalkyl, C3-C6-cyCloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, aryl-Ci-C 4 -alkoxy, arylthio, 20 aryl-Ci-C 4 -alkylthio, hetaryl, hetaryloxy, hetaryl-Ci-C 4 -alkoxy, hetarylthio, hetaryl-Ci-C 4 -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, 25 nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkylsulfonyl, Ci-C 6 -alkylsulfoxyl,

C

3

C

6 -cycloalkyl [sic], 30 Ci-C 6 -alkoxy, Ci-C 6 -haloalkoxy, Ci-C 6 -alkoxycarbonyl, Ci-C 6 -alkylthio, Ci-C 6 -alkylamino, di-Ci-C 6 -alkylamino, Ci-C 6 -alkylaminocarbonyl, di-Ci-C 6 -alkylaminocarbonyl, Ci-C 6 -alkylaminothiocarbonyl, di-Ci-C 6 -alkylaminothiocarbonyl,

C

2

-C

6 -alkenyl,

C

2

-C

6 -alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio and C (=NOR 7 ) -An-R 8 ; is C 3

-C

6 -cycloalkyl,

C

3

-C

6 -cycloalkenyl, heterocyclyl, 40 aryl, hetaryl, where the cyclic radicals may be partially or fully halogenated or may carry one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci-C 6 -alkyl, 45 Ci-C 6 -haloalkyl, Ci-C 6 -alkylsulfonyl, Ci-C 6 -alkylsulfOxyl,

C

3

-C

6 -cycloalkyl, Ci-C 6 -alkoxy, Ci-C 6 -haloalkoxy, Ci-C 6 -alkoxycarbonyl, Ci-C 6 -alkylthio, 4 Ci-C 6 -alkylamino, di-Ci-C 6 -alkylamino, Ci-C 6 -alkylaminocarbonyl, di-Ci-C 6 -alkylaminocarbonyl, Ci-C 6 -alkylaminothiocarbonyl, di-Ci-C 6 -alkylaminothiocarbonyl,

C

2

-C

6 -alkenyl, 5 C 2

-C

6 -alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl and hetaryloxy; where 10 A is oxygen, sulfur or nitrogen and where the nitrogen carries hydrogen or Ci-C 6 -alkyl; n is 0 or 1; 15 R7 is hydrogen or Ci-C 6 -alkyl and

R

8 is hydrogen or Ci-C 6 -alkyl, 20 and their salts, and 25 b) at least one fungicide selected from fungicides of the formulae II to VII 30 N 0 35 S 40 N N I (III) \;:N

CH

3 45 5 S CO2 CH(CH3)2 C 0 H 3)2 (I V ) S CO2CH(CH3)2 5 0 o - S- -S (V)

OCH

2

CH

3 15 C=N N C = N N(V I )

NH

20

CH

3 N

CH

3 25 CN O (VII) 30 F N H It is an object of the present invention to provide fungicidal 35 mixtures having good fungicidal activity, in particular against fungal diseases in rice, exceeding the activity of the mixture components on their own. 40 We have found that this object is achieved 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). 45 The fungicides of the formulae II to VII are also known and RAt< described in the literature. Additionally, they are commercially ( -17 h uniie fth omleIIt I r as nw n )401 6 available under the trade names mentioned below in brackets: II: GB 1,394,373; common name: pyroquilon (trade name: Coratop@, from Novartis); 5 III:GB 1,419,121, common name: tricyclazole (trade name Beam®, from Dow Elanco); 10 IV: Proc. Insect. Fungic. Conf. 8th, 2 (1975), 715, common name: isoprothiolane (trade name: Fuji-one@, from Nihon Noyaku); V: DE 14 93 736, common name: edifenphos (trade name: Hinosan®, from Bayer); 15 VI: GB-A 1,312,536, US-A 3,755,350; common name: ferimzone (from Takeda); VII:Pesticide Manual 10th Ed., 1994, 482; common name: -20 fludioxinil (trade name: Celest@,from Novartis). 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 25 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 30 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). Corresponding conversions may also occur after the use, for example in the treatment of plants in the treated plant or in the harmful fungus or animal pest to be 35 controlled. With regard to the C=X double bond, preference is given to the E isomers of the compounds I (configuration based on the -OCH 3 or the -CH 3 group in relation to the -C0 2

R

1 group) with respect to 40 their activity. With regard to the -C(R 3

)=NOCH

2 - double bond, preference is given to the cis isomers of the compounds I (configuration based on the 45 radical

R

3 in relation to the -OCH 2 - group) with respect to their activity. -, PR 7 In the definitions of the compounds I given at the outset, collective terms were used which generally represent the following groups: 5 Halogen: fluorine, chlorine, bromine and iodine; Alkyl: straight-chain or branched alkyl groups having 1 to 4, 6 or 10 carbon atoms, for example Ci-C 6 -alkyl such as methyl, ethyl, 10 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, 12,2-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; 20 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 Ci-C 2 -haloalkyl, such as 25 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, 30 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 35 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

C

2

-C

6 -alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 40 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, 45 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, r 1RAL -methyl-3-butenyl, 1,1-dimethyl-2-propenyl, S4 -dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl,

-T

8 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, 5 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, 10 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, 15 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 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; 20 Alkynyl: straight-chain or branched alkynyl groups having 2 to 10 carbon atoms and a triple bond in any position, for example

C

2

-C

6 -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, 25 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, 30 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; 35 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 40 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, 45 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, RA41 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 9 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidilyl, 4-imidazolidinyl, 1,2, 4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidil-3-y1, 1,2,4-thiadiazolidil-5-y1, 1,2,4-triazolidin-3-yl, 5 1,3,4-oxadiazolidil-2-y1, 1, 3,4-thiadiazolidil-2-yl, 1, 3,4-triazolidil-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-dihydrothiefl-2-yl, 2, 3-dihydrothien-3-yl, 2, 3-dihydrothien-4-yl, 10 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-.dihydro pyrrol-5-yl, 2 ,5-dihydropyrrol-2-y1, 2, 5-dihydropyrrol-3-yl, 2, 3-dihydroisoxazol-3-y1, 2, 3-dihydroisoxazol-4-yl, 15 2, 3-dihydroisoxazol-5-yl, 4, 5-dihydroisoxazol-3-yl, 4, 5-dihydroisoxazol-4-yl, 4, 5-dihydroisoxazol-5-yl, 2, 5-dihydroisothiazol-3-yl, 2, 5-dihydroisothiazol-4-y1, 2, 5-dihydroisothiazol-5-yl, 2,3-dihydroisopyrazol-3-y1, 2, 3-dihydroisopyrazol- 4 -yl, 2, 3-dihydroisopyrazo]l-5-yl, 20 4, 5-dihydroisopyrazol-3-yl, 4, 5-dihydroisopyrazol-4-yl, 4, 5-dihydroisopyrazo1-5-yl, 2, 5-dihydroisopyrazol-3-y1, 2, 5-dihydroisopyrazo1-4-yl, 2, 5-dihydroisopyrazol-5-y., 2, 3-dihydrooxazol-3-yl, 2, 3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-Yl, 4, 5-dihydrooxazol-3-yl, 25 4, 5-dihydrooxazol-4-yl, 4, 5-dihydrooxazol-5-yl, 2, 5-dihydrooxazol-3-y1, 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-y-, 30 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, 35 2, 5-dihydroimidazol-2-yl, 2, 5-dihydroimidazol-4-yl, 2, 5-dihydroimidazol-5-yl, 2-morpholinyl, 3-morpholinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-tetrahydropyridazinyl, 4-tetrahydropyridazilyl, 2-tetrahydropyrimidilyl, 4-tetrahydropyrimidilyl, 40 5 -tetrahydropyrimidilyl, 2 -tetrahydropyraz inyl, 1,3, 5-tetrahydrotriazil-2-y1, 1,2 ,4-tetrahydrotriazil-3-y1, 1, 3-dihydrooxazin-2-yl, 1, 3-dithian-2-yl, 2-tetrahydropyranyl, 1, 3-dioxolan-2-yl, 3,4,5, 6-tetrahydropyridin-2-y-, 4H-1,3-thiazin-2-yl, 4H-3,1-benzothiazin-2-yl, 45 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; 10 Arvl or aryloxv, arvlthio. arvicarbonyl and arvlsulfonyl: aromatic mono- or polycyclic hydrogen 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 5 group (-CO-) or (arylsulfonyl) via a sulfonyl group (-SO 2 -), for example phenyl, naphthyl and phenanthrenyl or phenyloxy, naphthyloxy and phenanthrenyloxy and the corresponding carbonyl and sulfonyl radicals; 10 Hetaryl or hetaryloxy, hetarvlthio, 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 15 attached to the skeleton directly or (hetaryloxy) via an oxygen atom (-0-) or (hetarylthio) a sulfur atom (-S-), (hetarylcarbonyl) via a carbonyl group (-CO-) or (hetarylsulfonyl) via a sulfonyl group (-S02-), for example 20 - 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, 25 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 30 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, 35 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, 40 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; 45 - 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 11 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 5 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, 10 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 15 one adjacent carbon ring member can be'bridged by a buta-1,3-dien-1,4-diyl group, these rings being attached to the skeleton via one of the nitrogen ring members; 20- 6-membered heteroaryl containing one to three and one to four nitrogen atoms, respectively: 6-membered heteroaryl groups which, beside carbon atoms, can contain one to three nitrogen atoms and one to four nitrogen atoms, respectively, as ring members, for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 25 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl and 1,2,4,5-tetrazin-3-yl; - benzo-fused 6-membered heteroaryl containing one to four 30 nitrogen atoms: 6-membered heteroaryl groups in which two adjacent carbon ring members can be bridged by a buta 1,3-dien-1,4-diyl group, for example quinoline, isoquinoline, quinazoline and quinoxaline, 35 and the corresponding oxy, thio, carbonyl or sulfonyl groups. 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 40 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 7A41 atoms as mentioned above.

12 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 formula I in which 5 R 1 is methyl. Besides, preference is given to compounds I in which R 3 is hydrogen, cyano, cyclopropyl, methyl, ethyl, 1-methylethyl or CF 3 10 Moreover, preference is given to compounds I in which R 3 is methyl. Besides, preference is given to compounds I in which R 3 is cyano. 15 Furthermore, preference is given to compounds I in which R 3 is cyclopropyl. 20 Additionally, preference is given to compounds I in which

R

3 is

CF

3 Additionally, preference is given to compounds I in which R 5 is hydrogen, cyclopropyl, methyl, ethyl, isopropyl, unsubstituted or 25 substituted aryl or hetaryl. Moreover, preference is given to compounds I in which R 5 is methyl. 30 Additionally, preference is given to compounds I in which R 5 is ethyl. Moreover, preference is given to compounds I in which R 5 is 35 isopropyl. Moreover, preference is given to compounds I in which R 5 is cyclopropyl. 40 Moreover, preference is given to compounds I in which R 5 is CF 3 Additionally, preference is given to compounds I in which R 5 is unsubstituted or substituted aryl or hetaryl. 45 Additionally, preference is given to compounds I in which R 5 is unsubstituted or substituted pyridyl, pyrimidyl, pyrazinyl, 13 pyridazinyl or triazinyl. Additionally, preference is given to compounds I in which R 5 is unsubstituted or substituted furyl, thienyl or pyrrolyl. 5 Additionally, preference is given to compounds I in which R 5 is unsubstituted or substituted oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl or imidazolyl. 10 Additionally, preference is given to compounds I in which R 5 is unsubstituted or substituted oxdiazolyl [sic], thiadiazolyl or triazolyl. 15 Moreover, preference is given to compounds I in which R 5 is phenyl which is unsubstituted or carries one or two of-the following groups: nitro, cyano, hydroxyl, amino, aminocarbonyl, aminothiocarbonyl, halogen, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, Ci-C 4 -alkylamino, 20 di-Ci-C 4 -alkylamino, Ci-C 4 -alkylsulfonyl, Ci-C 4 -alkoxycarbonyl, Ci-C 4 -alkylaminocarbonyl or di-Ci-C 4 -alkylaminocarbonyl. Moreover, preference is given to compounds I in which R 4 is hydrogen, Ci-C 6 -alkyl, C 2

-C

6 -alkenyl, C 2

-C

6 -alkynyl, allyl, 25 arylalkyl, hetarylalkyl, aryloxyalkyl, hetaryloxyalkyl, aryl or hetaryl. Additionally, preference is given to compounds I in which R 4 is 30 Ci-C 6 -alkyl. Further preferred compounds I are disclosed in WO 97/15,552. The compounds II which are contained in the mixtures according to 35 the invention are distinguished by excellent activity against a broad range of phytopathogenic fungi, in particular against fungi from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. 40 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 45 cane, and a variety of seeds.

14 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 5 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 10 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 15 species in vegetables and fruit, Mycosphaerella species in bananas and Fusarium and Verticillium species. The compounds II to VII are commercially available as fungicides. 20 When preparing the mixtures, it is preferred to employ the pure active ingredients I and II to VII, with which further active ingredients against harmful fungi or other pests, such as insects, arachnids or nematodes, or else herbicidal or 25 growth-regulating active ingredients or fertilizers can be admixed. The mixtures of the compounds I and at least one compound II to VII can be applied simultaneously, that is joined or separately, 30 and have outstanding action against a wide range of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes. Some of them act systematically and are therefore also suitable for use as folio and soil-acting fungicides. 35 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 40 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 45 cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in $RA. cucurbits, Podosphaera leucotricha in apples, Uncinula necator in grapevines, Puccinia species in cereals, Rhizoctonia species in -0 15 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 5 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 10 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. 15 The compounds I and at least one of the compounds II to VII can be applied simultaneously, either together or separately, or in succession, the sequence, in the case of separate application, 20 generally not having any effect on the control results. 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, 25 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 30 particular from 0.1 to 1.0 kg/ha. Correspondingly, in the case of the compounds II to VII, 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. 35 For seed treatment, the application rates of the mixture are generally from 0.001 to 250 g/kg of seed, preferably 0.01 to 100 g/kg, in particular 0.01 to 50 g/kg. 40 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 VII is effected by spraying or dusting the seeds, the plants or the soils before or after sowing the plants, 45 or before or after plant emergence. RA4 16 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, 5 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 10 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 15 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), 20 ketones (for example cyclohexanone), amines (for example ethanolamine, dimethylformamide) and water; carriers, such as natural ground minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example finely divided silica gel, silicates); emulsifiers, such as nonionic and anionic 25 emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates), and dispersants, such as ligninsulfite waste liquors and methylcellulose. 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, lauryl ethers 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, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl 40 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, 45 lignosulfite waste liquors or methylcellulose.

-

17 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 VII or the mixture of the compounds I and at least one of the compounds II to VII with a solid carrier. 5 Granules (eg. coated granules, impregnated granules or homogeneous granules) are usually prepared by binding the active ingredient, or active ingredients, to a solid carrier. 10 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, less, 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. 20 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 VII or of the mixture of the compounds I and at least one of the compounds II to VII. The 25 active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR or HPLC spectrum [sic]). The corresponding formulations are applied by treating the harmful fungi, their habitat or the plants, seeds, soils, areas, 30 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 VII in the case of separate application. 35 Application can be effected before or after infection by the harmful fungi. Examples of such preparations comprising the active ingredients 40 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; 45 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 18 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 5 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; 10 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 2800C, and 10 parts by weight of the adduct of 40 mol of 15 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 20 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 25 kaolin; this dust comprises 3% by weight of active ingredient; 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 30 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 40 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. 45 The synergistic activity of the mixtures according to the invention can be demonstrated by the following experiments:

R

-0 1 4 4I-41 19 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. 5 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: 10 W = (1 - a)-100/@ a corresponds to the fungal infection of the treated plants in % and 15 g corresponds to the fungal infection of the untreated (control) plants in % An efficacy of 0 means that the infection level of the treated 20 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 _j, 25 20-22 (1967)] and compared with the observed efficacies. Colby's formula: E = x + y - x-y/100 30 E is 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 is the efficacy, expressed in % of the untreated control, when using active ingredient A at the concentration a 35 y is the efficacy, expressed in % of the untreated control, when using active ingredient B at the concentration b Use Example 1 - Activity against Pyricularia oryzae (protective) 40 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 innoculated with an aqueous 45 spore suspension of Pyricularia oryzae. The test plants were sub sequently placed in climatized chambers at 22-24 0 C and 95-99% re tive atmospheric humidity for 6 days. The extent of the deve iiRA 20 lopment of the disease on the leaves was then determined visual ly. The visually determined values for the percentage of diseased 5 leaf area were converted into efficacies as percent of the un treated control. An efficacy of 0 means the same disease level as in the untreated control, an efficacy of 100 means 0% disease. The expected efficabies for active ingredient combinations were determined using Colby's formula (Colby, S. R.: "Calculating syn 10 ergistic and antagonistic responses of herbicide combinations", Weeds 15, pp. 20-22, 1967) and compared with the observed effica cies. As component a), use was made of the following compound I': 15

OH

3 H3C, ,N N 0 (I' ) CCH NH O-CH 20 OH N 3 N/ 3 3 O0 25 The test results are shown in Tables 1 and 2 below: 30 35 40 45 I-i 21 Table 1: Ex. Active ingredient Conc. in ppm fficacy in % of the untreated control 5 iC None (100% diseased) 0 2C Compound I' 2.0 20 0.5 0 3C Compound II 0.5 10 10 4C Compound IV 2.0 0 Table 2: Ex. Mixture according to the Observed Calculated 15 invention (conc. in ppm) efficacy efficacy * 5 2 ppm I' + 2 ppm IV 90 20 6 0.5 ppm I' + 0.5 ppm II 70 10 * calculated using Colby's formula 20 S I 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 30 35 40 45

Claims

2. A fungicidal mixture as claimed in claim 1, which is 45 conditioned in two parts, one part comprising the compound I in a solid or liquid carrier and the other part comprising at 27 least one of the compounds II to VII in a solid or liquid carrier.
3. A method for controlling harmful fungi, which comprises 5 treating the fungi, their habitat, or the materials, plants, seeds, soils, areas or spaces to be protected against fungal attack with a fungicidal mixture as claimed in either of claims 1 and 2, where the application of the compound I and at least one of the compounds II to VII may be carried out 10 simultaneously, either together or separately, or in succession.
4. A method as claimed in claim 3, wherein the harmful fungi, their habitat or the plants, seeds, soils, areas, materials 15 or spaces to be kept free from them are treated with from 0.005 to 1 kg/ha of a compound I as set forth in 7aim 1.
5. A method as claimed in claim 3, wherein the harmful fungi, their habitat or the plants, seeds, soils, areas, materials 20 or spaces to be kept free from them are treated with from 0.01 to 1 kg/ha of at least one of the compounds II to VII as set forth in claim 1. 25 30 35 40 45