DE19612685A1 - New pyrazolyl:carbonyl-oxathiin or -dithiin derivatives - Google Patents

Abstract

7-(1-Alkyl-5-hydroxypyrazol-4-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 alkenyl, 2-6C alkynyl or alkoxy (all optionally substituted by 1-5 halo or alkoxy); or halo, CN or NO2; X = O, S, SO or SO2; n = 0-2; R<1>-R<4> = H; 1-6C alkyl, 2-6C alkenyl, 2-6C alkenyl, 2-6C alkynyl or alkoxy (all optionally substituted by 1-5 halo or alkoxy); halo; or phenyl (optionally substituted by one or more of alkyl, H, alkoxy, haloalkyl, haloalkoxy, halo, NO2, CN and alkoxycarbonyl); or R<2>+R<3> form a bond; Q = substituted 4-pyrazolyl of formula (a); R<5> = alkyl; R<6> = H, alkyl or haloalkyl; R<7> = H, alkylsulphonyl, PhSO2 or alkylphenylsulphonyl (with no C-number for alkyl given); unless specified otherwise alkyl moieties have 1-4C.

Description

The present invention relates to new pyrazol-4-yl hetaroylde derivatives with herbicidal activity, process for the preparation of the Py razol-4-yl-hetaroyl derivatives, agents containing them and the use of these derivatives or compositions containing them Weed control.

Herbicidal pyrazolylaroyl derivatives are known from the literature known, for example from WO 9504054, WO 9401431 and EP 629623 and EP 344774.

The herbicidal properties of the known compounds and the Tolerance to crops can only be satisfy things.

The object of the present invention was to create new pyra zol-4-yl-hetaroyl derivatives with improved properties to fin the.

Pyrazol-4-yl-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; Halo gen, 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, what serstoff, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-halo alkoxy, halogen, nitro, cyano, C₁-C₄ -Alkyloxy carbonyl;
Q is a pyrazole ring of For mel II linked in position 4

in which
R⁵ C₁-C₄ alkyl,
R⁶ is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl and
R⁷ is hydrogen, C₁-C₄ alkylsulfonyl, phenylsulfonyl or alkylphenylsulfonyl,
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, R⁵, R⁶ and n die meaning given above.

The first step of the reaction sequence, the acylation, takes place in a generally known manner, for. B. by adding an acid chlo rids of formula III (T = Cl) or a z. B. with DCC (Dicyclocarbo diimide) or similar means known from the literature e.g. B. Triphe nylphosphine / DEAD = diethylazodicarboxylate, 2-pyridine disulfide / tri phenylphosphine activated carboxylic acid III (T = OH) for solution or Suspension of a cyclohexanedione II, optionally in the presence an auxiliary base. The reactants and the auxiliary base are thereby appropriately used in equimolar amounts. A little over shot, 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 rature from 20 to 100 ° C, in particular 25 to 50 ° C stirred until the Implementation is complete. 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 benzoic acid esters of 5-hydroxy pyrazoles are found e.g. B. in EP-A 282944 or in US 4,643,757.

The rearrangement of the 5-hydroxypyrazoylbenzoic acid ester to Ver Compounds of the formula I are advantageously carried out at temperatures of 20 up to 40 ° C in a solvent and in the presence of an auxiliary base  and with the help of a cyano compound as a catalyst gate.

As a solvent, for. B. acetonitrile, methylene chloride, tert-amyl alcohol, dioxane, 1,2-dichloroethane, ethyl acetate or Toluene can be used. Preferred solvents are aceto nitrile and dioxane. Suitable auxiliary bases are tertiary alkylamines, Pyridine or alkyl carbonates, preferably in equimolar Amount or up to a fourfold excess, based on the 5-Hydroxypyrazolbenzoic acid ester can be used. Preferred Auxiliary bases are triethylamine and alkali carbonate 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 rearrangement of benzoic acid esters from 5-hydroxypyra zolen can be found e.g. B. in EP-A 282 944 or in US 4,643,757.

The workup is carried out in a manner known per se, e.g. 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 ex trahed. For cleaning, the extract is cold with 5 to 10% alkali carbonate solution extracted, the end product in the aqueous phase of the formula Ia-Ie precipitated or again with Me extracted ethylene chloride or ethyl acetate, dried and then freed from the solvent.

The 5-hydroxypyrazoles of For mel II are known and can be made by methods known per se are produced (cf. EP-A 240 001 and J. Prakt. Chem. 315, 382 (1973)). 1,3-Dimethyl-5-hydroxypyrazole is commercially available Connection.

Benzoic acid derivatives of the formula III can be prepared as follows:
Benzoyl halides such as benzoyl chlorides of formula III (T = Cl) are prepared in a manner known per se by reacting the benzoic acids of 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 Phe represent nolcarboxylic acids IV or thiolcarboxylic acids V. Not be known compounds IV or V can be applied by using li reactions known from the literature (Lit .: Houben-Weyl, methods of Or ganischen Chemie Volume 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

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 under Nor color pressure or increased pressure. Preferred print range is 1 to 10 bar. The reaction mixture is preferred at 20-150 ° C, especially at 60-80 ° C, stirred. The processing tion takes place, for example, so that the reaction mixture on ver thin lye is poured like caustic soda and the product of value by extraction with z. B. ethyl acetate, dried and freed from the solvent, can be obtained.  

Then z. B. an exchange of Z with potassium methanthio sulfonate in alcoholic solution. Preferred solution with tel are ethanol, methanol and isopropanol. The reaction mixture 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 Wertpro product is suctioned off or extracted by extraction with ether, 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 formula III can also be obtained in to which the corresponding bromo or iodine substituted verb 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 especially palla dium can be metallic or in the form of conventional salts such as in the form of halogen compounds, e.g. B. PdCl₂, RhCl₃ · H₂O, acetates, e.g. B. Pd (OAc) ₂, cyanides, etc. in the known valence levels gen. Furthermore, metal complexes with tertiary phosphines, Me tallalkylcarbonyls, metal carbonyls, e.g. B. CO₂ (CO) ₈, Ni (CO) ₄, Me tallcarbonyl 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. There the type of phosphine ligands 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 R¹² 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 look out for, otherwise they can be varied widely and around summarize all inert C-organic radicals such as C₁-C₆ alkyl, z. B. Methyl, carboxyl residues such as COOH, COOM (M is e.g. an alkali, Alkaline earth metal or ammonium salt), or C-organic residues Oxygen bound 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 the 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) one carries out the order settlement with carbon monoxide and at least equimolar amounts of water, based on the starting materials VI. The Reacti partner water can also act as a solvent nen, d. H. the maximum amount is not critical.

But it can also be used depending on the type of raw materials and the Deten catalysts be advantageous instead of the reaction part ners another inert solvent or for the carboxy used base as a solvent.

Inert solvents used for carboxylation reactions Liche solvents such as hydrocarbons, e.g. B. toluene, xylene, Hexane, pentane, cyclohexane, ether e.g. B. methyl tert-butyl ether, Te trahydrofuran, dioxane, dimethoxyethane, substituted amides such as dimethylformamide, per-substituted ureas such as Te tra-C₁-C₄ alkylureas or nitriles such as benzonitrile or aceto nitrile into consideration.

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 iodide 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 te traalkyl-substituted urea derivatives such as tetra-C₁-C₄-alkyl urine fabric, 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 discounted carried out slowly. 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 pyrazoylhe taroyl 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-ethyl butyl, 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-Bu toxy, 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.

Pyrazol-4-yl-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.  

Pyrazol-4-yl-hetaroyl derivatives of the formula are also preferred Ib

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.

Pyrazol-4-yl-hetaroyl derivatives of the formula I are also preferred which is the residues L and M for hydrogen, methyl, methoxy, chlorine Cyano, nitro and trifluoromethyl are available.

Pyrazol-4-yl-hetaroyl derivatives are also preferred Formula Ic

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 ha ben.  

Pyrazol-4-yl-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.

Pyrazol-4-yl-hetaroyl derivatives of the formula are also preferred Id

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.

Pyrazol-4-yl-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.

Pyrazol-4-yl-hetaroyl derivatives of the formula I are also preferred to Id, their substituents from a combination of the preferred There are substituents.

Particularly preferred compounds of formula I are in the following tables 1-2.

Table 1

Connection of the structure

Table 2

Connection of the structure

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-methylbenzoic acid ethyl ester 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 Wertpro product 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-methylbenzoic acid ethyl ester 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-oxathine-7-carboxylic acid ethyl ester are combined with 1.0 g (0.0252 mol) of sodium hydroxide in 40 ml of methanol / water heated to reflux temperature. The mixture is stirred at the temperature for 2 hours 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-oxathiine-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 3

Manufacture of end products

4- (8-methyl-2,3-dihydro-4,4-dioxo-benz [1,4] oxathiin-7-yl carbonyl) -1-ethyl-5-hydroxypyrazole 0.9 g (3.72 mmol) 8-methyl 2,3-dihydro-4,4-dioxo-benz-1,4-oxathiin-7-carboxylic acid become together with 0.42 g (3.72 mmol) of 1-ethylpyrazolone in 20 ml of Aceto submitted nitrile. Then 0.81 g (3.9 mmol) of DCC are added and stir for several hours at RT. Then 0.75 g (7.44 mol) triethylamine and 0.2 ml trimethylsilyl cyanide and stirred for 3 hours at RT.

It is worked up by adding 100 ml of 2% sodium carbo nat solution and suction of the precipitate. The filtrate is with Washed ethyl acetate, adjusted to pH 4 with 2N HCl and the valuable product is extracted.

The organic phase is dried and on a rotary evaporator constricted.

The product is purified by recrystallization.
Yield: 0.3 g solid
Melting point 184 ° C.

Table 4

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 harmful grass water without significantly damaging the crops. This ef fect 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 offici nalis, Beta vulgaris spp. altissima, Beta vulgris 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, Ly copersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisumativ , Prunus avium, Prunus persica, Pyrus communis, Ribes sylestre, Ricinus communis, Saccharum officina rum, Secale cereale, Solanum tuberosum, Sorgnum bicolor (s. Vul gare), 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 by spraying, atomizing, dusting, scattering or pouring be used. The application forms depend on the  Uses; in any case, they should be as fine as possible Ensure the distribution of the active substances according to the invention

The following essentially come into consideration as inert additives: mine Potassium oil fractions from medium to high boiling point, such as kerosene or diesel oil, as well as coal tar oils and vegetable or of animal origin, aliphatic, cyclic and aromatic Hydrocarbons, e.g. B. paraffin, tetrahydronaphthalene, alky gated 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 obtained from emulsion concentrates, Sus pensions, pastes, wettable powders or water-dispersible Granules can be prepared by adding water. For the manufacture Emulsions, pastes or oil dispersions can be sub strate 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 agent and possibly Lö 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. Li gnin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, see above such as fatty acids, alkyl and alkyl aryl sulfonates alkyl, lau ryl ether and fatty alcohol sulfates, and salts of sulfated 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 ethyleno xid condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene alkyl ether, lauryl alcohol polyglycol etherace tat, sorbitol ester, lignin sulfite liquor or methyl cellulose Consideration.

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

Granules, e.g. B. coating, impregnation and homogeneous granules can Herge by binding the active ingredients to solid carriers be put. Solid carriers are mineral soils like pebbles acids, silica gels, silicates, talc, kaolin, limestone, lime, Chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and ma magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as flour, tree bark, wood and Nutshell flour, cellulose powder or other 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 in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

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

• I. 20 parts by weight of compound no. 4.1 are in a Mi solved, the 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. 4.1 are in a Mi solution, which consists 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 finely distributing the solution in 100,000 parts by weight of water gives one aqueous dispersion containing 0.02% by weight of the active ingredient.
• III. 20 parts by weight of active ingredient No. 4.1 are in a Mi solution, 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 add-on product tes of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000  Parts by weight of water give an aqueous dispersion which contains 0.02% by weight of the active ingredient.
• IV. 20 parts by weight of active ingredient No. 4.1 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 parts by weight of water contains a spray mixture which contains 0.1% by weight of the active ingredient.
• V. 3 parts by weight of active ingredient No. 4.1 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. 4.1 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 con densates and 68 parts by weight of a paraffinic minera löls intimately mixed. A stable oily dispersion is obtained sion.
• VII. 1 part by weight of compound 4.1 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 4.1 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 concentrate is obtained kicked.

To broaden the spectrum of activity and to achieve syner The pyrazol-4-yl-hetaroyl derivatives I can have gistic effects numerous representatives of other herbicides or growth regulations render Active ingredient groups mixed and applied together the. For example, 1,2,4-thiadia come as the mixing partner zoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and their Derivatives, aminotriazoles, anilides, (het) aryloxyalkanoic acid and their derivatives, benzoic acid and their derivatives, benzothia diazinone, 2-aroyl-1,3-cyclohexanedione, hetaryl aryl ketone, Ben cylisoxazolidinones, 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 heteroaryloxyphenoxypropionic acid reester, phenylacetic acid and its derivatives, phenylpropionic acid and their derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyri dincarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, Sulfonylureas, triazines, triazinones, triazolinones, triazole carboxamide, 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 stage of growth 0.001 to 3.0 preferably 0.01 to 1.0 kg / ha of active substance (see p.).

Examples of use

The herbicidal activity of the pyrazol-4-yl-hetaroyl derivatives of formula I was demonstrated by greenhouse experiments:
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 by means of a fine distribution lender nozzles applied. The vessels were irrigated slightly To promote germination and growth, and then with covered plastic hoods until the plants had grown This cover causes the test to germinate evenly plant, unless this is affected by the active ingredients has been.

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 Application rate for post-emergence treatment was 0.0625 or 0.0313 kg / ha a.S.

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 each treatment was evaluated tet.

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 3

Selective herbicidal activity in post-emergence application in the greenhouse

Claims (11)

1. Pyrazol-4-yl-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 pyrazole ring of the formula II linked in position 4 in which
R⁵ C₁-C₄ alkyl,
R⁶ is hydrogen, C₁-C₄-alkyl or C₁-C₄-halogen alkyl and
R⁷ is hydrogen, C₁-C₄ alkylsulfonyl, phenyl sulfonyl or alkylphenylsulfonyl,
as well as agriculturally useful salts. 2. Pyrazol-4-yl-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. Pyrazol-4-yl-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. pyrazol-4-yl-hetaroyl derivatives of the formula I according to claim 1 in which the radicals L and M represent hydrogen, methyl, methoxy, Chlorine cyano, nitro and trifluoromethyl are available. 5. Pyrazol-4-yl-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. Pyrazol-4-yl-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. Pyrazol-4-yl-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. Pyrazol-4-yl-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 IIa with an acid chloride of the formula IIIa or an acid of the formula IIIb wherein L, M, X, R¹ to R⁴, R⁵, R⁶ and n have the meaning given in claim 1, acylated and the acylation product in the presence of a catalyst to the compounds I um. 10. Herbicidal composition containing at least one pyrazol-4-yl hetaroyl derivative of formula I according to claim 1 and conventional inert additives. 11. methods for controlling undesirable plant growth, characterized in that a herbicidally effective amount of a pyrazol-4-yl-hetaroyl derivative of the formula I according to Claim 1 act on the plants or their habitat leaves.