WO1995023785A1

WO1995023785A1 - Carbamoyl carboxylic acid amides, process for producing them and their use as fungicides

Info

Publication number: WO1995023785A1
Application number: PCT/EP1995/000602
Authority: WO
Inventors: Oliver Wagner; Thomas Müller; Karl Eicken; Albrecht Harreus; Eberhard Ammermann; Gisela Lorenz; Frank Wetterich
Original assignee: Basf Aktiengesellschaft
Priority date: 1994-03-03
Filing date: 1995-02-20
Publication date: 1995-09-08
Also published as: AU1810595A

Abstract

Carbamoyl carboxylic acid amides of general formula (I) and their salts, in which the variables have the following means: R<1> - possibly substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heteroaryl or a possibly substituted non-aromatic carbo or hetero cycle; W<1>W<2>C=N-, in which W<1> is a possibly substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heteroaryl and W<2> is hydrogen or W<1>; R<2> - hydrogen or possibly halogenated alkyl or cycloalkyl; R<3> - possibly substituted alkyl, cycloalkyl or phenylalkyl; R<4> - hydrogen or a radical R<3>; or R<3> and R<4> together with the C atom to which they are bound are a possibly substituted saturated carbo or hetero cycle; R<5> - a radical R<2>; X - mutually independently hydrogen or possibly substituted alkyl or alkenyl; m - 0, 1, 2; A - possibly substituted cycloalkyl or cycloalkenyl; R<6> - possibly substituted aryl or heteroaryl; and agents containing them, process for their production and their use as fungicides.

Description

CARBAMOYL CARBONIC ACID AMIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES

description

The present invention relates to carbamoylcarboxamides of the general formula I.

and their salts, in which the variables have the following meaning:

R ^{1 is} C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl or C ₂ -C ₈ alkynyl, these

Residues can be partially or completely halogenated and / or can carry one to three of the following groups: cyano,

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, C ₃ -C ₇ cycloalkyl, C ₃ -C ₇ cycloalkenyl, aryl, aryloxy and

Heteroaryl, where the cyclic radicals themselves can carry one to three of the following substituents: 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,

C ₃ -C ₇ cycloalkyl or C ₃ -C ₇ cycloalkenyl, these radicals being partially or completely halogenated and / or carrying one to three of the following groups: 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 aryl- (C ₁ -C ₄ ) alkyl, the cyclic groups being one to three of the following substituents can wear: 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 and aryloxy, a non-aromatic 4- to 8-membered ring, which as ring members may contain one or two of the heteroatoms oxygen, sulfur and nitrogen in addition to carbon , wherein the carbon atoms in the ring are one or two of the can carry the following groups: 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 and aryloxy and wherein the second and each further nitrogen atom as a hetero atom in the ring carries hydrogen or a C ₁ -C ₄ alkyl group ,

Aryl or heteroaryl, where these radicals can carry one to three of the following groups: 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, in which the cyclic substituents in turn can carry one to three of the following substituents: 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 and C ₁ - C ₄ alkoxycarbonyl,

W ¹ W ² C = N-, where W ^{1 is} C ₁ -C ₈ -alkyl, which can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, 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, aryl, aryloxy and heteroaryl, where the cyclic groups in turn can carry one to three of the following substituents: 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,

C ₂ -C ₈ alkenyl or C ₂ -C ₈ alkynyl, these radicals being partially or completely halogenated and / or carrying one to three of the following groups: 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 and aryloxy, where the cyclic groups in turn can carry one to three of the following substituents:

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 and aryloxy, C ₃ -C ₇ cycloalkyl or C ₃ -C ₇ cycloalkenyl, where these radicals can carry one to three of the following groups: 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 and aryl- (C ₁ -C ₄ ) alkyl, where the groups containing aryl can carry one to three of the following substituents: 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 and aryloxy,

C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkoxycarbonyl, aryl and aryloxy and W ² hydrogen or one of the groups W ¹ ;

R ^{2 is} hydrogen or C ₁ -C ₈ alkyl or C ₃ -C ₇ cycloalkyl, which can be partially or completely halogenated; R ^{3 is} C ₁ -C ₈ alkyl, C ₃ -C ₇ cycloalkyl, where these radicals can carry one to three of the following groups: 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 and

C ₁ -C ₄ alkoxycarbonyl or phenyl- (C ₁ -C ₄ ) alkyl, where the phenyl radical can carry one to three of the following groups:

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 and aryloxy; R ^{4 is} hydrogen or one of the groups mentioned for R ³ or

R ³ and R ⁴ together with the carbon atom to which they are attached

a 4- to 8-membered ring, which can contain one or two of the heteroatoms oxygen, sulfur and nitrogen in addition to carbon as ring members, wherein the carbon atoms in the ring can carry one or two of the following groups: 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 and aryloxy and where nitrogen as a hetero atom is hydrogen or a

C ₁ -C ₄ alkyl group;

R ^{5 is} a radical R ² ; X independently of one another hydrogen, C ₁ -C ₈ alkyl and / or

C ₂ -C ₈ alkenyl, these radicals being partially or completely halogenated and / or bearing one to three of the following groups: cyano, 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 and

C ₁ -C ₄ alkoxycarbonyl, aryl and aryloxy, C ₃ -C ₇ cycloalkyl and / or C ₃ -C ₇ cycloalkenyl, these radicals being partially or completely halogenated and / or carrying one to three of the following groups: 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 aryl- (C ₁ -C ₄ ) alkyl, where the cyclic groups can in turn carry one to three of the following substituents: 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 and aryloxy; m 0, 1, 2; AC ₃ -C ₇ cycloalkyl or C ₃ -C ₇ cycloalkenyl, these radicals being partially or completely halogenated and / or bearing one to three of the following groups: 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 and aryl- (C ₁ -C ₄ ) alkyl, where in the groups which contain aryl this may be unsubstituted or can carry one to three of the following substituents: 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 and aryloxy;

R ⁶ aryl or heteroaryl, these radicals one to three of

can carry the following groups: 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 and aryloxy, where in the groups containing aryl this can carry one to three of the following substituents: 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.

In addition, the invention relates to processes for the preparation of the compounds I, compositions containing them, a process for the production of such compositions and a process for controlling harmful fungi and the use of the compounds I therefor.

Amino acid amides with fungicidal activity are known from the literature (cf. EP-A-0 398 072, EP-A-0 425 925, EP-A-0 472 996, EP-A-0 477 639, EP-A-0 485 794, EP-A-0 493 683, EP-A-0 496 239, EP-A-0 550 788, EP-A-0 554 729), which, however, are not yet satisfactory with regard to their fungicidal activity. The present invention was therefore based on new carbamoylcarboxamides with improved activity against harmful fungi. Accordingly, the compounds I defined at the outset and agents containing them were found.

Furthermore, processes for the preparation of the compounds I and the compositions comprising them were found, and furthermore a process for combating harmful fungi and the use of the

Connections I to this.

The compounds I can be prepared in a manner known per se starting from the corresponding carbamoylcarboxylic acids II. Compounds I are preferably obtained by processes A and B (the literature citations described below)

"Houben-Weyl" refer to: Houben-Weyl, Methods of Organic Chemistry, 4th edition, Thieme Verlag, Stuttgart). Procedure A

The carbamoylcarboxamides I are obtained by reacting the carbamoylcarboxylic acids II with the amines III.

The carbamoylcarboxylic acids II are known or can be prepared by known methods, especially starting from the underlying amino acids (cf. "Houben-Weyl", volume 15/1, page 46 to page 305, especially page 117 to page 125).

The amines III are also known or can easily be obtained (cf. Organikum, VEB Deutscher Verlag der Wissenschaften, 15th edition, Berlin, 1977, page 610 ff .; Indian J. Chem. 10, page 366 (1972), Tetrahedron 43 , Pages 4071 ff. (1987); J. Med. Pharm. Chem. 5, pages 1243 ff. (1962); US-A-4 126 613). Process A is preferably carried out in such a way that carbamoylcarboxylic acids II are first activated in carboxy

Derivatives, especially in acyl cyanides or anhydrides, are converted (cf. Tetrahedron Letters, volume 18, page 1595 to page 1598 (1973) or "Houben-Weyl", volume 15/1, page 28 to page 32). These derivatives are then reacted with the amines III in the presence of bases.

For the production of the carboxy-activated acyl cyanides e.g. the reaction of carbamoylcarboxylic acids II with diethyl cyanophosphonate, especially in an inert solvent such as tetrahydrofuran or toluene.

To prepare the carboxy-activated anhydrides, the reaction of the carbamoylcarboxylic acid II with carbonic acid chlorides such as isobutyl chloroformate in the presence of bases and, if appropriate, in an inert solvent such as toluene or tetrahydrofuran is preferred. The reaction of the amines III with the carboxy-activated carbamoylcarboxylic acids II is preferably carried out in a solvent such as dichloromethane, tetrahydrofuran or toluene.

In particular, the amines III themselves can serve as bases, usually being recovered from the crude product.

In a preferred embodiment of this process step, the carbamoylcarboxylic acid II, the amine III, the reagent suitable for producing the caboxy-activated derivative of carbamoylcarboxylic acid II and the base are reacted in a one-pot process, if appropriate in an inert solvent, and the crude product is then reacted in a manner known per se on the

Carbamoylcarboxamide I worked up. Procedure B

The carbamoylcarboxamides I are obtained by using the

Carbamoylcarboxamides I, in which the group R ^1- O- (CO) stands for a protective group which can be split off in a manner known per se, are converted into amino acid amides IV and reacted with chloroformyloximes V in the presence of bases. Stage Ba: preparation of the amino acid amides IV

The group R ¹ -O- (CO) can be split off from the carbamoylcarboxamides I in a manner known per se (cf. "Houben-Weyl", volume 15/1, page 46 to page 305, especially page 126 to page 129).

Suitable cleavable groups contain a tert-butyl group as well as the benzyl group as radical R ¹ .

In the case of R ¹ = tert-butyl, for example, the cleavage usually takes place by reaction with an acid, in particular a protonic acid such as, for example, hydrochloric acid or trifluoroacetic acid (ibid., Page 126 to page 129).

The carbamoylcarboxamides I suitable as starting materials can be obtained by known processes (cf. "Houben-Weyl", volume 15/1, page 28 to page 32) or in particular by process A according to the invention.

Step Bb: Preparation of the carbamoylcarboxamides I

The amino acid amides IV resulting from the synthesis stage (Ba) are reacted with the chloroformyloximes V in the presence of bases.

The chloroformyl oximes V are known or can be prepared by known processes, e.g. by phosgenation of oximes (see e.g. Zeitschrift für Chemie, Volume 9, page 344 to page 345 (1967)).

The reaction is preferably carried out in an organic solvent, especially toluene, methylene chloride or tetrahydrofuran, or mixtures of these solvents.

Inorganic and organic bases are equally suitable as bases, with organic bases and in turn tertiary amines such as triethylamine, pyridine and N-methylpiperidine being preferred.

The reaction is usually carried out at temperatures from (-40) to 50, preferably (-10) to 20 ° C.

In addition, the implementation of this reaction is familiar to the person skilled in the art, so that no further explanations are required (cf. "Houben-Weyl", volume 15/1, page 117 to page 125, or Dev. Endocrinol., 13 (Neurohypophyseal Pept Horm. Other Biol. Act. Pept.), Page 37 to page 47 (1981)). The reaction mixtures obtained by processes A and B are worked up in a conventional manner, for example by mixing with water, separating the phases and, if appropriate, purifying the crude products by chromatography. The intermediate and end products are partly in the form of colorless or slightly brownish, viscous oils, which can be freed from volatile components under reduced pressure and at a moderately elevated temperature. If the

Intermediate and end products are obtained as solids, the cleaning can also be carried out, for example, by recrystallization or digesting.

Depending on the nature of the substituents, the compounds of the formula I can optionally be in the form of geometric and / or optical isomers or isomer mixtures. Both the pure isomers and the mixtures of the isomers have the fungicidal activity.

Also part of the invention are the salts, especially of acid-resistant compounds I, which contain basic centers, especially basic nitrogen atoms, in particular with mineral acids such as sulfuric acid and phosphoric acid or Lewis acids such as zinc chloride. Usually, the type of salt is not important. For the purposes of the invention, preference is given to salts which do not damage the plants, surfaces, materials or spaces to be kept free from harmful fungi and which do not impair the action of the compounds I.

The salts of the compounds I are accessible in a manner known per se, above all by reacting the corresponding carbamoylcarboxamides I with the acids mentioned in water or an inert organic solvent at temperatures from -80 to 120 ° C., preferably 0 to 60 ° C.

The production of the salts is generally independent of the pressure, which is why one works primarily at atmospheric pressure.

In the definition of compounds I given at the outset, collective terms were used which represent the following substituents:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: straight-chain or branched alkyl groups with 1 to 8 carbon atoms, for example C ₁ -C ₆ -alkyl such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl,

1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl,

2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1- Ethyl butyl, 2-ethyl butyl, 1,1,2-trimethyl propyl, 1,2,2-trimethyl propyl, 1-ethyl-1-methyl propyl and 1-ethyl-2-methyl propyl;

Haloalkyl or partially or fully halogenated alkyl: straight-chain or branched alkyl groups having 1 to 4 or 8 carbon atoms (as mentioned above), in which the hydrogen atoms can be partially or completely replaced by halogen atoms (as mentioned above), e.g.

C ₁ -C ₂ haloalkyl such as 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; Alkoxy: straight-chain or branched alkoxy groups with 1 to 4 carbon atoms, for example C ₁ -C ₃ -alkoxy such as methyloxy, ethyloxy, propylσxy and 1-methylethyloxy;

Alkoxyalkyl: straight-chain or branched alkyl groups with 1 to 8 carbon atoms (as mentioned above), which in any position carry a straight-chain or branched alkoxy group (as mentioned above) with 1 to 4 carbon atoms in the case of C ₁ -C ₄ -alkoxyalkyl, such as Methoxymethyl, ethoxymethyl, n-propoxymethyl, n-butoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1-ethoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl and 2-butoxyethyl;

Haloalkoxy: straight-chain or branched alkoxy groups with 1 to 4 carbon atoms (as mentioned above), in which the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms (as mentioned above), for example C ₁ -C ₂ -haloalkoxy such as chloromethyloxy, dichloromethyloxy, Trichloromethyloxy, fluoromethyloxy, difluoromethyloxy, trifluoromethyloxy, chlorofluoromethyloxy, dichlorofluoromethyloxy, chlorodifluoromethyloxy, 1-fluoroethyloxy, 2-fluoroethyloxy, 2,2-difluoroethyloxy, 2,2,2-trifluoroethyloxy, 2-chloro-2-fluoroethyloxy,

2-chloro-2,2-difluoroethyloxy, 2,2-dichloro-2-fluoroethyloxy,

2,2,2-trichloroethyloxy and pentafluoroethyloxy;

Alkylthio: straight-chain or branched alkyl groups with 1 to 4 carbon atoms (as mentioned above) which are bonded to the skeleton via a sulfur atom (-S-), for example C ₁ -C ₄ -alkyl thio such as methylthio, ethylthio, propylthio, 1-methylethylthio, n-butylthio and tert-butylthio;

Alkoxycarbonyl: straight-chain or branched alkoxy groups with 1 to 4 carbon atoms (as mentioned above), which have a

Carbonyl group (-CO-) are attached to the skeleton;

Alkenyl: straight-chain or branched alkenyl groups with 2 to 8 carbon atoms and a double bond 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-methyl2-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl1-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, l-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-3butenyl, 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-chain or branched alkynyl groups with 2 to 8 carbon atoms and a triple bond 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-1methyl-2-propynyl; Cycloalkyl: monocyclic alkyl groups with 3 to 7 carbon ring members, for example C ₃ -C ₇ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl;

Cycloalkenyl: monocyclic alkyl groups with 5 to 7 carbon ring members which contain one or more double bonds, for example C ₅ -C ₇ -cycloalkenyl such as cyclopentenyl, cyclohexenyl and cycloheptenyl; non-aromatic 4- to 8-membered rings which, as ring members, contain one or two oxygen,

Sulfur or nitrogen atoms contain, like saturated 5- or 6-membered rings with 1 or 2 nitrogen and / or oxygen atoms such as 3-tetrahydrofuranyl, 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 2-tetrahydropyranyl, 3 -Tetrahydropyranyl, 4-tetrahydropyranyl, 2-morpholinyl and 3-morpholinyl;

Aryl: monocyclic or polycyclic aromatic groups with 6 to 10 carbon atoms, such as phenyl and naphthyl; Arylalkyl: aryl groups (as mentioned above) which, in the case of aryl (C ₁ -C ₄ ) alkyl, are bonded to the skeleton via alkyl groups having 1 to 4 carbon atoms (as mentioned above), for example phenyl (C ₁ -C ₄ ) ₄ ) alkyl such as benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 1-phenylethyl, 1-phenylpropyl and 1-phenylbutyl;

Aryloxy: aryl groups (as mentioned above) which are bonded to the structure via an oxygen atom (-O-), such as phenoxy, 1-naphthoxy and 2-naphthoxy; Heteroaryl: aromatic mono- or polycyclic radicals which, in addition to carbon ring members, additionally 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and one oxygen or one

Can contain sulfur atom or an oxygen or a sulfur atom, e.g .: - 5-membered heteroaryl containing 1 to 3 nitrogen atoms:

5-ring heteroaryl groups which, in addition to carbon atoms, may contain 1 to 3 nitrogen atoms as ring members, e.g. 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 atom or oxygen atom or 1 oxygen or 1 sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom or May contain 1 oxygen or sulfur atom as ring members, for example 2-furyl, 3-furyl,

2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5- Pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 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-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1, 3,4-triazol-2-yl; - Benzo-condensed 5-membered heteroaryl, containing 1 to 3 nitrogen atoms or 1 nitrogen atom and / or an oxygen or sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain 1 to 4 nitrogen atoms or 1 to

3 nitrogen atoms can contain 1 sulfur or oxygen atom or 1 oxygen or a sulfur atom as ring members, and in which 2 adjacent carbon ring members or 1 nitrogen and 1 adjacent carbon ring member are bridged by a buta-1,3-diene-1,4-diyl group could be;

- 5-membered heteroaryl bonded via nitrogen, containing 1 to 4 nitrogen atoms, or 5-membered heteroaryl bonded via nitrogen-bonded, containing 1 to 4 nitrogen atoms

3 nitrogen atoms: 5-ring heteroaryl groups which, in addition to carbon atoms, can contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms as ring members, and in which 2 adjacent carbon ring members or one nitrogen and one adjacent carbon ring member by a butane

1,3-diene-1,4-diyl group can be bridged, these rings being bonded to the skeleton via one of the nitrogen ring members; - 6-membered heteroaryl containing 1 to 3 or 1 to

4 nitrogen atoms: 6-ring heteroaryl groups which, in addition to carbon atoms, may contain 1 to 3 or 1 to 4 nitrogen atoms as ring members, for example 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 ; - Benzo-fused 6-membered heteroaryl, containing 1 to 4 nitrogen atoms: 6-ring heteroaryl groups, in which 2 adjacent carbon ring members can be bridged by a buta-1,3-diene-1,4-diyl group, for example quinoline, isoquinoline, quinazoline and quinoxaline.

The expression "partially or fully halogenated" is intended to express that the hydrogen atoms in the groups characterized in this way can be replaced in part or in full by the same or different halogen atoms as mentioned above.

With regard to their biological action against harmful fungi, compounds I are preferred in which R ^{1 is} C ₁ -C ₆ -alkyl, which can carry one to three of the following groups: halogen, C ₁ -C ₄ -alkoxyalkyl, phenyl and phenoxy . Among these, particular preference is given to those compounds I in which R ^{1 is} C ₁ -C ₄ -alkyl or benzyl. Compounds I are further preferred in which R ^{1 is} C ₃ -C ₇ cycloalkyl, which can carry one to three of the following groups: halogen, C ₁ -C ₄ alkoxyalkyl, phenyl and phenoxy. Among these, particular preference is given to those compounds I in which R ^{1 represents} cyclopropyl, cyclopentyl or cyclohexyl.

In addition, compounds I are preferred in which R ^{1 is} aryl, which can carry one to three of the following groups: halogen, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy, especially in which R ^{1 is} phenyl or naphthyl, which may be unsubstituted and / or carry one to three of the following groups: fluorine, chlorine, bromine, C ₁ -C ₄ -alkyl, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso -Butyloxy, tert-butyloxy. Compounds I in which R ^{1 is} unsubstituted phenyl, 1-naphthyl or 2-naphthyl are very particularly preferred.

Furthermore, compounds I are preferred in which R ^{1 is}

(W ¹ W ² C = N-), where W ^{1 is} C ₁ -C ₈ alkyl, which can be partially or completely halogenated. In addition, compounds I are preferred in which R ^{1 is} (W ¹ W ² C = N-), where W ^{2 is} aryl which can carry one to three of the following groups: halogen, C ₁ -C ₄ alkyl and

C ₁ -C ₄ alkoxy. Compounds I in which R ^{2 is} hydrogen are also preferred. Furthermore, compounds I are preferred in which R ^{2 is}

C ₁ -C ₄ alkyl.

In addition, compounds I are preferred in which R ^{3 is} C ₁ -C ₆ alkyl, particularly preferably C ₁ -C ₄ alkyl.

Compounds I are further preferred in which R ^{3 is} C ₃ -C ₆ cycloalkyl, particularly preferably cyclopropyl, cyclopentyl or cyclohexyl.

In addition, compounds I are preferred in which R ^{4 represents} hydrogen.

In addition, compounds I are preferred in which R ^{4 is}

C ₁ -C ₈ alkyl, C ₁ -C ₄ alkyl being particularly preferred.

Also preferred are compounds I in which R ^{4 is} C ₃ -C ₆ cycloalkyl, especially cyclopropyl, cyclopentyl or cyclohexyl.

In addition, compounds I are preferred in which R ^{4 is} hydrogen.

Compounds I are further preferred in which R ^{3 is}

C ₁ -C ₆ alkyl and R ^{4 represents} hydrogen.

Furthermore, compounds I are preferred in which R ^{5 is} hydrogen. In addition, compounds I are preferred in which R ^{3 is}

C ₃ -C ₆ cycloalkyl and R ^{4 represents} hydrogen.

Compounds I in which R ^{5 is} C ₁ -C ₄ -alkyl are further preferred, methyl and ethyl being particularly preferred.

In addition, compounds I are preferred in which R ^{5 is}

C ₃ -C ₆ cycloalkyl, especially cyclopropyl.

Compounds I are further preferred in which the radicals X independently of one another denote hydrogen.

Compounds I are furthermore preferred in which the radicals X independently of one another are C ₁ -C ₆ -alkyl, in particular C ₁ -C ₄ -alkyl. In addition, compounds I are preferred in which the radicals X independently of one another are C ₃ -C ₆ -cycloalkyl, in particular cyclopropyl, cyclopentyl or cyclohexyl. Compounds I in which m is 0 or 1 are also preferred.

In addition, compounds I are preferred in which A is

C ₃ -C ₇ cycloalkyl, which can carry one to three of the following groups: halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl,

C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy and C ₁ -C ₄ alkylthio, preferably such substituted C ₃ -C ₇ cycloalkyl and especially unsubstituted cyclopropyl, cyclopentyl or cyclohexyl. Furthermore, compounds I are preferred in which A is

C ₅ -C ₆ cycloalkenyl, which can carry one to three of the following groups: halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ -Halogenalkoxy and C ₁ -C ₄ alkylthio. In addition, compounds I are preferred in which R ^{6 is} phenyl, which may be unsubstituted or may carry one to three of the following groups: fluorine, chlorine, bromine, cyano,

C ₁ -C ₄ alkyl, trifluoromethyl, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, tert-butyloxy, trifluoromethoxy, phenyl and phenoxy.

Compounds I are further preferred in which R ^{6 is} naphthyl, which may be unsubstituted or carry one to three of the following groups: fluorine, chlorine, bromine, cyano,

With regard to their use, the compounds I compiled in the tables below, in particular Tables 11 to 13, are very particularly preferred, where C ₆ H _{11 is} cyclohexyl.

The new compounds of formula I are suitable as fungicides.

The new compounds, or the compositions containing them, can be sprayed, atomized, for example in the form of directly sprayable solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprays or granules. Dusting, scattering or pouring can be used. The application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

Usually the plants are sprayed or dusted with the active ingredients or the seeds of the plants are treated with the active ingredients.

The formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, and in the case of water as a diluent, other organic solvents can also be used as auxiliary solvents. The following are essentially considered as auxiliaries: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) ) and water; Carriers such as natural stone powder (eg kaolins, clays, talc, chalk) and synthetic stone powder (eg highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty acid alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.

The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin-,

Phenolic, naphthalene and dibutylnaphthalenesulfonic acid, as well as fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta and octadecanols, as well as fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde and formaldehyde . the

Naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated iso-octyl-, octyl- or nonylphenol, alkylphenol, tributylphenyl, alkylaryl polyether alcohols, isotridecyl alcohol alcohol, fatty alcohol condensates, ethoxylated castor oil, Polyoxyethylenalky ethers or polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors or Methyl cellulose into consideration. Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are mineral soils such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate,

Ammonium nitrate, ureas and herbal products, such as

Cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers. Examples of such preparations are (substance numbers refer to Table 11, see below):

I. a solution of 90 parts by weight of compound 1 and

10 parts by weight of N-methyl-2-pyrrolidone, which is suitable for use in the form of tiny drops;

II. A mixture of 10 parts by weight of compound no. 2,

70 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-monomethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole Castor oil; through fine Distributing the solution in water gives a dispersion.

III. an aqueous dispersion of 10 parts by weight of the compound

No. 3, 40 parts by weight of cyclohexanone, 30 parts by weight of iso¬

Butanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil;

IV. An aqueous dispersion of 20 parts by weight of the compound

No. 4, 25 parts by weight of cyclohexanol, 55 parts by weight of one

Mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil; V. a mixture of 80 ground in a hammer mill

5 parts by weight of compound no. 5, 3 parts by weight of the sodium salt of di-iso-butylnaphthalene-a-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of powdered silica gel; a spray mixture is obtained by finely distributing the mixture in water;

VI. an intimate mixture of 3 parts by weight of the compound

No. 6 and 97 parts by weight of finely divided kaolin; this dust contains 3% by weight of active ingredient;

VII. An intimate mixture of 30 parts by weight of the compound

No. 7, 62 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which was sprayed onto the surface of this silica gel; this preparation gives the active ingredient good adhesion;

VIII. A stable aqueous dispersion of 40 parts by weight of

Compound No. 8, 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2

Parts by weight of silica gel and 48 parts by weight of water, which can be further diluted;

IX. a stable oily dispersion of 20 parts by weight of compound no. 15, 2 parts by weight of the calcium salt of

Dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 50 parts by weight of a paraffinic mineral oil. The new compounds are distinguished by their outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Deuteromycetes,

Ascomycetes, Phycomycetes and Basidiomycetes from. Some of them are systemically effective and can be used as foliar and soil fungicides.

They are particularly important for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, lawn, cotton, soybeans, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as cucumbers, beans and Pumpkin family, as well as on the seeds of these plants. The compounds are used by treating the fungi or the seeds, plants, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds.

It is used before or after the infection of the materials, plants or seeds by the fungi.

The new compounds are particularly suitable for combating the following plant diseases:

Erysiphe graminis (powdery mildew) in cereals, Erysiphe

cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizoctonia species on cotton and lawn, Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helmin on cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mold) on strawberries, vines, ornamental plants and vegetables, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, Pyricularia oryzae on rice, Phytophthora

infestans on potatoes and tomatoes, Fusarium and Verticillium species of various plants, Plasmopara viticola on vines, Alternaria species on vegetables and fruits.

The new connections can also be used in material protection (wood protection), e.g. against Paecilomyces variotii.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.

Depending on the type of effect desired, the application rates are between 0.025 and 2, preferably between 0.1 and 1 kg of active ingredient per ha. In the case of seed treatment, amounts of active compound of 0.001 to 50, preferably 0.01 to 10 g per kg of seed are generally required. In the use form as fungicides, the compositions according to the invention can also be present together with other active compounds, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. When mixed with fungicides, the fungicidal activity spectrum is enlarged in many cases.

The following list of fungicides with which the compounds according to the invention can be used together is intended to explain, but not to limit, the possible combinations:

Sulfur, dithiocarbamates and their derivatives, such as iron, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediamine bisdithiocarbamate, Tetramethylthiuramdisulfide, ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate), ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene bis (thiocarbamoyl) disulfide;

Nitroderivatives, such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl-iso-propyl carbonate, 5 -Nitro-iso-phthalic acid di-iso-propyl ester; heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl-phthalimidophosphonothioate, 5-amino-1- [bis- ( dimethylamino) -phosphinyl] - 3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo [4,5-b] quinoxaline, 1- (Butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N- (1,1,2 , 2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthiophthalimide,

N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenyl-sulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodanmethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene,

4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone,

Pyridine-2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, 2,3-di hydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide,

2-methyl-5,6-dihydro-4H-pyran-3-carboxylic acid anilide, 2-methyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,4,5-trimethyl furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide, N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxylic acid amide, 2-methyl-benzoic acid anilide, 2-iodobenzoic acid anilide, N-formyl-N-morpholine-2,2,2-trichloroethyl acetal, piperazin-1,4-diyl-bis- (1- (2,2,2-trichloro-ethyl)) formamide, 1- (3rd , 4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecyl-morpholine or its salts,

2,6-Dimethyl-N-cyclododecyl-morpholine or its salts, N- [3- (p-tert-butylphenyl) -2-methylpropyl] -cis-2,6-dimethylmorpholine, N- [3- (p -tert.-butylphenyl) -2-methylpropyl] piperidine,

1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole 1- [2- (2,4-dichlorophenyl ) -4-n-propyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, N- (n-propyl) -N- (2,4,6- trichlorophenoxyethyl) -N'-imidazol-yl urea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone, (2nd -Chlorophenyl) - (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyridine-methanol, 1,2- Bis (3-ethoxycarbonyl-2-thioureido) benzene, 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene, [2- (4-chlorophenyl) ethyl] - (1,1-dimethylethyl) -1H-1,2,4-triazol-1-ethanol, 1- [3- (2-chlorophenyl) -1- (4-fluorophenyl) oxiran-2-ylmethyl] -1H-1,2,4- triazole and various fungicides, such as dodecylguanidine acetate,

3- [3- (3,5-Dimethyl-2-oxycyclohexyl) -2-hydroxyethyl)] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethyl-phenyl) -N-furoyl (2) alaninate , DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine, 3 - [(3,5-dichlorophenyl) (-5-methyl-5-methoxymethyl] -1,3-oxazolidine-2,4-dione, 3- (3,5-dichlorhenyl) -1-iso-propylcarbamoylhydantoin,

N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1- [2- (2,4- Dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4-difluoro-α- (1H-1,2,4-triazolyl-1-methyl) -benzhydryl alcohol,

N- (3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1 - ((bis- (4-fluorophenyl) methylsilyl) methyl) - 1H-1,2,4-triazole. Strobilurins such as methyl-E-methoximino- [α- (o-tolyloxy) -o-tolyl] acetate, methyl-E-2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl } -3-methoxyacrylate, methyl-E-methoximino- [α- (2-phenoxyphenyl)] acetamide, methyl-E-methoximino- [α- (2,5-dimethyloxy) -o-tolyl] acetamide.

Anilinopyrimidines such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline,

N- (4-methyl-6-cyclopropyl-pyrimidin-2-yl) aniline.

Phenylpyrroles such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile.

Cinnamic acid amides such as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acrylic morpholide.

Synthesis example

The procedure reproduced in the synthesis example below can be used to obtain further representatives of the compounds I by modifying the starting compounds. The physical data of the products manufactured in this way are shown in the tables below. N- (iso-propyloxycarbonyl) -L-valine (4-methoxyphenyl) cyclohexylamide (Compound 11.5 in Table 11)

To the solution of 5.43 g (25 mmol) of tert-butyloxycarbonyl-L-valine and 3.45 g (25 mmol) of 3- (4-methoxyphenyl) -cyclohexylamine in 100 ml of tetrahydrofuran were 3 g (30 mmol ) Triethylamine and 4.01 g (25 mmol) of diethyl cyanophosphonate were added with cooling. The mixture was stirred at 0 ° C for 1 hour and at 20 ° C for 15 hours. The solvent was then removed and the residue was taken up in ethyl acetate. The organic phase was washed with 40 ml of 10% hydrochloric acid, 10% sodium hydrogen carbonate solution and water. The organic phase was dried and then the solvent was removed. There remained 8.9 g of N- (tert-butyloxycarbonyl) -L-valine [3- (4-methoxyphenyl) cyclohexyl] amide (mp. 128 ° C; compound 11.2 in

Table 11).

50 ml of trifluoroacetic acid were added to 8.48 g (21 mmol) of this compound with cooling and the mixture was stirred at 0 ° for 1 hour. The mixture was then heated to 20 ° C, the trifluoroacetic acid largely distilled off, residual acid removed and the residue taken up with dichloromethane. 5.8 g of L-Va remained lin-3- (4-methoxyphenyl) cyclohexylamide, which could be used for the next step without further purification.

0.53 g (2.8 mmol) of this compound and 0.30 g (3 mmol) of triethylamine in 40 ml of toluene were mixed with 0.35 g (2.8 mmol) of isopropyl chloroformate at 0 ° C, 15 Stirred for hours at 20 ° C, the solvent removed and the residue taken up with ethyl acetate. The organic phase was washed with 40 ml of 10% hydrochloric acid, 10% sodium hydrogen carbonate solution and water and then dried. The solvent was then removed. 0.9 g of the title compound remained as a colorless crystalline residue (mp: 124 ° C.).

Examples of use

The fungicidal action of the compounds of general formula I was demonstrated by the following experiments: The active compounds were used as 20 wt .-% emulsion in a mixture of 70 wt .-% of cyclohexanol, 20 wt .-% Nekanil ^® LN (Lutensol ^® AP6 , Wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight Emulphor ^® EL

(Emulan ^® EL, emulsifier based on ethoxylated fatty alcohols) prepared and diluted with water according to the desired concentration.

Plasmopara viticola leaves of pot vines of the "Müller-Thurgau" variety were sprayed with an aqueous spray mixture containing 80% by weight of active ingredient and 20% by weight

Emulsifier contained in the dry substance, sprayed. In order to be able to assess the duration of action of the active ingredients, the plants were placed in the greenhouse for 8 days after the spray coating had dried on. Only then were the leaves with a

Zoospores suspension of Plasmopara viticola (vine peronospora) infected. The vines were first left in a cam for 48 hours mer with water vapor-saturated air at 24 ° C and then set up for 5 days in a greenhouse at temperatures between 20 and 30 ° C. After this time, the plants were again placed in the humid chamber for 16 hours to accelerate the sporangium carrier outbreak. The extent of the fungal outbreak on the undersides of the leaves was then assessed visually.

In this test, the plants treated with a 250 ppm aqueous preparation of the compounds 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8 and 11.20 (Table 11), furthermore 12.22 and 12.27 (Table 12), respectively, all showed one maximum infection of 10%, while untreated plants were 65% infected.

Phytophthora infestans

Leaves of potted plants of the "large meat tomato" variety were sprayed with an aqueous spray mixture which contained 80% by weight of active compound and 20% by weight of emulsifier in the dry matter. After 24 hours, the leaves were infected with a zoospore suspension of the Phytophthora infestans fungus. The plants were then placed in a chamber with water vapor-saturated air at temperatures between 16 and 18 ° C. After 6 days, the infestation on the untreated but infected control plants had developed to such an extent that the fungicidal activity of the substances could be assessed visually.

In this test, the aqueous preparation of the compounds 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.15 and 11.27 (Table 11), and also 12.15, 12.17, 12.18, 12.24, 12.27 each showed with a 250 ppm aqueous preparation or 12.37 (Table 12) treated plants a maximum infection of 5%, while untreated plants were 75% infected.

Claims

Claims 1. Carbamoylcarboxamides of the general formula I

and their salts, in which the variables have the following meaning:

R ^{1 is} C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl or C ₂ -C ₈ alkynyl, these radicals being partially or completely halogenated and / or bearing one to three of the following groups: cyano, 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, C ₃ -C _7- cycloalkyl, C ₃ ~ C ₇ -cycloalkenyl, aryl, aryloxy and heteroaryl, where the cyclic radicals in turn can carry one to three of the following substituents: 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, C ₃ -C ₇ cycloalkyl or C ₃ -C ₇ cycloalkenyl, these

Residues can be partially or completely halogenated and / or can carry one to three of the following groups: 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 aryl- (C ₁ -C ₄ ) - alkyl, the cyclic groups being one to three of the can carry the following substituents: 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 and aryloxy, a non-aromatic 4- to 8-membered ring which, as ring members, can contain, in addition to carbon, one or two of the heteroatoms oxygen, sulfur and nitrogen, where the carbon atoms in the ring can carry one or two of the following groups: 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 and aryloxy and where the second and each further nitrogen atom as the hetero atom in the ring bears hydrogen or a C ₁ -C ₄ alkyl group,

Aryl or heteroaryl, where these radicals can carry one to three of the following groups: 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, in which the cyclic substituents in turn can carry one to three of the following substituents: 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 and C ₁ -C ₄ alkoxycarbonyl,

W ¹ W ² C = N-, where W ^{1 is} C ₁ -C ₈ -alkyl, which can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, 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, aryl, aryloxy and heteroaryl, the cyclic groups in turn being able to carry one to three of the following substituents : 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,

C ₂ -C ₈ alkenyl or C ₂ -C ₈ alkynyl, these radicals being partially or completely halogenated and / or carrying one to three of the following groups: 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 and aryloxy, the cyclic groups in turn one to three of the following

Can carry substituents: 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 and aryloxy, C ₃ -C ₇ cycloalkyl or C ₃ -C ₇ cycloalkenyl, where these radicals can carry one to three of the following groups: 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 and

Aryl- (C ₁ -C ₄ ) -alkyl, where the groups which contain aryl can carry one to three of the following substituents: 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 and aryloxy,

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 and aryloxy and

W ^{2 is} hydrogen or one of the groups W ¹ ; R ^{2 is} hydrogen or C ₁ -C ₈ alkyl or C ₃ -C ₇ cycloalkyl, which can be partially or completely halogenated;

R ³ C ₁ -C ₈ alkyl, C ₃ -C ₇ cycloalkyl, where these radicals can carry one to three of the following groups: 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 and C ₁ -C ₄ alkoxycarbonyl or phenyl- (C ₁ -C ₄ ) alkyl, the phenyl radical being one to three of the following groups: 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 and aryloxy;

R ^{4 is} hydrogen or one of the groups mentioned for R ³ or R ³ and R ⁴ together with the C atom to which they are attached form a 4- to 8-membered ring which, as ring members, contains one or two of the heteroatoms oxygen in addition to carbon, Can contain sulfur and nitrogen, wherein the carbon atoms in the ring can carry one or two of the following groups: 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 and aryloxy and where nitrogen as the hetero atom carries hydrogen or a C ₁ -C ₄ alkyl group;

R ^{5 is} a radical R ² ; X independently of one another are hydrogen, C ₁ -C ₈ -alkyl and / or C ₂ -C ₈ -alkenyl, these radicals being partially or completely halogenated and / or carrying one to three of the following groups: cyano, 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 and C ₁ -C ₄ alkoxycarbonyl, aryl and aryloxy,

C ₃ -C ₇ cycloalkyl and / or C ₃ -C ₇ cycloalkenyl, these radicals being partially or completely halogenated and / or carrying one to three of the following groups: 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 aryl- (C ₁ -C ₄ ) - alkyl, where the cyclic groups in turn can carry one to three of the following substituents: 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 and aryloxy; m 0, 1, 2;

AC ₃ -C ₇ cycloalkyl or C ₃ -C ₇ cycloalkenyl, these

Residues can be partially or completely halogenated and / or can carry one to three of the following groups: 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 and aryl- (C ₁ -C ₄ ) alkyl, where in the groups which contain aryl this may be unsubstituted or may carry one to three of the following substituents: 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 and Aryloxy;

R ⁶ aryl or heteroaryl, where these radicals can carry one to three of the following groups: 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 and aryloxy, wherein in the

Groups which contain aryl can carry one to three of the following substituents: 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.

2. A process for the preparation of carbamoylcarboxamides of the general formula I according to claim 1, characterized in that a carbamoylcarboxylic acid of the general formula II

with an amine of the general formula III

implements.

3. A process for the preparation of carbamoylcarboxamides of the general formula I according to claim 1, characterized in that a) a carbamoylcarboxamide of the general formula I

in which the group R ¹ -O- (CO) stands for a protective group which can be split off in a manner known per se, into an amino acid amide IV

transferred and b) the amino acid amide IV thus obtained with a chloroformyloxime of the general formula V

in the presence of a base.

4. Suitable agents for combating harmful fungi, containing customary additives and an effective amount of a compound of the general formula I according to claim 1.

5. A process for the preparation of agents suitable for combating harmful fungi, characterized in that compounds of the general formula I according to Claim 1 are used here.

6. A method of combating harmful fungi, characterized in that the harmful fungi, their habitat or the plants, surfaces, materials or spaces to be kept free of them are treated with an effective amount of a compound of the general formula I according to claim 1.

7. Use of the compounds of general formula I according to claim 1 for combating harmful fungi.