WO1996016045A1 - DERIVATIVES OF α-HALOGEN CARBONYL COMPOUNDS, PROCESS AND INTERMEDIATE PRODUCTS FOR PREPARING THE SAME - Google Patents

Abstract

α-halogen carbonyl derivatives have the general formula (I), in which R is a formyl group, a CO2H group or a rest capable of being hydrolysed into COOH and the other substituents have the following meanings: R2 stands for halogen, C¿1?-C4alkyl, C1-C4alkyl halide, C1-C4alkoxy, C1-C4alkoxy halide or C1-C4alkylthio; X is nitrogen or CR?13¿, in which R13 is hydrogen or forms together with R3 a 3 to 4-membered alkylene or alkenylene chain in which a methylene group is substituted by oxygen; R3 is halogen, C¿1?-C4alkyl, C1-C4alkyl halide, C1-C4alkoxy, C1-C4alkoxy halide or C1-C4alkylthio, or R?3¿ is bound together with R13 into a 5 to 6-membered ring, as described above; R4 is a carbonyl group or a derivative of a carbonyl group; R5 is hydrogen, C¿1?-C4alkyl, C3-C6alkenyl, C3-C6alkinyl, C3-C8cycloalkyl, C1-C4alkyl halide, C1¿-C¿4alkoxyalkyl, C1-C4alkylthioalkyl or phenyl; Y is sulphur or oxygen or a simple bond; Z is halogen.

Description

Derivatives of α-halocarbonyl compounds, processes and intermediates for their preparation Description

The present invention relates to α-halocarbonyl derivatives of the general formula I,

in which R represents a formyl group, a group CO ₂ H or a radical which can be hydrolyzed to COOH and the other substituents have the following meaning: R ² halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ -alkoxy,

C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio;

X is nitrogen or CR ¹³ , where R ^{13 is} hydrogen or together with R ^{3 is} a 3- to 4-membered alkylene or

 Forms alkenylene chain, in each of which a methylene group is replaced by oxygen;

R ³ halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio or R ³ is linked to R ¹³ as stated above to form a 5- or 6-membered ring;

R ^{4 is} a group

is in the

Y ¹ , Y ² , Y ³ oxygen or sulfur, R ¹⁴ hydrogen, C ₁ -C ₈ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl,

C ₃ -C ₈ -cycloalkyl, where these radicals one to five halogen atoms and / or may carry one to two of the following groups: C ₁ -C 4 alkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy, C ₁ -C ₄ alkylthio, C ₃ -C ₆ alkenylthio, C ₃ -C ₆ alkynylthio, C ₁ -C ₄ haloalkoxy, cyano, C ₁ -C ₄ dialkylamino, phenyl, one or more times by halogen, Nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio substituted phenyl,

Phenyl, which can be substituted by one or more of the following radicals: halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ - Haloalkoxy or C ₁ -C ₄ alkylthio,

R ^{15 is} hydrogen, C ₁ -C ₈ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl,

C ₃ -C ₈ cycloalkyl, where these radicals can carry one to five halogen atoms and / or one or two of the following groups: C ₁ -C ₄ alkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy , C ₁ -C ₄ alkylthio, C ₃ -C ₆ alkenylthio, C ₃ -C ₆ alkynylthio, C ₁ -C ₄ haloalkoxy, cyano, C ₁ -C ₄ dialkylamino, phenyl one or more times by halogen, Nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio substituted phenyl,

Phenyl, which can be substituted by one or more of the following radicals: halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ - Halogenalkoxy or C ₁ -C ₄ alkylthio, furthermore a radical OR ¹⁸ , in which R ¹⁸

Hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl,

C ₃ -C ₆ cycloalkyl, where these radicals can carry one to five halogen atoms and / or one or two of the following groups: C ₁ -C ₄ alkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy , C ₁ -C ₄ alkylthio, C ₃ -C ₆ alkenylthio, C ₃ -C ₆ alkynylthio, C ₁ -C ₄ haloalkoxy, cyano, C: -C ₄ dialkylamino, phenyl, one or more times by halogen , Nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio substituted phenyl,

Phenyl, which can be substituted by one or more of the following radicals: halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ - Haloalkoxy or C ₁ -C ₄ alkylthio, furthermore a radical NR ¹⁹ R ²⁰ in which R ¹⁹ and R ^{20 can be the} same or different,

Hydrogen, C ₁ -C ₈ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl,

C ₃ -C ₆ cycloalkyl, where these radicals can carry one to five halogen atoms and / or one or two of the following groups: C ₁ -C ₄ alkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy , C ₁ -C ₄ alkylthio, C ₃ -C ₆ alkenylthio, C ₃ -C ₆ alkynylthio, C ₁ -C ₄ haloalkoxy, cyano, C ₁ -C ₄ dialkylamino, phenyl, one or more times by halogen , Nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio substituted phenyl,

Phenyl, which can be substituted by one or more of the following radicals: halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ - Haloalkoxy or C ₁ -C ₄ alkylthio, or R ¹⁹ and R ²⁰ together form an optionally substituted C ₄ -C ₇ alkylene chain which is closed to form a ring or together form an optionally stubstituted C ₃ -C ₆ alkylene chain which is formulated to form a ring a heteroatom selected from the group consisting of oxygen, sulfur or nitrogen,

R ¹⁶ and R ^{17 are} C ₁ -C ₈ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ cycloalkyl, these radicals having one to five halogen atoms and / or one or two of the following groups:

C ₁ -C ₄ alkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy, C ₁ -C ₄ alkylthio, C ₃ -C ₆ alkenylthio, C ₃ -C ₆ alkynylthio, C ₁ -C ₄ haloalkoxy, cyano, C ₁ -C ₄ dialkylanu.no, phenyl, one or more times by halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -haloalkoxy or C ₁ -C ₄ -alkylthio substituted phenyl,

Phenyl, which can be substituted by one or more of the following radicals: halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ - Haloalkoxy or C ₁ -C ₄ alkylthio, or R ¹⁶ and R ¹⁷ together form an optionally substituted C ₁ -C ₅ alkylene chain which is closed to form a ring;

R ^{5 is} hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl,

C ₃ -C ₈ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxyalkyl, C ₁ -C ₄ alkylthioalkyl or phenyl;

Y sulfur or oxygen or a single bond; Z halogen. Similar compounds are described in the literature, for example EP-A 347 811, EP-A 400 741, EP-A 409 368, DE 40 35 758, EP-A 517 215, but none which carry an α-halocarbonyl radical or derivative .

Because the biological effects and selectivity of the known

Compounds is not always satisfactory, the object of the invention was to provide compounds with improved selectivity towards crop plants and / or better herbicidal or bioregulatory activity.

It has now been found that the α-halocarbonyl derivatives defined at the outset have excellent herbicidal and plant growth-regulating properties.

The preparation of the compounds according to the invention starts from the epoxides IV, which are carried out in a generally known manner, e.g. as in J. March, Advanced Organic Chemistry, 2nd ed., 1983, p. 862 or p. 750 or in J.Org.Chem. 33 (1968) 3517, from the aldehydes or ketones II or the olefins III:

Halohydrins of the formula VI can be prepared by treating the epoxides of the formula IV (for example with R = COOR ⁹ ) with halogen derivatives MZ of the formula V in which Z has the meaning given in claim 1 and M is hydrogen, an alkali metal cation or the equivalent of one Alkaline earth metal cations means to react:

The reaction can also take place in the presence of a diluent. All solvents which are inert to the reagents used can be used for this purpose.

Examples of such solvents or diluents are water, aliphatic, alicyclic and aromatic hydrocarbons, each of which may optionally be chlorinated, such as, for example, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and trichlorethylene, Ethers such as diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, isopropanol and butanol Ethylene glycol, esters such as ethyl acetate and amyl acetate, acid amides such as dimethylformamide and dimethylacetamide, sulfoxides and sulfones such as dimethyl sulfoxide and sulfolane, and bases such as pyridine.

The reaction is preferably carried out in a temperature range between 0 ° C. and the boiling point of the solvent or solvent mixture.

The presence of a reaction catalyst can be advantageous. Organic and inorganic acids as well as Lewis acids can be used as catalysts. Examples include sulfuric acid, hydrochloric acid, trifluoroacetic acid, boron trifluoride etherate and titanium (IV) halides.

The compounds according to the invention in which Y is oxygen and the remaining substituents which have the meaning given under the general formula I can be prepared, for example, by reacting the halohydrins of the general formula VI with compounds of the general formula VII,

in which R ^{21 is} halogen or R ²² SO ₂ -, where R ^{22 is}

C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or phenyl, brings about the reaction. The reaction preferably takes place in one of the inert diluents mentioned above with the addition of a suitable base, ie a base capable of deprotonating compound VI, in a temperature range from room temperature to the boiling point of the solvent.

As a base, an alkali or alkaline earth metal hydride such as sodium hydride, potassium hydride or calcium hydride, a carbonate, e.g. Alkali metal carbonate such as sodium or potassium carbonate, an alkali metal hydroxide such as sodium or potassium hydroxide, an organometallic compound such as butyllithium or an alkali amide such as lithium diisopropylamide. The compounds according to the invention in which Y is sulfur and the remaining substituents have the meaning given under the formula I can be prepared, for example, in such a way that α-halocarbonyl derivatives of the general formula VIII,

which are obtainable in a known manner from compounds of the general formula VI and in which the substituents have the meaning given above, with compounds of the general formula IX,

in which R ² , R ³ and X have the meaning given under the general formula I, brings about the reaction.

The reaction preferably takes place in one of the inert diluents mentioned above with the addition of a suitable base, i.e. a base, which is able to deprotonate the intermediate IX, takes place in a temperature range from room temperature to the boiling point of the solvent. In addition to the abovementioned, organic bases such as triethylamine, pyridine, imidazole or diazabicycloundecane can also be used as the base.

Compounds of the formula I can also be prepared by starting from the corresponding carboxylic acids, ie compounds of the formula I in which R is COOH, and converting them first in the usual manner into an activated form such as a halide, an anhydride or imidazolide and this is then reacted with a corresponding hydroxyl compound HOR ⁹ . This reaction can be carried out in the customary solvents and is advantageously carried out in the presence of a base, the abovementioned being possible. These two steps can also be simplified, for example, by the

Carboxylic acid can act on the hydroxyl compound in the presence of a dehydrating agent such as a carbodiimide.

In addition, compounds of the formula I can also be prepared by starting from the salts of the corresponding carboxylic acids, ie, for example, from compounds of the formula I in which R is a group COR ¹ and R ^{1 is} OM, where M is, for example, an alkali metal cation or the Can be equivalent to an alkaline earth metal cation. These salts can be reacted with many compounds of the formula R ¹ -A, where A is a customary nucleofugic leaving group, for example halogen such as chlorine, bromine, iodine or aryl- or alkylsulfonyl optionally substituted by halogen, alkyl or haloalkyl, such as toluenesulfonyl and Methylsulfonyl or other equivalent leaving group. Compounds of the formula R ¹ -A with a reactive substituent A are known or easily accessible according to general specialist knowledge. This reaction can be carried out in the customary solvents and is advantageously carried out in the presence of a base, the abovementioned being possible.

Compounds of the general formula I can also be prepared in such a way that corresponding compounds of the general formula I in which R ^{4 is} a free carbonyl group, ie a radical

is going out and this in a generally known manner with hydroxylamines, hydrazines or alcohols to the invention

Connections implemented. The radical R in Formula I is widely variable. For example, R stands for a group

in which R ^{1 has} the following meaning: a) hydrogen; b) a succinylimidoxy group; c) a 5-membered heteroaromatic linked via a nitrogen atom, such as pyrrolyl, pyrazolyl, imidazolyl and triazolyl, which can carry one or two halogen atoms, in particular fluorine and chlorine and / or one or two of the following radicals:

C ₁ -C ₄ alkyl such as methyl, ethyl, 1-propyl, 2-propyl,

 2-methyl-2-propyl, 2-methyl-1-propyl, 1-butyl, 2-butyl;

C ₁ -C ₄ haloalkyl, in particular C ₁ -C ₂ haloalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trichloromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2- Trifluoro ethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;

C ₁ -C ₄ haloalkoxy, in particular C ₁ -C ₂ haloalkoxy such as difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy,

1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy,

1,1,2,2-tetrafluoroethoxy, 2,2,2-trifluoroethoxy,

2-chloro-1,1,2-trifluoroethoxy and pentafluoroethoxy, especially trifluoromethoxy; C ₁ -C ₄ alkoxy such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, in particular methoxy, ethoxy, 1-methylethoxy; C ₁ -C ₄ alkylthio such as methylthio, ethylthio, propylthio,

1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, especially methylthio and ethylthio; R ^{1 is} also a radical - (O) _m -NR ⁶ R ⁷ in which m is 0 or 1 and R ⁶ and R ⁷ , which may be the same or different, have the following meaning:

hydrogen

C ₁ -C ₈ alkyl, in particular C ₁ -C ₄ alkyl as mentioned above,

C ₃ -C ₆ alkenyl such as 2-propenyl, 2-butenyl, 3-butenyl,

1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl,

3-pentenyl, 4-pentenyl, 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-2-propenyl,

1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl,

5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,

3-methyl-2-pentenyl, 4-methyl-2-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-2-butenyl, 1,2-dimethyl-3-butenyl,

1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,

2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl,

2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl 2-propenyl, 1-ethyl-1-methyl-2-propenyl and 1-ethyl-2-methyl-2-propenyl, especially 2-propenyl,

2-butenyl, 3-methyl-2-butenyl and 3-methyl-2-pentenyl;

C ₃ -C ₆ alkynyl such as 2-propynyl, 2-butynyl, 3-butynyl,

1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl,

1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,

1-methyl-2-pentinyl, 1-methyl-3-pentinyl,

1-methyl-4-pentinyl, 2-methyl-3-pentinyl,

2-methyl-4-pentinyl, 3-methyl-4-pentinyl,

4-methyl-2-pentinyl, 1,1-dimethyl-2-butinyl,

1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,

2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl, preferably 2-propynyl , 2-butynyl, 1-methyl-2-propynyl and

1-methyl-2-butynyl, especially 2-propynyl;

C ₃ -C ₈ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohepthyl and cycclooctyl, these alkyl, cycloolkyl, alkenyl and alkynyl groups each having one to five, in particular one to three, halogen atoms, preferably fluorine or chlorine and / or wear one or two of the following groups:

C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkoxy as mentioned above, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkenylthio , C ₃ -C ₆ alkynyloxy, C ₃ -C ₆ alkynylthio, the alkenyl and alkynyl constituents present in these radicals preferably corresponding to the meanings given above;

C ₁ -C ₄ alkylcarbonyl such as in particular methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl, 1,1-dimethylethylcarbonyl;

C ₁ -C ₄ alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, 1-methylethoxycarbonyl, butyloxycarbonyl, 1-methylpropyloxycarbonyl, 2-methylpropyloxycarbonyl,

 1,1-dimethylethoxycarbonyl;

C ₃ -C ₆ alkenylcarbonyl, C ₃ -C ₆ alkynylcarbonyl, C ₃ -C ₆ alkenyloxycarbonyl and C ₃ -C ₆ alkynyloxycarbonyl, the alkenyl or. Alkynyl radicals are preferably defined as detailed above; Phenyl, optionally substituted one or more times by halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl,

C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio such as 2-fluorophenyl, 3-chlorophenyl, 4-bromophenyl, 2-methylphenyl, 3-nitrophenyl, 4-cyanophenyl, 2 -Trifluoromethylphenyl, 3-methoxyphenyl, 4-trifluoroethoxyphenyl,

 2-methylthiophenyl, 2,4-dichlorophenyl, 2-methoxy-3-methylphenyl, 2,4-dimethoxyphenyl, 2-nitro-5-cyanophenyl,

 2, 6-difluorophenyl;

Di-C ₁ -C ₄ alkylamino such as especially dimethylamino, dipropylamino, N-propyl-N-methylamino, N-propyl-N-ethylamino, diisopropylamino, N-isopropyl-N-methylamino, N-isopropyl-N-ethylamino, N -Isopropyl-N-propylamino;

R ⁶ and R ⁷ furthermore phenyl, which can be substituted by one or more of the following radicals: halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio, as mentioned in detail above; or R ⁶ and R ⁷ together form an optionally substituted C ₄ -C ₇ alkylene chain which is closed to form a ring and which may contain a heteroatom selected from the group consisting of oxygen, sulfur or nitrogen, such as - (CH ₂ ) ₄ -, - (CH ₂ ) s-,

- (CH ₂ ) ₆ -, - (CH ₂ ) ₇ -, - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -, -CH ₂ -S- (CH ₂ ) ₃ -,

- (CH ₂ ) ₂ -O- (CH ₂ ) ₃ -, -NH- (CH ₂ ) ₃ -, -CH ₂ -NH- (CH ₂ ) ₂ -,

-CH ₂ -CH = CH-CH ₂ -, -CH = CH- (CH ₂ ) ₃ -, where in particular C ₁ -C ₄ alkyl radicals are suitable as substituents; e) R ¹ also a group

in which k is 0, 1 and 2, p is 1, 2, 3 and 4 and R ^{8 is} C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or optionally substituted phenyl, as mentioned in particular for R ⁶ and R ⁷ ; f) R ^{1 is} also a radical OR ⁹ , where R ⁹ is: i) hydrogen, the cation of an alkali metal or the cation of an alkaline earth metal such as lithium, sodium, potassium, calcium, magnesium and barium or an environmentally compatible organic ammonium ion such as tert. -C ₁ -C ₄ alkyl ammonium or ammonium [NH ₄ +]; ii) C ₃ -C ₈ cycloalkyl as mentioned above, which can carry one to three C ₁ -C ₄ alkyl groups; iii) C ₁ -C ₈ alkyl, such as in particular methyl, ethyl, propyl,

 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2- Dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,

1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2- Trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, which can carry one to five halogen atoms, in particular fluorine and chlorine and / or one of the following radicals: C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, cyano, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₈ cycloakyl, C ₁ -C ₄ alkoxycarbonyl, phenyl, one or more times by halogen, nitro, cyano, C ₁ -C ₄ alkyl ,

C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy and / or C ₁ -C ₄ alkylthio substituted phenyl or phenoxy, as mentioned above in particular; iv) a C ₁ -C ₈ -alkyl group as mentioned above which can carry one to five, preferably one to three halogen atoms, in particular fluorine and / or chlorine and carries one of the following radicals: a 5-membered heteroaromatic containing one to three Nitrogen atoms or a

 5-membered heteroaromatic, containing a nitrogen atom and an oxygen or sulfur atom, such as pyrazolyl, imidazolyl, benzimidazolyl, triazolyl, benztriazolyl, isooxazolyl, oxazolyl, thiazolyl, bonded via a carbon atom or, if possible, nitrogen atom, the heteroaromatic atom being one to can carry four halogen atoms and / or one or two of the following radicals:

Nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl,

C ₁ -C ₄ alkoxy, phenyl, C ₁ -C ₄ haloalkoxy and / or

C ₁ -C ₄ alkylthio. The following may be mentioned in particular: 1-pyrazolyl, 3-methyl-1-pyrazolyl, 4-methyl-1-pyrazolyl,

3,5-dimethyl-1-pyrazolyl, 3-phenyl-1-pyrazolyl, 4-phenyl-1-pyrazolyl, 4-chloro-1-pyrazolyl, 4-bromo-1-pyrazolyl, 1-imidazolyl, 1-benzimidazolyl, 1,2,4-triazol-1-yl, 3-methyl-1, 2,4-triazol-1-yl,

 5-methyl-1,2,4-triazol-1-yl, 1-benzotriazolyl, 3-isopropylisoxazol-5-yl, 3-methylisoxazol-5-yl, oxazol-2-yl, thiazol-2-yl, Imidazol-2-yl, 3-ethylisoxazol-5-yl,

3-phenylisoxazol-5-yl, 3-tert-butylisoxazol-5-yl; v) a C ₂ -C ₆ alkyl group which bears one of the following radicals in the 2 position: C ₁ -C ₄ alkoxyimino, C ₃ -C ₆ alkynyloxyimino, C ₃ -C ₆ haloalkenyloxyimino or benzyloxyimino; vi) a C ₃ -C ₆ alkenyl or a C ₃ -C ₆ alkynyl group, these groups in turn being able to carry one to five halogen atoms; vii) R ⁹ furthermore a phenyl radical which can carry one to five halogen atoms and / or one to three of the following radicals: nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ Alkoxy, C ₁ -C ₄ haloalkoxy and / or C ₁ -C ₄ alkylthio, as mentioned above in particular; viii) a 5-membered heteroaromatic linked via a nitrogen atom, containing one to three nitrogen atoms, such as pyrazolyl, imidazolyl, benzimidazolyl, triazolyl, benzotriazolyl, preferably bonded via the 1-position, the heteroaromatic having one or two halogen atoms and / or one or two of the can carry the following leftovers:

C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, phenyl, C ₁ -C ₄ haloalkoxy and / or C ₁ -C ₄ alkylthio. The following may be mentioned in particular: 1-pyrazolyl, 3-methyl-1-pyrazolyl,

 4-methyl-1-pyrazolyl, 3, 5-dimethyl-1-pyrazolyl,

 3-phenyl-1-pyrazolyl, 4-phenyl-1-pyrazolyl,

 4-chloro-1-pyrazolyl, 4-bromo-1-pyrazolyl, 1-imidazolyl,

1-benzimidazolyl, 1,2,4-triazol-1-yl, 3-methyl-1,2,4-triazol-1-yl, 5-methyl-1,2,4-triazol-1-yl, 1- Benzotriazolyl, 3, 4-dichlorimidazol-1-yl; ix) R ⁹ also a group

wherein R ¹⁰ and R ¹¹ , which may be the same or different, mean:

C ₁ -C ₈ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ cycloalkyl, these radicals being a C ₁ -C ₄ alkoxy, C ₁ -C ₄ - Alkylthio and / or an optionally substituted phenyl radical, as mentioned above, can carry;

Phenyl, which can be substituted by one or more of the following radicals: halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ -haloalkoxy or C ₁ -C ₄ -alkylthio, these radicals corresponding in particular to those mentioned above for R ¹ ; or R ¹⁰ and R ¹¹ together form a C ₃ -C ₁₂ alkylene chain which carry one to three C ₁ -C ₄ alkyl groups and can contain a heteroatom from the group consisting of oxygen, sulfur and nitrogen, as in particular in the case of R ⁶ and R Called ⁷ . g) R ^{1 is} also a radical -NH-SO ₂ -R ¹² where R ¹² is: C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ - Cycloalkyl as mentioned above in particular for R ¹ , where these radicals can carry a C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio and / or a phenyl radical as mentioned above;

Phenyl, optionally substituted, in particular as mentioned above. In view of the biological action, α-halocarbonyl derivatives of the formula I are preferred, in which the other substituents have the following meanings:

R ² those mentioned for R ¹ in each C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ Alkylthio groups and halogen atoms, in particular chlorine,

Methyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, particularly preferably methoxy; X is nitrogen or CR ¹³ , wherein

R ¹³ preferably denotes hydrogen or together with R ^{3 forms} a 4- to 5-membered alkylene or alkenylene chain, in each of which one methylene group is replaced by oxygen, such as -CH ₂ -CH ₂ -O-, -CH = CH-O- , -CH ₂ -CH ₂ -CH ₂ -O-, -CH = CH- CH ₂ O-, especially hydrogen and -CH ₂ -CH ₂ -O-; R ^{3 is} the C ₁ -C ₄ -alkyl-, C ₁ -C ₄ -haloalkyl- mentioned for R ¹ ,

C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio groups and halogen atoms, in particular chlorine, methyl,

Methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, particularly preferably methoxy, or linked to R ¹³ as mentioned above to form a 5- or 6-membered ring;

R ⁴ a) a residue

in which Y ^{1 is} oxygen or sulfur and R ^{14 is} the C ₁ -C ₈ -alkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl mentioned in particular for R ¹ ,

C ₃ -C ₈ cycloalkyl groups or, if necessary. substituted phenyl means b) a radical

by doing

R ^{15 is} the C ₁ -C ₈ -alkyl mentioned in detail for R ¹ ,

C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ cycloalkyl or R ¹⁵ is a radical OR ^18, wherein R ¹⁸ is as set out in detail for R ¹ C ₁ -C ₈ - Alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl,

C ₃ -C ₈ cycloalkyl groups or optionally substituted phenyl, or

R ^{15 is} a radical NR ¹⁹ R ²⁰ , where R ¹⁹ and R ^{20 represent} the radicals mentioned in detail for R ⁶ and R ⁷ , c) a radical

in which Y2 and Y3 are oxygen or sulfur and R ¹⁶ and R ^{17 are} the radicals mentioned in detail for R ⁶ and R ⁷ .

R ^{5 is} hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl,

C ₃ -C ₈ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxyalkyl, C ₁ -C ₄ alkylthioalkyl or phenyl as mentioned above;

Y sulfur, oxygen or a single bond; Z halogen.

If the compounds contain one or more stereocenters, both the racemates and the respective enantiomers are the subject of the invention.

Compounds I with R ⁵ = methyl, X = CH, R ² and R ³ = methoxy are preferred. Furthermore, compounds I with R ⁵ = methyl, X = CH, Z = fluorine and R ² , R ³ = methoxy. In addition, R ¹ preferably represents a group OR ⁹ , where R ^{9 is} in particular hydrogen and

C ₁ -C ₄ alkyl.

The variable Y is preferably sulfur and especially oxygen. Particularly preferred compounds of the formula I are listed in Table 1 below. The definitions given therein and in Table 2 for R ⁴ are also to be regarded as preferred, regardless of the further radical definitions.

The compounds I or the herbicidal compositions comprising them and their environmentally compatible salts, e.g. of alkali metals, alkaline earth metals or ammonia and amines or the herbicidal compositions containing them, can be very well combated in crops such as wheat, rice and corn, soybeans and cotton, weeds and harmful grasses without damaging the crop plants, an effect which, above all occurs even at low application rates. Taking into account the versatility of the application methods, the compounds I according to the invention or compositions comprising them can also be used in a further number of crop plants for eliminating undesired plants. The following crops come into consideration, for example: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus

officinalis, Beta vulgaris spp. altissima, Beta vulgaris spp. rapa, Brassica napus var. napus, Brassica napus var.

napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora ,, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis

guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium, herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Humulus lupulus, Ipomoea batatas, Juglinarisisumers, Lyulinarisisumers, Lyulinarisisumers, Lyulinarisisum, Lyulinarisisumum Malus spp., Manihot esculenta, Medicago sativa, Musa spp., Nicotiana tabacum

 (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, sorghum bicolor (S. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.

In addition, the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods. The herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less compatible for certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not struck where possible, while the active ingredients are applied to the leaves underneath growing unwanted plants or the uncovered floor area (post-directed, lay-by).

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

The compounds I are generally suitable for the preparation of directly sprayable solutions, emulsions, pastes or old dispersions. Inert additives include Mineral oil fractions from medium to high boiling point, such as kerosene or diesel oil, also coal tarols and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone or highly polar solvents, such as N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or water .

Aqueous use forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.

The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, as well as of fatty alcohol glycol ethers, condensation products of sulfonated and its derivatives with formaldehyde, condensation products of naphthalene or

Naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulfite waste liquors or methyl cellulose.

Powders, materials for spreading and dusting can be produced by mixing or grinding the active substances together with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are mineral soils such as silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea and vegetable products, such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

The formulations generally contain between 0.01 and 95% by weight, preferably between 0.5 and 90% by weight, of active ingredient. The active ingredients are used in a purity of 90 to 100%, preferably 95 to 100% (according to the NMR spectrum).

The compounds I according to the invention can be formulated, for example, as follows: I. 20 parts by weight of compound no. 1.1 are in one

 Dissolved mixture, which consists of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor sol. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

II. 20 parts by weight of compound no. 1.5 are in one

Dissolved mixture, which consists of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of ricinusol. Through a pouring and finely distributing the solution in 100,000 parts by weight of water gives an aqueous dispersion which contains 0.02% by weight of the active ingredient. III. 20 parts by weight of active ingredient no. 1.7 are in a

 Dissolved mixture, which consists of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring and finely distributing the solution in 100

000 parts by weight of water gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.

IV. 20 parts by weight of active ingredient no. 1.10 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene α-sulfonic acid, 17 parts by weight of the sodium salt of lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient.

V. 3 parts by weight of active ingredient No. 1.11 are mixed with 97 parts by weight of finely divided kaolin. In this way a dust is obtained which contains 3% by weight of the active ingredient.

VI. 20 parts by weight of active ingredient no. 1.1 are mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8

Parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.

To broaden the spectrum of activity and to achieve synergistic effects, the α-halocarbonyl derivatives can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied together. For example, diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiol carbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3- dione derivatives which carry a carboxy or carbimino group in the 2-position, quinolinecarboxylic acid derivatives, imidazolinones, sulfonamides, sulfonylureas, aryl oxy-, heteroaryloxyphenoxypropionic acids and their salts, esters and amides and others into consideration.

It may also be useful to apply the compounds I alone or in combination with other herbicides, mixed with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.

The application rates of active ingredient are 0.001 to 3.0 kg / ha, preferably 0.01 to 1.0 kg / ha active substance (a.S.) depending on the control target, the season, the target plants and the growth stage.

The compounds of formula I can influence practically all developmental stages of a plant in various ways and are therefore used as growth regulators. The variety of effects of the plant growth regulators depends above all a) on the plant type and variety,

b) the time of application, based on the stage of development of the plant and the season,

c) the place and method of application (e.g. seed dressing,

 Soil treatment, leaf application or tree trunk injection),

d) climatic factors, e.g. Temperature, amount of precipitation, day length and light intensity,

e) the nature of the soil (including fertilization), f) the formulation or application form of the active ingredient and finally

 g) the concentration of active substance used. Some of the various uses of the plant growth regulators of the formula I in plant cultivation, in agriculture and in horticulture are mentioned below. A. With the compounds which can be used according to the invention, the vegetative growth of the plants can be strongly inhibited, which manifests itself in particular in a reduction in the growth in length.

The treated plants accordingly have a compact stature; a darker leaf coloration can also be observed. A reduced intensity of the growth of grassers and crops that are susceptible to storage, such as cereals, corn, sunflowers and soybeans, has proven to be advantageous in practice. The resulting shortening and strengthening of the stalk reduce or eliminate the risk of "storing" (twisting) of plants under unfavorable weather conditions before harvesting.

It is also important to use growth regulators to inhibit the growth of length and to change the ripening process of cotton over time. This enables fully mechanized harvesting of this important crop. In the case of fruit and other trees, the growth regulators can save cutting costs. In addition, the alternance of fruit trees can be broken by growth regulators. The use of growth regulators can also increase or inhibit the lateral branching of the plants. There is interest in this, e.g. if in tobacco plants the formation of side shoots (stinging shoots) should be inhibited in favor of leaf growth.

With growth regulators, for example, frost resistance can also be significantly increased in winter rape. On the one hand, the growth in length and the development of a lush (and therefore particularly susceptible to frost) leaf or plant mass are inhibited. On the other hand, the young rapeseed plants are held back after sowing and before the onset of winter frosts, despite favorable growth conditions in the vegetative development stage. This also eliminates the risk of frost for plants that tend to prematurely degrade flowering and switch to the generative phase. It is also advantageous for other crops, for example winter cereals, if the stocks are well planted in autumn by treatment with the compounds according to the invention, but do not go into the winter too abundantly. This can prevent the increased sensitivity to frost and - due to the relatively small leaf or plant mass - the infestation with various diseases (eg fungal disease). With the growth regulators, additional yields can be achieved both on parts of plants and on plant ingredients. For example, it is possible to grow larger To induce amounts of buds, flowers, leaves, fruits, seeds, roots and tubers, to increase the sugar content in sugar beets, sugar cane and citrus fruits, to increase the protein content in cereals or soybeans or to stimulate rubber trees to increase the flow of latex.

The compounds of formula I can increase yields by interfering with the plant metabolism or by promoting or inhibiting vegetative and / or generative growth.

C. Finally, with plant growth regulators

 achieve both a shortening or lengthening of the development stages and an acceleration or delay in the ripeness of the harvested plant parts before or after the harvest.

For example, the

 Harvest relief, which is made possible by the temporally concentrated drop or decrease of the adhesive strength on the tree with citrus fruits, olives or other types and varieties of pome, stone and nuts. The same mechanism, i.e. The promotion of the formation of separating tissue between the fruit, leaf or shoot part of the plant is also essential for a well controllable defoliation of useful plants such as cotton.

D. Growth regulators can further reduce the water consumption of plants. By using the substances according to the invention, the intensity of irrigation can be reduced and thus more economical management can be carried out because, among other things, the opening width of the stomata is reduced,

 - a thicker epidermis and cuticila are formed, - the root penetration of the soil is improved and

 - The microclimate in the crop is favorably influenced by a more compact growth. Compounds I are particularly suitable for shortening the stalks of crops such as barley, rapeseed and wheat.

The active compounds of the formula I to be used according to the invention can be added to the crop plants both from the seed (as a seed dressing) and via the soil, ie through the root and particularly preferred - be supplied by spraying over the sheet.

The amount of active ingredient is not critical due to the high tolerance to plants. The optimal application rate varies depending on the control target, season, target plants and growth stages.

In the case of seed treatment, amounts of active ingredient of 0.001 to 50 g, preferably 0.01 to 10 g, are generally required per kilogram of seed.

For leaf and soil treatment, doses of 0.001 to 10 kg / ha, preferably 0.01 to 3 kg / ha, in particular 0.01 to 0.5 kg / ha, are generally sufficient.

Synthesis examples:

example 1

2- (4,6-Dimethoxypyrimidin-2-yl) oxy-3-fluoro-4-methoxyimino-3-methylvaleric acid a) 2,3-epoxy-4-methoxyimino-3-methylvaleric acid methyl ester 43.2 g ( 0.8 mol) of sodium methylate in 500 ml of dry THF, cooled to -10 ° C. and a mixture of 57.5 g (0.5 mol) of 3-methoxyimino-2-butenone and 87.2 g ( 0.5 mol) of methyl chloroacetate, allowed to come to room temperature and stirred one

 Hour after. The mixture was then poured onto 1 liter of ice water, extracted three times with 200 ml of diethyl ether each time and the solvent was removed on a rotary evaporator. Distillation over a Vigreux column (20 cm) in a water jet vacuum gave a slightly yellow liquid at a transition temperature of 114 ° C., which is a 1: 1 mixture (cis: trans) of the mixed epoxide.

 Yield: 65.5 g (≙ 70% of theory)

¹ H NMR (CDCI ₃ ): 3.90; 3.85 (s, 3H, COOCH ₃ ); 3.80; 3.75 (S, 3H, OCH ₃ ); 3.65; 3.60 (S, 1H, CH); 1.9; 1.7 (s, 3H, CH _3); 1.60: 1.55 (d, 3H, CH ₃ ). b) 3-Fluoro-2-hydroxy-4-methoxyimino-3-methylvaleric acid methyl ester

17.6 ml of an HF-pyridine complex (70% HF) were dissolved in 18 ml of dried dichloromethane and 33 g (176 mmol) of the expoxide 1a) in 8 ml of dichloromethane were added dropwise with ice cooling (temperature 9-28 ° C.). After stirring at room temperature for 18 hours, the mixture was poured onto 50 g of ice, the organic phase was separated off, washed with sodium bicarbonate solution and dried over magnesium sulfate. After concentrating on the rotary evaporator, a slightly yellow oil remained.

 Yield: 31.7 g (87% of theory), diastereomers 1: 1

1H NMR (CDCl ₃ ): 4.4 (dd, 1H, -CH), 3.95; 3.90 (s, 3H, COOCH ₃ ); 3.60 (d, 1H, OH); 1.95 (s, 3H, -CH _3); 1.60, 1.50 (d, 3H, -CH _3). c) Methyl 2- (4,6-dimethoxypyrimidin-2-yl) oxy-3-fluoro-4-methoxyimino-3-methylvalerate

31.2 g (150 mmol) of the fluorohydrin 1b) were dissolved in 100 ml of DMF, 10.4 g (75 mmol) of potassium carbonate and 34 g (150 mmol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine were added and the mixture was heated

 8 hours at 50 ° C. After cooling to room temperature, the mixture was stirred into 500 ml of water and the precipitate formed was filtered off with suction.

Yield: 42.0 g (81% of theory), diastereomer 3: 2 mp: 95-97 ° C. 1H NMR (CDCl ₃ ) 5.75 (s, 1H, Py-H); 5.60; 5.35 (d, 1H, -CH); 3.90 (s, 6H, -OCH ₃ ), 3.85; 3.80 (d, 3H, COOCH ₃ ); 3.75; 3.70 (d, 3H, -OCH ₃ ) 2.05; 2.0 (s, 3H, CH _3); 1.75; 1.70 (d, 3H, -CH _3). d) 2- {4,6-Dimethoxypyrimidin-2-yl) oxy-3-fluoro-4-methoxyimino-3-methylvaleric acid

20 g (58 mmol) of compound 1c) were dissolved in 100 ml of methanol and 100 ml of THF, 69 g (174 mmol) of sodium hydroxide solution were added

 10% solution and stirred at 60 ° C for 8 hours. After removing the solvent in vacuo, the residue became

 200 ml of water was added, which was extracted twice with 50 ml of ethyl acetate. Then a pH of 2 was set with 10% hydrochloric acid and extracted again with ethyl acetate. After drying over magnesium sulfate and distilling off the solvent, the residue was added

 Diethyl ester added and the precipitate formed is suction filtered.

Yield: 9.6 g (49% of theory), 1 diastereomer 1H NMR (CDCI ₃ ); 10.4 (s, 1H, COOH); 5.75 (S, 1H, Py-H); 5.45 (d, 1H, -CH); 3.90 (s, 6H, -OCH ₃ ); 3.80 (s, 3H, -OCH ₃ ); 2.0 (s, 3H, -CH _3); 2.85 (d, 3H, -CH _3). Example 2:

 Methyl 2- (4,6-dimethoxyprimidin-2-yl) oxy-3-fluoro-3- (2-methyl-1,3-dioxolan-2-yl) -butyrate a) 2,3-epoxy-3- (2-methyl-1,3-dioxolan-2-yl) methyl butyrate

Analogously to Example 1a), 142 g (1.1 mol) are obtained from

 3-Acetyl-2-methyl-1,3-dioxolane after distillation under high vacuum 102 g (0.5 mol) of the desired compound as a 1: 1 mixture (cis-trans).

 Yield: 50% of theory

1H NMR (CDCl ₃ ): 3.9-4.1 (m, 4H, -O-CH ₂ -CH ₂ O); 3.90; 3.75 (s, 3H, COOCH ₃ ); 3.85, 3.3 (S, 1H, -CH); 1.40-1.50 (4s, 6H, -CH ₃ ). b) 3-Fluoro-2-hydroxy-3- (2-methyl-1,3-dioxolan-2-yl) -butyric acid methyl ester

Opening the epoxide from 2a) using HF / pyridine analogously to 1b) gave a mixture which, in addition to 45.5% of the desired compound, also contained 37.5% of 3-fluoro-2-hydroxy-3-methyl-4-oxovaleric acid methyl ester and without further cleaning was used in the next stage. c) 2- (4,6-Dimethoxypyrimidin-2-yl) oxy-3-fluoro-3- (2-methyl-1,3-dioxolan-2-yl) butyric acid methyl ester

The mixture from 2b) was reacted analogously to 1c) with 4,6-dimethoxy-2-methylsulfonylpyrimidine. After working up, the mixture was purified by flash chromatography on silica gel with n-hexane / ethyl acetate 9: 1 as the eluent. The second fraction contained the desired product.

Mp: 87-89 ° C (1 diastereomer). 1H NMR (CDCI ₃ ): 5.70 (s, 1H, Py-H); 5.35 (d, 1H, -CH);

4.05 to 4.00 (m, 4H, O-CH ₂ -CH ₂ -O); 3.90 (s, 6H, -OCH ₃ ); 3.75 (s, 3H, -COOCH ₃ ); 1.65 (d, 3H, -CH _3); 1.55 (s, 3H, -CH _3). Example 3:

 2- (4,6-Dimethoxypyrimidin-2-yl) oxy-3-fluoro-3-methyl-4-oxovaleric acid methyl ester The first fraction of the flash chromatography from 2c) contained the desired keto compound as a 9: 1 mixture of the two diastereomers.

¹ H NMR: 5.75 (S, 1H, Py-H); 5.40 (d, 1H, -CH); 3.85 (s, 6H, -OCH ₃ ); 3.80 (s, 3H, -COOCH ₃ ); 2.45 (d, 3H, -CH _3); 1.55 (d, 3H, -CH _3).

Example 4:

 2- (4,6-Dimethoxypyrimidin-2-yl) oxy-3-fluoro-4-allyloxyimino-3-methylvaleric acid methyl ester

3.2 g (10 mmol) of the ketone from Example 3 were in 100 ml

Dissolved methanol, mixed with 1.2 g (11 mmol) of allyloxyamine hydrochloride and stirred at reflux for 8 hours. After the solvent had been distilled off, the residue was taken up in 50 ml of dichloromethane, mixed with sodium bicarbonate solution, dried over magnesium sulfate and concentrated. 3.5 g of a white powder remained.

Yield 94% of theory

Example 5:

 4,4-Dimethoxy-2- (4,6-dimethoxypyrimidin-2-yl) oxy-3-fluoro-3-methylvaleric acid methyl ester 3.2 g (10 mmol) of the ketone from Example 3 were in 100 ml

 Dissolved methanol, mixed with a spatula tip Amberlyst and stirred at reflux for 8 hours. After cooling, the catalyst was filtered off and concentrated in vacuo. 3.3 g of the desired acetal were obtained.

Yield: 91% of theory

Analogously to the examples above, all the compounds in the table below were synthesized.

Examples of use

The herbicidal activity of the α-halocarbonyl derivatives of the general formula I was demonstrated by greenhouse tests:

Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels. The seeds of the test plants were sown separately according to species.

In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles. The tubes were lightly sprinkled to promote germination and growth, and then covered with clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients. For the purpose of post-emergence use, the test plants, depending on the growth habit, are first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. The test plants are either sown directly and grown in the same containers, or they are first grown separately as seedlings and transplanted into the test containers a few days before the treatment. The application rate for follow-up treatment is 0.5 or

0.25 kg / h a.S. The plants were kept in a species-specific manner at temperatures of 10 to 25 ° C and 20 to 35 ° C. The trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated.

It was rated on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal

 Growth course.

The plants used in the greenhouse experiments are composed of the following types:

Claims

claims

1. α-halocarbonyl derivatives of the general formula I

in which R represents a formyl group, a group CO ₂ H or a radical which can be hydrolyzed to COOH and the other substituents have the following meanings:

R ² halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio;

X is nitrogen or CR ¹³ , where R ^{13 is} hydrogen or together with R ^{3 is} a 3- to 4-membered alkylene or

Forms alkenylene chain, in each of which a methylene group is replaced by oxygen;

R ^{3 is} halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio or R ³ is with R ¹³ linked into a 5- or 6-membered ring as entered above;

R ^{4 is} a group

is in the

Y ¹ , Y ² , Y ³ oxygen or sulfur, R ^{14 is} hydrogen, C ₁ -C ₈ alkyl, C ₃ -C ₆ alkenyl,

C ₃ -C ₆ alkynyl, C ₃ -C ₈ cycloalkyl, where these radicals can carry one to five halogen atoms and / or one or two of the following groups:

C ₁ -C ₄ alkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy,

C ₁ -C ₄ alkylthio, C ₃ -C ₆ alkenylthio, C ₃ -C ₆ alkynylthio, C ₁ -C ₄ haloalkoxy, cyano, C ₁ -C ₄ dialkylamino, phenyl, one or more times by halogen, Nitro, cyano,

C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio substituted

Phenyl,

 Phenyl, which can be substituted by one or more of the following radicals: halogen, nitro, cyano,

C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio,

R ^{15 is} hydrogen, C ₁ -C ₈ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ cycloalkyl, these radicals having one to five halogen atoms and / or one or two of the can carry the following groups:

C ₁ -C ₄ alkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy,

C ₁ -C ₄ alkylthio, C ₃ -C ₆ alkenylthio, C ₃ -C ₆ alkynylthio, C ₁ -C ₄ haloalkoxy, cyano, C ₁ -C ₄ dialkylamino, phenyl, one or more times by halogen, Nitro, cyano,

C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio substituted phenyl,

Phenyl, which can be substituted by one or more of the following radicals: halogen, nitro, cyano,

C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio, furthermore a radical OR ¹⁸ , in which R ¹⁸

Hydrogen, Cχ-Ca alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ cycloalkyl, where these radicals can carry one to five halogen atoms and / or one or two of the following groups :

C ₁ -C ₄ alkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy,

C ₁ -C ₄ alkylthio, C ₃ -C ₆ alkenylthio, C ₃ -C ₆ alkynylthio, C ₁ -C ₄ haloalkoxy, cyano, C ₁ -C ₄ dialkylamino, phenyl, one or more times by halogen, Nitro, cyano,

C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio substituted phenyl, Phenyl, which can be substituted by one or more of the following radicals: halogen, nitro, cyano,

C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio, furthermore a radical NR ¹⁹ R ²⁰ , in which R ¹⁹ and R ^{20 can be} identical or different,

Hydrogen, C ₁ -C ₈ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ cycloalkyl, these radicals having one to five halogen atoms and / or one or two of the following groups can carry: C ₁ -C ₄ alkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy,

C ₁ -C ₄ alkylthio, C ₃ -C ₆ alkenylthio, C ₃ -C ₆ alkynylthio, C ₁ -C ₄ haloalkoxy, cyano, C ₁ -C ₄ dialkylamino, phenyl, one or more times by halogen, Nitro, cyano,

C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio substituted phenyl,

 Phenyl, which can be substituted by one or more of the following radicals: halogen, nitro, cyano,

C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio, or R ¹⁹ and R ²⁰ together form an optionally substituted C ₄ -C ₇ alkylene chain which is closed to form a ring or together form an optionally stubstituted C _{3 which is} closed to form a ring -C ₆ alkylene chain with a heteroatom selected from the group consisting of oxygen, sulfur or nitrogen,

R ¹⁶ and R ^{17 are} C ₁ -C ₈ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ cycloalkyl, these radicals having one to five halogen atoms and / or one or two of the following groups: C ₁ -C ₄ alkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy,

C ₁ -C ₄ alkylthio, Cs-Cc-alkenylthio, C ₃ -C ₆ alkynylthio, C ₁ -C ₄ haloalkoxy, cyano, C ₁ -C ₄ dialkylamino, phenyl, one or more times by halogen, nitro, Cyano,

C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio substituted phenyl,

Phenyl, which can be substituted by one or more of the following radicals: halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio, or R ¹⁶ and R ¹⁷ together form an optionally substituted C ₁ -C ₅ alkylene chain which is closed to form a ring;

R ^{5 is} hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ - Alkoxyalkyl, C ₁ -C ₄ alkylthioalkyl or phenyl;

Y sulfur or oxygen or a single bond;

Z halogen. 2. α-halocarbonyl derivatives of the general formula I according to claim 1 in the R for a group

where R ^{1 has} the following meaning: a) hydrogen; b) a succinylimidoxy group; c) a 5-membered heteroaromatic linked via a nitrogen atom, containing two to three nitrogen atoms, which can carry one or two halogen atoms and / or one or two of the following radicals: C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl , C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy and / or C ₁ -C ₄ alkylthio; d) a radical - (O) _m -NR ⁶ R ⁷ , in which m represents 0 or 1 and R ⁶ and R ⁷ , which may be the same or different, have the following meaning:

Hydrogen; C ₁ -C ₈ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ cycloalkyl, these radicals each carrying one to five halogen atoms and / or one or two of the following groups can: C ₁ -C ₄ alkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy, C ₁ -C ₄ alkylthio, C ₃ -C ₆ alkenylthio, C ₃ -C ₆ alkynylthio, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₆ alkenylcarbonyl, C ₃ -C ₆ alkynylcarbonyl, C ₁ -C ₄ alkoxycarbonyl, C ₃ -C ₆ alkenyl oxycarbonyl, C ₃ -C ₆ alkynyloxycarbonyl, di-C ₁ -C ₄ alkylamino, C ₃ -C ₈ cycloalkyl, phenyl, one or more times by halogen, nitro, cyano, C ₁ -C ₄ alkyl,

C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio substituted phenyl;

Phenyl, which can be substituted by one or more of the following radicals: halogen, nitro, cyano,

C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio;

R ⁶ and R ⁷ together form a closed, optionally substituted C ₄ -C ₇ alkylene chain or together form a closed, optionally substituted C ₃ -C ₆ alkylene chain with a hetero atom, selected from the group consisting of oxygen, sulfur or Nitrogen; e) R ¹ also a group

in which R ^{8 is} C ₁ -C ₄ -alkyl, phenyl, one or more times by halogen, nitro, cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio substituted phenyl, C ₁ -C ₄ haloalkyl,

Is C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl, p is 1,

2, 3 or 4 and k assume the values 0, 1 or 2; f) an OR ⁹ radical in which R ⁹ denotes: i) hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation, the ammonium cation or an organic ammonium ion; ii) a C ₃ -C ₈ cycloalkyl group which one to three

C ₁ -C ₄ alkyl radicals can carry; iii) a C ₁ -C ₈ alkyl group which can carry one to five halogen atoms and / or one of the following radicals: C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, cyano, C ₁ -C ₄ - Alkylcarbonyl, C ₃ -C ₈ cycloalkyl, C ₁ -C ₄ alkoxycarbonyl, phenyl, one or more times by halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ - C ₄ alkoxy, C ₁ -C ₄ halo genalkoxy and / or C ₁ -C ₄ alkylthio substituted phenyl or phenoxy; iv) a C ₁ -C ₈ -alkyl group which can carry one to five halogen atoms and carries one of the following radicals: a 5-membered heteroaromatic containing one to three nitrogen atoms, or a 5-membered heteroaromatic containing a nitrogen atom and a

Oxygen or sulfur atom, which can carry one to four halogen atoms and / or one or two of the following radicals: nitro, cyano, C ₁ -C ₄ alkyl,

C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy and / or C ₁ -C ₄ alkylthio; v) a C ₂ -C ₆ alkyl group which is in the 2-position

carries one of the following radicals: C ₁ -C ₄ alkoxyimino, C ₃ -C ₆ alkenyloxyimino, C ₃ -C ₆ haloalkenyloxyimino or benzyloxyimino; vi) a C ₃ -C ₆ alkenyl or a C ₃ -C ₆ alkynyl group, these groups in turn being able to carry one to five halogen atoms; vii) a phenyl radical which can carry one to five halogen atoms and / or one to three of the following radicals: nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy and / or

C ₁ -C ₄ alkylthio; viii) one linked via a nitrogen atom

5-membered heteroaromatic, containing one to three nitrogen atoms, which can carry one or two halogen atoms and / or one or two of the following radicals: nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy and / or

C ₁ -C ₄ alkylthio; ix) R ⁹ also a group

wherein R ¹⁰ and R ¹¹ , which are the same or different, mean: C ₁ -C ₈ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ cycloalkyl, these radicals can carry a C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio and / or a phenyl radical;

Phenyl, which can be substituted by one or more of the following radicals:

Halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio; or R ¹⁰ and R ¹¹ together form a C ₃ -C ₁₂ alkylene chain which can carry one to three C ₁ -C ₄ alkyl groups; g) or R ¹ forms a radical -NH-SO ₂ -R ¹² , in which R ¹² means: C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ - C ₈ cycloalkyl, where these radicals can carry a C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio and / or a phenyl radical; Phenyl, which can be substituted by one or more of the following radicals: halogen, nitro, cyano,

C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio.

3. α-halocarbonyl derivatives of the formula I according to claim 1, in which R ^{5 is} methyl or phenyl, X CH, R ² and R ^{3 are} methoxy and Y, Z, R and R ^{4 have} the meaning given in claim 1.

4. α-halocarbonyl derivatives of the formula I according to claim 1, in which Z is fluorine, R ^{5 is} methyl or phenyl, X is CH, R ² and R ^{3 are} methoxy and Y, R and R ⁴ are as defined in claim 1.

5. α-halocarbonyl derivatives of the formula I according to claim 1, in which R ^{5 is} methyl or phenyl, X CH, R ² and R ^{3 are} methoxy, Y is oxygen, Z is fluorine, R is COOH and R ^{4 has} the meaning given in Claim 1.

6. Herbicidal composition comprising a compound of the formula I according to claim 1 and customary inert additives.

7. A method of combating undesirable plant growth, characterized in that a herbicidally effective amount of a compound of the formula I according to claim 1 is allowed to act on the plants or their habitat.

8. Agent for influencing plant growth, containing a compound of formula I according to claim 1 and customary inert additives.

9. A method for regulating plant growth, characterized in that a bioregulatory amount of a compound of formula I according to claim 1 is allowed to act on the plants or their habitat.

10. α-halocarbonyl derivatives of the general formula VI,

in which R, R ⁴ , R ⁵ and Z have the meaning given in claim 1.

11. Process for the preparation of α-halocarbonyl derivatives of the general formula VI,

characterized in that epoxides of the general formula IV,

in which R, R ⁴ and R ^{5 have} the meaning given in claim 1, with compounds of the general formula V, MZ V in which Z is halogen and M is an alkali metal cation which is equivalent to an alkaline earth metal cation or hydrogen, optionally in an inert solvent and / or with the addition of a suitable catalyst.

12. A process for the preparation of α-halocarbonyl derivatives of the general formula I as claimed in claim 1, where Y is oxygen, characterized in that α-halocarbonyl derivatives of the formula VI,

 in which the substituents have the meaning given in claim 1, with compounds of the general formula VII,

in which R ^{23 is} halogen or R ²⁴ SO ₂ -, where R ^{24 is}

C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or phenyl, is reacted in an inert solvent in the presence of a base.

13. A process for the preparation of α-halocarbonyl derivatives of the general formula I according to claim 1, where Y is sulfur, characterized in that α-halocarbonyl derivatives of the formula VIII,

 in which the substituents have the meaning given in claim 11, with compounds of the general formula IX,

in which R ² , R ³ and X have the meaning given in Claim 1, brings about a reaction.

Derivatives of α-halocarbonyl compounds, processes and intermediates for their preparation Summary α-halocarbonyl derivatives of the general formula I,

in which R represents a formyl group, a group CO ₂ H or a radical which can be hydrolyzed to COOH and the other substituents have the following meanings:

R ² halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy or C ₁ -C ₄ alkylthio;

X is nitrogen or CR ¹³ , where R ^{13 is} hydrogen or together with R ^{3 is} a 3- to 4-membered alkylene or

 Forms alkenylene chain, in each of which a methylene group is replaced by oxygen;

R ³ halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy,

C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio or R ³ is linked to R ¹³ as stated above to form a 5- or 6-membered ring;

R ^{4 is} a carbonyl group or a derivative of a carbonyl group;

R ^{5 is} hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl,

C ₃ -C ₈ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxyalkyl, C ₁ -C ₄ alkylthioalkyl or phenyl;

Y sulfur or oxygen or a single bond; Z halogen.