DE3933898A1 - New amino-carbonyl-substd. iso-thiazole or isoxazole carboxylic acid d - Google Patents

Abstract

Aminocarbonyl-substd. isoxazole and isothiazole derivs. of formula (Ia)-(Id) are new: X = O or S; R1 = H; halo; 1-6C alkyl; 1-4C alkoxy or alkylthio; benzyl; phenyl; phenoxy or phenylthio; 5-6 membered, satd. or aromatic heterocycle contg. 1 or 2 O, S or N, and opt. substd. by 1 or 2 halo, 1-3C alkyl, alkoxy or alkoxycarbonyl; 3-8C cycloalkyl(1-6C)alkyl; 2-6C alkenyl or alkynyl, both opt. substd. by 1-3 halo or 1-3C alkoxy and/or by one cyclopropyl or phenyl; or 3-8C cycloalkyl or 3-6C cycloalkenyl, both opt. substd. by 1-3 1-4C alkyl or halo; R'1 = 3-8C cycloalkyl(1-6C)alkyl; 2-6C alkenyl or alkynyl as for R1, or 3-6C cycloalkenyl opt. substd. by 1-3 halo or 1-4C alkyl; R2 = HCO, 4,5-dihydrooxazol-2-yl, COYR5 or CONR6R7; Y = O or S; R5 = H; 1-6C alkyl; R3 = H, 1-6C alkyl; R4 = H; OH, 1-4C alkoxy; 1-6C alkyl, etc., their environmentally acceptable salts are included.

Description

The present invention relates to azole-carboxylic acid amides of the general Formula I

in which the variables have the following meaning:
X oxygen or sulfur;
R¹ is a C₁-C₆-alkyl group substituted by C₃-C₈-cycloalkyl,
a C₂-C₆ alkenyl group whose double bond may be epoxidized or a C₂-C₆ alkynyl group, where both groups may be substituted one to three times by halogen, C₁-C₃ alkoxy and / or once by cyclopropyl or phenyl, said Phenyl radical may additionally carry up to three of the following substituents: halogen, cyano, nitro, C₁-C₄-alkyl which unsubsti tuiert or may be partially or fully halogenated, C₁-C₄-alkoxy or C₁-C₄-alkylthio, both of which are unsubstituted or may be partially or completely halogenated,
- A C₃-C₆-cycloalkenyl group which may be substituted one to three times by halogen or C₁-C₄-alkyl;
R2 - a formyl group, a 4,5-dihydrooxazol-2-yl group, a residue
- COYR⁵ or CONR⁶R⁷, where
Y oxygen or sulfur and
R⁵ - hydrogen,
- A C₁-C₆-alkyl group which may carry one to five halogen atoms and / or one of the following radicals: hydroxy, cyano, C₂-C₄-alkoxy, C₁-C₄-alkoxy-C₂-C₄-alkoxy, C₁-C₃-alkylthio , C₁-C₃alkylamino, di (C₁-C₃) alkylamino, C₃-C₆cycloalkylamino, di (C₃-C₆) cycloalkylamino, trimethylsilyl, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, carboxyl, C₁ C₃-alkoxycarbonyl, C₁-C₃-alkoxycarbonyl-C₁-C₃-alkoxy, C₁-C₃-alkoxycarbonyl-C₁-C₃-alkoxy-C₁-C₃-alk oxycarbonyl, di- (C₁-C₃) -alkylaminocarbonyl, di- (C₁ to C₁-C₃) -alkoxy-carbonyl; -C₃) -alk oxyphosphonyl, C₁-C₃ alkanecimnoxy, thienyl, furanyl, tetrahydrofuranyl, N-phthalimido, pyridyl, benzyloxy, benzoyl, these cyclic radicals may additionally carry one to three of the following groups: halogen, C₁-C₃ alkyl or C₁-C₃alkoxy;
- C₃C₈-cycloalkyl;
C₃-C₆-alkenyl, C₅-C₆-cycloalkenyl, C₃-C₆-alkynyl, where these radicals may carry one of the following groups: hydroxy, halogen, C₁-C₄-alkoxy or phenyl, wherein the aromatic in turn one to three of the following groups can carry: halogen, nitro, cyano, C₁-C₄-alkyl, partially or fully halogenated C₁-C₄-alkyl or C₁-C₄-alkoxy; Phenyl which may carry one to three of the following groups:
- Halogen, nitro, cyano, C₁-C₄-alkyl, partially or fully halogenated C₁-C₄-alkyl, C₁-C₄-alkoxy, partially or completely halogenated C₁-C₄-alkoxy or C₁-C₄-alkoxycarbonyl;
Benzyl, which may carry one to three of the following groups: halogen, nitro, cyano, C₁-C₃-alkyl which may be unsubstituted or partially or completely halogenated or C₁-C₃-alkoxy;
- A five- to six-membered heterocyclic radical with
one or two heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen or a Benzotri azolrest;
Phthalimido, tetrahydrophthalimido, succinimido, maleimido;
- In the case of Y = O: one equivalent of a cation from the group of alkali or alkaline earth metals, manganese, copper, iron, ammonium and with up to 4 C₁-C₃-alkyl substituted ammonium or
- a residue -N = CR⁸R⁹, where
R⁸, R⁹ is hydrogen, C₁-C₄-alkyl, C₃-C₆-cycloalkyl, phenyl, furyl, or together denote a methylene chain having 4 to 7 members;
R⁶ hydrogen; C₁-C₆-alkyl or C₃-C₈-cycloalkyl and
R⁷ is hydrogen, C₁-C₆-alkyl or
R⁶, R⁷ together represent a methylene chain with 4 or 5 members;
R3 is hydrogen; C₁-C₆ alkyl which may carry one to three of the following substituents: hydroxy, halogen, C₁-C₄ alkoxy, C₁-C₄ alkylthio or di (C₁-C₄) alkylamino;
C₃-C₈-cycloalkyl which may be substituted one to three times by halogen, C₁-C₄-alkyl, and partially or fully halogenated C₁-C₄-alkyl;
R⁴ hydrogen; hydroxyl; a C₁-C₄ alkoxy group;
a C₁-C₆-alkyl group which may carry one to three of the following radicals: halogen, cyano, C₁-C₄-alkoxy, partially or completely halogenated C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, Di (C₁-C₄) -alkylamino, C₃-C₈-cycloalkyl or phenyl, wherein the phenyl ring in turn may carry one to three of the following radicals: halogen, cyano, nitro, C₁-C₄-alkyl, partially or completely halogenated C₁- C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio or C₁-C₄-haloalkylthio;
a C₃-C₈-cycloalkyl group which may carry one to three of the following radicals: halogen, nitro, cyano, C₁-C₆-alkyl, partially or fully halogenated C₁-C₆-alkyl, C₁-C₄-alkoxy or partially or completely halogenated C₁ -C₄ alkoxy;
a C₃-C₆ alkenyl or C₃-C₆ alkynyl group, which may be substituted one to three times by halogen and / or once by phenyl, wherein the phenyl radical in turn may carry one to three of the following groups: C₁-C₄-alkyl , C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, halogen, cyano or nitro;
a di (C₁-C₄) alkylamino group
a 5- to 6-membered heterocyclic saturated or aromatic radical having one or two heteroatoms selected from the group oxygen, sulfur and nitrogen, which may be substituted one to three times by C₁-C₄-alkyl or halogen;
a phenyl group which may carry one to four of the following groups: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, Halogen, nitro, cyano, formyl, C₁-C₄-alkanoyl, C₁-C₄-haloalkanoyl or C₁-C₄-alk oxycarbonyl;
a naphthyl group which may be substituted one to three times by C₁-C₄ alkyl or halogen, or
R³, R⁴ together a methylene chain having 4 to 7 members, which may be interrupted by oxygen, sulfur or N-methyl, or the radical - (CH₂) ₃-CO-.

Moreover, the invention relates to herbicidal compositions containing these Contain compounds as active substances.

Isoxazole and isothiazole carboxylic acids or their derivatives are known. These are the 5-aminocarbonyl-3-methyl-4-isoxazolecarboxylic acid, the 5-aminocarbonyl-3-methyl-4-isoxazolecarboxylic acid ethyl ester, the 4,5-iso thiazoldicarboxamide and 5-carbamoyl-4-isothiazolecarboxylic acid (J.Chem.Soc.Perkin Trans. I, 1982, 2391; J. Heterocyclic, Chem. 1561 (1985); J. Chem. Soc. 1959, 3961). A use of this However, compounds as herbicides are unknown.

Object of the present invention was to provide new herbicidally active Provide connections.

Accordingly, the Azol-carboxamides I defined above were found.

In addition, there have been processes for their preparation and their containing herbicidal agent found.

The azole-carboxylic acid amides I according to the invention are available in various ways preparable, preferably by the following methods:

a) A process for the preparation of compounds of formula I, in which R 2 is COOR⁵ and R⁵ is hydrogen or C₁-C₆-alkyl (see Scheme 1), based on the reaction of an isoxazole or isothiazole-4,5-dicarbon acid dialkyl ester II (R⁸ = C₁-C₆-alkyl) with aqueous base and subsequent reaction with mineral acid to give a carboxylic acid III. As dicarboxylic acid II especially low alkyl (R⁵ = R⁸ = C₁-C₄-alkyl) into consideration, wherein dimethyl ester and diethyl esters are particularly preferred.  

The reaction is carried out by reacting a dicarboxylic acid dialkyl ester II at temperatures between about 0 and 80 ° C, preferably between 0 and 50 ° C, in an organic solvent, for. b. methanol or ethanol, with a strong base, e.g. B. NaOH, KOH or Ca (OH) ₂, treated. In general, about 1 equivalent of the strong Base used in aqueous solution. After the implementation is cooled and treated with a strong mineral acid, eg. As hydrochloric acid or Sulfuric acid, acidified. The resulting carboxylic acid III can on usual way z. B. by suction or by extraction with be isolated an organic solvent.

For the conversion of the carboxylic acid III into the carboxylic acid halide IV bring the acid III in the usual manner with an anor ganic acid halide, such as thionyl chloride, phosphorus tri- or Phosphorpentahalogeniden, for reaction, with the chlorides being preferred are. In this case, the inorganic acid halide is expediently in 1 to 5 molar equivalents, preferably 1 to 2 molar equivalents puts. You can without solvent or in the presence of an inert organic solvent such. As benzene or toluene at temperatures between room temperature and the boiling point of the inorganic Acid halide or the inert organic solvent work. In some cases, the addition of a catalyst, such as Dimethylformamide or 4-dimethylaminopyridine, be of advantage. To Termination of the reaction, the acid halide IV in the usual way and isolated manner, for. B. by distilling off the excess inorganic acid halide and the organic solvent and subsequent distillation of the acid chloride IV at atmospheric pressure or reduced pressure.

The carboxylic acid amides of the formula I in which R² is COOR⁵ and R⁵ is C₁-C₆-alkyl mean, obtained from the carboxylic acid halides IV by reaction with an amine V. It is generally in such a way that the Carboxylic acid halide in an inert organic solvent such as Dichloroethane, or an ether such as diethyl ether or methyl tert. butyl ether with an amine V, also dissolved in an organic Solvent, brings to reaction. This is the amine V conveniently in the 2- to 5-fold molar amount, preferably 2- to 3 times the molar amount to the resulting hydrogen halide to tie. One can also in the presence of an auxiliary base such as a tertiary one Amine, e.g. For example, triethylamine, work. In this case, 1 to suffice 1.5 molar equivalents of amine V. The reaction temperature may, for. B. between 0 and 50 ° C, preferably between 0 and 20 ° C. The reaction is generally completed after 1 to 12 hours. The mixture can be like be worked up usual, for example by hydrolysis with water  and extraction of the product of formula I with an organic Solvent and concentration of the organic solvent. To the Reini tion, the product of formula I, for example recrystallized or be chromatographed.

Advantageously, the representation of the acid amide I (R² = COOR⁵) from the Carboxylic acid III can also be carried out in one step. This is the Carboxylic acid III with an amine V in the presence of a dehydrating Means, for. For example, propanephosphonic (PPA) or dicyclohexyl carbodiimide (DCC), at temperatures from 0 to 50 ° C, preferably 5 to 25 ° C in an inert solvent such as dichloromethane, tetrahydrofuran or toluene reacted.

From the 4-alkoxycarbonyl-isoxazole-5-carboxamides or 4-alkoxycarbonyl-isothiazole-5-carboxamides I (R² = COOR⁵ with R⁵ = C₁-C₆-alkyl), the free carboxylic acids I (R² = COOH) z. B. obtained by reaction with aqueous bases and subsequent hydrolysis with mineral acids. The reaction is carried out by reacting the ester I (R² = COOR⁵, R⁵ = C₁-C₆-alkyl) at temperatures between 0 and 80 ° C, preferably between 0 and 50 ° C, in an organic solvent, for. For example, methanol or ethanol with a base, e.g. B. NaOH, KOH or Ca (OH) ₂ treated. In general, about 1 to 3 equivalents, preferably 1 to 1.5 equivalents of the strong base in aqueous solution are used. After the reaction is cooled with a strong mineral acid, eg. Hydrochloric acid or sulfuric acid, acidified. The resulting carboxylic acids I (R 2 = COOH) can be isolated by suction or by extraction with an organic solvent and concentration of this organic solvent. Further purification takes place for. B. by recrystallization or chromatography.
Scheme 1:

The isothiazole required as starting material for this process 4,5-dicarboxylic acid esters II are known (R.M. Paton, J. Stobie, R.M. Mortier, Phosphorus Sulfur, 15 (2), 137 (1983) or may be incorporated by reference be prepared per se known methods.

The isoxazole-4,5-dicarboxylic acid diesters are from the aldoximes VI and Acetylendicarbonsäurediestern VII produced (see DE-A 27 54 832; Synthesis, 508 (1982)):

In this reaction, the aldoxime VI in the reaction medium by the Hypohalogenite oxidized to the corresponding nitrile oxide, which is a very is reactive 1,3-dipole, and also present in the reaction medium Continuing dipolarophile acetylenedicarboxylic acid diester as it arises in a 1,3-dipolar cycloaddition to form the Isoxazole compound II intercepted.  

Conveniently, equimolar amounts of aldoxime VI and the Acetylenedicarboxylic acid diesters VII reacted with the hypohalogenite. The hypohalite can be in stoichiometric amount to the reaction However, it usually gets in slightly over schüssiger amount, up to a two-fold excess, the reaction batched. For procedural reasons, it may possibly be advantageous, the conversion by using substoichiometric Amounts of hypohalite - about 50 to 90 mol% hypohalite per mol VI - to limit. It is also possible with under or over stoichiometric amounts of reactants VI or VII to work.

Hypohalites are generally hyprobromites and hypo chlorites, the latter preferred. It can for this purpose aqueous solutions of hypochlorous or unterbromigen acid are set, but are preferably alkali metal or alkaline earth metal hypochlorites or hypobromites, for example sodium hypo chlorite, potassium hypochlorite, calcium hypochlorite, magnesium hypochlorite, Strontium hypochlorite, barium hypochlorite or the like Hypobromites used. Particularly preferred are sodium, potassium and Calcium hypochlorite in the form of their commercial, aqueous Applied solutions.

Suitable solvents for the process are, for. As alcohols, such as Methanol, ethanol, propanol or isopropanol, ketones such as acetone or Methyl ethyl ketone, ethers, such as diethyl ether, methyl tert-butyl ether, Tetrahydrofuran or dioxane, hydrocarbons such as pentane, hexane, Cyclohexane, petroleum ether, white oils or ligroin, halogenated alipha table hydrocarbons, such as methylene chloride, chloroform, tetra Chlorocarbon, dichloroethane, trichloroethane, tetrachloroethane or Perchloroethane, aromatic compounds such as benzene, toluene, xylenes or chlorobenzenes, esters, such as ethyl acetate and dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, etc.

The temperature at which the reaction is carried out may be in wide ranges are varied. In general, the implementation takes place even at temperatures of (-15) ° C and lower, and upwards the temperature range is in principle only by the boiling point of the used limited solvent, since the reaction expediently is carried out at atmospheric pressure. Preferably, at tempera Tures in the range of 0 to 40 ° C worked. The reaction can also be carried out under elevated pressure, especially under autogenous generated pressure, but preferred is working at atmospheric pressure.  

The Aldoxime VIs required for this process are either known or can be prepared by methods known per se (eg Houben-Weyl, Methods of Organic Chemistry, Vol. 10/4, pages 55 to 56, Thieme Verlag, Stuttgart 1968) by reaction of the corresponding aldehydes with hydroxylamine. The Aldoxime VI can self understandable both in the form of their E or Z isomers as well as Mixtures of these stereoisomers can be used. The acetylenedicar Biconic acid diesters are commercially available or known per se Methods (for example, Organic Syntheses Coll., Vol. 4, page 329) adjustable.

b) Another way to represent the compounds I with R² = COYR⁵ or CONR⁶R⁷ consists in the implementation of a carboxylic acid I (R 2 = COOH) with an alcohol or thiol VIII or with an amine IX in the presence of a dehydrating agent, e.g. For example, propanephosphone acid anhydride (PPA) or dicyclohexylcarbodiimide (DCC) in a Temperature between (-20) and 50 ° C, preferably between 0 and 30 ° C:

The educts are advantageous in about stoichiometric amount reacted, preferably in the presence of an inert solvent such as Tetrahydrofuran, dichloromethane or toluene.

With regard to the pressure, those made for process variant a) apply Information.

c) Compounds I, in which R² is 4,5-dihydrooxazol-2-yl, receives one z. B. in that the carboxylic acid amides of formula I, in the R² COOH or COOR⁵ means (R⁵ = substituted subst. C₁-C₄-alkyl as under the R⁵ listed radicals), in a conventional manner with an amino be reacted alcohol of formula X:

The reaction is carried out by reacting the compounds at 0 to 180 ° C, preferably at the reflux temperature of the mixture used with an aminoalcohol X, optionally in the presence of an inert Solvent, reacted. Ester or carboxylic acid and aminoalcohol X are in the ratio 1: 1 to 1: 2.5, preferably 1: 1 to 1: 1.5 used.

The solvent used is conveniently halocarbon such as chlorobenzene and 1,2-dichlorobenzene, ethers, z. Methyl tert-butyl ether, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, Tetrahydrofuran and dioxane, alcohols such as methanol, ethanol, propanol or ethylene glycol, dipolar aprotic solvents, e.g. B. aceto nitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyletrahydro-2 (1H) -pyrimidinone and 1,3-dimethylimidazolin-2-one or aromatics, e.g. As benzene, toluene and Xylene. The concentration of the educts in the solvent is in general 0.1 to 5.0 mol / l, preferably 0.2 to 2.0 mol / l.

The reaction is generally complete after 14 hours; the azole Carboxylic acid amides I (with R² = 4,5-dihydrooxazol-2-yl) are then given If necessary, precipitated by addition of water, filtered with suction or with a extracted organic solvent and using standard methods such as recrystallization or chromatography. Regarding the Printing apply the information given for process a).

d) Compounds I, in which R² is formyl, are obtained, for example in that a corresponding azole-carboxamide of the formula I, in which R² is the group CO₂H, according to the methods of a) described conditions activated and the thus obtained activated Form of the carboxylic acid reduced in a conventional manner.

Preferably, the carboxylic acid is converted into the corresponding one Chloride and reduces this carboxylic acid chloride at temperatures of (-100) to 0 ° C, especially (-80) to (-50) ° C with a complex Hydride such as, in particular, lithium tri-tertiary-butylaluminum hydride. When Solvents in this case particularly preferably serve ethers, such as di  ethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, diethylene glycol and Dioxane (J.Am.Chem.Soc.80, 5372 (1958); J. Am. Chem. Soc. 80, 5377 (1958)).

With regard to the pressure, the information given for method a) applies.

e) compounds of the formula I in which R¹ is an epoxidized C₂-C₆ alkenyl group means one to three times by halogen, C₁-C₃-alkoxy and / or once by cyclopropyl or geg. subst. Phenyl as under R¹ mentioned, may be substituted, obtained for example by in that an azole-carboxylic acid amide of the formula I in which R¹ is a C₂-C₆ alkenyl group, those mentioned above Can carry substituents, in a conventional manner with suitable Oxidizing agents is expoxidized (eg, J. March, Advanced Organic Chemistry, Third Edition, John Wiley and Sons, 1985, p. 735ff.).

The substituents in the compounds I according to the invention have, for example, the following meaning:
R¹ - a C₃-C₈-cycloalkyl-C₁-C₆-alkyl group, preferably a C₃-C₆-cycloalkyl-C₁-C₄-alkyl group such as cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, 1-cyclopropylethyl, 2-cyclopropylethyl, 1-cyclopropyl-1-methylethyl , 2-cyclopropyl-1-methylethyl or 4-cyclohexyl-n-butyl;
a C₂-C₆ alkenyl group whose double bond may be epoxidized, preferably a C₂-C₄ alkenyl group such as ethenyl or isopropenyl, which is one to three times by halogen such as fluorine, chlorine, bromine or iodine, C₁-C₃ alkoxy such as methoxy, Ethoxy or isopropoxy and / or may be substituted once by cyclopropyl or phenyl,
a C₂-C₆ alkynyl group, preferably a C₂-C₄ alkynyl group such as ethynyl or n-butynyl, which is one to three times by halogen such as fluorine, chlorine, bromine or iodine, C₁-C₃ alkoxy such as methoxy or isopropoxy and / or once substituted by cyclopropyl or phenyl,
- A C₃-C₆-cycloalkenyl, preferably a C₅-C₆-cyclo alkenyl group which may be substituted one to three times by halogen such as fluorine, chlorine, bromine or iodine or C₁-C₄-alkyl such as methyl, ethyl or tert-butyl .
a formyl group,
a 4,5-dihydrooxazol-2-yl group,
- a rest COYR⁵ or CONR⁶R⁷ with
- hydrogen
- C₁-C₆-alkyl, preferably C₁-C₄-alkyl such as methyl, ethyl or tert-butyl, which carry one to five halogen atoms such as fluorine, chlorine, bromine or iodine, in particular fluorine and chlorine, and / or one of the following radicals may be: hydroxy, cyano, C₁-C₄-alkoxy, especially methoxy, ethoxy, isopropoxy and tert-butoxy, C₁-C₄-alkoxy-C₂-C₄-alkoxy, in particular methoxy-ethoxy, ethoxy-ethoxy and propoxy-ethoxy, trimethyl silyl, C₁-C₃-alkylthio, in particular methylthio and ethyl thio, C₁-C₃-alkylamino such as methylamino, ethylamino and isopropylamino, di- (C₁-C₃) -alkylamino such as dimethylamino, diethylamino, dipropylamino, di (1-methylethyl) amino and methylethylamino, C₃-C₆cycloalkylamino or di (C₃-C₆) cycloalkylamino such as cyclopropylamino or dicyclopropylamino, C₁-C₃alkylsulfinyl such as methylsulfinyl, 1-methylethylsulfinyl and n-propylsulfinyl, C₁-C₃alkylsulfonyl such as methylsulfonyl, ethylsulfonyl and isopropylsulfonyl , Carboxyl, C₁-C₃-alkoxycarbonyl as Methoxycarbonyl and isopropoxycarbonyl, C₁-C₃-alkoxy carbonyl-C₁-C₃-alkoxy such as methoxycarbonylmethoxy, C₁-C₃-alk oxycarbonyl-C₁-C₃-alkoxy-C₁-C₃-alkoxycarbonyl such as Methoxycarbonylethoxymethoxycarbonyl, di (C₁-C₃) alkylamino carbonyl such as dimethylaminocarbonyl, methylethylaminocarbonyl and di-isopropylaminocarbonyl, di- (C₁-C₃) -alkoxyphosphonyl such as dimethoxyphosphonyl and diisopropoxyphosphonyl, C₁-C₃alkaniminoxy such as 2-propaniminoxy, thienyl, furanyl, tetrahydrofuranyl, N-phthalimido, pyridyl, benzyloxy or benzoyl, wherein these cyclic radicals may carry one to three of the following groups: halogen such as fluorine and chlorine, C₁-C₃alkyl such as methyl and isopropyl or C₁-C₃alkoxy such as methoxy or isopropoxy;
- C₃-C₈-cycloalkyl, preferably C₃-C₆-cycloalkyl such as cyclopropyl, cyclopentyl and cyclohexyl;
Phenyl which may carry one to three of the following groups:

Halogen such as fluorine, chlorine, bromine and iodine, nitro, cyano, C₁-C₄-alkyl such as methyl, ethyl and tert-butyl, C₁-C₄-haloalkyl such as trifluoromethyl, 1,1,2,2-tetrafluoroethyl and trichloromethyl, C₁ C₄-alkoxy such as methoxy, ethoxy and isopropoxy, C₁-C₄-haloalkoxy such as trifluoromethoxy, chlorodifluoromethoxy, 1-fluoroethoxy, pentafluoroethoxy and 2-chloro-1,1,2-trifluoroethoxy or C₁-C₄-alkoxycarbonyl such as methoxycarbonyl, n-propoxycarbonyl and tert-butoxycarbonyl;
C₃-C₆-alkenyl, preferably C₃-C₄-alkenyl such as 2-propenyl and 2-butenyl, C₅-C₆-cycloalkenyl such as 2-cyclopentenyl and 2-cyclohexenyl, C₃-C₆-alkynyl, preferably C₃-C₄-alkenyl such as 2 Propinyl, 2-butynyl and 3-butynyl, where the 3 last-mentioned groups can carry one of the following radicals: hydroxyl, halogen such as fluorine, chlorine, bromine and iodine, C₁-C₄-alkoxy such as methoxy and tert-butoxy or phenyl, which in turn may carry one to three of the following groups: halogen such as fluorine, chlorine or bromine, nitro, cyano, C₁-C₄-alkyl such as methyl, ethyl or tert-butyl, C₁-C₄-haloalkyl such as fluoromethyl, trifluoromethyl, chlorodifluoromethyl, Pentafluoroethyl and 2-chloro-1,1,2-trifluoroethyl or C₁-C₄-alkoxy such as methoxy, isopropoxy and tert-butoxy;
- Benzyl which may carry one to three of the following groups: halogen such as fluorine and chlorine, nitro, cyano, C₁-C₃-alkyl such as methyl or isopropyl, C₁-C₃-haloalkyl such as trifluoromethyl, 1,1,2,2-tetrafluoroethyl and trichloromethyl or C₁-C₃ alkoxy such as methoxy and isopropoxy;
a 5- or 6-membered heterocyclic radical having one or two heteroatoms selected from the group consisting of oxygen, sulfur or nitrogen, such as 2-tetrahydrofuranyl, 3-tetrahydrothienyl, 4-tetrahydropyranyl, 2-furanyl, 2-thienyl, 4-isoxazolyl, 5- Isothiazolyl, 2-oxazolyl, 4-thiazolyl, 2-imidazolyl, 2-pyrrolyl, 3-pyrazolyl and 4-pyridyl or a benzotriazole radical;
N-phthalimido, tetrahydrophthalimido, succinimido or maleimido;
- In the case of Y = O: one equivalent of a cation from the group of alkali and alkaline earth metals such as sodium, potassium and calcium, manganese, copper, iron, ammonium and with up to 4 C₁-C₃-alkyl groups substituted ammonium such as tetramethylammonium;
- a rest -N = CR⁸R⁹ with
R⁸, R⁹ - hydrogen;
- C₁-C₄-alkyl such as methyl, ethyl, isopropyl and tert-butyl;
C₃-C₆cycloalkyl such as cyclopropyl, cyclopentyl and cyclohexyl;
- phenyl, furyl
- Together, a methylene chain with 4-7, preferably 4-5 members;
R⁶ - hydrogen,
- C₁-C₆-alkyl, preferably C₁-C₄-alkyl such as methyl, ethyl, isopropyl and tert-butyl;
- C₃-C₈-cycloalkyl, preferably C₃-C₆-cycloalkyl such as cyclopropyl, cyclopentyl and cyclohexyl;
R⁷ - hydrogen;
- C₁-C₆-alkyl, preferably C₁-C₄-alkyl, such as methyl and tert-butyl;
R⁶, R⁷ - together a methylene chain with 4-7, preferably 4-5 members;
R³ - hydrogen
C₁-C₆-alkyl, preferably C₁-C₄-alkyl such as methyl, ethyl and tert-butyl, which may carry one to three of the following substituents: hydroxy, halogen, C₁-C₄-alkoxy such as methoxy and tert-butoxy, C₁-C₄-alkylthio such as methylthio and tert-butylthio or di- (C₁-C₄) -alkylamino, preferably di- (C₁-C₂) -alkylamino such as dimethylamino and diethylamino;
- C₃-C₈-cycloalkyl, preferably C₃-C₆-cycloalkyl such as cyclopropyl, cyclopentyl and cyclohexyl, one to three times by halogen such as fluorine, chlorine and bromine, C₁-C₄-alkyl such as methyl and tert-butyl or C₁-C₄ Haloalkyl such as fluoromethyl, trifluoromethyl, chlorodifluoromethyl, penta fluoroethyl and 2-chloro-1,1,2-trifluoroethyl may be substituted;
R⁴ - hydrogen, hydroxyl;
- C₁-C₄-alkoxy such as methoxy, ethoxy and tert-butoxy;
- branched or unbranched C₁-C₆-alkyl, preferably C₁-C₄-alkyl such as methyl, ethyl, isopropyl and tert-butyl, which may carry one to three of the following radicals: halogen such as fluorine, chlorine and bromine, cyano, C₁- C₄-alkoxy such as methoxy and tert-butoxy, C₁-C₄-haloalkoxy such as fluoro methoxy, trichloromethoxy, 2-chloro-1,1,2-trifluoroethoxy and pentafluoroethoxy, C₁-C₄-alkylthio such as methylthio and tert-Buylthio, C₁ C₄-haloalkylthio, such as fluromethylthio, trichloromethylthio, 2-chloro-1,1,2-trifluoroethylthio and pentafluoroethylthio, di- (C₁-C₄) -alkylamino, especially di- (C₁-C₂) -alkylamino, such as dimethylamino and diethylamino, C₃- C₈-cycloalkyl, in particular C₃-C₆-cycloalkyl such as cyclopropyl, cyclopentyl and cyclohexyl or phenyl, where the phenyl radical in turn can carry up to three of the following groups: halogen such as fluorine, chlorine and bromine, cyano, nitro, C₁-C₄-alkyl such as methyl and tert-butyl, C₁-C₄-haloalkyl such as fluoromethyl, trichloromethyl, 2-chloro-1,1,2-trifluoroethyl and pentafluoroethyl, C₁-C₄-alkoxy such as methoxy and tert-butoxy, C₁-C₄-haloalkoxy such as fluoromethoxy, trichloromethoxy, 2-chloro-1,1,2-trifluoroethoxy and pentafluoroethoxy C₁-C₄-alkylthio such as methylthio and tert-butylthio or C₁-C₄-haloalkylthio such as fluoromethylthio, trichloromethylthio, 2-chloro-1,1,2-trifluoroethylthio and pentafluoroethylthio;
C₃-C₈-cycloalkyl, preferably C₃-C₆-cycloalkyl, in particular cyclopropyl, cyclopentyl and cyclohexyl, which may each carry one to three of the following radicals: halogen such as fluorine, chlorine and bromine, nitro, cyano, C₁-C₆-alkyl, preferably C₁-C₄-alkyl such as methyl and tert-butyl, C₁-C₆-haloalkyl, preferably C₁-C₄-haloalkyl such as fluoromethyl, trichloro-methyl, 2-chloro-1,1,2-trifluoroethyl and pentafluoroethyl, C₁-C₄- Alkoxy such as methoxy and tert-butoxy, or C₁-C₄-haloalkoxy such as fluoromethoxy, trichloromethoxy, 2-chloro-1,1,2-trifluoroethoxy and pentafluoroethoxy;
C₃-C₆-alkenyl or C₃-C₆-alkynyl, preferably C₃-C₄-alkenyl or C₃-C₄-alkynyl, such as 2-propenyl, 2-butenyl, 2-propynyl, 1,1-dimethyl-2-propynyl and 3- Butinyl, which may be substituted by up to three times by halogen such as fluorine, chlorine or bromine and / or once by phenyl, wherein the phenyl radical in turn may carry one to three of the following substituents: halogen, in particular fluorine and chlorine, cyano, nitro, C₁ C₄-alkyl such as methyl and tert-butyl, C₁-C₄-haloalkyl such as fluoromethyl, trifluoromethyl, trichloromethyl, 2-chloro-1,1,2-trifluoroethyl and pentafluoroethyl, C₁-C₄-alkoxy such as methoxy and tert.- Butoxy, C₁-C₄-haloalkoxy such as fluoromethoxy, trifluoromethoxy, trichloromethoxy, 2-chloro-1,1,2-trifluoroethoxy and pentafluoroethoxy, C₁-C₄-alkylthio such as methylthio and tert-butylthio, C₁-C₄-haloalkylthio such as fluoromethylthio, trifluoromethylthio Trichloromethylthio, 2-chloro-1,1,2-trifluoroethylthio and pentafluoroethylthio;
- Di (C₁-C₄) -alkylamino, preferably di- (C₁-C₂) -alkylamino such as dimethylamino and diethylamino;
a 5- to 6-membered saturated or aromatic heterocyclic radical containing one or two heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, such as 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-furanyl, 3-furanyl, 2-thienyl, 3-thienyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2 -Oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl , 5-pyrazolyl, 2-pyridyl, 3-pyridyl and 4-pyridyl, which may carry one to three of the following substituents: C₁-C₄-alkyl as mentioned above, in particular methyl or halogen as mentioned above, in particular fluorine and chlorine;
- Phenyl, which may carry one to four of the following groups: C₁-C₄-alkyl as mentioned above, in particular methyl, ethyl and 1-methylethyl; C₁-C₄-haloalkyl as mentioned above, in particular trifluoromethyl and chlorodifluoromethyl; C₁-C₄-alkoxy as mentioned above, in particular methoxy and ethoxy; C₁-C₄-haloalkoxy as mentioned above, in particular trifluoromethoxy, trichloromethoxy and pentafluoroethoxy; C₁-C₄-alkylthio as mentioned above, in particular methylthio and ethylthio; C₁-C₄-haloalkylthio as mentioned above, in particular difluoromethylthio, trifluoromethylthio and pentafluoromethylthio, halogen as mentioned above, in particular fluorine and chlorine, cyano, nitro, formyl, C₁-C₄-alkanoyl such as acetyl, propionyl, butyryl, in particular acetyl, C₁-C₄ Haloalkanoyl such as trifluoroacetyl, trichloroacetyl, pentafluoropropionyl, in particular trifluoroacetyl or C₁-C₄-alkoxycarbonyl such as methoxycarbonyl and tert-butoxycarbonyl;
- Naphthyl which may be substituted one to three times by C₁-C₄-alkyl such as methyl and tert-butyl, especially methyl and ethyl, or halogen such as fluorine and chlorine;
R³ and R⁴ together form a C₄-C₇-methylene chain which may be interrupted by oxygen, sulfur or N-methyl, such as - (CH₂) ₃-, - (CH₂) ₄-, - (CH₂) ₅-, - (CH₂) ₆-, -CH₂-O-CH₂-, -CH₂-CH₂-O-CH₂-CH₂-, -CH₂-S-CH₂, -CH₂-CH₂-S-CH₂-CH₂-, -CH₂-CH₂-N (CH₃ ) -CH₂-CH₂-, in particular - (CH₂) ₅- and -CH₂-CH₂-O-CH₂-CH₂-;
- or the rest of the formula - (CH₂) ₃-CO-.

Particularly preferred compounds I are in Tables A and B listed.  

Table A

Table B

Preparation Examples Example A 5-cyclopropylaminocarbonyl-3-isopropenyl-isoxazole-4-carboxylic acid methyl-lester (No. 2 in Table 1) Stage A.1 E-3-styryl-isoxazole-4,5-dicarboxylic acid

A mixture, cooled to 0 ° C., of 14.7 g (0.1 mol) of E-cinnamaldehyde oxime, 1.8 g (0.01 mol) disodium hydrogen phosphate dihydrate, 1.6 g (0.01 mol) Sodium dihydrogen phosphate dihydrate, 50 ml dichloromethane and 50 ml water, was adjusted to pH = 6.3 with hydrochloric acid / sodium hydroxide solution. After adding 14.2 g (0.1 mol) of dimethyl acetylenedicarboxylate were within a Hour at 0-10 ° C 61.2 g (0.11 mol) of a 13.4% aqueous Natriumhypo Chloride solution is added dropwise while maintaining the pH by adding Hydrochloric acid or sodium hydroxide solution kept constant. Subsequently, 1 hr. stirred at room temperature, the phases separated and the aqueous phase extracted twice with 100 ml of dichloromethane. After drying the ver The organic solvent was dissolved in concentrated organic phases over sodium sulfate Vacuum removed and the more volatile components at 120 ° C (0.1 Torr) distilled off.

Yield: 56%; 1 H-NMR (in CDCl₃): δ = 3.9 ppm (s, 3H), 4.0 ppm (s, 3H), 7.2 ppm (d, 1H), 7.3-7.7 ppm (m, 6H).

Analogously to Example A.1 was also the 3-isopropenyl-isoxazole-4,5-dicarbon acid dimethyl ester synthesized.

Yield: 26%; 1 H-NMR (in CDCl₃): δ = 2.2 ppm (s, 3H), 3.9 ppm (s, 3H), 4.0 ppm (s; 3H), 5.45 ppm (m; 2H).

Stage A.2 3-isopropenyl-4-methoxycarbonyl-isoxazole-5-carboxylic acid

To 20.0 g (0.09 mol) of dimethyl 3-isopropenylisoxazole-4,5-dicarboxylate (from stage A.1) in 150 ml of methanol at 0 ° C, a solution of 3.6 g Added dropwise (0.09 mol) of sodium hydroxide in 75 ml of water and then Stirred for 14 hours at room temperature. After addition of 250 ml of water was  adjusted to pH = 8, extracted with 200 ml of dichloromethane, the aqueous Phase adjusted to pH = 1-2 with 6N hydrochloric acid and three times with 250 ml each Extracted dichloromethane. The combined organic extracts were over Dried magnesium sulfate and the solvent in vacuo distilled off.

Yield: 97%; 1 H-NMR (in CDCl₃): δ = 2.12 ppm (s, 3H), 4.07 ppm (s, 3H), 5.41 ppm (m; 2H); 8.00 ppm (bs, 1H).

Stage A.3 Preparation of acid amide

To a solution of 9.0 g (0.043 mol) of 3-isopropenyl-4-methoxycarbonyl Isoxazole-5-carboxylic acid (from step A.2) in 200 ml of dichloromethane was added 3.1 g (0.055 mol) of cyclopropylamine, 16.0 g (0.158 mol), successively 5 ° C. 4-methylmorpholine, 1.73 g (0.014 mol) of 4-dimethylaminopyridine and 37.0 g (0.058 mol) of a 50% solution of propanephosphonic anhydride in Dropped dichloromethane. After stirring for 12 hours at room temperature the solvent was removed, the residue was taken up in 250 ml of ethyl acetate taken, twice with saturated sodium bicarbonate solution and each once with 5% citric acid solution, saturated sodium carbonate and Extracted sodium chloride solution. After drying over magnesium sulfate was distilled off the solvent at reduced pressure.

Yield: 54%; 1 H-NMR (in CDCl₃): δ = 0.63-0.92 ppm (m, 4H), 2.10 ppm (bs; 3H), 2.93 ppm (m; 1H), 3.93 ppm (s; 3H), 5.40 ppm (m; 2H), 8.40 ppm (bs, 1H, NH).

Example B 5-Cyclopropylaminocarbonyl-3-isopropenyl-isoxazole-4-carboxylic acid (No. 5 in Table 1)

To a solution of 4.0 g (0.016 mol) of 5-cyclopropylaminocarbonyl-3-iso-propenyl-4-carboxylic acid methyl ester (from Example A) in 50 ml of methanol was added at 5 to 10 ° C 0.68 g (0.017 mol) of sodium hydroxide , After 12 hours of stirring at room temperature, the solvent was removed, the residue taken up in 150 ml of water, the mixture adjusted to pH = 8-9 and extracted twice with 100 ml of diethyl ether. The aqueous phase was then acidified with 6N HCl to pH = 2, extracted four times with 200 ml of ethyl acetate, dried the combined organic phases over magnesium sulfate and the solvent was distilled off under reduced pressure.
Yield: 74%; Mp: 96-100 ° C.

Example C 5-tert-butylaminocarbonyl-3-isopropenyl-isoxazol-4-carbonsäureaceto-noxim ester (# 8 in Table 1)

To a solution of 4.0 g (0.016 mol) of 5-tert-butylaminocarbonyl-3-iso propenyl-isoxazole-4-carboxylic acid (# 6 in Table 1) and 1.5 g (0.021 mol) Acetone oxime in 200 ml of dichloromethane was 5.9 g at room temperature (0.059 mol) of 4-methylmorpholine and 1.94 g (0.016 mol) of 4-dimethylamino pyridine and after stirring for 5 minutes 13.7 g (0.0215 mol) of a Added 50% solution of propanephosphonic anhydride in dichloromethane give. After 8 hours of heating to reflux, the Solvent, the residue dissolved in 100 ml of ethyl acetate and as worked up according to the product under A.3.

Yield: 55%; 1 H-NMR (in CDCl₃): δ = 1.44 ppm (s, 9H), 2.07 and 2.10 ppm (2s; 6H), 2.17 ppm (s; 3H), 5.42 ppm (m; 2H), 8.17 ppm (bs; 1H, NH).  

Table 1

The azole-carboxamides I or herbicidal compositions containing them For example, in the form of directly sprayable solutions, powders, Suspensions, even high-percentage aqueous, oily or other Sus pensions or dispersions, emulsions, oil dispersions, pastes, dusts spraying, misting, ver Dusting, scattering or pouring are applied. The application forms depend on the intended use; they should in any case as possible the finest distribution of the active compounds according to the invention Afford.

The compounds I are generally suitable for the preparation of direct ver sprayable solutions, emulsions, pastes or oil dispersions. As inert Additives come from mineral oil fractions of medium to high boiling point point, such as kerosene or diesel oil, coal tar oils and oils of animal or animal origin, aliphatic, cyclic and aromatic Hydrocarbons, eg. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, Butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone or strong polar solvents, such as N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.

Aqueous application forms can be prepared from emulsion concentrates, dispersions, Pastes, wettable powders or water-dispersible granules by Zu set of water. For the preparation of emulsions, pastes or oil dispersions may be the substrates as such or in an oil or Solvent dissolved by means of wetting, adhesive, dispersing or emulsifying be homogenized in water. It can also be more effective Substance, wetting, adhesive, dispersing or emulsifying agent and possibly Lö or concentrates produced for the purposes of the present invention Dilution with water are suitable.

As surface-active substances are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. As lignin, phenol, naphthalene and di butylnaphthalenesulfonic acid, as well as fatty acids, alkyl and alkylarylsul fonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts sulfa hexa-, hepta- and octadecanols, as well as fatty alcohol glycol ethers, Condensation products of sulfonated naphthalene and its derivatives with Formaldehyde, condensation products of naphthalene or naphthalenesul with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol, tributyl phenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, Fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethyl lenalkylether or polyoxypropylene, lauryl alcohol polyglycol ether acetate, Sorbitol esters, lignin-Sulphatablaugen or methylcellulose into consideration.  

Powders, litter and dusts can be mixed or mixed Grinding the active substances with a solid carrier Herge be presented.

Granules, for. B. coated, impregnated and homogeneous granules be prepared by binding the active compounds to solid carriers. Solid carriers are mineral earths such as silica gel, silicic acid, pebbles gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, Dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ge ground plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products, such as cereal flour, Bark, wood and nutshell flour, cellulose powder or other solid Carriers.

The formulations generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90 wt .-%, active ingredient. The active ingredients are while in a purity of 90% to 100%, preferably 95% to 100% (according to NMR / HPLC / GC spectrum) used.

Examples of such preparations are:

• I. a solution of 90 parts by weight of compound no. 1 and 10 parts by weight Share N-methyl-α-pyrrolidone, which is suitable for use in the form of smallest Drop is suitable;
• II. A mixture of 20 parts by weight of compound no. 2, 80 parts by weight of xylene, 10 parts by weight of the addition from 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N- monoethanolamide, 5 parts by weight calcium salt of dodecylbenzene sulfonic acid, 5 parts by weight of the adduct and 40 mol Ethylene oxide to 1 mole of castor oil. By finely distributing the Mixture in 100 000 parts by weight of water gives one Dispersion containing 0.02 wt .-% of the active ingredient.
• III. an aqueous dispersion of 20 parts by weight of Compound No. 3, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mol Castor oil. The mixture of this dispersion with 100,000 parts by weight Water contains 0.02% by weight of the active ingredient.
• IV. An aqueous dispersion of 20 parts by weight of compound no. 4, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280 ° C and 10 parts by weight of the  Addition product of 40 mol of ethylene oxide to 1 mol of castor oil. The mixture of this dispersion with 100,000 parts by weight of water contains 0.02% of the active ingredient;
• V. a milled in a hammer mill mixture of 80 parts by weight the compound no. 5, 3 parts by weight of the sodium salt of Diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of sodium salts of a lignosulfonic acid from a sulfite liquor and 7 parts by weight of powdered silica gel. By fine Ver Share the mixture in 20 000 parts by weight of water to get one Spray mixture containing 0.1% by weight of the active ingredient;
• VI. an intimate mixture of 3 parts by weight of compound no. 6 and 97 parts by weight of finely divided kaolin. Contains this dust 3% by weight of active ingredient;
• VII. An intimate mixture of 30 parts by weight of compound no. 7, 92 parts by weight of powdered silica gel and 8 parts by weight Paraffin oil, which is on the surface of this silica gel was sprayed. This preparation gives the active ingredient a good Adhesiveness;
• VIII. A stable aqueous dispersion of 40 parts by weight of the compound No. 8, 10 parts by weight of the sodium salt of a phenosulfonic acid urea-formaldehyde condensates, 2 parts by weight of silica gel and 48 parts by weight of water, which can be diluted further;
• IX. a stable oily dispersion of 20 parts by weight of the compound No. 9, 2 parts by weight of the calcium salt of dodecylbenzenesulfone acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight the sodium salt of phenol sulfonic acid-urea-formaldehyde Condensates and 68 parts by weight of a paraffinic mineral oil;
• X. A ground in a hammer mill mixture of 10 parts by weight compound No. 10, 4 parts by weight of the sodium salt of diiso butylnaphthalene-α-sulfonic acid, 20 parts by weight of the sodium salt a lignosulfonic acid from a sulfite liquor, 38 parts by weight Silica gel and 38 parts by weight of kaolin. By fine distribution The mixture is obtained in 10 000 parts by weight of water, a spray broth containing 0.1% by weight of the active ingredient.

The application of the herbicidal agents or the active ingredients can in advance run or post-emergence. Are the active ingredients for ge If crops are less compatible, application techniques may be used be applied, in which the herbicidal agents with the aid of spray devices are sprayed so that the leaves of sensitive culture Plants, if possible, are not taken while the active ingredients on the leaves underneath growing unwanted plants or the unbe covered floor surface (post-directed, lay-by).

The application rates of active ingredient are depending on the control target, year time, target plants and growth stage 0.001 to 5, preferably 0.01 to 1 kg / ha of active substance (a.S.).

In view of the versatility of the application methods, the Compounds according to the invention or agents containing them in one further number of crops for the removal of unwanted plants be used. For example, the following cultures may be considered:

Botanical name German name Allium cepa onion Pineapple comosus pineapple Arachis hypogaea Peanut Asparagus officinalis asparagus Avena sativa oats Beta vulgaris spp. altissima sugar beet Beta vulgaris spp. rapa mangel Beta vulgaris spp. esculenta Red beet Brassica napus var. Napus rape Brassica napus var. Napobrassica Turnip Brassica napus var. Rapa White turnip Brassica rapa var. Silvestris beets Camellia sinensis Teestrauch Carthamus tinctorius Safflower safflower Carya illinoinensis Pecan Citrus limon lemon Citrus maxima grapefruit Citrus reticulata tangerine Citrus sinensis Orange, orange Coffea arabica (Coffea canephora, Coffea liberica) coffee Cucumis melo melon Cucumis sativus cucumber Cynodon dactylon Bermuda grass Daucus carota carrot Elaeis guineensis oil palm Fragaria vesca strawberry Glycine max Soybean Gossypium hirsutum (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) cotton Helianthus annuus sunflower Helianthus tuberosus Jerusalem artichokes Hevea brasiliensis Para rubber tree Hordeum vulgare barley Humulus lupulus hop Ipomoea batatas sweet potatoes Juglans regia walnut tree Lactuca sativa lettuce Lens culinaris lens Linum usitatissimum flax Lycopersicon lycopersicum tomato Malus spp. Apple Manihot esculenta manioc Medicago sativa alfalfa Mentha piperita peppermint Musa spp. Fruit and flour banana Nicotiana tabacum (N. rustica) tobacco Olea europaea olive tree Oryza sativa rice Panicum miliaceum Rispenhirse Phaseolus lunatus butterbean Phaseolus mungo Erdbohne Phaseolus vulgaris bush beans Pennisetum glaucum Perl or cattail millet Petroselinum crispum spp. tuberosum root parsley

Botanical name German name Picea abies Rotfichte Abies alba white fir Pinus spp. pine Pisum sativum garden pea Prunus avium sweet cherry Prunus domestica plum Prunus dulcis almond Prunus persica peach Pyrus communis pear Ribes sylvestre Red currant Ribes uva-crispa gooseberry Ricinus communis castor-oil plant Saccharum officinarum sugarcane Secale cereal rye Sesamum indicum sesame Solanum tuberosum potato Sorghum bicolor (see vulgare) sorghum Sorghum dochna sweet sorghum Spinacia oleracea spinach Theobroma cacao cacao Trifolium pratense Red clover Triticum aestivum wheat Triticum durum durum wheat Vaccinium corymbosum Cultivated blueberry Vaccinium vitis-idaea Preißelbeere Vicia faba horse beans Vigna sinensis (V. unguiculata) cowpea Vitis vinifera grapevine Zea mays Corn

To broaden the spectrum of action and to achieve synergistic Effects can the azole-carboxamides I with numerous representatives other herbicidal or growth-regulating active ingredient groups mixed and applied together. For example, come as a mixture Diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-di nitroanilines, N-phenyl carbamates, thiocarbamates, halocarboxylic acids, Triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzo furan derivatives, cyclohexane-1,3-dione derivatives, quinolinecarboxylic acid derivatives, Aryloxy, Heteroaryloxyphenoxypropionsäuren and their salts, esters and Amides and others into consideration.

In addition, it may be useful to use the compounds I alone or in Combination with other herbicides even with further crop protection mixed media, for example, with funds for Control of pests or phytopathogenic fungi or bacteria. From Interest is also the miscibility with mineral salt solutions, which for Eliminate nutritional and trace element deficiencies. It It is also possible to add non-phytotoxic oils and oil concentrates.

Claims (4)

1. azole-carboxamides of the general formula I. in which the variables have the following meaning:
X oxygen or sulfur;
R¹ is a C₁-C₆-alkyl group substituted by C₃-C₈-cycloalkyl,
a C₂-C₆ alkenyl group whose double bond may be epoxidized or a C₂-C₆ alkynyl group, where both groups may be substituted one to three times by halogen, C₁-C₃ alkoxy and / or once by cyclopropyl or phenyl, said Phenyl radical may additionally carry up to three of the following substituents: halogen, cyano, nitro, C₁-C₄-alkyl which may be unsubstituted or partially or completely halogenated, C₁-C₄-alkoxy or C₁-C₄-alkylthio, both unsubstituted or partially or completely halogenated,
- A C₃-C₆-cycloalkenyl group which may be substituted one to three times by halogen or C₁-C₄-alkyl;
R² is a formyl group, a 4,5-dihydrooxazol-2-yl group,
- a remainder COYR⁵ or CONR⁶R⁷, where
Y oxygen or sulfur and
R⁵ - hydrogen,
a C₁-C₆-alkyl group which may carry one to five halogen atoms and / or one of the following radicals: hydroxy, cyano, C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₂-C₄-alkoxy, C₁-C₃- Alkylthio, C₁-C₃alkylamino, di (C₁-C₃) alkylamino, C₃-C₆cycloalkylamino, di (C₃-C₆) cycloalkylamino, trimethylsilyl, C₁-C₃alkylsulfinyl, C₁-C₃alkylsulfonyl, carboxyl , C₁-C₃-alkoxycarbonyl, C₁-C₃-alkoxycarbonyl-C₁-C₃-alkoxy, C₁-C₃-alkoxy-carbonyl-C₁-C₃-alkoxy-C₁-C₃-alkoxycarbonyl, di- (C₁-C₃) -alkylaminocarbonyl, di- (C₁-C₃) alkoxy phosphonyl, C₁-C₃ alkaniminoxy, thienyl, furanyl, tetrahydrofuranyl, N-phthalimido, pyridyl, benzyloxy, benzoyl, these cyclic radicals may additionally carry one to three of the following groups: halogen, C₁-C₃ Alkyl or C₁-C₃ alkoxy;
- C₃-C₈-cycloalkyl;
- C₃-C₆-alkenyl, C₅-C₆-cycloalkenyl, C₃-C₆-alkynyl, where these radicals may carry one of the following groups: hydroxy, halogen, C₁-C₄-alkoxy or phenyl, wherein the aromatic in turn one to three of the following Can carry groups: halogen, nitro, cyano, C₁-C₄-alkyl, partially or fully halogenated C₁-C₄-alkyl or C₁-C₄-alkoxy;
- Phenyl, which may carry one to three of the following groups: halogen, nitro, cyano, C₁-C₄-alkyl, partially or fully halogenated C₁-C₄-alkyl, C₁-C₄-alkoxy, partially or fully halogenated C₁-C₄-alkoxy or C₁-C₄-alkoxycarbonyl;
- Benzyl, which may carry one to three of the following groups: halogen, nitro, cyano, C₁-C₃-alkyl, which may be unsubstituted or partially or completely halo geniert or C₁-C₃-alkoxy;
a five- to six-membered heterocyclic radical having one or two heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen or a benzotriazole radical;
Phthalimido, tetrahydrophthalimido, succinimido, maleimido;
- In the case Y = O: one equivalent of a cation from the group of alkali or alkaline earth metals, manganese, copper, iron, ammonium and with up to 4 C₁-C₃-alkyl groups substituted ammonium or
- a residue -N = CR⁸R⁹, where
R⁸, R⁹ is hydrogen, C₁-C₄-alkyl, C₃-C₆-cycloalkyl, phenyl, furyl, or together a methylene chain having 4 to 7 members;
R⁶ hydrogen; C₁-C₆-alkyl or C₃-C₈-cycloalkyl and
R⁷ is hydrogen, C₁-C₆-alkyl or
R⁶, R⁷ together represent a methylene chain with 4 or 5 members;
R3 is hydrogen;
- C₁-C₆-alkyl which may carry one to three of the following substituents: hydroxy, halogen, C₁-C₄-alkoxy, C₁-C₄-alkylthio or di- (C₁-C₄) -alkylamino;
- C₃-C₈-cycloalkyl which may be substituted one to three times by halogen, C₁-C₄-alkyl, and partially or fully halogenated C₁-C₄-alkyl;
R⁴ - hydrogen; hydroxyl; a C₁-C₄ alkoxy group;
a C₁-C₆-alkyl group which may carry one to three of the following radicals: halogen, cyano, C₁-C₄-alkoxy, partially or fully halogenated C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, Di-C₁-C₄-alkylamino, C₃-C₈-cycloalkyl or phenyl, wherein the phenyl ring in turn may carry one to three of the following radicals: halogen, cyano, nitro, C₁-C₄-alkyl, partially or fully halogenated C₁-C₄-alkyl , C₁-C₄-alkoxy, C₁-C₄-halo genalkoxy, C₁-C₄-alkylthio or C₁-C₄-haloalkylthio;
- A C₃-C₈-cycloalkyl group which may carry one to three of the following radicals: halogen, nitro, cyano, C₁-C₆-alkyl, partially or fully halogenated C₁-C₆-alkyl, C₁-C₄-alkoxy or partially or fully halogenated C₁-C₄ alkoxy;
a C₃-C₆-alkenyl or C₃-C₆-alkynyl group which may each be substituted one to three times by halogen and / or once by phenyl, the phenyl radical in turn being able to carry one to three of the following groups: C₁-C₄- Alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, halogen, cyano or nitro;
a di (C₁-C₄) alkylamino group;
- A 5- to 6-membered heterocyclic saturated or aromatic radical having one or two heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, which may be substituted one to three times by C₁-C₄-alkyl or halogen;
- A phenyl group which may carry one to four of the following groups: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl thio , Halogen, nitro, cyano, formyl, C₁-C₄-alkanoyl, C₁-C₄-haloalkanoyl or C₁-C₄-alkoxycarbonyl;
- A naphthyl group which may be substituted one to three times by C₁-C₄-alkyl or halogen; or
R³, R⁴ together a methylene chain having 4 to 7 members, which may be interrupted by oxygen, sulfur or N-methyl, or the radical - (CH₂) ₃-CO-. 2. Azolcarbonsäureamide I according to claim 1, wherein R³ is hydrogen means. 3. A herbicidal composition containing at least one azole-carboxylic acid amide of Formula I according to claim 1 and inert carriers. 4. A method for controlling undesired plant growth, thereby characterized in that a herbicidally effective amount of Azole-carboxamide of the formula I according to claim 1 on plants, their habitat or seed.