DE19612687A1 - New di:oxo:cyclohexyl:carbonyl-oxathiin or -dithiin derivatives - Google Patents

Abstract

7-(1,3-Dioxocyclohex-2-ylcarbonyl)-1,4-oxathiin or -dithiin derivatives of formula (I) and their salts are new. L,M = H; 1-6C alkyl, 2-6C alkenyl, 2-6C alkynyl or alkoxy (all optionally substituted by 1-5 halogen or alkoxy); or halogen, CN or NO2; X = O, S, SO or SO2; n = 0-2; R1-R4 = H; 1-6C alkyl, 2-6C alkenyl, 2-6C alkynyl or alkoxy (all optionally substituted by 1-5 halogen or alkoxy); halogen; or phenyl (optionally substituted by one or more of alkyl, H, alkoxy, haloalkyl, haloalkoxy, halogen, NO2, CN and alkoxycarbonyl); or R2+R3 form a bond; Q = 1,3-dioxocyclohex-2-yl of formula (a); R5,R6,R8,R10 = H or alkyl; R7 = H; alkyl or 3-4C cycloalkyl (both optionally substituted by 1-3 of halogen, alkylthio and alkoxy); or alkoxy, 1-6C alkoxyalkyl or tetrahydropyran-3- or 4-yl; R9 = H, alkyl or COOR11; or R7+R9 complete a bond or a 3-6 membered carbocyclic ring; R11 = alkyl; unless specified otherwise alkyl moieties have 1-4C. Intermediates of formula (III) are also new. T = Cl, OH or alkoxy.

Description

The present invention relates to new hetaroyl derivatives bicidal activity, process for the preparation of the hetaroyl derivatives, Means that contain them and the use of these Derivatives or weed control compositions containing them.

Herbicidal 2-hetaroylcylohexadiones are known from the literature known, for example from WO 948988, WO 9404524 and EP 283261.

The herbicidal properties of the known compounds and the However, tolerance to crops can only to satisfy conditionally.

The object of the present invention was to create new ones 2-hetaroylcyclohexanediones with improved properties Find.

Hetaroyl derivatives of the formula I were found

in which the substituents have the following meaning:
L, M is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, where these groups may optionally be substituted by one to five halogen atoms or C₁-C₄-alkoxy; Halogen, cyano, nitro;
X is oxygen or sulfur, which can be substituted with one or two oxygens;
n zero, one, two;
R¹ is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, these groups being optionally substituted by one to five halogen atoms or C₁-C--alkoxy; Halogen;
Phenyl which can be substituted one or more times by the following groups: C₁-C₄-alkyl, what serstoff, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-halo alkoxy, halogen, nitro, cyano, C₁-C₄ -Alkyloxy carbonyl;
R² is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, where these groups can optionally be substituted by one to five halogen atoms or C₁-C₄-alkoxy; Halogen;
Phenyl which can be substituted one or more times by the following groups: C₁-C₄-alkyl, what serstoff, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-halo alkoxy, halogen, nitro, cyano, C₁-C₄ -Alkyloxy carbonyl; R² and R³ can form a bond;
R³ is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, which groups may optionally be substituted by one to five halogen atoms or C₁-C₄-alkoxy; Halogen;
Phenyl, which can be substituted one or more times by the following groups: C₁-C₄-alkyl, what serstoff, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-halo alkoxy, halogen, nitro, cyano, C₁-C₄ -Alkyloxy carbonyl; R³ and R² can form a bond;
R⁴ is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, where these groups may optionally be substituted by one to five halogen atoms or C₁-C₄-alkoxy; Halogen;
Phenyl which can be substituted one or more times by the following groups: C₁-C₄-alkyl, hydrogen, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro, cyano, C₁-C₄-alkyloxycarbonyl ;
Q is a cyclohexane-1,3-dione ring of the formula II linked in the 2-position

in which the substituents have the following meaning:
R⁵, R⁶ and R¹⁰ are hydrogen, C₁-C₄ alkyl;
R⁷ is hydrogen, C₁-C₄-alkyl, C₃-C₄-cycloalkyl, these groups optionally being able to carry one to three of the following substituents: halogen, C₁-C₄-thioalkyl or C₁-C₄-alkoxy; or
C₁-C₄ alkoxy; C₁-C₆ alkoxyalkyl, tetrahydro pyranyl-3, tetrahydropyranyl-4; or
R⁷ and R⁹ together can form a bond or a three to six-membered carbocyclic ring;
R⁸ is hydrogen, C₁-C₄ alkyl;
R⁹ is hydrogen, C₁-C₄ alkyl or a group COOR¹¹;
R¹¹ C₁-C₄ alkyl;
as well as agriculturally useful salts.

Compounds of formula I are obtained by connecting gene of formula II with a benzoic acid derivative of formula III sets and rearranged to hetaroyl derivatives of formula I.  

Scheme 1

In scheme 1 above, T has the meaning in the formulas mentioned tung halogen or OH and L, M, X, R¹, R², R³, R⁴ and n the above given meaning.

The first step of the reaction sequence, the acylation, takes place in a generally known manner, for. B. by adding an acid chloride of the formula III (T = Cl) or a z. B. with DCC (Dicyclo carbodiimides) or similar means known from the literature, for. B. Tri phenylphosphine / DEAD = diethylazodicarboxylate, 2-pyridine disulfide / tri phenylphosphine activated carboxylic acid III (T = OH) to the solution or suspension of a cyclohexanedione II, optionally in counter were an auxiliary base. The reactants and the auxiliary base are appropriately used in equimolar amounts. A little Excess, e.g. B. 1.2 to 1.5 molar equivalents, based on II, the Auxiliary base can U. be advantageous.

Suitable auxiliary bases are tertiary alkylamines, pyridine or Alkali carbonates. As a solvent, for. B. methylene chloride, Dioxane, diethyl ether, toluene, acetonitrile or ethyl acetate esters can be used.

During the addition of the acid chloride, the reaction mixture preferably cooled to 0 to 10 ° C, then at a Temperature of 20 to 100 ° C, in particular 25 to 50 ° C stirred until the implementation is finished. The processing takes place in the usual way Way, e.g. B. the reaction mixture is poured into water and that  Product of value extracted, e.g. B. with methylene chloride. After drying the organic phase and removal of the solvent raw enol esters used for rearrangement without further purification will. Production examples for benzoylenol esters from Cyclo hexane-1,3-diones are found e.g. B. EP-A 186118 or US 4,780,127.

The rearrangement of the enol esters to the compounds of the formula Ia-Ie conveniently takes place at temperatures of 20 to 40 ° C in one Solvent and in the presence of an auxiliary base and with the help a cyano compound as a catalyst.

As a solvent, for. B. acetonitrile, methylene chloride, 1,2-dichloroethane, ethyl acetate or toluene is used will. The preferred solvent is acetonitrile. As an auxiliary base tertiary alkyl amines, pyridine or alkali carbonates are suitable, which are preferably in equimolar amounts or up to a four fold excess, based on the benzoylenol ester will. The preferred auxiliary base is triethylamine in double amount.

Potassium cyanide, acetone cyanohydrin and Trimethylsilyl cyanide, preferably in an amount of 1 to 50 mole percent, based on the enol ester. It is preferred to bet Acetone cyanohydrin, e.g. B. in the amount of 5 to 15, in particular 10 mole percent. Examples of the cyanide-catalyzed rearrangement of One finds enol esters e.g. B. in EP-A 186118 or US 4,780,127.

The processing takes place in a manner known per se, for. B. will the reaction mixture with dilute mineral acids such as 5% Acidified hydrochloric acid or sulfuric acid and with an organic Solvents such as methylene chloride or ethyl acetate extracted. For cleaning, the extract is cold with 5 to 10% alkali carbonate solution extracted, the final product passes into the aqueous phase. By acidifying the aqueous solution the product of the formula Ia-Ie is precipitated or again with Extracted methylene chloride or ethyl acetate, dried and then freed from the solvent.

The 1,3-diketones of the formula II used as starting material are known and can be made by methods known per se are produced, as they are for example in EP-A 71707, EP-A 142741, EP-A 243313, US 4,249,937 and WO 92/13821 are described. Cyclohexanedione and dimedone are commercially available Links.  

Benzoic acid derivatives of the formula III can be prepared as follows:
Benzoyl halides such as benzoyl chlorides of the formula III (T = Cl) are prepared in a manner known per se by reacting the benzoic acids of the formula III (T = OH) with thionyl chloride.

The benzoic acids of formula III (T = OH) can be known Way by acidic or basic hydrolysis from the corresponding Esters of the formula III (T = C₁-C₄ alkoxy) are prepared.

The intermediates of formula III can be started from partially known compounds such as substituted Represent phenol carboxylic acids IV or thiol carboxylic acids V. Not known compounds IV or V can be obtained by using reactions known from the literature (Lit .: Houben Weyl, methods of Build up organic chemistry volumes VI, IX and E11).

The further implementation of the intermediates of formula III runs via methods known from the literature (e.g. Synthesis 1975, 451; J. Org. Chem. 1974, 39-1811; J. Am. Chem. Soc. 1954, 76, 1068; Heterocyclic Compounds, Volume: Multi-Sulfur and Sulfur and Oxygen Five an Six-Membered Heterocycles; J. Org. Chem. 1979, 44, 1977).

Scheme 2

or

or

or

Then 2,3-dihydrobenz-1,4-oxathiinderivate z. B. how shown in Scheme 2A by intramolecular nucleophilic sub Establish the aromatic substitution (X = O, S; T = OH, C₁-C₄-alkoxy) (Lit .: J. Heterocycl. Chem. 20, 867, 1983) Describe path B and C. the route given in the literature to 2-alkoxy-2,3-dihydro benz-1,4-oxathiine derivatives. (Lit: J. Am. Chem. Soc. 76, 1068, 1954; J. Org. Chem. 44, 1977, 1979) As in Scheme 2 in D and E shown, phenols or thiols with alkyl bromides in Alkylate alkaline solution. The reactants and the base will expediently used in equimolar amounts. On Excess base can be beneficial. As a solvent Alcohols such as ethanol or DMF and as bases alcoholates such. B. Sodium ethanolate or NaH preferred. The reaction can take place under Normal pressure or at elevated pressure. More preferred Pressure range is 1 to 10 bar. The reaction mixture is preferably at 20-150 ° C, especially at 60-80 ° C, stirred. Working up is carried out, for example, in such a way that the reaction mixture is poured onto dilute alkali such as caustic soda and that  Product of value by extraction with z. B. ethyl acetate, dried and freed from solvent, can be obtained.

Then z. B. an exchange of Z with potassium methanthio sulfonate in alcoholic solution. Preferred solution ethanol, methanol and isopropanol are medium. The reaction Mixing is preferably at 20-100 ° C, especially at 60-80 ° C, stirred.

Working up is carried out, for example, by adding water, the valuable product is suctioned off or by extraction with e.g. B. methylene chloride is extracted and dried.

Cyclization to dihydrobenzoxathiine or dihydrobenzdi The thinning scaffold is carried out in a solvent with the addition of a Lewis acid th solvent. Aluminum trichloride is used as the Lewis acid and nitromethane or methylene chloride as the inert solvent prefers. The reaction mixture is at a temperature of Kept at 20-50 ° C. The workup is carried out, for example, by Add diluted mineral acid such as hydrochloric acid and the value product is suctioned off or by extraction with ether extra hiert, dried and freed from solvent.

By oxidation according to methods known from the literature and / or dehy drierung (Houben Weyl Methods of Organic Synthesis Volume IV / 1a and b) the compounds can be further functionalized will.

The benzoic acids of the formula III can also be obtained by the corresponding bromine or iodine substituted Ver compounds of the formula XVIII

Scheme 3

in which
T OH, C₁-C₄ alkoxy; and
L, M, X, R¹ to R⁴ and n have the meaning described above;
in the presence of a palladium, nickel, cobalt or rhodium transition metal catalyst and a base with carbon monoxide and water under elevated pressure.

The catalysts nickel, cobalt, rhodium and in particular Palladium can be metallic or in the form of conventional salts as in Form of halogen compounds, e.g. B. PdCl₂, RhCl₃ · H₂O, acetates, e.g. B. Pd (OAc) ₂, cyanides, etc. in the known valence levels available. Furthermore, metal complexes with tertiary phosphines, Metal alkylcarbonyls, metal carbonyls, e.g. B. CO₂ (CO) ₈, Ni (CO) ₄, Metal carbonyl complexes with tertiary phosphines, e.g. B. (PPh₃) ₂Ni (CO) ₂, or over complexed with tertiary phosphines gear metal salts are present. The latter embodiment is particularly preferred in the case of palladium as a catalyst. The type of phosphine ligand is widely variable. Example they can be wisely represented by the following formulas:

where k is the numbers 1, 2, 3 or 4 and the radicals R² to R¹⁵ for low molecular weight alkyl, e.g. B. C₁-C₆ alkyl, aryl, C₁-C₄ alkylaryl, e.g. B. benzyl, phenethyl or aryloxy. Aryl is e.g. B. naphthyl, anthryl and preferably optionally substituted phenyl, with respect to the substituents only on their inertness to the carboxylation reaction has to watch out, otherwise they can be varied widely and include all inert C-organic radicals such as C₁-C₆ alkyl radicals, e.g. B. methyl, carboxyl radicals such as COOH, COOM (M is z. B. Alkali, alkaline earth metal or ammonium salt), or C-organic Residues bound via oxygen such as C₁-C₆ alkoxy.

The phosphine complexes can be prepared in a manner known per se Way, e.g. B. as described in the documents mentioned at the beginning, respectively. For example, one starts from usual commercial ones commercial metal salts such as PdCl₂ or Pd (OCOCH₃) ₂ from and adds the phosphine z. B. P (C₆H₅) ₃, P (n-C₄H₉) ₃, PCH₃ (C₆H₅) ₂, 1,2-bis (diphenylphosphino) ethane added.

The amount of phosphine, based on the transition metal, is usually 0 to 20, in particular 0.1 to 10 mol equivalents, particularly preferably 1 to 5 molar equivalents.  

The amount of transition metal is not critical. Of course it will rather a small amount for cost reasons, e.g. B. from 0.1 to 10 mol%, in particular 1 to 5 mol%, based on the starting material Use fabric II or III.

To produce the benzoic acids III (T = OH), the Reaction with carbon monoxide and at least equimolar amounts of water, based on the starting materials VI. The reak Water can also act as a solvent serve, d. H. the maximum amount is not critical.

However, depending on the type of raw materials and the ver used catalysts may be advantageous instead of the reaction partners another inert solvent or those for the Carboxylation used base to use as a solvent.

Inert solvents for carboxylation reactions Common solvents such as hydrocarbons, e.g. B. toluene, xylene, Hexane, pentane, cyclohexane, ether e.g. B. methyl tert-butyl ether, Tetrahydrofuran, dioxane, dimethoxyethane, substituted amides such as dimethylformamide, per-substituted ureas such as Tetra-C₁-C₄-alkylureas or nitriles such as benzonitrile or acetonitrile.

In a preferred embodiment of the method one uses one of the reactants, especially the base, in excess, so that no additional solvent is required.

Bases suitable for the process are all inert bases the hydrogen iodine or bromine released during the reaction able to bind hydrogen. For example, here are tertiary Amines such as tert-alkyl amines, e.g. B. trialkylamines such as triethylamine, cyclic amines such as N-methylpiperidine or N, N'-dimethyl piperazine, pyridine, alkali or bicarbonates, or tetra alkyl-substituted urea derivatives such as tetra-C₁-C₄-alkyl urea, e.g. B. tetramethyl urea to name.

The amount of base is not critical, usually 1 to 10, in particular 1 to 5 moles used. With simultaneous Ver If the base is used as a solvent, the amount is usually dimensioned so that the reactants are dissolved, whereby from Practicality reasons avoids unnecessarily high surpluses in order Saving costs, being able to use small reaction vessels and to ensure maximum contact with the reactants.  

During the reaction, the carbon monoxide pressure is adjusted that there is always an excess of CO, based on VI. Preferential the carbon monoxide pressure at room temperature is 1 to 250 bar, in particular 5 to 150 bar CO.

The carbonylation is usually at temperatures from 20 to 250 ° C, especially at 30 to 150 ° C continuously or dis carried out continuously. With discontinuous operation expediently to maintain a constant pressure continuously carbon monoxide added to the reaction mixture presses.

The aryl halogen compounds used as starting compounds XVIII are known or can be easily obtained by a suitable combination known syntheses and reaction sequences described above getting produced.

With regard to the intended use of the benzoyl derivatives of the general formula I, the following radicals are suitable as substituents:
L, M hydrogen,
C₁-C₆-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1- Dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methyl-propyl,
in particular methyl, ethyl, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl and 1,1-dimethylpropyl;
C₂-C₆ alkenyl such as 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 3-methyl- 2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-4-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, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3- pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl,
1, 1-dimethyl-3-butenyl, 1,2-dimethyl-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 ethyl-2-methyl-2-propenyl,
especially 1-methyl-2-propenyl, 1-methyl-2-butenyl, 1,1-dimethyl-2-propenyl and 1,1-dimethyl-2-butenyl;
C₂-C₆-alkynyl such as propargyl, 2-butynyl, 3-butenyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2- butinyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3- pentynyl, 1-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2- Dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2- propinyl;
C₁-C₄ alkoxy such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy,
in particular C₁-C₃ alkoxy such as methoxy, ethoxy, i-propoxy,
these groups may optionally be substituted by one to five halogen atoms such as fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine or C₁-C₄alkoxy as mentioned above.

Hetaroyl derivatives of the formula Ia are preferred,

in which L is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆ alkynyl, C₁-C₄ alkoxy, C₁-C₄ haloalkyl, C₁-C₁ halogen alkoxy, halogen, cyano or nitro and M for hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄ haloalkyl, C₁-C₄ haloalkoxy, halogen, cyano or nitro  stands and Q, X, R₁ to R₄ and n have the meanings given above to have.

Hetaroyl derivatives of the formula Ib are also preferred

in which L is C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄ alkoxy, C₁-C₄ haloalkyl, C₁-C₄ haloalkoxy, halogen, Cyano or nitro and M for hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄ haloalkoxy, halogen, cyano or nitro and Q, X, R₁ to R₄ and n have the meanings given above.

Preference is also given to hetaroyl derivatives of the formula I in which the Residues L and M for hydrogen, methyl, methoxy, chlorine cyano, Nitro and trifluoromethyl are available.

Hetaroyl derivatives of the formula Ic are also preferred

in which L is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆ alkynyl, C₁-C₄ alkoxy, C₁-C₄ haloalkyl, C₁-C₁ halogen alkoxy, halogen, cyano or nitro and M for hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄ haloalkyl, C₁-C₄ haloalkoxy, halogen, cyano or nitro stands and Q, R₁ to R₄ and n have the meanings given above to have.  

Hetaroyl derivatives of the formula Id are also preferred

in which L is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆ alkynyl, C₁-C₄ alkoxy, C₁-C₄ haloalkyl, C₁-C₁ halogen alkoxy, halogen, cyano or nitro and M for hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄ haloalkyl, C₁-C₄ haloalkoxy, halogen, cyano or nitro stands and Q, R₁, R₄ and n have the meanings given above.

Hetaroyl derivatives of the formula Id are also preferred

in which L is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆ alkynyl, C₁-C₄ alkoxy, C₁-C₄ haloalkyl, C₁-C₁ halogen alkoxy, halogen, cyano or nitro and M for hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄ haloalkyl, C₁-C₄ haloalkoxy, halogen, cyano or nitro and m stands for zero, one or two and Q, R₁, R₄ and n die have the meanings given above.

Hetaroyl derivatives of the formula Ie are also preferred

in which L is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆ alkynyl, C₁-C₄ alkoxy, C₁-C₄ haloalkyl, C₁-C₁ halogen alkoxy, halogen, cyano or nitro and M for hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄ haloalkyl, C₁-C₄ haloalkoxy, halogen, cyano or nitro  and m stands for zero, one or two and Q, R₁ to R₄ and n have the meanings given above.

Hetaroyl derivatives of the formula I to Id are also preferred Substituents from a combination of the preferred substituents consist.

Particularly preferred compounds of formula I are in the following tables 1-6.

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Manufacturing examples A) Production examples of the starting materials and intermediate Products 1. Ethyl 3- (2-bromoethoxy) -2-methylbenzoate

13.6 g (0.2 mol) of sodium methylate are dissolved in 200 ml of ethanol. 36 g (0.2 mol) of 3-hydroxy-2-methylbenzoate are then added and the mixture is heated under reflux for 2 hours. Then 61.4 g (0.32 mol) of 1,2-dibromoethane are added dropwise and the mixture is heated to the reflux temperature for 20 hours. The cooled reaction mixture is concentrated on a rotary evaporator. The residue is taken up in ethyl acetate and washed 3 times with dilute sodium hydroxide solution. The organic phase is dried and the solvent is distilled off. The product of value is purified by column chromatography.
Yield: 14.6 g of oil
NMR (270 MHz; CDCl₃; δ in ppm): 7.4 (d, 1H), 7.2 (tr, 1H), 6.9 (d, 1H), 4.4 (tr, 2H), 4, 3 (q, 2H), 3.7 (tr, 2H), 2.4 (s, 3H), 1.5 (tr, 3H).

2. Ethyl 3- (2-methylsulfonylthioethoxy) -2-methylbenzoate

2 g (7 mmol) of 3- (2-bromoethoxy) -2-methylbenzoate and 1.1 g (7.3 mmol) of potassium thiomethanesulfonate are dissolved in 10 ml of abs. Ethanol dissolved. The reaction mixture is heated under reflux for 20 hours. The solvent is then distilled off and the residue is taken up in methylene chloride and washed with water. The organic phase is dried over sodium sulfate and the solvent is removed. The product of value is purified by column chromatography.
Yield 1.1 g (50%)
NMR (270 MHz; CDCl₃; δ in ppm): 7.4 (d, 1H), 7.2 (tr, 1H), 7.0 (d, 1H), 4.5 (tr, 2H), 4, 3 (q, 2H), 3.6 (tr, 2H), 3.4 (s, 3H), 2.4 (s, 3H), 1.4 (tr, 3H).

3. 8-methyl-2,3-dihydro-benz-1,4-oxathiin-7-carboxylic acid ethyl ester

1.0 g (3.4 mmol) of 3- (2-methylsulfonylthioethoxy) -2-methylbenzoate are dissolved in 5 ml of nitromethane. 0.42 g (3.14 mmol) aluminum trichloride are added. The mixture is stirred at room temperature for 45 min. The mixture is worked up by adding 10 ml of 2N hydrochloric acid and then extracting with MTB ether. The combined organic phases are washed with water and sodium carbonate solution, dried over sodium sulfate and the solvent is distilled off.
Yield: 0.7 g (93%)
NMR (270 MHz; CDCl₃; δ in ppm): 7.5 (d, 1H), 6.9 (d, 1H), 4.5 (tr, 2H), 4.3 (q, 2H), 3, 2 (tr, 2H), 2.4 (s, 3H), 1.4 (tr, 3H).

4. 8-methyl-2,3-dihydro-benz-1,4-oxathiin-7-carboxylic acid

4.0 g (0.0168 mol) of 8-methyl-2,3-dihydro-benz-1,4-oxathiin-7-carboxylic acid ethyl ester together with 1.0 g (0.0252 mol) of sodium hydroxide in 40 ml of methanol / Water heated to reflux temperature. The mixture is stirred for 2 hours at the temperature and then the solvent is distilled off. The residue is taken up in water. The mixture is extracted with ether and then the aqueous phase is acidified with 2N hydrochloric acid. The valuable product precipitates, is filtered off and washed with a little water. The product is dried in a vacuum drying cabinet at 40 ° C.
Yield: 2.9 g (82%)
NMR (270 MHz; d⁶-DMSO; δ in ppm): 12.3 (bs, 1H), 7.3 (d, 1H) 6.9 (d, 1H), 4.4 (tr, 2H), 3 , 2 (tr, 2H), 2.4 (s, 3H).

5. 8-methyl-2,3-dihydro-4,4-dioxo-benz-1,4-oxythiine-7-carbon acid

2.8 g (0.013 mol) of 8-methyl-2,3-dihydro-benz-1,4-oxathiin-7-carboxylic acid are placed together with a spatula tip of sodium tungstate in 30 ml of acetic acid. It is heated to 50 ° C. 3.3 g (0.029 mol) of hydrogen peroxide (30%) are added dropwise. The reaction solution is kept for 4 hours at 50-60 ° C. The solution is poured onto ice water. The precipitate is filtered off, washed with water and dried in a vacuum drying cabinet at 40 ° C.
Yield: 2.7 g
Melting point 234 ° C.

Table 7

Manufacture of end products 1. 2- (8-methyl-2,3-dihydro-4,4-dioxo-benz-1,4-oxathiine 7-carbonyl) -1,3-cyclohexanedione

0.9 g (3.72 mmol) of 8-methyl-2,3-dihydro-4,4-dioxo-benz-1,4-oxathiin-7-carboxylic acid and 0.42 g (3.72 mmol) of 1.3 Cyclohexadione are dissolved in 20 ml of acetonitrile. Then 0.81 g (3.9 mmol) of DCC (dicyclohexylcarbodiimide) are added and the mixture is stirred for several hours until the reaction is complete. Then 0.75 g (7.44 mmol) of triethylamine and 0.2 ml of trimethylsilyl cyanide are added dropwise. The mixture is stirred at RT for 3 hours. For working up, the reaction mixture is poured into 100 ml of 2% sodium carbonate solution. The precipitate is suction filtered and the aqueous phase is washed with ethyl acetate. The aqueous phase is then acidified with 2N hydrochloric acid. The valuable product fails. It is suctioned off, washed with water and dried in a vacuum drying cabinet.
Yield: 0.6 g
Melting point: 201 ° C.

Table 8

The compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of pure isomers - as herbicides. The herbicides containing I Agents fight plant growth on non-cultivated areas very well, especially with high application rates. In crops like wheat, rice, Corn, soybeans and cotton act against weeds and damage grasses without significantly damaging the crops. This The effect occurs especially at low application rates.

Depending on the particular application method, the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants. The following crops are considered, for example:
Allium cepa, pineapple comosus, Arachis hypogaea, Asparagus offi cinalis, Beta vulgaris spp. altissima, Beta vulagris spp. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinc torius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica) v, Cucumis Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Lensum batulinas, Humomo lupules, I Linum usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medi cago sativa, Musa spp., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum , Prunus avium, Prunus per sica, Pyrus communis, Ribes sylestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. Vulgare), Theobroma cacao, Trifolium pratens e, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.

In addition, the compounds I can also be used in cultures which through breeding including genetic engineering methods against the The effects of herbicides are tolerant.

The application of the herbicidal compositions or the active compounds can be carried out in Pre-emergence or post-emergence. Are the real substances less tolerable for certain crops, so can Spreading techniques are applied in which the herbizi the agents are sprayed with the help of sprayers so that the leaves of sensitive crops if possible not to be taken while the active ingredients are on the leaves including growing unwanted plants or the uncovered Floor space (post-directed, lay-by).

The compounds I or the herbicidal compositions comprising them can, for example, in the form of directly sprayable aqueous Solutions, powders, suspensions, including high-proof aqueous oily or other suspensions or dispersions, emulsions, Oil dispersions, pastes, dusts, spreading agents or granules laten by spraying, atomizing, dusting, scattering or Pouring can be applied. The application forms depend on the uses; in any case, they should, if possible finest distribution of the active ingredients according to the invention Afford.

The following are essentially considered as inert additives:
Mineral oil fractions from medium to high boiling point, such as kerosene or diesel oil, also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for. B. paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, e.g. B. amines such as N-methylpyrrolidone or water.

Aqueous use forms can be made from emulsion concentrates, Suspensions, pastes, wettable powders or water dispersants granules can be prepared by adding water. For The production of emulsions, pastes or oil dispersions Substrates as such or dissolved in an oil or solvent, using wetting agents, adhesives, dispersants or emulsifiers in water be homogenized. But it can also be made from an active substance, Wetting, adhesive, dispersing or emulsifying agents and possibly  Concentrates containing solvents or oil are produced, which are suitable for dilution with water.

The surface-active substances (adjuvants) are the alkali, Alkaline earth metal, ammonium salts of aromatic sulfonic acids, e.g. B. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as fatty acids, alkyl and alkylarylsulfonates, alkyl, Lauryl ether and fatty alcohol sulfates, as well as sulfated salts Hexa-, hepta- and octadecanols as well as fatty alcohol glycol ether, Condensation products of sulfonated naphthalene and its Derivatives with formaldehyde, condensation products of naphthalene or the naphthalenesulfonic acids with phenol and formaldehyde, poly oxyethylene 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 ester, lignin sulfite liquor or methyl cellulose into consideration.

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

Granules, e.g. B. coating, impregnation and homogeneous granules can Herge by binding the active ingredients to solid carriers be put. Solid carriers are mineral soils like pebbles acids, silica gels, silicates, talc, kaolin, limestone, lime, Chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and Magnesium sulfate, magnesium oxide, ground plastics, fertilizers agents such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or others solid carriers.

The concentrations of the active ingredients I in the ready-to-use Preparations can be varied in a wide range. The Formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95 wt .-%, active ingredient. The active ingredients are preferably in a purity of 90% to 100% 95% to 100% (according to the NMR spectrum) used.  

The compounds I according to the invention can, for example, how can be formulated as follows:

• I. 20 parts by weight of compound no. 8.1 are in one Dissolved mixture that alkylated from 80 parts by weight Benzene, 10 parts by weight of the adduct of 8 up to 10 moles of ethylene oxide in 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 There is ethylene oxide in 1 mol of castor oil. By pouring and finely distribute the solution in 100,000 parts by weight water is obtained an aqueous dispersion which 0.02 wt .-% of Contains active ingredient.
• II. 20 parts by weight of compound no. 8.1 are in one Dissolved mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the plant tion product of 40 mol isooctylphenol and 10 weight divide the adduct of 40 moles of ethylene oxide There is 1 mole of castor oil. By pouring and fine Ver divide the solution in 100,000 parts by weight of water an aqueous dispersion containing 0.02% by weight of the active ingredient contains.
• III. 20 parts by weight of active ingredient No. 8.1 are in one Dissolved mixture consisting 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 addition product of 40 moles of ethylene oxide with 1 mole of castor oil consists. By pouring and finely distributing the solution in 100,000 parts by weight of water are aqueous Dispersion containing 0.02% by weight of the active ingredient.
• IV. 20 parts by weight of active ingredient No. 8.1 are with 3 parts by weight of the sodium salt of diisobutyl naphthalene-sulfonic acid, 17 parts by weight of the sodium salt a lignin sulfonic acid from a sulfite waste liquor and 60 Parts by weight of powdered silica gel mixed well and ground in a hammer mill. Through fine distribution the mixture in 20,000 weight steep water contains a spray mixture which contains 0.1% by weight of the active ingredient.
• V. 3 parts by weight of active ingredient No. 8.1 are with 97 parts by weight of finely divided kaolin mixed. You get in this way a dusting agent containing 3% by weight of the active ingredient contains.  
• VI. 20 parts by weight of active ingredient no. 8.1 are included 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight share sodium salt of a phenol-urea-formaldehyde Condensates and 68 parts by weight of a paraffinic Mineral oil mixed intimately. A stable oily is obtained Dispersion.
• VII. 1 part by weight of compound 8.1 is in a mixture dissolved, the 70 parts by weight of cyclohexanone, 20 Parts by weight of ethoxylated isooctylphenol and 10 Parts by weight of ethoxylated castor oil. You get a stable emulsion concentrate.
• VIII. 1 part by weight of compound 8.1 is in a mixture solved that from 80 parts by weight of cyclohexanone and 20 parts by weight of Emulphor EL (ethoxylated castor oil / approx steroil). A stable emulsion cone is obtained concentrate.

To broaden the spectrum of activity and to achieve syner The 2-hetaroylcyclohexane-1,3-dione I with numerous representatives of other herbicides or growth regulating drug groups mixed and applied together will. For example, 1,2,4-thia come as mixing partner diazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and their Derivatives, aminotriazoles, anilides, (het) aryloxyalkanoic acid and their derivatives, benzoic acid and their derivatives, benzothia diazinones, 2-aroyl-1,3-cyclohexanediones, hetaryl aryl ketones, Benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, Quinoline carboxylic acid and its derivatives, chloroacetanilides, cyclo hexane-1,3-dione derivatives, diazines, dichloropropionic acid and their Derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, Dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imi dazolinone, N-phenyl-3,4,5,6-tetrahydrophthalimide, oxadiazole, Oxiranes, phenols, aryloxy or heteroaryloxyphenoxypropion acid esters, phenylacetic acid and their derivatives, phenylpropion acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, Pyridinecarboxylic acid and its derivatives, pyrimidyl ether, sulfone amides, sulfonylureas, triazines, triazinones, triazolinones, Triazolcarboxamide, Uracile into consideration.

It may also be useful to use the compounds I alone or in combination with other herbicides also with others Mixed crop protection products to apply together, for example with pest control agents or  phytopathogenic fungi or bacteria. It is also of interest the miscibility with mineral salt solutions, which are used to eliminate Nutritional and trace element deficiencies are used. It can non-phytotoxic oils and oil concentrates can also be added.

Depending on the target, the amount of active ingredient applied is Season, target plants and growth stage 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a.s.).

Examples of use

The herbicidal activity of the 2-hetaroylcyclohexane-1,3-diones of the 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 or suspended in water emulsified active ingredients directly after sowing using fine ver dividing nozzles applied. The vessels were irrigated slightly To promote germination and growth, and then with plastic hoods until the plants have grown were. This cover causes the test to germinate evenly plant, unless this is affected by the active ingredients has been. The application rate for the pre-emergence treatment was 0.0625 or 0.0313 kg / ha a. S.

For the purpose of post-emergence treatment, the test plants are each depending on the growth form only up to a height of 3 to 15 cm pulled and only then with the suspended in water or emul treated active ingredients. The test plants are ent neither sown directly and grown in the same containers or they are first grown separately as seedlings and some Planted into the test tubes days before treatment.

The plants became species-specific at temperatures of 10-25 ° C or kept at 20-35 ° C. The trial period spanned 2 to 4 weeks. During this time, the plants were cared for, and their response to the individual treatments was determined evaluates.

It was rated on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the above-ground parts and 0 no damage or normal waking course of life.  

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

Table 9

Selective herbicidal activity in post-emergence application in the greenhouse

Claims (13)

1. Hetaroyl derivatives of the formula I. in which the substituents have the following meaning:
L, M is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, where these groups may optionally be substituted by one to five halogen atoms or C₁-C₄-alkoxy; Halogen, cyano, nitro;
X is oxygen or sulfur, which can be substituted with one or two oxygens;
n zero, one, two;
R¹ is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, these groups being optionally substituted by one to five halogen atoms or C₁-C--alkoxy; Halogen;
Phenyl which can be substituted one or more times by the following groups: C₁-C₄-alkyl, hydrogen, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro, cyano, C₁-C₄- Alkyloxycarbonyl;
R² is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, where these groups can optionally be substituted by one to five halogen atoms or C₁-C₄-alkoxy; Halogen;
Phenyl which can be substituted one or more times by the following groups: C₁-C₄-alkyl, hydrogen, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro, cyano, C₁-C₄- Alkyloxycarbonyl; R² and R³ can form a bond;
R³ is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, which groups may optionally be substituted by one to five halogen atoms or C₁-C₄-alkoxy; Halogen;
Phenyl which can be substituted one or more times by the following groups: C₁-C₄-alkyl, hydrogen, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro, cyano, C₁-C₄- Alkyloxycarbonyl; R³ and R² can form a bond;
R⁴ is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, where these groups may optionally be substituted by one to five halogen atoms or C₁-C₄-alkoxy; Halogen;
Phenyl which can be substituted one or more times by the following groups: C₁-C₄-alkyl, hydrogen, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro, cyano, C₁-C₄- Alkyloxycarbonyl;
Q is a cyclohexane-1,3-dione ring of the formula II linked in the 2-position in which the substituents have the following meaning:
R⁵, R⁶ and R¹⁰ are hydrogen, C₁-C₄ alkyl,
R⁷ is hydrogen, C₁-C₄-alkyl, C₃-C₄-cycloalkyl, these groups optionally being able to carry one to three of the following substituents: halogen, C₁-C₄-thioalkyl or C₁-C₄-alkoxy; or
R⁷ C₁-C₄ alkoxy; C₁-C₆ alkoxyalkyl, tetrahydro pyranyl-3, tetrahydropyranyl-4; or
R⁷ and R⁹ together can form a bond or a three- to six-membered carbocyclic ring;
R⁸ is hydrogen, C₁-C₄ alkyl;
R⁹ is hydrogen, C₁-C₄ alkyl or a group COOR¹;
R¹¹ C₁-C₄ alkyl;
as well as agriculturally useful salts. 2. Hetaroyl derivatives of the formula Ia in the L for hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-halo alkoxy, halogen, cyano or nitro and M represents hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, cyano or nitro and Q, X, R₁ to R₄ and n have the meanings given in claim 1. 3. Hetaroyl derivatives of the formula Ib in the L for C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, cyano or nitro and M for hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, cyano or nitro and Q, X, R₁ to R₄ and n have the meanings given in claim 1. 4. hetaroyl derivatives of the formula I according to claim 1 in which the Residues L and M for hydrogen, methyl, methoxy, chlorine, cyano, Nitro and trifluoromethyl are available. 5. Hetaroyl derivatives of the formula Ic in the L for hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-halo alkoxy, halogen, cyano or nitro and M represents hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, cyano or nitro and Q, R₁ to R₄ and n have the meanings given in claim 1. 6. Hetaroyl derivatives of the formula Id in the L for hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-halo alkoxy, halogen, cyano or nitro and M represents hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, cyano or nitro and Q, R₁, R₄ and n have the meanings given in claim 1. 7. Hetaroyl derivatives of the formula Id in the L for hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-halo alkoxy, halogen, cyano or nitro and M for hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, cyano or nitro and m for zero, one or two and Q, R₁, R₄ and n have the meanings given in claim 1. 8. Hetaroyl derivatives of the formula Ie in the L for hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-halo alkoxy, halogen, cyano or nitro and M for hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, cyano or nitro and m for zero, one or two and Q, R₁ to R₄ and n have the meanings given in claim 1. 9. A process for the preparation of the compound of formula I according to claim 1, characterized in that the respective starting materials of formula II with an acid chloride of the formula IIIa or an acid of the formula IIIb wherein L, M, X, R¹ to R⁴ and n have the meaning given in claim 1, acylated and rearranged the acylation product in the presence of a catalyst to the compounds I. 10. Hetaroyl derivatives of the formula IIIc in which T, L, M, X, R¹ to R⁴ and n have the following meaning:
T is chlorine, OH or C₁-C₄ alkoxy;
L is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, where these groups can optionally be substituted by one to five halogen atoms or C₁-C₄-alkoxy; Halogen, cyano, nitro;
M is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, where these groups can optionally be substituted by one to five halogen atoms or C₁-C₄-alkoxy; Halogen, cyano, nitro;
X, R¹, R², R³, R⁴ and n as specified in claim 1. 11. Hetaroyl derivatives of the formula IIId in which T, L, M, X, R¹ to R⁴ and n have the following meaning:
T is chlorine, OH or C₁-C₄ alkoxy;
L C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, where these groups may optionally be substituted by one to five halogen atoms or C₁-C₄-alkoxy; Halo gen, cyano, nitro;
M is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, where these groups can optionally be substituted by one to five halogen atoms or C₁-C₄-alkoxy; Halogen, cyano, nitro;
X, R¹, R², R³, R⁴ and n as specified in claim 1. 12. Herbicidal composition containing at least one hetaroyl derivative of formula I according to claim 1 and additives. 13. methods for controlling undesirable plant growth, characterized in that a herbicidally effective amount of a hetaroyl derivative of the formula I according to claim 1 to the Plants or their habitat can act.