SK282770B6 - Fungicidal mixture - Google Patents

Abstract

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

Description

The invention relates to a fungicidal composition which is suitable for controlling harmful fungi.

BACKGROUND OF THE INVENTION

Said compounds of the formula (I) are known (EP-A 339418, EP-A 653417, EP-A 653418 and German Published Patent Application No. Az. 045459999 and 1954070.1).

The active compounds of formula (IIA) and (IIB) mentioned are described, for example, in the following patents:

EP-A 178 826, EP-A 203 606, EP-A 203 608. EP-A 206 523, EP-A 212 859, EP-A 226 917. EP-A 229 974, EP-A 242 070, EP-A 242 081. EP-A 243 012. EP-A 243 014, EP-A 251 No. 082, EP-A 253 213. EP-A 254 426 EP-A 256 667, EP-A 260 794, EP-A 260 832. EP-A 267 734th EP-A 273 572, EP-A 274 825, EP-A 278 595. EP-A 280 185. EP-A 291 196, EP-A 299 694, EP-A 307 101 EP-A 307 103rd EP-A 310 954, EP-A 312 221. EP-A 312 243. EP-A 329 011- EP-A 331 966, EP-A 335 519, EP-A 336 211. EP-A 337 211. EP-A 341 845, EP-A 3S0 691, EP-A 354 571. EP-A 363 818th EP-A 370 629, EP-A 373 775, EP-A 374 811. EP-A 378 308. EP-A 378 755, EP-A 379 No. 098, EP-A 382 375th EP-A 383 117. EP-A 384 211, EP-K 385 224, EP-X 385 3S7. EP-A 386 561st EP-A 386 681, EP-A 389 901, EP-A 391 451. EP-A 393 428th EP-A 393 861, EP-A 398 692, EP-A 400 417th EP-A 402 246th EP-A 405 782, EP-A 407 873, EP-A 409 369. EP-A 414 153rd EP-A 416 746, EP-A 420 No. 091, EP-A 422 597. EP-A 426 460. EP-A 429 968, EP-A 430 471, EP-A 433 233. EP-A 433 899. EP-A 439 785, EP-A 459 285, EP-A 460 575. EP-A 463 488. EP-A 463 513, EP-A 464 381. EP-A 468 6B4, EP-A 468 695. EP-A 468 775, EP-A 471 261, EP-A 472 224. EP-A 472 300th EP-A 474 042, EP-A 475 158, EP-A 477 631. EP-A 480 795. EP-A 483 851, EP-A 483 985, EP-A 487 409. EP-A 493 711.

EP-A 498 188, EP-A 498 396, EP-A 499 823, EP-A 503 436th 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 54 6 387, EP-A 548 650, EP-A 564 928, EP-A 566 455. EP-A 567 028, EP-A-571 326, EP-A 579 071, EP-A 579 124th EP-A 579 908, ΈΡ-Α 581 No. 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-A90 / i 37.493, WO-A9: No. 1 / 13,830, WO-A 92 / 18,487,

WO-A 53 / 18,484, WO-A 92 / 21,653, WO-A 93 / 07,116, WO-A 93 / 08,1B0, WO-A 93 / 08,183, WO-A 93 / 15,046, WO-A 93 / 16,986 , WO-A 94 / 00,436, WO-A 34/051626, WO-A 94 / 00,948, WO-A 94 / 08.96B, 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 / 056,755, FR-A 2,670,781, G3-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,

DB · -A 39 05 9 11 DE Pat. ANM. 43 05 502.8 DE Pat. ANM. 43 10 143.7. , DE Pat. ANM. 43 18 397.2. DB Pat. annu 43 34 709.6. , DB Pat. ANRT. 44 03 446.6. DB Pat. ANM. 44 03 447.4. , DB Pat. Anrr. 44 03 44B.2. DB Five. ANM. 44 10 424.3. , DB Pat. Anrn. 44 21 180.5. DB Pat. ANM. 44 21 182.1. , D2 Pat. ANM. 44 15 483.6. DE Pat. Ar.ir .. 44 23 615.8 DE Pat. ANM. 44 23 612.3

The object of the invention is to increase the fungicidal action of the following compounds of the formula I by mixing with suitable other fungicidally active substances.

It has been found that this object can be solved by a formulation comprising an active compound of the formula (I) known in the art in synergistic admixture with other specified compounds of the formula (IIA) or (IIB).

SUMMARY OF THE INVENTION

The present invention provides a fungicidal composition comprising a) a p-hydroxyaniline derivative of the general formula (I) (I) wherein:

R ¹ is hydrogen, C 1 -C 8 alkyl optionally partially or fully halogenated and / or optionally having one or two substituents from the group consisting of C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, alkylthio C 1 -C 4 -cycloalkyl, C 3 -C 7 -cycloalkyl, C 5 -C 7 -cycloalkenyl, wherein the cyclic groups may have one to three halogen atoms, C 1 -C 3 alkyl and / or or (C 1 -C 3) alkoxy and an aryl group which is optionally partially or fully halogenated and / or optionally has one to three substituents selected from the group consisting of nitro, cyano, (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl; carbon atoms, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy C 1 -C 4 alkylthio, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkenyl, which are optionally partially or fully halogen and / or optionally have from one to five substituents selected from C 1 -C 6 alkyl; (C-C), (C až-C hal) haloalkyl, (C až-C hal) alkoxy, (C až-C 4) haloalkoxy and aryl, optionally partially or fully halogenated and / or optionally having one to three substituents selected from the group consisting of C súboru-C atóm-C atóm; nitro, cyano, (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl, (C 1 -C 4) alkoxy, (C 1 -C 4) haloalkoxy, (C 1 -C 4) alkylthio, (C 6 -C 4) alkyl group 15 carbon atoms or a bicycloalkenyl group having 7 to 15 carbon atoms, which are optionally partially or fully halogenated and / or optionally have one to five substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy C 1 -C 4 alkyl, optionally substituted partially or fully halogenated and / or optionally having one to three substituents selected from nitro, cyano, (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl, (C 1 -C 4) alkoxy (C atóm-C,), (C hal-C hal) haloalkoxy and (C až-C alkyl) alkylthio,

R ² and R ³ independently of one another are halogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl, C 1 -C 4 alkyl or C 1 -C 4 alkyl, Z is H or R ⁴ - (CO) -, where is

R ^{4 is} C 1 -C 6 alkyl, C 2 -C 6 alkenyl optionally optionally partially or fully halogenated and / or optionally having one substituent selected from C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy carbon, C 1 -C 4 alkylthio, C 3 -C 7 cycloalkyl, C 5 -C 7 cycloalkenyl and aryl, the aromatic groups optionally having one to three 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 group, (C 3 -C 7) cycloalkyl or a C 5 -C 7 cycloalkenyl group optionally having one to three substituents selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl and C 1 -C 4 alkoxy, an aryl group which is optionally partially or fully halogenated and / or optionally has one to two carbon atoms; three substituents from the group consisting of nitro, cyano, (C1-C4) alkyl, (C1-C4) haloalkyl, (C1-C4) alkoxy, (C1-C4) haloalkoxy and (C1-C4) alkylthio , a group of the formula OR ⁵ , NR ⁶ R ⁷ , wherein R ^{5 represents a} C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group which are optionally partially or fully halogenated and / or optionally have one substituent from the group; C1-C4alkoxy, C1-C4haloalkoxy, alkylthio C 1 -C 4 -cycloalkyl, C 3 -C 7 -cycloalkyl, C 5 -C 7 -cycloalkenyl and aryl, the aromatic groups optionally having one to three of nitro, cyano, halogen, alkyl (C až-C 4), (C až-C hal) haloalkyl, (C až-C alko) alkoxy, (C až-C hal) haloalkoxy and (C až-C alkyl) alkylthio, (C až-C 7) cycloalkyl or cycloalkenyl (C až-C prípadne) group optionally having one to three substituents selected from halo, (C až-C alky) alkyl, (C až-Cog) haloalkyl, (C až-C alko) alkoxy, aryl, which is optionally partially or fully halogenated and / or optionally has one to three substances a radical selected from the group consisting of nitro, cyano, (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl, (C 1 -C 4) alkoxy, (C 1 -C 4) haloalkoxy, (C 1 -C 4) alkylthio,

R ^{6 is} C 1 -C 6 alkyl, C 2 -C 6 alkenyl optionally partially or fully halogenated and / or optionally having one substituent selected from C 1 -C 4 alkylthio, C 3 -C 4 cycloalkyl C 7 -C 7 cycloalkenyl and C 5 -C 7 aryl, the aromatic groups optionally having one to three groups selected from nitro, cyano, halogen atoms, 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 optionally having 1 to 4 carbon atoms three substituents selected from the group consisting of halogen, alkyl of 1 to 4 C 1 -C 4 haloalkyl and C 1 -C 4 alkoxy, aryl optionally partially or fully halogenated and / or optionally having one to three substituents from the group consisting of nitro, cyano, C 1 -alkyl; C 1 -C 4 haloalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy and C 1 -C 4 alkylthio.

R ( ⁷⁾ is hydrogen or (C1-C6) -alkyl,

(b) an active substance of formula (IIA) or (IIB)

IIA

where it means

R 1 -C [CO ₂ CH ₃ ] = CHOCH ₃ , -C [CO ₂ CH ₃ 1 = NOCH _{3 j} -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 ,

-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) -CO ₂ CH _3,

R is an organic group which is bonded directly or through an oxy, mercapto, amino or alkylamino group, or together with the group X and the ring Q or T to which are bonded an unsubstituted or substituted bicyclic, partially or fully unsaturated system which in addition to the ring carbon atom contains heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen;

R * -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 ] = CHOCH ₃ , -SC [CO ₂ CH ₃ ] = CHCH _3i -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 ] = 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 ;

R ^y is an oxygen or sulfur atom, the group = CH- or = N-, n 0,1,2 or 3, wherein X is the same or different when n is greater than 1,

X is cyano, nitro, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio or in the case where n is greater than 1, it is C 3 -C 5 alkylene, C 3 -C 5 alkenylene, C 2 -C 4 oxyalkylene, C 1 -C 3 oxyalkyleneoxy, C 2 -C 4 oxyalkenylene C 2 -C 4 oxyalkenyleneoxy, or a butadiene-diyl group attached to two adjacent carbon ring atoms of the phenyl ring, the chains may carry one to three groups independently selected from halogen, C 1 -C 4 alkyl. , (C1-C4) -haloalkyl, (C1-C4) -alkoxy, halogen C 1 -C 4 alkoxy and C 1 -C 4 alkylthio, Y = C- or = N-,

Q a phenyl, pyrrolyl, thienyl, furyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, thiadiazolyl, triazolyl, pyridinyl, 2-pyridinyl, pyrimidinyl or triazinyl group;

A T, phenyl, oxazolyl, thiazolyl, thiadiazolyl, oxadiazolyl, pyridinyl, pyrimidinyl or triazinyl group, in a synergistically effective amount for controlling harmful fungi.

For the synergistic mixtures according to the invention, the compounds of the general formula (I) according to Table 1.1 are suitable.

Table 1.1

Preferred compounds of formula (I)

R ¹ R ²

Nr. R ⁵ R ^a R ¹ Literature *) X.1.1 CI CI C (CH 2) 2 - CH 2 - (A), (C). (D) 1.1.2 F CH, (A), (C), (D) 1.1.3 F CH, CÍCHjh-CHI-C (A), (C). (D) R.1.4 F CH, CtCS.h — CH3 — CI (A), tCl. TD) 1.1.5 C1 CH, CtCHjh-CHjCHaCH. (A), (C). (D) 1.1.6 F CH, C (CH>, - CH ₂ CH ₂ CH 3 (A), (C), (D) 1.1.7 F CH, CÍCHjh-CBjBr (A), (C), (D) I.l.fl CI CI C (CH,) j-CH (A), (C). (D) 1.1.9 CI C1 CfCHjh'CHjBs (A), (C). (D) 1.1.10 CI CH, ClCH, h-CHjCl (A), (C), (D) 1.1.11 CI CH, C (CH,), - CH Br (A). (C). (D) 1.1.12 CI CH, CtCHjhCK. (Al, (C), (O)) 1.1.13 CI CH, c ICH, C: -; (A1, (C), (Dl 1.1.14 C CH, 2 * CH 3 -2.2.1] Heptin-2-yl (B), (C), (D)

^'/ (A) = EP-A 653 417 (B) = EP-A 653 418 (C) = Deutsche Patentanmeldung Az. 195 04 599.8 (D) = Deutsche Patentanmeldung Az. 195 40 970.1

For the synergistic mixtures according to the invention, the compounds of the general formula (I) according to Table 1.2 are particularly suitable.

Table 1.2

Particularly preferred compounds of formula (I) (References to the literature and formula are given in Table 1.1)

Nr. R ³ R ² rI literature 1.2.1 CI ci C (CH,), - CH, C1 (A), (C), (D) 1.2.2 CI CL CICHjírCHjCH. (A), (C), (D) 1.2.3 CI CI C (CH ₂ ) ₂ -CH ₂ CH, CH] (A), (C), (D) 1.2.4 CI CI CICHjIj-CHi-Cl (A), (C), (D) 1.2.5 CI CI 2-CH 2 · (2.2.1) -heptan-2-yl (B), (C), (D) 1.2.6 CI CI 2-CH 2 • [2.2.1] 'lepten-2-yl (B), (C), (D) 1.2.7 C CI f - CH 2 -Cyclohexyl EP-A 339,418

Compounds (IIA) and (ΠΒ) are described, for example, in the following publications: EP-A 178 826, EP-A 203 606, EP-A 203 608,

EP-A 206,523, EP-A 212,859, EP-A 226917,

EP-A-229 974, EP-A-242 070, EP-A-242 081, EP-A-243012,

EP-A 243 014, EP-A 251 082, EP-A2S3 213, EP-A 254425,

EP-A 256,667, EP-A 260,794, EP-A 260,832, EP-A 267734,

EP-A 273,572, EP-A 274,825, EP-A 278,595, EP-A 280185,

EP-A 291,196, EP-A 299,694, EP-A 307,101, EP-A 307,103,

EP-A 310,954, EP-A 312,221, EP-A 312,243, EP-A 329011,

EP-A 331,966, EP-A 335,519, EP-A 336,211, EP-A 337211,

EP-A 341,845, EP-A 350,691, EP-A 354,571, EP-A 353818,

EP-A 370,629, EP-A 373,775, EP-A 374,811, EP-A 378,308,

EP-A 373,755, BP-A 379,098, EP-A 382,375, EP-A 383,117,

EP-A 384,211, EP-A 385,224, ΕΛ-S 38S 357, EP-A 386561,

EP-A-386,681, EP-A-389,901, EP-A-391,451, EP-A-393428,

EP-A-393 861, BP-A-398 692, EP-A-400 417, EP-A-402246,

EP-A 405,782, BP-A 407,873, EP-A 409,369, EP-A 414,153,

EP-A-416 746, EP-A-420 091, EP-A-422 597, EP-A-426460,

EP-A-429 968, EP-A-430 471, EP-A-433 233, EP-A-433899,

EP-A 439,785, EP-A 459,285, EP-A 460,575, EP-A 463488,

EP-A 463,513, EP-A 464,381, EP-A 468,684, EP-A 468,695,

EP-A 468,775, EP-A 471,261, EP-A 472,224, EP-A 472300,

EP-A 474,042, EP-A 475,158, EP-A 477,631, EP-A 480,795,

EP-A 483,851, EP-A 483,985, EP-A 487,409, EP-A 493711,

EP-A-498,188, EP-A-498,396, EP-A-499,823, EP-A-503436,

EP-A 508,901, EP-A 509,857, EP-A 513,580, EP-A 515901,

EP-A-517 301, EP-A-528 245, EP-A-532 022, EP-A-532126,

EP-A-532 127, EP-A-S3S 980, EP-A-538 097, EP-A-544587,

EP-A 546,387, EP-A 548,650, EP-A 564,928, EP-A 566,455,

EP-A 567 028, BP-A 571 326, BP-A 579 071, BP-A 579124

BP-A 579 908, EP-A 5S1 095, EP-A 5S2 902, EP-A 582925

BP-A 584 625, BP-A 585 751, BP-A 590610,

BP-A 596 254, WO-A 90707,493, HO-A 92 / 13,830, WO-A 9 / 18,4S7,

HO-A 92 / 13,494, 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 / 15,986, WO -A 94 / 00,436, WO-A 94 / 05,626, WO-A 94 / 08,948, WO-A 94 / 08.96B, WO-A 94 / 10.159, WO-A 94 / 11.334, JP-A 02 / 121.970, JP-A 04 / 192,461, JP-A 05 / 201,945, JP-A 05 / 201,960, JP-A 05 / 255,012. JP-A 05 / 294,948, JP-A 06 / 025,133, JP-A 06 / 025,142

JP-A 06 / 055,756, FR-A 2,570,781, CB-A 2,210,041, SB-A 21B 702,

GB-A 2,238,308, GB-A 2,249,092, GB-A 2,2S,024, GB-A 2,255,092,

The primary object of the preceding inventions was to enhance the effect of the fungicide of formula (I) by mixing with other corresponding fungicides.

Accordingly, it has been found that harmful fungi are substantially better treated when an active compound of formula (IIA) or an active compound of formula (IIB) is used in addition to the active compound (I).

The combination of the active compound of the formula (I) and (IIA) or (IIB) results in a more effective reduction of harmful fungi, since a smaller amount of individual active compounds can be used for the synergistic action of the components.

All compounds of formula (IIA) and (IIB) mentioned in the above-mentioned publications are suitable for the purposes of the invention.

Of particular interest are those compounds of formula (IIA) and (IIB) in which R is selected from the group consisting of:

an optionally substituted aryloxy group, an optionally substituted hetaryloxy group, an optionally substituted aryloxymethylene group, an optionally substituted hetaryloxymethylene group, an optionally substituted aryletenylene group, an optionally substituted hetaryletenylene group, or an R 1 ^R C = NOCH 2 - or R ^r ON = CR ⁵ CR ^e = NOCH 2 wherein R 1, R ^p , R ⁷ , R ⁵ and R ⁶ are generally and particularly as defined in the patents and patent applications EP-A 370629

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. ANM. 44 03 447, DE Pat. ANM. No. 44 03 448 .., DE Pat. ANM. 44 21 180.S DE Pat. ANM. 44 21 182.1;

as particularly preferred groups referred to as "optionally substituted aryloxy", "optionally substituted hetaryloxy" have the general and particularly the meaning given in the patents and patent applications EP-A 178826

EP-A 242 070. EP-A 242 081. EP-A 256 667. EP-A 260 794. EP-A 341 845. EP-A 382 375th EP-A 405 782. EP-A 430 471. EP-A 477 631. EP-A 483 985. EP-A 515 901. WO-A 93 / 15.04 JP-A 04 / 182.4 ' 61 & DE Pat.

BP-A 253 213. EP-A 254 426. EP-A 280 185. EP-A 307 103. EP-A 393 861 BP-A 398 692. EP-A 468 684. EP-A 468 695. EP-A 498 188. EP-A 513 580. WO * • A 9 ‘ 4 / 10.159, GB-A 2,253 624 Arun. 44: 23 612 !. 31

as particularly preferred groups referred to as "optionally substituted aryloxymethylene group", "optionally substituted hetaryloxymethylene group" have the general and particular meaning given in the patents and patent applications EP-A 178 826, EP-A 226 917, EP-A 253 213 .

ΕΡ-Λ 254,426,

EP-A 335 519

EP-A 378 308

EP-A-400 417,

EP-A 498,188,

EP-A 278 595

EP-A 350 691

EP-A 385,224,

EP-A 407 873

EP-A-498,396,

EP-A 280 185

EP-A 363 818

EP-A 386 S61

EP-A 472,224,

EP-A 513,580,

EP-A 299,694,

EP-A 373 775

EP-A-398,692,

EP-A 477,631

EP-A 515 901

EP-A 579 134, WO-A 93/08, 190, WO-A 93 / 15,045, WO-A 94 / 00,436, JP-A 04 / 182,461, DZ Anm. Wr. 43 05 502., DE Anm. Hr. 44 10 424 ..

, DE Pat. ANM. 44 15 4S3.6;

as particularly preferred groups referred to as "optionally substituted aryletenylene group", "optionally substituted hetatyletenylene group" have the general and particularly the meaning given in the patents and patent applications number

EP-A 178 826, EP-A 203 606, EP-A 253 213, EP-A 254426,

EP-A 280 18S, EP-A 378,755, EP-A 398,692, EP-A 402246,

EP-A-474,042, EP-A-475,158, EP-A-477,631, EP-A-437409,

EP-A 498,188, EP-A 498,396, EP-A 513,580, EP-A 515901,

EP-A 523 245, EP-A 544 507, WO-A 93 / 15.046, WO-A 94 / 11.334,

EP-A 2 670 701 Ä-DE Pat. ANM. 44 23 615.8;

Particularly preferred active compounds of formula (IIA) where R ¹ is -C [CO ₂ CH _3] = CHOCH ₃ corresponds in general and in particular to the compounds of patent documents and the number of applications of the invention

EP-A 178 826. EP-A 203 606, EP-A 226 917, EP-A 242 070. EP-A 24 2 081. 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 755th EP-A 382 375, EP-A 385 224, EP-A 386 561. EP-A 393 861st EP-A 402 246, EP-A 465 782, BP-A 4 07 973. EP-A 414 1S3. EP-A 426 460, EP-A 430 471, BP-A 463 488. EP-A 468 695th 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 90/0 7,493, WO- Ä 92 / 18,487, W Ό-Α 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, 966, NO-A 94 / 10,159, WO-A 94 / 11,334, FR-A 2,670,761.

JP-A 06/025, 133, DB Anm. Nr. 44 03 447., DE Anm. Nr. 44 10 424. DE Pat. Anra. 44 21 180.S;

particularly preferred active substances of type II, wherein R 'is -C [CO ₂ CH ₃ ] = NOCH _3, correspond in general and in particular to the compounds described in the patents and patent applications number

EP-A-2S3 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 Anm. Nr. 44 03 447., DE Anm. Nr. 44 10 424 .. Λ- DE Pat. ANM. 44 21 180.5;

Particularly preferred active substances of type II in which R 'is -C [CONHCH ₃ ] = NOCH ₃ correspond in general and in particular to the compounds described in the patents and patent applications number

EP-A 398,592; 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, G3-A 2,253,624, JP-A 04 / 182,461. JP-A 05 / 201,946, JP-A 05 / 2S5.012,

JP-A 05 / 294,948, DE Απλ. Nr. 43 05 $ 01 ..,

DE Anm. Nr. 44 03 448 ... DE Anm. Nr. 44 10 424 ..,

DB Pat. ANM. Nr. 44 23 615.8 DE Pat. ANM. 44 21 182.1;

particularly preferred active substances of type II, wherein R 'is -C (CO ₂ CH ₃ ) -CHCH ₃ or -C (CO ₂ CH ₃ ) = CHCH ₂ CH _3, correspond in general and in particular to the compounds described in the patents and applications EP-A-280185, EP-A-463488,

EP-A 501,901, EP-A 513,580, EP-A 515,901,

DE Anm. Nr. 44 03 447., DE Arun. Nr. 44 10 424 ..,

DE Pat. Ann. Nr. 44 21 180.5 Φ DE Pat. ANM. Nr. 44 15 483.6;

particularly preferred type II active ingredients. wherein R 'is -C [COCH ₃ ] = NOCH ₃ or -C [COCH ₂ CH ₃ ] = NOCH _3, in general and in particular, correspond to the compounds disclosed in EP-A 498188;

particularly preferred type II active compounds wherein R 'is -N (OCH ₃ ) CO ₂ CH ₃ or -N (CH ₃ ) -CO ₂ CH ₃ or -N (CH ₂ CH ₃ ) -CO ₂ CH ₃ generally correspond to and in particular to the compounds disclosed in EP-A 498396, WO-A 93 / 15,046, JP-A 06 / 025,142 and DE Pa. ANM. 44 23,612 3;

particularly preferred Type II active compounds wherein R 'is a group

-OCtCOjCK ,! OCKOCH -OCÍCOjCHil ,, ^ CHC H, -OC (CO, CH _{3 I-2} CH ,, Chck -0C [COCHjCHj] 'NOCHj, "SCÍCOjCHj] = ₃₁ -SCÍCOjCHj CKD-CHC H, -SC (COjCHj]" CHCHjCHj - N _(CH3) C [COjCHj] CHOCHj =, -N _(CH3) C (CO ₂ CH] cNOCHj, _2-CU CTCAE ₂ CH _3] -CHOCH _third -CKaCÍCOjCHj] & NOCHj or -CH ₂ C [CONHCH ₃ ] = NOCH ₃ correspond in general and in particular to the compounds described in patent specification no

EP-A 212 859. EP-A 331 966, EP-A 383117

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-548650,

EP-A 579 908 and / or EP-A 584 625.

Examples of particularly preferred type II active ingredients are in the following tables.

Table II. 1A

Compounds of formula (IIa) wherein Q is phenyl, R 1 -C (CO ₂ CH ₃ ) = CHOCH ₃ , n zero, R optionally substituted hetaryloxymethylene, wherein the optionally substituted (het) aryl moiety has the following meaning

Number Alternatively, subsLit. (Het) aryl Lii.eraLura II.1-1 _{2-CH3-C e} H ₄ EP-A 226 917 II.1-2 J / S tOhh-CíHj EP-A 226 917 H.1A-3 2-CH 3, 4-CH 3) (CH 2 Cl 2) -CH 2 EP-A-386,561 H.1A-4 1-CH 3 CH 3 CH 3, 6-CF, -pyrrolidin-1-yl EP-A-407 873 II.1-5 2.4 "(CH) ₃ CFH ₂ EP-A 226 917

Table II.2A

Compounds of formula (IIA) wherein Q is phenyl, R '-C (CO ₂ CH ₃ ) = NOCH ₃ , n zero, R "optionally substituted hetaryloxymethylene, wherein the optionally substituted (het) aryl moiety has the following meaning

Table II. 1B

Compounds of formula (IIA) wherein Q is phenyl, R 1 -C (CO ₂ CH ₃ ) = CHOCH ₃ , n zero, R optionally substituted hetaryloxy, wherein the optionally substituted (het) aryl moiety has the following meaning

Number Alternatively, aubst.it. (HEL) aryl L ileratura ΙΙ.2Λ-1 2-CH 3 -C ₄ H 4 EP-A 253,213 II.2-2 2,5- (CH) _and C _{(H S} EP-A-400 417 II.2-3 2,4- (CH ₃ ) ₃ -C ₆ H ₃ EP-A-400 417 1 ΙΪ.2Λ-4 2,3,5- (CH) j CjHj EP-A-400 417 II.2-5 2-CL, 5-CH ₃ -C ₄ H ₃ EP-A-400 417 XI.2-6 _2-CH3, 4-C [CHjJ _'NOCHj-ct R BP-Ä ₃ 86 SS1 |

UČÍslo Alternatively, subst.it. (Het) aryl Lí teratura [XX.lB-1 C ₆ H _S EP-A 178 826 jlI.lB-2 6- 12-CN-C ₄ H ₄ -J-Pyrithiidin-4-yl ep-A 382,375

Table II. 1C

Compounds of formula (IIA) wherein Q is phenyl, R 1 -C (CO ₂ CH ₃ ) = CHOCH ₃ , n zero, R optionally substituted hetaryletenylene, wherein the optionally substituted (het) aryl moiety has the following meaning

Table II.2B

Compounds of formula (IIA) wherein Q is phenyl, R 1 -C (CO ₂ CH ₃ ) = NOCH ₃ , n zero, R optionally substituted hetaryloxy, wherein the optionally substituted (het) aryl moiety has the following meaning

(Number Optionally substit. (Het) aryl Li teratura jlI.2B-l C _S H _S EP-A 253,213 | Ir.2B-2 6- (2-CN-C 5 H, -01-pyrimidin-4-yl) EP-A 468,684

[[number Optionally substit. (Het) aryl literature II.1C-1 1- (2,4-C1-C8Hy), S-CF1-pyrazol-4-yl EP-A 528,245 xi.xc-2 X- (4-Cl-C _e H ₄₎ pyrazol-4-yl EP-A 379,755 II.1C-3 3-CFj-CíHt EP-A 203,606 II.1C-4 3-Cl-C _TH < EP-A 203,606 II.1C-5 4-C4H5-C6H4 EP-A 203,606

Table II.2C

The compounds of formula (IIA), wherein Q is phenyl, R ¹ is -C (CO ₂ CH ₃₎ = NOCH _3, n is zero, R is CH ₂ ON = CR "R ^{| 3,} wherein R" and R ¹³ is the following meaning

Table II. 1D

Compounds of formula (IIA) wherein Q is phenyl, R 1 -C (CO ₂ CH ₃ ) = CHOCH ₃ , n zero, R ₂ CH ₂ ON = CR 1 ^J R ^P. wherein R 1 and R ^p have the following meanings

[Number R ' «Ϋ ——— - , --- L i teratura | IX.1D-1 CH 4-C1-C _with K4 EP-A 370,629 III.10-2 CH 3-CF ₃ -C «H ₄ EP-A 370,629 | II «10-3 CH 4-OCH ₂ CH ₃ -pyrimidin-2-yl WO-A-S2 / 18.4S7

Table II. IE

The compounds of formula (IIA), wherein Q is phenyl, R 'is --C _{(CO2 CH3)} = CKD _3, n is zero, R is CH ₂ ON = CR ^{8 R} R ^E = NOR, wherein R ^7, R ⁸ and R ^E is as follows

number R ⁶ R 7 literature CH ₃ c £ ch ₃ DE Arun. Hr. 44 03 447.4 II.1-2 ch ₃ CH ck ₂ ch ₃ DE Anni. Nr. 44 03 447.4 II.1B-3 ch ₃ C _S H _S CH DE ATJB. Nr. 44 03 447.4 1 II.18-4 CH C5H5 ch ₂ ch ₃ DB Ar.it. Hr. 44 03 447.4 1 II.18-5 ch ₃ 4-CL-C _e H < CH DE Ar.ir .. Nr. 44 21 180.5 XI.18-6 CH 4-Cl-C _e H < CHjCHs DE Am. Nr. 44 21 180.5

| Number R® ' Rľ ..... Li teratura I1.2C-1 CH 4-Cl-C _e H ₄ EP-A-463,488 II.SC-2 CH 3-Cl-C ₄ H ₄ EP-A-463,488 II.2C-3 CH <-CF ₃ -C ₆ H ₄ EP-A-463,488 II.2C-4 CH 3-CF ₃ -C ₄ H ₄ EP-A-463,488 IX.2C-5 CH 4-CH ₃ -C ₆ H 4 EP-A-463,480 I1.2C-6 CH 4-OCH ₃ CH ₃ -pyrimidin-2-yl EP-A 472,300 | | Rr.2c-7 CH 3,5-Clj-CeHj EP-A 463,488 |

Table II.2D

Compounds of formula (IIA) wherein Q is phenyl, R 'is -C (CO ₂ CH ₃ ) = NOCH ₃ , n is zero, R is CH ₂ ON = CR ^Y R ⁸ = NOR ^E , wherein R ⁷ , R ^{7 8} and R ^E is as follows

^{1-1 1} ~~ Number Rf r Li teratura II.2D-1 CH CH CH DE Ansr. Hr. 44 03 447.4 II.2D-2 CH CH CHiCHj An E Anm. Hr. 44 03 447.4 II.2D-3 CH CIHS CH DE Ana. Hr. 44 03 447.4 II.2D-4 ch ₃ cghj CHjCHj DE Anm. Hr. 44 03 447.4 11.20-5 CH 4-CX-C ₄ H ₄ CH DE Aran. Hr. 43 21 180.5 II.2D-6 ch ₃ 4-Cl-CIH » CHjCHj DB Anm. Hr. 45 21 X80.S

Table II.3A

Compounds of formula (IIA) wherein Q is phenyl, R 'is -C (CONHCH ₃ ) = NOCH ₃ , n is zero, R is optionally substituted hetaryloxymethylene, wherein the optionally substituted (het) aryl moiety has the following meaning

Number ΙΓ.3Α-1 Optionally, (het) aryl Literature 1 2-CKj-C ₄ K < EP-A 477,631 II.3-2 2.5 "(CH 3 | ₂ -C ₁ H 3 EP-A 477,631 II.3-3 2,4- (CH 1j-C ₄ H ₃ EP-A 47? 631 rr.3 -4 * Z.l.S-ÍCHjh'CíHi EP-A 47? 631 II.3-5 2-CH 3, 4-ClCH 3] = NOCH 3 -CH 2 EP-A-573,124 ΙΙ.3Λ-6 l- [4-Cl-C6Kj-pyrazol-3-yl DE Anm. Nr. 43 05 502.8 II.3-7 1- [2,4-Cl-C1-H] -pyrazol-3-yl DE Anm. Nr. 43 05 502.B

Table II. 3 B

Compounds of formula (IIA) wherein Q is phenyl, R 'is -C (CONHCH ₃ ) = NOCH ₃ , n is zero, R is optionally substituted hetaryloxy, wherein the optionally substituted (het) aryl moiety has the following meaning

flčíslo Optionally substit. (Het) aryl L1Leratára | II.3B-1 c ₆ h _p EP-A-398,692 6- 12-CN-C ₆ H (O) -pyrimidin-4-yl IgB-A 2,253,624

Table II.3C

Compounds of formula (IIA) wherein Q is phenyl, R 'is -C (CONHCH ₃ ) = NOCH ₃ , n is zero, R is optionally substituted hetaryletenylene, wherein the optionally substituted (het) aryl moiety has the following meaning

Number - R literature II.3-1 CH CH CH DE Pat. ANM. 44 21 182.1 II.3B-2 CH CH CHjCHj DE pat. ANM. 44 21 182.1 ΪΙ.3Β-3 CH C ₄ H, CH DE Pat. ANM. 44 21 182.1 II.38-4 CH C ₍ H _S CHj CHj DE Pat. ANM. 44 21 182.1 II.38-5 CH 4-Cl-C ₄ H ₄ CH DE Pat. ANM. 44 21 182.1 II.3B-6 CH 4-C1 _4-CJB CHjCHj DE Pat. Arim. 44 21 182.1 IX.3-7 CH 4-FC ₆ H ₃ CH DE Pat. ANM. 44 21 182.1

Table I1.4A

Compounds of formula (IIA) wherein Q is phenyl, R 'is -C (CO ₂ CH ₃ ) = CHCH ₃ , n is zero, R is optionally substituted hetaryloxymethylene, wherein the optionally substituted (het) aryl moiety has the following meaning

[number Eventually Shubbat, (het) ary] L iteraLura II.4-1 2-CH-C _t E ₄ EP-A 280 105 II.4-2 2.5- (CH) _{p, and} C Hj EP-A 513,580 II.4-3 2,4 (0 ^) ^ 3 3-0 EP-A 513,530 ΪΙ.4Λ-4 2,3,5- (CH ₃ > 3-C -H ₂ EP-A 513,580 II.4-5 2-Cl, 5-CH 3 -C 8 H 3 BP-A 513,580 Ii.4-6 2-CH 3, 4-C [CH 3] ^x NOCH 3 -C ₄ H 3 EP-A 513,580 i | LI.4A-7 1- (4-C 1 -C ₄ H ₄ -pyrrolol-3-yl) DE Pat. ANM. 44 15 483.6

Table II.4B

Compounds of formula (IIA) wherein Q is phenyl, R 'is -C (CO ₂ CH ₃ ) = CHCH ₃ , n is zero, R is optionally substituted hetaryloxy, wherein the optionally substituted (het) aryl moiety has the following meaning

Jčíslo Alternatively, subs. (Het) aryl literature 1- (2,4-Cl ₂ -CH ₃ ) .S-CF 3 -pyrazol-4-yl DE Anm. Nr. 44 23 615.8

substate. (het.) ary 1

Table II.3D

Compounds of formula (IIA) wherein Q is phenyl, R 'is -C (CONHCH ₃ ) = NOCH ₃ , n is zero, R is CH, ON = CR "R ^P , wherein R" and R * ³ have the following meanings

Table II.4C

Compounds of formula (IIA) wherein Q is phenyl, R 1 -C (CO ₂ CH ₃ ) = NOCH ₃ , n zero, R ₂ CH ₂ ON-CR ^Y R ⁸ = NOR ^e , wherein R ^T , R ® and R ^E have the following meanings

Number R ĽiLeraLura 1 II.3D-1 ca ₃ 4-Cl-C ₄ H ₄ EP-A-463,488 II.3D-2 ch ₃ 3-Cl-C ₄ H ₄ EP-A-463,488 II.3D-3 CH 4-CF 3 -C ₆ H 1 EP-A 585 75L II.3D-4 CH 3-CF 3 -C ₄ H ₄ Ep-A 585,751 II.3D-S CH 4-CH-C H _E < EP-A-463,488 XI.3D-6 CH 3,5-CIJ-CíHj EP-A-463,488 II.3D-7 CH 2-DCH] CH-pyrimidin-2-yl WO-A 92 / 13,830

Number R? R ¹ L i teratura II.4C-1 CH CH CK i DE Pat. Anna. 44 21 180.5 II.4C-2 CH CH CHjCHj DE Pat. ANM. 43 21 180.5 II.4C-3 CH c ₆ h _p CH DE Pat. ANM. 43 21 180.5 II.4C-4 CH C _t H _p CHjCHj DE Pat. ANM. 43 21 180.5 II.4C-5 CH; 4-Cl-C * E ₄ CH DE Pat. ANM. 43 21 180.5 II.4C-6 CH 4-Cl-C ₄ H? CHjCHj DE Pat. ANM. 43 21 180.5

Table 11.3E

Compounds of formula (IIA) wherein Q is phenyl, R 1 -C (CONHCH ₃ ) = NOCH ₃ , n is zero, R ₂ CH ₂ ON = CR ¹ 'R ⁵ = NO R ^E , wherein R ¹ , R ⁵ and R ^E is as follows

Table II. 5 A

Compounds of formula (IIA) wherein Q is phenyl, R 'is -C (CO ₂ CH ₃ ) = CHCH ₂ CH ₃ , n is zero, R 1 or a substituted hetaryloxymethylene group, wherein the optionally substituted (het) aryl moiety has the following meaning

jčíslo Optionally fubstit- (het) aryl Li Ueratura ii.sa-i 3 -CMi'QKm EP-A SXJ 58Ô IX.ÍA-2 EP-A 513 SfiO XI.Sa-3 J. I-fCHjh-CSH, EP-A 513,580 U.ÍA-4 EP-A 513 56Q Π.5Α-5 2-Cl, 5-CH 3 -C 1 H 3 EP-A 513,580 II.SA-6 2-CH. 4-C [CK ₃ ] = NOCH 3 -C ₄ H 3 EP-A-S13 580 |

Table 1I.7A

Compounds of formula (IIA) wherein Q is phenyl, R 1 -C (COCH ₂ CH ₃ ) = NOCH ₃ , n zero, R optionally substituted hetaryloxymethylene, wherein the optionally substituted (het) aryl moiety has the following meaning

Table II.5B

Compounds of formula (IIA) wherein Q is phenyl, R 1 -C (CO ₂ CH ₃ ) = CHCH ₂ CH ₃ , n zero, R optionally substituted hetalkyloxy, wherein optionally substituted (het) aryl is as follows | No ³¹ ° [ir.SB-1

Optionally substit. (Het) aryl

literature

EP-A 513,580

Table II.5C

Compounds of formula (IIA) wherein Q is phenyl, R 'is -C (CO ₂ CH ₃ ) = CHCH ₂ CH ₃ , n is zero, R ₂ CH ₂ ON = CR ⁷ R ^S = NOR ⁵ , wherein R 1 is R ⁶ and R ^E have the following meanings

Number Optionally substit. (het) aryl literature II.7-1 2-CK ₃ -C (H ₎ EP-A 498,188 II.7-2 2,5 (CHjh-CeHj EP-A 498,188 rr.7A-3 2,4- (CH ₃ ) ₂ -C ₆ H 3 EP-A 498,188 IZ.7A-4 2,3,5-ÍCHjIj-C.Hj EP-A 498,188 II.7-5 2-CH, 4-C [CH] ^R Hochjoch-C 'Hj EP-A 498,188

Table II.7B

Compounds of formula (IIA) wherein Q is phenyl, R 'is -C (COCH ₂ CH ₃ ) = NOCH ₃ , n is zero, R is optionally substituted hetaryloxy, wherein the optionally substituted (het) aryl moiety has the following meaning

I No 0 Optionally substit. (het) aryl literature c ₆ h ₅ EP-A 498,188 | LI.7B-2 6- [2-CN-C.H.-O) -pyrimidin-4-yl EP-A 498,188 j

figures RY R ¹ R literature II.5C-1 Honors ₃ CH CH DE Pat. Annu 44 20 180.5 II.5C-2 CH CH CKjCHj DE Pat. Anro. 43 21 180.5 II.5C-3 CH C _S H _S CH DE Pat. Annu 44 21 180 .5 II.SC-4 CH CTHS CHjCHj DE Pat. Annu 44 20 180.5 II.SC-S CH 4-C ₆ H 4 -C CH DE Pat. Annu 44 20 180.5 IX.5C-6 CH 4-C1-CíK4 CH ₂ CH 3 DE Pat. ANM. 43 21 180.5

Table II.8A

The compounds of formula (IIA), wherein Q is phenyl, R ¹ is -N (OCH ₃₎ -CO ₂ CH _3, n is zero, R hetaryloxymetylénovú optionally substituted group, the optionally substituted (het) aryl group has the following meaning

Table II. 6A

Compounds of formula (ΠΑ) wherein Q is phenyl, R '-C (COCH ₃ ) = NOCH ₃ , n zero, R optionally substituted hetaryloxymethylene, wherein the optionally substituted (het) aryl moiety has the following meaning

Number Or suhstit. (Het) aryl literature II.6-1 2-CR3-C5H4 EP-A 498,188 II.6-2 2,5- (CH 3) ₂ -C ₆ H 3 EP-A 498,188 II.6-3 2,4- (CH) j C ₆ Hj EP-A 498,188 II.6-4 2,3,5- (CH 3) 3 C ₄ H ₂ EP-A 498,188 II.6-5 2-CH3, 4-ClCH3-HOCH3-C.H, EP-A 498,188

Table II.6B

Compounds of formula (IIA) wherein Q is phenyl, R 1 -C (COCH ₃ ) = NOCH _3> n zero, R optionally substituted hetaryloxy, wherein optionally substituted (het) aryl moiety has the following meaning

clean Optionally, the substrate. (Het) aryl) Li teratura II.8-1 2-CH-C _e H ₄ WO-A 93 / 15,046 IX.8-2 2,5- (CH ₂ J ₂ -C ₆ H 3) WO-A 93 / 01.046 II.8-3 2,4- (CH 3) _r C ₆ H 3 WO-A 93 / 15,046 II.8-4 2,3,5- (CH) 3-C5H2 WO-A 93 / 15,046 1 ΙΣ.8Α-5 2-Cl, 5-CH 3 -C ₆ H 3 WO-A 93 / 15,046 II.8-6 2-CK, 4-C (CH ₃ ) "NOCH ₃ -CH ₂ H" WO-A 93 / 15,046 II.8-7 2-CH 3, 4-C (CH ₃ ) e NOCH ₃ CH ₃ -C ₁ H ₃ WO-A 93 / 15,046 II.BA-8 2-CH 3, 4-C (CH ₂ CH 3) • NOCH 3 -C _with H 3 WO-A 93 / 15,046 II.BA-9 2-CH 3, 4-C (CH 3 CH 3) -NCH 3 CH 3 -C 1 H 3 WO-A 93 / 15,046 ΙΪ.8Α-10 1- (4-Cl-C4H4) -pyrazol-3-yl DE Pat. Arun. 44 23 612.3

Table II.8B

Compounds of formula (IIA) wherein Q is phenyl, R 'is -N (OCH ₃ ) -CO ₂ CH ₃ , n is zero, R _{2 is} CH ₂ ON = CR 1 R ¹ , wherein R 1 and R ^p have the following meaning

Ičíslo R R * ¹ Literature 1 | II.8B-1 CH 3,5-Clj-CjHj WO-A 93 / 15,046 J

Kčíslo Optionally substit. (Bot) aryl Literature 1 C _$ H _S EP-A 498,188 I LI.6B-2 || 6- [2-CN-C 5 H 4 -O) -pyrimidin-4-yl EP-A 498,188 j

Pure active compounds of the general formula (I) and (IIA) or (IIB) are preferably used in the preparation of the mixture, but other active compounds against pests (for example against insects, spiders or nematodes) or harmful fungi may be mixed into these mixtures. but also herbicidal active substances, active substances influencing growth or fertilizers.

Mixtures of compounds of formula (I) and (Ι1Α) or (IIB) or the separate use of compounds of formula (I) and (IIA) or (ΠΒ) have an excellent action against a broad spectrum of particularly pathogenic fungi attacking plants. In part, they are systemically acting (that is, when used for plant protection they can be taken up by the plant without loss of efficacy and possibly transported in the plant) and therefore can be used as foliar and soil fungicides.

Of particular importance in destroying multiple fungi on different crop plants such as cotton, vegetables (such as cucumbers, legumes and pumpkins), cereals, grass, oats, coffee, corn, fruit plants, rice, rye, soybean, vine, wheat, decorative plants, sugar cane and multiple seeds.

They are particularly suited to destroying the following pathogenic fungi: Erysiphe graminis (powdery mildew) on grain, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin stands, Podosphaera leucotricha on apples, Puccinia on grain, Rhizoctonia on cotton, rice and rice, , Venturia inaequalis (applewood), Helminthosporium grains, Septoria nodorum on wheat, Botrytis cinera (gray mold) on strawberries, vegetables, ornamental plants and vines, Cercospora arachidicola underwater pseudococcus, Pseudocercosporella orpotrichi on rice, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, Pseudoperonospora species on hops and cucumbers, Arternaria on vegetables and fruits and Fusarium and Vertocollium species.

In addition, they protect the material (e.g. wood) against Paecilomyces variotii.

The compounds of formulas (I) and (IIA) and optionally of formulas (I) and (IIB) can be applied simultaneously, together or separately, or sequentially, and the sequential application sequence does not generally affect the treatment result.

The compounds of formula (I) and (IIA) are used in a weight ratio of 10: 1 to 1:20, preferably 5: 1 to 1: 3 and especially 3: 1 to 1: 1 (I: IIA).

The compounds of formula (I) and (IIB) are used in a weight ratio of 10: 1 to 1:20, preferably 5: 1 to 1: 3 and especially 3: 1 to 1: 1 (1: IIB).

The amount used depends on the desired effect and is 0.015 to 10 kg / ha, preferably 0.1 to 7 kg / ha, and in particular 0.2 to 3 kg / ha.

The amount of the compound of the formula I to be used is 0.005 to 3 kg / ha, preferably 0.02 to 2 kg / ha, and in particular 0.05 to 1 kg / ha.

The amount of the compound of the formula IIA used is 0.005 to 5 kg / ha, preferably 0.01 to 2 kg / ha, and in particular 0.01 to 1 kg / ha.

The amount of the compound of the formula IIB used is 0.005 to 5 kg / ha, preferably 0.01 to 2 kg / ha, and in particular 0.01 to 1 kg / ha.

In the treatment of seed, the amount of mixture used is 0.001 to 0.1 g / kg of seed, preferably 0.002 to 0.052 g / kg and in particular 0.005 to 0.5 g / kg.

If pathogenic fungi are to be destroyed on the plants, the compounds of formulas (I) and (IIA) or (IIB) may be applied together or separately, or a mixture of compounds of formulas (I) and (IIA) or (IIB) may be applied by spraying or by dusting plants or soil before sowing or after sowing seeds, or before germination or after germination of plants.

The fungicidal synergistic mixtures of the invention or the compounds of formula (I) and (IIA) or (I) and (IIB) according to the invention can be applied in the form of directly sprayable solutions, powders or suspensions, or in the form of highly concentrated aqueous, oily oils. or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, sprinkles or granules by spraying, fogging, spraying, sprinkling or pouring. The form of use depends on the desired effect. In any case, it is desirable to form as fine and uniform a distribution of the mixture as possible.

The compositions are prepared by known methods, for example by adjusting the active ingredient with a solvent and / or carriers, optionally using emulsifiers and dispersants.

Suitable surfactants are alkali metal, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, for example ligninsulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid and fatty acids, alkyl aryl sulfonates, alkyl sulfates, alkyl sulfates, alkyl sulfates, alkyl sulfates, alkyl sulfates, alkyl sulfates hexa-, hepta- and octadecanols and fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl alcohols, alkylaryl polyether alcohols, isotridecyl alcohol, condensates of ethylene oxide and fatty alcohols, ethoxylated castor oil, polyoxyethylene alkyl ethers, poly yoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors and methylcellulose.

Powder, spray and spreading agents can be produced by mixing or co-milling the compounds of formulas (I) and (IIA), optionally (I) and (IIB), or by mixing the compounds of formulas (I) and (IIA), optionally (I) and (IIB) together with a solid support. Granules, for example coated, impregnating and homogeneous granules, can be prepared by binding the active compounds or active compound mixtures to solid carriers.

Mineral clays such as silica gel, silica, silicates, siliceous gels, talc, kaolin, limestone, lime, chalk, bolus, clay, float clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate are used as fillers or as solid carriers. , magnesium oxide, ground plastics, fertilizers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, ureas and plant products such as cereal flour, tree bark flour, wood and nut shell meals and other solid carriers.

The compositions according to the invention contain in general 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of a compound of formula (IA) or (IB), (IIA) or (IIB), or mixtures of compounds of formula (I) and ( IIA), optionally (I) and (IIB).

Active substances with a purity of 90 to 100%, preferably 95 to 100% (according to 1 H-NMR or HPLC spectrum) are used.

The compounds of the formulas (I), (IIA) and (IIB), or mixtures thereof or the corresponding compositions, are used in such a way that harmful fungi, their environment, fungi on protected materials such as plants, seeds, soil, areas or areas are treated with a fungicidally effective amount of a mixture or compounds of formula (I) and (IIA) or (I) and (IIB) in a separate application.

The following examples illustrate the synergistic action against harmful fungi with the composition according to the invention. Percentages are by weight unless otherwise indicated.

DETAILED DESCRIPTION OF THE INVENTION

Tests are carried out with the following compounds, which for convenience are designated (A), (B), (C), (D), (E) and (F).

Cl Cl

(A) Compound 1.2.1

compound 1.2.5 endo: exo = 1: 1

(C)% of the double bonds marked with an asterisk are in configuration E.

Example 1

Efficacy against Botrytis cinerea

Pepper seeds of the 'Neusiedler Ideal Elite' type are sprayed into droplets with an aqueous suspension containing 80% active ingredient and 20% emulsifier, based on the dry matter content in the four to five leaf state. After the spray has dried, the plants are sprayed with a conidia suspension of Botrytis cinerea and placed in a 22-24 ° C high humidity chamber. After five days, the disease development is so high on untreated control plants that most of the leaves have necrosis.

The evaluation is carried out by visual assessment of the percentage of leaf area attack and expressed as a percentage with respect to the untreated control. A score of 0 means the same attack as an untreated control, and a score of 100 means 0% attack. In theory, the expected degree of action of the active compound mixtures is determined according to the formula derived by Colby (Colby S. R., &quot; Calculating synergistic and antagonistic respoonses of herbicide Combinations &quot;

The results are shown in the following Table 1.1 (column I shows the active substance, column II the concentration of the active substance in the spray suspension in ppm, column III the percentage efficiency with respect to the untreated control, the untreated control having 100% infestation.

Table 1.1 Compound 1.1.15

O (D)

I II III (AJ 100 84 25 40 (B) 100 80 25 65 (C) 100 70 25 35 (D) 25 0 (E) 25 0 (F) 25 0

compound II.2A-1

Table 1.2

(E)

Degree of effectiveness of the mixture

Withstand the active substances Observed effect Expected effect 100 ppm (A) + 25 ppm (D) 4: 1 mixture ratio 100 84 25 ppm (A) + 25 ppm (D) 1: 1 mixture ratio 92 40 100 ppm (A) + 25 ppm (E) 4: 1 mixture ratio 99 84 25 ppm (E) + 25 ppm (E) 83 40

compound II.1B-2

compound Ι1.3Ε-3 mixture ratio ltl

100 ppm (A) + 25 ppm (F) 4: 1 mixture ratio 98 84 25 ppm (A) - 25 ppm (F) 99 40 mixture ratio 1: 1

(F)

100 ppm (B) + 25 ppm (D) 4: 1 mixture ratio 99 80 25 ppm (B) 4- 25 ppn (D) 1: 1 ratio 99 65 100 ppm (B) + 25 ppm (E) 4: 1 ratio 99 80 25 ppm (B) 4- 25 ppm (E) 1: 1 ratio 99 65 100 ppm (B) 4- 25 ppm (F) 4: 1 mixture ratio 100 80 25 ppm (B) 4- 25 ppm (F) ratio is 1: 1 99 65 100 ppm (C) + 25 ppm (D) 4: 1 mixture ratio 99 70 25 ppm (C) 4- 25 ppm (D) ratio is 1: 1 75 35

100 ppn (C) 4- 25 ppm (E) 4: 1 mixture ratio 99 70 25 ppm (C) + 25 ppm (E) 1: 1 ratio 65 35 100 ppm (C) + 25 ppm (F) 4: 1 mixture ratio 98 70 25 ppm (C) 4- 25 ppm (F) mixture ratio 1: 1 97 38

From the results, it is clear that the observed degree of efficacy for the mixtures at all ratios tested is higher than would be expected by calculation using the Colby formula, i.e. the tests confirm a synergistic effect.

Example 2

Activity against Botrytis cinerea on peppers

The green peppers are sprayed into drops with an aqueous suspension containing 80% active ingredient and 20% emulsifier, based on the dry matter content. Two hours after spraying, the coating dries and the fruits are inoculated with a spore suspension of Botrytis cinerea sponge containing 1.7 x 10 ⁶ spores per ml of 2% Biomalz solution and placed in an 18 ° C high humidity chamber. After four days, visual development of the disease is observed on the infected fruit.

Assessment shall be carried out by visual assessment of the percentage infestation of the fruit area and shall be expressed as a percentage of the untreated control. A score of 0 means the same attack as an untreated control, and a score of 100 means 0% attack. Theoretically expected degree of action of the active compound mixture is determined according to the formula derived by Colby (Colby S.R., &quot; Calculating synergistic and antagonistic respoonses of herbicide Combinations &quot;

The results are shown in the following Table 1.1 (column I shows the active substance, column II the concentration of the active substance in the spray suspension in ppm, column III the percentage efficiency with respect to the untreated control, the untreated control having 100% infestation.

Table II. 1

I II XII (A) 100 20 (B) 100 25 25 10 (C) 100 25 25 30 (D) 25 77 (F) 25 10

Table II.2

Degree of effectiveness of the mixture

The degree of effectiveness can withstand

Mixture of active substances Observed effect Expected effect 100 ppn (A) 4- 25 ppn (F) 4: 1 mixture ratio 77 48 25 ppm (B) + 25 ppm (D) is 1: 1 90 79 100 ppm (B) 4- 25 ppm (F) 4: 1 mixture ratio 80 51 25 ppn (B) 4- 25 ppn (F) 1: 1 mixture ratio 75 42 100 ppm (C) 4- 25 ppm (F) ratio was 4: 1 97 51 25 ppm (C) 4 25 ppm (F) 1: 1 mixture ratio 89 55

From the results, it is clear that the observed degree of efficacy for the mixture at all tested ratios is higher than would be expected by calculation using the Colby formula, i.e. the tests confirm synergistic action.

Industrial usability

A synergistic mixture based on p-hydroxyaniline derivative for the production of fungicides for agricultural and industrial purposes.

Claims (10)

PATENT CLAIMS What is claimed is: 1. A fungicidal composition comprising a) p-hydroxyaniline derivative of general formula (I) R ³ R ² (I), where is R ^{@ 1} is hydrogen, C1 -C8 alkyl which is optionally partially or fully halogenated and / or optionally has one or two substituents selected from C1 -C4 alkoxy, halo C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 3 -C 7 -cycloalkyl, C 5 -C 7 -cycloalkenyl, wherein the cyclic groups may have one to three groups selected from atoms halogen, (C1-C3) -alkyl and / or (C1-C3) -alkoxy and aryl, which is optionally partially or fully halogenated and / or optionally has one to three substituents selected from the group consisting of nitro, cyano, (C1-C3) alkyl; (C 1 -C 4), (C 1 -C 4) haloalkyl, (C 1 -C 4) alkoxy, (C 1 -C 4) haloalkoxy and (C 1 -C 4) alkylthio, (C 3 -C 6) cycloalkyl or (C 3 -C 6) cycloalkyl group 3 to 6, which are optionally partially or fully halogenated and / or optionally have one up to five substituents selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, and aryl, optionally partially or fully halogenated, and or optionally has one to three substituents selected from the group consisting of 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 group C 1 -C 4, C 6 -C 15 bicycloalkyl, or C 7 -C 15 bicycloalkenyl, optionally partially or fully halogenated and / or optionally having from 1 to 5 substituents selected from C 1 -C 4 alkyl C 1 -C 4 haloalkyl; C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy and aryl, optionally partially or fully halogenated and / or optionally having one to three substituents selected from 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 ² and R ³ independently of one another are halogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl, C 1 -C 4 alkyl or C 1 -C 4 alkyl, Z is H or R ⁴ - (CO) -, where is R ^{4 is} C 1 -C 6 alkyl, C 2 -C 6 alkenyl optionally optionally partially or fully halogenated and / or optionally having one substituent selected from C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy carbon, C 1 -C 4 alkylthio, C 3 -C 7 cycloalkyl, C 5 -C 7 cycloalkenyl and aryl, the aromatic groups optionally having one to three 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 group, (C 3 -C 7) cycloalkyl or a C 5 -C 7 cycloalkenyl group optionally having one to three substituents selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl and C 1 -C 4 alkoxy, aryl which is optionally partially or fully halogenated and / or optionally has one to two carbon atoms; three substituents from the group consisting of nitro, cyano, (C1-C4) alkyl, (C1-C4) haloalkyl, (C1-C4) alkoxy, (C1-C4) haloalkoxy and (C1-C4) alkylthio , OR ⁵ , NR ⁶ R ⁷ , wherein R ^{5 is} C 1 -C 6 alkyl, C 2 -C 6 alkenyl, which are optionally partially or fully halogenated and / or optionally have one substituent from the group. C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, alkylthio (C 1 -C 4), (C 3 -C 7) cycloalkyl, (C 5 -C 7) cycloalkenyl, and aryl group, optionally having from one to three nitro, cyano, halogen, alkyl (C až-C 4), (C až-C hal) haloalkyl, (C až-C alko) alkoxy, (C až-C hal) haloalkoxy and (C až-C alkyl) alkylthio, (C až-C 7) cycloalkyl or cycloalkenyl (C až-C prípadne) group optionally having one to three substituents selected from halo, (C až-C alky) alkyl, (C až-C hal) haloalkyl, (C až-C alko) alkoxy, aryl, which is optionally partially or fully halogenated and / or optionally has one to three subst ituents from the group consisting of nitro, cyano, (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl, (C 1 -C 4) alkoxy, (C 1 -C 4) haloalkoxy, (C 1 -C 4) alkylthio, R ^{6 is} C 1 -C 6 alkyl, C 2 -C 6 alkenyl, which is optionally partially or fully halogenated and / or optionally has one substituent selected from C 1 -C 4 alkylthio, C 3 -C 4 cycloalkyl C 7 -C 7 cycloalkenyl and C 5 -C 7 aryl and the aromatic groups optionally having one to three groups selected from 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 optionally having one to one carbon atoms three substituents from the group consisting of a halogen atom, an alkyl group having from 1 to 3 carbon atoms; (C uhlí-C hal), (C až-C hal) haloalkyl and (C až-C alko) alkoxy, aryl, which is optionally partially or fully halogenated and / or optionally has one to three substituents selected from nitro, cyano, (C s-C alky) alkyl; C 1 -C 4 halogen, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy and C 1 -C 4 alkylthio. R ( ⁷⁾ is hydrogen or (C1-C6) -alkyl, (b) an active substance of formula (IIA) or (IIB) A fungicidal mixture according to claim 1, characterized in that it contains a p-hydroxyaniline derivative of the general formula (I), in which Z represents a hydrogen atom and the other symbols have the meaning given in claim 1. R ³ R ² R ¹ Cl Cl C (CH3) j-CH3CL Cl Cl C (Ct H) -CH 2 CH 3 Cl Cl C (CH 2 J 2 -CH ₂ CH ₂ CH 3 Cl Cl C (CH, 11-CK, -Cl Cl CL 2-CH 3 - (2.2.1) -heptarx-2-yl Cl Cl 2-CH 3 · [2.2.1] β-ipten-2 * yi CL CL l-CK i-cyclohexYi A fungicidal mixture according to claim 2, characterized in that it comprises a p-hydroxyaniline derivative of the general formula (I) which is a compound of the general formula: ...... double or single bond, R 1 -C [CO ₂ CH ₃ ] = CHOCH ₃ , -C [CO ₂ CH ₃ ] = NOCH ₃ , -C [CONHCH ₃ ] = NOCH _3j -C [CO ₂ CH ₃ ] = CHCH ₃ , -C [CO ₂ CH ₃ ] = CHCH ₂ CH ₃ , -C [COCH ₃ ] = NOCH ₃ , -C [COCH ₂ CH ₃ ] = NOCH ₃ , -N (OCH ₃ ) -CO, CH ₃ , -N (CH ₃ ) -CO ₂ CH ₃ , -N (CH ₂ CH ₃ ) -CO ₂ CH _3> R is an organic group which is bonded directly or through an oxy group, a mercapto group, an amino group or an alkylamino group, or together with a group X and a ring Q or T to which an unsubstituted or substituted bicyclic, partially or fully unsaturated system is bound; contains heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen; R ^x -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 ] = CHOCH ₃ , -SC [CO 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 ] = NOCH _3> -CH ₂ C [CO ₂ CH ₃ = CHOCH ₃ , -CH ₂ C [CO ₂ CH ₃ ] = NOCH ₃ , -CH ₃ C [CONHCH ₃ ] = NOCH ₃ ; R ^y is oxygen or sulfur, = CH- or = N-, n 0, 1, 2 or 3, wherein X is the same or different when n is greater than 1, X is cyano, nitro, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio or in the case where n is greater than 1, it is C 3 -C 5 alkylene, C 3 -C 5 alkenylene, C 2 -C 4 oxyalkylene, C 1 -C 3 oxyalkyleneoxy, C 2 -C 4 oxyalkenylene C 2 -C 4 oxyalkenyleneoxy, or a butadiene-diyl group attached to two adjacent carbon ring atoms of the phenyl ring, the chains may carry one to three groups independently selected from halogen, C 1 -C 4 alkyl. , (C1-C4) -haloalkyl, (C1-C4) -alkoxy, halogen C 1 -C 4 alkoxy and C 1 -C 4 alkylthio, Y = C- or = N-, Q a phenyl, pyrrolyl, thienyl, furyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, thiadiazolyl, triazolyl, pyridinyl, 2-pyridinyl, pyrimidinyl or triazinyl group; A phenyl, oxazolyl, thiazolyl, thiadiazolyl, oxadiazolyl, pyridinyl, pyrimidinyl or triazinyl T group in a synergistically effective amount for controlling harmful fungi. A fungicidal mixture according to claims 1 to 3, characterized in that it comprises a p-hydroxyaniline derivative of the formula (I) and a compound of the formula (IIA) or (IIB) in a weight ratio of 20: 1 to 0.05: 1. 5. A method for controlling harmful fungi, characterized in that the harmful fungi, their environment or the materials attacked by them, plants, seeds, soil, areas or premises are treated with a p-hydroxyaniline derivative of the formula I and a compound of the formula IIA) or (IIB) according to claim 1. The method according to claim 5, characterized in that the treatment is carried out with a p-hydroxyaniline derivative of the formula (I) and a compound of the formula (IIA) or (IIB) by simultaneous application, jointly or separately, or subsequent application. Process according to Claim 5 or 6, characterized in that the p-hydroxyaniline derivative of the general formula (I) is used in an amount of 0.05 to 1 kg / ha. Process according to claims 5 to 7, characterized in that the compound of formula (IIA) or (IIB) is used in an amount of 0.01 to 1 kg / ha. Use of a p-hydroxyaniline derivative of the general formula (I) according to claim 1 for the production of a fungicidal synergistic mixture. Use of a compound of formula (IIA) or (IIB), according to claim 1, for the preparation of a fungicidal synergistic mixture.