EP1788877A1 - Fungicidal synergistic mixtures made of triazolopyrmidine derivatives - Google Patents

Abstract

The invention relates to fungicidal mixtures containing, as active components, 1) a 5-chlor-6-phenyl-7-heterocyclylamino-triazolopyrimidine of formula (I), wherein D forms a pyrrolidine, piperidine or azepine ring, together with the nitrogen atom, said rings being substituted or not substituted by one or two methyl groups or by an ethyl, propyl or butyl group; and L represents methyl, fluorine or chlorine; and 2) at least one active ingredient II which is selected from the following groups: A) azoles; B) strobilurines; C) acylalanines; D) amine derivatives; E) anilinopyrimidines; F) dicarboximides; G) cinnamic acid amides and analoges; H) antibiotics; K) dithiocarbamates; L) heterocylic compounds which are cited in the description; M) sulfur and copper fungicides N) nitrophenyl derivatives; O) phenylpyrroles; N) sulfenic acid derivatives; Q) other fungicides which are cited in the description; or R) growth retardants; in a synergistically active amount. The invention also relates to novel triazolopyrimidines, to a method for controlling harmful fungi by means of compounds of formula (I) or mixtures of a compound of formula (I) with an active ingredient from the groups A) - R) and to the use of compounds of formula (I) with the active ingredients of groups A) - R) for the production of said type of mixtures and means containing said compounds or mixtures.

Description

 FUNGICIDAL SYNERGISTIC MIXTURES FROM TRIAZOLOPYRMIDINE DERIVATIVES

description

The present invention relates to fungicidal mixtures containing as active Kompo¬ components

1) an S-chloro-6-phenyl-γ-heterocyclylamino-triazolopyrimidine of the formula I,

in the

D together with the nitrogen atom forms a pyrrolidine, piperidine or azepin ring, which rings are unsubstituted or substituted by one or two methyl groups or by an ethyl, propyl or butyl group; and L is methyl, fluorine or chlorine;

and

2) at least one active ingredient II selected from the following groups:

A) Azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prochlorazone, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, Triadimol, triflumizole, triticonazole;

B) strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoximethyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin or 2- (ortho- (2,5-dimethylphenyloxymethylene) phenyl) -3-methoxy-acrylic acid methyl ester;

C) acylalanines such as benalaxyl, metalaxyl, mefenoxam, ofurace, oxadixyl;

D) amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph,

Fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph; E) anilinopyrimidines such as pyrimethanil, mepanipyrim or cyprodinil;

F) dicarboximides such as iprodione, myclozoline, procymidone, vinclozolin;

G) cinnamic acid amides and analogs such as dimethomorph, flumetover or fluorom;

H) antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxine or streptomycin;

K) dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamate, Thiram, Ziram, Zineb;

L) heterocyclic compounds selected from anilazine, benomyl, boscalid,

Carbendazim, Carboxin, Oxycarboxin, Cyazofamide, Dazomet, Dithianon, Famoxadone, Fenamidon, Fenarimol, Fuberidazole, Flutolanil, Furametpyr, Isoprothiolane, Mepronil, Nuarimol, Picobenzamide, Probenazole, Proquinazide, Pyrifenox, Pyroquilon, Quinoxyfen, Silthiofam, Thiabendazole, Thifluzamide, Thiophanate methyl, tiadinil, tricyclazole, triforine, 3- [5- (4-chlorophenyl) -2,3-dimethyl-isoxazolidin-3-yl] -pyridine, (2-chloro-5- [1- (3-methyl-benzyloyimino ethyl (ethyl) benzyl) carbamate, (methyl 2-chloro-5- [1- (6-methyl-pyridin-2-yl-methoxyimino) -ethyl] -benzyl) -carbamate,

Benzoimidazole derivatives of the formula IIA,

in which Y is chlorine or bromine;

Sulfamoyl compounds of the formula

in which the substituents have the following meanings: R ³¹ is hydrogen, halogen, cyano, C ₁ -C ₄ -AIRyI, CrC ₂ -HalogenalkyI,

C ₁ -C ₄ -alkoxy, C _r C ₄ -AlkyIthio, C ₁ -C ₄ alkoxycarbonyl, phenyl, benzyl,

Formyl or CH = NOR ³¹¹ ;

R ³¹¹ is hydrogen, C _r C ₄ alkyl, CiC ₄ -AlkyIcarbonyl; R ³² is hydrogen, halogen, cyano, C _r C ₄ alkyl, CRCA haloalkyl,

C _r C ₆ alkoxycarbonyl; R ³³ is halogen, cyano, nitro, C _r C ₄ alkyl, C _r C ₂ haloalkyl, C ₁ -C ₄ -AIk- oxy, C _r C ₄ -AIkylthio, CrOrAlkoxycarbonyl, formyl, or CH = NOR ^311; n is 0, 1, 2, 3 or 4; R ³⁴ is hydrogen, halogen, cyano, C _r C ₄ alkyl or CRCA haloalkyl; or

Thiophene derivatives of the formula IV,

in which the variables have the following meanings:

Ar is phenyl or a five- or six-membered aromatic heterocycle containing one to four heteroatoms from the group O, N or S, where the rings are unsubstituted or may be substituted by one to three groups R ⁴¹ : R ^{41 is} halogen, C ₁ -C ₄ -alkyl or C _r C ₄ haloalkyl;

R is phenyl, C _r C ₈ alkyl, C _r C ₈ haloalkyl, C ₁ -C ₈ -alkoxy, C ₁ -C ₈ -HaIo- genalkoxy; Q is hydrogen, C ₁ -C ₈ -alkyl, C _r C ₈ haloalkyl, C _r C ₈ alkoxy,

C _r C ₈ halogenoalkoxy;

M) sulfur and copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate;

N) nitrophenyl derivatives, such as binapacryl, dinocap, dinobutone, nitrophthalic isopropyl;

O) phenylpyrroles such as fenpiclonil or fludioxonil;

P) sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanide;

(Q) Other fungicides, such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamid, cymoxanil, dazomet, diclomezine, diclock cymet, diclofluanid, diethofencarb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, phosphorous acid, iprovalicarb, hexachlorobenzene, mandipropamide, metrafenone, pencycuron, propamocarb, phthalide, tol-clofos- methyl , Quintozene, Zoxamide,

Oxime ether derivatives of the formula V,

in the

X C ^^ - haloalkoxy, n is 0, 1, 2 or 3,

R is halogen, C ₁ -C ₄ -alkyl, Ci-C ₄ haloalkyl, C ₁ -C ₄ -alkoxy, or halo- genalkoxy;

Phenylamidine derivatives of the formula VI,

in which the variables have the following meanings: R ⁶¹ is hydrogen, C _r C ₈ alkyl, C ₂ -C ₈ alkenyl or C ₂ -C ₈ -alkynyl which are unsubstituted or may be substituted by one to three groups R ^a:

R ^a halogen, C _r C ₈ alkoxy, CrCs-haloalkoxy, C _r C ₈ alkylthio or

Phenyl which may be substituted by halogen, CrCβ alkyl, C _r C ₈ haloalkyl, C ₁ -C ₈ -alkoxy, CRCS Halo¬ genalkoxy or C _r C ₈ alkylthio; R ⁶² , R ⁶³ may be the same or different and may be hydrogen, cyano,

C, -. C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C _r C ₈ alkoxy, C ₁ -C ₈ alkyl -AIkOXy-, benzyloxy or CpCβ-alkylcarbonyl which are unsubstituted or may be substituted by one to three groups R ^a ; R ^{64 is} hydrogen, C ₁ -C ₈ -alkyl, C ₂ -C ₈ -alkenyl or C ₂ -C ₈ -alkynyl, which are unsubstituted or may be substituted by one to three groups R ^b :

R ^{b is} one of the groups mentioned under R ^a , cyano, C (OO) R ^C , C (SS) R ^C or S (O) _P R ^C ,

R ^c d-Cs-alkyl, d-Cs-haloalkyl, C ₁ -C ₈ -alkoxy, C ₁ -C ₈ logenalkoxy -Ha-, -C ₈ alkylthio, amino, d-Cs-alkylamino, di (C _r C _8- alkyl) amino or

Phenyl which Ci-C may be substituted by halogen, Cn-Ca-alkyl, ₈ haloalkyl, C ₁ -C ₈ -alkoxy, dC ₈ -haloalkoxy or C _r C ₈ alkylthio; m is 0 or 1;

R ^{65 is} one of the groups mentioned in R ⁶⁴ ; A is a direct bond, -O-, -S-, NR ^d , CHR ^e or -O-CHR ^e ; R ^d , R ^{e is} one of the groups mentioned in R ^a ;

R ^{66 is} phenyl or five- or six-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S, where the groups R ^{66 are} unsubstituted or by one to three R ^f R ^{f is} one of the groups mentioned for R ^b or

Amino, C _r C ₈ alkylamino, di (C | -C ₈ alkyl) amino, C _r C ₈ alkyl-halo, C _r C ₈ alkoxyalkyl, C ₂ -C ₈ -Alkenyloxyalkyl, C ₂ -C ₈ oxyalkyl alkynyl, d-Cs-alkylcarbonyloxy CRCS alkyl, Cyanooxy-C _r C ₈ - alkyl, C ₃ -C ₆ -cycloalkyl or phenoxy, where the cyclic groups may be substituted by halogen, C ₁ -C ₈ -alkyl, d-Cs-haloalkyl, C _r C ₈ alkoxy, C _r C ₈ haloalkoxy, or d-Cs-alkylthio; or

a compound of formula VII,

in which the variables have the following meaning: A 'O or N; GC or N; BN, or a direct bond;

R ⁷¹ C _r C ₄ alkyl; R ^{72 is} C ₁ -C ₄ -alkoxy; and R ⁷³ halogen;

R) growth retardants such as prohexadione and its salts, trinexapacethyl, chlormequat, mepiquat chloride and diflufenzopyr;

in a synergistically effective amount.

In addition, the invention relates to novel fungicidal triazolopyrimidines, a method for controlling harmful fungi with mixtures of a compound I with an active compound of groups A) to R) and the use of the compounds I with the active compounds of groups A) to R) for the preparation of such mixtures and Means containing these mixtures.

The compounds I referred to above as component 1, their preparation and their action against harmful fungi are generally proposed in the literature (US Pat. No. 5,593,996). Individual compounds of the formula I are known from US Pat. No. 5,593,996; WO 02/02563; WO 02/94020).

Mixtures of 5-chlorotriazolopyrimidines with various active ingredients are generally known from EP-A 988 790 and US Pat. No. 6,268,371.

With a view to reducing the application rates of the known compounds, the present invention was based on new active substances or mixtures which show an improved action against harmful fungi with a reduced total amount of active substances applied.

Accordingly, the mixtures and novel active ingredients defined above were found. It has also been found that in the case of simultaneous joint or separate application of a compound I and of an active compound II from the groups A) to R) or when using a compound I and an active ingredient from the groups A) to R) successively controlling harmful fungi than with the individual compounds (synergistic mixtures).

For the use according to the invention, in particular the compounds compiled in the following table are suitable, in which the groups D and L have the following meanings:

Table A

! - ² HO- ² HO- ^ HO) HO- ³ HO- ( ⁸ HO) HO- ^ HO- ² HO- ² HO- ( ⁵ HO) HO- ( ⁸ HO) HO-

! - ² HO- ² HO- ( ^ε Hθ) HO- ² HO- ² HO- '- ( ^ε H0) H0- ² H0- ² H0- ( ^ε H0) H0-

! - ² HO- ² HO- ² HO- ² HO- ( ⁸ HO) HO-: - ^S ( ² H0) "! - ² HO- ( ⁸ HO) HO- ² HO- ( ⁸ HO) HO-

! - ² HO- ( ⁸ HO) HO- ( ⁸ HO) HO- ² HO-

! - ² HO- ² HO- ( ⁸ HO) HO- ( ⁸ HO) HO-! - ² HO- ² HO- ( ⁸ HO) HO- ² HO-! - "( ² HO) -

: * Ei | ueßurnnepsg uepusßioj jep ΘUJΘ α pun ^ napeq | Λißθ [/ \ | η usuap ιu '| uaßunpuiqjθΛ

8 zβuoomozdwiDά 8Z / .SΪ0 / 900Z OΛV -CH (CH ₃ ) -CH ₂ -CH ₂ -CH (CH ₃ ) -CH ₂ -; -CH (CHa) -CH ₂ -CH ₂ -CH ₂ -CH (CH ₃ ) -; -CH ₂ -CH (CH ₃ ) -CH (CH ₃ ) - (CH ₂ ) ₂ -; -CH ₂ -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ -; - (CH ₂ ) ₂ -CH (CH [CH ₃ ] ₂ ) - (CH ₂ ) ₂ -;

-CH (CH ₂ CHa) -CH ₂ -CH ₂ -CH ₂ -CH ₂ -; -CH-CH (CH ₂ CH _S ) -CH ₂ -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH (CH ₂ CH ₃ ) -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH (CH ₂ CH ₂ CH ₃ ) -CH ₂ -CH ₂ -;

-CH ₂ -CH ₂ -CH (C [CH ₃ ] ₃ ) -CH ₂ -CH ₂ - and - (CH ₂ ) ₆ - are new. They represent a preferred subject of the invention.

In addition, compounds I are also preferred in which L is fluorine and D has one of the following meanings:

- (CHz) ₄ -; -CH ₂ -CH (CH ₃ ) -CH ₂ -CH ₂ -; -CH (CH ₃ ) -CH (CH ₃ ) -CH ₂ -CH ₂ -;

-CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ -; -CH (CH _{2 S} ) -CH ₂ -CH ₂ -CH (CH ₃ ) -;

-CH ₂ -CH (CH _S ) -CH ₂ -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH (CH _S ) -CH ₂ -CH ₂ -;

-CH ₂ -CH (CH ₃ ) -CH (CH ₃ ) -CH ₂ -; -CH (CH ₃ ) -CH (CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -; -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ -CH ₂ -;

-CH (CH ₃ ) -CH ₂ -CH ₂ -CH (CH ₃ ) -CH ₂ -; -CH (CHa) -CH ₂ -CH ₂ -CH ₂ -CH (CH ₃ ) -;

-CH ₂ -CH (CH ₃ ) -CH (CH ₃ ) - (CH ₂ ) ₂ -; -CH ₂ -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ -;

- (CH ₂ ) ₂ -CH (CH [CH ₃ ] ₂ ) - (CH ₂ ) ₂ -;

-CH (CH ₂ CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH ₂ -; -CH-CH (CH ₂ CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH (CH ₂ CH ₃ ) -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH (CH ₂ CH ₂ CHa) -CH ₂ -CH ₂ - and

-CH ₂ -CH ₂ -CH (C [CH ₃ ] ₃ ) -CH ₂ -CH ₂ -. They too are new.

In addition, compounds I are also preferred in which L is chlorine and D has one of the following meanings: -CH (CH ₃ ) -CH (CH ₃ ) -CH ₂ -CH ₂ -; -CH ₂ -CH (CHs) -CH ₂ -CH ₂ -;

-CH (CH ₃ ) -CH ₂ -CH (CHs) -CH ₂ -; -CH (CHa) -CH ₂ -CH ₂ -CH (CH ₃ ) -;

-CH ₂ -CH (CH ₃ ) -CH (CH ₃ ) -CH ₂ -; -CH (CHa) -CH (CHs) -CH ₂ -CH ₂ -CH ₂ -;

-CH (CH ₃ ) -CH ₂ -CH ₂ -CH (CH ₃ ) -CH ₂ -; -CH (CH _S ) -CH ₂ -CH ₂ -CH ₂ -CH (CH ₃ ) -;

-CH ₂ -CH (CH ₃ ) -CH (CH ₃ ) - (CH ₂ ) ₂ -; - (CH _{2) 2} -CH (CH [CH _{3] 2} HCH _{2) 2} -; -CH (CH ₂ CH _S ) -CH ₂ -CH ₂ -CH ₂ -CH ₂ -; -CH-CH (CH ₂ CH _S ) -CH ₂ -CH ₂ -CH ₂ -;

-CH ₂ -CH ₂ -CH (CH ₂ CH ₃ ) -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH (CH ₂ CH ₂ CH _S ) -CH ₂ -CH ₂ - and

-CH ₂ -CH ₂ -CH (C [CH ₃ ] ₃ ) -CH ₂ -CH ₂ -.

They are new.

The new compounds can be obtained in various ways. They are advantageously prepared by reacting dichlorotriazolopyrimidines of the formula II 'in which L is methyl, fluorine or chlorine, with amines of the formula III' in which D is as defined for formula I under conditions generally known from WO 98/46608 receive.

The reaction of II 'with amines III' is advantageously carried out at ^{0 0} C to 7O ⁰ C, preferably 1O ⁰ C to 35 ⁰ C, preferably in the presence of an inert solvent such as ethers, eg. As dioxane, diethyl ether or especially tetrahydrofuran, halogenated hydrocarbons, such as dichloromethane and aromatic hydrocarbons, such as spielsweise toluene.

The use of a base, such as tertiary amines, for example triethylamine or inorganic bases, such as potassium carbonate, is preferred; Excess amine of the formula III 'can also serve as a base.

Amines of the formula III 'are commercially available.

The active compounds of groups A) to R) mentioned above as component 2, their preparation and their action against harmful fungi are generally known (cf.: http://www.hclrss.demon.co.uk/index.html):

Bitertanol, / S - ([1,1-biphenyl] -4-yloxy) -α- (1, 1-dimethylethyl) -1 W -1, 2,4-triazo! -1-ethanol;

Bromoconazole, 1 - [4-bromo-2- (2,4-dichloro-phenyl) -tetrahydrofuran-2-ylmethyl] -1 H-

[1,2,4] triazole (Proc. Br. Crop Prot. Conf.-Pests Dis., 5-6, 439 (1990)); Cyproconazole, 2- (4-chlorophenyl) -3-cyclopropyl-1- [1,2,4] triazol-1-yl-butan-2-ol

(US 4,664,696);

Difenoconazole, 1- {2- [2-chloro-4- (4-chloro-phenoxy) -phenyl] -4-methyl- [1,3-dioxolan-2-ylmethyl} -1 H- [1, 2,4 ] triazole (GB-A 2 098 607);

Dinitroconazole, 1- (2,4-dichloro-phenyl) -4,4-dimethyl-2- [1,2,4] triazol-1-yl-pent-1-en-3-ol (CAS RN [83657- 24-3]);

Epoxiconazole, (2RS, 3SR) -1 - [3- (2-chlorophenyl) -2,3-epoxy-2- (4-fluorophenyl) propyl] - 1 H-

1, 2,4-triazole (EP-A 196 038);

Fenbuconazole, 3- (4-chloro-phenyl) -2-phenyl-2- [1,2,4] triazol-1-yl-propionitrile (EP-A

251 775); Fluquiconazole, 3- (2,4-dichloro-phenyl) -6-fluoro-2- [1, 2,4] -triazol-1-yl-3H-quinazolin-4-one

(Proc. Br. Crop Prot. Conf.-Pests Dis., 5-3, 411 (1992));

Flusilazole, 1 - {[bis (4-fluoro-phenyl) -methylsilanyl] -methyl} -1H- [1,2,4] triazole (Proc. Br.

Crop Prot. Conf.-Pests Dis., 1, 413 (1984));

Flutriafol, 1- (4-fluoro-phenyl) -1- (2-fluoro-phenyl) -2- [1,2,4] triazol-1-yl-ethanol (CAS RN [76674-21-0]);

Hexaconazole, 2- (2,4-dichlorophenyl!) - 1- [1,2,4] triazol-1-yl-hexan-2-o! (CAS RN

[79983-71-4]); W

11

imazalil,

Ipconazole, 2- (4-chloro-benzyl) -5-isopropyl-1- [1,2,4] triazol-1-ylmethyl-cyclopentanol (EP-

A 267 778);

Metconazole, 5- (4-chloro-benzyl) -2,2-dimethyl-1- [1,2,4] triazol-1-ylmethyl-cyclopentanol (GB 857,383);

Myclobutanil, 2- (4-Chloro-phenyl) -2- [1,2,4] triazol-1-ylmethyl-pentane-nitrile (CAS RN

[88671-89-0]);

Penconazole, 1- [2- (2,4-dichloro-phenyl) -pentyl] -1 H- [1,2,4] triazole (Pesticide Manual, 12th

Ed. (2000), page 712); Propiconazole, 1- [2- (2,4-dichloro-phenyl) -4-propyl- [1,3-dioxolan-2-ylmethyl] -1 H-

[1, 2,4] triazole (GB 15 22 657);

Prochlorazolimidazole-1-carboxylic acid-propyl- [2- (2,4,6-trichloro-phenoxy) -ethyl] -amide (US Pat

3,991,071);

Prothioconazole, 2- [2- (1-Chloro-cyclopropyl) -3- (2-chloro-phenyl) -2-hydroxypropyl] -2,4-dihydro- [1,2,4] triazole-3-thione (WO 96/16048);

Simeconazole, 1- (4-fluoro-phenyl) -2- [1,2,4] triazol-1-yl-1-trimethylsilanylethanol (The

BCPC Conference Pests and Diseases 2000, pp. 557-562);

Tebuconazole, 1- (4-chlorophenyl) -4,4-dimethyl-3- [1,2,4] triazol-1-ylmethylpentan-3-ol

(EP-A 40 345); Tetraconazole, 1- [2- (2,4-dichloro-phenyl) -3- (1,1,2,2-tetrafluoroethoxy) -propyl] -1H-

[1, 2,4] triazole (Proc. Br. Crop Prot. Conf.-Pests Dis., 1, 49 (1988));

Triadimefon, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1Ay-1, 2,4-triazol-1-yl) -2-butanone;

Triadimenol, ^ - (4-chlorophenoxy) -σ- (1,1-dimethylethyl) -1H-1, 2,4-triazole-1-ethanol;

Triflumizole, (4-chloro-2-trifluoromethyl-phenyl) - (2-propoxy-1- [1,2,4] triazol-1-yl-ethylidene) -amine (JP-A 79/119 462);

Triticonazole, 5- (4-chloro-benzylidene) -2,2-dimethyl-1- [1,2,4] triazol-1-ylmethylcyclopentanol (EP-A 378 953);

Azoxystrobin, 2- {2- [6- (2-cyano-1-vinyl-penta-1,3-dienyloxy) -pyrimidin-4-yloxy] -phenyl} -

Methyl 3-methoxy-acrylate (EP-A 382 375) dimoxystrobin, (E) -2- (methoxyimino) -Λ / -methyl-2- [α- (2,5-xyloxy) -o-tolyl] -acetamide (EP-

A 477 631);

Fluoxastrobin, (£) - {2- [6- (2-chlorophenoxy) -5-fluoropyrimidin-4-yloxy] phenyl} (5,6-dihydroxy)

1, 4,2-dioxazin-3-yl) methanone O-methyloxime (WO 97/27189);

Kresoxim-methyl, (£) -methoxyimino [<7- (o-to) -yloxy) -o-tolyl] -acetic acid methyl ester (EP-A 253 213);

Metominostrobin, (E) -2- (methoxyimino) - / V-methyl-2- (2-phenoxyphenyl) acetamide (EP-A

398 692);

Orysastrobin, (2E) -2- (methoxyimino) -2- {2 - [(3E, 5E, 6E) -5- (methoxyimino) -4,6-dimethyl-

2,8-dioxa-3,7-diazanona-3,6-dien-1-yl] phenyl} -Λ / -methylacetamide (WO 97/15552); Picoxystrobin, 3-methoxy-2- [2- (6-trifluoromethylpyridin-2-yloxymethyl) -phenyl] -acryic acid methyl ester (EP-A 278 595);

Pyraclostrobin, / V- {2- [1- (4-chlorophenyl) -1H-pyrazol-3-yloxymethyl] -phenyl} (/ V-methoxy) -carbamic acid methyl ester (WO-A 96/01256); Trifloxystrobin, (E) -methoxyimino-{(ε) -σ- [1- (σ, σ, σ-trifluoro-77-tolyl) ethylideneaminooxy] o-tolyl} acetic acid methyl ester (EP-A 460 575);

2- (ortho- (2,5-dimethylphenyloxymethylene) phenyl) -3-methoxy-acrylic acid methyl ester

(EP-A 226 917);

Benalaxyl, metalaxyl, methyl A / (methoxyacetyl) -A / - (2,6-xylyl) -DL-alaninate (GB 15 00 581);

Mefenoxam, methyl N- (methoxyacetyl) -N- (2,6-xylyl) -D-alaninate (WO 96/01559);

Ofurace, (/? S) -σ- (2-chloro-Λ / -2,6-xylylacetamido) -κ-butyrolactone;

oxadixyl; Λ / - (2,6-dimethylphenyl) -2-methoxy-Λ / - (2-oxo-3-oxazolidinyl) acetamide;

Aldimorph, 4-alkyl-2,5 (or 2,6) -dimethylmorpholines containing 65-75% 2,6-dimethyl-morpholines and 25-35% 2,5-dimethylmorpholines, wherein more than 85% of 4-dodecyl-

2,5 (or 2,6) -dimethylmorpholine and "alkyl" ^{may also be} octyl, decyl, tetradecyl or hexadecyl, and wherein the cis / trans ratio is 1: 1;

Dodine, (2,4-dichlorophenoxy) acetic acid (US 2,867,562);

Dodemorph, 4-cyclododecyl-2,6-dimethylmorpholine (DE 11 98 125); Fenpropimorph, 4- [3- (4-tert-butylphenyl) -2-methyl-propyl] -2,6-dimethyl-morpholine (DE

26 56 747);

Fenpropidin, 1- [3- (4-tert-butyl-phenyl) -2-methyl-propyl] -piperidine (DE-OS 27 52 096);

Guazatine, mixture containing iminoctadine, bis (8-guanidino-octyl) amine (GB

11 14 155); Spiroxamine, (8-tert-butyl-1,4-dioxa-spiro [4.5] dec-2-yl) -diethyl-amine (EP-A 281 842);

Tridemorph, a mixture of N-alkylmorpholine derivatives containing 2,6-

Dimethyl-4-tridecylmorpholine contains (DE-AS 11 64 152);

Pyrimethanil, 4,6-dimethyl-pyrimidin-2-yl) -phenyl-amine (DD-A 151 404);

Mepanipyrim, (4-methyl-6-prop-1-ynyl-pyrimidin-2-yl) -phenyl-amine (EP-A 224 339); Cyprodinil, (4-cyclopropyl-6-methyl-pyrimidin-2-yl) -phenyl-amine (EP-A 310550);

Iprodione, 3- (3,5-dichloro-phenyl) -2,4-dioxo-imidazolidine-1-carboxylic acid isopropylamide

(GB 13 12 536);

Myclozoline, (RS) -3- (3,5-dichlorophenyl) -5-methoxymethyl-5-methyl-1,3-oxazolidine-2,4-dione; Procymidone, / V- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide (US Pat

3,903,090);

Vinclozoline, 3- (3,5-dichloro-phenyl) -5-methyl-5-vinyl-oxazolidine-2,4-dione (DE-OS

22 07 576);

Dimethomorph, 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) -1-morpholin-4-yl-propenone (EP-A 120 321); flumetover

Flumorph, 3- (4-fluorophenyl) -3- (3,4-dimethoxyphenyl) -1-morpholin-4-yl-propenone (EP-A

860 438);

Cycloheximide, 4 - {(2R) -2 - [(1S, 3S, 5S) -3,5-dimethyl-2-oxocyclohexyl] -2-hydroxyethyl} piperidine-2,6-dione;

Griseofulvin, 7-chloro-2 ', 4,6-trimethoxy-6-methylspiro [benzofuran-2 (3H _), 1'-cyclohex-2'-ene] -3,4'-dione;

Kasugamycin, 1 L-1, 3,4 / 2,5,6-1-deoxy-2,3,4,5,6-pentahydroxycyclohexyl 2-amino

2,3,4,6-tetradeoxy-4- (α'-iminoglycino) - <7-D-ara / -) / y7θ-hexopyranoside; Natamycin, (8E, 14 pounds, 16E, 18 pounds, 20E) - (1R, 3S, 5R, 7R, 12f, 22R, 24S, 25R ₎ 26S) -22- (3

Amino-3,6-dideoxy- / - D-mannopyranosyloxy) -1,3,26-trihydroxy-12-methyl-10-oxo

6,11,28-trioxatricyclo [22.3.1.0 ^{5 | 7} ] octacosa-8, 14,16,18,20-pentaene-25-carboxylic acid;

Polyoxine, 5- (2-amino-5-O-carbamoyl-2-deoxy-L-xylonamido) -1- (5-carboxy-1,2,3,4-tetrahydro-2,4-dioxopyrimidine-1 -yl) -1, 5-dideoxy - ^ - D-allofuranuronic acid and its salts; Streptomycin, 0-2-deoxy-2-methylamino-α'-L-glucopyranosyl- (1 → 2) -O-5-deoxy-3-C-formyl-σ-L-lyxofuranosyl- (1 → 4) - / V ¹ , Λ / ³ -diamidino-D-streptamine;

Ferbam, iron (3+) dimethyldithiocarbamate (US 1,972,961);

Nabam, disodium ethylenebis (dithiocarbamate) (U.S. 2,317,765);

Maneb, manganese ethylene bis (dithiocarbamate) (US 2 504 404); Mancozeb, manganese ethylene bis (dithiocarbamate) zinc complex (U.S. 3,379,610);

Metam, methyldithiocarbamic acid (US 2,791,605)

Metiram, zinc ammonium ethylenebis (dithiocarbamate) (U.S. 3,248,400);

Propineb, zinc propylene bis (dithiocarbamate) polymer (BE 611 960);

Polycarbamate, thiram, bis (dimethylthiocarbamoyl) disulphide (DE 642 532);

Ziram, dimethyldithiocarbamate;

Zineb, zinc ethylene bis (dithiocarbamate) (US 2 457 674);

Anilazine, 4,6-dichloro-Λ / - (2-chlorophenyl) -1, _3> 5-triazin-2-amine (US 2,720,480);

Benomyl, 2-acetylamino-benzoimidazole-1-carboxylic acid butylamide (U.S. 3,631,176); Boscalid, 2-chloro-N- (4'-chlorobiphenyl-2-yl) nicotinamide (EP-A 545 099);

Carbendazim, (1H-benzoimidazol-2-yl) -carbamic acid methyl ester (US 3,657,443);

Carboxin, 2-methyl-5,6-dihydro- [1,4] oxathiin-3-carboxylic acid phenylamide (US Pat

3,454,391);

Oxycarboxine, 5,6-dihydro-2-methyl-1,4-oxathi-in-3-carboxanilide 4,4-dioxide (US 3,454,391);

Cyazofamide, 4-chloro-2-cyano- / V, Λ / -dimethyl-5-p-tolylimidazole-1-sulfonamide (EP-A

298 196)

Dazomet, 3,5-dimethyl-1,3,5-thiadiazinan-2-thione;

Dithianone, 5,10-dioxo-5,10-dihydro-naphtho [2,3-b] [1,4] dithiine-2,3-dicarbonitrile (GB 857,383); Famoxadone, (RS) -3-anilino-5-methyl-5- (4-phenoxyphenyl) -1,3-oxazolidine-2,4-dione;

Fenamidone, (S) -1 -anilino-4-methyl-2-methylthio-4-phenylimidazolinyl-5-one;

Fenarimol, (4-Chloro-phenyl) - (2-chloro-phenyl) -pyrimidin-5-yl-methanol (GB 12 18 623);

Fuberidazole, 2- (2-furanyl) -1H-benzimidazole (DE 12 09 799); Flutolanil, N- (3-isopropoxyphenyl) -2-trifluoromethylbenzamide (JP 1104514);

Furametpyr, (ftS) -5- chloro- / V- (1,3-dihydro-1,1,3-trimethylisobenzofuran-4-yl) -1,3-dimethylpyrazole-4-carboxamide;

Isoprothiolane, indole-3-ylacetic acid;

Mepronil, 3'-isopropoxy-o-toluanilide (U.S. 3,937,840); Nuarimol, σ- (2-chlorophenyl) -σ- (4-fluorophenyl) -5-pyrimidinemethanol (GB 12 18 623);

Picobenzamide, 2,6-dichloro-N- (3-chloro-5-trifluoromethylpyridin-2-ylmethyl) benzamide

(WO 99/42447);

Probenazole, 3-allyloxy-1,2-benzothiazole 1,1-dioxide;

Proquinazide, 6-iodo-2-propoxy-3-propylquinazolin-4 (3H) -one (WO 97/48684); Pyrifenox, 1- (2,4-dichlorophenyl) -2- (3-pyridinyl) ethanone-0-methyloxime (EP-A 49 854);

Pyroquilone, 1, 2,5,6-tetrahydropyrrolo [3,2,1-] quinolin-4-one (GB 13 94 373);

Quinoxyfen, 5,7-dichloro-4- (4-fluoro-phenoxy) -quinoline (US 5,240,940);

Silthiofam, Λ / -allyl-4,5-dimethyl-2- (trimethylsilyl) thiophene-3-carboxamide;

Thiabendazole, 2- (thiazol-4-yl) benzimidazole (U.S. 3,017,415); Thifluzamide, Λ / - [2,6-dibromo-4- (trifluoromethoxy) phenyl] -2-methyl-4- (trifluoromethyl) -5-thiazolecarboxamide;

Thiophanate-methyl, 1, 2-phenylenebis (iminocarbonothioyl) bis (dimethylcarbamate) (DE-OS

19 30 540);

Tiadinil, 3'-chloro-4,4'-dimethyl-1,2,3-thiadiazole-5-carboxanilide; Tricyclazole, 5-methyl-1,2,4-triazolo [3,4-fe] benzothiazole (GB 14 19 121);

Triforins, Λ /, Λ / '- {piperazine-1,4-diylbis [(trichloromethyl) methylene] diformamide (DE

19 01 421);

3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] -pyridine (EP-A 1035 122);

(2-Chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl) -carbamic acid, methyl ester, (2-chloro-5- [1- (6-methyl-pyridin-2-yl-methoxyimino ethyl) -benzyl) -carbamic acid methyl ester (EP-A 1201 648);

Sulfur;

Bordeaux broth the mixture of calcium hydroxide and copper (II) sulfate;

copper; copper oxychloride; basic copper sulfate; Binapacryl, (/? S) -2-sec-butyl-4,6-dinitrophenyl 3-methylcrotonate;

Dinocap, the mixture of 2,6-dinitro-4-octylphenyl crotonate and 2,4-dinitro-6-octylphenyl crotonate, where "octyl" is a mixture of 1-methylheptyl, 1-ethylhexyl and 1-methylheptyl.

Propylpentyl means (US 2 526 660);

Dinobutone, (RS) -2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate; Nitrophthal-isopropyl; Diisopropyl 5-nitroisophthalate; Fenpiclonil, 4- (2,3-dichlorophenyl) -1H-pyrrole-3-carbonitrile (Proc. 1988 Br. Crop Prot.

Conf. - Pests Dis., Vol. 1, p. 65);

Fludioxonil, 4- (2,2-difluoro-benzo [1,3-dioxol-4-yl] -1H-pyrrole-3-carbonitrile (The Pecticide

Manual, ed. The British Crop Protection Council, 10th Ed. (1995), p. 482); Captafol, Λ / - (1, 1, 2,2-tetrachloroethyl) thio) cyclohex-4-ene-1,2-dicarboximide;

Captan, 2-trichloromethylsulfanyl-3a, 4,7,7a-tetrahydroisoindole-1,3-dione (US Pat

2 553 770);

Dichlofluanid, N-dichlorofluoromethylthio-A / ', Λ /' - dimethyl-Λ / -phenylsulfamide (DE

11 93 498); Folpet, 2-trichloromethylsuifanylisoindole-1,3-dione (US 2,553,770);

Tolylfluanid, / V-dichlorofluoromethylthio-Λ / ', / \ /' - dimethyl-Λ / -p-tolylsulfamide (DE 11 93 498);

Acibenzolar-S-methyl, benzo [1,2,3] thiadiazole-7-carbothionic acid methyl ester;

Benthiavalicarb, {(S) -1 - [(1R) -1- (6-fluoro-benzothiazol-2-yl) -ethylcarbamoyl] -2-methyl-propyl} -carbamic acid isopropyl ester (JP-A 09/323 984); Carpropamide, 2,2-dichloro-Λ / - [1- (4-chlorophenyl) ethyl] -1-ethyl-3-methylcyclopropanecarboxamide;

Chlorothalonil, 2,4,5,6-tetrachloroisophthalonitrile (US 3,290,353);

Cyflufenamide, (Z) -Λ / - [σ- (Cyclopropylmethoxyimino) -2,3-difluoro-6- (trifluoromethyl) benzyl] -

2-phenylacetamide (WO 96/19442); Cymoxanil, 1- (2-cyano-2-methoxyiminoacetyl) -3-ethylurea (U.S. 3,957,847);

Diclomethine, 6- (3,5-dichlorophenyl-p-tolyl) pyridazine-3 (2 / - /) - on;

Diclocymet, 2-cyano-Λ / - [(1R) -1- (2,4-dichlorophenyl) ethyl] -3,3-dimethylbutanamide;

Diclofluanide, N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfonamide (DE-AS 11 93

498); Diethofencarb, isopropyl 3,4-diethoxycarbanilate;

Edifenphos, O-ethyl S, S-diphenyl phosphorodithioate;

Ethaboxam, Λ / (cyano-2-thienylmethyl) -4-ethyl-2- (ethylamino) -5-thiazolecarboxamide;

Fenhexamide, N- (2,3-dichloro-4-hydroxyphenyl) -1-methylcyclohexanecarboxamide (Proc.

Br. Crop Prot. Conf. - Pests Dis., 1998, vol. 2, p. 327); Fentin acetate, triphenyltin acetate;

Fenoxanil, Λ / - (1-cyano-1,2-dimethylpropyl) -2- (2,4-dichlorophenoxy) propanamide;

Ferric zone, (Z) -2'-methylacetophenone 4,6-dimethylpyrimidin-2-ylhydrazone;

Fluazinam, S-chloro-N-IS-chloro-β-dinitro-ortho-fluoro-methyl-phenyl-S-ori-fluoro-methyl) -pyridine-amine (The Pecticide Manual, Ed. The British Crop Protection Council, 10th edition (1995), P. 474);

Phosphoric acid, fosetyl, fosetyl-aluminum, (aluminum) ethylphosphonate (FR 22

54 276);

Iprovalicarb, [(1S) -2-methyl-1- (1-p-tolyl-ethylcarbamoyl-O-propyl] -carbamic acid isopropyl ester (EP-A 472 996); hexachlorobenzene; Mandipropamide, 4-chloro-N- [2- [3-methoxy-4- (2-propynyloxy) phenyl] ethyl] -α- (2-propynyloxy) benzylacetamide (WO 03/042166);

Metrafenone, 3-bromo-2,3,4,6'-tetramethoxy-2 ', 6-dimethylbenzophenone (U.S. 5,945,567);

Pencycuron, 1- (4-chlorobenzyl) -1-cyclopentyl-3-phenylurea (DE 27 32 257); Propamocarb, 3- (dimethylamino) propylcarbamic acid propyl ester (DE 1643 040);

phthalide,

Toloclofos-methyl, O-2,6-dichloro-p-tolyl 0,0-dimethyl phosphorothioate (GB 14 67 561);

Quintozene, pentachloromitrobenzene (DE 682 048);

Zoxamide, ^(/? S)! -3,5-like or-Λ / - (3-chloro-1-ethyl-1-methyl-2-oxo-propyl) -p-toluamide; Prohexadione and its salts (EP-A 123 001),

Trinexapac-ethyl, 4-Cyciopropyl (hydroxy) methylene-3,5-dioxocyclohexanecarboxylic acid ethyl ester (EP-A 126 713);

Chlormoquat, 2-chloroethyltrimethylammonium salt (US 3,395,009);

Mepiquat chloride, 1, 1-dimethylpiperidinium chloride (DE 22 07 575); Diflufenzopyr, 2- {1- [4- (3,5-difluorophenyl) semicarbazono] ethyl} nicotinic acid;

Benzoimidazolderivate of formula IIA (see EP-A 10 17 671); Sulfamoyl compounds of the formula III (cf., EP-A 10 31 571, JP-A 2001-192 381); Thiophene derivatives of formula IV (see JP 10130268); Oxime ether derivatives of the formula V (see WO 99/14188);

Phenylamidine derivatives of the formula VI (cf., WO 00/46184);

Compounds of the formula VII (cf., WO 97/48684, WO 02/094797, WO 03/14103).

The mixtures of the compounds I and the active compounds from groups A) to R) or the simultaneous joint or separate use of the compounds I and the active compounds from the groups A) to R) are distinguished by an outstanding activity against a broad spectrum Spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Oomycetes and Basiliomycetes. They are partially systemically effective and can be used in crop protection as foliar, pickling and soil fungicides.

They are of particular importance for controlling a large number of fungi on various crop plants such as bananas, cotton, vegetables (eg cucumbers, beans and cucurbits), barley, grass, oats, coffee, potatoes, corn, fruit plants, rice, rye , Soy, tomato, wine, wheat, ornamental plants, sugarcane and a variety of seeds.

Advantageously, they are suitable for controlling the following phytopathogenic fungi: Blumeria graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphae- rotheca fuliginea on cucurbits, Podosphaera leucotήcha on apples, Uncinula necator on vines, Pucc / n / a species of cereals, Rhizoctonia acai on cotton, rice and turf, Ustilago acai on cereals and sugarcane, Venturia inaequalis on apples, Bipolaris and Drechslera aries on cereals, rice and turf, Sepfor / a species on wheat, Botrytis cinerea on strawberries, vegetables, ornamental plants and vines, Mycosphaerel / a species on bananas, peanuts and cereals, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, PΛa / cσpsora Types of soya, Phytophthora infestans on potatoes and tomatoes, Pseudoperonospora species on pumpkin plants and hops, Plasmopara viticola on vines, Alternaria Aύen on vegetables and fruits and Fusarium and Verticillium species.

They are also applicable to material protection (e.g., wood preservation), for example to Paecilomyces variotii.

The compound I and the active compounds from groups A) to R) can be applied simultaneously together or separately or in succession, the sequence generally not having any effect on the control result when applied separately.

In the definitions of the symbols given in the above formulas, collective terms have been used that are generally representative of the following substituents:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 6, 8 or 10 carbon atoms, for example C ₁ -C ₆ -AlkVl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl , 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1 Methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3 Dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;

Haloalkyl: straight-chain or branched alkyl groups having 1 to 2, 4 or 6 carbon atoms (as mentioned above), in which groups the hydrogen atoms may be partially or completely replaced by halogen atoms as mentioned above: in particular C ₁ -C ₂ Haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoro ethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2- Trichloroethyl, pentafluoroethyl or 1,1,1-trifluoroprop-2-yl;

Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 6, 8 or 10 carbon atoms and one or two double bonds in any position, for example C ₂ -C ₆ alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl , 1-Butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2 Pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl , 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butyl-, 1, 1-dimethyl-2-propenyl, 1, 2-dimethyl 1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1 -Methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl 2-pentenyl, 4-methyl-2-pentenyl, 1-methyl) -3-pentenyl, 2-methyl-3-pentenyl, 3-methyl 1-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1- Dimethyl 2-butenyl, 1, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3 Dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2, 3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl _f 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 1,2-trimethyl-2- propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;

Haloalkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 10 carbon atoms and one or two double bonds in any Positi¬ on (as mentioned above), wherein in these groups, the hydrogen atoms partially or completely against halogen atoms as mentioned above, in particular fluorine, chlorine and bromine , can be replaced;

Alkynyl: straight-chain or branched hydrocarbon groups having 2 to 4, 6, 8 or 10 carbon atoms and one or two triple bonds in any position, for example C ₂ -C ₆ alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2 Butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl 3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl , 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3 Methyl 4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1, 1-dimethyl-2-butynyl, 1, 1-dimethyl-3-butynyl, 1, 2-dimethyl-3 -butynyl, 2,2- Dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, and 1-ethyl-1-methyl-2- propynyl;

Cycloalkyl: mono- or bicyclic, saturated hydrocarbon groups having 3 to 6 or 8 carbon ring members, for example C ₃ -C ₈ -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;

5- to 10-membered saturated, partially unsaturated or aromatic heterocycle containing one to four heteroatoms from the group O, N or S: - 5- or 6-membered heterocyclyl containing one to three nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms, eg 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5- isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolindinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2- Pyrrolin-2-yl, 2-pyrroline-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-di- oxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl and 2-piperazinyl;

5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: 5-membered heteroaryl groups which contain, in addition to carbon atoms, one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members can, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1, 3,4-triazol-2-yl;

6-membered heteroaryl containing one to three or one to four nitrogen atoms: 6-membered ring heteroaryl groups, which in addition to carbon atoms may contain one to three or one to four nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl;

Alkylene: divalent linear chains of 3 to 5 CH ₂ groups, eg CH ₂ , CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ CH ₂ and CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ;

Oxyalkylene: divalent unbranched chains of 2 to 4 CH ₂ groups, wherein a Va¬ lenz is bound via an oxygen atom to the skeleton, for example OCH ₂ CH ₂ , OCH ₂ CH ₂ CH ₂ and OCH ₂ CH ₂ CH ₂ CH ₂ ; Oxyalkylenoxy: divalent unbranched chains of 1 to 3 CH ₂ groups, both valences being bonded to the skeleton via an oxygen atom, eg OCH ₂ O, OCH ₂ CH ₂ O and OCH ₂ CH ₂ CH ₂ O;

Formula IIA represents compounds in which Y is bromo (11-1) or chloro (II-2).

In particular, formula III represents compounds in which the subscript n is 0, 1 or 2, preferably O or 1.

If n is 1, the group R ^{33 is} preferably in the 5- or 6-position. These compounds are particularly suitable for use in the mixtures according to the invention.

In addition, compounds III are preferred in which R ^{31 is} hydrogen, methyl, ethyl, n- or iso-propyl, fluorine, chlorine, bromine, iodine, methylthio, ethylthio, trifluoromethyl, pentafluoroethyl, cyano, phenyl or formyl.

Equally preferred are compounds III in which R ^{32 is} hydrogen, fluorine, chlorine, bromine, iodine, methyl, trifluoromethyl, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl or n-butoxycarbonyl.

Preference is furthermore given to compounds III in which R ^{33 is} fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, methoxy, trifluoromethyl, in particular fluorine, chlorine, bromine, cyano, methyl, trifluoromethyl or methoxy.

In particular, with regard to their use in the mixtures according to the invention, the compounds III compiled in the following tables are preferred.

Table 1

Compounds of the formula III in which n is zero and R ^{34 is} hydrogen and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III Table 2

Compounds of the formula III in which n is zero and R ^{34 is} fluorine and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 3

Compounds of the formula III in which n is zero and R ^{34 is} chlorine and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 4 Compounds of the formula III, in which n is zero and R ^{34 is} methyl and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 5

Compounds of the formula III in which n 1, R ^{33 is} 4-fluoro and R ^{34 is} hydrogen and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III

Table 6

Compounds of the formula III in which n 1, R ^{33 is} 5-fluoro and R ^{34 is} hydrogen and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III

Table 7

Compounds of the formula III in which n 1, R ^{33 is} 6-fluoro and R ^{34 is} hydrogen and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III

Table 8

Compounds of the formula III in which n 1, R ^{33 is} 7-fluoro and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III

Table 9

Compounds of the formula III in which n 1, R ^{33 is} 4-chloro and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 10

Compounds of the formula III in which n 1, R ^{33 is} 5-chloro and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 11 Compounds of the formula III, in which n 1, R ^{33 is} 6-chloro and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 12 Compounds of the formula III, in which n 1, R ^{33 is} 7-chloro and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 13 Compounds of the formula III, in which n 1, R ^{33 is} 4-bromo and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 14 Compounds of the formula III, in which n 1, R ^{33 is} 5-bromo and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III

Table 15 Compounds of the formula III in which n 1, R ^{33 is} 6-bromo and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III

Table 16 Compounds of the formula III, in which n 1, R ^{33 is} 7-bromo and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 17 Compounds of the formula III, in which n 1, R ^{33 is} 4-iodo and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III

Table 18 Compounds of the formula III, in which n 1, R ^{33 is} 5-iodo and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 19 Compounds of the formula III in which n 1, R ^{33 is} 6-iodo and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 20 Compounds of the formula III in which n is 1, R ^{33 is} 7-iodo and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III

Table 21 Compounds of the formula III in which n 1, R ^{33 is} 4-methyl and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 22 Compounds of the formula III in which n 1, R ^{33 is} 5-methyl and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III

Table 23 Compounds of the formula III, in which n 1, R ^{33 is} 6-methyl and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III

Table 24 Compounds of the formula III, in which n 1, R ^{33 is} 7-methyl and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 25 Compounds of the formula III, in which n 1, R ^{33 is} 4-ethyl and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 26 Compounds of the formula III, in which n 1, R ^{33 is} 5-ethyl and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 27 Compounds of the formula III in which n 1, R ^{33 is} 6-ethyl and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III

Table 28 Compounds of the formula III in which n 1, R ^{33 is} 7-ethyl and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 29 Compounds of the formula III in which n 1, R ^{33 is} 4-methoxy and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III

Table 30 Compounds of the formula III in which n 1, R ^{33 is} 5-methoxy and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III

Table 31 Compounds of the formula III in which n 1, R ^{33 is} 6-methoxy and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III

Table 32 Compounds of the formula III in which n 1, R ^{33 is} 7-methoxy and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 33 Compounds of the formula III in which n 1, R ^{33 is} 4-nitro and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 34 Compounds of the formula IiI in which n 1, R ^{33 is} 5-nitro and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of the table

Table 35 Compounds of the formula III in which n 1, R ^{33 is} 6-nitro and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 36 Compounds of the formula III, in which n 1, R ^{33 is} 7-nitro and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 37 Compounds of the formula III in which n 1, R ^{33 is} 4-cyano and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 38 Compounds of the formula III, in which n 1, R ^{33 is} 5-cyano and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 39 Compounds of the formula III in which n 1, R ^{33 is} 6-cyano and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table III

Table 40 Compounds of the formula III, in which n 1, R ^{33 is} 7-cyano and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 41 Compounds of the formula III in which n 1, R ^{33 is} 4-trifluoromethyl and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 42 Compounds of the formula III in which n 1, R ^{33 is} 5-trifluoromethyl and R ^{34 is} hydrogen and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 43 Compounds of the formula III, in which n 1, R ^{33 is} 6-trifluoromethyl and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 44 Compounds of the formula III, in which n 1, R ^{33 is} 7-trifluoromethyl and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 45 Compounds of the formula III, in which n 1, R ^{33 is} 4-methoxycarbonyl and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 46 Compounds of the formula III, in which n 1, R ^{33 is} 5-methoxycarbonyl and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table I.

Table 47 Compounds of the formula III, in which n 1, R ^{33 is} 6-methoxycarbonyl and R ^{34 is} hydrogen, and the combination of R ¹ and R ² for a compound corresponds in each case to one row of Table III

Table 48 Compounds of the formula III, in which n 1, R ^{33 is} 7-methoxycarbonyl and R ^{34 is} hydrogen, and the combination of R ¹ and R ² for a compound corresponds in each case to one row of Table III

Table 49 Compounds of the formula III in which n 2, R ^{33 is} 5,6-difluoro and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 50 Compounds of the formula III in which n 2, R ^{33 is} 5,6-dichloro and R ^{34 is} hydrogen. tet, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 51 Compounds of the formula III in which n 2, R ^{33 is} 5,6-dibromo and R ^{34 is} hydrogen, and the combination of R ³¹ and R ³² for each compound corresponds to one row of Table II

Table 52 Compounds of the formula III, in which n 2, R ^{33 is} 5,6-difluoro and R ^{34 is} fluorine, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 53 Compounds of the formula III, in which n 2, R ^{33 is} 5,6-dichloro and R ^{34 is} fluorine, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 54 Compounds of the formula III, in which n 2, R ^{33 is} 5,6-dibromo and R ^{34 is} fluorine, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table II

Table 55 Compounds of the formula III in which n 2, R ^{33 is} 5,6-difluoro and R ^{34 is} chlorine, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 56 Compounds of the formula III, in which n 2, R ^{33 is} 5,6-dichloro and R ^{34 is} chlorine, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 57 Compounds of the formula III, in which n 2, R ^{33 is} 5,6-dibromo and R ^{34 is} chlorine, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 58 Compounds of the formula III, in which n 2, R ^{33 is} 5,6-difluoro and R ^{34 is} methyl, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 59

Compounds of the formula III in which n 2, R ^{33 is} 5,6-dichloro and R ^{34 is} methyl, and the combination of R ³¹ and R ³² for a compound corresponds in each case to one row of Table III

Table 60

Compounds of formula Ml ₁ in which n is 2, R ³³ 5,6-dibromo, and R ³⁴ is methyl and the combination of R ³¹ and R ³² for each compound corresponds to one line of Tabel¬ le III corresponds

Table III

Particular preference is given to the combinations of a compound I with one of the compounds 111-135, 111-161 and 111-187 of Table 3, III-27 of Table 4, III-62 of Table 7 and II1-22 of Table 55.

In another embodiment of the invention, mixtures of a compound I with at least one compound of the formula IV are present.

In formula IV, the following meanings of the substituents, alone or in combination, are preferred:

Ar is preferably phenyl or a five-membered aromatic heterocycle, in particular a five-membered heteroaryl radical, which is unsubstituted or substituted by one or two groups R ⁴¹ . In addition, Ar preferably represents the following groups: phenyl, pyridine, pyrazine, furan, thiophene, pyrazole and thiazole. Particularly preferred groups Ar are: 3-pyridinyl, pyrazinyl, 3-furyl, 3-thiophenyl, 4-pyrazolyl, 5-thiazolyl.

Most preferably, a group R ^{41 is} ortho to the amide moiety.

Preferred groups R ⁴¹ are halogen, in particular chlorine, alkyl, in particular methyl, and halomethyl, in particular fluoromethyl, difluoromethyl or trifluoromethyl.

Preferred groups R are alkyl groups, in particular branched C ₃ -C ₈ -alkyl groups, in particular 4-methyl-pent-2-yl.

For the intended use in admixture with the compound I, in particular the following compounds of the formula IV are suitable:

If two groups R ⁴¹ are present in a formula, these groups may be the same or different.

Particular preference is given to compounds IV.A, in particular compounds of the formulas IV.A.1 and IV.B.1, in which R ^{41 can be} identical or different and is methyl and halomethyl and R is alkyl, such as branched C ₃ -C ₈ -alkyl, in particular 4-methyl-pent-2-yl:

Particular preference is given to compound IV.A.11 (common name: penthiopyrad) and IV.B.11, which are present in the form of their R and S isomers:

In a further embodiment of the invention are mixtures of a compound I with at least one oxime ether derivative of the formula V,

Among the compounds of the formula V, preference is given to those in which X is a difluoromethoxy group. In addition, compounds of the formula V are particularly preferred in which the index n is equal to zero.

Particularly preferred compounds V are in particular the compounds listed in Table V below:

Table V

Especially preferred is compound V-2.

In a further embodiment of the invention, mixtures of a compound I are present with at least one compound of the formula VI.

With regard to their intended use of the compounds VI, the following meanings of the substituents, in each case alone or in combination, are particularly preferred:

FT ¹ is hydrogen;

R ⁶² is C ₁ -C ₆ -alkyl, such as methyl and ethyl, in particular methyl,

R ⁶³ is C ₁ -C ₆ alkyl, such as methyl and ethyl, in particular ethyl;

R ⁶⁴ is C ₁ -C ₆ -alkyl, in particular methyl;

R ⁶⁵ is C ₁ -C ₆ -alkyl, in particular methyl; m is 1, wherein R ^{65 is} para to R ⁴ ;

A is oxygen (-O-);

R is phenyl, which is preferably unsubstituted or substituted by one to three groups R ^f , in particular by one or two groups R ^f ;

R ^f is halogen, in particular fluorine or chlorine, alkyl, in particular methyl, ethyl, n- and iso-propyl and tert. Butyl and haloalkyl, especially thfluoromethyl.

The groups R ^f are preferably in the 3- or 3,4-position.

For the intended use in admixture with the compound I, the compounds of the formula VI.A mentioned in the following Table VI are suitable in particular:

In another embodiment of the invention are mixtures of a compound I with at least one compound of formula VII.

Compounds of the formula VII are preferred in which R ^{71 is} n-propyl or n-butyl, in particular n-propyl.

In addition, compounds of the formula VII are particularly preferred in which R ^{73 is} iodine or bromine, in particular iodine.

In particular, formula VII represents compounds of formulas VII.1, VII.2 and VI 1.3:

in which the variables have the meaning given for formula VII.

The compound of the formula VII.1 in which R ^{71 is} n-propyl, R ^{72 is} n-propoxy and R ^{73 is} iodine, is also known under the common name proquinazide (compound VII.1-1). Mixtures of a compound of the formula I and proquinazide are a preferred embodiment of the invention.

In addition, mixtures containing a compound of formula I and a compound of formula VII.2, a preferred embodiment of the invention.

In particular, the mixtures with a compound I and one of the following compounds of the formula VII.2 are preferred:

A further preferred embodiment of the invention relates to mixtures of a compound I and one of the following compounds of the formula VII.3:

As a mixing partner for the compounds I, active compounds of the groups A) to R) selected from one of the following groups are preferred:

A) azoles such as bromoconazole, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, ipazanolazole, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothio-conazole, simeconazole, tebuconazole, tetraconazole, Triflumizole, triticonazole;

B) strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin; C) acylalanines such as metalaxyl, mefenoxam;

D) amine derivatives such as dodine, fenpropimorph, fenpropidin, spiroxamine, tridemorph;

E) anilinopyrimidines such as pyrimethanil, mepanipyrim or cyprodinil;

F) dicarboximides such as iprodione, procymidone, vinclozolin;

G) cinnamic acid amides and analogs such as dimethomorph, or flumorph; K) dithiocarbamates such as Maneb, Mancozeb, Metiram, Thiram;

L) heterocyclic compounds selected from benomyl, boscalid, carbendazim, carboxin, cyazofamide, dithianone, fenarimol, flutolanil, penthiopyrad, picobenzamide, proquinazide, pyrifenox, quinoxyfen, thiophanate-methyl, benzoimidazole derivatives of the formula II, Sulfamoyl compounds of the formula III, M) sulfur and copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate; N) nitrophenyl derivatives such as dinocap; O) phenylpyrroles such as fenpiclonil or fludioxonil;

P) sulfenic acid derivatives such as captan, folpet, tolylfluanid;

Q) Other fungicides selected from benthiavalicarb, chlorothalonil, cyflufenamide, diclofluanide, fenhexamide, fluazinam, fosetyl, fosetyl-aluminum, phosphorous acid, iprovalicarb, metrafenone, pencycuron, oxime ether derivatives of formula V,

Phenylamidine derivatives of the formula VI,

Compounds of formula VII, or R) growth retardants such as Prohexadion calcium, Trinexapac-ethyl, Chlorme- quat, mepiquat chloride and Diflufenzopyr.

The compounds I and the active compounds of groups A) to R) are able to form salts or adducts with inorganic or organic acids or with metal ions because of the basic character of the nitrogen atoms or carboxylate groups contained in them.

Examples of inorganic acids are hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and nitric acid.

Examples of suitable organic acids are formic acid, carbonic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid and 2-acetoxybenzoic acid into consideration.

The metal ions are in particular the ions of the elements of the first to eighth subgroup, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc, the first main group, in particular lithium, sodium and potassium and the second main group, in particular calcium and magnesium third and fourth main group, in particular aluminum, tin and lead into consideration. If appropriate, the metal ions can be present in various valences.

Preference is given to the provision of the mixtures, the pure active ingredients I and II, which, depending on the need for further active ingredients against harmful fungi or others Pests such as insects, spider animals or nematodes, or herbicidal or wax¬ tumsregulierende agents or fertilizers can mix.

As "further active ingredients" in the above sense, in particular fungicides from the groups A) to R) defined at the outset, in particular the above-mentioned preferred representatives, come into question.

In addition to a compound of the formula I and an active compound from groups A) to R), the mixtures according to the invention may contain as active components further active components from compounds of the formula I and active compounds from groups A) to R).

One embodiment of the mixtures contains, in addition to a compound of the formula I and an active compound from the groups A) to R) as active components one or two, in particular an active compound from group A) to R).

The compound I and the active compound from groups A) to R) are usually employed in a weight ratio of from 100: 1 to 1: 100, preferably from 20: 1 to 1:20, in particular from 10: 1 to 1:10. In the case of the mixtures of a compound I and Diflufenzopyr also mixing ratios of 1000: 1 to 1: 1 come into question.

If desired, the further active components are added to compound I in a ratio of from 20: 1 to 1:20.

Depending on the nature of the compounds and the desired effect, the application rates of the mixtures according to the invention are from 5 g / ha to 2000 g / ha, preferably from 50 to 900 g / ha, in particular from 50 to 750 g / ha.

The application rates for the compound I are accordingly generally 1 to 1000 g / ha, preferably 10 to 900 g / ha, in particular 20 to 750 g / ha.

The application rates for the active compound from groups A) to R) are correspondingly generally 1 to 2000 g / ha, preferably 10 to 900 g / ha, in particular 40 to 750 g / ha. The application rates for Diflufenzopyr are usually 0.01 to 50 g / ha, preferably 0.1 to 10 g / ha

In seed treatment, application rates of mixture of 1 to 1000 g / 100 kg of seed, preferably 1 to 750 g / 100 kg, in particular 5 to 500 g / 100 kg, are generally used. The method for controlling harmful fungi is carried out by the separate or common application of the compound I and the active compound from groups A) to R) or the mixtures of the compound I and the active compound from groups A) to R) by spraying or Dusting the seeds, plants or soils before or after sowing the plants or before or after emergence of the plants.

The mixtures according to the invention or the active components can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the respective purpose; In any case, it should ensure a fine and uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, e.g. by stretching the active compound with solvents and / or excipients, if desired with use of emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially:

Water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (Glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and

Fatty acid ester. In principle, solvent mixtures can also be used

Excipients such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin-sulphite liquors and methylcellulose.

The surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristerylphenyl polyglycol ethers, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene , Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration. For the production of directly sprayable solutions, emulsions, pastes or oil dispersions, there are mineral oil fractions of medium to high boiling point, such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg toluene, Xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, such as e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as wheat flour, bark, wood and nutshell flour, cellulose powder and other solid carriers.

The formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredients. The active compounds are employed in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

Examples of formulations according to the invention are: 1. Products for dilution in water

A Water-soluble concentrates (SL) 10 parts by weight of the active ingredients are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with an active substance content of 10% by weight.

B Dispersible Concentrates (DC)

20 parts by weight of the active compounds are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution in water results in a dispersion. The active ingredient content is 20% by weight C Emulsifiable Concentrates (EC)

15 parts by weight of the active compounds are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion. The formulation has an active ingredient content of 15% by weight.

D emulsions (EW, EO)

25 parts by weight of the active compounds are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is added to water by means of an emulsifying machine (e.g., Ultraturax) in 30 parts by weight and made into a homogeneous emulsion. Dilution in water results in an emulsion. The formulation has an active ingredient content of 25% by weight.

E Suspensions (SC, OD) 20 parts by weight of the active compounds are comminuted to a fine suspension of active substance in an agitating ball mill with the addition of 10 parts by weight of dispersing and wetting agents and 70 parts by weight of water or an organic solvent. Dilution in water results in a stable suspension of the active ingredient. The active ingredient content in the formulation is 20% by weight.

F Water-dispersible and water-soluble granules (WG, SG) 50 parts by weight of the active compounds are finely ground with the addition of 50 parts by weight of dispersing and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient. The formulation has an active ingredient content of 50% by weight.

G Water-dispersible and water-soluble powders (WP, SP) 75 parts by weight of the active compounds are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight.

2. Products for direct application

H dusts (DP)

5 parts by weight of the active ingredients are finely ground and finely divided with 95 parts by weight

Kaolin intimately mixed. This gives a dust with an active ingredient content of 5 wt .-%. I Granules (GR, FG, GG, MG)

0.5 parts by weight of the active ingredients are finely ground and combined with 99.5 parts by weight of carrier. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with an active ingredient content of 0.5 wt .-%.

J ULV solutions (UL)

10 parts by weight of the active compounds are dissolved in 90 parts by weight of an organic solvent, e.g. XyIoI solved. This gives a product for direct application with an active ingredient content of 10 wt .-%.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, misting, dusting, scattering or pouring. The forms of application depend entirely on the intended use; In any case, they should ensure as far as possible the finest distribution of the active compounds according to the invention.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders, oil dispersions) by addition of water. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. However, it is also possible to prepare from effective substance wetting agents, adhesives, dispersants or emulsifiers and any concentrates which are solvent or oil, which are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.

To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, optionally also just before use (tank mix), are added. These funds will be Usually admixed to the inventive compositions in a weight ratio of 1:10 to 10: 1.

The compounds I and II or the mixtures or the corresponding formulations ^ιK - approximations are applied by treating the harmful fungi or the of plants, seeds, soils, areas, materials or spaces with a fungicidally wirksa¬ amount of the mixture , or the compounds I and Ii with separate application treated. The application can take place before or after infestation by the harmful fungi.

synthesis Examples

The novel compounds of the formula I can be prepared analogously to the process known from US Pat. No. 5,593,996. The instructions reproduced in the synthesis example below were used to obtain further compounds I with a corresponding modification of the starting compounds. The compounds obtained in this way are listed in the following table with physical data.

Example 1 - Preparation of 5-chloro-6- (2-methylphenyl) -7- (4-methylpiperidin-1-yl) -1,2,4-triazolo [1,5a] pyrimidine [I-9 ]

A solution of 1 g (3.6 mmol) of 5,7-dichloro-6- (2-methylphenyl) -1, 2,4-triazolo [1,5a] pyrimidine (prepared analogously to WO 1994/20501) , 0.36 g (3.62 mmol) of 4-methylpiperidine and 0.37 g (3.62 mmol) of triethylamine in 10 ml of methylene chloride were stirred at about 20-25 ⁰ C for about 1.5 hours. The reaction mixture was then freed from the solvent and the residue was taken up in acetonitrile. By preparative MPLC on Kie¬ selgel RP-18 was obtained from it 1.1 g of the title compound as a colorless crystal mass, mp 170-180 ⁰ C.

¹ H NMR (CDCl ₃ , δ in ppm): 8.4 (s, 1H); 7.3 (m, 3H); 7.1 (d, 1H); 3.85 (m, 1H); 3.45 (m, 1H); 2.7 (m, 1H); 2.6 (m, 1H); 2.2 (s, 3H); 1, 55 (m, 2H); 1, 45 (m, 1H); 1, 25 (m, 2H); 0.9 (d, 3H)

The fungicidal activity of the compound and of the mixtures was demonstrated by the following experiments:

Use Example 1 - Efficacy against Venturia inequalis (protective)

Leaves of pot-grown apple seedlings of the variety "Common" were sprayed to drip point with aqueous active ingredient preparation, which was prepared with a stock solution of 5% active ingredient, 94% acetone and 1% emulsifier (Tween 20). After the spray coating had dried (3-5 h), the leaves were inoculated with an aqueous spore suspension of Venturia inequalis. The test plants were then placed in climatic chambers at 22-24 ° C. and 95-99% relative atmospheric humidity for 2 days and then cultivated in the greenhouse at 21-23 ° C. and approximately 95% relative humidity for a further 2 weeks. Then the extent of infestation development on the leaves was visually determined.

In this test, the plants treated with 200 ppm of the active compounds 1-1, 1-2 or 1-10 showed a maximum of 15% infestation, while the untreated plants were 90% infected.

Use Example 2 - Activity Against Aliernaria solani on Tomatoes (Protective)

Leaves of tomato plants of the cultivar "Pixie II", which had been cultured in pots up to the 4-leaf stage, were prepared with aqueous active ingredient preparation, which was prepared with a stock solution of 5% active ingredient, 94% acetone and 1% emulsifier (Tween 20) was sprayed until dripping wet. After the spray coating had dried (3-5 h), the leaves were inoculated with an aqueous spore suspension of Alternaria solani (density 15 × 10 ³ spores per ml). Subsequently, the test plants in Klima¬ chambers at 22 - 24 ⁰ C and 96 - 99% relative humidity were set up for 36 hours and then cultivated in the greenhouse at 21 - 23 ° C and about 95% relative humidity for a further 2 to 3 days , Then the extent of infestation on the leaves was visually determined In this test, the plants treated with 200 ppm of the active ingredients 1-1, 1-2, 1-5, 1-6, 1-7, 1-9, and 1-11 showed a maximum of 15% infestation, while the untreated plants 90% were affected.

For use examples 3 to 9, the active compounds were prepared separately or together as a stock solution with 0.25% by weight of active compound in acetone or DMSO. To this solution was added 1% by weight of emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and diluted with water according to the desired concentration.

The active ingredients fosetyl-Al, epoxiconazole, triticonazole and pyraclostrobin were applied in their commercial formulation.

Use Example 3 - Efficacy against Tomato Drought Bacteria caused by Alternaήa solani

Leaves of potted plants of the "golden queen" variety were sprayed to drip point with an aqueous suspension in the concentration of active compound stated below. The following day, the leaves were infected with an aqueous spore suspension of Alternaria solani in 2% biomalt solution with a density of 0.17 x 10 ⁶ spores / ml. Subsequently, the plants were placed in a water vapor-saturated chamber at temperatures between 20 and 22 ° C. After 5 days, the disease on the untreated, but infected control plants had developed so strongly that the infestation could be determined visually in%.

In this test, the plants treated with 63 ppm of the active ingredient 1-12 showed no infestation, while the untreated plants were 90% infected.

Use Example 4 - Efficacy against the net blotch of barley caused by Pyrenophora teres at 1 day of protective application

Leaves of potted barley seedlings were sprayed to drip point with aqueous suspension in the concentration of active compound given below. Twenty-four hours after the spray coating had dried on, the test plants were incubated with an aqueous spore suspension of Pyrenophora [syn. Drechslera] teres, the causative agent of net blotch inoculation. The test plants were wächshaus in Ge at temperatures between 20 and placed 24 ⁰ C and 95 to 100% relative atmospheric humidity. After 6 days, the extent of disease development was determined visually as% of total leaf area. In this test, the plants treated with 63 ppm of the active ingredient 1-12 showed 7% infestation, while the untreated plants were 90% infected.

Synergistic effects

Use Example 5 - Efficacy against the Dürrfleckkrankheit of tomato caused by Altemaria solani

Another trial employment according to Application Example 3 was evaluated as follows:

The visually determined values for the percentage of affected leaf areas were converted into efficiencies as% of the untreated control:

The efficiency (W) is calculated according to the formula of Abbot as follows:

W = (1-α / β) -W0

α corresponds to the fungal infestation of the treated plants in% and β corresponds to the fungal infestation of the untreated (control) plants in%

With an efficiency of 0, the infestation of the treated plants corresponds to those of the untreated control plants; at an efficiency of 100, the treated plants have no infestation.

The expected efficacies for drug combinations were determined according to the Colby formula (Colby, S.R. (Calculating synergistic and antagonistic responses of herbicide combinations), Weeds, 15, pp. 20-22, 1967) and compared with the observed efficiencies.

Colby formula:

E = x + y - χ-y / 100

E Expected efficiency, expressed as% of untreated control, using the mixture of Active Agents A and B at concentrations a and b x. the efficiency, expressed in% of untreated control, when using active substance A at concentration a y the efficiency, expressed in% of the untreated control, when using active substance B in concentration b

The following results were obtained:

Table 2 - mixtures according to the invention

*) calculated efficiency according to the Colby formula

Use Example 6 Protective Efficacy Against Puccinia recondita on Wheat (Wheat Brown Rust)

Leaves of potted wheat seedlings of the variety "Chancellor" were sprayed to drip point with an aqueous suspension in the active ingredient concentration given below. The next day, the treated plants were inoculated with a spore suspension of the wheat brown rust (Puccinia recondita). The plants were then placed in a high humidity chamber (90 to 95%) at 20 to 22 ° C for 24 hours. During this time, the spores germinated and the germ tubes penetrated the leaf tissue. On the following day, the test plants were returned to the greenhouse and cultured at temperatures between 20 and 22 ° C and 65 to 70% relative humidity for a further 7 days. Then the extent of rust fungus development on the leaves was visually determined.

The following results were obtained:

Table 3 - Single agents

*) calculated efficiency according to the Colby formula

Use Example 7 - Efficacy against the net blotch of barley caused by Pyrenophora teres at 1 day of protective application

In a further experimental employment according to application example 4 the following results were obtained:

Table 5 - Single agents

Table 6 - mixtures according to the invention

Active substance calculated and observed

Example concentration efficiency efficiency *) mixing ratio

A-31 + spiroxamine

71 63 + 16 ppm 83 67 4: 1

^* ) calculated efficiency according to the Colby formula

Use Example 8 - Activity against wheat powdery mildew caused by Erysiphe [syn. Blumeria] graminis forma specialis. tritici

Leaves of potted wheat seedlings were sprayed to drip point with aqueous suspension in the concentration of active compound given below. The suspension or emulsion was prepared as described above. Spores of wheat powdery mildew (Erysiphe [syn. Blumeria] graminis forma specialis. Tritici) are pollinated 24 hours after the spray coating has dried on. The test plants were then placed in a greenhouse at temperatures between 20 and 24 ° C and 60 to 90% relative humidity Luft¬. After 7 days, the extent of mildew development was determined visually in% infestation of the entire leaf area.

Table 7 - Single agents

*) calculated efficiency according to the Colby formula

Use Example 9 Activity against tomato late blight caused by Phytophthora infestans in protective treatment

Leaves of potted tomato plants were sprayed to drip point with an aqueous suspension in the drug concentration below. The following day, the leaves were infected with an aqueous sporangia suspension of Phytophthora infestans. Subsequently, the plants were placed in a water vapor-saturated chamber at temperatures between 18 and 20 ⁰ C. After 6 days, the late blight on the untreated but infected control plants developed so strongly that the infestation could be determined visually in%.

Table 9 - Single agents

Table 10 - mixtures according to the invention

^* ) calculated efficiency according to the Colby formula The results of the experiments show that the mixtures according to the invention are more effective than predicted according to the Colby formula.

Claims

claims

1. Fungicidal mixtures for controlling harmful fungi, containing

1) a δ-chloro-θ-phenyl-y-heterocyclylamino-triazolopyrimidine of the formula I ₁

in the

D together with the nitrogen atom, a pyrrolidine, piperidine or

Azepine ring forms which rings are unsubstituted or substituted by one or two methyl groups or by an ethyl, propyl or butyl group; and L is methyl, fluorine or chlorine;

and

2) at least one active ingredient II selected from the following groups:

A) Azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole,

Dinitroconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, mycollananil, penconazole, propiconazole, prochlorazone, prothioconazole, simonazole, tebuconazole, tetraconazole, triadimefon, triadimol, triflumizole, triticonazole;

B) strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, cres oxime-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclobutin, trifloxystrobin or 2- (ortho- (2,5-dimethylphenyloxymethylene) phenyl) -3-methoxy-acrylic acid methyl ester;

C) acylalanines such as benalaxyl, metalaxyl, mefenoxam, ofurace, oxadixyl;

D) amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph;

E) anilinopyrimidines such as pyrimethanil, mepanipyrim or cyprodinil; 5 008192

59

F) dicarboximides such as iprodione, myclozoline, procymidone, vinclozolin;

G) cinnamic acid amides and analogs such as dimethomorph, flumetover or flumorph;

H) antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin;

K) dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamate, Thiram, Ziram, Zineb;

L) Heterocyclic compounds selected from anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamide, dazoetine, dithianone, famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, picobenzamide,

Probenazole, proquinazide, pyrifenox, pyroquilon, quinoxyfen, silthiofam, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricylo lazol, triforine, 3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3- yl] - pyridine, (2-chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl) -carbamic acid methyl ester, (2-chloro-5- [1- (6-methyl-pyridine-2-yl) methyl yl-methoxyimino) ethyl] benzyl) carbamate;

Benzoimidazole derivatives of the formula IIA,

in which Y is chlorine or bromine;

Sulfamoyl compounds of the formula

in which the substituents have the following meanings: R ^{31 is} hydrogen, halogen, cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl,

C ₁ -C ₄ -alkoxy, C _r C ₄ alkylthio, C-rC ^ alkoxycarbonyl, phenyl,

Benzyl, formyl or CH = NOR ³¹¹ ;

R ³¹¹ is hydrogen, C _r C ₄ alkyl, C _r C ₄ alkylcarbonyl; R ^{32 is} hydrogen, halogen, cyano, C ₁ -C ₄ -alkyl, C-rC ₂ -haloalkyl,

CRCE alkoxycarbonyl; R ³³ is halogen, cyano, nitro, C _r C ₄ alkyl, CiC ₂ -haloalkyl, C ₁ -C ₄ -

Alkoxy, d ^ -Alkylthio, CrC ₄ alkoxycarbonyl, formyl or

CH = NOR ³¹¹ ; n is 0, 1, 2, 3 or 4;

R ³⁴ is hydrogen, halogen, cyano, C _r C ₄ alkyl or C ₁ -C ₂ -

haloalkyl; or

Thiophene derivatives of the formula IV,

AΓ ^Λ NQ IV

H ^S in which the variables have the following meanings: Ar is phenyl or a five- or six-membered aromatic hetero- rocyclus, containing one to four heteroatoms from the group O, N or S, where the cycles are unsubstituted or substituted by one to three groups R ⁴¹ may be substituted: R ⁴¹ is halogen, C _r C ₄ alkyl or C _r C ₄ haloalkyl; R is phenyl, -C ₈ alkyl, -C ₈ haloalkyl, C ₁ -C ₈ -alkoxy, C ₁ -C ₈ -

haloalkoxy; Q is hydrogen, C _r C ₈ alkyl, C _r C ₈ haloalkyl, C _r C ₈ alkoxy,

CRCS haloalkoxy;

M) sulfur and copper fungicides such as Bordeaux broth, copper acetate,

Copper oxychloride, basic copper sulfate;

N) nitrophenyl derivatives, such as binapacryl, dinocap, dinobutone, nitrophthalic isopropyl;

O) phenylpyrroles such as fenpiclonil or fludioxonil;

P) sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, toluylfluanid; Other fungicides selected from Acibenzolar-S-methyl, Benthiavalicarb, Carpropamid, Chlorothalonil, Cyflufenamid, Cymoxanil, Dazomet, Diclomezine, Diclocymet, Diclofluanid, Diethofencarb, Edifenphos, Ethaboxam, Fenhexamid, Fentin-Acetate, Fenoxanil, Ferimzone, Fluoroacetamide ziname, fosetyl, fosetyl-aluminum, phosphorous acid, iprovalicarb, hexachlorobenzene, mandipropamide, metrafenone, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamide,

Oxime ether derivatives of the formula V ₁

in the

X is CrCrHalogenalkoxy, n is 0, 1, 2 or 3,

R is halogen, C ₁ -C ₄ -AIRyI, -C ₄ haloalkyl, C ₁ -C ₄ -alkoxy, or haloalkoxy;

Phenylamidine derivatives of the formula VI,

in which the variables have the following meanings: R ⁶¹ is hydrogen, C _r C ₈ alkyl, C ₂ -C ₈ alkenyl or C ₂ -C ₈ -alkyl kinyl, wel¬ che are unsubstituted or substituted by one to three groups R ^a R ^{a is} halogen, C ₁ -C ₈ -alkoxy, C _r C ₈ -haloalkoxy,

C _r -C ₈ -alkylthio or phenyl which may be substituted by halogen,

C ₁ -C ₈ -alkyl, CrC ₈ haloalkyl, C ₁ -C ₈ -alkoxy, C-pCs-haloalkoxy or C _r C ₈ alkylthio; R ⁶² , R ⁶³ may be the same or different and may be hydrogen, cyano,

C _r C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₁ -C ₈ -alkoxy, C ^ Cs-alkoxyalkyl, benzyloxy or C-RCS alkylcarbonyl which are unsubstituted or may be substituted by one to three groups R ^a ;

R ^{64 is} hydrogen, C ₁ -C ₈ -alkyl, C ₂ -C ₈ -alkenyl or C ₂ -C ₈ -alkynyl, which are unsubstituted or may be substituted by one to three groups R ^b :

R ^{b is} one of the groups mentioned under R ^a , cyano, C (= O) R ^C ,

C (= S) R ^C or S (O) _P R ^C ,

R ^c d-Cβ-alkyl, C _r C ₈ haloalkyl, C _r C ₈ alkoxy, CrC ₈ haloalkoxy, CRCS Aikylthio, amino, C _r C ₈ alkylamino, di (C _r C ₈ alkyl) amino or

Phenyl which may be substituted by halogen, CRCS alkyl, C _r C ₈ haloalkyl, C ₁ -C ₈ -alkoxy, Ci-C ₈ haloalkoxy, or C ^ Cs-alkylthio; m is 0 or 1; R ^{65 is} one of the groups mentioned in R ⁶⁴ ;

A is a direct bond, -O-, -S-, NR ^d , CHR ^e or -O-CHR ^Θ ;

R ^d , R ^{e is} one of the groups mentioned in R ^a ; R ^{66 is} phenyl or five- or six-membered saturated, partially unsaturated or unsaturated heterocycle containing one to four heteroatoms from the group O, N or S, wherein the groups R ^{66 are} unsubstituted or substituted by one to three R ^f substitu¬ R ^{f is} one of the groups mentioned in R ^b or

Amino, C _r C ₈ alkylamino, di (C _r C ₈ alkyl) amino, CrCβ haloalkyl, CRCS alkoxyalkyl, C ₂ -C ₈ oxyalkyl alkenyl, C ₂ -C ₈ -Alkinyloxyalkyl, C _r C ₈ -Alkylcarbonyloxy-Ci-C ₈ -alkyl, cyanooxy-Ci-Cs-alkyl, C ₃ -C ₆ -cycloalkyl or phenoxy, wherein the cyclic. C ₁ groups may be substituted by halogen, -C ₈ -alkyl, CRCS haloalkyl, C ₁ -C ₈ -alkoxy, CRCS haloalkoxy or C _r C ₈ alkylthio; or

a compound of formula VII,

in which the variables have the following meaning:

A 'O or N; BN, or a direct bond; GC or N;

R ^{71 is} C ₁ -C ₄ alkyl;

R ^{72 is} C ₁ -C ₄ -alkoxy; and

R ⁷³ halogen; or

R) growth retardants such as prohexadione and its salts, trinexapac-ethyl, chlormequat, mepiquat chloride and diflufenzopyr;

in a synergistically effective amount.

2. Fungicidal mixtures according to claim 1, comprising a compound of formula I and an active ingredient II in a weight ratio of 100: 1 to 1: 100.

3. Compounds of formula I according to claim 1, in which L is methyl and D has one of the following meanings:

- (CHz) ₄ -; -CH ₂ -CH (CHs) -CH ₂ -CH ₂ -; -CH (CH ₃ ) -CH (CH ₃ ) -CH ₂ -CH ₂ -;

-CH ₂ -CH (CH ₃ ) -CH (CH ₃ ) -CH ₂ -;

-CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ -; - (CHa) ₅ -; -CH (CHg) -CH ₂ -CH ₂ -CH ₂ -CH ₂ -;

-CH (CH ₃ ) -CH ₂ -CH ₂ -CH (CH ₃ ) -; -CH ₂ -CH ₂ -CH (CH ₃ ) -CH ₂ -CH ₂ -; -CH (CH _S ) -CH (CH _S ) -CH ₂ -CH ₂ -CH ₂ -; -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ -CH ₂ -;

-CH (CH ₃ ) -CH ₂ -CH ₂ -CH (CH ₃ ) -CH ₂ -; -CH (CHS) -CH ₂ -CH ₂ -CH ₂ -CH (CHS) -;

-CH ₂ -CH (CH ₃ ) -CH (CH ₃ ) - (CH ₂ ) ₂ -; -CH ₂ -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ -;

- (CH ₂ ) ₂ -CH (CH [CH ₃ ] ₂ ) - (CH ₂ ) ₂ -;

-CH (CH ₂ CHS) -CH ₂ -CH ₂ -CH ₂ -CH ₂ -; -CH-CH (CH ₂ CHg) -CH ₂ -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH (CH ₂ CH _S ) -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH (CH ₂ CH ₂ CH ₃ ) -CH ₂ -CH ₂ -;

-CH ₂ -CH ₂ -CH (C [CH ₃ ] _S ) -CH ₂ -CH ₂ - and - (CH ₂ ) ₆ -.

4. Compounds of formula I according to claim 1, in which L is fluorine and D has one of the following meanings: - (CH ₂ J ₄ -; -CH ₂ -CH (CH ₃ ) -CH ₂ -CH ₂ -; -CH (CH ₃ ) -CH (CH ₃ ) -CH ₂ -CH ₂ -;

-CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ -; -CH (CHS) -CH ₂ -CH ₂ -CH (CHS) -;

-CH ₂ -CH (CH _S ) -CH ₂ -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH (CH ₃ ) -CH ₂ -CH ₂ -;

-CH ₂ -CH (CH ₃ ) -CH (CH ₃ ) -CH ₂ -;

-CH (CH ₃ ) -CH (CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -; -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ -CH ₂ -; -CH (CH ₃ ) -CH ₂ -CH ₂ -CH (CH ₃ ) -CH ₂ -; -CH (CH _S ) -CH ₂ -CH ₂ -CH ₂ -CH (CH ₃ ) -;

-CH ₂ -CH (CH ₃ ) -CH (CH ₃ ) - (CH ₂ ) ₂ -; -CH ₂ -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ -;

- (CH ₂ ) ₂ -CH (CH [CH ₃ ] ₂ ) - (CH ₂ ) ₂ -;

-CH (CH ₂ CH _S ) -CH ₂ -CH ₂ -CH ₂ -CH ₂ -; -CH-CH (CH ₂ CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -;

-CH ₂ -CH ₂ -CH (CH ₂ CH ₃ ) -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH (CH ₂ CH ₂ CH _S ) -CH ₂ -CH ₂ - and -CH ₂ -CH ₂ -CH (C [CH ₃ ] _S ) -CH ₂ -CH ₂ -.

5. Compounds of formula I according to claim 1, in which L is chlorine and D has one of the following meanings: -CH (CH ₃ ) -CH (CH ₃ ) -CH ₂ -CH ₂ -; -CH ₂ -CH (CHs) -CH ₂ -CH ₂ -; -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ -; -CH (CH ₃ ) -CH ₂ -CH ₂ -CH (CH ₃ ) -;

-CH ₂ -CH (CH ₃ ) -CH (CH ₃ ) -CH ₂ -; -CH (CH ₃ ) -CH (CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -; -CH (CH ₃ ) -CH ₂ -CH ₂ -CH (CH ₃ ) -CH ₂ -; -CH (CHS) -CH ₂ -CH ₂ -CH ₂ -CH (CH ₃ ) -; -CH ₂ -CH (CH ₃ ) -CH (CH ₃ ) - (CH ₂ ) ₂ -; - (CH ₂ ) ₂ -CH (CH [CH ₃ ] ₂ ) - (CH ₂ ) ₂ -; -CH (CH ₂ CHS) -CH ₂ -CH ₂ -CH ₂ -CH ₂ -; -CH-CH (CH ₂ CHS) -CH ₂ -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH (CH ₂ CH _S ) -CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -CH (CH ₂ CH ₂ CH ₃ ) -CH ₂ -CH ₂ - and

-CH ₂ -CH ₂ -CH (C [CH ₃ ] ₃ ) -CH ₂ -CH ₂ -.

6. Process for the preparation of the compounds of the formula I according to one of claims 3 to 5, by reacting a dichlorotriazolopyrimidine of the formula II '

with amines of the formula II

H

to compounds of the formula I.

7. A composition comprising a liquid or solid carrier and a mixture ge according to claim 1 or 2 or a compound of formula I according to any one of claims 3 to 5.

8. A method for controlling phytopathogenic harmful fungi, characterized ge indicates that the fungi, their habitat or the plants to be protected against fungal attack, the soil or seed with an effective amount ei¬ ner compound I and an active ingredient Il from the groups A ) to R) according to claim 1 or a compound of the formula I according to one of claims 3 to 5.

9. The method according to claim 8, characterized in that the compound I and the active ingredient II from the groups A) to R) according to claim 1 simultaneously, and jointly or separately, or successively.

10. The method according to claims 8 or 9, characterized in that the compound I and the active ingredient Ii from the groups A) to R) according to claim 1 or the mixtures according to claim 1 or 2 in an amount of 5 g / ha to 2000 g / ha.

11. The method according to claims 8 or 9, characterized in that the compound I and the active ingredient II from the groups A) to R) according to claim 1 or the mixture according to claim 1 or 2 in an amount of 1 to 1000 g / 100 kg of seed.

12. Seed containing the mixture according to claim 1 or 2 or a compound I according to any one of claims 3 to 5 in an amount of 1 to 1000 g / 100 kg.

13. Use of the compounds I and the active compounds from groups A) to R) according to claim 1 for the preparation of a ge suitable for controlling harmful fungi agent.