KR100560595B1 - Fungicide Mixtures Based on Triple Oxime Ether Derivatives and Additional Fungicides - Google Patents

Abstract

The present invention relates to the active ingredient a) phenylacetic acid derivatives of formula I (wherein the substituents and indices have the meanings mentioned in the detailed description of the invention) and salts thereof and b) 1 of the compounds of formulas (II) to (V). A fungicidal mixture comprising at least a species in a synergistically effective amount.

<Formula I>

<Formula II>

<Formula III>

<Formula IV>

<Formula V>

In the above formulas, the substituents are each as defined herein.

Fungicidal mixtures, trioxime ether derivatives, phenylacetic acid derivatives, harmful fungi, control, pyricularia orizae

Description

Fungicide Mixtures Based on Triple Oxime Ether Derivatives and Additional Fungicides}             

The present invention relates to a fungicidal mixture for controlling harmful fungi comprising a) a phenylacetic acid derivative of formula (I) and a salt thereof and b) at least one fungicide selected from fungicides of formulas (II) to (V). .

Where

X is NOCH ₃ , CHOCH ₃ or CHCH ₃ ,

Y is O or NR,

R ¹ and R are each independently of the other hydrogen or C ₁ -C ₄ -alkyl,

R ² is cyano, nitro, trifluoromethyl, halogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy,

m is 0, 1 or 2, and when m is 2 the radicals R ² may be different,

R ³ is hydrogen, cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl or C ₃ -C ₆ -cycloalkyl,

R ⁴ and R ⁶ are each independently of each other hydrogen,

C ₁ -C ₁₀ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₂ -C ₁₀ -alkenyl, C ₂ -C ₁₀ -alkynyl, C ₁ -C ₁₀ -alkylcarbonyl, C ₂ -C ₁₀ -Alkenylcarbonyl, C ₃ -C ₁₀ -alkynylcarbonyl or C ₁ -C ₁₀ -alkylsulfonyl, these radicals may be partially or fully halogenated, or cyano, nitro, hydroxyl, mer Capto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₁ -C ₆ -alkylsulfonyl, C ₁ -C ₆ -Alkylsulfoxy, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -haloalkoxy, C ₁ -C ₆ -alkoxycarbonyl, C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkylamino, Di-C ₁ -C ₆ -alkylamino, C ₁ -C ₆ -alkylaminocarbonyl, di-C ₁ -C ₆ -alkylaminocarbonyl, C ₁ -C ₆ -alkylaminothiocarbonyl, di-C ₁ -C ₆ -alkylaminothiocarbonyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkenyloxy, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyloxy, Heterocyclyl, heterocyclyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio groups may have 1 to 3, wherein the cyclic groups are partially Or can be fully halogenated, or cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -halo Alkyl, C ₁ -C ₆ -alkylsulfonyl, C ₁ -C ₆ -alkylsuloxyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -haloalkoxy, C ₁ -C ₆ -alkyloxycarbonyl, C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkylamino, di-C ₁ -C ₆ -alkylamino, C ₁ -C ₆ -alkylaminocarbonyl, di -C ₁ -C ₆ -alkylaminocarbonyl, C ₁ -C ₆ -alkylaminothiocarbonyl, di-C ₁ -C ₆ -alkylaminothiocarbonyl, C ₂ -C ₆ -alkenyl, C _2- C ₆ - alkenyloxy, benzyl, benzyloxy, aryl, When, arylthio, taril H., H. taril oxy, H. taril thio or _{^{C (= NOR 7) -A n}} -R , or may have 1 to 3 out of ⁸ dogs group,

Aryl, arylcarbonyl, arylsulfonyl, hetaryl, hetarylcarbonyl or hetarylsulfonyl, these radicals may be partially or fully halogenated, or cyano, nitro, hydroxyl, mercapto, amino, carbon Carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₁ -C ₆ -alkylcarbonyl, C ₁ -C ₆ -alkylsulfonyl, C ₁ -C ₆ -alkylsuloxyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -haloalkoxy, C ₁ -C ₆ -alkyloxycarbonyl, C _1- C ₆ -alkylthio, C ₁ -C ₆ -alkylamino, di-C ₁ -C ₆ -alkylamino, C ₁ -C ₆ -alkylaminocarbonyl, di-C ₁ -C ₆ -alkylaminocarbonyl, C ₁ -C ₆ -alkylaminothiocarbonyl, di-C ₁ -C ₆ -alkylaminothiocarbonyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkenyloxy, benzyl, benzyloxy, Within 1 of aryl, aryloxy, hetaryl, hetaryloxy or C (= NOR ⁷ ) -A _n -R ⁸ groups Can have three

R ⁵ is hydrogen,

C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, and the hydrocarbon radicals of these groups may be partially or fully halogenated, or may be cyano, nitro, hydroxyl , Mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C ₁ -C ₆ -alkylaminocarbonyl, di-C ₁ -C ₆ -alkylaminocarbonyl, C ₁ -C _6- alkylamino-thiocarbonyl, di -C ₁ -C ₆ - alkylamino-thiocarbonyl, C ₁ -C ₆ - alkylsulfonyl, C ₁ -C ₆ - alkyl sulfoxylates, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ -haloalkoxy, C ₁ -C ₆ -alkoxycarbonyl, C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkylamino, di-C ₁ -C ₆ -alkylamino, C ₂ -C ₆ -alkenyloxy, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, aryl-C ₁ -C ₄ -alkoxy, aryl thio, aryl -C ₁ -C ₄ - alkylthio, taril H., H. taril oxy, H. taril -C ₁ -C ₄ - alkoxy, H. Reel alkylthio, H. taril -C ₁ -C ₄ - alkylthio, and may have 1 to 3 in the radical, where the cyclic radicals may be partially or fully halogenated and (or), cyano, nitro, hydroxyl , Mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₁ -C ₆ -alkylsulfonyl, C ₁ -C ₆ -Alkylsulfoxy, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -haloalkoxy, C ₁ -C ₆ -alkoxycarbonyl, C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkylamino, di-C ₁ -C ₆ -alkylamino, C ₁ -C ₆ -alkylaminocarbonyl, di-C ₁ -C ₆ -alkylaminocarbonyl, C ₁ -C _6- Alkylaminothiocarbonyl, di-C ₁ -C ₆ -alkylaminothiocarbonyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, aryl alkylthio, taril H., H. taril oxy, thio H. taril and _{^{C (= NOR 7) -A n}} -R 1 in ⁸ groups If you can have three,

C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkenyl, heterocyclyl, aryl and hetaryl, wherein the cyclic radicals can be partially or fully halogenated, or cyano, nitro, hydrate Hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₁ -C ₆ -alkylsulfonyl, C ₁ -C ₆ -alkylsulfoxy, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -haloalkoxy, C ₁ -C ₆ -alkoxycarbonyl, C ₁ -C _6- Alkylthio, C ₁ -C ₆ -alkylamino, di-C ₁ -C ₆ -alkylamino, C ₁ -C ₆ -alkylaminocarbonyl, di-C ₁ -C ₆ -alkylaminocarbonyl, C _1- C ₆ -alkylaminothiocarbonyl, di-C ₁ -C ₆ -alkylaminothiocarbonyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkenyloxy, benzyl, benzyloxy, aryl, aryl May have 1 to 3 of oxy, hetaryl and hetaryloxy groups,

A is oxygen, sulfur or nitrogen, wherein nitrogen has hydrogen or C ₁ -C ₆ -alkyl,

n is 0 or 1,

R ⁷ is hydrogen or C ₁ -C ₆ -alkyl,

R ⁸ is hydrogen or C ₁ -C ₆ -alkyl.

Where

A is C ₃ -C ₆ -cycloalkyl which may have 1 to 3 substituents selected from the group consisting of halogen and C ₁ -C ₃ -alkyl;

R ⁹ is C ₁ -C ₆ -alkyl or C ₂ -C ₆ -alkenyl, these radicals may be partially or fully halogenated and / or C ₁ -C ₄ -alkoxy, C ₁ -C _4- May have one or two of haloalkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkoxycarbonyl, C ₃ -C ₆ -cycloalkyl, and a phenyl group, wherein the phenyl group is partially or completely Can be halogenated and / or nitro, cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -haloalkoxy, C ₁ -C _May have 1 to 3 of ₄ -alkylthio, C ₃ -C ₆ -cycloalkyl and heterocyclyl radicals;

R ¹⁰ , R ¹¹ and R ¹² are each hydrogen or independently one of the above R ⁹ radicals;

n is 0 or 1;

Y is cyano or halogen;

W is phenyl, naphthyl or heteroaryl, these radicals are nitro, halogen, cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C _May have 1 to 3 of ₄ -haloalkoxy, C ₁ -C ₄ -alkylthio, C ₃ -C ₆ -cycloalkyl and C ₁ -C ₄ -alkoxycarbonyl groups;

R ¹³ is C ₆ -C ₁₅ -bicycloalkyl or C ₇ -C ₁₅ -bicycloalkenyl, wherein these radicals can be fully halogenated and, if they are not fully halogenated, two carbon atoms in these radicals will be C _May form a 5- to 7-membered saturated carbocyclic ring with a ₃ -C ₅ -alkylidene group and / or may be cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ - alkoxy, C ₁ -C ₄ - haloalkoxy, and aryl groups may have one or independently two, three, four or five pieces from each other, when the aryl group is partially or completely may be halide ( Or), nitro, cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -haloalkoxy and C ₁ -C ₄ -alkylthio May have one or two independently from each other or three;

R ¹⁴ , R ¹⁵ and R ¹⁶ independently of one another are hydrogen, may be partially or fully halogenated, and / or may be C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -haloalkoxy, C ₁ -C ₄ -alkyl C ₁ -C ₈ -alkyl which may have one or two of thio, C ₃ -C ₇ -cycloalkyl, C ₅ -C ₇ -cycloalkenyl groups, wherein the cyclic groups are 1 or independently of each other 2 Or three halogen atoms, a C ₁ -C ₃ -alkyl group and / or a C ₁ -C ₃ -alkoxy group and an aryl group, where aryl may be partially or fully halogenated and / or nitro, cyano , One of C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -haloalkoxy and C ₁ -C ₄ -alkylthio substituents or independent of one another Can have two or three, or

C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkenyl or heterocyclyl, these radicals may be partially or fully halogenated and / or cyano, C ₁ -C ₆ -alkyl, C _{May have 1} or 2 independently of ₁ -C ₆ -haloalkyl, C ₂ -C ₆ -alkenyl, C ₁ -C ₆ -alkoxy and C ₁ -C ₆ -alkylthio groups or independently of one another;

Ar is aryl or heteroaryl, wherein these radicals are halogen, cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxyalkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy , C ₁ -C ₄ -haloalkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkoxycarbonyl, aryl, aryloxy and heteroaryl groups, which may have two or three independently of one another Wherein the ring in the groups is halogen, cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxyalkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy, C ₁ It may have one or two independently of one of or -C ₄ -haloalkoxy, C ₁ -C ₄ -alkylthio and C ₁ -C ₄ -alkoxycarbonyl substituent.

It is an object of the present invention to provide fungicidal mixtures which have good fungicidal activity in excess of the fungicidal activity of each of the fungicidal mixture components, in particular against fungal diseases of rice.

The inventors have found that this object is achieved by a mixture as claimed in claim 1.

Compounds of formula (I) are known per se and are described in WO 97/15552.

Fungicides of formula (II) and formula (III) are also known and described in the literature. They are also commercially available under the trade names mentioned in parentheses below:

II: European Patent Publication No. 341,475, Generic Name: Caprofamide (trade name: WIN®, Bayer)

III: CAS RN 139 920-32-4, proposed common name: Diclocimet (developed by Sumitomo)

Compound V and also methods for its preparation are disclosed in WO 97/35838.

Compound IV and its preparation are described in more detail below; Corresponding compounds are disclosed in earlier patent application PCT / EP 98/01031 or in German patent 19710618.8.

Because of the C═C and C═N double bonds, the preparation of compounds of formula (I) may produce an E / Z isomer mixture that may be separated into individual compounds in a conventional manner, for example by crystallization or chromatography. have.

However, if an isomeric mixture is produced by synthesis, in some cases the individual isomers can be converted to one another during use or during use (eg, under the action of light, acid or base), separation is generally It is not necessary. Similar conversions may also occur after use, for example, in harmful fungi or animal pests to treat or control treated plants.

For C = X double bonds, the cis isomers of the compounds of formula (I) relative to the activity (coordination based on —OCH ₃ or —CH ₃ groups relative to —CO ₂ R ¹ — groups) are preferred.

For -C- (R ³ ) = NOCH ₂ -double bonds, the cis isomer of the compound of formula (I) with respect to activity (coordination based on radical R ³ with respect to -OCH ₂ -group) is preferred.

For its biological activity, compounds of formula (I) in which m is zero are preferred.

Likewise preferred are compounds of formula I, wherein R ¹ is methyl.

In addition, preference is given to compounds I in which R ³ is hydrogen, cyano, cyclopropyl, methyl, ethyl, 1-methylethyl or CF ₃ .

Furthermore, preference is given to compounds of the formula (I) in which R ³ is methyl.

In addition, preference is given to compounds I in which R ³ is cyano.

Furthermore, preference is given to compounds of the formula (I) in which R ³ is cyclopropyl.

Also preferred are compounds of formula I, wherein R ³ is CF ₃ .

Also preferred are compounds of formula I, wherein R ⁵ is hydrogen, cyclopropyl, methyl, ethyl, isopropyl, unsubstituted or substituted aryl or hetaryl.

Furthermore, preference is given to compounds of the formula (I) in which R ⁵ is methyl.

Also preferred are compounds of formula I, wherein R ⁵ is ethyl.

Furthermore, preference is given to compounds of the formula (I) in which R ⁵ is isopropyl.

Furthermore, preference is given to compounds of the formula (I) in which R ⁵ is cyclopropyl.

Furthermore, compounds of formula I wherein R ⁵ is CF ₃ are preferred.

Also preferred are compounds of formula I, wherein R ⁵ is unsubstituted or substituted aryl or hetaryl.

Also preferred are compounds of formula I, wherein R ⁵ is unsubstituted or substituted pyridyl, pyrimidyl, pyrazinyl, pyridazinyl or triazinyl.

Also preferred are compounds of formula I, wherein R ⁵ is unsubstituted or substituted furyl, thienyl or pyrrolyl.

Preference is furthermore given to compounds of the formula (I) in which R ⁵ is unsubstituted or substituted oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl or imidazolyl.

Also preferred are compounds of formula I, wherein R ⁵ is unsubstituted or substituted oxadiazolyl, thiadiazolyl or triazolyl.

Furthermore, R ⁵ is nitro, cyano, hydroxyl, amino, aminocarbonyl, aminothiocarbonyl, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy , C ₁ -C ₄ -haloalkoxy, C ₁ -C ₄ -alkylamino, di-C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylsulfonyl, C ₁ -C ₄ -alkoxycarbonyl, Preference is given to compounds of the formula (I) which are phenyl having 1 or 2 or unsubstituted C ₁ -C ₄ -alkylaminocarbonyl or di-C ₁ -C ₄ -alkylaminocarbonyl groups.

Furthermore, R ⁴ is hydrogen, C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, allyl, arylalkyl, hetarylalkyl, aryloxyalkyl, hetaryloxyalkyl Preference is given to compounds of the formula (I) which are aryl or hetaryl.

Also preferred are compounds of formula I, wherein R ⁴ is C ₁ -C ₆ -alkyl.

Further preferred compounds of formula (I) are disclosed in International Patent No. 97 / 15,552.

For fungicidal activity against harmful fungi, for example Pyricularia oryzae , cycloalkylalkanecarboxamides of the formula IV having the following substituents are preferred, in each case alone Or combination.

Carbon atoms having R ⁹ and R ¹⁰ groups preferably have an R configuration.

Preference is given to cycloalkylalkanecarboxamides of the formula (IV) in which R ⁹ is methyl and R ¹⁰ is either methyl or hydrogen, particularly preferred is compound IV in which R ⁹ is methyl and R ¹⁰ is hydrogen.

Furthermore, cycloalkylalkanecarboxamides of formula IV are preferred, wherein W is in particular substituted or unsubstituted phenyl substituted in the 2- or 2 and 4 positions. Particular preference is given to having a substituent at the 4-position of the phenyl ring, with preferred substituents being cyano or methoxy, preferably methyl, in particular halogen, which in this case is preferably chlorine.

Also preferred is cycloalkylalkanecarboxamide IV with n = 1. R ³ and R ⁴ substituents are preferably C ₁ -C ₄ -alkyl, especially methyl. Also preferred are combinations in which one of the two substituents is hydrogen and the remainder is C ₁ -C ₄ -alkyl, especially methyl.

Furthermore, α-chloro- or α-bromocycloalkylalkanecarboxamide IV (Y = bromine or chlorine) is preferred. Especially preferred is α-cyanocycloalkylalkanecarboxamide IV (Y = cyano).

Finally, cycloalkylalkanecarboxamides of formula IV wherein A is unsubstituted or substituted cyclopropyl are preferred. Particular preference is given to cyclopropyl having 1 to 3 substituents selected from the group consisting of chlorine and C ₁ -C ₃ -alkyl, especially methyl. The chlorinated cyclopropyl preferably has two chlorine atoms at the gem position of the cyclopropane ring. The alkylated or preferably methylated cyclopropyl preferably has one alkyl (methyl) substituent at the carbon atom of the site where the cyclopropane ring is linked to the residue of the molecule.

For this use, the formula (I) supplemented in Tables 1 to 13 below is particularly preferred.

TABLE 2

Carboxamides IVb.001 to IVb.108 of formula IVb, meaning the combination of Z ¹ , Z ² and “*” given in the lines of Table 1

TABLE 3

Carboxamides IVc.001 to IVc.108 of formula IVc, meaning the combination of Z ¹ , Z ² and “*” given in the lines of Table 1

TABLE 4

Carboxamides IVd.001 to IVd.108 of formula IVd, meaning the combination of Z ¹ , Z ² and “*” given in the lines of Table 1

TABLE 5

Carboxamides IVe.001 to IVe.108 of formula IVe, meaning the combination of Z ¹ , Z ² and “*” given in the lines of Table 1

TABLE 6

Carboxamides IVf.001 to IVf.108 of formula IVf, meaning the combination of Z ¹ , Z ² and “*” given in the lines of Table 1

TABLE 7

Carboxamides IVg.001 to IVg.108 of formula IVg, meaning the combination of Z ¹ , Z ² and “*” given in the lines of Table 1

TABLE 8

Carboxamides IVh.001 to IVh.108 of formula IVh, meaning the combination of Z ¹ , Z ² and “*” given in the lines of Table 1

TABLE 9

Carboxamides IVi.001 to IVi.108 of formula IVi, meaning the combination of Z ¹ , Z ² and "*" given in the row of Table 1

TABLE 10

Carboxamides IVk.001 to IVk.108 of formula IVk, meaning the combination of Z ¹ , Z ² and “*” given in the lines of Table 1

TABLE 11             

Carboxamides IVm.001 to IVm.108 of formula IVm, meaning the combination of Z ¹ , Z ² and “*” given in the lines of Table 1

TABLE 12

Carboxamides IVn.001 to IVn.108 of formula IVn, meaning the combination of Z ¹ , Z ² and “*” given in the lines of Table 1

TABLE 13

Carboxamides IVo.001 to IVo.108 of Formula IVo, meaning the combination of Z ¹ , Z ² and "*" given in the row of Table 1

In addition, the inventors have discovered a process for the preparation of carboxamide IV which can be produced in good yields.

In a preferred process, carboxamide IV is obtained by reacting a carboxylic acid derivative of formula VI with an amine of formula VII.

The production of amides is carried out according to methods known in the literature. Free carboxylic acids of formula VI ', wherein Z is hydroxyl, are generally first converted to activated carboxylic acid derivative VI, wherein Z is, for example, chlorine.

Activation of the carboxylic acid VI ′ is also preferably performed, for example, dicyclohexylcarbodiimide, ethylchloroformate, diethyl cyanophosphonate, triphenylphosphine / azodicarboxyl ester, 2-pyridine disulfide It can be carried out in situ using carboxylic acid VI ′ with the addition of feed / triphenylphosphine, carbonyldiimidazole, thionyl chloride, phosphorus trichloride, phosphorus pentachloride and the like directly. Generally, for example, carbodiimide is added in equimolar amounts based on carboxylic acid VI '.

Activation of the carboxylic acid via acyl cyanide is carried out, for example, by reacting carboxylic acid VI 'with diethyl cyanophosphonate in an inert solvent, preferably tetrahydrofuran, toluene or dichloromethane. (See Tetrahedron Lett. 18 (1973), 1595-8).

Activation via anhydrides is carried out, for example, by reacting the carboxylic acid VI 'with a chloroformate such as ethyl chloroformate, usually in the presence of a base, suitably in an inert solvent such as toluene or tetrahydrofuran ( See Houben-Weyl, 4th Ed. (1974), 15/1, pages 28-32).

The amide formation is preferably carried out in the presence of a base such as, for example, tertiary amines such as triethylamine or dimethylcyclohexylamine, alkali metal carbonates, alkali metal hydroxides, pyrimidines and the like. Starting materials and auxiliary bases are advantageously used in equimolar amounts. In certain cases, it may be advantageous for the minor base to be in excess of 0.1 to 0.5 equivalents.

Suitable solvents include aliphatic hydrocarbons such as hexane and ligroin, aromatic hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as methylene chloride and 1,2-dichloroethane, ethers such as methyl tert-butyl ether and tetrahydrofuran, acetonitrile and Polar aprotic solvents such as dimethylformamide or esters such as ethyl acetate, or mixtures thereof.

The molar ratio of carboxylic acid derivative VI to amine VII is generally from 0.8 to 1.5, preferably from 0.9 to 1.1.

After the reaction is complete, the workup is usually carried out, for example, by incorporating the reaction mixture into water and then extracting the amine.

Amines of formula (VII) are known or readily obtainable (see Organanikum (1993) Barth Verlagsgesellschaft mbH Leipzig, p. 509 ff .; Indian J. Chem. 10 (1972), 366).

 Preparation of α-cyanocyclopropane acetic acid is described in Org. Prep. Proced. Int. 5 (1973), 25-29. Scheme 1 below represents a general route for preparing carboxylic acids of Formula VI ′ (Collect. Czech. Chem. Commun. 48 (1983), 1597-1601 and J. Polym. Sci., Polym. Chem. Ed 14 (1976), 2357-9).             

Carboxylic acid derivatives of the general formula (VIA) can also be prepared according to Scheme 2 below.

Cycloalkylacetic acid of formula VIII as A is as defined in claim 1 is described in J. Chem. Technol. Biotechnol., Chem. Technol., 33A (1983), 109-15; Dutch Patent No. 65 06 881; Chem, Ber. 41 (1908), 2627; Chem. Ber. 35 (1902), 2688.

Cycloalkylacetic acid VIII is described in J. Am. Chem. Soc 70 (1948), 3626] can be brominated at the α-position. Workup in the presence of C ₁ -C ₆ -alcohols directly yields the corresponding esters. The bromine / cyano exchange is then described by Synth. Commun. 23 (1993), 2323-9. Hydrolysis of the esters to obtain carboxylic acid VIAA 'is carried out by standard methods (Organikum 1993 Barth Verlagsgesellschaft mbH, Leipzig, p. 431ff.).

Carboxylic acid derivatives of Formula VIB can be obtained, for example, according to the route shown in Scheme 3.             

Starting materials, acyl- or formylcycloalkanes of formula IX are generally available (J. Chem. Soc., Perkin Trans. I, 6 (1994), 739-752). They react with C ₁ -C ₆ -alkyl α-halo or α-cyanoacetate in the Knoevenagel reaction to give Michael system X (Chem. Heterocycl. Compd. 24 (1988) , 860-4).

Condensation is generally carried out while removing the water produced during the reaction in a water immiscible solvent such as hexane, toluene or xylene. According to the object of the present invention, the reaction mixture is heated to reflux for several hours under reflux.

For example, bases such as piperidine, pyridine, ammonia or β-alanine serve as catalysts, for example in the presence of an acid such as glacial acetic acid.

An alkyl Grignard reagent of formula (XI), wherein R ³ is as defined in claim 1 and Hal is chlorine, bromine or iodine, is subsequently added to the Michael system of formula (X) to obtain a saturated system of type VIB.

The reaction is carried out in an inert solvent under reaction conditions. Preference is given to ethers such as tetrahydrofuran, diethyl ether, dimethoxyethane or methyl tert-butyl ether. The reaction temperature is generally set at -10 to 80 캜, preferably 10 to 60 캜.

Grignard Reagent XI is generally used in equimolar amounts based on Michael X. In any case, it is advantageous to use Grignard reagent in excess of 0.2 to 0.5 molar equivalents.

Generally, the addition is facilitated by copper and is carried out by adding 1 to 10 mol%, for example, copper iodide (I). This results in a high selectivity of 1,2-addition to 1,4-addition.

Finally, the free carboxylic acid VIB 'is prepared by alkaline hydrolysis of the corresponding ester (see Organickum 1993 Barth Verlagsgesellschaft mbH, Leipzig, p. 431ff.).

The preferred route of 2-cyano-3- (2,2-dichlorocyclopropyl) -3-methylbutanoic acid is shown in Scheme 4 below.             

The preparation of 2-cyano-3,3-dimethylpent-4-enoic acid from 3-methylbut-2-enyl ester of cyanoacetic acid is described in German Patent No. 26 49 711 and Res. Discl. 249 (1985), 55. 2-cyano-3- (2,2-dichloro-cyclopropyl) -3-methylbutanoic acid can be obtained directly by adding dichlorocarbene which can be obtained from chloroform and alkaline metal hydroxides by standard methods. In order to increase the yield, it is advantageous to protect the carboxylic acid functional group (eg, convert to tert-butyl ester) before the cyclopropaneation step.

By the above-mentioned method, for example, carboxylic acid derivatives VI suitable for the preparation of carboxamide IV according to the invention can be obtained.

A particularly preferred embodiment of the carboxylic acid derivative VI for the R ¹¹ , R ¹² , A and Y substituents corresponds to carboxamide IV.

Z is hydroxyl, C ₁ -C ₄ -alkoxy, halogen, for example bromine or chlorine, hetaryl, for example imidazolyl or pyridyl, carboxylate, for example acetate or trifluoride Nucleophilic substitutable radicals such as acetates and the like.

Particular preference is given to carboxylic acid derivatives of formula VI, wherein n is 1 and A is unsubstituted or substituted cyclopropyl. When n is 0, preference is given to carboxylic acid derivatives of the formula VIA in which A is cyclopropyl which may have from 1 to 3 of, for example, chlorine and / or C ₁ -C ₃ -alkyl groups. The chlorinated cyclopropyl preferably has two chlorine atoms in the gem position in the cyclopropane ring.

Formula V may be prepared by reacting with amine XIII starting from the corresponding carboxylic acid XIIa (reference “Houben-Weyl” is described by Houben-Weyl, Methoden der Organischen Chemie, 4th Edition, Thieme Verlag, Stuttgart) As a guide).

R ¹³ -COOH

Carboxylic acid XIIa is known from European Patent Publication No. 653 418.

Amine XIII is also generally known or can be obtained by known methods (see International Publication No. 95/23 784).

The reaction is preferably carried out by initially converting carboxylic acid XIIa to a carboxyl-activated derivative XII, in particular to acyl halide, eg acyl chloride, acyl cyanide or acyl anhydride (Tetrahedron Letters , Volume 18, page 1595-1598 (1973) or Houben-Weyl, Volume 15/1, pages 28-32). This derivative XII is then reacted with amine XIII in the presence of a base.

For example, it is suitable to react the carboxylic acid XIIa with diethyl cyanophosphonate, in particular to prepare acyl cyanide in an inert solvent such as tetrahydrofuran, toluene or dichloromethane.

To prepare the carboxyl-activated anhydride, it is preferred to react the carboxylic acid XIIa with chloroformate such as isobutyl chloroformate in the presence of a base, if appropriate in an inert solvent such as toluene or tetrahydrofuran.

The reaction of amine XIII with carboxyl-activated carboxylic acid XIIa is preferably carried out in a solvent such as dichloromethane, tetrahydrofuran or toluene.

In addition, amine XIII acts as a base itself, which is usually recovered from the crude product.

In a preferred embodiment of the process steps of the invention, reagents and bases suitable for the preparation of carboxyl-activated derivatives of carboxylic acid XIIa, amine XIII, carbamoyl carboxylic acid XII are, if appropriate, in situ in an inert solvent. Respond.

The reaction mixture obtained by the process of the invention is worked up by conventional methods of obtaining compound V, for example by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude product. Any desired product is obtained under reduced pressure in the form of a colorless or pale brown viscous oil which may be free of volatile components at moderately elevated temperatures. If the final product is obtained as a solid, purification may also be carried out, for example by recrystallization or dipping.             

Depending on the nature of the substituents, the compounds of formula V may exist in geometric and / or optical isomers or isomer mixtures. In particular, the carbon atoms of compound V having R ³ and R ⁴ groups may have an R or S configuration according to the IUPAC nomenclature. Both pure isomers and isomeric mixtures described herein have fungicidal activity.

In formula (V), the remainder of the molecule can be coordinated to exo or endo with respect to the R ¹³ radical. Both isomers and mixtures thereof have fungicidal activity in each case.

With respect to its biological action on harmful fungi, compounds V in which the carbon atoms having R ¹⁵ and R ¹⁶ have an R configuration are preferred.

Furthermore, preference is given to compounds V in which R ¹⁵ is hydrogen and R ¹⁶ is C ₁ -C ₄ -alkyl, in particular methyl.

Preference is furthermore given to compounds V in which Ar is optionally substituted phenyl, in particular substituted in 2-position or 2- and 4-position, especially in 4-position. Preferred single substituents in the 4-position are cyano, preferably methyl, especially halogen, in particular chlorine.

In addition, a compound V in which R ¹³ is unsubstituted or substituted bicycloalkyl having 6 to 10 carbon atoms is preferable.

Furthermore, preference is given to compounds V in which R ¹³ is unsubstituted or substituted bicycloalkenyl having 7 to 10 carbon atoms.

Particularly preferred for their use are the compounds disclosed in Tables 1-29 of WO97 / 35838.

In the definitions of the compounds of the formulas I, IV and V given at the outset, collective terms are generally used which represent the following groups.

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: straight or branched chain alkyl groups of 1 to 4, 6 or 10 carbon atoms, for example C ₁ -C ₆ -alkyl (eg methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl , 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 or branched chain alkyl groups of 1 to 6 carbon atoms (some or all of the hydrogen atoms of these groups may be replaced by halogen atoms as described above), for example C ₁ -C ₂ -haloalkyl (eg For example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2 -Fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl);

C ₁ -C ₄ -alkoxy and alkoxy residues of C ₁ -C ₄ -alkoxycarbonyl: methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy And 1,1-dimethylethoxy;

C ₁ -C ₄ -haloalkoxy: the above-mentioned C ₁ -C ₄ -alkoxy radicals partially or completely substituted with fluorine, chlorine, bromine and / or iodine (eg fluoromethoxy, difluoromethoxy , Trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2,2-difluoro Roethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoro Loethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bro Morphopoxy, 3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy, 3,3,3-trifluoropropoxy , 3,3,3-trichloropropoxy, 2,2,3,3, 3-pentafluoropropoxy, heptafluoropropoxy, 1- (fluoromethyl) -2-fluoroethoxy, 1- (chloromethyl) -2-chloroethoxy, 1- (bromomethyl)- 2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and nonafluorobutoxy);

Cycloalkyl: a monocyclic alkyl group having 3 to 6 carbon ring members (eg cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl);

Alkenyl: straight or branched chain alkenyl groups having 2 to 6 or 10 carbon atoms and having a double bond in any position, for example C ₂ -C ₆ -alkenyl (eg 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-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl- 3-butenyl, 3-methyl-3-butenyl, 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-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, 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);

Alkynyl: straight or branched chain alkynyl groups having 2 to 10 carbon atoms and having triple bonds at any position, for example C ₂ -C ₆ -alkynyl (eg, ethynyl, 2-propynyl, 2 -Butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl , 2-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4 -Pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2- Dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl);

Heterocyclyl or heterocyclyloxy, heterocyclylthio and heterocyclylamino: containing one to three heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur, directly attached to the skeleton or by means of an oxygen atom ( Heterocyclyloxy) or a 3- to 6-membered saturated or partially unsaturated monocyclic or polycyclic heterocycle (e.g., bonded by a hetero atom (heterocyclylthio) or by a nitrogen atom (heterocyclylamino) For example, 2-tetrahydrofuranyl, oxiranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isooxa Zolidinyl, 4-isooxazolidinyl, 5-isooxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxa Ridinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazoli Din-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl , 1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4 -Triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,3-dihydrofur-4-yl, 2,3-di Hydrofur-5-yl, 2,5-dihydrofur-2-yl, 2,5-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothiene -3-yl, 2,3-dihydrothien-4-yl, 2,3-dihydrothien-5-yl, 2,5-dihydrothien-2-yl, 2,5-dihydrothiene-3 -Yl, 2,3-dihydropyrrole-2-yl, 2,3-dihydropyrrole-3-yl, 2,3-dihydropyrrole-4-yl, 2,3-dihydropyrrole-5-yl , 2,5-dihydropyrrole-2-yl, 2,5-dihydropyrrole-3-yl, 2,3-dihydroisoxazole-3- , 2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazole-4 -Yl, 4,5-dihydroisoxazol-5-yl, 2,5-dihydroisothiazol-3-yl, 2,5-dihydroisothiazol-4-yl, 2,5-dihydro Isothiazol-5-yl, 2,3-dihydroisopyrazol-3-yl, 2,3-dihydroisopyrazol-4-yl, 2,3-dihydroisopyrazol-5-yl, 4,5-dihydroisopyrazol-3-yl, 4,5-dihydroisopyrazol-4-yl, 4,5-dihydroisopyrazol-5-yl, 2,5-dihydroisopyra Zol-3-yl, 2,5-dihydroisopyrazol-4-yl, 2,5-dihydroisopyrazol-5-yl, 2,3-dihydrooxazol-3-yl, 2,3 -Dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 4,5-dihydrooxazol-3-yl, 4,5-dihydrooxazol-4-yl, 4 , 5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-3-yl, 2,5-dihydrooxazol-4-yl, 2,5-dihydrooxazol-5-yl , 2,3-dihydrothiazol-2-yl, 2,3- Dihydrothiazol-4-yl, 2,3-dihydrothiazol-5-yl, 4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazol-4-yl, 4, 5-dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl, 2,3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4,5-dihydroimidazol-2- 1,4,5-dihydroimidazol-4-yl, 4,5-dihydroimidazol-5-yl, 2,5-dihydroimidazol-2-yl, 2,5-dihydroimidazole- 4-yl, 2,5-dihydroimidazol-5-yl, 2-morpholinyl, 3-morpholinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-tetra Hydropyridazinyl, 4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetrahydropyrazinyl, 1,3,5- Tetrahydrotriazin-2-yl, 1,2,4-tetrahydrotriazin-3-yl, 1,3-dihydrate Oxazin-2-yl, 1,3-ditian-2-yl, 2-tetrahydropyranyl, 1,3-dioxolan-2-yl, 3,4,5,6-tetrahydropyridin-2- 1,4H-1,3-thiazin-2-yl, 4H-3,1-benzothiazin-2-yl, 1,1-dioxo-2,3,4,5-tetrahydrothiene-2- 1,2H-1,4-benzothiazin-3-yl, 2H-1,4-benzoxazin-3-yl, 1,3-dihydrooxazin-2-yl, 1,3-dithia-2 -Day);

Aryl or aryloxy, arylthio, arylcarbonyl and arylsulfonyl: bonded directly to the backbone or by an oxygen atom (-O-) (aryloxy) or by a sulfur atom (-S-) (arylthio) or Aromatic monocyclic or polycyclic hydrogen radicals (e.g., phenyl, naph) bound by a carbonyl group (-CO-) (arylcarbonyl) or by a sulfonyl group (-SO _2- ) (arylsulfonyl) Til and phenanthrenyl or phenyloxy, naphthyloxy and phenanthrenyloxy and the corresponding carbonyl and sulfonyl radicals);

Hetaryl or hetaryloxy, hetarylthio, hetarylcarbonyl and hetarylsulfonyl: in addition to carbon ring members, additionally 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 oxygen or 1 sulfur atom or 1 It may contain two oxygen or one sulfur atom and is directly attached to the skeleton or by oxygen atom (-O-) (hetaryloxy) or by sulfur atom (-S-) (hetarylthio) by a carbonyl group (-CO-) (H. taril carbonyl) or a sulfonyl group (-SO ₂ -) by (Mtskheta rilsul sulfonyl) coupled aromatic monocyclic or polycyclic radicals, e.g.

5-membered heteroaryl containing 1 to 3 nitrogen atoms: 5-membered heteroaryl group which may contain 1 to 3 nitrogen atoms as ring members in addition to carbon atoms (eg 2-pyrrolyl, 3 -Pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-triazol-3-yl and 1,3,4- Triazol-2-yl);

5 membered heteroaryl containing 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom or 1 oxygen or 1 sulfur atom: 1 to 4 nitrogens as ring members in addition to carbon atoms 5 membered heteroaryl groups (eg, 2-furyl, 3-furyl, 2-thienyl) which may contain atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom or 1 oxygen or sulfur atom , 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothia Zolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imi Dazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl , 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxa 2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl), and;

Benzo-fused 5 membered heteroaryl containing 1 to 3 nitrogen atoms or 1 nitrogen atom and / or 1 oxygen or sulfur atom: from 1 to 4 nitrogen atoms or from 1 to 4 as ring members in addition to carbon atoms It may contain three nitrogen atoms and one sulfur or oxygen atom or one oxygen or one sulfur atom and two adjacent carbon ring members or one nitrogen atom and one adjacent carbon ring member are buta-1,3 5-membered heteroaryl groups which may be crosslinked by diene-1,4-diyl groups;

5-membered heteroaryl bonded by nitrogen and containing 1 to 4 nitrogen atoms, or benzo-fused 5-membered heteroaryl bonded by nitrogen and containing 1 to 3 nitrogen atoms: ring in addition to carbon atoms As a circle, it may contain 1 to 4 nitrogen atoms and 1 to 3 nitrogen atoms, respectively, and two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member may be buta-1,3-diene-1, A 5 membered heteroaryl group which can be crosslinked by a 4-diyl group (these rings are bonded to the skeleton by one of the nitrogen ring members);

6-membered heteroaryl containing 1 to 3 nitrogen atoms and 1 to 4 nitrogen atoms each: 6 which may contain 1 to 3 nitrogen atoms and 1 to 4 nitrogen atoms, respectively, as ring members in addition to carbon atoms Circle heteroaryl groups (eg 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5 -Pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl and 1,2,4,5-tetrazin-3-yl )ego;

Benzo-fused 6 membered heteroaryl containing 1 to 4 nitrogen atoms: 6 membered hetero, wherein two adjacent carbon ring members can be crosslinked by buta-1,3-diene-1,4-diyl groups Aryl groups (eg, quinoline, isoquinoline, quinazoline and quinoxaline) and

Corresponding oxy, thio, carbonyl or sulfonyl groups;

Hetarylamino: aromatic monocyclic, which may contain, in addition to a carbon ring member, additionally 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 oxygen or 1 sulfur atom and bonded to the skeleton by a nitrogen atom Or polycyclic radicals.

Bicycloalkyl: Bicyclic alkyl groups having 6 to 15 carbon ring members (eg, bicyclo [2.1.1] hex-5-yl, bicyclo [2.2.1] -hept-2-yl, bicyclo [2.2.2] oct-2-yl, bicyclo [3.2.1] oct-6-yl, bicyclo [3.2.2] non-6-yl, bicyclo [4.2.2] dec-7-yl, Bicyclo [3.1.0] hex-1-yl, bicyclo [4.1.0] hept-1-yl, bicyclo [4.3.0] non-1-yl, bicyclo [4.4.0] dec-1- Is particularly preferably 5-methylbicyclo [2.1.1] hex-5-yl, 2-methylbicyclo [2.2.1] hept-2-yl, 2-methylbicyclo [2.2.2] oct -2-yl, 6-methylbicyclo [3.2.1] oct-6-yl, 6-methylbicyclo [3.2.2] non-6-yl, 7-methylbicyclo [4.2.2] dec-7 -Yl, 1-methylbicyclo [3.1.0] hex-1-yl, 1-methylbicyclo [4.1.0] hept-1-yl, 1-methylbicyclo [4.3.0] non-1-yl , 1-methylbicyclo [4.4.0] dec-1-yl, 2-methylbicyclo [3.1.0] hex-1-yl, 2-methylbicyclo [4.1.0] hept-1-yl, 2 -Methylbicyclo [4.3.0] non-1-yl, 2-methyl ratio Chloride [4.4.0] des-yl, adamantyl), and;

Bicycloalkenyl: Bicyclic alkenyl groups having 7 to 15 carbon ring members (eg, bicyclo [2.2.1] hept-2-en-5-yl, bicyclo [2.2.2] oct-2 -En-5-yl, bicyclo [4.2.2] dec-7-en-2-yl, bicyclo [4.3.0] non-7-en-1-yl, bicyclo [4.4.0] des- 3-en-1-yl, bicyclo [4.1.0] hept-3-en-1-yl, 5-methylbicyclo [2.2.1] hept-2-en-5-yl, 5-methylbicyclo [2.2.2] oct-2-en-5-yl, 2-methylbicyclo [4.2.2] des-7-en-2-yl, 2-methylbicyclo [4.3.0] non-7-ene -1-yl, 2-methylbicyclo [4.4.0] dec-3-en-1-yl, 2-methylbicyclo [4.1.0] hept-3-en-1-yl)

Alkylidenes: straight or branched chain alkylidene groups having 3 to 5 carbon atoms (eg 1,3-propylidene, 1,4-butylidene, 1-methyl-1,3-propylidene, 2 -Methyl-1,3-propylidene, 2,2-dimethyl-1,3-propylidene, 1,5-pentylidene, 1-methyl-1,4-butylidene);

Cycloalkenyl: Monocyclic alkyl groups having from 5 to 7 carbon rings and having at least one double bond, for example C ₅ -C ₇ -cycloalkenyl (eg cyclopentenyl, cyclohex Cenyl and cycloheptenyl);

Heterocyclyl: A 3-6 membered saturated or partially unsaturated mono- or polycyclic heterocycle containing 1 to 3 heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur and bonded to its backbone (eg For example, 2-tetrahydrofuranyl, oxiranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazoli Diyl, 4-isoxazolidinyl, 5-isooxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5 -Pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4- Imidazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4- Adiazolidin-5-yl, 1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidine-2 -Yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,3-dihydro-fur- 4-yl, 2,3-dihydro-fur-5-yl, 2,5-dihydro-fur-2-yl, 2,5-dihydro-fur-3-yl, 2,3-dihydrothiene -2-yl, 2,3-dihydrothien-3-yl, 2,3-dihydrothien-4-yl, 2,3-dihydrothien-5-yl, 2,5-dihydrothien-2 -Yl, 2,5-dihydrothien-3-yl, 2,3-dihydropyrrole-2-yl, 2,3-dihydropyrrole-3-yl, 2,3-dihydropyrrole-4-yl , 2,3-dihydropyrrole-5-yl, 2,5-dihydropyrrole-2-yl, 2,5-dihydropyrrole-3-yl, 2,3-dihydroisoxazol-3-yl, 2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4- 1,4,5-dihydroisoxazol-5-yl, 2,5-dihydroisothiazol-3-yl, 2,5-dihydroiso Thiazol-4-yl, 2,5-dihydroisothiazol-5-yl, 2,3-dihydroisopyrazol-3-yl, 2,3-dihydroisopyrazol-4-yl, 2 , 3-dihydroisopyrazol-5-yl, 4,5-dihydroisopyrazol-3-yl, 4,5-dihydroisopyrazol-4-yl, 4,5-dihydroisopyrazole -5-yl, 2,5-dihydroisopyrazol-3-yl, 2,5-dihydroisopyrazol-4-yl, 2,5-dihydroisopyrazol-5-yl, 2,3 -Dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 4,5-dihydrooxazol-3-yl, 4 , 5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-3-yl, 2,5-dihydrooxazol-4-yl , 2,5-dihydrooxazol-5-yl, 2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl, 2,3-dihydrothiazole-5 -Yl, 4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazol-4-yl, 4,5-dihydrothiazol-5-yl, 2,5-dihydrothiazole -2-yl, 2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl, 2,3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4,5-dihydroimidazol-2- 1,4,5-dihydroimidazol-4-yl, 4,5-dihydroimidazol-5-yl, 2,5-dihydroimidazol-2-yl, 2,5-dihydroimidazole- 4-yl, 2,5-dihydroimidazol-5-yl, 2-morpholinyl, 3-morpholinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-tetra Hydropyridazinyl, 4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-tetrapyridpyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetrahydropyrazinyl, 1,3,5 Tetrahydrotriazin-2-yl, 1,2,4-tetrahydrotriazin-3-yl, 1,3-dihydrooxazin-2-yl, 1,3-ditian-2-yl, 2 Tetrahydropyranyl, 1,3-dioxolan-2-yl, 3,4,5,6-tetrahydropyridin-2-yl, 4H-1,3-thiazin-2-yl, 4H-3, 1-benzothiazin-2-yl, 1,1-dioxo-2,3,4,5-tetrahydrothien-2-yl, 2H-1,4-benzo Thiazin-3-yl, 2H-1,4-benzooxazin-3-yl, 1,3-dihydrooxazin-2-yl, 1,3-ditian-2-yl).

The description “partially or fully halogenated” is intended to indicate that some or all of the hydrogen atoms of the groups so characterized may be replaced with the same or different halogen atoms as described above.

When preparing the mixture, it is preferable to use the compounds of the formula I and the formulas II to V pure active ingredients, together with further addition to harmful fungi or other pests (for example insects, arthropods or nematodes). The active ingredient or else herbicidal or growth-regulating active ingredient or fertilizer can be mixed.

A mixture of compounds with formula (II) to at least one compound of the compound of formula (V) of formula (I) at the same time, that is united or may be applied separately, a wide range of phytopathogenic fungi, in particular ascorbyl fine test (Ascomycetes), Bridge video fine test ( It shows excellent action against phytopathogenic fungi of the class of Basidiomycetes , Phycomycetes and Deuteromycetes . Some of these act systemically and are therefore also suitable for use as leaf- and soil-acting fungicides.

These include cotton, vegetable species (e.g. cucumbers, beans, tomatoes, potatoes and calabash), barley, grass, oats, bananas, coffee, corn, fruit species, rice, rye, soybeans, grapevines, wheat, decorative plants, It is particularly important for controlling a large number of fungi in various crops such as sugar cane and various seeds.

They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery powdery mildew) on grains , Erysiphe cichoracearum and calabash Sphaerotheca fuliginea , Podosphaera leucotricha of apples, Unchinula necator of grapevines , Puccinia species of grains, and lizarthonia of cotton, rice and grass Rhizoctonia species, Ustilago species of cereals and sugar cane, Venturia inaequalis (spot disease) of apples, Helminthosporium species of cereals and rice, Septoria nordo of wheat Room ( Septoria nodorum ), Botrytis cinera (gray mold) of strawberries, vegetables, ornamental plants and grapevines, groundnut chercospora arachidola ( Cercospora arachidicola), shoe conductor Le courses included Pasteurella Herzegovina wheat and barley Portree Koh Death (Pseudocercosporella herpotrichoides), rice and (Pyricularia oryzae) on flutes Kula Leah Duck sleeping in the grass, blood, potatoes and tomatoes Saratov Torah inpe Afghanistan's (Phytophthora infestans ), Plasmopara viticola of grapevines , Pseudoperonospora species of hops and cucumbers, Alternaria species of vegetables and fruits, and Mycosphaerella species of bananas and Fusarium (Fusarium) and Verbier tichil Leeum (Verticillium) species.

The mixture according to the invention can be used particularly preferably for controlling Pyricularia oryzae .

One or more of the compounds of formula (I) and compounds of formulas (II) to (V) may be applied together or separately simultaneously or sequentially, in the case of separate applications the order generally does not have any effect on the control results.

Depending on the nature of the effect desired, the application rate of the mixtures according to the invention is, in particular in crops, from 0.01 to 8 kg / ha, preferably from 0.1 to 5 kg / ha, in particular from 0.5 to 3.0 kg / ha.

In the case of compounds of formula (I), the application rate is from 0.01 to 2.5 kg / ha, preferably from 0.05 to 2.5 kg / ha, in particular from 0.1 to 1.0 kg / ha.

Correspondingly, for compounds of the formulas (II) to (V), the application rate is from 0.001 to 5 kg / ha, preferably from 0.005 to 2 kg / ha, in particular from 0.01 to 1.0 kg / ha.

In the case of seed treatment, the application rate of the mixture is generally from 0.001 to 250 g / kg (seed), preferably from 0.01 to 100 g / kg, in particular from 0.01 to 50 g / kg.

In the case of controlling phytopathogenic harmful fungi, one or more separate or combined applications of the compounds of formula (I) and compounds of formulas (II) to (V) may be used to seed, plant or soil before or after planting or before or after plant germination. Spray or spray on.

The fungicidal synergistic mixtures according to the invention are, for example, aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, powders, in the form of solutions, powders and suspensions which can be sprayed immediately or in concentrated form. It can be formulated in the form of spraying substances or granules and applied by spraying, spraying, spraying, spraying or spraying. The form of use depends on the intended purpose, in which case the distribution of the mixtures according to the invention should be as fine and uniform as possible.

The formulation is prepared in a known manner, for example by expanding the active ingredient with a solvent and / or carrier, using emulsifiers and dispersants, if desired. If the diluent used is water, it is also possible to use other organic solvents as auxiliary solvents. Suitable auxiliaries are essentially aromatic (eg xylenes), chlorinated aromatics (eg chlorobenzene), paraffins (eg mineral fractions), alcohols (eg methanol, butanol), ketones (eg Solvents such as, for example, cyclohexanone), amines (eg ethanolamine, dimethylformamide) and water; Carriers such as natural ground minerals (eg kaolin, clay, talc, chalk) and ground synthetic minerals (eg finely divided silica gel, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg, polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates); And dispersants such as lignosulphite waste liquor and methylcellulose.

Suitable surfactants include alkali metal salts, alkaline earth metal salts and ammonium salts and fatty acids, alkyl- and alkylaryl-sulfonates, alkyl, lauryl of aromatic sulfonic acids such as ligno-, phenol-, naphthalene- and dibutylnaphthalene-sulfonic acid. Alkali metal salts, alkaline earth metal salts and ammonium salts of ethers and fatty alcohol sulfates and salts of sulfated hexa-, hepta- and octa-decanol, or salts of fatty alcohol glycol ethers, sulfated naphthalenes and derivatives thereof Salts of formaldehyde condensates, salts of condensates of naphthalene or naphthalenesulfonic acid with phenols and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl-, octyl- or nonyl-phenols, alkylphenol polyglycol ethers, tributylphenyl Polyglycol Ether, Alkylaryl Polyether Alcohol, Isotridecyl Alcohol, Fatty Alcohol Ethylene Oxide Condensate, Ethoxylation Castor oil, polyoxyethylene alkyl ether or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol ester, lignosulphite waste liquor or methylcellulose.

Powders, spargers and powders are mixed or pulverized with at least one of the compounds of formula (I) and (II) to (V) or a mixture of compounds of formula (I) and at least one of compounds (II) to (V) with a solid carrier It can manufacture by doing.

Granules (eg coated granules, impregnated granules or homogeneous granules) are generally prepared by binding the active ingredient or active ingredients to a solid carrier.

Fillers or solid carriers are, for example, mineral earth (e.g., silica gel, silicic acid, silica gels, silicates, talc, kaolin, limestone, lime, chalk, church clay, ocher, clay, dolomite, diatomaceous earth, calcium sulfate) , Magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers (eg ammonium sulfate, ammonium phosphate, ammonium nitrate, urea), products of plant origin (eg grain flour, bark flour, wood flour and Nut shell powder), cellulose powder or other solid carriers.

The blend is generally from 0.1 to 95% by weight, preferably at least one of the compounds of formula (I) and at least one of the compounds of formulas (II) to (V) or a mixture of at least one of 0.5 to 90 weight percent. The active ingredient is used at a purity of 90% to 100%, preferably 95% to 100% (according to NMR or HPLC spectra).

Corresponding formulations are fungicidally effective amounts of the compounds of formula I in the case of a fungicidally effective amount of said mixture or separate application of harmful fungi, their breeding grounds or plants, seeds, soil, ground, substances or spaces to which harmful fungi are to be removed, and It is applied by treating with one or more of the compounds of the formulas (II) to (V).

Application can be done before or after infection with harmful fungi.

Examples of such formulations comprising the active ingredient are as follows.

I. A solution of 90 parts by weight of active ingredient and 10 parts by weight of N-methylpyrrolidone; This solution is suitable for use in the form of microdroplets.

II. 20 parts by weight of the active ingredient, 80 parts by weight of xylene, 8 to 10 moles of ethylene oxide and 1 part of an adduct of 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonate, 40 moles of ethylene oxide, A mixture of 5 parts by weight of an adduct of 1 mole of castor oil; The solution is finely dispersed in water to obtain a dispersion.

III. 20 parts by weight of the active ingredient, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an adduct of 40 moles of ethylene oxide and 1 mole of castor oil.

IV. An aqueous dispersion of 20 parts by weight of the active ingredient, 25 parts by weight of cyclohexanol, 65 parts by weight of mineral oil having a boiling point of 210 to 280 ° C. and 10 parts by weight of an adduct of 40 moles of ethylene oxide and 1 mole of castor oil.

V. 80 parts by weight of active ingredient, 3 parts by weight of sodium salt of diisobutylnaphthalene-1-sulfonic acid, 10 parts by weight of sodium salt of lignosulfonic acid from sulfite waste liquor and 7 parts by weight of finely divided silica gel hammer mill A mixture ground in the; This mixture is finely distributed in water to obtain a spray mixture.

VI. A homogeneous mixture of 3 parts by weight of the active ingredient and 97 parts by weight of finely divided kaolin; This powder contains 3% by weight of active ingredient.

VII. A homogeneous mixture of 30 parts by weight of the active ingredient, 92 parts by weight of finely divided silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of the silica gel; This formulation imparts good adhesion to the active ingredient.

VIII. 40 parts by weight of the active ingredient, 10 parts by weight of the sodium salt of the phenolsulfonic acid / urea / formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water, a stable aqueous dispersion; This dispersion may be diluted further.

IX. 20 parts by weight of active ingredient, 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of sodium salt of phenolsulfonic acid / urea / formaldehyde condensate and 88 parts by weight of paraffin mineral oil Dispersion.

The synergistic activity of the mixtures according to the invention can be demonstrated by the following experiment.

The active ingredients are separately or together formulated as 10% emulsions in a mixture of 63% cyclohexanone and 27% by weight emulsifier and correspondingly diluted with water to the desired concentration.

The evaluation is performed by determining the infected leaf area as a percentage. This percentage is converted into efficacy. Efficacy (W) is calculated as follows using Abbot's formula.

Where

α corresponds to the percentage of fungal infections of treated plants,

β corresponds to the percentage of fungal infections of untreated (control) plants.

An efficacy of zero means that the infection level of the treated plant corresponds to that of an untreated control plant, while an efficacy of 100 means that the treated plant is not infected.

The expected potency of the mixture of active ingredients was determined using the following Colby's formula (Weeds 15 , 20-22 (1967) by Colby) and compared with the observed potency.

Where

E is the expected potency expressed as a percentage of untreated control when using a mixture of active ingredients A and B at concentrations a and b,

x is the efficacy expressed as percent of untreated control when active ingredient A at concentration a is used,

y is the efficacy expressed as percentage of untreated control when using active ingredient B at concentration b.

Use Example 1 Activity against Pyricularia oryzae (prophylactic)

To the leaves of the potted rice seedling variety "Tai-Nong 67", sprayed with an aqueous formulation of the active ingredient prepared from the mother liquor comprising 10% active ingredient, 63% cyclohexanone and 27% emulsifier Let it flow down. The next day, the plants were inoculated with an aqueous spore suspension of Pycuraria Orissa. The test plants were then placed in a climate controlled chamber at 22-24 ° C. and 95-99% relative atmospheric humidity for 6 days. Then, the extent of infection of the leaves was visually determined.

The visually determined value for the percentage of diseased leaf area was converted into efficacy as a percentage of untreated control. Efficacy 0 means the same disease level as in the untreated control, and efficacy 100 means 0% disease. The expected efficacy of the active ingredient combination was determined using Colby's formula ("Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, pp.20-22, 1967) and compared with the observed efficacy. It was.

The following compound of formula I 'was used as component a):

The results of the experiments are shown in Tables 2 and 3 below:

Example Active ingredient Concentration (ppm) Efficacy (% of untreated control) 1C none (Disease 100%) 0 2C Compound of formula (I ') 2.0 0.5 20 0 3C Compound of formula II 2.0 0.5 20 0

Example Mixture according to the invention (concentration, ppm) Observed efficacy Calculated Efficacy ^* 4 I '2ppm + II 2ppm 99 36 5 I '0.5 ppm + II 0.5 ppm 25 0 ^* Calculated using Colby's formula

The test results showed that the observed efficacy was higher than previously calculated efficacy using Colby's equation at all mixing ratios.

Claims (5)

A fungicidal mixture for crop protection comprising as an active ingredient a) a phenylacetic acid derivative of formula (I) or a salt thereof and b) at least one of the compounds of formulas (II) and (III) in a synergistically effective amount. <Formula I>

Where X is NOCH ₃ or CHOCH ₃ , Y is O or NR, R ¹ and R are each independently of the other hydrogen or C ₁ -C ₄ -alkyl, R ² is cyano, nitro, trifluoromethyl, halogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy, m is 0, R ³ to R ⁶ are C ₁ -C ₄ alkyl or C ₃ -C ₆ cycloalkyl. <Formula II>

<Formula III>

The composition of claim 1 comprising two parts consisting of one part comprising a compound of formula (I) in a solid or liquid carrier and the other part comprising one or more of the compounds of formula (II) and (III) in a solid or liquid carrier. Fungicidal mixture. Treating the fungi, their breeding grounds or substances, plants, seeds, soil, ground or spaces which are to be prevented from fungal attack with a fungicidal mixture as claimed in claim 1, or a compound of formula (I), and A process for controlling harmful fungi, wherein the application of one or more of the compounds of formula (II) and (III) is carried out together or separately simultaneously or sequentially. The process according to claim 3, wherein the harmful fungi, their breeding grounds or the plants, seeds, soils, ground, substances or spaces to which the harmful fungi are to be removed are treated with 0.005 to 1 kg / ha of the compound of formula (I) as described in claim 1. Way. 4. The method of claim 3, wherein the plant, seed, soil, ground, material or space for which harmful fungi, their breeding grounds or harmful fungi are to be removed, is at least 0.01 to 0.01 of the compounds of formulas II and III described in claim 1. Process at 1 kg / ha.