AU729337B2

AU729337B2 - Fungicidal mixture

Info

Publication number: AU729337B2
Application number: AU76268/96A
Authority: AU
Inventors: Eberhard Ammermann; Gisela Lorenz; Siegfried Strathmann; Oliver Wagner
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1995-11-24
Filing date: 1996-11-18
Publication date: 2001-02-01
Anticipated expiration: 2016-11-18
Also published as: AR004744A1; CZ293592B6; SK282770B6; DE19543746A1; SK50798A3; ZA969796B; ES2163046T3; CN1202798A; CO4770920A1; CA2235039C; KR19990071590A; EP0863702B1; NZ322502A; AU7626896A; KR100428275B1; CN1214717C; IL123896A; PT863702E; EP0863702A1; CZ161098A3

Description

Fungicidal mixture The present invention relates to a fungicidal mixture including a) a p-hydroxyaniline derivative of the formula I

R

3

R

2 zo NH- C- RI where the radicals have the following meanings:

R

1 is hydrogen, Cl-C 8 -alkyl which can be partially or fully halogenated and/or can have attached to it one or two of the following groups: Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 -alkylthio, C 3

-C

7 -cycloalkyl, C 5

-C

7 -cycloalkenyl, it being possible for the cyclic groups, in turn, to have attached to them one to three halogen atoms, CI-C 3 -alkyl 20 groups and/or Cl-C 3 -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, Cl-C 4 -alkyl, Cl-C 4 -haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy and Cl-C 4 -alkylthio;

C

3

-C

6 -cycloalkyl or C 3

-C

6 -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: Cl-C 4 -alkyl, Cl-C 4 -haloalkyl, Cl-C 4 -al- 30 koxy, Cl-C 4 -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, Cl-C 4 -alkyl, Cl-C 4 -haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloal- Skoxy and Cl-C 4 -alkylthio; C6-Cls-bicycloalkyl or C 7 -C js-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: Cl-C 4 -alkyl, Cl-C 4 -haloalkyl, Ci-C 4 -alkoxy, Cl-C 4 -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, Cl-C 4 -alkyl, Cl-C 4 -haloalkyl, Cl-C 4 -alkoxy, Ci-C 4 -haloalkoxy and Cl-C 4 -alkylthio; t 0050/46382 2

R

2 and R 3 independently of one another are halogen, Cl-C 4 -alkyl, Cl-C 4 -haloalkyl, Cl-C 4 alkoxy or Ci-C 4 haloalkoxy; Z is H or R 4 where

R

4 is Cl-C 6 -alkyl or C 2

-C

6 -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: Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 -alkylthio, C 3

-C

7 -cycloalkyl, C 5

-C

7 -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, Cl-C 4 -alkyl, Cl-C 4 -haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy and Cl-C 4 -alkylthio;

C

3

-C

7 -cycloalkyl or C 5

-C

7 -cycloalkenyl, it being possible for these groups to have attached to them one to three of the following radicals: halogen, Cl-C 4 -alkyl, Cl-C 4 -haloalkyl and Cl-C 4 -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, Cl-C 4 -alkyl, Cl-C 4 -haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy and Cl-C 4 -alkylthio;

OR

5 or NR 6

R

7 where

R

5 is Cl-C 6 -alkyl or C 2

-C

7 -cyc loalkyl, C 5

-C

C

3

-C

7 -cycloalkyl or C 5

-C

7 -cycloalkenyl, it being possible for these groups to have attached to them one to three of the following radicals: 0050/46382 3 halogen, C 1

-C

4 -alkyl, C 1

-C

4 -haloalkyl and

C

1

-C

4 -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,

C

1

-C

4 -alkyl, C 1

-C

4 -haloalkyl, C 1

-C

4 -alkoxy,

C

1

-C

4 -haloalkoxy and C 1

-C

4 -alkylthio;

R

6 is C 1

-C

6 -alkyl or C 2

-C

6 -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: C 1

-C

4 -alkylthio, C3-C 7 -cycloalkyl, Cs-C 7 -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,

C

1

-C

4 -alkyl, C 1

-C

4 -haloalkyl, C 1

-C

4 -alkoxy, Ci-C 4 -haloalkoxy and Ci-C 4 -alkylthio;

C

3

-C

7 -cycloalkyl or C 5

-C

7 -cycloalkenyl, it being possible for these groups to have attached to them one to three of the following radicals: halogen, C 1

-C

4 -alkyl, C 1

-C

4 -haloalkyl and

C

1

-C

4 -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,

C

1

-C

4 -alkyl, C 1

-C

4 -haloalkyl, C 1

-C

4 -alkoxy,

C

1

-C

4 -haloalkoxy and C 1

-C

4 -alkylthio; and

R

7 is hydrogen or C 1

-C

6 -alkyl, and b) an active ingredient of the formula IIA or IIB R' /R x Xn Xn RY C R"

R"

IIA IIB where .is a double or single bond and the index and the radicals have the-following meanings: R' -CEC0 2

CE

3

]-CHOCH

3

-C[(CO

2

CH

3

]-NOCH

3 -C (CONHCE 3

J-NOCH

3 -C (CO 2

CH

3

]-CHCH

3 -C [CO 2

CH

3

])=CHCH

2

CH

3 -C (COCH 3 3 NOCH 3 -C [COCH 2

CH

3 3-NOCH 3 -N (OCH 3

)-CO

2

CH

3 -N (CH 3

)-CO

2

CH

3 -N (CH 2

CH

3

)-CO

2

CH

3 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 bicyclic, 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 (CO 2

CH

3

]CHOCH

3 -OC (CO 2

CH

3

]=CHCH

3 OC (CO 2

CH

3 3 =CHCH 2

CH

3 -SC (CO 2

CH

3 J CHOCH 3 20 -SC [C02CH 3

]J=CHCH

3

-SC[(CO

2

CH

3

]=CHCH

2

CH

3

-N(CH

3

)CCO

2

CH

3

]=CHOCH

3

-N(CH

3

)C[CO

2

CH

3

J=NOCH

3 9: ~-CH 2 C (CO 2

CH

3 ]3=CHOCH 3

-CH

2 C (CO 2

CH

3

]=NOCH

3

-CH

2 C (CONHCH 3 3 NOCH 3 RY is oxygen, sulfur, =CH- or is 0, 1, 2 or 3, it being possible for the radicals X to be different when n 1; x is cyano, nitro, halogen, Cl-C 4 -alkyl, Cl-C 4 -haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 -alkylthio; in the event that n 1, a C 3 -Cs-alkylene, C 3 -C-alkenylene, OXY-C 2

-C

4 -alkylene, OXY-Cl-C 3 -alkyleneoxy,

OXY-C

2

-C

4 -alkenylene, oxy-C 2

-C

4 -alkenyleneoxy or butadienediyl 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, Cl-C 4 -alkyl, Cl-C 4 -haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloal koxy or Cl-C 4 -alkylthio; Y or Q is phenyl, pyrrolyl, thienyl, furyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, thiadiazolyl, triazolyl, pyridinyl, 2-pyridinyl, pyrimidinyl and triazinyl; and T is phenyl, oxazolyl, thiazolyl, thiadiazolyl, oxadiazolyl, pyridinyl, pyrimidinyl and triazinyl, in a synergistically active amount, but excluding mixtures where the formula IIA is (methoxyimino) -N-methyl-2-phenoxy-benzacetamide, or (methoxyimino) -N-methyl-2- 5-diznethyl-phenoxy-methyl) benzacetamide.

Compounds of the formula I are disclosed in EP-A 339 418, :EP-A 653 417, EP-A 653 418 and the German Patent Applications File *Ref. Nos. 195 04 599.8 and 195 40 970.1.

:Compounds of the formula I which are preferably suitable for the mixtures according to the invention are those in Table 1.1.

***.Table 1.1: Preferred compounds of the formula I 3 2 R R n*T TJ No. R 3

R

2 RlReferences*) 1.1.1 Cl Cl C(CH 3 )r-CH 2

CH

3

(D)

1.1.2 F CH 3

C(CH

3 2

CH

3 2 (D) 1.1.3 F CH 3

C(CHI)

2

-CH

2 -C1 (D) 1.1.4 F CH 3 C(CH3)2 CH 2 -o c.

(D)

1.1.5 Cl CH 3

C(CH

3 2 -CH2CH 2

CH

3

(D)

1.1.6 F CH 3

C(CH

3 2

-CH

2

CH

2

CH

3

(D)

1.1.7 F CH 3

C(CH

3 2

-CH

2 Br (D) 1.1.8 Cl Cl C(CH 3 2

-CH

3

(D)

1.1.9 Cl Cl C(CH 3 2

-CH

2 Br (D) 1.1.10 Cl CH 3

C(CH

3 2

-CH

2 Cl (D) 11111 Cl CH 3

C(CH

3 2

-CH

2 Br (D) 1.1.12 Cl CH 3

C(CH

3 2

-CH

3

(D)

1-.1.13 Cl CH 3

C(CH

3 2

CH

2 G@ Cl (D) I 1..14 Cl -1CH 3 12-CH 3 -(2.2.1]-heptan-2-yl (D) 4 0050/46382 6 EP-A 653 417 EP-A 653 418 German Patent Application File Ref. No. 195 04 599.8 German Patent Application File Ref. No. 195 40 970.1.

Especially preferred compounds of the formula I are those of Table 1.2.

Table 1.2: (References Especially preferred compounds of and formula as in Table I.1) the formula I No. R 3

R

2

R

1 References 1.2.1 Cl Cl C(CH 3 2

-CH

2 C1

(D)

1.2.2 Cl Cl C(CH 3 2

-CH

2

CH

3 (D) 1.2.3 Cl Cl C(CH 3 2

-CH

2

CH

2

CH

3 (D) 1.2.4 Cl Cl C(CH 3 2

-CH

2 /-Cl

(D)

1.2.5 Cl Cl 2-CH 3 -[2.2.1]-heptan-2-yl

(D)

1.2.6 Cl Cl 2-CH 3 -[2.2.1]-hepten-2-yl

(D)

1.2.7 Cl Cl 1-CH 3 -cyclohexyl EP-A 339 418 The active ingredients IIA and IIB are described, for example, in the following EP-A 203 608, EP-A 229 974, EP-A 243 014, EP-A 256 667, EP-A 273 572, EP-A 291 196, EP-A 310 954, EP-A 331 966, EP-A 341 845, EP-A 370 629, EP-A 378 755, EP-A 384 211, EP-A 386 681, EP-A 393 861, EP-A 405 782, EP-A 416 746, EP-A 429 968, EP-A 439 785, EP-A 463 513, EP-A 468 775, SEP-A 474 042, 4 \EP-A 483 851, publications: EP-A 206 EP-A 242 EP-A 251 EP-A 260 EP-A 274 EP-A 299 EP-A 312 EP-A 335 EP-A 350 EP-A 373 EP-A 379 EP-A 385 EP-A 389 EP-A 398 EP-A 407 EP-A 420 EP-A 430 EP-A 459 EP-A 464 EP-A 471 EP-A 475 EP-A 483 523, 070, 082, 794, 825, 694, 221, 519, 691, 775, 098, 224, 901, 692, 873, 091, 471, 285, 381, 261, 158, 985, EP-A 178 EP-A 212 EP-A 242 EP-A 253 EP-A 260 EP-A 278 EP-A 307 EP-A 312 EP-A 336 EP-A 354 EP-A 374 EP-A 382 EP-A 385 EP-A 391 EP-A 400 EP-A 409 EP-A 422 EP-A 433 EP-A 460 EP-A 468 EP-A 472 EP-A 477 EP-A 487 826, 859, 081, 213, 832, 595, 101, 243, 211, 571, 811, 375, 357, 451, 417, 369, 597, 233, 575, 684, 224, 631, 409, EP-A 203 EP-A 226 EP-A 243 EP-A 254 EP-A 267 EP-A 280 EP-A 307 EP-A 329 EP-A 337 EP-A 363 EP-A 378 EP-A 383 EP-A 386 EP-A 393 EP-A 402 EP-A 414 EP-A 426 EP-A 433 EP-A 463 EP-A 468 EP-A 472 EP-A 480 EP-A 493 606, 917, 012, 426, 734, 185, 103, 011, 211, 818, 308, 117, 561, 428, 246, 153, 460, 899, 488, 695, 300, 795, 711, 0050/46382 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.

It is an object of the present invention to enhance the fungicidal 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 active 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 individual 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 especially important: S 0050/46382 8 unsubstituted or substituted aryloxy, unsubstituted or substituted hetaryloxy, unsubstituted or substituted aryloxymethylene, unsubstituted or substituted hetaryloxymethylene, unsubstituted or substituted arylethenylene, unsubstituted or substituted hetarylethenylene, or a group RaRC=NOCH 2 or RyON=CR6CRE=NOCH 2 where the radicals Ra, RO Ry, R6 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 05/201,946, 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 aryloxy, unsubstituted or substituted hetaryloxy" in general and in particular have the meanings described in the following publications: 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 hetaryloxymethylene" 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 278 595, 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. 44 424.. and DE Pat. Appl. 44 15 483.6; especially preferred radicals "unsubstituted or substituted arylethenylene, unsubstituted or substituted hetarylethenylene" in general and in particular have the meanings described in the following 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,

,^C

Z

0050/46382 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[C0 2

CH

3

]=CHOCH

3 generally and in particular have the meanings of the compounds described in the following publications: EP-A 178 826, EP-A 203 606, EP-A 226 917, 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. 44 424.. and DE Pat. Appl. 44 21 180.5; especially preferred active ingredients of type II where R' is -C[C0 2

CH

3

]=NOCH

3 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[CONHCH

3

]=NOCH

3 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[C0 2

CH

3

]=CHCH

3 or -C[CO 2

CH

3

]=CHCH

2

CH

3 generally and in particular have the meanings of the compounds described in the following 0050/46382 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 10 424.., 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[COCH

3

]=NOCH

3 or -C[COCH 2

CH

3

]=NOCH

3 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(OCH

3

)CO

2

CH

3

-N(CH

3

)-CO

2

CH

3 or -N(CH 2

CH

3

)-CO

2

CH

3 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[C0 2

CH

3

]=CHOCH

3

-OC[CO

2

CH

3

]=CHCH

3

-OC[CO

2

CH

3

]=CHCH

2

CH

3

-OC[COCH

2

CH

3

]=NOCH

3

-SC[CO

2

CH

3

]=CHOCH

3 -SC[C02CH 3

=CHCH

3 -SC [C0 2

CH

3

]=CHCH

2

CH

3

-N(CH

3 C[ C0 2

CH

3

]=CHOCH

3

-N(CH

3

)C[CO

2

CH

3

]=NOCH

3

-CH

2

C[CO

2

CH

3

]=CHOCH

3

-CH

2

C[CO

2

CH

3

]=NOCH

3 or

-CH

2

C[CONHCH

3

]=NOCH

3 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.1A Compounds of the formula IIA where Q is phenyl, R' is -C(C0 2

CH

3

)=CHOCH

3 n has a value of 0, R" is unsubstituted or substituted (het)aryloxymethylene, the unsubstituted or substituted (het)aryl group having the following meanings: 0050/46382 No. unsubstituted or substituted Reference (het)aryl II.* A-i 2-CH 3

-C

6

H

4 EP-A 226 917 II.1A-2 2,5-(CH 3 2

-C

6

H

3 EP-A 226 917 II.1A-3 2-CH 3 4-C[CH 3 ]=IqOCH 3

-C

6

H

3 EP-A 386 561 II.1A-4 2-CH 2

CH

2

CH

3 6-CF 3 pyrimidin-4-yl EP-A 407 873 2, 4- (CH 3 2

-C

6

H

3 EP-A 226 917 Table II.1B Compounds of the formula IIA where R' is -C(CO 2

CH

3

)=CHOCH

3 ,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: jNo. unsubstituted or substituted Reference 1 (het)aryl

I

II.1B-1 C 6

H

5 EP-A 178 826 1 g~.1-2 6-[2-CN-C 6

H

4 -OIJ-pyrimidin-4-yl EP-A 382 375 j Table II.1C Compounds of the formula IIA where R' is -C(CO 2

CH

3

)=CHOCH

3 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: unsubstituted or substituted Reference (het) aryl II.1C-1 1-(2,4-Cl 2

-C

6

H

3 5-CF 3 -pyrazol-4-yl EP-A 528 245 35II.1C-2 1- (4-Cl-C 6

H

4 -pyrazol-4-yl EP-A 378 755 1- -C3CH P- 0 0 1I1.1C-4 3-CF 3

-C

6

H

4 EP-A 203 606 II.1C-543-ClH-C 6

H

4 EP-A 203 606 0050/46382 Table II. 1D Compounds of the formula IIA where Q is phenyl, R' is -C (CO 2

CH

3

=CHOCH

3 n has a value of 0, R" is CH 2 ON=CRaRO Ra' and RO having the following meanings: No. Ra RPReference II.1D-1 CH 3 4-Cl-C 6

H

4 EP-A 370 629 II.1D-2 CH 3 3-CF 3

-C

6

H

4 EP-A 370 629 11. 1D-3 ICH 3 14-OCH 2

CH

3 -pyrimidin-2-yl WO-A 92/1848 Table II.lE Compounds of the formula hIA where Q is phenyl, R' is

-C(CO

2

CH

3

)=CHOCH

3 n has a value of 0, R" is CH 2 ON=CRYCR6=NOR'E, OF, Rand RE- having the following meanings: R' W 0 r Reference II.1E-1 CH 3

CH

3

CH

3 DE Appl. No. 44 03 447.4 II.1E-2 CH 3

CH

3

CH

2

CH

3 DE Appl. No. 44 03 447.4 I1.1E-3 ICH 3

C

6

H

5

CH

3 DE Appl. No. 44 03 447.4 II.1E-4 CH 3

C

6

H

5

CH

2

CH

3 DE Appl. No. 44 03 447.4

CH

3 4-Cl-C 6

H

4

CH

3 DE Appl. No. 44 21 180.5 II.1E-6 CH 3 4-Cl-C 6

H

4

CH

2

CH

3 DE Appl. No. 44 21 180.5 Table II.2A Compounds of the formula hIA where Q is phenyl, R' is

-C(CO

2

CH

3

)=NOCH

3 n has a value of 0, R" is unsubstituted or substituted (het)aryloxymethylene, the unsubstituted or substituted (het)aryl group having the following meanings: No. unsubstituted or substituted Reference (het) aryl II. 2A-1 2-CH 3

-C

6

H

4 EP-A 253 213 II.2A-2 2 (CH 3 2

-C

6

H

3 EP-A 400 417 II.2A-3 2,4-(CH 3 2

-C

6

H

3 EP-A 400 417 II.2A-4 2,3,5-(CH 3 3

-C

6

H

2 EP-A 400 417 II.2A-5 2-Cl, 5-CH 3

-C

6

H

3 EP-A 400 417 II.2A-6 2-CH 3 4-C[CH 3

]=NOCH

3

-C

6

H

3 IEP-A 386 561 0050/46382 13 Table II.2B Compounds of the formula IIA where Q is phenyl, RI is

-C(CQ

2

CH

3

)=NOCH

3 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

J

II.2B-1 C 6

H

5 EP-A 253 213 II. 2B-2 j6-[2-CN-C 6

H

4 -0]-pyrimidin-4-yl JEP-A 468 684 iTable II.2C Compounds of the formula hIA where Q is phenyl, R' is

-C(CO

2

CH

3

)=NOCH

3 n has a value of 0, R" Is CH 2 ON=CR, where R a and RP 3 have the following meanings: No. R a RP Reference 11.2C-1 CH 3 4-Cl-C 6

H

4 EP-A 463 488 II.2C-2 CH 3 3-Cl-C 6

H

4 EP-A 463 488 II.2C-3 CH 3 4-CF 3

-C

6

H

4 EP-A 463 488 II.2C-4 CH 3 3-CF 3

-C

6

H

4 EP-A 463 488 11.2C-5 CH 3 4-CH 3

-C

6

H

4 EP-A 463 488 II.2C-6 CH 3 4-OCH 2

CH

3 -pyrimidin-2-yl EP-A 472 300 II.2C-7 CH 3 3,5-C 2

-C

6

H

3 EP-A 463 488 Table II.2D Compounds of the formula IIA where Q is phenyl, R' is

-C(CO

2

CH

3

)=NOCH

3 n has a value of 0, R"I is CH 2

ON=CRYCR

6 =~NORE, where Ry, R 6 and RS have the following meanings: No. Ry R5_ RE Reference 11.2D-1 CH 3 GCl 3 GCl 3 DE Appl. No. 44 03 447.4 II.2D-2

CH

3 GCl 3 CH 2

CH

3 DE Appl. No. 44 03 447.4 1 II.2D-3 GCl 3

C

6

H

5

CH

3 DE Appl. No. 44 03 447.4 II.2D-4 CH 3

C

6

H

5

CH

2

CH

3 DE Appl. No. 44 03 447.4 0050/46382 No. Ry R" R E Reference 11.2D-5 CH 3 4-Cl-C 6

H

4

CH

3 DE Appi. No. 44 21 180.5 II.2D-6 CH 3 4-Cl-C 6

H

4

CH

2

CH

3 DE Appi. No. 44 21 180.5 U Table II.3A Compounds of the formula IIA where Q is phenyl, R' is

-C(CONHCH

3

)=NOCH

3 n has a value of 0, R" is unsubstituted or substituted (het)aryloxymethylene, the unsubstituted or substituted (het)aryl group having the following meanings: unsubstituted or substituted Reference (het)aryl II.3A-1 2-CH 3

-C

6

H

4 EP-A 477 631 II.3A-2 2,5-(CH 3 2

-C

6

H

3 EP-A 477 631 II.3A-3 2,4-(CH 3 2

-C

6

H

3 EP-A 477 631 II.3A-4 2,3,5-(CH 3 3

-C

6

H

2 EP-A 477 631 2-CH 3 4-C[CH 3

]=NQCH

3

-C

6

H

3 EP-A 579 124 II.3A-6 1-[4-Cl-C 6

H

4 ]-pyrazol-3-yl DE Appl. No. 43 05 502.8 I.A71-[(2, 4-C1 2

-C

6

H

3 ]-pyrazol-3-yl DE Appl. No. 43 05 502.8 Table II.3B Compounds of the formula hIA where Q is phenyl, R' is

-C(CONHCH

3

)=NOCH

3 n has a value of 0, R" is unsubstituted or substituted (het)aryloxy, the unsubstituted or substituted (het)aryl group having the following meanings: unsubstituted or substituted Reference II (het) II.3B-1 C 6

H

5 EP-A 398 692 III3B-2 6-([2-CN-C 6

H

4 -pyrimidin-4-yl GB-A 2 253 624 Afl% 1.t 0050/46382 Table II.3C Compounds of the formula IIA where Q is phenyl, R' is

-C(CONHCH

3

)=NOCH

3 n has a value of 0, R" is unsubstituted or substituted (het)arylethenylene, the unsubstituted or substituted (het)aryl group having the following meaning: No. unsubstituted or substi- Reference tuted (het)aryl .0II.3C-1 1-[2,4-C1 2

-C

6

H

3 DE Appl. No. 44 23 615.8 3 -pyrazol-4-yl Table II.3D Compounds of the formula IIA where Q is phenyl, R' is

-C(CONHCH

3

)=NOCH

3 n has a value of 0, R- is CH 2 ON=CR'RP, where R' and RPhave the following meanings: No. Ra RT_ Reference II.3D-1 CH 3 4-Cl-C 6

H

4 EP-A 463 488 II.3D-2 CH 3 3-Cl-C 6

H

4 EP-A 463 488 II.3D-3 CH 3 4-CF 3

-C

6

H

4 EP-A 585 751 II.3D-4 CH 3 3-CF 3

-C

6

H

4 EP-A 585 751

CH

3 4-CH 3

-C

6

H

4 EP-A 463 488 II.3D-6 CH 3 3, 5-C1 2

-C

6

H

3 EP-A 463 488 II.3AD-7 ICH 3 2-OCH 2

CH

3 -pyrimidin-2-yl WO-A 92/13,830 Table II.3E Compounds of the formula hIA where Q is phenyl, R' is

-C(CONHCH

3

)=NOCH

3 n has a value of 0, R"I is CH 2

ON=CRYCR

6

=NOR':,

where Ry, R6 and R6 have the following meanings: No. Ry Rb R E Reference II.3E-1 CH 3

CH

3

CH

3 DE Pat. Appl. 44 21 182.1 II.3E-2 CH 3

CH

3 CH 2

CH

3 DE Pat. Appl. 44 21 182.11 Ix.3E-3 CH 3

C

6

H

5

CH

3 DE Pat. Appl. 44 21 182.1 II.3E-4 CH 3

C

6

H

5

CH

2

CH

3 DE Pat. Appl. 44 21 182.1 111.3E-5 ICH 3 j4-Cl-C 6

H

4

ICH

3 1DE Pat. Appl. 44 21 182.1 0050/46382 No. Jy II.3E-6

CH

3 II.3E-7 jCH 3 16 R Reference

CH

2

CH

3 DE Pat. Appi. 44 21 182.1

CH

3 DE Pat. Appi. 44 21 182.1 Table II.AA Compounds of the formula IIA where Q is phenyl, R' is

-C(CO

2

CH

3

)=CHCH

3 n has a value of 0, R"I is unsubstituted or substituted (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-CH 3

-C

6

H

4 EP-A 280 185 II.4A-2 2,5-(CH 3 2

-C

6

H

3 EP-A 513 580 20II.4A-3 2,4-(CH 3 2

-C

6

H

3 EP-A 513 580 II.4A-4 2,3,5-(CH 3 3

-C

6

H

2 EP-A 513 580 2-Cl, 5-CH 3

-C

6

H

3 EP-A 513 580 II.4A-6 2-CH 3 4-C[CH 3

]=NOCH

3

-C

6

H

3 EP-A 513 580 11.4A-7 1-[4-Cl-C 6

H

4 ]-pyrazol-3-yl DE Pat. Appl. 44 15 483.6 Table II.4B Compounds of the formula hIA where Q is phenyl, R' is

-C(CO

2

CH

3

)=CHCH

3 n has a value of 0, R" is unsubstituted or substituted (het)aryloxy, the unsubstituted or substituted (het)aryl group having the following meaning:

INO.

unsubstituted or substituted (het) aryl Reference 11. 4B-1 C 6

H

5 EP-A 513 580 0050/46382 Table II.4C Compounds of the formula

-C(CO

2

CH

3

)=CHCH

3 n has a re Ry, R 6 and Re have the IIA where Q is phenyl, R' is value of 0, R- is CH 2

ON=CRYCR

6 =~NQRC, whefollowing meanings: No. R'y R6 Re Reference II.4C-1 CH 3

CH

3

CH

3 DE Pat. Appi. 44 21 180.5 II.4C-2 CH 3

CH

3

CH

2

CH

3 DE Pat. Appl. 44 21 180.5 II.4C-3 CH 3

C

6

H

5

CH

3 DE Pat. Appl. 44 21 180.5 II.4C-4 CH 3

C

6

H

5

CH

2

CH

3 DE Pat. Appi. 44 21 180.5

CH

3 4-Cl-C 6

H

4

CH

3 DE Pat. Appl. 44 21 180.5 II.4C-6 ICH 3 14-Cl-C 6

H

4

CH

2

CH

3 DE Pat. Appl. 44 21 180.5 Table Compounds of the formula IIA where Q is phenyl, R' is

-C(CO

2

CH

3

)=CHCH

2

CH

3 n has a value of 0, R" is unsubstituted or substituted (het)aryloxymethylene, the unsubstituted or substituted (het)aryl group having the following meanings: No. unsubsti.tuted or substituted Reference (het)aryl 11.5A-1 2-CH 3

-C

6

H

4 EP-A 513 580 30II.5A-2 2 (CH 3 2

-C

6

H

3 EP-A 513 580 _513 __580 II.5A-3 2,4,-(CH 3

)-C

6 H2 EP-A 513 580 II.5-4 23,5-CH 3 3 -c 6 2 EPA 51 58 11.5A-5 2-Cl, 5-CH 3

-C

6

H

3 EP-A 513 580 II.5A-6 2-CH 3 4-C[CH 3

]=NOCH

3

-C

6

H

3 EP-A 513 580 Table Compounds of the formula hIA where Q is phenyl, R' is

-C(CO

2

CH

3

)=CHCH

2

CH

3 n has a value of 0, R" is unsubstituted or substituted (het)aryloxy, the unsubstituted or substituted (het)aryl group having the following meaning: 0050/46382 Table Compounds of the formula IIA where Q is phenyl, R' is

-C(CO

2

CH

3

)=CHCH

2

CH

3 n has a value of 0, R" is CH 2 ON=CR7CR6=NORE,, where R7, R 6 and R' have the following meanings: No'. R7 R6 R Reference II.5C-1 CH 3

CH

3

CH

3 DE Pat. Appl. 44 21 180.5 .0 II.SC-2 CH 3

CH

3 CH 2

CH

3 DE Pat. Appl. 44 21 180.51 II.5C-3 CH 3

C

6

H

5

CH

3 DE Pat. Appl. 44 21 180.5 11.5C-4 CH 3

C

6

H

5

CH

2

CH

3 DE Pat. Appl. 44 21 180.5 1I.5C-5 CH 3 4-Cl-C 6

H

4

CH

3 DE Pat. Appl. 44 21 180.5 11.5C-6 CH 3 4-Cl-C 6

H

4

CH

2

CH

3 _DE Pat. Appl. 44 21 180.5 Table II.6A Compounds of the formula IIA where Q is phenyl, R' is

-C(COCH

3

)=NOCH

3 n has a value of 0, R" is unsubstituted or substituted (het)aryloxymethylene, the unsubstituted or substituted (het)aryl group having the following meanings: No. unsubstituted or substituted Reference (het) aryl II.6A-1 2-CH 3

-C

6

H

4 EP-A 498 188 II.6A-2 12,5-(CH 3 2

-C

6

H

3 EP-A 498 188 II.6A-3 12,4-(CH 3 2

-C

6

H

3 EP-A 498 188 II.6A-4 12, 3,5- (CH 3 3

-C

6

H

2 EP-A 498 188 2-CH 3 4-C[CH 3

J=NOCH

3

-C

6

H

3 EP-A 498 188 0050/46382 19 Table II.6B Compounds of the formula IIA where Q is phenyl, R' is -C (COCH 3

=NOCH

3 n has a value of 0, R" is unsubstituted or substituted (het)aryloxy, the unsubstituted or substituted (het)aryl group having the following meanings: jNo. unsubstituted or substituted reference II (het)aryl

J

II6- 65EP-A 498 188 LI. 6B-2 16- [2-C1N-C 6

H

4 -pyrimidin-4-yl JEP-A 498 188 Table II.7A Compounds of the formula IIA where Q is phenyl, R' is

-C(COCH

2

CH

3 )=qOCH 3 n has a value of 0, R" is unsubstituted or substituted (het)arylokymethylene, the unsubstituted or substituted (het)aryl group having the following meanings: No. unsubstituted or substituted Reference (het)aryl II. 7A-1 2-CH 3

-C

6

H

4 EP-A 498 188 II.7A-2 2,5-(CH 3 2

-C

6

H

3 EP-A 498 188 II.7A-3 2,4-(CH 3 2

-C

6

H

3 EP-A 498 188 11.7A-4 2,3,5-(CH 3 3

-C

6

H

2 EP-A 498 188 II.7A-5 2-CH 3 4-C[CH 3

]=NOCH

3

-C

6

H

3 EP-A 498 188 H Table II.7B Compounds of the formula hIA where Q is phenyl, R' is

-C(COCH

2

CH

3

)=NOCH

3 n has a value of 0, R"I is unsubstituted or substituted (het)aryloxy, the unsubstituted or substituted (het)aryl group having the following meanings: No. unsubstituted or substituted Reference (het) aryl j II.7B-1 C 6

H

5 EP-A 498 188 II.7B-2 6-[2-CN-C 6

H

4 -0]-pyrimidin-4-yl EP-A 498 188 0050/46382 Table II.8A Compounds of the formula IIA where Q is phenyl, R' is

-N(OCH

3

)-CQ

2

CH

3 n has a value of 0, R" is unsubstituted or substituted (het)aryloxymethylene, the unsubstituted or substituted (het)aryl group having the following meanings: No. unsubstituted or substituted Reference (het) aryl 11.8A-1 2-CH 3

-C

6

H

4 WQ-A 93/15,046 II.8A-2 2,5-(CH 3 2

-C

6

H

3 WO-A 93/15,046 II.8A-3 2,4-(CH 3 2

-C

6

H

3 WO-A 93/15,046 II.8A-4 2,3,5-(CH 3 3

-C

6

H

2 WO-A 93/15,046 2-Cl, 5-CH 3

-C

6

H

3 WO-A 93/15,046 II.8A-6 2-CH 3 4-C[CH 3

]=NOCH

3

-C

6

H

3 WO-A 93/15,046 II.8A-7 2-CH 3 4-C[CH 3

]=NOCH

2

CH

3

-C

6

H

3 WO-A 93/15,046 II.8A-8 2-CH 3 4-C[CH 2

CH

3

]=NOCH

3

-C

6

H

3 WO-A 93/15,046 II.8A-9 2-CH 3 4-C[CH 2

CH

3

]=NOCH

2

CH

3

-C

6

H

3 WO-A 93/15,046 1-t4-Cl-C 6

H

4 ]-pyrazol-3-yl DE Pat. Appl.

23 612.3 Table II.8B Compounds of the formula hIA where Q is phenyl, R' is

-N(OCH

3

)-CO

2

CH

3 n has a value of 0, R" is CH 2 ON=CRoRP, where Ra and ROhave the following meaning: INo. Ra IRP Reference I 35II.8B-1 CH 3 13,5-Cl 2

-C

6

H

3 WO-A 93/15,046 When providing the mixtures, it is preferred to employ the pure active ingredients I and IIA or hIb, with which it is possible to admix further active ingredients against pests (for example insects, arachnids or nematodes) or harmful fungi, or else herbicidally active ingredients or growth-regulating active ingredients or fertilizers, as required.

4The mixtures of the compounds I and IIA or IIB, or the simultaneous joint or separate use of the compounds I and IIA or I and IIB, are distinguished by an outstanding activity against a broad 0050/46382 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 cucurbits, Podosphaera leucotricha on apples, Puccinia species on 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, vegetables, ornamentals and grapevines, Cercospora arachidicola on peanuts, 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.

The compounds I and IIA, or I and IIB, can be applied simultaneously, 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).

S 0050/46382 22 Depending on the nature of the desired effect, the rates of application 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 compounds I and IIA, or I and IIB, are applied together or separately 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 suspensions 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 guarantee as fine and uniform a distribution as possible of the mixture 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 emulsifiers 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-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acid, S//S ~of alkyl- and alkylarylsulfonates, of alkyl, lauryl ether and S/A (7_ S 0050/46382 23 fatty alcohol sulfates, and the salts of sulfated hexa-, heptaand 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 tributylphenyl polyglycol ether, 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, 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, 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 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 1 H NMR or HPLC spectrum [sic]).

The compounds I, IIA and IIB, or the mixtures, or the corresponding 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 fungicidally active amount of the mixture, or of the compounds I and 0050/46382 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 and were assigned for reasons of clarity: Cl Cl HO NH- CO- C(CH 3 2

CH

2 C1

(A)

Compound 1.2.1 C1 Cl HO-- NH--CO

(B)

CH

3 Compound 1.2.5 endo exo 1 1 Cl Cl 3 HO- NH--CO

(C)

H

3

C

Compound 1.1.15

CH

3 O- CH 2 (D) H3CO- C N- OCH 3 I I Compound II.2A-1 0 0050/46382 N H c OCH 3 CN H3CO-C" Compound II.1B-2

H

3 CO- N C- C(CH 3 N- O- CH 2 cH 3 C- N C N- OCH 3 H3C--N-C/3 H 0 Compound II.3E-3 of the double bonds denoted by were in the E configuration.

Use example 1 Activity against Botrytis cinerea Bell pepper seedlings cv. "Neusiedler Ideal Elite" which had 4 to well developed leaves were sprayed to run-off point with aqueous suspensions comprising 80 of active ingredient and 20 of emulsifier 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 240C. 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 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 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 r 0050/46382 Table 1.1: Efficacies of the individual active ingredients Active Active ingredient coningred- centration in the spray Efficacy of untreated ient mixture [ppm] control] 100 84

(A)

100

(B)

25 100

(C)

25 0 25 0 25 0 Table 1.2: Efficacy of the mixture Active ingredient mixture Observed Expected efficacy efficacy 100 ppm 25 ppm 100 84 Mixing ratio 4 1 ppm 25 ppm 92 Mixing ratio 1 1 100 ppm 25 ppm 99 84 Mixing ratio 4 1 ppm 25 ppm 83 Mixing ratio 1 1 100 ppm 25 ppm 98 84 Mixing ratio 4 1 ppm 25 ppm 99 Mixing ratio 1 1 100 ppm 25 ppm 99 Mixing ratio 4 1 ppm 25 ppm 99 Mixing ratio 1 1 100 ppm 25 ppm 99 Mixing ratio 4 1 ppm 25 ppm 99 Mixing ratio 1 1 100 ppm 25 ppm 100 Mixing ratio 4 1 ppm 25 ppm 99 Mixing ratio 1 1 0050/46382 Active ingredient mixture 100 ppm 25 ppm Mixing ratio 4 1 ppm 25 ppm Mixing ratio 1 1 100 ppm 25 ppm Mixing ratio 4 1 ppm 25 ppm Mixing ratio 1 1 100 ppm 25 ppm Mixing ratio 4 1 ppm 25 ppm 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 0 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 R. Colby "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, pages 20 to 22 (1967)) and compared with the observed efficacies.

S 0050/46382 28 Untreated control: Disease level 100 Table 2.1: Efficacies of the individual active ingredients Active Active ingredient coningred- centration in the spray Efficacy of untreated ient mixture [ppm] control] 100 100

(B)

100

(C)

25 77 25 Table 2.2: Efficacy of the mixture Active ingredient mixture Observed Expected efficacy efficacy 100 ppm 25 ppm 77 48 Mixing ratio 4 1 ppm 25 ppm 90 79 Mixing ratio 1 1 100 ppm 25 ppm 80 51 Mixing ratio 4 1 ppm 25 ppm 75 42 Mixing ratio 1 1 100 ppm 25 ppm 97 51 Mixing ratio 4 1 ppm 25 ppm 89 Mixing ratio 1 1 Test result: For all mixing ratios, the observed efficacy exceeds the value calculated beforehand using Colby's formula.

Claims

1. A fungicidal mixture including a) a p-hydroxyaniline derivative of the formula I R 3 R 2 ZONH-C- R 1 I where the radicals have the following meanings: R 1 i~s hydrogen, Cl-Ce-alkyl which can be partially or fully halogenated and/or can have attached to it one or two of the following groups: C 1 -C 4 -alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 -alkylthio, C 3 -C 7 -cycloalkyl, C 5 -C 7 -cycloalkenyl, it being possible for the cyclic :groups, in turn, to have attached to them one to three halogen atoms, Cl-C 3 -alkyl groups and/or Cl-C 3 -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, Cl- 4 -alkyl, Cl-C 4 -haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy and Cl-C 4 -alkylthio; .C 3 -C 6 -cycloalkyl or C 3 -C 6 -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: Cl-C 4 -alkyl, Cl-C 4 haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -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, Cl-C 4 -alkyl, Cl-C 4 -halo- alkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy and Cl-C 4 -al- kylthio; C 6 -C 1 -bicycloalkyl or C 7 -C-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: Cl-C 4 -alkyl, Cl-C 4 -haloalkyl, Cl-C 4 alkoxy, Cl-C 4 -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, Cl-C 4 -alkyl, '1 0050/46382 C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy and C 1 -C 4 -alkylthio; R 2 and R 3 independently of one another are halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 haloalkoxy; Z is H or R 4 where R 4 is C 1 -C 6 -alkyl or C 2 -C 6 -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: C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 3 -C 7 -cyclo- alkyl, C 5 -C 7 -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, C 1 -C 4 alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 haloalkoxy and C 1 -C 4 -alkylthio; C 3 -C 7 -cycloalkyl or C 5 -C 7 -cycloalkenyl, it being possible for these groups to have attached to them one to three of the following radicals: halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl and C 1 -C 4 -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-C 4 -alkyl, C1-C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy and C 1 -C 4 -alkylthio; OR 5 or NR 6 R 7 where R 5 is C 1 -Cs-alkyl or C 2 -C 6 -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: C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkyl- thio, C 3 -C 7 -cycloalkyl, C 5 -C 7 -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, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 4 0050/46382 31 C1-C 4 -alkoxy, C 1 -C 4 -haloalkoxy and C 1 -C 4 -al- kylthio; C 3 -C 7 -cycloalkyl or C 5 -C 7 -cycloalkenyl, it being possible for these groups to have attached to them one to three of the follow- ing radicals: halogen, C 1 -C 4 -alkyl, C 1 -C 4 haloalkyl and C 1 -C 4 -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, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, Ci-C 4 -haloalkoxy and C 1 -C 4 -alkylthio; R 6 is C 1 -C 6 -alkyl or C 2 -C 6 -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: C 1 -C 4 -alkylthio, C 3 -C 7 -cycloalkyl, C 5 -C 7 -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, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, Ci-C 4 -haloalkoxy and C 1 -C 4 -alkylthio; C 3 -C 7 -cycloalkyl or C 5 -C 7 -cycloalkenyl, it being possible for these groups to have attached to them one to three of the following radicals: halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl and Ci-C 4 -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, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, Ci-C 4 -alkoxy, C 1 -C 4 -haloalkoxy and C 1 -C 4 alkylthio; and R 7 is hydrogen or Ci-C6-alkyl, and b) an active ingredient of the formula IIA or IIB y C IIA IIB where is a double or single bond and the index and the radicals have the following meanings: R' -C [CO 2 CH 3 ]=CHOCH 3 -C[(CO 2 CH 3 ]=NOCH 3 -C(CONHCH 3 ]=NOCH 3 -C[CO 2 CH 3 ]=CHCH 3 C [CO 2 CH 3 ]=CHCH 2 CH 3 -C (COCH 3 ]=NOCH 3 (COCH 2 CH 3 ]=NOCH 3 -N (OCH 3 )-CO 2 CH 3 -N(CH 3 )-CO2CH 3 -N(CH 2 CH 3 )-CO 2 CH 3 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 (CO 2 CH 3 ]=CHOCH 3 -OC (CO 2 CH 3 ]=CHCH 3 -OC (CO 2 CH 3 ]=CHCH 2 CH 3 -SC (CO 2 CH 3 ]J=CHOCH 3 -SC(CQ 2 CH 3 ]=CHCH 3 -SC(CO 2 CH 3 )]CHCH 2 CH 3 -N (CH 3 )C (CO 2 CH 3 ]=CHOCH 3 -N (CH 3 )C CO 2 CH 3 j=NOCH 3 -CH 2 C (CO 2 CH 3 ]=CHOCH 3 -CH 2 C[(CO 2 CH 3 ]=NOCH 3 -CH 2 C[(CONHCH 3 ]=NOCH 3 RY is oxygen, sulfur, =CH- or 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, Cl-C 4 -alkyl, Cl-C 4 -halo- alkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 -alkyl- thio; in the event that n 1, a C 3 -Cs-alkylene, C 3 -CS-al- kenylene, OXY-C 2 -C 4 -alkylene, OXY-Cl-C 3 alkyleneoxy, OXY-C2-C 4 -alkenylene, N OXY-C 2 -C 4 -alkenyleneoxy or butadienediyl group which LU~ 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, C 1 -C 4 -alkyl, Cl- C 4 -haloalkyl, Cl-CI-alkoxy, C 1 -C 4 -haloalkoxy or C±L- C 4 -alkylthio, Y is or Q is phenyl, pyrrolyl, thienyl, furyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, thiadiazolyl, triazolyl, pyridinyl, 2-pyridinyl, pyrinidinyl and triazinyl; and T is phenyl, oxazolyl, thiazolyl, thiadiazolyl, oxadiazolyl, pyridinyl, pyrimidinyl and triazinyl, in a synergistically active amount, but excluding mixtures where the formula IIA is CE) (methoxyimino) -N-methyl-2-phenoxy-benzacetamide, or (methoxyimino) -N-methyl-2- 5-dimethyl-phenoxy-methyl) :999 benzacetamide.

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 follows: 3 D R 3 R 2 C1 C1 C (CHA) 2 -CH 2 Cl Cl Cl C (CHA) 2 -CH 2 CH 3 Cl Cl C (CHA) 2 -CH 2 CH 2 CH 3 Cl Cl C (CH 3 2 -CH 2 C1 Cl C1 2-CH 3 2.1]-heptan-2-yl C1 C1 2-CH 3 1]-heptan-2-yl Cl Cl 1-CH 3 -cyclohexyl

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. A method of controlling harmful fungi, which 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. The use of the compound I as set forth in claim 1 for the preparation of a fungicidally active synergistic mixture as claimed in claim 1. S: 10. The use of the compound IIA or IIB as set forth in claim 1 for the preparation of a fungicidally active synergistic mix- ture as claimed in claim 1.

11. A fungicidal mixture according to claim 1 and as herein described with reference to the examples.

12. A method of controlling harmful fungi according to claim 5 and as herein described with reference to the use examples. DATED this 26th day of October, 1999 BASF AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA L LCG:CLR:JL Case No. P14098AU00 0050/46382 Fungicidal mixture Abstract Fungicidal mixture comprising a) a p-hydroxyaniline derivative of the formula I R 3 R 2 ZO NH- R1 R 1 H, unsubstituted of substituted: alkyl, cycloalkyl, cycloalkenyl, bicycloalkyl, bicycloalkenyl; R 2 R 3 independently of one another: halogen, alkyl, haloalkyl, alkoxy, haloalkoxy; Z H, R 4 where R 4 unsubstituted or substituted: alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, OR 5 NR 6 R 7 where R 5 ,R 6 independently of one another unsubstituted or substituted: alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl; R 7 H, alkyl, and b) an active ingredient of the formula IIA or IIB /Rx Xn Xn T RY R" R" IIA IIB 4 where is a double or single bond and the index and the substituents have the following meanings: STA ,o,7 0050/46382 R' -C[CO 2 CH 3 ]=CHOCH 3 -C[CO 2 CH 3 ]=NOCH 3 -C [CONHCH 3 ]I=NOCH 3 -C [CO 2 CH 3 ]=CHCH 3 -C[CO 2 CH 3 J=CHCH 2 CH 3 -C[COCH 3 ]=NOCH 3 -C[COCH 2 CH 3 ]=NOCH 3 -N(OCH 3 )-CO 2 CH 3 -N (CH 3 )-CO 2 CH 3 -N (CH 2 CH 3 )-CO 2 CH 3 R" 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 bicyclic, partially or fully unsaturated system which, besides carbon ring members, may contain hetero atoms from the group consisting of oxygen, sulfur and nitrogen; Rx O COC 2 CH 3 ]I=CHQCH 3 -OC (CO 2 CH 3 I CHCH 3 -OC (CO 2 CH 3 ]I=CHCH 2 CH 3 -SC [CO 2 CH 3 ]=CHOCH 3 -SC [CO 2 CH 3 ]I=CHCH 3 -SC [CO 2 CH 3 )I=CHCH 2 CH 3 -N(CH 3 )C[CO 2 CH 3 ]=CHOCH 3 -N(CH 3 )C[CO 2 CH 3 ]=NOCH 3 -CH 2 C [CO 2 CH 3 ]=CHOCH 3 -CH 2 C [CO 2 CH 3 ]=NOCH 3 -CH 2 C[CONHCH 3 ]NOCH 3 RY oxygen, sulfur, =CH- or n 0, 1, 2 or 3, it being possible for the radicals X to be different when n 1; X cyano, nitro, halogen, Cl-C 4 -alkyl, Cl-C 4 -haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 -alkylthio; in the event that n 1, a C 3 -C 5 -alkylene, C3-C 5 -alkenylene, OXY-C 2 -C 4 -alkylene, OXY-Cl-C 3 -alkyle- neoxy, OXY-C2-C 4 -alkenylene, OXY-C 2 -C 4 -alkenyleneoxy or butadienediyl 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, C 1 -C 4 -alkyl, C 1 -C 4 haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy or C 1 -C 4 alkylthio, Y C- [sic] or Q phenyl, pyrrolyl, thienyl, furyl, pyrazolyl, imidazo- lyl, oxazolyl, isoxazolyl, thiazolyl, thiadiazolyl, triazolyl, pyridinyl, 2-pyridinyl, pyrimidinyl and triazinyl; and '4 \L 0050/46382 T phenyl, oxazolyl, thiazolyl, thiadiazolyl, oxadia- zolyl, pyridinyl, pyrimidinyl and triazinyl, in a synergistically active amount, and its use for control- ling harmful fungi.