SK50798A3 - 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

Technical field

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 Patent Application Publication No. Az.195 04 599 8 and 195 40 970.1).

The active compounds of the formulas 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 251 082. EP-A 253 213. EP-A 254 426. EP-A 256 667. EP-A 260 794. EP-A 260 832. EP-A 267 734. EP-A 273 572. EP-A 274 825 EP-A 278 595. EP-A 280 185. EP-A 291 196. EP-A 299 694. EP-A 307 101 EP-A 307 103. EP-A 310 954. EP-A 312 221. EP-A 312 243. EP-A 329 011. EP-A 331 966. EP-A 335 519. EP-A 336 211. EP-A 337 211. EP-A 341 845. EP-A 350 691. EP-A 354 571. EP-A 363 818. EP-A 370 629 EP-A 373 775 EP-A 374 811. EP-A 378 308. EP-A 378 755. EP-A 379 098. EP-A 382 375. EP-A 383 117. EP-A 384 211. EP-A 385 224. EP-A 385 357. EP-A 386 561. EP-A 386 681. EP-A 389 901. EP-A 391 451. EP-A 393 428. EP-A 393 861 EP-A 398 692. EP-A 400 417. EP-A 402 246. EP-A 405 782. EP-A 407 873. EP-A 409 369. EP-A 414 153. EP-A 416 746. EP-A 420 091. EP-A 422 597. EP-A 426 460. EP-A 429 968. EP-A 430 471. EP-A 433 233. EP-A 433 899. EP-A 439 785. EP-A 459 285. EP-A 460 575. EP-A 463 488. EP-A 463 513. EP-A 464 381. EP-A 468 684. EP-A 468 695. EP-A 468 775 EP-A 471 261. EP-A 472 224. EP-A 472 300. EP-A 474 042. EP-A 475 158. EP-A 477 631. EP-A 480 795. EP-A 483 851. EP-A 483 985. EP-A 487 409. EP-A 493 711.

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 No. 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. 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 / 07,49 3, 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-A2 DE-A-39 05 911, DE Pat. ANM. 43 05 502 .8. DE Pat. ANM. 43 10 143.7, DE Pat. ANM. 43 18 397.2 DE Pat. ANM. 43 34 709.6, DE Pat. ANM. 44 03 446.6 DE Pat. ANM. 44 03 447.4, DE Pat. ANM. 44 03 448.2 DE Pát. ANM. 44 10 424.3, DE Pat. ANM. 44 21 180.5 DE Pat. ANM. 44 21 182.1, DE Pat. ANM. 44 15 483.6 DE Pat. ANM. 44 23 615.8 SE DE Pat. ANM. 44 23 612.3.

SUMMARY OF THE INVENTION It is an object of the present invention to increase the fungicidal action of the following compounds of the formula I by mixing with suitable other fungicidally active compounds.

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 formula I

C I) where is

R @ 1 is hydrogen, C1 -C8 alkyl optionally partially or fully halogenated and / or optionally having one or two substituents selected from C1 -C4 alkoxy, C1 -C4 haloalkoxy; C 1 -C 4 alkylthio, 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 (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; up to 4 carbon atoms, 1 to 4 alkoxy, 1 to 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 one to five substituents selected from C 1 -C 6 alkyl; C 1 -C 4 haloalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy and aryl optionally optionally partially or fully halogenated and / or optionally having one to three substituents selected from the group consisting of C 4-C prípadne-C 4; including 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, bicycloalkyl or C 7 -C 15 bicycloalkenyl which are optionally partially or fully halogenated and / or optionally have from 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 carbon atoms 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, (C 1 -C 4) alkoxy (C 4-C atóm), (C až-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 hydrogen or R ⁴ - (CO) - where it is

R ^{4 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 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 , a group of the formula OR ⁵ , NR ⁶ R ⁷ , where is

R ^{5 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 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 selected from nitro, cyano, (C1-C4) alkyl, (C1-C4) haloalkyl, (C1-C4) alkoxy, (C1-C4) haloalkoxy and (C1-C4) 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 aryl, wherein the aromatic groups optionally have 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 1 to 4 carbon atoms three substituents selected from the group consisting of halogen, alkyl of 1-4; C 1 -C 4 -halogenoalkyl and C 1 -C 4 -alkoxy, aryl which is optionally partially or fully halogenated and / or optionally has one to three substituents 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.

R ( ⁷⁾ is hydrogen or (C1-C6) -alkyl,

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

IIA where it means

R 1 -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 , -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 ' ^{1 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 is attached an unsubstituted or substituted bicyclic, partially or fully unsaturated system, which in the ring 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 ₂ 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 when 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 carbon atoms, C 2 -C 4 oxyalkenyleneoxy, or a butadiene-diyl group attached to two adjacent phenyl ring carbon atoms, which chains may carry one to three groups independently selected from the group consisting of halogen, C 1 -C 4 alkyl C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, halogen (C 1 -C 4) alkoxy and (C 1 -C 4) alkylthio group;

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.

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

Table I.1

Preferred compounds of formula I

Nr. R3 R 2 R ¹ literature *) 1.1.1 Cl Cl C (CH ₃ ) 2 -CK ₂ -? - ^CH 3 (A), (C), (D) 1.1.2 F ch ₃ C (CH ₃ ) ₂ -CK ₃ (A), (C), (D) 1.1.3 F ch ₃ C (CH ₃ ) ₂ -CH ₂ -C 1 (A), (C), (D) 1.1.4 F ch ₃ c (ch ₃ ) ₂ -ch ₂ —— ci (A), (C), (D) 1.1.5 Cl ch ₃ C (CH ₃ ) ₂ -CK ₂ CH ₂ CH ₃ (A), (C), (D) 1.1.6 F ch ₃ C (CH ₃ ) ₂ -CK ₂ CH ₂ CH ₃ (A), (C), (D) 1.1.7 F ch ₃ C (CH ₃ ) ₂ -CK ₂ Er (A). (C), (D) 1.1.8 Cl Cl C (CH ₃ ) ₂ -CK ₃ (A). (C), (D) 1.1.9 Cl Cl C (CH ₃ j ₂ -CH ₂ Sr (A), (C), (D) 1.1.10 Cl ch ₃ C (CH ₃ ) ₂ -CK ₂ Cl (A), (C), (D) 1.1.11 Cl ch ₃ C (CH ₃ ) ₂ -CK ₂ Sr (A), (C), (D) 1.1.12 Cl ch ₃ C (CK ₃ ) ₂ -CH ₃ (A), (C). (D) 1.1.13 Cl ch ₃ C _(CH3) 2 C _'2 - C (A), (C), (D) 1.1.14 Cl ch ₃ 2-CH ₃ '[2.2.1] heptan-2-yl (3), (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 formula I according to the table are particularly preferred

1.2.

Table I.2

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

Nr. R ³ R 2 R ¹ literature 1.2.1 Cl Cl C [CH ₃ ) ₂ -CH ₂ Cl (A), (C), (D) 1.2.2 Cl Cl C (CH ₃ ) ₂ -CH ₂ CH ₃ (A), (C), (D) 1.2.3 Cl Cl C (CH ₃ ) ₂ -CH ₂ CH ₂ CH ₃ (A), (C), (D) 1.2.4 Cl Cl c (CH ₃ ) 2 - CH ₂ —— C1 (A), (C), (D) 1.2.5 Cl Cl 2-CH ₃ - [2.2.1] Heptan-2-yl (B), (C), (D) 1.2.6 Cl Cl 2-CH ₃ - [2.2.1] Hepten-2-yl (B), (C), (D) 1.2.7 Cl Cl 1-CH ₃ -Cyclohexyl EP-A 339,418

Compounds HA and IIB are described, for example, in the following publications: EP-A 178 826, EP-A 203 606, EP-A 203 608,

EP-A 206,523, EP-A 212,859, EP-A 226,917,

EP-A 229 974, EP-A 242,070, EP-A 242,081, EP-A 243,012,

EP-A 243,014, EP-A 251,082, EP-A 253,213, EP-A 254,426,

EP-A 256,667, EP-A 260,794, EP-A 260,832, EP-A 267,734,

EP-A 273,572, EP-A 274,825, EP-A 278,595, EP-A 280,185,

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

EP-A 310,954, EP-A 312,221, EP-A 312,243, EP-A 329,011,

EP-A 331,966, EP-A 335,519, EP-A 336,211, EP-A 337,211,

EP-A 341,845, EP-A 350,691, EP-A 354,571, EP-A 363,818,

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

EP-A 378,755, EP-A 379,098, EP-A 382,375, EP-A 383,117,

EP-A 384,211, EP-A 385,224, EP-A 385,357, EP-A 386,561,

EP-A 386,681, EP-A 389,901, EP-A 391,451, EP-A 393,428,

EP-A 393,861, EP-A 398,692, EP-A 400,417, EP-A 402,246,

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

EP-A 416,746, EP-A 420,091, EP-A 422,597, EP-A 426,460,

EP-A 429,968, EP-A 430,471, EP-A 433,233, EP-A 433,899,

EP-A 439,785, EP-A 459,285, EP-A 460,575, EP-A 463,488,

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

EP-A 468,775, EP-A 471,261, EP-A 472,224, EP-A 472,300,

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

EP-A 483,851, EP-A 483,985, EP-A 487,409, EP-A 493,711,

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,

ΞΡ-Α 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. ΞΡ-Α 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 3 08. GB · -A 2 24 9 o: 92 GB-A 2 25: 3 6: 24, GB-A2 DE- -A 39 05 9 n. DE Pat. ANM. 43 05 502 • 8, DE Pat. Anni. 43 10 143.7. DE stalemate . ANM. 43 18 397.2. DE Pat. ANM. 43 34 709.6. DE stalemate . ANM. 44 03 446.6. DE Pat. ANM. 44 03 447.4. DE stalemate . ANM. 44 03 448.2. DE Pat. ANM. 44 10 424.3. DE stalemate . ANM. 44 21 180.5. DE Pat. ANM. 44 21 182.1. DE stalemate . ANM. 44 15 483.6. DE Pat. ANM. 44 23 615.8 CT DE: Pat. ANM. 44 23 612.3.

The primary object of the present invention 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 significantly 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.

By combining the active compound of the formula I and IIA or IIB, harmful fungi are more effectively reduced, since a smaller amount of individual active compounds can be used for the synergistic action of the ingredients.

For the purposes of the invention, all the compounds of the formulas IIA and IIB mentioned above are suitable.

Of particular interest are compounds of formula (IIA) or (IIB) wherein R '* is selected from the group consisting of:

optionally substituted aryloxy, optionally substituted hetaryloxy, optionally substituted aryloxymethylene, optionally substituted hetaryloxymethylene, optionally substituted aryletenylene, optionally substituted hetaryletenylene or RaRpc = NOCH ₂ - or ON = CR 5 CR 8 = NOCH ₂ -, wherein R a, R a, a1 have the general and particular meaning given 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. 44 03 448

DE Pat. ANM. 44 21 180.5 DE Pat. ANM. 44 21 182.1;

as particularly preferred groups, referred to as substituted aryloxy or hetaryloxy, in general and in particular, in the patents and EP-A-178826, the optionally substituted meaning of the present invention is

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 No. 93 / 15,046, WO-A 94/10, 159, GB-A 2 253 JP-A 04 / 182,461 ex DE Pat. ANM. 44 23 61 2.3;

as especially substituted substituted preferred groups, referred to as an optionally aryloxymethylene group or optionally a hetaryloxymethylene group, have the general and particular meaning given in the patents and applications

no lo E P-A 178,826, E P-A 226 9 U7, E P-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 692nd 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.

ΕΡ-Α 579,124, WO-A 93 / 08,180, WO-A 93 / 15,046, WO-A 94/00, 436,

JP-A 04 / 182,461, DE Anm. Nr. 43 05 502., DE Anm. Nr. 44 10 424 ..

in DE Pat. ANM. 44 15 483.6;

as particularly preferred groups, referred to as an optionally substituted aryletenylene group, an optionally substituted hetaryletenylene group, have generally 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 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. 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 93/1 5,046 ;, wo- A 94 T / 11,334, FR-A 2,670,781 a. DE Pat. ANM. 4 4 23 615th 8;

the particularly preferred active compounds of the formula IIA in which R 'is -C [CO ₂ CH ₃ ] = CHOCH ₃ correspond in general and in particular to the compounds according to the patents and applications of the invention no.

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- No. 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 Anm. Nr. 44 03 447., DE Anm. Nr. 44 10 424 ..

DE Pat. ANM. 44 21 180.5;

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

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 No. 901, WO-A 94 / 00,436, WO-A 94 / 08,948 1, WO-A 94/10, 159, WO-A No. 94 / 11,334, JP-A 05/201 JP-A No. 05 / 255,012, JP-A 05 / 294,948, DE ANM. Nr. 44 03 447

DE Anm. Nr. 44 10 424 .. óL DE Pat. ANM. 44 21 180.5;

Particularly preferred active substances of type II, wherein R 'is -C [CONHCH ₃ ] = NOCH _3, correspond in general and in particular to the compounds described in the patents and patent applications no.

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 Anm. Nr. 43 05 503 ..,

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

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

particularly preferred type II active compounds 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 Anm. Nr. 44 10 424 ..,

DE Pat. ANM. Nr. 44 21 180.5 DE DE Pat. ANM. Nr. 44 15 483.6?

particularly preferred type II active compounds wherein R 'is -C [COCH ₃ ] = NOCH ₃ or -C [COCH ₂ CH ₃ ] = NOCH ₃ correspond in general and in particular 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

-OC [CO 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 [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 or -CH ₂ C [ CONHCH ₃ ] = NOCH ₃ correspond generally and particularly to the compounds described in patent specification no

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 Λ / EF ’-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 ¹ optionally substituted hetaryloxymethylene, wherein the optionally substituted (het) aryl moiety has the following meaning

Number Optionally substit. (het) aryl L i t.eralura II.1-1 2-CH ₃ -C ₆ H ₄ EP-A 226 917 II.1-2 2,5- (CH ₃ ) 2 -C ₆ H ₃ EP-A 226 917 II.II-3 2-CH ₃ , 4-C [CH ₃ ] = NOCH ₃ -C _s H ₃ EP-A-386,561 II.1-4 2-CH ₂ CH ₂ CH ₃ , 6-CF ₃ -pyrimidin-4-yl EP-A-407 873 II.1-5 2,4- (CH ₃₎ 2 -C ₆ H ₃ EP-A 226 917

Table II.1B

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

Ičíslo Optionally substit. (Het) aryl FROM Li teratura II.1B-1 C ₆ Hs EP-A 178 826 II.lB-2 6- [2-CN-C 6 H ₄ O] -pyrimidŕn-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 ¹ 'optionally substituted hetaryletenylene, wherein the optionally substituted (het) aryl moiety has the following meaning

Number Possibly substlit. (het) aryl L i Leratura II.1C-1 1- (2,4-C 1 _{2 3} -CsH), 5-CF ₃ H -pyrazol-4-yl EP-A 528,245 II.1C-2 1- _(4-Cl-4 CGH) pyrazol-4-yl EP-A 378,755 II.1C-3 3-CF ₃ -C ₆ H ₄ EP-A 203,606 II.1C-4 3-Cl-C ₆ H ₄ EP-A 203,606 II.1C-5 4-C ₆ H ₅ -C ₆ H ₄ EP-A 203,606

Table II.1D

Compounds of formula (IIA) wherein Q is phenyl, R 'is -C (CO ₂ CH ₃ ) = CHOCH ₃ , n is zero, R ^{1 is} CH ₂ ON = Cl 1: R 1, wherein R 1 and R 2 are as follows

Number R ' Rt: L i Leratura 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 II.1D-3 ch ₃ 4-OCH ₂ CH ₃ -pyrimidin-2-yl WO-A 92 / 18,487

Table II.1E

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

Number RY R ^ô R ^e T L i teraLura II.L-1 ch ₃ ch ₃ ch ₃ DE Anm. Nr. 44 03 447.4 II.1-2 ch ₃ ch ₃ ch ₂ ch ₃ DE Anm. Nr. 44 03 447.4 II.1-3 ch ₃ c ₆ h ₅ ch ₃ · DE Anm. Nr. 44 03 447.4 II.1-4 ch ₃ C ₆ Hs ch ₂ ch ₃ DE Anm. Nr. 44 03 447.4 II.1-5 ch ₃ 4-Cl-C ₆ H ₄ ch ₃ DE Anm. Nr. 43 21 180.5 II.1-6 ch ₃ 4-Cl-C ₆ H ₄ ch ₂ ch ₃ DE Anm. Nr. 43 21 180.5

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

Number Optionally, L. (het) aryl 1 Li Leratura II.2-1 2-CH ₃ -C ₆ H 4 EP-A 253,213 II.2-2 2,5- (CH ₃ ) 2 -C ₆ H ₃ EP-A-400 417 II.2-3 2,4- (CH ₃ ) ₂ -C ₆ H ₃ EP-A-400 417 II.2-4 2,3,5? (CH ₃ ) ₃ -C ₆ H ₂ EP-A-400 417 II.2-5 2-Cl, 5-CH ₃ -C ₆ H ₃ EP-A-400 417 II.2-6 2-CH ₃ , 4-C [CH ₃ ] = NOCH ₃ -C ₆ H ₃ EP-A-386,561

Table II.2B

Compounds of formula (IIA) wherein Q is phenyl. a group, R '-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) ary1 Literature II.2B-1 c ₆ h _p EP-A 253,213 | II.2B-2 6- [2-CN-C6H4-O] -pyrimidin-4-yl EP-A 468 684

Table II.2C

Compounds of formula (IIA) wherein Q is phenyl, R 'is -C (CO ₂ CH ₃ ) = NOCH ₃ , n is zero, R 1' is C 1-4 ONsd 6 R ⁰ , wherein R 6 and R ⁴ are as follows

Number R '' R ** Li teratúra II.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 II.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-Cl ₂ -C ₆ H ₃ EP-A-463,488

Table II.2D

Compounds of formula (IIA) wherein Q is phenyl, R 1 -C (CO ₂ CH ₃ ) = NOCH ₃ , n is zero, R ¹ 'CH ₂ ON = Cl 2 R ^c = NOE, wherein R 1, R 2 is and R ^a is as follows

Table II.3k

Number RY R R ^s Li Leratura J II.2D-1 ch ₃ ch ₃ ch ₃ DE Anra. Nr. 44 03 447.4 IX.2D-2 CH ch ₃ ch ₂ ch ₃ DE.Anm. Nr. 44 03 447.4 II.2D-3 ch ₃ C ₆ Pcs ch ₃ DE Anra. Nr. 44 03 447.4 1 II.2D-4 ch ₃ C ₆ H ₅ ch ₂ ch ₃ DE Anra. Nr. 44 03 447.4 1 II.2D-5 ch ₃ 4-Cl-C ₆ K ₄ ch ₃ DE Anm. Nr. 44 21 180.5 n II.2D-6 ch ₃ 4-Cl-C ₆ H ₄ ch ₂ ch ₃ DE Anra. Nr. 44 21 180.5

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

Number Alternatively, the substi t. (het) ary2 FROM Li teratúra II.3-1 2-CH ₃ -C ₆ H ₄ EP-A 477,631 II.3-2 2.5- _(CH3) 2 _3-CGH EP-A 477,631 II.3-3 2,4- (CH ₃ ) ₂ -C ₆ H ₃ EP-A 477,631 II.3-4 2,3,5- (CH ₃ ) ₃ -C ₆ H ₂ EP-A 477,631 II.3-5 2-CH ₃ , 4-C [CH ₃ ] = NOCH ₃ -C ₆ H ₃ EP-A 579,124 Ii.3-6 1- [4-Cl-C 6 H ₄ l H -pyrazol-3-yl DE Anm. Nr. 43 05 502.8 II.3-7 1- [2,4-Cl 2 -C 6 H ₃ ] -pyrazol-3-yl DE Anm. Nr. 43 05 502.8

Table II. 3B

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

Number Optionally substit. (hetlaryl L i Leratore II.3B-1 c ₆ h ₅ EP-A-398,692 II.3B-2 6- [2-CN-C ₅ H ₄ -O] -pyrimidin-4-yl GB-A 2,253,624

Table II.3C

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

[number Alternatively, subs. (hetlaryl Li teratura | II.3C-1 1- [2,4-Cl ₂ -C ₆ H ₃ ], 5-CF ₃ -pyrazol-4-yl DE Anm. Nr. 44 23 615.8

Table II.3D

The compounds of formula IIa, wherein Q is phenyl, R 'is C (CONHCH ₃₎ = NOCH _3, n is zero, R' is CH ₂ ON = ^{CRI> and} t ^IB, wherein R ⁰ and R ^o is the following meaning

Number R ^a r · * L i LeraLura 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 II.3D-5 ch ₃ 4-CH ₃ -C ₆ H ₄ EP-A-463,488 II.3D-6 ch ₃ 3,5-Cl ₂ -C ₆ K ₃ EP-A-463,488 II.3D-7 ch ₃ 2-OCH 2 CH ₃ -pyrimidin-2-yl WO-A 92 / 13,830.

Table Ij. .3E

Compounds of formula (IIA) wherein Q is phenyl, R 'is -C (CONHCH ₃ ) = NOCH ₃ , n is zero, R ¹ ' is CH ₂ ON = CR 4 R 6 ^; = NOR ⁶ ', wherein R *', R 6a is as follows

Number B? R ^ô R ^e Li teratúra II.3-1 ch ₃ ch ₃ ch ₃ DE Pat. ANM. 44 21 182.1 II.3-2 ch ₃ ch ₃ ch ₂ ch ₃ DE Pat. ANM. 44 21 182.1 II.3-3 ch ₃ C ₆ Hs ch ₃ DE Pat. ANM. 44 21 182.1 II.3-4 ch ₃ c ₆ h ₅ ch ₂ ch ₃ DE Pat. ANM. 44 21 182.1 II.3-5 ch ₃ 4-Cl-C ₆ H ₄ ch ₃ DE Pat. ANM. 44 21 182.1 Ii.3-6 ch ₃ 4-Cl-C ₆ H ₄ ch ₂ ch ₃ DE Pat. ANM. 44 21 182.1 II.3-7 ch ₃ 4-FC ₆ H ₃ ch ₃ DE Pat. ANM. 44 21 182.1

Table II.4A

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

Number Optionally subsL, (het) aryl L iLeraLura II.4-1 2-CH ₃ -C ₆ K ₄ EP-A 280 185 II.4-2 2,5- (CH ₃ ) ₂ -C ₆ H ₃ EP-A 513,580 II.4-3 2,4- (CH ₃ ) ₂ -C ₆ H ₃ EP-A 513,580 II.4-4 2,3,5- (CH ₃ ) ₃ -C ₆ H ₂ EP-A 513,580 II.4-5 2-Cl, 5-CH ₃ -C ₆ H ₃ EP-A 513,580 Ii.4-6 2-CH ₃ , 4-C [CH ₃ ] = NOCH ₃ -C ₆ H ₃ EP-A 513,580 II.4-7 1- [4-Cl-C ₆ H _4] pyrazol-3-yl DE Pat. ANM. 44 15 483.6

Table II.4B

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

Number Optionally substit. (het) aryl Li teratúra II.4B-1 c ₆ h ₅ EP-A 513,580

Table II. 4C

The 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 = NOR CRER ^Cl- ^ _'/ wherein R, R and R 1 has the following meaning

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

Table II.5B

Number Alternatively, subsLit. (BEL) aryl L i teratúra II.5-1 2-CH ₃ -CíK ₄ EP-A 513,580 II.5-2 2,5- (CH 3) 2-06¾ EP-A 513,580 II.5-3 2,4- (CH ₃₎ 2 -C ₆ H ₃ EP-A 513,580 XI.5-4 2,3,5- (CH 3) 3 -C ₆ H ₂ EP-A 513,580 II.5-5 2-Cl, 5-CH ₃ -C ₆ H ₃ EN 513 580 II.5-6 2-CH 3, 4-C (CH ₃ J = NOCH 3 -C ₆ H 3 EP-A 513,580

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

C o s 1 o Optionally substit. (Het) aryl Literature (II.5B-1 c ₆ h ₅ 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 1' is CH 2 ON-CR 4 R 6 NO 1, wherein R 6 is and R ^ is as follows

Number RY R ^ô R ^e Literature j II.5C-1 ch ₃ ch ₃ ch ₃ DE Pat. ANM. 44 21 180.5 II.5C-2 ch ₃ ch ₃ ch ₂ ch ₃ DE Pat. ANM. 43 21 180.5 II.5C-3 ch ₃ c ₆ h ₅ ch ₃ DE Pat. ANM. 43 21 180.5 II.5C-4 ch ₃ C ₆ H _S ch ₂ ch ₃ DE Pat. ANM. 43 21 180.5 II.5C-5 ch ₃ 4-Cl-C ₆ H ₄ ch ₃ DE Pat. ANM. 43 21 180.5 8 II.5C-6 ch ₃ 4-Cl-C ₆ H ₄ ch ₂ ch ₃ DE Pat. ANM. 44 21 180.5

Table II.6A

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

Number Or suhstit. (Het) aryl Li teratura II.6-1 2-CH ₃ -C ₆ H ₄ 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 ₃ ) ₂ -C ₆ H ₃ EP-A 498,188 II.6-4 2,3,5- (CH ₃ ) ₃ -C ₆ H ₂ EP-A 498,188 II.6-5 2-CH ₃ , 4-C [CH ₃ ] = NOCH ₃ -C ₆ H ₃ EP-A 498,188

Table II.6B

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

Number Or suhstit. (Het) aryl Li teratura II.6B-1 c ₆ h ₅ EP-A 498,188 II.6B-2 6- [2-CN-C 8 H ₄ -O] -pyrimidin-4-yl EP-A 498,188

Table II.7A

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

Number Optionally substit. (BET) aryl ^{r 1} , i Li teralura II.7-1 2-CH ₃ -C ₆ H ₄ EP-A 498,188 II.7-2 2,5- (CH ₃ ) 2 -C ₆ H ₃ EP-A 498,188 II.7-3 2,4- (CH ₃ ) ₂ -C ₆ H ₃ EP-A 498,188 II.7-4 2,3,5- (CH ₃ ) ₃ -C ₆ H ₂ EP-A 498,188 II.7-5 2-CH ₃ , 4-C [CH ₃ ] = NOCH ₃ -C ₆ H ₃ EP-A 498,188 j

Table II.7B

Compounds of formula (IIA) wherein Q is phenyl, R '-C (COCH 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) ary1 Li teratura II.7B-1 c ₆ h ₅ EP-A 498,188 II.7B-2 6- [2-CN-C 6 H 4 -O] -pyrimidin-4-yl EP-A 498,188

Table II.8A

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

Number Optionally, substiL. (Het) ary1 L ileratura II.8-1 2-CH ₃ -C ₆ H ₄ WO-A 93 / 15,046 II.8-2 2,5- (CH ₃ ) ₂ -C ₆ H ₃ WO-A 93 / 15,046 II.8-3 2,4- _{(CH3) 2-C} H ₃ WO-A 93 / 15,046 II.8-4 2,3,5- (CH ₃ ) ₃ -C ₆ H ₂ WO-A 93 / 15,046 II.8-5 2-Cl, 5-CH ₃ -C ₆ H ₃ WO-A 93 / 15,046 II.8-6 2-CH ₃ , 4-C [CH ₃ ] = NOCH ₃ -C ₆ H ₃ WO-A 93 / 15,046 II.8-7 2-CH ₃ , 4-C [CH ₃ ] = NOCH ₂ CH ₃ -C ₆ H ₃ WO-A 93 / 15,046 II.8-8 2-CH ₃ , 4-C [CH ₂ CH ₃ ] = NOCH ₃ -C ₆ H ₃ WO-A 93 / 15,046 II.8-9 2-CH ₃ , 4-C (CH ₂ CH ₃ ) = NOCH ₂ CH ₃ -C ₆ H ₃ WO-A 93 / 15,046 II.8-10 1- [4-Cl-C ₆ H _4] 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 1' is CH ₂ ON = cR ¹ 'R 2 wherein R 1 and R 2 have the following: meaning

| Number R ^a R0 - - ··· 1LiLeratura | II.8B-1 CH ₃ 3,5-Cl ₂ C 6 H ₃ ~ WO-A 93 / 15,046

Pure active compounds of the formulas I and IIA or IIB are preferably used in the preparation of the mixtures, but other active compounds against pests (e.g. insects, spiders or nematodes) or against harmful fungi, but also herbicidal active compounds, may be added to these mixtures, active substances affecting growth or fertilizers.

Mixtures of compounds of formulas I and IIA or IIB or the separate use of compounds of formulas I and IIA or IIB show an excellent action against a broad spectrum of particularly pathogenic fungal infestations of plants. In part, they are systemically acting (i.e. they can be taken up by the plant without loss of efficacy and possibly transported in the plant when used for plant protection) and therefore can be used as foliar and soil fungicides.

Of particular importance in destroying multiple fungi on various 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 for 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 grain, Septoria nodorum on wheat, Botrytis cinera (strawberry) on strawberries, vegetables, ornamental plants and vines, Cercospora arachidicola on peanuts, Pseudocercosporella austrico oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vine, Pseudoperonospora on hops and cucumbers, Arternaria on vegetables and fruits and Fusarium and Vertocollium.

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

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

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 in particular 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 in particular 3: 1 to 1: 1 (I: 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 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 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 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 the formulas I and IIA or IIB may be applied together or separately or a mixture of the compounds of the formulas I and IIA or IIB may be applied by spraying or dusting the plants or soil before sowing or after sowing or after germination of plants.

The fungicidal synergistic mixtures according to the invention or the compounds of the formulas 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 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, alkylarylsulfonates, alkyl sulfates, alkyl sulfates, 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 compositions can be prepared by mixing or co-milling the compounds of formula I and IIA or I and IIB, or by mixing the compounds of formula X and IIA and optionally I and IIB together with a solid carrier. Granules, for example coated granules, impregnating granules and homogeneous granules, may 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 generally 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of a compound of the formula IA or IB, IIA or IIB or mixtures of the compounds of the formula I and IIA or 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 or corresponding compositions thereof, are used by treating the harmful fungi, their environment, fungi on protected materials such as plants, seeds, soil, areas or spaces with a fungicidally effective amount of the mixture or compounds. of formula I and IIA or I and IIB in separate deposition.

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

Examples of use

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

Cl Cl

HO

NH-CO-C (CH ₃₎ 2 -CH ₂ C 1 (A) 1.2.1 Compound cl cl it

NH-CO ₃ (B) compound 1.2.5 ar.do: exo = 1: 1

Cl Cl

HO - ^NH - ~~ ^QQ / \ c h ₃ (C) Compound Compound II.2 1.1.15-1

CN

n ^ n, AA ₀

(E) (D)

H3CO-CII o

c = c- ₃ Compound II.1B-2

H 3 CO-N == CC (CH 3) == N-O-CH ₂

H ₃ C - N - C '

I II

H 0

C = N-OCH ₃ (F) Compound II.3E-3% of the double bonds marked with an asterisk are in the E configuration.

Example 1

Efficacy against Botrytis cinerea

Neusiedler Ideal Elite pepper seeds 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 exhibit necrosis.

The assessment shall be carried out by visual assessment of the percentage attack on the leaf 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, the expected degree of action of the active compound mixtures is determined according to the formula derived by Colby (Colby S.R., Calculating synergistic and antagonistic respoonses of herbicide Combinations Weeds 15, 20-22, 1967) and compared to the degree of action found.

The results are shown in Table 1.1 below (column I shows the active substance, column II the concentration of the active substance in the spray suspension in ppm, column III the percentage of activity with respect to the untreated control, with the untreated control showing 100% attack.

Table I.1

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

Table 1.2

Degree of effectiveness of the mixture

Mixture of 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 ratio 99 84 25 ppm (A) + 25 ppm (E) 1: 1 mixture ratio 83 40 100 ppm (A) + 25 ppm (F) 4: 1 mixture ratio 98 84 25 ppm (F) + 25 ppm (F) 99 40

mixture ratio 1: 1

Table 1.2 (continued)

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

mixture ratio 1: 1

100 ppm (C) + 25 ppm (E) 4: 1 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) + 25 ppm (F) 1: 1 ratio 97 35

From the results it is clear that the observed degree of efficacy in the mixtures, if any, is higher in all tested ratios 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 the spray coating had dried on, the fruit are inoculated with a spore suspension of Botrytis cinerea containing 1.7 x 10 ⁶ spores per ml of a 2% strength Biomalz solution and placed in a chamber at 18 ^E C. at high atmospheric humidity. 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 ingredient mixture is determined by the Colby-derived formula (Colby S.R., Calculating Synergistic and Antagonist Response of Herbicide Combinations Weeds 15, 20-22, 1967) and compared to the observed degree of action.

The results are shown in Table 1.1 below (column I shows the active substance, column II the concentration of the active substance in the spray suspension in ppm, column III the percentage of activity with respect to the untreated control, with the untreated control showing 100% attack.

Table II.1

I II III (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

Mixture of active substances observed effect expected effect 100 ppm (A) + 25 ppm (F) 4: 1 mixture ratio 77 48 25 ppm (B) + 25 ppm (D) 1: 1 mixture ratio 90 79 100 ppm (B) + 25 ppm (F) 4: 1 ratio 80 51 25 ppm (B) + 25 ppm (F) 1: 1 mixture ratio 75 42 100 ppm (C) + 25 ppm (F) 4: 1 mixture ratio 97 51 25 ppm (C) + 25 ppm (F) 1: 1 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 p-hydroxyaniline derivative based compound for the production of fungicides for agricultural and industrial purposes.

Claims (10)

1, A fungicidal composition comprising a) a p-hydroxyaniline derivative of the general formula I wherein is 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 a) alkoxy, (C až-C 4) haloalkoxy; 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 Or a C 7 -C 15 bicycloalkenyl group 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 carbon atoms 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, (C 1 -C 4) alkoxy (C 4-C atóm), (C až-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 hydrogen or R ⁴ - (CO) - where it is R ^{4 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 alkoxy, C 1 -C 4 haloalkoxy 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 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 group, (C 3 -C 7) cycloalkyl or a C 5 -C 7 cycloalkenyl group optionally having one to 5 carbon atoms three substituents selected from the group consisting of halogen, C1-C4alkyl, C1-C4haloalkyl and C1-C4alkoxy, aryl which is optionally partially or fully halogenated and / or optionally has one up 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 carbon, a group of the formula OR ⁵ , NR ⁶ R ⁷ , where is R ^{5 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 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), (C 1 -C 4) alkoxy, (C 1 -C 4) haloalkoxy, (C 1 -C 4) alkylthio (C 3 -C 7) cycloalkyl group or a C 5 -C 7 cycloalkenyl group optionally having from 1 to 5 carbon atoms ri is a halogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 haloalkyl group and a C 1 -C 4 alkoxy group, an aryl group which is optionally partially or fully halogenated and / or optionally has one up to three substituents selected from the group consisting of nitro, cyano, (C1-C4) alkyl, (C1-C4) haloalkyl, (C1-C4) alkoxy, (C1-C4) haloalkoxy and (C1-C4) 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 aryl, wherein the aromatic groups optionally have 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 three carbon atoms substituents selected from the group consisting of halogen, C1-4 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 three substituents from the group consisting of nitro, "cyano, 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 group. R? a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, (b) an active substance of the formula IIA or IIB ..... double or single bond, R 1 -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 , -c [coch ₂ ch ₃ ] = noch ₃ , -n (and ₃ ) -co ₂ ch ₃ , -n (ch ₃ ) -co ₂ ch ₃ , -n (ch ₂ ch ₃ ) -co ₂ ch ₃ , 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 an unsubstituted partially or fully ring carbon atom or a substituted bicyclic, unsaturated system are bound, which in addition contains heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, R ^{v * * * * 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 ₂ C [CONHCH ₃ ] = noch ₃ ; an oxygen or sulfur atom, a 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 when 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 4 oxyalkylene, C 4 carbon atoms or, on two adjacent atoms, a C 2 -C 2 oxyoxyenyleneoxy C 2 -C 4 butadiene-diyl group bonded to the phenyl ring, which chains may carry one to three groups independently selected from a halogen atom, a C 1 -C 4 alkyl group C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, halogen (C 1 -C 4) alkoxy and (C 1 -C 4) alkylthio group; Y = C- or = N-, Q a phenyl, pyrrolidyl, 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. A fungicidal mixture according to claim 1, characterized in that it comprises 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. A fungicidal mixture according to claim 2, characterized in that it comprises a p-hydroxyaniline derivative of the formula I which is a compound of the formula R ³ R ² R ¹ Cl Cl C (CH ₃ ) ₂ -CH ₂ Cl Cl Cl C (CH ₃ ) ₂ -CH ₂ CH ₃ Cl Cl C (CH ₃ ) ₂ -CH ₂ CH ₂ CH ₃ Cl Cl c (ch ₃ ) 2 -ch ₂ —— Cl Cl Cl 2-CH ₃ - [2.2.1] Heptan-2-yl Cl Cl 2-CH ₃ - [2.2.1] hepten-2-yl Cl Cl 1-CH ₃ -Cyclohexyl 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. Method according to claim 5, characterized in that the treatment is carried out by a p-hydroxyaniline derivative of the formula I and a compound of the formula IIA or IIB by simultaneous application, either jointly or separately, or by subsequent application. 7th 8th Process according to claim 5 or 6, characterized in that a p-hydroxyaniline derivative of the formula I is used in an amount of 0.05 to 1 kg / ha. Process according to claims 5 to 7, characterized in that a compound of the 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 for the production of a fungicidal synergistic mixture according to claim First Use of a compound of formula IIA or IIB for the manufacture of a fungicidal synergistic composition according to claim