DE4419516A1 - Carbamoyl carboxylic acid hydrazide derivs. - Google Patents

Abstract

Carbamoyl carboxylic acid hydrazide derivs. of formula (I) and their salts are new: R<1> = 1-8 C alkyl, 2-8 C alkenyl or 2-8 C alkynyl (these 3 gps. each opt. partially or completely halogenated and/or mono-, di- or tri-substd. by T gps.), 3-7 C cycloalkyl or 4-7 C cycloalkenyl (these 2 gps. each opt. partially or completely halogenated and/or mono-, di- or tri-substd. by U gps. or aryl (1-4 C) alkyl,etc.; R<2>,R<5> = 1-8 C alkyl or 3-7 C cycloalkyl, etc.;R<3>,R<4> = 1-8 C alkyl (opt. mono-, di- or tri-substd. by halo, CN, 1-4 C alkoxy, etc.;R<3> and R<4> together with the C atom to which they are attached form a 4-8 membered ring (contg. in addition to C ring members,1 or 2 heteroatoms e.g. O,S, etc.);R<6>=H or as R<1>,except T and U gps. do not include 1-4C alkoxy carbonyl;R<7>= as R<6> but is not H;T = CN, 1-4 C alkoxy, 1-4 C haloalkoxy, etc.;U = CN, 1-4 C alkyl, 1-4 C alkoxyalkyl, etc..The following cpds. are excluded, e.g. (Ia)-(Id), where R<1> = PhCH2; R<2> = H; R<3> = Me, n-Pr, i-Pr or PhCH2; R<4> = R<5>=H; R<6>=R<7>=CH2CH2Cl; etc..

Description

The present invention relates to carbamoylcarboxylic acid hydrazides of the general formula I

and their salts, in which the residues have the following meaning:
R¹ C₁-C₈-alkyl, C₂-C₈-alkenyl or C₂-C₈-alkynyl, these Re be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C₁-C₄-alkoxy, C₁- C₄-haloalkoxy, C₁-C₄-alkylthio C₁-C₄-alkoxycarbonyl, C₃-C₇-cycloalkyl C₃-C₇-cycloalkenyl, aryl, aryloxy and heteroaryl, where the cyclic radicals can in turn carry one to three of the following substituents: halogen, cyano , C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl, aryloxy and heteroaryl,
C₃-C₇-cycloalkyl or C₃-C₇-cycloalkenyl, these radicals can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄- Haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl, aryloxy and aryl- (C₁-C₄) alkyl, the cyclic groups being one to three of the following substituents can wear: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl and aryloxy,
a non-aromatic 4- to 8-membered ring, which may contain one or two of the heteroatoms oxygen, sulfur and nitrogen as ring members in addition to carbon, wherein the carbon atoms in the ring can carry one or two of the following groups: halogen, cyano, C₁-C₄ -Alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl and aryloxy and where the second and each further nitrogen atom as a hetero atom in the ring carries hydrogen or a C₁-C₄ alkyl group,
Aryl or heteroaryl, where these radicals can carry one to three of the following groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl, aryloxy and heteroaryl, in which the cyclic substituents may in turn carry one to three of the following substituents: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy alkyl , C₁-C₄ haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₁ alkylthio and C₁-C₄ alkoxycarbonyl or
W¹W²C = N-, where
W¹ is C₁-C₈-alkyl, which can be partially or completely halogenated and / or carry one to three of the following groups: cyano, C₁-C₄-alkoxy, C₁-C₄-halogen alkoxy, C₁-C₄-alkylthio, aryl, Aryloxy and heteroaryl, where the cyclic groups can in turn carry one to three of the following substituents: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄- Haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl and aryloxy,
C₂-C₈-alkenyl or C₂-C₈-alkynyl, these radicals being partially or completely halogenated and / or carrying one to three of the following groups: cyano, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄ -Alkylthio, C₁-C₄-alkoxycarbonyl, aryl and aryloxy, where the cycli groups can in turn carry one to three of the following substituents: halogen, cyano, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄ alkoxycarbonyl, aryl and aryloxy,
C₃-C₇-cycloalkyl or C₃-C₇-cycloalkenyl, these Re ste can carry one to three of the following groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄ -Alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl and aryl- (C₁-C₄) -alkyl, where the groups containing aryl can carry one to three of the following substituents : Halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl and aryloxy or
Aryl or heteroaryl, where these radicals can carry one to three of the following groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl and aryloxy and
W² is hydrogen or one of the groups W¹;
R² is hydrogen or C₁-C₈-alkyl or C₃-C₇-cycloalkyl, which can be partially or completely halogenated;
R³ C₁-C₈-alkyl, which radical can carry one to three of the following groups: halogen, cyano, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio and C₁-C₄-alkoxycarbonyl,
C₃-C₇-cycloalkyl or phenyl- (C₁-C₄) alkyl, the rings of these radicals can carry one to three of the following groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄ -Halogenalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl and aryloxy;
R⁴ is hydrogen or one of the radicals R³ or
R³ and R⁴ together with the carbon atom to which they are attached, a 4- to 8-membered ring, which as ring members can contain one or two of the heteroatoms oxygen, sulfur and nitrogen in addition to carbon, the carbon atoms in the ring one or two of the following groups: gene halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄ -Alkoxycarbonyl, aryl and aryloxy and wherein nitrogen as the hetero atom carries hydrogen or a C₁-C₄ alkyl group;
R⁵eins of the residues R²;
R⁶ C₁-C₈-alkyl, C₂-C₈-alkenyl or C₄-C₈-alkynyl, these radicals being partially or completely halogenated and / or carrying one to three of the following groups: cyano, C₁-C₄-alkoxy, C₁- C₄-haloalkoxy, C₁-C₄-alkylthio, C₃-C₇-cycloalkyl, C₃-C₇-cycloalkenyl, aryl, aryloxy and heteroaryl, where the cyclic radicals in turn can carry one to three of the following substituents: halogen, cyano, C₁-C₄- Alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl, aryloxy and heteroaryl,
C₃-C₇-cycloalkyl or C₃-C₇-cycloalkenyl, these radicals can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄- Haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl, aryloxy and aryl- (C₁-C₄) alkyl, where the cyclic groups can carry one to three of the following substituents: halogen, cyano , C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl and aryloxy,
a non-aromatic 4- to 8-membered ring, which may contain one or two of the heteroatoms oxygen, sulfur and nitrogen as ring members in addition to carbon, wherein the carbon atoms in the ring can carry one or two of the following groups: halogen, cyano, C₁-C₄ -Alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl and aryloxy and where the second and each further nitrogen atom as a hetero atom in the ring Bears hydrogen or a C₁-C Alkyl alkyl group,
Aryl or heteroaryl, where these radicals can carry one to three of the following groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl, aryloxy and heteroaryl, in which the cyclic substituents in turn can carry one to three of the following substituents: Ha logen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-halogen alkyl , C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and C₁-C₄-alkylthio or
when R³ is isopropyl, hydrogen;
R⁷eins of the residues R⁶, except hydrogen;
except for the compounds defined in the following definition:
Ia-d (R¹ = Ph-CH₂; R² = H; R³ = CH₃, (CH₂) ₂CH₃, CH (CH₃) ₂ or Ph-CH₂; R⁴, R⁵ = H; R⁶, R⁷ = CH₂CH₂Cl),
Ie-h (R¹ = C (CH₃) ₃; R² = H; R³ = CH₃, CH (CH₃) ₂, CH (CH₃) CH₂CH₃, CH₂CH (CH₃) ₂ or Ph-CH₂; R⁴, R⁵ = H; R⁶, R⁷ = CH₂CH₂Br),
Ii (R¹ = Ph-CH₂; R² = H; R³ = CH₃; R⁴, R⁵ = H; R⁶ = CH₃; R⁷ = Ph),
Ij-k (R¹ = Ph-CH₂; R² = H; R³ = CH (CH₃) ₂ or CH₂CH (CH₃) ₂; R⁴, R⁵ = H; R⁶, R⁷ = Ph),
Il (R¹ = C (CH₃) ₃; R² = H; R³ = CH (CH₃) ₂; R⁴, R⁵, R⁶ = H; R⁷ = Ph), Im (R¹ = Ph-CH₂; R² = H; R³ = Ph -CH₂; R⁴, R⁵ = H; R⁶, R⁷ = CH₂CH₃),
In-o (R¹ = Ph-CH₂; R² = H; R³ = CH₂SCH₃ or CH₂CH₂SCH₃; R⁴, R⁵ = H; R⁶, R⁷ = CH₂CH₂Cl).

The invention also relates to processes for producing the Compounds I and their salts, agents containing these substances as well as a method for combating harmful fungi and the ver use of these substances for this.

The present invention further relates to amino acid hydra zid intermediates of the general formula IV

in which R³ represents a group CH (CH₃) ₂, CH₂CH (CH₃) ₂ or CH (CH₃) C₂H₅ and R⁴, R⁵, R⁶ and R⁷ have the meaning given in claim 1, except for the compounds according to the following definition of the radicals:
IVa-b (R³ = CH (CH₃) ₂ or (CH₂) ₂CH₃; R⁴, R⁵ = H; R⁶, R⁷ = CH₂CH₂Cl)
Ivc-e (R³ = CH (CH₃) ₂, CH (CH₃) CH₂CH₃ or CH₂CH (CH₃) ₂; R⁴, R⁵ = H; R⁶, R⁷ = CH₂CH₂Br),
IVf (R³ = CH (CH₃) ₂; R⁴, R⁵, R⁶ = H; R⁷ = Ph),
IVg (R³ = CH (CH₃) ₂; R⁴, R⁵ = H; R⁶, R⁷ = Ph).

From DE-B 11 99 540 agents are known which are alkyl carbon acid hydrazides, e.g. B. the compound of the following formula

contain and which have an effect against powdery mildew point.  

Furthermore, JP-A 69/27 997 teaches the use of 4-methoxycar bonyl terephthalic acid hydrazide or terephthalic acid bishydrazide for Fight rice rice.

However, these agents are not yet satisfactory as fungicides dig.

Other carboxylic acid hydrazides are known from the literature; of a fungicidal activity of these compounds nothing reported (see Pharmacy 44, page 608 to page 611 (1989); Pharmazie 44, page 316 to page 317 (1989); J. Org. Chem. 36, pages 1580 to 1584 (1971); Farm. Pole. 28, page 615 (1972); EP-A 361 977; Collect. Czech. Commun. 49, page 2551 to page 2561 (1989)).

The present invention was therefore new carbamoylcarboxylic acid Hydrazides with improved activity against harmful fungi as a task underlying.

Accordingly, the compounds I defined at the outset and their Salts found.

Furthermore, the important for the production of these substances Intermediates of the general formula IV found.

Furthermore, they were agents containing, methods of manufacture of the compounds I and their salts and those containing them Found means and also a method for combating Harmful fungi and the use of the compounds I and their salts For this.

The compounds I and their salts can be derived from the ent speaking carbamoyl carboxylic acids II are prepared. Before it is obtained by the method described below A, B and C (the literature quotes "Houben-Weyl" refer to: Houben-Weyl, Methods of Organic Chemistry, 4th edition, Thieme Verlag, Stuttgart).

Procedure A

The carbamoylcarboxylic acid hydrazides I are obtained by the Reacts carbamoyl carboxylic acids II with the hydrazines III.

The carbamoyl carboxylic acids II are known or according to known Me methods, especially based on the underlying amino acid ren, available (cf. "Houben-Weyl", volume 15/1, page 46 to Page 305, especially page 117 to page 125).

The hydrazines III are also known or are readily available (see "Houben-Weyl", volume 10/2, page 1 to page 71 and page 169 to page 409, especially page 396 to page 399 and page 402 to page 405).

In this process A it is preferred to work in such a way that next the carbamoylcarboxylic acids II in carboxy-activated Derivatives, especially in acyl cyanides or anhydrides, converted (see Pharmacy 44, page 316 to page 317 and page 608 to Page 611 (1989); Tetrahedron Letters, volume 18, pages 1595 to Page 1598 (1973) or "Houben-Weyl", volume 15/1, page 28 to Page 32). These derivatives are then in with the hydrazines III The presence of bases reacted.

Suitable for the production of carboxy-activated acyl cyanides e.g. B. the reaction of carbamoylcarboxylic acids II with cyanophosphone acid diethyl ester, especially in an inert solvent such as Tetrahydrofuxan, toluene or dichloromethane.

The conversion is used to produce the carboxy-activated anhydrides tion of carbamoylcarboxylic acids II with carbonic acid chlorides such as Isobutyl chloroformate in the presence of bases and counter optionally in an inert solvent such as toluene or tetra hydrofuran preferred.  

The implementation of the hydrazine III with the carboxy-activated carba moylcarboxylic acids II are preferably carried out in a solvent such as dichloromethane, tetrahydrofuran or toluene.

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

In a preferred embodiment of this process stage who the the carbamoyl carboxylic acid II, the hydrazine III, the Erzeu supply of the caboxy-activated derivative of carbamoylcarboxylic acid II suitable reagent and the base in the one-pot process, given if reacted in an inert solvent, and the crude product then in a manner known per se on the Carbamoylcarboxylic acid hydrazide I worked up.

Procedure B

The carbamoylcarboxylic acid hydrazides I, in which R¹ represents a group -W¹W² C = N- is also obtained by using the carbamoyl carbon Acid hydrazides I, in which the group R¹-O- (CO) for protection Group stands, which are split off in a manner known per se can, converted into carboxylic acid hydrazides IV and this with chlorine formyloximen V in the presence of bases.

Ba level Preparation of carboxylic acid hydrazides IV

Cleavage of the group R¹-O- (CO) from the carbamoylcarboxylic acid hydrazides I can be carried out in a manner known per se (cf. "Houben-Weyl", volume 15/1, page 46 to page 305, especially Page 126 to page 129; Pharmacy 44, page 316 to page 317 (1989)).  

Suitable groups which can be split off contain, in particular, the radical R 1 tert-butyl, and next to it the benzyl group.

In the case of R 1 = tert-butyl, for example, the separation takes place tion usually by reaction with an acid, in particular a protonic acid such as hydrochloric acid, hydrobromic acid or tri fluoroacetic acid (loc. cit.).

The carbamoylcarboxylic acid hydrazides I suitable as starting materials are by known methods (see. Pharmacy 44, page 316 to Page 317 or page 608 to page 611 (1989); "Houben-Weyl" Volume 15/1, page 28 to page 32) or in particular according to Process A according to the invention obtainable.

Level Bb Preparation of carbamoylcarboxylic acid hydrazides 1

The carboxylic acid hydra resulting from the synthesis stage (Ba) zide IV with the chloroformyloximes V in the presence of bases implemented.

The chloroformyloximes V are known or according to known processes ren, e.g. B. by phosgenation of oximes, available (cf. Z. Chem. 9, page 344 to page 345 (1967)).

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

Inorganic and organic bases come equally as bases into consideration, whereby organic bases and again ter tiary amines such as triethylamine, pyridine and N-methylpiperidine be are preferred.

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

Otherwise, the implementation of this reaction is ge skilled in the art common, so that no further explanations are required (cf. "Houben-Weyl", volume 15/1, page 117 to page 125; Dev. En docrinol. 13 (Neurohypophyseal Pept. Horm. Other Biol. Act. Pept.), Page 37 to page 47 (1981)).

Procedure C

The carbamoylcarboxylic acid hydrazides of the general formula I according to Claim 1, in the R⁶ for C₁-C₈-alkyl, C₄-C₇-cycloalkyl or Aryl- (C₁-C₄) alkyl is also by reaction of carba moylcarboxylic acid hydrazides of the general formula I according to claim 1, in which R⁶ is hydrogen, with a compound of the general my formula R⁶-X, in which R⁶ for C₁-C₈-alkyl, C₄-C₇-cycloalkyl or aryl- (C₁-C₄) alkyl and X is a negative leaving group means available with the use of a base.

The carbamoylcarboxylic acid hydrazides of the general formula I, in the R⁶ is hydrogen are in a conventional manner (cf. DE-A 10 89 390; Zh. Org. Khim. 14, page 1086 (1978)), or ins particularly obtainable by process A according to the invention.

The negative leaving group X are methylsulfonyl, which 4-methylphenylsulfonyl anion and preferably halide anions such as iodide and especially chloride and bromide.

Alkali metal carbonates and -alkanolates such as sodium carbonate, sodium methoxide and sodium ethanolate, in addition alkaline earth metal carbonates such as calcium carbonate, Alkali metal or alkaline earth metal hydroxides, e.g. B. sodium hydroxide and calcium hydroxide, hydrides, e.g. B. sodium hydride, hydrogen carbonates, e.g. B. sodium bicarbonate, alkanes, e.g. B. n-butyl lithium or tertiary amines such as triethylamine.

The reaction can be solvent-free or in one under the reak conditions of inert solvents such as dimethylformamide, Tetrahydrofuran, dichloromethane or alkanols such as methanol or Ethanol.  

The reaction is usually carried out at a temperature of 10 up to 60 ° C and under normal pressure.

Otherwise, the method is carried out in itself known manner (cf. "Houben-Weyl", volume 10/2, page 402 to page 404).

The reaction mixtures obtained by processes A, B and C, respectively are worked up in the usual way for the compounds I, e.g. B. by mixing with water, separation of the phases and given if chromatographic purification of the raw products. The intermediate and end products fall e.g. T. in the form of colorless or slightly brown Licher, viscous oils that are under reduced pressure and at moderate volatile components can be freed at elevated temperatures nen. If the intermediate and end products are received as solids cleaning, for example, by recrystallization siering or digesting.

The compounds of formula I may optionally be dependent the nature of the substituents as geometric and / or op table isomers or mixtures of isomers are present. Both the pure Isomers as well as the mixtures of the isomers have fungicidal Wir kung on.

The salts, in particular of the acid, are also part of the invention permanent connections I, which basic centers, especially ba sic nitrogen atoms contain, especially the salts with mineral acids such as sulfuric acid and phosphoric acid or Lewis Acids such as zinc chloride. Usually it depends on the type of Do not add salt. For the purposes of the invention, such salts are before moves the plants, areas, Do not damage materials or spaces and the effect of Do not affect connections I.

The salts of the compounds I are known per se accessible, especially by implementing the appropriate carba moylcarbonsäurehydrazide I with the acids mentioned in water or an inert organic solvent at temperatures of -80 to 120, preferably 0 to 60 ° C.

In the preparation of the carbamoylcarboxylic acid hydrazides I according to Process B are also new intermediates of the general Formula IV received

in which R⁴, R⁵, R⁶, and R⁷ have the meaning given in claim 1 and R³ represents a group CH (CH₃) ₂, CH₂CH (CH₃) ₂ or CH (CH₃) C₂H₅, the compounds according to the following definition of Re are already known:
IVa-b (R³ = CH (CH₃) ₂ or (CH₂) ₂CH₃; R⁴, R⁵ = H; R⁶, R⁷ = 3CH₂CH₂Cl),
IVc-e (R³ = CH (CH₃) ₂, CH (CH₃) CH₂CH₃ or CH₂CH (CH₃) ₂; R⁴, R⁵ = H; R⁶, R⁷ = CH₂CH₂Br),
IVf (R³ = CH (CH₃) ₂; R⁴, R⁵, R⁶ = H; R⁷ = Ph),
IVg (R³ = CH (CH₃) ₂; R⁴, R⁵ = H; R⁶, R⁷ = Ph)
(see Pharmazie, 44, page 608 to page 611 (1989); Pharmazie, 44 page 316 to page 317 (1989); EP-A 0 361 977; Int. J. Pept. Protein Res. 21 page 406 (1983) ; Farm. Pol. 28, pages 615 to 619 (1972)).

Among the new amino acid hydrazides IV preferred are those in which R³ represents a group CH (CH₃) ₂, R⁴ and R⁵ have the meaning given in claim 1,
R⁶ represents C₁-C₈-alkyl, this radical being partially or fully halogenated and / or can carry one to three of the following groups: cyano, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₃ -C₇-cycloalkyl, C₃-C₇-cycloalkenyl, aryl, aryloxy and heteroaryl, where the cyclic radicals can in turn carry one to three of the following substituents: Ha logen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁- C₄-halo alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and C₁-C₄-alkylthio, aryl, aryloxy and heteroaryl and
R⁷ represents aryl, this radical can carry one to three of the following groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl, aryloxy and heteroaryl, in which the cyclic substituents in turn can carry one to three of the following substituents: Ha logen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-halogen alkyl , C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and C₁-C₄-alkylthio.

Are particularly preferred with regard to their use in the manufacture position of the carbamoylcarboxylic acid hydrazides I in the following Compounds IV.

Table 1

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, e.g. B. C₁-C₆-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- Dimethyl butyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1 , 2,2-trimethylpropyl, 1-ethyl-1-methyl propyl and 1-ethyl-2-methylpropyl;
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 groups the hydrogen atoms can be partially or completely replaced by halogen atoms (as mentioned above), for . B. C₁-C₂-haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2nd - 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, e.g. B. C₁-C₃ alkoxy such as methyloxy, ethyloxy, propyloxy and 1-methylethyloxy;
Alkoxyalkyl: straight-chain or branched alkyl groups with 1 to 8 carbon atoms (as mentioned above), which in a random position bear a straight-chain or branched alkoxy group (as mentioned above) with 1 to 4 carbon atoms in the case of C₁-C₄-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 these groups the hydrogen atoms can be partially or completely replaced by halogen atoms (as mentioned above), e.g. B. C₁-C₄-haloalkoxy such as chloromethyloxy, dichloromethyloxy, tri chloromethyloxy, fluoromethyloxy, difluoromethyloxy, trifluoromethyl oxy, chlorofluoromethyloxy, dichlorofluoromethyloxy, chlorodifluoromethyloxy, 1-fluoroethyloxy, 2-fluoroethyloxy, 2,2-difluoroethyloxy, 2,2ethyl-trifluoromethyloxy , 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-), e.g. B. C₁-C₄ 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 are bonded to the skeleton via a carbonyl group (-CO-);
Alkenyl: straight-chain or branched alkenyl groups with 2 to 8 carbon atoms and a double bond in any position, e.g. B. C₂-C₆ alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propene, 2-methyl-1-propenyl, 1-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-di methyl-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, e.g. B. C₄-C₄-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-pentinyl, 2-methyl-4-pentinyl, 3-methyl-1-pentinyl, 3-methyl-4-pentinyl, 4-methyl-1-pentinyl, 4-methyl-2-pentinyl, 1,1- Dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl 2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;
Cycloalkyl: monocyclic alkyl groups with 3 to 7 carbon ring members, e.g. B. C₄-C₇ 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 z. B. C₅-C₇ cycloalkenyl such as cyclopentenyl, cyclohexenyl and cyclo heptenyl;
non-aromatic 4- to 8-membered rings, which contain one or two oxygen, sulfur or nitrogen atoms in addition to carbon as ring members, such as 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-tetrahydro pyranyl, 4-tetrahydropyranyl, 2-morpholinyl and 3-morpholinyl;
Aryl: monocyclic or polycyclic aromatic groups with 6 10 to 10 carbon atoms such as phenyl and naphthyl;
Arylalkyl: aryl groups (as mentioned above) which, in the case of aryl (C₁-C₄) alkyl, are bonded to the skeleton via alkyl groups having 1 to 4 carbon atoms (as mentioned above), for. B. phenyl (C₁-C₄) 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, can additionally contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one sulfur atom, e.g. B .:

• 5-membered heteroaryl containing 1 to 3 nitrogen atoms: 5-ring heteroaryl groups, which in addition to carbon atoms 1 can contain up to 3 nitrogen atoms as ring members, e.g. B. 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 acid substance atom or 1 oxygen or 1 sulfur atom: 5-ring Heteroaryl groups which, in addition to carbon atoms 1 to 4 Nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom or 1 oxygen or sulfur atom as May contain ring members, for. B. 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-oxa zolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazole 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 acid Substance or sulfur atom: 5-ring heteroaryl groups, which in addition to carbon atoms 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom or 1 Contain oxygen or a sulfur atom as ring members can, and in which 2 adjacent carbon ring members or 1 nitrogen and 1 adjacent carbon ring member may be bridged by a buta-1,3-diene-1,4-diyl group nen;
• - 5-membered heteroaryl bound via nitrogen, incl tend 1 to 4 nitrogen atoms, or nitrogen bound benzo-fused 5-membered heteroaryl containing 1 to 3 nitrogen atoms: 5-ring heteroaryl groups, which next to Carbon atoms 1 to 4 nitrogen atoms or 1 to 3 stick can contain atoms of matter as ring members, and in which 2 adjacent carbon ring members or a nitrogen and an adjacent carbon ring member through a buta- 1,3-diene-1,4-diyl group can be bridged, this Rings over one of the nitrogen ring members on the frame are bound;
• - 6-membered heteroaryl containing 1 to 3 or 1 to 4 nitrogen atoms: 6-ring heteroaryl groups, which next to Carbon atoms 1 to 3 or 1 to 4 nitrogen atoms as May contain ring members, for. B. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-tri azin-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 be neighboring carbon ring members through a buta-1,3-diene 1,4-diyl group can be bridged, e.g. B. quinoline, iso quinoline, quinazoline and quinoxaline.

The statement "partially or completely halogenated" is intended to end bring pressure that in the groups so characterized the Hydrogen atoms partially or completely by the same or various halogen atoms as mentioned above can be replaced can.  

With regard to their biological action against harmful fungi, compounds I are preferred in which
R⁷ is C₃-C₇-cycloalkyl or C₃-C₇-cycloalkenyl, these radicals being partially or completely halogenated and / or carrying one to three of the following groups: cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁- C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl, aryloxy and aryl- (C₁-C₄) alkyl, where the cyclic groups can carry one to three of the following substituents: Ha logen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-halogeno alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl and aryloxy or R⁷eine non-aromatic 4 - to 8-membered ring means which, as ring members, can contain one or two of the heteroatoms oxygen, sulfur and nitrogen in addition to carbon, the carbon atoms in the ring being able to carry one or two of the following groups: halogen, cyano, C₁-C₄alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl and aryloxy and wherein the second and each further nitrogen atom as a hetero atom in the ring carries hydrogen or a C₁-C₄-alkyl group or
R⁷aryl or heteroaryl means, these radicals can carry one to three of the following groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy , C₁-C₄-alkylthio, aryl, aryloxy and heteroaryl, in which the cyclic substituents can in turn carry one to three of the following substituents: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy and C₁-C₄ alkylthio.

Compounds I in which the radicals have the following meanings are particularly preferred, individually or in combination:
R¹ C₁-C₆-alkyl, this radical can carry one to three of the following groups: halogen, C₁-C₄-alkoxy, phenyl and phen oxy, especially C₁-C₄-alkyl and benzyl,
R¹ C₃-C₇-cycloalkyl, this radical can carry one to three of the following groups: halogen, C₁-C₄-alkoxyalkyl, phenyl and phenoxy and especially cyclopropyl, cyclopentyl and cyclohexyl,
R¹Aryl, which radical can carry one to three of the following groups: halogen, C₁-C₄-alkyl and C₁-C₄-alkoxy, especially phenyl and naphthyl, which may be unsubstituted and / or may in turn carry one to three of the following groups :
Fluorine, chlorine, bromine, C₁-C₄-alkyl, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy and iso-butyloxy and tert-butyloxy and in particular unsubstituted phenyl, 1-naphthyl and 2-naphthyl,
R² is hydrogen,
R³ C₁-C₆-alkyl, especially C₁-C₄-alkyl,
R³ C₃-C₆-cycloalkyl, especially cyclopropyl, cyclopentyl or cyclohexyl,
R⁴ hydrogen,
R⁴ C₁-C₈-alkyl, especially C₁-C₄-alkyl,
R⁴ C₃-C₆-cycloalkyl, especially cyclopropyl, cyclopentyl or cyclohexyl,
R⁴ hydrogen,
R³ C₁-C₆-alkyl and R⁴ hydrogen,
R⁵ hydrogen,
R³ C₃-C₆-cycloalkyl and R⁴ hydrogen,
R⁵ C₁-C₄ alkyl, especially methyl or ethyl,
R⁵ C₃-C₆-cycloalkyl, especially cyclopropyl,
R⁶ C₁-C₆-alkyl, especially methyl, ethyl, n-propyl or iso-propyl,
R⁶ C₃-C₇ cycloalkyl,
R⁶Aryl, which radical can be unsubstituted or can carry one to three of the following groups: fluorine, chlorine, bromine, cyano, C₁-C₄-alkyl, trifluoromethyl, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, tert-butyloxy, trifluoromethoxy, phenyl and phenoxy,
R⁷phenyl, which radical can be unsubstituted or can carry one to three of the following groups: fluorine, chlorine, bromine, cyano, C₁-C₄-alkyl, trifluoromethyl, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, tert-butyloxy, trifluoromethoxy, phenyl and phenoxy,
R⁷naphthyl, which radical can be unsubstituted or can carry one to three of the following groups: fluorine, chlorine, bromine, cyano, C₁-C₄-alkyl, trifluoromethyl, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, tert-butyloxy, trifluoromethoxy, phenyl and phenoxy,
R⁷ C₃-C₇-cycloalkyl, which radical may be unsubstituted or carry one to three of the following groups: halogen, C₁-C₄-alkyl and C₁-C₄-alkoxy, especially C derart-C₇- and especially C₆-cycloalkyl substituted in this way.

With regard to their use, the in the following tables Compounds I.

Table 2

Table 3

Table 4

The new compounds of formula I are suitable as fungicides.

The new compounds or the compositions containing them can for example in the form of directly sprayable solutions, Powders, suspensions, including high-proof aqueous, oily or other suspensions or dispersions, emulsions, oil dispersers sions, pastes, dusts, sprinkles or granules Spraying, atomizing, dusting, scattering or pouring be applied. The application forms depend on the uses purposes; in any case, they should be the finest Ensure distribution of the active ingredients according to the invention.

The plants are usually sprayed with the active ingredients or pollinated or the seeds of the plants with the active ingredients acts.

The formulations are prepared in a known manner, e.g. B. by stretching the active ingredient with solvents and / or Carriers, if desired using emulsifier agents and dispersants, where in the case of water as Ver other organic solvents as auxiliary solvents can be used. As auxiliary agents come there for essentially: 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 rock powder (e.g. kaolins, Clays, talc, chalk) and synthetic stone powder (e.g. finely divided silica, silicates); Emulsifiers like not ionogenic and anionic emulsifiers (e.g. polyoxyethylene fat alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants agents such as lignin sulfite liquor and methyl cellulose.

The alkali, alkaline earth, Ammonium salts of aromatic sulfonic acids, e.g. B. lignin, Phenolic, naphthalene and dibutylnaphthalenesulfonic acid, as well as from Fatty acids, alkyl and alkyl aryl sulfonates, alkyl and lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, as well as fatty alcohol glycol ethers, condensates tion products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or Naphthalenesulfonic acids with phenol and formaldehyde, polyoxy ethylene octyl phenol ether, ethoxylated iso-octyl, octyl or Nonylphenol, alkylphenol, tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, iso-tridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene, lauryl alcohol polyglycol ether acetate,  Sorbitol ester, lignin sulfite liquor or methyl cellulose in Be dress.

Powders, materials for spreading and dusts can be mixed or mixed joint grinding of the active substances with a solid Carrier are manufactured.

Granules, e.g. B. coating, impregnation and homogeneous granules can Herge by binding the active ingredients to solid carriers be put. Solid carriers are mineral earths such as silica gel, silicas, silica gels, silicates, talc, kaolin, lime stone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, Calcium and magnesium sulfate, magnesium oxide, ground art substances, fertilizers, such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and herbal products such as Ge cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

Examples of such preparations are:
I. a solution of 90 parts by weight of a compound I according to the invention 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 a compound I according to the invention, 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-N-monoethanolamide, 5 parts by weight of calcium salt the dodecylbenzenesulfonic acid, 5 parts by weight of the plant product of 40 moles of ethylene oxide and 1 mole of castor oil; A dispersion is obtained by finely distributing the solution in water.
III. an aqueous dispersion of 10 parts by weight of a compound I according to the invention, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil;
IV. An aqueous dispersion of 10 parts by weight of a compound I according to the invention, 25 parts by weight of cyclohexanol, 55 parts by weight of a mineral oil fraction from 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil;
V. a mixture of 80 parts by weight, preferably a solid compound I according to the invention, 3 parts by weight of the sodium salt of di-isobutylnaphthalene-2-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid, ground in a hammer mill 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 a compound I according to the invention 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 a compound I according to the invention, 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 a compound I according to the invention, 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, the further can be diluted;
IX. a stable oily dispersion of 20 parts by weight of a compound I according to the invention, 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 connections are characterized by an excellent Efficacy against a wide range of plant pathogens Mushrooms, especially from the class of Deuterornycetes, Ascomycetes, Phycomycetes and Basidiomycetes. You are for Partly systemic and can act as foliar and soil fungicides be used.

They are particularly important for combating a large number of mushrooms on various crops such as wheat, rye, Barley, oats, rice, corn, grass, cotton, soy, coffee, Sugar cane, wine, fruit and ornamental plants and vegetables such as Cucumbers, beans and squash, as well as on the seeds of these Plants.  

The compounds are applied by using the mushrooms or the Seeds, plants, materials to be protected from fungal attack or the soil with a fungicidally effective amount of the active fabrics treated.

It is used before or after infection Materials, plants or seeds through the mushrooms.

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 turf, Ustilago sugar species on cereals, Ustilago sugar on cereals, Ustilago varieties on cereals, Ustilago sugar varieties on cereals, Ustilago varieties on cereals, Ustilago varieties inaequalis (scab) on apples, Helminthosporium species 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, Reisicularia oryza Phytophthora infestans on potatoes and tomatoes, Fusarium and Verticillium species on various plants, Plasmopara viticola on vines, Alternaria species on vegetables and fruits.

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

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% active ingredient.

The application rates depend on the type of effect desired between 0.025 and 2, preferably 0.1 to 1 kg of active ingredient per ha.

When treating seeds, amounts of active ingredient are generally used from 0.001 to 50, preferably 0.01 to 10 g per kilogram of seed needed.

The agents according to the invention can be used as Fungicides are also present together with other active ingredients, e.g. B. with herbicides, insecticides, growth regulators, fungicides or with fertilizers.

When mixed with fungicides you get in many cases an increase in the fungicidal spectrum of activity.  

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 ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylhbisdithio carbamate, manganese ethyl hbisdithiocarbamate, manganese-zinc ethylene di-bis-dithiocarbamate, tetramethylthiaminodiamide dithiodiamide di - Complex of zinc (N, N, propylene bis-dithiocarbamate), zinc (N, N-propylene bis-dithiocarbamate), N, N, polypropylene bis (thio carbamoyl) 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-benz imidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benz imidazole, 2- (furyl- (2)) - benzimidazole, 2- (thiazolyl- (4)) - benz imidazole, N- (1,1 , 2,2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio phthalimide,
N-dichlorofluoromethylthio-N ′, N′-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodanemethylthiobenzothiazole, 1,4-dichloro-2,5- dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thione-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-di hydro-5-carboxanilido-6-methyl -1,4-oxathiin, 2,3-dihydro-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-car bonic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,4,5 trimethyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan carboxylic acid cyclohexylamide, N- Cyclohexyl-N-methoxy-2,5-dimethyl furan-3-carboxamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, N-formyl-N-morpholine-2,2,2-trichloroethyl acetal, Piperazine 1,4-diylbis- (1- (2,2,2-trichloro-ethyl) -formamide, 1- (3,4-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-di oxolan-2-yl -ethyl] -1H-1,2,4-triazole, N- (n-propyl) -N- (2,4,6-tri chlorophenoxyethyl) -N, -imidazol-yl-urea, 1- (4-chlorophenoxy ) - 3, 3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone, (2-chlorophenyl) - (4-chlorophenyl) -5-pyrimidine-methanol, 5 -Butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyridinomethanol, 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-triazole-1-ethanol , 1- [3- (2-chlorophenyl) -1- (4-fluorophenyl) oxiran-2-yl-methyl] - 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-aminobutyrene acton, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2, 4-dioxo-1,3-oxazolidin, 3 - [(3,5-dichlorophenyl) -5-methyl-5-methoxymethyl-1,3-oxazolidin-2,4-dione, 3- (3,5- Dichlorophenyl) -1-iso-propylcarbamoyl hydantoin, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-meth oximino] acetamide, 1- [2- (2,4 dichlorophenyl) pentyl] -1H-1,2,4-tri azole, 2,4-difluoro-α- (1H-1,2,4-triazolyl-1-methyl) - benzhydryl alcohol, N- (3-chloro-2,6-dinitro-4-trifluoromethylphenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1 - ((bis- (4-fluorophenyl) methyl silyl ) -methyl) -1H-1,2,4-triazole,
Strobilurins such as methyl-E-methoximino- [α- (o-tolyloxy) tolyl] acetate, methyl -E-2- {2- [6- (2-cyanophenoxy) pyridimin-4-yl oxy] pheny} -3-methoxyacrylate , Methyl-E-methoximino- [α- (2,5-di methyloxy) -o-tolyl) acetamide.

Anilino-pyrimidines 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-dimethoxy phenyl) acrylic acid morpholide.

Synthesis examples

The examples given in the synthesis examples below Writings can be modified from the starting compounds Obtaining further representatives of the compounds IV and I used become. The physical data of the Pro Products are shown in the following tables.

example 1 L-valine - [(2-methyl-2- (4-methylphenylhydrazide)]

To 1 g (3 mmol) of N ^α - (tert-butyloxycarbonyl) -L-valine - [(2-methyl-2- (4-methylphenyl)] - hydrazide were added 10 ml of trifluoroacetic acid with cooling and the mixture for one hour at 0 ° C. The mixture was then heated to 20 ° C., the trifluoroacetic acid was largely distilled off and the residue was taken up in dichloromethane, and the organic phase was washed with 40 ml of 10% strength by weight sodium hydroxide solution and water and dried After the solvent was removed, 0.7 g of L-Va lin- [2-methyl-2- (4-methylphenylhydrazide)] remained, which was used in the subsequent step without purification.

The following table lists the results in an analogous manner th intermediate IV of the type shown.

Table 5

Example 2 N ^a - (sec-butyloxycarbonyl) -L-valine [2-methyl-2- (4-methyl phenyl)] - hydrazide

To 0.7 g (3 mmol) of L-valine [2-methyl-2- (4-methylphenyl)] hydrazide and 0.32 g (3.2 mmol) of triethylamine in 10 ml of toluene were at 0 ° C 0.39 g (2.9 mmol) sec-butyl chloroformate was added dropwise. After 15 hours at 20 ° C, the organic phase with 20 ml 10% by weight hydrochloric acid, sodium hydrogen carbonate solution and Washed water. The organic phase was dried and there after the solvent is removed. 0.6 g of the title remained compound as an oil (compound 6 in Table 6).

Example 3 N ^α - (tert-Butyloxycarbonyl) -L-valine [2-methyl-2- (4-chlorophenyl)] hydrazide

To 10.9 g (0.05 mol) of tert-butyloxycarbonyl-L-valine in 200 ml Dimethylformamide were ge at -15 ° C 5 g (0.05 mol) of triethylamine drips and the whole is stirred for 15 minutes. Then you gave 6.8 g (0.05 mol) of isobutylchlorocarbonic acid ester and left 10 Minutes at -15 ° C. 7.8 g (0.05 mol) of N-Me ethyl N- (4-chlorophenyl) hydrazine in 50 ml of dimethylformamide ben. The mixture was stirred at -15 ° C for 1 hour and the reaction mixture Leave the mixture at 20 ° C for a further 2 hours. Then that was The solvent was distilled off, the residue in ethyl acetate ester added and the organic phase in succession with each because 10 ml of 5 wt .-% citric acid, 5 wt .-% sodium hy bicarbonate solution and water washed. The organic phase was dried, concentrated and the remaining residue Chromatographed on silica gel (methyl tert-butyl ether: n-hexane = 1: 1). 5.5 g of the title compound were obtained as an orange-red resin (Compound 27 in Table 6).

Example 4 N ^α - (tert-Butyloxycarbonyl) -L-valine [2-methyl-2- (4-methylphenyl)] hydrazide

To the solution of 10.85 g (0.05 mol) of N-tert-butyloxycarbonyl-L-valine and 5.95 g (0.05 mol) of 4-methylphenylhydrazine in 100 ml of tetrahydrofuran were added 5.1 g (0.051 mol ) Triethylamine and then at 0 ° C 8.31 g (0.051 mol) of diethyl cyanophosphonate. The mixture was stirred at 0 ° C. for one hour and at 20 ° C. for a further 15 hours, and after removal of the solvent, the residue was taken up in ethyl acetate. The organic phase was washed with 40 ml each of 10% by weight sodium hydroxide solution, 10% by weight hydrochloric acid, saturated sodium hydrogen carbonate solution and water. The organic phase was dried and then the solvent was removed. There remained 9.8 g of N ^α - (tert-butyloxycarbonyl) -L-valine [2- (4-methylphenyl)] hydrazide (mp: 163-164 ° C, compound 21 in Table 6).

To 1 g (3.1 mmol) of this compound in 10 ml of dimethylformamide 0.48 g (3.4 mmol) of methyl iodide and 0.47 g (3.4 mmol) of potassium carbonate. It was left at this temperature until no more starting compound was detectable and distilled then stripped off the solvent. The backlog was in Ethyl acetate added. The organic phase was with Washed water, dried and concentrated. The remaining oil was chromatographed on silica gel (cyclohexane: ethyl acetate ester = 2: 1) and 0.3 g of the title compound was obtained as a yellow Oil (Compound 28 in Table 6).

Table 6

Table 7

Examples of use

The fungicidal activity of the compounds of the general formula I was shown by the following experiments:

The active ingredients were given as a 20% by weight emulsion in a mixture from 70% by weight cyclohexanol, 20% by weight Nekanil® LN (Lutensol® AP6, Wetting agent with an emulsifying and dispersing effect on the base ethoxylated alkylphenols) and 10% by weight Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols) processed and in accordance with the desired concentration Diluted water.

Plasmopara viticola

Leaves of pot vines of the "Müller-Thurgau" variety were washed with aq spray liquor, the 80 wt .-% active ingredient and 20 wt .-% Emulsifier contained in the dry substance, sprayed. To the To be able to assess the duration of action of the active ingredients Plant 8 days in the crop after the spray coating has dried on set up house. 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 for 5 days in a greenhouse at temperatures between 20 and 30 ° C set up. After this time the plants became accelerators of the sporangia carrier outbreak again for 16 hours in the damp chamber. Then the visual assessment took place the extent of the fungal outbreak on the undersides of the leaves.

In this test each showed those containing 250 ppm aqueous preparation of compounds 4, 6, 9, 10, 12, 13, 14, 15, 16, 17, 18, 19, 20 and 22 plants treated from Table 6  a maximum infestation of 15%, while untreated plants too 70% were infected.

Claims (9)

1. Carbamoylcarboxylic acid hydrazides of the general formula I and their salts, in which the residues have the following meaning:
R¹ C₁-C₈-alkyl, C₂-C₈-alkenyl or C₂-C₈-alkynyl, these radicals being partially or completely halogenated and / or bearing one to three of the following groups: cyano, C₁-C₄-alkoxy, C₁-C₄ -Halogenalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, C₃-C₇-cycloalkyl, C₃-C₇-cyclo alkenyl, aryl, aryloxy and heteroaryl, the cyclic radicals in turn can carry one to three of the following substituents: Halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxy carbonyl, aryl, aryloxy and Heteroaryl,
C₃-C₇-cycloalkyl or C₄-C₇-cycloalkenyl, these Re ste partially or completely halogenated and / or can carry one to three of the following groups: cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄ -Halogenalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl, aryloxy and aryl- (C₁-C₄) alkyl, the cyclic groups being one to three of the following Can carry substituents: Halo gene, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-halogeno alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄- Alkoxycarbonyl, aryl and aryloxy,
a non-aromatic 4- to 8-membered ring, which may contain one or two of the heteroatoms oxygen, sulfur and nitrogen as ring members in addition to carbon, wherein the carbon atoms in the ring can carry one or two of the following groups: halogen, cyano, C₁-C₄ -Alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl and aryloxy and where the second and each further nitrogen atom as a hetero atom in the ring carries hydrogen or a C₁-C₄ alkyl group,
Aryl or heteroaryl, where these radicals can carry one to three of the following groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl, aryloxy and heteroaryl, in which the cyclic substituents in turn can carry one to three of the following substituents: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁ -C₄-haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio and C₁-C₄alkoxycarbonyl or
W¹W² C = N-, where
W¹ is C₁-C₈-alkyl, which can be partially or fully halogenated and / or carry one to three of the following groups: cyano, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl, aryloxy and heteroaryl, where the cyclic groups can in turn carry one to three of the following substituents: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄- Haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxy carbonyl, aryl and aryloxy,
C₂-C₈-alkenyl or C₂-C₈-alkynyl, these radicals being partially or completely halogenated and / or bearing one to three of the following groups: cyano, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄- Alkyl thio, C₁-C₄-alkoxycarbonyl, aryl and aryloxy, where the cyclic groups in turn can carry one to three of the following substituents: halogen, cyano, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkyl thio, C₁-C₄ alkoxycarbonyl, aryl and aryloxy,
C₃-C₇-cycloalkyl or C₃-C₇-cycloalkenyl, where these radicals can carry one to three of the following groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄ -Alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl and aryl- (C₁-C₄) -alkyl, where the groups containing aryl can carry one to three of the following substituents: Halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxy carbonyl, aryl and aryloxy or
Aryl or heteroaryl, where these radicals can carry one to three of the following groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl and aryloxy and
W² is hydrogen or one of the groups W¹;
R² is hydrogen or C₁-C₈-alkyl or C₃-C₇-cycloalkyl, which can be partially or completely halogenated;
R³ C₁-C₈-alkyl, which radical can carry one to three of the following groups: halogen, cyano, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio and C₁-C₄-alkoxy carbonyl,
C₃-C₇-cycloalkyl or phenyl- (C₁-C₄) alkyl, the rings of these radicals can carry one to three of the following groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy alkyl, C₁-C₄ -Halogenalkyl, C₁-C₄-alkoxy, C₁-C₄-halogen alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl and aryloxy;
R⁴ is hydrogen or one of the radicals R³ or
R³ and R⁴ together with the carbon atom to which they are attached, a 4- to 8-membered ring, which as a ring members may contain one or two of the hetero atoms oxygen, sulfur and nitrogen in addition to carbon, the carbon atoms in the ring being one or can carry two of the following groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄ -Alkoxycarbonyl, aryl and aryloxy and where nitrogen as a hetero atom carries hydrogen or a C₁-C₄-alkyl group;
R⁵eins of the residues R²;
R⁶ C₁-C₈-alkyl, C₂-C₈-alkenyl or C₂-C₈-alkynyl, these radicals being partially or completely halogenated and / or bearing one to three of the following groups: cyano, C₁-C₄-alkoxy, C₁-C₄ -Halogenalkoxy, C₁-C₄-alkylthio, C₃-C₇-cycloalkyl, C₃-C₇-cycloalkenyl, aryl, aryloxy and heteroaryl, where the cyclic radicals in turn can carry one to three of the following substituents: halogen, cyano, C₁-C₄- Alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-halogeno alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl, aryloxy and heteroaryl,
C₃-C₇-cycloalkyl or C₃-C₇-cycloalkenyl, these radicals can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄- Haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl, aryloxy and aryl- (C₁-C₄) alkyl, where the cyclic groups can carry one to three of the following substituents: halogen, cyano , C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl and aryloxy,
a non-aromatic 4- to 8-membered ring, which may contain one or two of the heteroatoms oxygen, sulfur and nitrogen as ring members besides carbon, the carbon atoms in the ring being able to carry one or two of the following groups: halogen, cyano, C₁- C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl and aryloxy and where the second and each further nitrogen atom as a hetero atom in the ring Bears hydrogen or a C₁-C Alkyl alkyl group,
Aryl or heteroaryl, where these radicals can carry one to three of the following groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl, aryloxy and heteroaryl, in which the cyclic substituents can in turn carry one to three of the following substituents: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl , C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and C₁-C₄-alkylthio or
when R³ is isopropyl, hydrogen;
R⁷eins of the residues R⁶, except hydrogen;
except the compounds according to the following definition of the residues:
Ia-d (R¹ = Ph-CH₂; R² = H; R³ = CH₃, (CH₂) ₂CH₃, CH (CH₃) ₂ or Ph-CH₂; R⁴, R⁵ = H; R⁶, R⁷ = CH₂CH₂Cl),
Ie-h (R¹ = C (CH₃) ₃; R² = H; R³ = CH₃, CH (CH₃) ₂, CH (CH₃) CH₂CH₃, CH₂CH (CH₃) ₂ or Ph-CH₂; R⁴, R⁵ = H; R⁶, R⁷ = CH₂CH₂Br),
Ii (R¹ = Ph-CH₂; R² = H; R³ = CH₃; R⁴, R⁵ = H; R⁶ = CH₃; R⁷ = Ph),
Ij-k (R¹ = Ph-CH₂; R² = H; R³ = CH (CH₃) ₂ or CH₂CH (CH₃) ₂; R⁴, R⁵ = H; R⁶, R⁷ = Ph),
I1 (R¹ = C (CH₃) ₃; R² = H; R³ = CH (CH₃) ₂; R⁴, R⁵, R⁶ = H; R⁷ = Ph),
Im (R¹ = Ph-CH₂; R² = H; R³ = Ph-CH₂; R⁴, R⁵ = H; R⁶₁R⁷ = CH₂CH₃),
In-o (R¹ = Ph-CH₂; R² = H; R³ = CH₂SCH₃ or CH₂CH₂SCH₃; R⁴, R⁵ = H; R⁶, R⁷ = CH₂CH₂Cl). 2. A process for the preparation of carbamoylcarboxylic acid hydrazides of the general formula I or salts thereof according to claim 1, characterized in that a carbamoylcarboxylic acid of the general formula II with a hydrazine of the general formula III reacted and the compound I thus obtained, if desired, converted into one of its salts in a manner known per se. 3. A process for the preparation of carbamoylcarboxylic acid hydrazides of the general formula I in which R¹ is a group W¹W² C = N-, or their salts according to claim 1, characterized in that a carbamoylcarboxylic acid hydrazide of the general formula I in which the group R¹-O- (CO) stands for a protective group which can be split off in a manner known per se, into an amino acid hydrazide IV transferred, the amino acid hydrazide IV thus obtained with a chloroformyloxime of the general formula V reacted in the presence of a base and the compound I thus obtained, if desired, converted into one of its salts in a manner known per se. 4. Process for the preparation of carbamoylcarboxylic acid hydrazides of the general formula I or salts thereof according to claim 1, in the R⁶ for C₁-C₈-alkyl, C₄-C₇-cycloalkyl or Aryl- (C₁-C₄) alkyl, characterized in that one Carbamoylcarboxylic acid hydrazide of the general formula I according to Claim 1, in which R⁶ is hydrogen, with a ver Binding of the general formula R⁶-X, in which R⁶ for C₁-C₈-alkyl, C₄-C₇-cycloalkyl or aryl- (C₁-C₄) alkyl and X represents a negative leaving group, under Mit uses a base and the resulting Ver if desired, bond I in a manner known per se in transferred one of their salts. 5. Containing agents suitable for combating harmful fungi usual additives and an effective amount of a compound of the general formula I or one of its salts according to An Proverb 1, except the connections Ia to Io. 6. A method of combating harmful fungi, thereby records that the harmful fungi, their habitat or the plants, surfaces, materials or Spaces with an effective amount of a compound of general my formula I or one of its salts according to claim 1 finally the compounds Ia to Io, or an I included tendency agents treated according to claim 5. 7. Use of the compounds of general formula I or one of its salts according to claim 1, including the Compounds Ia to Io, for controlling harmful fungi. 8. Amino acid hydrazides of the general formula IV in which R³ represents a group CH (CH₃) ₂, CH₂CH (CH₃) ₂ or CH (CH₃) C₂H₅ and R⁴, R⁵, R⁶ and R⁷ have the meaning given in claim 1, except for the compounds according to the following definition of the radicals:
IVa-b (R³ = CH (CH₃) ₂ or (CH₂) ₂CH₃; R⁴, R⁵ = H; R⁶, R⁷ = CH₂CH₂Cl)
IVc-e (R³ = CH (CH₃) ₂, CH (CH₃) CH₂CH₃ or CH-CH (CH₃) ₂; R⁴, R⁵ = H; R⁶, R⁷ = CH₂CH₂Br),
IVf (R³ = CH (CH₃) ₂; R⁴, R⁵, R⁶ = H; R⁷ = Ph),
IVg (R³ = CH (CH₃) ₂; R⁴, R⁵ = H; R⁶, R⁷ = Ph). 9. amino acid hydrazides of the general formula IV according to claim 8, in which R³ represents a group CH (CH₃) ₂, R⁴ and R⁵ have the meaning given in claim 1,
R⁶ is C₁-C₈-alkyl, this radical being partially or completely halogenated and / or can carry one to three of the following groups: cyano, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₃- C₇-cycloalkyl, C₃-C₇-cycloalkenyl, aryl, aryloxy and heteroaryl, where the cyclic radicals in turn can carry one to three of the fol lowing substituents: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄ -Halogenalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl, aryloxy and heteroaryl and
R⁷ is aryl, this radical can carry one to three of the fol lowing groups: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy , C₁-C₄-alkylthio, aryl, aryloxy and heteroaryl, in which the cyclic substituents can in turn carry one to three of the following substituents: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl , C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and C₁-C₄-alkylthio.