DE4434462A1 - Carbamoyl carboxylic acid amide derivs. - Google Patents

Abstract

Carbamoyl carboxylic acid amide derivs. of formula (I) and their salts are new R1 = 1-8C alkyl, 2-8C alkenyl, or 2-8C alkynyl (these gps. being opt. partially or completely halogenated and/or mono-, di- or tri-substd. with T gps.); 3-7C cycloalkyl or 3-7C cycloalkyl (these last 2 gps. being opt. partially or completely halogenated and/or mono-, di- or tri-substd. with T gps. (excluding cycloalkyl, cycloalkenyl and heteroaryl) or with 1-4C alkyl or aryl(1-4C)alkyl (this last gp. itself opt. substd. with T gps. excluding cycloalkyl or cycloalkenyl)); a non-aromatic 4-8 membered ring contg. in the ring, in addition to C, 1 or 2 heteroatoms chosen from O, S and N (the ring C being opt. mono-, di- or tri-substd. with halogen, 1-4C alkyl, T gps. (excluding cycloalkyl, cycloalkenyl and heteroaryl) and the second and any further N heteroatom carrying H or 1-4C alkyl); aryl or heteroaryl (these 2 gps. opt. mono-, di- or tri-substd. with halogen, 1-4C alkyl or T gps. (excluding cycloalkyl and cycloalkenyl)) or W1W2C=N; W1 = 1-8C alkyl (opt. partially or completely halogenated and/or opt. mono-, di- or tri-substd. with T gps. (excluding alkoxycarbonyl, cycloalkyl and cycloalkenyl)), 2-8C alkenyl, 2-8C alkynyl (opt. partially or completely halogenated and opt. mono-, di- or tri-substd. with 1-4C alkyl or T gps. (excluding cycloalkyl, cycloalkenyl and heteroaryl), 3-7C cycloalkyl or 3-7C cycloalkenyl (opt. mono-, di- or tri-substd. with halogen, 1-4C alkyl, aryl(1-4C)alkyl (this last gp. itself opt. substd. with halogen, 1-4C alkyl or T gps., excluding cycloalkyl, cycloalkenyl or heteroaryl) or T gps. (excluding cycloalkyl, cycloalkenyl, aryloxy or heteroaryl)), aryl or heteroaryl (these last 2 gps. opt. substd. with T gps., excluding cycloalkyl, cycloalkenyl or heteroaryl); W2 = H or a gp. W1; R2 = H, 1-8C alkyl or 3-7C cycloalkyl (these last 2 gps. opt. partially or completely halogenated); R3 = 1-8C alkyl, 3-7C cycloalkyl (opt. mono-, di- or tri-substd. with halogen, 1-4C alkyl, phenyl(1-4C)alkyl (in which the Ph gp. is opt. mono-, di- or tri-substd. with halogen, 1-4C alkyl or T gps., excluding cycloalkyl, cycloalkenyl, aryl, aryloxy or heteroaryl)); R4 = one of the R3 gps.; or R3 and R4 together with the C atom to which they are attached form a 4-8 membered ring which contains, in addition to C, 1 or 2 heteroatoms chosen from O, S and N (the ring C being opt. mono- or di-substd. with halogen, 1-4C alkyl and T gps. (excluding cycloalkyl, cycloalkenyl and heteroaryl) and the N heteroatom carrying H or 1-4C alkyl); R5 = a R2 gp.; X = H, 1-8C alkyl and/or 2-8C alkenyl (these last 2 gps. opt. partially or completely halogenated and opt. mono-, di- or tri-substd. with T gps., excluding cycloalkyl, cycloalkenyl or heteroaryl), 3-7C cycloalkyl and/or 3-7C cycloalkenyl (these 2 gps. opt. partially or completely halogenated and opt. mono-, di- or tri-substd. with 1-4C alkyl, aryl(1-4C) alkyl (this last opt. substd. with halogen, 1-4C alkyl and T gps., excluding cycloalkyl, cycloalkenyl and heteroaryl), or T gps. (excluding cycloalkyl, cycloalkenyl or heteroaryl)); m = 0-2; A = 3-7C cycloalkyl or 3-7C cycloalkenyl (opt. partially or completely halogenated and/or opt. mono-, di- or tri-substd. with 1-4C alkyl, aryl(1-4C)alkyl (thus last opt. mono-, di- or tri-substd. on aryl with halogen, 1-4C alkyl or T gps., excluding cycloalkyl, cycloalkenyl and heteroaryl) or T gps. excluding cycloalkyl, cycloalkenyl, aryloxy and heteroaryl); R6 = aryl or heteroaryl (these gps. opt. mono-, di- or tri-substd. with halogen or T gps., excluding cycloalkyl, cycloalkenyl or heteroaryl); T = CN, 1-4C alkoxyalkyl, 1-4C haloalkyl, 1-4C alkoxy, 1-4C haloalkoxy, 1-4C alkylthio, 1-4C alkoxycarbonyl, 3-7C cycloalkyl, 3-7C cycloalkenyl, aryl, aryloxy or heteroaryl, the cyclic gps. themselves being opt. mono-, di- or tri-substd. with halogen, CN, 1-4C alkyl, 1-4C alkoxy alkyl, 1-4C haloalkyl, 1-4C alkoxy, 1-4C haloalkoxy, 1-4C alkylthio, 1-4C alkoxycarbonyl, aryl, aryloxy or heteroaryl.

Description

The present invention relates to carbamoylcarboxamides general formula I.

and their salts, in which the variables have the following meaning:
R¹ C₁-C₈-alkyl, 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-alkoxyalkyl, C₁-C₄ -Halogenalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, C₃-C₇-cycloalkyl, C₃-C₇-cycloalkenyl, 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-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 carries further nitrogen atom as hetero atom in the ring 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-C₄-alkylthio and C₁-C₄-alkoxycarbonyl,
W¹W²C = N-, where W¹ is C₁-C₈-alkyl, which can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄ -Alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, aryl, aryloxy and heteroaryl, where the cyclic groups 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-alkoxycarbonyl, aryl, 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-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄- Haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, 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-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-halogeno alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, 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 alkoxycarbonyl, aryl and aryloxy,
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, C₃-C₇-cycloalkyl, 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 and C₁-C₄-alkoxycarbonyl or phenyl- (C₁-C₄) -alkyl, where the phenyl radical can carry one to three of the following groups: halogen, 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;
R⁴ is hydrogen or one of the groups mentioned in R³ or
R³ and R⁴ together with the carbon atom to which they are attached form 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 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 wherein nitrogen as the hetero atom is hydrogen or a C₁-C₄ alkyl group;
R⁵ is R²;
X independently of one another hydrogen, C₁-C₈-alkyl and / or C₂-C₈-alkenyl, these radicals being partially or completely halogenated and / or bearing one to three of the following groups: cyano, C₁-C₄-alkoxyalkyl, C₁-C₄ -Haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio and C₁-C₄-alkoxycarbonyl, aryl and aryloxy,
C₃-C₇-cycloalkyl and / or C₃-C₇-cycloalkenyl, these radicals being partially or completely halogenated and / or bearing 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 in turn 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;
m 0, 1, 2;
A 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 -Halogenalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl and aryl- (C₁-C₄) alkyl, being unsubstituted in the groups containing aryl or 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;
R⁶ 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, where in the groups containing aryl, this 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.

The invention also relates to processes for producing the Compounds I, compositions containing them, a process for the preparation provision of such means and a method for combating Harmful fungi and the use of compounds I for this.

Amino acid amides with fungicidal activity are known from the literature known (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), but with regard to their fungicidal effect can not satisfy.  

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

Accordingly, the compounds I defined at the outset were found as well as means containing them.

Furthermore, processes for the preparation of compounds I and found agents containing them and also a process to combat harmful fungi and the use of Connections I to this.

The compounds I can start in a manner known per se of the corresponding carbamoylcarboxylic acids II who produced the. The compounds I are preferably obtained according to the following the described methods A and B (the literature citations "Houben-Weyl" refer to: Houben-Weyl, Methods of Or ganischen Chemie, 4th edition, Thieme Verlag, Stuttgart).

Procedure A

The Carbamoylcarbonsäureamide I, is obtained by the Carba reacted moylcarboxylic acids II with the amines III.

The carbamoyl carboxylic acids II are known or can be after known methods, especially based on the underlying Amino acids are produced (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 (see Organikum, VEB German Publishing House of Sciences, 15th edition, Berlin, 1977, page 610 ff .; Indian J. Chem. 10, Page 366 (1972), Tetrahedron 43, page 4071 ff. (1987); J. Med. Pharm. Chem. 5, page 1243 ff. (1962); US-A-4 126 613).  

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 Tetrahedron Letters, Volume 18, page 1595 to page 1598 (1973) and "Houben-Weyl", volume 15/1, page 28 to page 32). These derivatives are then with the amines III in 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 Tetrahydrofuran or toluene.

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

The implementation of the amines III with the carboxy-activated carbamoyl carboxylic 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, where they are usually recovered from the raw product.

In a preferred embodiment of this process stage who the the carbamoyl carboxylic acid II, the amine III, which is used to produce of the caboxy-activated derivative of carbamoylcarboxylic acid II suitable reagent and the base in a one-pot process, if appropriate in an inert solvent, reacted and the Crude product then in a known manner on the Carbamoylcarboxamide I worked up.

Procedure B

The carbamoylcarboxamides I are obtained by converting the carbamoylcarboxamides I, in which the group R¹-O- (CO) stands for a protective group which can be separated in a manner known per se, into amino acid amides IV and convert them with chloroformyloximes V in Implemented presence of bases.
Stage Ba: preparation of the amino acid amides IV

Cleavage of the group R¹-O- (CO) from the Carbamoylcarbonsäurea miden 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).

Suitable cleavable groups contain a tert-Bu as the radical R¹ tyl 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 B. 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 reversed with the chloroformyloximes V in the presence of bases puts.

The chloroformyloximes V are known or can be according to known ones Methods such as B. prepared by phosgenation of oximes (see e.g. Zeitschrift für Chemie, Volume 9, page 344 bis Page 345 (1967)).

The reaction is preferably carried out in an organic solution medium, especially toluene, methylene chloride or 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, 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, respectively worked up in the usual way, e.g. B. by mixing with what water, separation of the phases and, if necessary, chromatographic Cleaning the raw products. The intermediate and end products fall e.g. T. in the form of colorless or slightly brownish, viscous oils, the under reduced pressure and at a moderately elevated temperature can be exempted from volatile components. If the Intermediate and end products can be obtained as solids cleaning, for example by recrystallization or Digestion done.

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

The salts, especially the acid-resistant, are also part of the invention compounds I, which are basic centers, especially basic Contain nitrogen atoms, especially with mineral acids such as Sulfuric acid and phosphoric acid or Lewis acids such as zinc chloride. Usually it depends on the type of salt not at. For the purposes of the invention, those salts are preferred which plants, areas, materia to be kept free from harmful fungi lien or rooms do not damage and the effect of the connections I don't interfere.

The salts of the compounds I are in a manner known per se common, especially by reacting the appropriate carbamoyl carboxamides I with the acids mentioned in water or inert organic solvents at temperatures from -80 to 120 ° C, preferably 0 to 60 ° C.

The production of the salts is usually independent of the pressure, which is why you work 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, 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 any position, carry 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;
Halogenalkoxy: straight-chain or branched alkoxy groups with 1 to 4 carbon atoms (as mentioned above), in which groups the hydrogen atoms can be partially or completely replaced by halogen atoms (as mentioned above), e.g. B. C₁-C₂-haloalkoxy such as chloromethyloxy, dichloromethyloxy, tri chloromethyloxy, fluoromethyloxy, difluoromethyloxy, trifluoromethyl oxy, chlorofluoromethyloxy, dichlorofluoromethyloxy, chlorodifluoromethyloxy, 1-fluoroethyloxy, 2-fluoroethyloxy, 2,2-difluoromethyloxy, 2,2,2-oxyoxy-2,2,2-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-propenyl, 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 -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, e.g. B. C₂-C₆-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- butinyl, 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, e.g. B. C₃-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 ring or carbon as well as one or two oxygen, sulfur or nitrogen atoms 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 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-fused 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 can be replaced as mentioned above can.

With regard to their biological action against harmful fungi Compounds I preferred in which R¹ is C₁-C₆ alkyl, wel ches can carry one to three of the following groups: halogen, C₁-C₄ alkoxyalkyl, phenyl and phenoxy. Are particularly preferred including those compounds I in which R¹ is C₁-C₄-alkyl or Benzyl stands.

Compounds I are also preferred in which R¹ is for C₃-C₇-cyclo alkyl, which carry one to three of the following groups can: halogen, C₁-C₄ alkoxyalkyl, phenyl and phenoxy. Especially preferred among these are those compounds I in which R¹ is Cyclopropyl, cyclopentyl or cyclohexyl.

In addition, compounds I are preferred in which R¹ is aryl stands, which can carry one to three of the following groups: Halogen, C₁-C₄-alkyl and C₁-C₄-alkoxy, especially in which R¹ for Phenyl or naphthyl, which are unsubstituted and / or can carry one to three of the following groups: fluorine, chlorine, Bromine, C₁-C₄ alkyl, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, tert-butyloxy. Especially before are added compounds I in which R¹ is unsubstituted phenyl, 1-naphthyl or 2-naphthyl.

Furthermore, compounds I are preferred in which R¹ is (W¹W²C = N-), where W¹ is C₁-C₈-alkyl, which is partial or can be fully halogenated.

In addition, compounds I are preferred in which R¹ is (W¹W²C = N-), where W² is aryl, which is one to three can carry the following groups: halogen, C₁-C₄-alkyl and C₁-C₄ alkoxy.

Compounds I are further preferred in which R 2 is hydrogen stands.  

Furthermore, compounds I are preferred in which R² is C₁-C₄ alkyl.

In addition, compounds I are preferred in which R³ is C₁-C₆ alkyl, particularly preferably C₁-C₄-alkyl means.

Compounds I are also preferred in which R³ C₃-C₆-cyclo alkyl, particularly preferably cyclopropyl, cyclopentyl or cyclo means hexyl.

In addition, compounds I are preferred in which R⁴ for What stands.

In addition, compounds I are preferred in which R⁴ for C₁-C₈-alkyl, with C₁-C₄-alkyl being particularly preferred.

Furthermore, compounds I are preferred in which R⁴ for C₃-C₆-cyclo alkyl stands, especially for cyclopropyl, cyclopentyl or cyclo hexyl.

In addition, compounds I are preferred in which R⁴ is hydrogen means.

Furthermore, compounds I are preferred in which R³ is for C₁-C₆ alkyl and R⁴ is hydrogen.

Furthermore, compounds I are preferred in which R⁵ is hydrogen means.

In addition, compounds I are preferred in which R³ is for C₃-C₆-cycloalkyl and R⁴ is hydrogen.

Furthermore, compounds I are preferred in which R⁵ is C₁-C₄ alkyl stands, with methyl and ethyl are particularly preferred.

In addition, compounds I are preferred in which R⁵ for C₃-C₆-cycloalkyl, especially cyclopropyl.

Compounds I are further preferred in which the radicals X are independent dependent on each other mean hydrogen.

Furthermore, compounds I are preferred in which the radicals X un depending on each other C₁-C₆-alkyl, in particular C₁-C₄-alkyl be interpret.  

In addition, compounds I are preferred in which the radicals X independently of one another C₃-C₆-cycloalkyl, especially cyclo propyl, cyclopentyl or cyclohexyl.

Compounds I are further preferred in which m is 0 or 1 stands.

In addition, compounds I are preferred in which A is C₃-C₇-cycloalkyl, which is one to three of the following groups pen can carry: halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy and C₁-C₄ alkylthio, preferably such substituted C₃-C₇ cycloalkyl and especially unsubsti tuated cyclopropyl, cyclopentyl or cyclohexyl.

Furthermore, compounds I are preferred in which A is C₅-C₆-cycloalkenyl, which is one to three of the following Groups can carry: halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy and C₁-C₄ alkylthio.

In addition, compounds I are preferred in which R⁶ is phenyl which is unsubstituted or one to three of the the following groups: fluorine, chlorine, bromine, cyano, C₁-C₄ alkyl, trifluoromethyl, methoxy, ethoxy, n-propyloxy, iso- Propyloxy, n-butyloxy, iso-butyloxy, tert-butyloxy, trifluoro methoxy, phenyl and phenoxy.

Compounds I are also preferred in which R⁶ is naphthyl which is unsubstituted or one to three of the the following groups: fluorine, chlorine, bromine, cyano, C₁-C₄ alkyl, trifluoromethyl, methoxy, ethoxy, n-propyloxy, iso- Propyloxy, n-butyloxy, iso-butyloxy, tert-butyloxy, trifluoro methoxy, phenyl and phenoxy.

With regard to their use, the in the following tables, especially tables 11 and 12, Compounds I, where C₆H₁₁ for cyclohexyl stands.  

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

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, pul vern, suspensions, also high-proof aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, 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 fatty al 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 alkylarylsulfonates, alkyl, lauryl ether and Fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and Octadecanols, as well as fatty alcohol glycol ethers, condensates products of sulfonated naphthalene and its derivatives 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 ethyleno xid condensates, ethoxylated castor oil, polyoxyethylene alkyl ether  or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulfite liquor or methyl cellulose.

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 Cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

Examples of such preparations are (refer to substance numbers refer to Table 11, p. u.):

• I. a solution of 90 parts by weight of compound 1 and 10 parts by weight of N-methyl-2-pyrrolidone for use in the form of tiny drops is suitable;
• II. A mixture of 10 parts by weight of compound no. 2, 70 parts by weight of xylene, 10 parts by weight of the addition pro product of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N- monoethanolamide, 5 parts by weight of calcium salt of dodecyl benzenesulfonic acid, 5 parts by weight of the adduct 40 moles of ethylene oxide to 1 mole of castor oil; through fine Distributing the solution in water gives a disper sion.
• 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 with 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 from boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 mol Ethylene oxide in 1 mol castor oil;  
• V. a mixture of 80 ground in a hammer mill Parts by weight of compound no. 5, 3 parts by weight of 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 powder Silica gel; by finely distributing the mixture in Water is obtained from a spray liquor;
• VI. an intimate mixture of 3 parts by weight of the compound No. 6 and 97 parts by weight of finely divided kaolin; this Dusts contain 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 on the surface of this Silica gel was sprayed; this processing exists the active ingredient has good adhesiveness;
• VIII. A stable aqueous dispersion of 40 parts by weight of Compound No. 8, 10 parts by weight of the sodium salt of one Phenolsulfonic acid-urea-formaldehyde condensate, 2 Parts by weight of silica gel and 48 parts by weight of water, the white can be thinned;
• IX. a stable oily dispersion of 20 parts by weight of Ver Binding No. 15, 2 parts by weight of the calcium salt of Dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol poly glycol ether, 20 parts by weight of the sodium salt of one 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 Deuteromycetes class, Ascomycetes, Phycomycetes and Basidiomycetes from. 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 pumpkin plants, 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 of the materia lien, 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 mushrooms) on strawberries, vines, ornamental plants and vegetables, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, or rice rice , 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 between 0.1 and 1 kg of active ingredient fabric 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 Ferridimethyl dithiocarbamate, zinc dimethyldithiocarbamate, Zinkethylenbisdithio carbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylene diamine min 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- (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-ben methyl zimidazole-carbamate, 2-methoxycarbonylamino-benz imidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N- (1st , 1,2,2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophtha-imide, 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-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl- 1,4-oxathiin, 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-carboxamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, N-formyl-N-morpholine-2,2 , 2-trichloroethyl valley, piperazin-1,4-diyl-bis- (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-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, N- (n -Pro pyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazol-yl-urea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4 tri azol-1-yl) -2-butanone, (2-chlorophenyl) - (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine , Bis- (p-chlorophenyl) -3-pyridinium 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-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-fu royl (2) -alaninate, DL-N- (2,6-dimethyl-phenyl) -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-dicarboxylic acid imide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1 - [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4-di fluoro-a- (1H-1,2,4-triazolyl-1-methyl) - benzhydryl alcohol, N- (3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoro methyl-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-phenoxy phenyl)] - 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 acid morpholide.

Synthesis example

The above reproduced in the synthesis example below writing can change the starting connections to the profit tion of other representatives of the compounds I are used. The physical data of the products manufactured accordingly are in reproduced in the following tables.

N- (iso-propyloxycarbonyl) -L-valine (4-methoxyphenyl) cyclohexyl amid

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) of triethylamine and under Cool 4.01 g (25 mmol) of diethyl cyanophosphonate was added. 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 added with ethyl acetate. The organic phase was each with 40 ml of 10% hydrochloric acid, 10% sodium hydrogen carbonate solution and water washed. The organic phase was dried and then the solvent removed. There remained 8.9 g of N- (tert-butyloxycarbonyl) -L-valine [3- (4-methoxy phenyl) cyclohexyl] amide (mp. 128 ° C).

To 8.48 g (21 mmol) of this compound was added 50 ml with cooling Trifluoroacetic acid added and the mixture ge for 1 hour at 0 ° stirs. The trifluoroacetic acid was then heated to 20 ° C. largely distilled off, residual acid removed and the back was recorded with dichloromethane. 5.8 g of L-Va remained lin-3- (4-methoxyphenyl) -cyclohexylamide, which without further Rei could be used for the next stage.

0.53 g (2.8 mmol) of this compound and 0.30 g (3 mmol) of triethyl amine in 40 ml of toluene at 0 ° C with 0.35 g (2.8 mmol) of chlora isopropyl formate added, after 15 hours at 20 ° C. stirred, the solvent removed and the residue with vinegar acid ethyl ester added. The organic phase was with because 40 ml of 10% hydrochloric acid, 10% sodium hydrogen carbonate Washed solution and water and then dried. After that  the solvent was removed. 0.9 g of the title remained compound as a colorless crystalline residue (mp: 124 ° C.).  

Table 11

Table 12

Examples of use

The fungicidal activity of the compounds of the general formula I was demonstrated by the following tests:
The active ingredients were in the form of a 20% by weight emulsion in a mixture of 70% by weight cyclohexanol, 20% by weight 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 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 1, 2, 3, 4, 5, 6, 7, 8 and 20 (Table A), and 64 and 69 (Table B) Plant a maximum infestation of 10% while untreated Plants were 65% infected.

Phytophthora infestans

Leaves of potted plants of the "large meat tomato" variety with aqueous spray liquor containing 80% by weight of active ingredient and 20% by weight Emulsifier contained in the dry substance, sprayed. To The leaves were exposed to a zoospore suspension for 24 hours of the fungus Phytophthora infestans infected. The plants were then in a chamber with water vapor-saturated air at tempera doors between 16 and 18 ° C. After 6 days had the infestation of the untreated but infected control plants developed so strongly that the fungicidal effectiveness of the Substances could be assessed visually.

In this test each showed those containing 250 ppm aqueous preparation of compounds 1, 2, 3, 4, 5, 6, 7, 8, 15 and 27 (Table A), further 57, 59, 60, 66, 69 and 79 (Ta belle B) treated plants a maximum infestation of 5%, while untreated plants were 75% infected.

Claims (7)

1. Carbamoylcarboxamides of the general formula I and their salts, in which the variables have the following meaning:
R¹ C₁-C₈-alkyl, 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-alkoxyalkyl, C₁-C₄ -Halogenalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxy carbonyl, C₃-C₇-cycloalkyl, C₃-C₇-cycloalkenyl, aryl, aryloxy and heteroaryl, the cyclic radicals on the one hand they 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, 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 can contain one or two of the heteroatoms oxygen, sulfur and nitrogen in addition to carbon as ring members, 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, 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-halo alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio and C₁-C₄-alkoxycarbonyl,
W¹W²C = N-, where W¹ is C₁-C₈-alkyl, which can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C₁-C₄-alkoxy alkyl, C₁-C₄-haloalkyl, 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, 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-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄ -Halogenalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, 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-alkyl, C₁-C₄-alkoxyalkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxy carbonyl, 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 ,
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, C₃-C₇-cycloalkyl, 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 and C₁-C₄-alkoxycarbonyl or phenyl- (C₁-C₄) -alkyl, where the phenyl 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, C₁-C₄-alkoxycarbonyl, aryl and aryloxy;
R⁴ is hydrogen or one of the groups mentioned in R³ or
R³ and R⁴ together with the carbon atom to which they are attached form a 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, 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 -Alkoxy carbonyl, aryl and aryloxy and wherein nitrogen as a hetero atom carries hydrogen or a C₁-C₄ alkyl group;
R⁵ is R²;
X independently of one another hydrogen, C₁-C₈-alkyl and / or C₂-C₈-alkenyl, these radicals being partially or completely halogenated and / or bearing one to three of the following groups: cyano, C₁-C₄-alkoxyalkyl, C₁- C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio and C₁-C₄-alkoxycarbonyl, aryl and aryl oxy,
C₃-C₇-cycloalkyl and / or C₃-C₇-cycloalkenyl, these radicals being partially or completely halogenated and / or bearing 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 in turn 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;
m 0, 1, 2;
A 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 -Halogenalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkoxycarbonyl, aryl and aryl- (C₁-C₄) -alkyl, being unsubstituted in the groups containing aryl can be or 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;
R⁶ 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, where in the groups containing aryl this 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. 2. 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 one

• a) a carbamoylcarboxamide 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 amide IV transferred and
• b) the amino acid amide IV thus obtained with a chloroformyl oxime of the general formula V in the presence of a base.

4. Containing agents suitable for combating harmful fungi usual additives and an effective amount of a compound of the general formula I according to claim 1. 5. Process for the production of to control harmful fungi suitable means, characterized in that one Compounds of general formula I according to claim 1 used. 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 treated my formula I according to claim 1. 7. Use of the compounds of general formula I according to Claim 1 for combating harmful fungi.