MXPA97006123A - Derivatives of pirazolil-benzo - Google Patents

Abstract

The present invention relates to a pyrazol-4-yl-benzoyl compound of the formula I: wherein the substituents have the following meanings: L, M are hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy, this being possible for those not to be substituted or substituted by one to five halo atoms or C 1 -C 4 -alkoxy, or they are halogen, cyano, nitro, a group - (Y) nS (O ) mR7 or a group - (Y) n-CO-R8; Z is a saturated or unsaturated 5 or 6 membered heterocyclic radical, having from one to three heteroatoms, selected from the group consisting of oxygen, sulfur and nitrogen, and which is unsubstituted or which is substituted by halogen, cyano, nitro, a group -CO-R8, C1-C4-alkyl, C1-C4-haloalkyl, C3-C8-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy , C1-C4-alkylthio, C1-C4-haloalkylthio, di-C1-C4-alkylamino, by phenyl which is unsubstituted or which is substituted by halogen, cyano, nitro, C1-C4-alkyl or C1-C4-haloalkyl, or by a group or oxo, which may also be present in the tautomeric form as a hydroxyl group, or which forms a bicyclic system together with a fused phenyl ring, which is unsubstituted or which is substituted by halogen, cyano, nitro, C1-C4-alkyl or C1-C4-haloalkyl, or with a fused carbocycle or with a second fused heterocycle which is unsubstituted or which is substituted by halogen, cyano, nitro, C1-C4-alkyl, di-C1-C4-alkylamino, C1-C4-alkoxy, C1-C4-halogenoalkoxy or C1-C4-halogenoalk

Description

Pyrazolyl-benzoyl derivatives Description The present invention relates to pyrazolyl-benzoyl derivatives of herbicidal action, to a process for obtaining the pyrazolyl-benzoyl derivatives, to products that contain them, as well as to the use of these derivatives to combat weeds.

Pyrazolyl-benzoyl derivatives of herbicidal action are known from the literature, for example from EP 352543.

The herbicidal properties of the known compounds, as well as their compatibility with the crop plants, are not entirely satisfactory.

The purpose of the invention was to find new pyrazoyl-benzoyl derivatives with improved properties.

New pyrazolyl-benzoyl derivatives of the formula I have now been found wherein the substituents have the following meanings: L, M hydrogen, Ci-Cs-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C? -C4-alco? I, whose groups may be optionally substituted by one to five halogen atoms or C? -C4 -alkoxy, halogen, cyano, nitro, a group - (Y) nS (0) mR7 or a group - (Y) n-CO-R8 Z a saturated heterocyclic radical or unsaturated with 5 or 6 members, containing one to three heteroatoms, selected from the group oxygen, sulfur or nitrogen, which may possibly be substituted by halogen, cyano, nitro, a group -CO-R8, C1-C4-alkyl, C? -C4-haloalkyl, C3-C? -cycloalkyl, C? -C4-alkoxy, C? -C4-haloalkoxy, C? -C4-alkylthio, C? -C4-haloalkylthio, di- C? -C4-alkylamino, phenyl optionally substituted by halogen, cyano, nitro, C? -C4-alkyl or C? -C4-haloalkyl or an oxo group, which may optionally also be present in the tautomeric form or as a hydroxy group, or forming a bicyclic system with a fused phenyl ring, optionally substituted by halogen, cyano, nitro, C? -C4 -alkyl or C? -C4-haloalkyl, or with a fused carbocycle or a second heterocycle Condensate, optionally substituted by halogen, cyano, nitro, C? -C4-alkyl, Di-C1- C4- alky1ru.no, C? -C4? alkox ?, C? -C4-halogenoalkoxy, or C? -C4 -halogenoalkyl; I, NR9 n zero or one m zero, one or two R7 C? -C4-alkyl, C? -C4-haloalkyl or R9R10 R8 C? -C4-alkyl, C? -C4-haloalkyl, C? -C4-alkoxy , or NR9R10 R9 hydrogen or C? -C4-Rio C? -C4 alkyl-alkyl Q a pyrazole ring linked at position 4 and corresponding to formula II where R 1 is C? -C 4 -alkyl R 2 is hydrogen, C? -C4 -alkyl or C? -C4-haloalkyl R3 is hydrogen, C? -C4-alkyl, phenylsulphonyl or alkylphenylsulfonyl, as well as the salts of the compounds I usual in agriculture.

The compounds of the formula I are obtained by acylating 5-hydroxyipyrazoles of the formula Ia with a benzoyl derivative of the formula III (CT = Cl) and transposing the pyrazole ester formed to give the compounds of the formula le.

In the formula mentioned above it means T halogen and L, M and Z have the meanings indicated above.

The first step in the course of the reaction, the acylation, is carried out conodically, eg by pro-addition of a benzoyl derivative of the formula III (T = Cl) to the solution or suspension of a 5-hydroxypyrazole lia, in the presence of an auxiliary base. The reaction components and the auxiliary base are used here, conveniently, in amounts aprx. equimolars If necessary, it may be advantageous to use a slight excess of the auxiliary base, eg. from 1.2 to 1.5 equivalents in mole, with respect to II.

As an auxiliary base, for example, tertiary alkylamines, pyridine or alkyl carbonates are suitable, while methylene chloride, diethyl ether, toluene or ethyl acetate can be used as the solvent. During the addition of the acid chloride it is convenient to cool the reaction mixture to 0-10 ° C, and then stir at a higher temperature, eg 25-50 ° C, until the conversion is complete.

Further processing is carried out in the usual manner, eg the reaction mixture is poured into water and extracted with methylene chloride. After the organic phase has dried and the solvent removed, the crude 5-hydroxypyrazole ester can be used without further purification for transposition.

Examples of obtaining benzoic acid esters of 5-hydroxy-pyrazoles are found, for example, in EP-A-282 944 or in US 4,643,757.

The transposition of the 5-hydroxypyrazole esters to the compounds of the formula Ic is conveniently carried out at temperatures of 20 ° C to 40 ° C in a solvent and in the presence of an auxiliary base, as well as with the help of a cyano compound as a catalyst. Suitable solvents are, for example, acetonitrile, methylene chloride, 1,2-dichloroethane, ethyl acetate or toluene. The preferred solvent is acetonitrile. Suitable auxiliary bases are tertiary alkylamines, pyridine or alkyl carbonates, which are used in an equimolar amount up to a fourfold excess. Preferred auxiliary base is triethylamine used in double quantity. Suitable cyanide compounds are catalysts, such as potassium cyanide or aceton.cianhydrin, eg used in an amount of 1 to 50, in particular 5-20 per cent in mole, with respect to 5-hydroxy -pirazole ester. It is preferred to add the acetonitrolhydrin, for example, in an amount of 10 mol%.

Examples of the transposition of benzoic acid esters of 5-hydroxypyrazoles are found, for example, in EP-A 282 944 or US Pat. No. 4,643,757, but in these patents they only use potassium carbonate or sodium carbonate in dioxane as a catalyst. The use of potassium cyanide or acetonicyanhydrin is known in connection with the analogous transposition of enol esters of cyclohexane-1,3-diones (US 4,695,673), but no examples are found in the literature, from which it can be inferred that the cyanide compounds are especially well suited for transpositions of Fries or derivatives of O-acyl or 5-hydroxypyrazole.

Further processing is carried out in a customary manner, for example, the reaction mixture is acidified with dilute mineral acids, such as e.g} . 5% hydrochloric acid or sulfuric acid and extracted with, for example, methylene chloride or ethyl acetate. For the purification, the extract is extracted with cold solution of alkali carbonate at 5-10%, the final product passing to the aqueous phase. By acidifying the aqueous solution, the product of the formula is precipitated, or it is extracted again with methylene chloride, dried and then freed of the solvent.

The 5-hydroxypyrazoles of the formula II used as a starting material can be prepared according to known processes (see EP-A 240 001 and J. Prakt.Chem. 115., 382 (1973)). 1,3-Dimethyl-5-hydroxypyrazole is a commercial compound.

The benzoic acid derivatives of the formula III can be obtained in the following manner: Benzoyl halides, such as, for example, benzoyl chlorides of the formula III (T = Cl), are prepared in a manner known per se by reaction of the benzoic acids of the formula III (T = OH) with thionyl chloride.

The benzoic acids of the formula III (T = OH) can be obtained in a manner known per se by acid or basic hydrolysis from the corresponding esters of the formula III (T = C? -C4-alkoxy).

The intermediates of the formula III can be obtained, for example, according to the methods shown in schemes 2 and 3.

Scheme 2 IV V III TC? -C4-alkoxy, X Cl, Br, J, -OS (0) 2CF3, -OS (0) 2F A1 Sn (C? -C4-alkyl) 3, B (OH) 2, ZnHal, where Hai means Cl or Br L, M, Z as defined above.

Thereafter, the aryl-halogen compounds or aryl sulfonates IV can be converted in a manner known per se with heteroaryl stannates (Stille couplings), heteroaryl boron compounds (Suzuki couplings) or heteroaryl compounds. zinc (Negishi reaction) V (see, for example, Synthesis 1987, 51-53, Synthesis 1992, 413) in the presence of a transient metal catalyst of palladium or nickel and optionally in the presence of a base, giving the novel compounds of the general formula III.

The benzoic acid derivatives of the formula III can also be obtained by reacting substituted compounds with corresponding bromine or iodine of the formula VI Scheme 3 VI III ' z Z or CN t OH, C? -C4-alkoxy where L and M have the meanings indicated above, in the presence of a transition metal catalyst of palladium, nickel, cobalt or rhodium, and in the presence of a base, with carbon monoxide and high pressure water.

In the present invention, the benzoyl derivatives of the formula Illa are preferred where T, L, M and Z have the following meanings: T chloro, OH or C? -C4-alkoxy LC? -C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C? -C4-alkoxy, C? -C4 alkylthio, C? -C4 -halogenoalkyl, C?-C4-halogenoalkoxy, C?-C4-haloalkylthio, C?-C4-alkylsulfonyl, halogen, nitro or cyano M Ci-Cβ-alkyl, C2-C6-alkenyl, C2-Cg-alkynyl, C? -C4-alkoxy, C? -C4-alkylthio, C? -C4-haloalkyl, C? -C4-halogenoalkoxy, C? -C4-haloalkylthio, C? -C4-alkylsulfonyl, halogen, nitro or cyano Z as indicated above.

The benzoyl derivatives of the formula Illb are preferred wherein T, L, M and Z have the following meanings: T chloro, OH or C? -C4-alkoxy, MC? -C6-alkyl, C2-C6-alkenyl, Ca-Ce-alkynyl, C? ~ C4 -alkoxy, C? -C4-alkylthio, C? -C4-haloalkyl, C? -C4-halogenoalkoxy, C? -C4-haloalkylthio, C? -C4-alkylsulfonyl, halogen, nitro or cyanoZ as above indicated.

The nickel, cobalt, rhodium and especially palladium catalysts may be present in metallic form, in the form of their customary salts or also as halogen compounds, such as, for example, PdCl2, RhCl3-H20, acetates, e.g. Pd (OAc) 2, cyanides, etc. in the known valences. In addition, metal complexes can be present with tertiary phosphines, metal alkylcarbonyls, metal carbonyls, eg C? (CO) s, Ni (CO) 4, metalcarbonyl complexes with tertiary phosphines, eg (PPh3) 2Ni (CO) 2, or transient metal salts complexed with tertiary phosphines. This last mentioned variant is especially preferred in the case of the palladium catalyst. The type of physphine ligand can vary widely here. For example, they can be represented by means of the following formulas: ^ Rii Ri ^ ^ R P Ri2 or. P - (CH2) n - p. Ri3 R R14 where n means the numbers 1, 2, 3 or 4 and the radicals Rn to Ri mean low molecular weight alkyl, eg Ci-Ce-alkyl, aryl, C? -C4-alkylaryl, eg benzyl, phenethyl or aryloxy. Aryl is, for example, naphthyl, anthryl and preferably optionally substituted phenyl, it being only necessary to ensure that the substituents are inert towards carboxylation reactions, otherwise, these substituents can be varied widely, including the inert organic C radicals, such as, for example, the Ci-Cd-alkyl radicals, eg methyl, the carboxyl radicals, such as COOH, COOM (M is, for example, an alkali metal or alkaline earth metal or an ammonium salt), or the radicals of organic C linked via oxygen, such as the Ci-Cβ-alkoxy radicals.

The preparation of the phosphine complexes can be carried out in a conventional manner, for example in the manner described in the documents cited above. For example, commercial metal salts, such as PdCl2 or Pd (OCOCH3) 2, are added and phosphine is added, eg P (C6H5) 3, P (n-C4H9) 3, PCH3 (C6H5) 2 / 1,2-bis (diphenylphosphino) ethane.

The amount of phosphine with respect to the transient metal is generally from 0 to 20, in particular from 0.1 to 10 mol equivalents, in particular from 1 to 5 mol equivalents.

The amount of transient metal is not critical. Of course, a reduced amount will be used for price reasons, eg from 0.1 to 10% mol, especially 1 to 5 mol%, based on the starting substance II or III.

To obtain the benzoic acids III (T = OH), the reaction is carried out with carbon monoxide with at least an equimolar amount of water, with respect to the starting substances VI. The water reaction component can be used simultaneously as a solvent, that is, the maximum amount is not critical.

Depending on the starting materials and the catalysts used, it may be advantageous to use another inert solvent or the base used for the non-solvent carboxylation instead of the reaction component.

Suitable inert solvents are the usual solvents, such as hydrocarbons, eg toluene, xylene, hexane, pentane, cyclohexane, ethers, eg methyl-tert. butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted amides, such as dimethylformamide, unsubstituted ureas, such as tetra-C? -C4-alkyl ureas or nitriles, such as benzo-nitrile or acetonitrile.

In a preferred variant of the process of the invention, one of the reaction components, especially the base, is used in an excess, so that it is not necessary to use an additional solvent.

Suitable bases for the process are all the inert bases capable of fixing the hydrogen iodide or hydrogen bromide released in the reaction. Can be mentioned here the tertiary amines, such as tere. alkylamines, eg trialkylamines, such as triethylamine, cyclic amines, such as N-methylpiperidine or N, N'-dimethylpiperazine, pyridine, alkali carbonates or alkali hydrogencarbonates, or urea-substituted tetraalkyl derivatives, as tetra-C? -C4-alkylurea, eg tetramethylurea.

The amount of the base is not critical, generally 1 1 to 10, especially 1 to 5 moles, will be used. When the base is used simultaneously as a solvent, then it is used in a quantity, that the reaction components are dissolved, avoiding for practical reasons too high excess, to save costs, to be able to use small reaction vessels and to guarantee that the components of reaction have a maximum 5 contact.

During the reaction, the carbon monoxide pressure is regulated in such a way that an excess of CO is always present with respect to VI. Preferably, the carbon monoxide pressure will range from 1 to 250 bar, especially 5 to 0 150 bar of CO.

The carbonylation is carried out, as a rule, at temperatures of 20 to 250 ° C, especially at 30 to 150 ° C in a continuous or discontinuous manner. In discontinuous operation, carbon monoxide is continuously introduced in order to maintain a constant pressure.

The aryl-amino compounds VI used as starting compounds are known or can be prepared easily by correspondingly combining the known syntheses.

For example, the halogen VI compounds can be obtained by a Sandmeyer reaction from the corresponding anilines, which in turn are synthesized by reduction of appropriate nitro compounds (see, for example, for VI with Z1 = CN : Liebigs Ann. Chem. 1980, 768-778). The aryl bromides VI can be obtained, furthermore, by direct bromination of appropriate starting compounds [see, eg, Monatsh. Chem. 99, 815-822 (1968)].

Scheme 4 L ivd C? -C4-alkoxy X Cl, Br, J, -OS (0) 2? P3, -0 $ (0) 2F L, M, Z as defined above Rl5 hydrogen, C? -C4-alkyl, C? -C4- haloalkyl, C ^ -Cs-cycloalkyl, phenyl event. sust or trimethylsilyl, Rl6 hydrogen, C? -C4-haloalkyl, C-C8-cycloalkyl or phenyl event. sust ..

Starting from the arylhalogen compounds or aryl IV sulfonates, they can be prepared in the presence of a transitory metal catalyst of palladium or nickel and optionally in the presence of a base, arylmethyl ketones IVa according to processes known from the literature, by reaction of vinylalkyl ethers and subsequent hydrolysis [see, eg, Tetrahedron Lett. 32, 1753-1756 (1991)].

The ethynylated aromatics IVb can be obtained in a manner known per se by reaction of arylhalogen compounds or aryl sulphonates IV with substituted acetylenes, in the presence of a transition metal catalyst of palladium or nickel (eg Heterocycles, 24, 31- 32 (1986)). The IVb derivatives with Ri5 = H are conveniently obtained from the silyl compounds IVb, Ri5 = -Si (CH3) 3 [J.Org. Chem. 46, 2280-2286 (1981)].

By the Heck reaction of arylhalogen compounds or aryl IV sulfonates with olefins in the presence of a palladium catalyst, the arylketenes IVc can be obtained (see, eg, Heck, Palladium Reagents in Organic Synthesis, Academic Pres, London 1985 bzw. Synthesis 1993, 735-762).

The benzoyl derivatives IV used as starting compounds are known [see, eg, Col. Czech Chem. Co mn. 40, 3009-3019 (1975)] or can be obtained by suitable combination of known syntheses.

For example, the sulfonates IV (X = -OS (0) 2CF3, -OS (0) 2F) can be obtained from the corresponding phenols, which in turn are known (see eg EP 195247) or can be prepared according to known methods (see, for example, Synthesis 1993, 735-762).

The halogen compounds IV (X = Cl, Br or I) can be obtained, for example, by Sandmeyer reaction from the corresponding anilines.

Scheme 5 A S, NH or NOH T is C? -C4-alkoxy and L, M as above defined.

The isophthalic acid derivatives IVf can be obtained from the ive aldehydes according to known procedures [see J. March Advanced Organic Chemistry 3rd ed. , p. 629 and next , iley-Interscience Publication (1985)].

The oximes IVg are advantageously obtained by the reaction of ive aldehydes with hydroxylamines [see J. March Advanced Organic Chemistry 3rd ed., P. 805-806, Wiley-Interscience Publication (1985)].

The transferleici; a < ~ lac?? hñé IVg ¡\ Í '*? Üitriles IVh can also be carried out according to known procedures [see J. March Advanced Organic Chemistry 3rd ed. , p. 931-932, iley-lnterscience Publication (1985)].

The aldehydes IVe required as starting substances are known or can be obtained according to known methods. For example, they can be synthesized from the methyl compounds VII according to scheme 6.

Scheme 6 VII VIII IVe The radicals T, M and L have the meaning indicated in connection with Scheme 5. The methyl compounds VII can be transformed according to generally known methods, for example with N-bromosuccinimide or 1,3-dibromo-5,5-dimethylhydan- toin, giving the benzyl VIII bromides. The transformation of benzyl bromides into benzaldehydes IVe is also known from the literature [see Synth. Commun. 22 1967-1971 (1992)].

The starting materials IVa to IVh are suitable for the composition of heterocyclic intermediates III.

For example, derivatives of 5-oxazolyl derivatives can be obtained from acetophenones IVa via the intermediate stage halogen IVd [see, for example, J. Heterocyclic Chem., 28, 17-28 (1991)] or derivatives of 4-oxazolyl. -thiazolyl (see, for example, Metzger, Thia-zoles in: The Chemistry of heterocyclic compounds, Vol.34 pp. 175 et seq. (1976)].

The acetylenes ivb or the alkenes IVe are suitable for the composition of the 4-isoxazolyl, 5-isoxazoyl, 4,5-dihydroisoxazol-4-yl, 4,5-dihydroisoxazol-5-yl derivatives [cf. p. eg Houben-Weyl, Methoden der organischen Chemie, 4th ed., vol. X / 3, pgs. 843 and next (1965)].

The benzoic acids IVf or the IVi acid chlorides prepared therefrom according to the standard procedure can be obtained according to processes known from the literature, for example, 2-oxazolyl, 1,2,4-oxadiazole derivatives. 5-yl, 1, 3, 4-oxadiazol-2-yl [see, for example, J. Heterocyclic Chem., 28, 17-28 (1991)] or 2-pyrro-lyl derivatives [see, e.g. Heterocycles 26, 3141-3151 (1987)].

Derivatives of l, 2,4-triazol-3-yl can be prepared from benzuthitriles iVh, using known methods [see e.g. J. Chem. Soc. 3461-3464 (1954)].

The benzitrilels ivh can be obtained via the intermediate products thioamides, amidoximes or amidines iVm in the derivatives of l, 2,4-oxadiazol-3-yl [see, for example, J. Heterocyclic Chem., 28, 17-28 ( 1991)] of 2-thiazolyl, 4,5-dihydro-thiazol-2-yl or of 5,6-dihydro-4-Hl, 3-thiazin-2-yl [see, for example, Houben-Weyl, Methoden der organischen Chemie, 4th ed., vol. E5, pgs. 1268 and next (1985)]. 2,4-thiadiazol-5-yl derivatives can also be prepared from the IVm thioamides (A = S) according to known methods of the literature [see, for example, J. Org. hem 45 3750-3753 (1980)] or 1, 3, 4-thiadiazol-2-yl derivatives [see, eg, J. Chem. Soc., Perkin Trans. I 1987-1991 (1982)].

The transformation of oximes IVg into 3-isoxazoyl derivatives can be carried out in a manner known per se via the intermediate stage hydroxamic acid chlorides IVk [see, for example, Houben-Weyl, Methoden der organischen Chemie, 4th ed. , vol. X / 3, pgs. 843 and next (1965)].

With respect to the use to which the benzoyl derivatives of the general formula I are intended, the following radicals come into consideration as substituents: L, M hydrogen, C6-C6-alkyl such as, for example, 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-methylpropyl, especially methyl, ethyl, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl and 1,1-dimethylpropyl; C2-C6-alque ': > íi .fc titrated i-j.e?,. • 2-bufeenyl, 3-bute-nyl, l-met? L-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 3-methy1-2-butenyl, l- methyl-2-bute-nile, 2-methyl-2-butenyl, l-methyl-3-butenyl, 2-methyl-4-bute-nyl, 3-methyl-3-butenyl, 1, l-dimethyl-2-propenyl , 1,2-dimethyl-2-propenyl, l-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, l-methyl-2-pentenyl, 2-methyl-2 -pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, l-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, l-dimethyl-2-butenyl, 1, 1-dimeti1-3- bu-tenyl, 1,2-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl- til-3-butenyl, l-ethyl-2-butenyl, l-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-eti1-3-butenyl, 1, l, 2-trimethyl-2-prope-nyl , l-ethyl-l-methyl-2-propenyl and ethyl-2-methyl-2-propenyl, especially l-methyl-2-propenyl, l-methyl-2-butenyl, 1,1-di-methyl-2-propenyl and 1,1-dimethyl-2-butenyl; C2-C6-alkynyl, for example, propargyl, 2-butynyl, 3-bute-nyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-3-buty-nyl, 2-methyl-3 -butynyl, l-methyl-2-butynyl, l, l-dimethyl-2-propynyl, l-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexy-nyl, 5-hexynyl, l-methyl- 2-pentynyl, l-methyl-3-pentynyl, l-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1, l-dimethyl-2-butynyl, 1, l- dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, l-ethyl-2-butynyl, l-ethyl-3-butynyl, 2-ethyl-3- butynyl and l-ethyl-l-methyl-2-propynyl; C? -C4-alkoxy s..cp.c p e. , luGr.oyi. etox;., 1-methyle-toxy, n-butoxy, 1-mepropropoxy, 2-methylpropoxy and 1, 1-dimethylethyl, especially C? -C3-alkoxy such as, for example, methoxy, ethoxy, i-pro-poxy, Whose groups can be optionally substituted by one to five halogen atoms, such as, for example, fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine or C 1 -C 4 alkoxy, such as, for example, those mentioned above.

The group - (Y) n-S (O) mR7 above defined means, for example: C? -C4-alkylthio, such as, for example, methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,1-dimethylethylthio, especially methylthio; C? -C4-alkylsulfinyl such as, for example, methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl and 1,1-di-methylethylsulphinyl, especially methylsulfinyl; C? -C4-alkylsulfonyl such as, for example, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1-methylethylsulfonyl, n-butylsulfo-nyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and 1,1-di-methylethylsulfonyl, especially methylsulfonyl; C? -C4-alkoxy-phenyl-ept! IJ co-ethoxysulfo-nyl, n-propoxysulfonyl, 1-methylethoxysulfonyl, n-butoxysul-fonyl, 1-methylpropoxysulfonyl, 2-methylpropoxysulfonyl and 1,1-dimethylethoxysulfonyl, especially methoxysulfonyl; NC? -C4-alkylsulfamoyl such as, for example, N-methylsulfamoyl, N-ethylsulphamoyl, Nn-propylsulfamoyl, N-1-methylethylsulfa-moyl, Nn-butylsulfamoyl, N-1-methylpropylsulphamoyl, N-2-methylpropylsulfamoyl and N, 1-dimethylethylsulfamoyl, especially N-methylsulfamoyl; N-C? -C4-alkylsulfinamoyl such as, for example, N-methylsulfinamoyl, N-ethylsulfinamoyl, N-n-propy1sulfinamoyl, N-1-methylethylsulfinymoyl, N-n-butylsulfinamoyl, N-1-methylpropylsulfinamoyl, N-2-methylpropylsulfinamoyl and N-1, 1-dimethylethylsulfinamoyl, especially N-methy1sulfinamoyl; di-C? -C4-alkylsulfamoyl as, for example, , dimethylsulphamoyl, diethylsulphamoyl, dipropylsulphamoyl, dibutylsulphamoyl, N-methyl-N-ethylsulphamoyl, N-methyl-N-propylsulphamoyl, N-methyl-N-1-methylethyl-sulphamoyl, N-methyl-N-1, 1-dimethylethylsulfamoyl , di-1-methylethylsulfamoyl, N-ethyl-N-1-methylethylsulfamoyl and N-ethyl-N-1,1-dimethylethylsulfamoyl; especially dimethylsulfamoyl; di-C? -C4-alkylsulfinamoyl such as, eg, dimethylsulfinamoyl, diethylsulfinamoyl, dipropylsulfinamoyl, dibutylsulfinamoyl, N-methyl-N-ethylsulfinamoyl, N-methyl-N-propylsulfinamoyl, N-methyl-N-1-methylethylsulfinamoyl, N- methyl-N-1, 1-dimethylethylsulfinamyl, di-1-methylethylsulfinamoyl, N-ethyl-N-1-methylethyl-sulfinamoyl and N-ethyl-N-1, 1-dimethyl-bis-sulfinamoyl; especially dimethylsulfinamoyl, C 1 -C 4 -alkylsulfinyloxy such as, for example, methylsulfinyloxy, ethylsulfinyloxy, n-propylsulfinyloxy, 1-methylethylsulfinyloxy, n-bu-tylsulfinyloxy, 1-methylpropylsulfinyloxy, 2-methylpropylsulfonynyloxy and 1,1-dimethylethylsulfinyloxy, especially methylsulfi -niloxy; C 1 -C 4 -alkylsulfonyloxy, such as, for example, methylsulphonyloxy, ethylsulphonyloxy, n-propylsulphonyloxy, 1-methylethylsulphonyloxy, n-buylsulphonyloxy, 1-methylpropylsulfonyloxy, 2-methylpropylsulfo-nyloxy and 1,1-dimethylethylsulphonyloxy, especially methylsulfo -niloxy; C? -C4-alkylsulfinylamino such as, for example, methylsulfinylamino, ethylsulfinylamino, n-propylsulfinylamino, 1-methylethylsulfini-lamino, n-butylsulfinylamino, 1-methylpropylsulfinylamino, 2-methylpropylsulfinylamino and 1,1-dimethylethylsulfinylamino, especially methylsulfinylamino; C? -C4-alkylsulfonylamino, for example, methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, 1-methylethylsulfoni-lamino, n-butylsulfonylamino, 1-mepropylsulfonylamino, 2-methylpropylsulfonylamino and 1,1-dimethylethylsulfonylamino, especially methylsulfonylamino; NC? -C4-alkylsulfinyl-N-methyl-amino such as, for example, N-methylsulfi-nyl-N-methyl-amino, N-ethylsulfinyl-N-methyl-amino, N-propyl-sulfinyl-N-methyl- amino, N-1-methylethylsulfinyl-N-methyl-amino, Nn-butylsulfinyl-N-methyl-amino, N-methylpropylsulfinyl-N-methyl-amino, N-2-methylpropylsulfinyl-N-methyl-amino and N, l-dimethyl-ylsulphyl-yl-r, : rVí? la? .ir,.: », espe:; l < i.iu;?! -.? ts N-methylsulfinyl-N-methyl-amino; NC] .- C4-alkylsulfinyl-N-ethyl-amino such as, for example, N-methylsulfi-nyl-N-ethyl-amino, N-ethylsulfinyl-N-ethyl-amino, N-propylsulfinyl-N-ethyl -amino, N-1-methylethylsulfinyl-N-ethyl-amino, Nn-butylsulfinyl-N-ethyl-amino, N-methylpropylsulfinyl-N-ethyl-amino, N-2-methylpropylsulfinyl-N-ethyl-amino and N, 1 -dimethylethylsulfinyl-N-ethyl-amino, especially N-methylsulfinyl-N-ethyl-amino; NC? -C4-alkylsulfonyl-N-methyl-amino such as, for example, N-methylsulfo-nyl-N-methyl-amino, N-ethylsulfonyl-N-methyl-amino, N-propyl-sulfonyl-N-methyl- amino, N-methylethylsulfonyl-N-methyl-amino, Nn-butylsulfonyl-N-methyl-amino, N-methylpropylsulfonyl-N-methyl-amino, N-2-methylpropylsulfonyl-N-methyl-amino and N, l- dimethylethyl-sulfonyl-N-methyl-amino, especially N-methylsulfonyl-N-methyl-amino; NC? -C4-alkylsulfonyl-N-ethyl-amino such as, for example, N-methylsulfo-nyl-N-ethyl-amino, N-ethylsulphonyl-N-ethyl-amino, N-propylsul-fonyl-N-ethyl- amino, N-1-methylethylsulfonyl-N-ethyl-amino, Nn-butylsulfonyl-N-ethyl-amino, N-methylpropylsulfonyl-N-ethyl-amino, N-2-methylpropylsulfonyl-N-ethyl-amino and N, 1- dimethylethylsulfonyl-N-ethyl-amino, especially N-methylsulfonyl-N-ethyl-amino; C 1 -C 4 -haloalkylthio, such as, for example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2- trifluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-di-chloro-2-fluorosytlitium, 2, -2, = -cycloryl, and pentafluoroethylthio, especially trifluoromethylthio. the group - (Y) n-CO-R8 above defined means, for example: C? -C4-alkylcarbonyl such as, for example, methylcarbonyl, ethylcarbo-nyl, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbo-nyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl and 1,1-di-methylethylcarbonyl, especially methylcarbonyl; C? -C4-alkoxycarbonyl such as, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, 1-methylethoxycarbonyl, n-butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl and 1,1-dimethylethoxycarbonyl, especially methoxycarbonyl; NC? -C4-alkylcarbamoyl such as, for example, N-methylcarbamoyl, N-ethylcarbamoyl, Nn-propylcarbamoyl, N-1-methylethylcarbamoyl, Nn-butylcarbamoyl, N-1-methylpropylcarbamoyl, N-2-methylpro-pilcarbamoyl and Nl, 1-dimethylethylcarbamoyl, especially N-methylcarbamoyl; di-C? -C4-alkylcarbamoyl such as, for example, dimethylcarbamoyl, diethylcarbamoyl, dipropylcarbamoyl, dibutylcarbamoyl, N-methyl-N-ethylcarbamoyl, N-methyl-N-propylcarbamoyl, N-methyl-N-methyl-ethylcarbamoyl, N- methyl-N-1, 1-dimethylethylcarbamoyl, di-1-methylethylcarbamoyl, N-ethyl-N-1-methylethylcarbamoyl and N-ethyl-N-1,1-dimethyl ethylcarbamoyl; especially dimethylcarbamoyl; C? -C4-alkylcarbonyloxy such as, for example, methylcarbonyloxy, ethylcar bonylkoxy, n-propylcarbonyloxy, 1-methylethylcarbonyloxy, n-butylcarbonyloxy, 1-methylpropylcarbonyloxy, 2-methylpropylcarbo-nyloxy and 1, 1-dimethylethylenedryloxy, especially methylcarbo -niloxy; C, -C 4 -alkylcarbonylamino, such as, for example, methylenecarbonylamino, ethylcarbonylamino, n-propycarbonylamino, 1-methylethylcarbonylamino, n-butycarbonylamino, 1-methylpropylcarbonylamino, 2-methylpropycarbonylamino and 1,1-dimethylethylcarbonylamino, especially methylenecarbonylamino; NC? -C4-alkylcarbonyl-N-methyl-amino such as, for example, N-methylcarbo-nyl-N-methyl-amino, N-ethylcarbonyl-N-methyl-amino, N-propyl-carbonyl-N-methyl-? amino, Nl-methylethylcarbonyl-1-N-methy1-amino, Nn-butylcarbonyl-N-methyl-amino, N-methylpropylcarbonyl-N-methyl-amino, N-2-methylpropylcarbonyl-N-methyl-amino and N, l-dimethyl-ethylcarbonyl-N-methyl-amino, especially N-methylcarbonyl-N-methyl-amino.

Z means, for example:: a saturated or unsaturated 5 or 6 membered heterocyclic radical, containing one to three heteroatoms, selected from the group oxygen, sulfur or nitrogen, for example, pentacyclic heteroa-romates, such as, eg, 2-furyl, 3- furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazoyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadia-zol-3 ilo, l, 2,4-oxadiazol-5-yl, 1, 3, 4-oxadiazol-2-yl, 1,2, 3-oxadiazol-4-yl, 1,2, 3-oxadiazol-5-yl, 1,2,5-oxadia-zol-3-yl, 1,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,4-thiadiazol-2-yl , 1,2,3-thiadiazol-4-yl, 1,2,3-thiadia-zol-5-yl, 1, 2,5-thiadiazol-3-yl, 1,2,4-triazol-3-yl ,, 1,3, 4-triazol-2-yl, 1,2,3-triazol-4-yl, 1,2,3-triazol-5-yl, 1, 2,4-triazol-5-yl, tetrazol-5-yl, especially 2-thiazolyl and 3-isoxa zolyl; Heterocyclic heteroatoms, such as, for example, 2-pyridinyl, 3-pi-ridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pi-rimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1, 3, 5-triazin-2-yl, 1, 2, 4-triazin-5-yl and 1,2,4-tria-cin-3-yl, 1, 2,4-triazin-6-yl, 1,2,4,5-tetrazin-3-yl; saturated or partially unsaturated heterocycles with 5 to 6 members and containing one to three nitrogen atoms and / or one or two oxygen or sulfur atoms, such as, for example, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, -tetrahydrothienyl, 3-tetrahydrothienyl, tetrahydrothiopyran-2-yl, tetrahydrothio-pyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-dithiolan-2-yl, 1,3-dithiolan-4-yl, l-3 -dithian-2-yl, l, 3-dithian-4-yl, 5,6-dihydro-4H-l, 3-thiazin-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxa -thian-2-yl, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazo-lidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl , 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1, 2, 4-oxadiazolidin-3-yl, 1, 2, 4-oxadiazoli-din-5-yl, l, 2,4-thiadiazolidin-3 -yl, 1,2,4-thiadiazoli-din-5-yl, l, 3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazoli-din-2-yl, 1,3-triazolidin -2-yl, 2, 3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydro-fur-3-yl, 2, 3 -dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2,3-pyrro-lin-2-yl, Á , -pyriruyl-'i "lid, 2,4-yr bi-yl-2-yl, 2,4-pyrro-lin-3-yl, 2,3-isoxazolin-3-yl, 3,4-isoxazolin-3 -yl, 4,5-isoxazolin-3-yl, 2,3-isoxazolin-4-yl, 3,4-isoxazo-lin-4-yl, 4,5-isoxazolin-4-yl, 2,3-isoxazolin -5-yl, 3,4-isoxazolin-5-yl, 4,5-isoxazolin-5-yl, 2,3-isothiazo-lin-3-yl or, 3,4-isothiazolin-3-yl, 4,5-isothiazolin-3-yl, 2,3-isothiazolin-4-yl, 3,4-isothiazolin-4-yl, 4,5-isothiazo-lin 4-yl, 2, 3-isothiazolin-5-yl, 3,4-isothiazolin-5-yl, 4,5-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydro- pyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3, 4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyral-zol-3 ilo, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihi-drooxazole- 4-yl, 2,3-dihydrooxazol-5-yl, 4,5-dihydrooxa-zol-2-yl, 4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl, 1, 3- dioxolan-2-yl, 1,3-dioxolan-4-yl, 1,3-dioxan-5-yl,1-yl 4-dioxan-2, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-tetrahidropiridacinilo, 4-tetrahidropiridacinilo, 2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetrahidropiracinilo, 1, 3, 5-tetrahydro-triazin-2-yl and 1,2,4-tetrahydrotriazin-3-yl, especially 2-tetrahydrofuranyl, 1,3-dioxolan-2-yl and 1, 3-dioxan-2-yl, which is eventually replaced by halogen such as those mentioned above, especially fluoro or chloro, cyano, nitro, a -COR group, for example, alkylcarbaryl, such as, for example, those mentioned above, alkoxycarbonyl, such as, for example, those mentioned above, N-alkylcarbamoyl, such as those mentioned above, dialkylcarbamoyl, such as those mentioned above; C? -C4-alkyl as mentioned above, C? C4-halogenoalkyl as for example, chloromethyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 1,1,2, 2-tetrafluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-l, 1,2-trifluoroethyl and pentafluoroethyl, decafluorobu-linden, 1, l-bis-trifluoromethyl-2, 2, 2-trifluoroethyl, preferably difluoromethyl, trifluoromethyl, trichloromethyl and chloro-difluoromethyl; C-Cs-cycloalkyl, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, especially cyclopropyl and cyclohexyl; C? -C4-alkoxy, eg,. the above mentioned, C? -C4-haloalkoxy as eg, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2, 2-difluoroethoxy, 1, 1,2, 2- tetrafluoroethoxy, 2, 2, 2-trifluoroethoxy, 2-chloro-l, 1,2-trifluoroethoxy and penta-fluoroethoxy, especially C? -C3-haloalkoxy as for example, 2, 2, 2-trifluoroethoxy and 2-chloro -2,2-difluoroethoxy; C? -C4-alkylthio as p. ex. , the above-mentioned, C? -C4-halogehoalkitthium coitus p.éj., those mentioned above, di-C? -C4-alkylamino such as, for example, dimethylamino, diethylamino, dipropylamino, dibutylamino, N-methyl-N-ethylamino, N-methyl-N-propylamino, N-methyl-N-methylethylamino, N-methyl- N-1, 1-dimethylarylamino, di-1-methylethylamino, N-ethyl-N-1-methylethylamino and N-ethyl-N-1,1-dimethylethylamino; phenyl optionally substituted or an oxo group which may optionally also be present in the tautomeric form as a hydroxy group, for example thiazo-lin-4,5-dion-2-yl, 3-oxo-3H-1, 2,4-dithiazolyl or 2- oxo-2H-1, 3,4-dithiazolyl.

Heteroaromatics benzocondensates penta or hexacyclic are, for example; benzofuranyl, benzothienyl, indolyl, benzoxazo-Lilo, benzisoxazolyl, benzthiazolyl, benzisothiazolyl, benz-pyrazolyl, indazolyl, 1,2, 3-benzothiadiazolyl, 2,1,3-benzothiadiazolyl, benzotriazolyl, benzofuroxanilo, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl or phthalazinyl. Examples of especially preferred compounds of the formula I are summarized in the following tables 1 to 5.

Examples of especially preferred compounds of the general formula I are summarized in the following table 1: Table 1: Compounds of the structure Id fifteen twenty Do not . Rl R2 R ^ M 1 .187 CH3 CF3 H St 2 f§ 2- & 188 CH3 CF3 S? 2CH3 Cl 5-oxazolyl The compounds I and < its salts useful for agriculture are suitable - both as isomeric mixtures and also in the form of pure isomers - as herbicides. The herbicidal products containing I are very well suited to combat the growth of plants in areas not intended for cultivation, especially when used in high quantities. In crops, such as wheat, rice, maize, soybeans and cotton, they are active against unwanted grasses and grasses, without any damage worth mentioning in crop plants. This effect is particularly marked with low amounts of application.

Considering the multiple possible methods of application, the compounds I or the products containing them can be used in many other crops to eliminate the growth of unwanted plants there. The following crops are considered: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spp. altissima, Beta vulgaris spp. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestrist Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus lemon, Citrus sinensis Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceu, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Culinary Lens.- Liftii ?? üßitatisßifluim. Lycopersicon 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., Pisum sativu, Prunus avíum, Prunus pérsica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Sécale cereale, Solanum tuberosum, Sor-ghum bicolor (S. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays In addition, compounds I can also be used in crops which have been made tolerant to the action of herbicides by culture or genetic engineering methods.

The products or the herbicidal substances can be applied before or after the emergency. When the active substances are less tolerated by the crop plants, then application methods may be used in which the herbicidal products are sprayed with the aid of spraying apparatus in such a way that they do not fall on the leaves of the sensitive crop plants , but only on the leaves of unwanted plants that grow below the first ones or on the ground covered with unwanted plants (post-directed, lay-by).

The compounds I or the herbicidal products containing them can be used, for example, in the form of aqueous solutions, powders directly spray suspensions, also in the form of suspensions, dispersions or emulsions aqueous, oleic or otherwise, dispersions of oil, pastes, spraying, dusting or granulating agents, by spraying * spraying, spraying, sprinkling or spraying. The forms of application depend on the purpose of the use; In any case, they must guarantee the finest possible distribution of the active substances of the invention.

Suitable inert additives are mineral oil fractions from medium to high boiling point, such as kerosene, or diesel oil, as well as coal tar oils, as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, paraffin, tetrahydronaphthaline, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone and strongly polar solvents, such as N-methylpyrrolidone or water.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders or granules dispersible in water by the addition of water. To obtain emulsions, pastes or oil dispersions, the substances can be homogenized as such or dissolved in an oil or solvent, by means of wetting agents, tackifiers, dispersants or emulsifiers, in water. However, a humectant, adherent, dispersant or emulsifier and, optionally, a solvent or an oil, can also be prepared from the active substance, which can be diluted with water.

Suitable surfactants (additives) are alkali metal, alkaline earth metal, ammonium salts of lithosulfonic acid, naphthalene sulphonic acid and dibutylnaphthalisulfonic acid, as well as fatty acids, alkyl and alkylaryl sulfonates, lauryl ether sulphates and of fatty alco-hol, as well as salts of sulfated hexa, hepta and octadecanols, as well as glycol ethers of fatty alcohol, sulfonated naphthalene condensates and their derivatives with formaldehyde, condensates of naphthalene or of naphthaminosulfonic acids with phenol and formaldehyde, polyoxyethylethyl -phenol ethers, isooctylphenol, octylphenol or nonylphenol ethoxylates, alkylphenol polyglycol ethers, tributylphenylpolyolol ethers, alkylaryl polyether alcohols, iso-tridecyl alcohol, condensates of fatty alcohol-ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ethers , polyoxypropylene, acetal polyglycol ether lauryl alcohol, sorbitol esters, sulphite residual liquors and methylcellulose.

The spraying, spraying and atomizing agents can be obtained by mixing the active substances together with a solid support.

Granules, eg coated granules, impregnates and homogeneous granules can be prepared by bonding the active substances with solid supports. Suitable solid supports are mineral earths, such as silica gel, silicic acids, silica gels, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, milled plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as stone powders, tree bark powders, wood and nut shell powders, cellulose powders or other supports solid The concentrations of the active substances I in the ready formulations can vary in a wide range. The formulations generally contain from 0.001 to 98% by weight, preferably from 0.01 to 95% by weight of active substance. The active substances are used in a purity of 90% bis 100%, vorzugsweise 95% up to 100% (according to NMR spectrum).

The compounds I of the invention can be formulated, for example in the following manner: I. 20 parts by weight of compound No. 1.28 are dissolved in a mixture containing 80 parts by weight of alkylated benzene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide to 1 mole of N-monoethane - oleic acid lick, 5 parts by weight of the calcium salt of dedecylbenzenesulfonic acid and 5 parts by weight of the addition product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100 000 parts by weight of water and distributing it finely therein, an aqueous dispersion containing 0.02% by weight of the active substance is obtained. ?? 20 parts by weight of compound No. 1.28 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 7 moles of ethylene oxide to 1. mol of isooctylphenol and 10 parts by weight of the addition product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100 000 parts by weight of water and distributing it finely therein, an aqueous dispersion containing 0.02% by weight of the active substance is obtained.

III. 20 parts by weight of compound No. 1.28 are dissolved in a mixture consisting of 25 parts by weight cyclohexanone, 65 parts by weight of a mineral oil fraction from the boiling point of 210 to 280 ° C and 10 parts by weight. of the addition product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100 000 parts by weight of water and distributing it finely therein, an aqueous dispersion containing 0.02% by weight of the active substance is obtained.

IV. 20 parts by weight of compound No. 1.28 are intimately mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulphonic acid, 17 parts by weight of the sodium salt of a lignin sulphonic acid of a sulphite-containing waste liquor and 60 parts by weight. weight of powdered silica gel and milled in a hammer mill. By distributing the mixture finely in 20,000 parts by weight of water, a spray mixture containing 0.1% by weight of the active substance is obtained V. 3 parts by weight of compound No. 1.28 are mixed with 97 parts by weight of finely particulate kaolin. In this way, a spray agent containing 3% by weight of the active substance is obtained.

SAW. 20 parts by weight of compound No. 1.28 are intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of ether of graao-poltglicsl alcohol, 2 palenes by weight of the sodium salt of an acid condensate phenolsulfonic-urea-for aldehyde and 68 parts by weight of a paraffinic mineral oil. A stable oleic dispersion is obtained. vile. 1 part by weight of compound No. 1.28 is dissolved in a mixture consisting of 70 parts by weight of cyclohexane, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. stable emulsion.

VIII. 1 part by weight of compound No. 1.28 is dissolved in a mixture consisting of 80 parts by weight of cyclohexane, 20 parts by weight of Emulphor EL. A stable emulsion concentrate is obtained.

In order to broaden the spectrum of action and to achieve synergistic effects, benzoyl derivatives I can be mixed with numerous representatives of other groups of hervicidal active substances and growth regulators and applied in conjunction with these. Examples of suitable mixing components are diacins, 4H-3, 1-benzoxa-cin derivatives, benzo-iadi cinnanes, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halogenated carboxylic acids, triazines. , amides, ureas, diphenyl ethers, triacinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, which in the 2-position carry, for example, a carboxy or carbonylamino group, quinolinecarboxylic acid derivatives, imidazouns, sulfonamides, sulfonylureas, aryloxy and heteroaryloxyphenoxypropionic acids, as well as their salts, esters and amides.

In addition, it may be useful to use the calculations alone or in combination with other herbicides also mixed with other phytosanitary products, for example products for controlling pests or phytopathogenic fungi or bacteria. Also interesting is the miscibility with solutions of mineral salts, which are used to alleviate nutrient deficiencies or microelements. Non-phytotoxic oils and oil concentrates can also be used.

The amounts of application of active substance amount according to the purpose of application, the season, the recipient plants and the growth stage to 0.001 to 3.0, preferably to 0.01 to 1.0 kg / ha of active substance (s.a.).

Application examples The fungicidal action of the pyrazole-benzoyl derivatives of the formula I can be demonstrated by tests in the greenhouse: Plastic pots filled with clay sand with approx. 3.0% humus as substrate. The seeds of the test plants are sown separately according to the species.

In the treatment before the emergency, actibas substances suspended or emulsified in water are applied directly after sowing by means of fine distribution nozzles. The containers are irrigated slightly to encourage germination and growth, and then the pots are covered with transparent plastic bags until the plants will do so. laid roots. With this covering a uniform germination of lié plantas is achieved ?? SH *.? I, e? However, this is not counteracted by the active substances.

For post-emergence treatment, the test mats are grown until they have reached a growth height of 3 to 15, depending on their growth pattern, and are then treated with the active substances suspended or emulsified in water. For this purpose, the test plants are sown directly in the same containers in which they are grown, or they are sown in separate germination containers and the seedlings are planted some days before the treatment in the test vessels.

The plants are stored according to their species at temperatures of 10 - 25 ° C or 20 - 35 ° C. The trial period lasts 2 to 4 weeks. During this time the plants are taken care of and their reaction to the different treatments is evaluated.

The evaluation is based on a scale of 0 to 100, where 100 means no emergence or total destruction of at least the parts of the plants surfaced, and = means no damage or normal development of growth.

Table 2 - Herbicide activity in post-emergence treatments in the greenhouse Table 3 - Herbicide activity in treatments after emergence in the greenhouse Collection examples * • A) Obtaining the starting substances 1. Methyl 2-chloro-3-formyl-4-methylsulfonylbenzoate to. To a suspension of 286 g (2.14 moles) of aluminum trichloride in 420 ml of 1,2-dichloroethane is added dropwise at 15-20 ° C a solution of 157 g (2 moles) of acetyl chloride in 420 moles of 1,2-dichloroethane. Then, a solution of 346 g (2 moles) of 2-chloro-6-methylthio-toluene in 1 l of 1,2-dichloroethane is added dropwise. After stirring for 12 hours, the reaction mixture was poured into a mixture from 3 1 of ice and 1 1 of concentrated HCl. It is washed with methylene chloride, the organic phase is washed with water, dried over sodium sulfate and concentrated. The residue is distilled in a vacuum. 256 g (60% of theory) of 2-chloro-3-methyl-4-methylthioacetophenone are obtained, mp .: 46 ° C. b. 163 g (0.76 mol) of 2-chloro-3-methyl-4-methylthioacetophenone are dissolved in 1.51 g of glacial acetic acid, mixed with 18.6 g of sodium tungstate and, under cooling, 173.3 g of water are added. 30% hydrogen peroxide solution. It is still stirred for 2 days and then diluted with water. The precipitated solid is filtered by suction, washed with water and dried. 164 g (88% of theory) of 2'-chloro-3-methyl-4-methylsulfonyl-acetophenone are obtained, mp .: 110-111 ° C. 82 g (0.33 mol) of 2-chloro-3-methyl-4-methylsulfonyl-acetophenone are dissolved in 700 ml of dioxane and mixed at room temperature with 1 l of a 12.5% solution of sodium hypochlorite. Then, stirring for 1 hour at 80 ° C. After cooling, two phases are formed, the lower one of which is diluted with water and slightly acidified. The precipitated solid is washed further with water and dries. 60 g (73% of theory) of 2-chloro-3-methyl-4-methylsulfonyl-benzoic acid are obtained, mp: 230-231 ° C. 100 g (0.4 mole) of 2-chloro-3-methyl-4-methyl-15-sulphonyl-benzoic acid are dissolved in 11 ml of methanol and at a reflux temperature HCl gas is added over 5 hours. Next, concentrate. 88.5 g (84% of theory) of methyl 2-chloro-3-methyl-4-methylsulfonyl-benzoate, m.p .: 20-107 ° -8 ° C are obtained. and. 82 g (0.31 mol) of methyl 2-chloro-3-methyl-4-methylsulfonylbenzoate are dissolved in tetrachloromethane and under exposure to light are mixed in increments with 56 g (0.31 mol) of N. -bromosuccinimide. The reaction mixture is filtered, the filtrate is concentrated and the residue is taken up in 200 ml of methyl tert. -butyl ether. The solution is mixed with petrolether, the precipitated solid is filtered off by suction and dried. 74.5 g (70% of theory) of methyl 3-bromomethyl-2-chloro-4-methylsulfonyl-benzoate, m.p .: 74-75 ° C are obtained.

A solution of 41 g (0.12 mol) of methyl 3-bromomethyl-2-chloro-4-methylsulfonylbenzoate in 250 ml of acetonitrile is mixed with 42.1 g (0.36 mol) of N-N-oxide. methylmorpholine. The preparation is stirred for 12 hours at room temperature, then it is concentrated and the residue is taken up in acetic ester. The solution is extracted with water, dried over sodium sulfate and concentrated. 31.2 g (94% of theory) of methyl 2-chloro-3-for-mil-4-methylsulfonyl-benzoate, m.p .: 98-105 ° C are obtained.

Methyl 2-chloro-4-methylsulfonyl-3- (trifluoromethylsulfonyl) oxy-benzoate 101 g (0.41 mol) of 2-chloro-3-hydroxy-4-methylsulfonyl-benzoic acid are dissolved in 1.31 methanol and under reflux 4 hours of HCl gas are introduced. The solution is concentrated, the residue is taken up in dichloromethane and extracted with K2C03 solution. The aqueous phase is adjusted with dilute hydrochloric acid to pH 7 and washed with dichloromethane. It is then acidified to pH 1 and the product is extracted with dichloromethane. 76.2 g (71% of theory) of methyl 2-chloro-3-hydroxy-4-methylsulfonylbenzoate are obtained. b. A solution from 76 g (0.29 mol) of methyl 2-chloro-3-hydroxy-4-methylsulfonylbenzoate and 68 g of pyridine in 700 ml of dichloromethane is mixed at -20 ° C with 89 g ( 0.32 moles) of trifluoromethanesulfonic acid anhydride. The solution is further stirred for 12 hours at room temperature, diluted with dichloromethane and extracted with water. The organic phase is dried over magnesium sulfate and concentrated. 94 g (82% of theory) of methyl 2-chloro-4-methylsulphonyl-3- (trifluoromethylsulfonyl) oxy-benzoate, m.p .: 69 ° C are obtained.

Obtaining intermediate products Methyl 3- (3-isopropylisoxazol-5-yl) -4-methylsulfonylbenzoate to. 30 g (102 mmol) of methyl 3-bromo-4-methylsulfonylbenzoate, 90 mg of palladium dichloride and 240 mg of triphenylphosphine in 200 ml of diethylane and 60 ml of dimethylformamide are mixed with 10 g (102 mmoles) of (trimethylsilyl) -acetylene and 180 mg of copper iodide I and stirred 4.5 hours at 40 ° C. Then, it is stirred for 12 hours at room temperature. The reaction mixture is filtered, the filtrate is concentrated and the residue 36 purifies r < - »? T? At.? Graphically on silica gel with toluene as eluent. 17.3 g (55% of theory) of methyl 4-methylsulphonyl-3- (trimethylsilyl) ethynyl-benzoate are obtained as oil. b. 25 g of methyl 4-methylsulfonyl-3- (trimethylsilyl) ethynyl-benzoate are stirred with 100 ml of methanol and 0.9 g of potassium carbonate for 18 hours at room temperature. It is then filtered from the solid, concentrated and extracted with acetic ester / water. The organic phase is dried over sodium sulfate and concentrated. g (79% of th.D.) methyl 4-methylsulfonyl-3-ethynyl-benzoate, m.p .: 95-98 ° C are obtained. c. 13.5 g (57 mmol) of methyl 4-methylsulfonyl-3-ethynyl-benzoate are dissolved in 50 ml of dichloromethane, mixed with 5.2 g (60 mmol) of isobutyraldehyde oxime and 41 g are added. of a 12.5% solution of sodium hypochlorite. Then, it is still stirred 24 hours at room temperature. The reaction mixture is then extracted with dichloromethane / water, the organic phase is concentrated and the residue is purified on silica gel with toluene / acetic ester as eluent. 3.8 g (48% of theory) of methyl 3- (3-isopropylisoxazol-5-yl) -4-methylsulfonyl-benzoate, m.p .: 102-104 ° C are obtained.

Methyl 2-chloro-3- (isoxazol-3-yl) -4-methylsulfonylbenzoate to. 15 g (54 mmol) of methyl 2-chloro-3-formyl-4-methylsulphonylbenzoate (Ex. Al) and 4.2 g (60 mmol) of hydroxylahydrochloride are stirred with 300 ml of methanol and a solution of 3.18 g (30 mmol) of sodium carbonate in 80 ml of water is added. The reaction mixture is stirred overnight at room temperature, then the methanol is distilled off and the preparation is extracted with ether / water. The ether phase is dried with sodium sulfate and concentrated. 14.4 g (91% of theory) of methyl 2-chloro-3-hydroxy-iminomethyl-4-methylsulfonyl-benzoate, m.p .: 126-128 ° C are obtained. b. 5.3 g (18 mmol) of methyl 2-chloro-3-hydroxyiminomethyl-4-methylsulfonyl-benzoate are dissolved in 50 ml of dichloromethane and acetylene is introduced at 0-5 [deg.] C. for 30 minutes. It is then mixed with a sodium acetate spatula tip and 15ml of a 10% solution of sodium hypochlorite is added in drops at 10 ° C, while more acetylene is added. After the addition, acetylene is introduced for another 15 minutes at 10 ° C and then stirred for another 12 hours. The phases are then separated, the organic phase is washed with water, dried over sodium sulfate and concentrated. 4.8 g (84% of theory) of methyl 2-chloro-3- (isoxazol-3-yl) -4-methylsulfonyl-benzoate, m.p .: 145-147 ° C are obtained.

Methyl 2-chloro-3- (thiazol-2-yl) -4-methylsulfonylbenzoate 33 g (88 mmol) of 2- (tributylstannyl) -thiazole, 17.5 g (44 mmol) of methyl 2-chloro-4-methylsulfonyl-3- (trifluoromethyl-sulfonyl) oxy-benzoate (Ex. A.2) .), 5.8 g of lithium chloride, 1 g tetrakis- (triphenylphosphine) -pala-dio- (0), a spatula tip of 2,6-di-tert-butyl-4-methyl-phenol and 200 ml of 1,4-dioxane are stirred for 3 hours in an autoclave at 140 ° C and under its own pressure. After cooling the reaction mixture, the reaction mixture is filtered through a layer of silica gel, washed further with methyl tert. -butyl ether and concentrate. The residue is purified chromatographically on silica gel with toluene / acetic ester as eluent. 9.1 g (62.6% of theory) of methyl 2-chloro-3- (thia-zol-2-yl) -4-methylsulfonyl-benzoate, m.p .: 135-138 ° C are obtained.

Methyl 2-chloro-3- (oxazol-5-yl) -4-methylsulfonylbenzoate g (0.09 mole) of methyl 2-chloro-3-formyl-4-methylsulfonylbenzoate (Example Al), 17.6 g (0.09 mole) of tosylmethylene isocyanide and 6, 2 g (0.045 mol) of finely powdered potassium carbonate are stirred with 450 ml of methanol for 5 hours at reflux temperature. The solvent is then removed, the residue is taken up in acetic acid and extracted with water. The acetic ester phase is dried with sodium sulfate and concentrated. 24.7 g (87% of theory) of methyl 2-chloro-3- (oxazol-5-yl) -4-methylsulfonyl-benzoate, 1H-NMR (CDC13) are obtained. d: 8.24 (d, 1H), 8.15 (S, 1H), 8.01 (d, 1H), 7.40 (s, lH), 4.0 (s, 3H), 2.96 (s, 3H) The intermediate products indicated in the following table are obtained analogously: Table 4 fifteen twenty Table 5 C) Obtaining the final products 1. 1, 3-Dimethyl-4- [2-chloro-4-methylsulfonyl-3- (oxa-zol-5-yl) -benzoyl] -5-hydroxy-pyrazole (Example 1.28) 1.22 g (10.9 mmol) of 1,3-dimethyl-5-hydroxy-propylol and 1.1 g (10.9 mmol) of triethyl amine are dissolved in 75 ml of acetonitrile and mixed at 0 ° C with 3.5 g (10.9 mmol) of 2-chloro-4-methylsulfonyl-3- (oxazol-5-yl) -benzoyl chloride in 50 ml of acetonitrile. The mixture is stirred for one hour at 0 ° C and then 4.45 g (44 mmol) of triethylamine and 0.61 g (7.2 mmol) of acetocyanhydrin are added dropwise at room temperature. The solution is stirred for 12 hours at room temperature. For further processing, it is mixed, first with dilute hydrochloric acid and then extracted with methyl-tert. -butyl ester. The ether phase is then extracted with 5% poresium carbonate solution. From the aqueous phase, the product is extracted with acetic ester after acidification with hydrochloric acid. The acetic acid phase is dried with sodium sulfate and concentrated. 1.2 g of crude product is obtained which is purified by column chromatography. 0.4 g are obtained (27% of the theory) 1, 3-dimethyl-4- [2-chloro-4-methylsulfonyl-3- (oxazol-5-yl) -benzoyl] -5-hydroxy-pyrazole, m.p .: 236-241 ° C.

The compounds indicated in the following table are obtained analogously: Table 5 fifteen twenty

Claims (1)

Claims

1. Pyrazol-4-yl-benzoyl derivatives of the formula I wherein the substituents have the following meanings: L, M hydrogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cj.-C4-alkoxy, whose groups may be optionally substituted by one to five halogen atoms or Cj.-C4 -alkoxy, halogen, cyano, nitro, a group - (Y) nS (0) mR7 or a group - (Y) n-CO-R8 Z a saturated heterocyclic radical or unsaturated with 5 or 6 members, containing one to three heteroatoms, selected from the group oxygen, sulfur or nitrogen, which may possibly be substituted by halogen, cyano, nitro, a group -CO-R8, C? -C4 -alkyl, Cj.-C4-haloalkyl, C3-C8-cycloalkyl, C? -C4-alkoxy, C? -C4-haloalkoxy, C? -C4-alkylthio, C? -C4-haloalkylthio, di-C? -C4-alkylamino, phenyl optionally substituted by halogen, cyano, nitro, C? -C4-alkyl or C? -C4-haloalkyl or an oxo group, which may optionally also be present in the tautomeric form or as a hydroxy group, or forming a bicyclic system with a fused phenyl ring, optionally substituted by halogen, cyano, nitro, C? -C4-aikyl or C? -C4-halogenoalkyl, or with a carbocyclic ring or a second cyclic ring condensate, optionally substituted by halogen, cyano, nitro, C? -C4-alkyl, Di-C1- C4- alky1rd.no, C? -C4-alkoxy, C? -C4-halogenoalkoxy, or C? -C4-halogenoalkyl; Y 0, NR9 n zero 0 one m zero, one or two R7 C? -C4-alkyl, C? -C4-haloalkyl or NR9R10 R8 C? -C4-alkyl, C? -C4-haloalkyl, C? -C4- alkoxy, or NR ° Rl ° R9 hydrogen or C? -C4-alkyl Ri ° C? -C4-alkyl Q a pyrazole ring linked at position 4 and corresponding to formula II where Ri is C? -C4-alkyl R2 means hydrogen, C? -C4-alkyl or C? -C4-haloalkyl R3 means hydrogen, C? -C4-alkyl, phenylsulfonyl or alkylphenylsulfonyl, as well as the salts of the compounds I usual in agriculture. Derivatives of pyridyl-4-yl-benzyl of the formula wherein L means C? -C6-alkyl, C2-C6-alkenyl, C-C6-alkynyl, C? -C4-alkoxy, C? -C4-alkylthio, C? -C4-haloalkyl, C? ~ C4- haloalkoxy, C? -C4-halogen-noalkylthio, C? -C4-alkylsulfonyl, halogen, nitro or cyano and M means hydrogen, Ci-Cd-alkyl, C2-C6-alkenyl, C2-Ce-alkynyl, C? -C4-alkoxy, C? -C4-alkylthio, C? -C4-halogenoalkyl, C? -C -haloalkoxy, C? -C4 -halo-noalkylthio, C? -C4-alkylsulfonyl, halogen, nitro or cyano and Q and Z have the meanings indicated in claim 1. Pyrazole-benzoyl derivatives of the formula Ib wherein L and Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C? -C4-alkoxy, C? -C4-alkylthio, C? -C4-halogenoalkyl, C? -C4- haloalkoxy, C? -C4? halogenalkylthio, C? -C4-alkylsulfonyl, halogen, nitro or cyano, and Q and Z have the meanings indicated in claim 1. Pyraol-4-yl-benzoyl derivatives of the formula I according to claim 1, wherein the radicals L or M mean hydrogen, methyl, methoxy, methylthio, chloro cyano, methylsulfonyl, nitro or trifluoromethyl. Process for obtaining the pyrazol-4-yl-benzoyl derivatives of the formula I according to claim 1, characterized in that the pyrazoles of the formula lía are transformed Rl with a benzoyl derivative of formula III where T = halogen and L, M and Z have the meanings indicated in claim 1. A herbicidal product containing at least one pyrazole-4-benzoyl derivative of the formula I according to claim 1 and the usual inert additives. Process for combating the growth of unwanted plants, characterized in that a herbicidal active amount of a pyrazole-4-yl-benzoyl derivative of the formula I according to claim 1 is activated on the plants or their living space. Pyrazol-4-yl-benzoyl derivatives of the formula I 'according to claim 1 wherein Z means a 5- or 6-membered heteroaromatic containing from one to three heteroatoms selected from the oxygen group, sulfur and nitrogen, and which is optionally substituted by halogen, cyano, nitro, C? -C4-alkyl, C? -C4-haloalkyl, C3-C8-cycloalkyl, C? -C4-alkoxy, C? -C4-haloalkoxy, C? -C4-alkylthio, C? -C4-haloalkylthio, di-C] -C4-alkylamino, phenyl optionally substituted by halogen, cyano, nitro, C? -C4 -alkyl or C? -C4-haloalkyl, or a penta or hexacyclic benzo-fused heteroaromatic, optionally substituted by halogen, cyano, nitro, C? -C4-alkyl or C? -C4-halogen-alkyl; and L, M and Q have the meanings indicated in claim 1. SUMMARY OF THE INVENTION Pyrazol-4-yl-benzoyl derivatives of the formula I wherein the substituents have the following meanings: L, M hydrogen, Ci-Cg-alkyl, C2-Cg-alkenyl, C2-C6-alkynyl, C? -C4-alkoxy, the groups of which may be optionally substituted by one to five halogen atoms or C? -C4-al - coxi, halogen, cyano, nitro, a group - (Y) nS (0) mR7 or a group - (Y) n-CO-R8 Z a saturated heterocyclic radical or unsaturated with 5 or 6 members, containing one to three heteroatoms, selected from the group oxygen, sulfur or nitrogen, which may possibly be substituted by halogen, cyano, nitro, a group -CO-R8, C? -C4-alkyl, C? -C4-haloalkyl, C3-C8-cycloalkyl, C? -C4-alkoxy, C? -C4-haloalkoxy, C? -C4-alkylthio, C? -C4-haloalkylthio, di- Cj-C4-alkylamino, phenyl optionally substituted by halogen, cyano, nitro, C? -C4-alkyl or C? -C4-haloalkyl or an oxo group, which may optionally also be present in the tautomeric form or as a hydroxy group, or forming a bicyclic system with a fused phenyl ring, optionally substituted by halogen, cyano, nitro, C? -C4 -alkyl or C? -C4-hayogenoalkyl, or with a fused carbocycle or a second heterocycle condensate, optionally substituted by halogen, cyano, nitro, C? -C4-alkyl, Di-C? -C4-alkylamino, C? -C4-alkoxy, C? -C4-halogenoalkoxy, or C? -C 4-haloalkyl; I, 'NR9 n zero or one m zero, one or two R7 C? -C4-alkyl, C? -C4-haloalkyl or NR9R10 R8 C? -C4-: alkyl, C? -C4-haloalkyl, C? -C4 -alcoxy, or NR9R ° R9 hydrogen or C? -C4-alkyl Ri? C? -C4-alkyl Q a pyrazole ring linked at position 4 and corresponding to formula II where Ri is C? -C4-alkyl R2 means hydrogen, C?, -C4-alkyl or C? -C4-haloalkyl R3 means hydrogen, C? -C4-alkyl, phenylsulfonyl or alkylphenylsulfonyl, as well as the salts of the I compounds usual in agriculture.