MXPA00004809A - Benzylidene pyrazolones and use as herbicide - Google Patents

Abstract

The invention relates to benzylidene pyrazolones of formula (I), wherein the substituents and index n have the following meanings:R1=optionally substituted C1-C6 alkyl;R2=optionally substituted C1-C6 alkyl, optionally substituted C1-C6 alkoxy, halogen, nitro, cyano;R3=hydrogen, halogen, nitro, cyano, a group NR5R6, OCOR5, NR5COR6,CO2R5, -COSR5, -CONR5R6, C1-C4-alkoxyiminoalkyl, C1-C6 alkoxycarbonyl, optionally substituted C1-C6 alkyl, optionally substituted C1-C6 alkoxy, optionally substituted C1-C6 alkylthio, optionally substituted C2-C6 alkenyl, optionally substituted phenyl, optionally substituted phenoxy, an optionally substituted 5- or 6-membered saturated or unsaturated heterocycle which can contain up to 4 nitrogen atoms and/or up to 2 oxygen or sulphur atoms as ring members;R4=C1-C6 alkyl, C1-C4 halogen alkyl;or R3 and R4=an optionally substituted saturated or unsaturated 2- or 3-membered bridge which can contain one sulphur atom which can be oxidized into sulfoxide or sulfone, R5=hydrogen or optionally substituted C1-C6 alkyl;R7=hydrogen, C1-C6 alkyl or C1-C4 halogenalkyl;n=0, 1 or 2;X=hydrogen, chlorine or bromine. The compounds to which claim is laid are available in both a trans and a cis form or can be a mixture of these isomers.

Description

BENCILIDENPIRAZOLONAS, ITS OBTAINING AND USE.

Description The present invention relates to benzylidene pyrazolones of formula I in which the substituents and the index have the following meanings: R1 Ci-Cβ-alkyl event. sust .; 20 R2 Ci-Cß-alkyl event. sust., Ci-Cg-alkoxy event. Substance, halogen, nitro, cyano; R3 hydrogen, halogen, nitro, cyano, a group NR5R6, OCO NR5COR6, C02R5, -COSR5, -CONR5R6, C? -C4-alkoxyiminoalkylC? -C6-alkylcarbonyl, C? -C6-alkyl event. sust., C? ~ C6-alkoxy event. sust., Ci-Cg-alkylthio event. sust C-C6 ~ alkenyl event. sust., C-Cg-alkynyl event. your phenyl event. sust., phenoxy event. sust., a heterocic e ^ 5 or 6 members, saturated or unsaturated, event. sust Which may contain up to 4 nitrogen atoms, and / or sulfur atom as ring members; R4 Ci-Cβ-alkyl, C? -C4-haloalkyl? O well R3 'R4 a bridge of 2 or 3 members, saturated or unsaturated, event. sust, which may contain a sulfur atom, which can be oxidized to sulfoxide or sulfone; R5 hydrogen C? -C6-alkyl event. sust .; R6 C? -C6-alkyl event. sust; R7 hydrogen, Ci-Cg-alkyl or C? -C4-haloalkyl; n 0.1 or 2; X hydrogen, chlorine or bromine; whose claimed compounds may be present both (trans form, as in the cis form or represent a mixture of these isomers) In addition, the invention relates to products containing the compounds of the formula I, as well as to the use of the compounds I and the products that the contain for the control of harmful plants, new benzoylpyrazoles of the formula II, As well as a process for obtaining compounds I and II.

From the literature, for example from EP-A 282 944 or WO 96/26206, 4-benzoyl-pyrazoles of herbicidal action are known. However, 4-benzoyl-5-chloro-pyrazoles are not disclosed to date. In EP-A 282 944 it is only mentioned in general terms that the reaction of 4-benzoyl-5-hydro pyrazoles with acid halides should result in 4-benzoyl-5-chloro-pyrazoles.

Benzylidene diazolones which have, in part, a herbicidal action are known from US 4,382,948 and JP 61268670. All the structures known up to now have a specific mu substitution model in the lower part of the benzylidenepirazolone: in the position opposite to the bridge of methino, for example, is always a hydrogen atom or halogen atom or a trifluoromethyl or nitro group.

The herbicidal properties of the compounds known to date, as well as their compatibility with the crop plants, are only partly satisfactory. Therefore, the present invention had the task of finding new compounds, especially of herbicidal action, with improved properties Therefore, the benzylidene pyrazolones according to the invention of the formula I were found, as well as their herbicidal action.

The object of the present invention are also the stereoisomers of the compounds of the formula I. The pure stereoisomers, as well as their mixtures, are thus included.

The compounds of formula I can be present as cis or trans isomers and contain, depending on their model, substitution of one or several centers of chirality, and can also be present as enantiomeric or diastereomeric mixtures. Both isomers are subject of the present invention. , pure enantiomers or diastereomers, as well as their mixtures.

The benzylidene pyrazolones according to the invention of the formula benzoylpyrazoles of the formula II can be prepared in the manner described hereinafter.

The benzylidene diazolones of the formula la (X = hydrogen) can be synthesized by Knoevenagel condensation of pyraz. canvases of the formula III, wherein the radicals Reste R1 and R have the meanings indicated above, and a benzaldehyde the formula IV, in which the radicals R2 to R4 have the meanings indicated above, in analogy to the method described in the US 4,382,948. r III IV the and In addition, the compounds can be obtained, for example p Reductive dehalogenation from compounds of the formula I, wherein X means bromine.

The benzylidene diazolones ib (x = bromine or chlorine) can be obtained by halogenation of the above-described compounds with bromine or chlorine and subsequent dehalogenation with the presence of a base.

Preferably, the benzylidene pyrazolone Ib can be prepared from ketones of the formula V, which are known or can be prepared analogously to the known compounds (see DE-A 19709118.0 and WO 96/26200), by reaction with halufros of acid. c Suitable acid halides are, for example, the halur of sufluric acid, carbonic acid and phosphoric acid. Thionyl chloride is preferred for the exchange for chlorine, phosgene, phosphoric pentachloride, and, especially, phosphoric oxychloride. For the bromine substitution, the phosphoric oxybromide is preferably used.

The reaction can be done in a usual way, with or without d inert solvent under the reaction conditions. The selectivity of the reaction can be regulated, generally, by the addition of a low nucleophilic base, such as, for example, pyridine and dimethylaminopyridine, dimethylformamide.

The reaction temperature is generally at 0 ° C to 200 ° C, preferably at 50 ° C to 140 ° C.

Ib 10 c In this reaction both isomers can be obtained in the newly formed double bond in the form of a mixture. In this case, the isomers can be separated, if necessary (eg by crystallization, extraction or chromatography). fifteen A secondary product of this reaction are compounds I which, depending on the model of substitution and the embodiment of the reaction, can be obtained in reduced, com parable or predominant properties. These compounds are in many cases new and extremely interesting as starting materials for active herbicidal substances (see, for example, EP-A 282 944).

/ * "The parts of organic molecules mentioned for substituents R1 - R7 or as radicals on phenyl or het rings rociclos are representative collective terms for the individual analysis of each one of the members of the respective group. All the hydrocarbon chains, namely, all the alkyl, halogenalyl, cycloalkyl, alkoxy, haloalkoxy, alkylcarbonyl, alkenyl, alkynyl groups can be linear or branched. Unless otherwise indicated, the halogenated substituents preferably have one to five identical or different halogen atoms. Halogen if gnifica in each case fluoro, chlorine, bromine or iodine.

In addition, they mean, for example: C? -C4-alkyl, as well as the alkyl portions of other radicals such as, for example, C? -C4-alkoxy, C? -C4-alkylcarbonyl, C? -C4-alkylthio: methyl, ethyl, n -propyl, 1-methylethyl butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl Ci-Cβ-alkyl, as well as the alkyl portions of other radicals such as, for example, Ci-Cg-alkoxy, C6-alkylcarbonyl, C6-alkynylthio: C4-alkyl, like above, as well as pentyl, 1-methylbutyl, 2-methylbutyl, 3-butyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-di-ethylpropyl, 1-methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1- ethylbyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-3-methylpropyl; C? -C4-halogenoalkyl: a C1-C4-alkyl radical, as mentioned above, which is partially or completely substituted by fluoro, chloro, bromo and / or iodo s, namely, eg chloromethyl, dichloromethyl, trichloromethyl , fluoro methyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-diflumethyl, 2,2,2-trifluoroethyl, 2-chloro- 2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl. 2, 2, 2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-br mopropyl, 3- bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3-pentafluoropropyl, hep tafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloro methyl) - 2-chloroethyl, 1- (bromomethyl) -2-bromoethyl, 4-fluo robutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl C1-C4-halogenoalkoxy: a C1-C4 -alkoxy radical, like the above mentioned, which is partially or completely substituted by fluoro, chloro, bromo and / or iodo, namely, eg fluoromethoxy, difluoromethoxy, trifluoromethoxy , chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloro-15-ethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2 - chloro-2, 2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2, 2, 2-ricloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromo propoxy, 3-bromopropoxy, 2, 2-difluoropropoxy, 2,3-difluoro-ropropoxy, 2,3-dichloropropoxy, 3, 3,3-trifluoropropoxy, 3, 3, 3-ricloropropoxy, 2, 2, 3, 3 3-pentafluoropropoxy, hep tafluoropropoxy, 1- (fluoromethyl) -2-fluoroethoxy, 1- (chloro methyl) -2-chloroethoxy, 1- (bromomethyl) -2-bromoethoxy, 4-fluo Robutoxy, 4-chlorobutoxy, 4-bromobutoxy and nonafluorobutox C -C6-alkenyl: ethenyl, prop-1-en-l-yl, prop-2-en-l-yl-1-methylethenyl, buten-1-yl, buten-2-yl, buten-3-yl, 1 -methyl-prop-l-en-l-yl, 2-methyl-prop-l-en-1-yl, 1-methyl prop-2-en-1-yl, 2-methyl-prop-2-en-l-yl, penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1 -methyl- but- 1-en-l -yl, 2-methyl-but-1-en-l-yl, 3-methyl- but-1-en-l-yl, l-methyl-but-2-en-l-yl, 2-methyl-but-2-en-l-yl, 3-methyl-but-2-en-l -yl, 1-methyl-but-3-en-l-yl, 2-methyl-but-3-en-l-yl, 3-methyl-but-3-en-l-yl, 1,1-dimethyl -prop- 2 -en-l-yl, 1,2-dimethyl-prop-1-en-l-yl, 1,2-dimethyl-prop-2-en-l-yl, 1-ethyl-propyl- en-2-yl, l-ethyl-prop-2-en-l-yl, hex-1-en-l-yl, hex-2-en-l-yl, hex-3-en-1-yl, hex-4-en-l-yl, hex-5-en-l-yl, 1-methyl -pent-1-en-l-yl, 2-methyl-pent-1-en-l-yl, 3- methyl-pent-l-en-l-yl, 4-methyl-10 pent-1-en-l-yl, l-methyl-pent-2-en-l-yl, 2-methyl-pent-2-en -l-yl, 3-methyl-pent-2-en-l-yl, 4-methyl-pent-2-en-l-yl, l-methyl-pent-3-en-l-yl, 2-methyl - pent-3-en-l-yl, 3-methyl-pent-3-en-l-yl, 4-methyl-pent-3-en-l-yl, l-methyl-pent-4-en-l -yl, 2-methyl-15 pent-4-en-l-yl, 3-methyl-pent-4-en-l-yl, 4-methyl-pent-4-en-l-yl, 1, l- dimethyl-but-2-en-l-yl, 1,1-dimethyl-but-3-en-l-yl, 1,2-dimethyl-but-l-en-l-yl, 1,2-dimethyl-butyl -2-en-l-yl, l, 2-dimethyl-but-3-en-l-yl, 1,3-dimethyl-but-l-en-l-yl, 1,3-dimet il-but-2-en-l-yl, 1,3-dimethyl-20 but-3-en-l-yl, 2,2-dimethyl-but-3-en-l-yl, 2,3-dimethyl - but-l-en-l-yl, 2,3-dimethyl-but-2-en-l-yl, 2,3-dimethyl-but-3-en-l-yl, 3,3-dimethyl-but -l-en-l-yl, 3,3-dimethyl-but-2-en-l-yl, 1-ethyl-but-l-en-l-yl, 1-ethyl-but-2-en-l -yl, l-ethyl-but-3-en-l-yl, 2-ethyl-25 but-1-en-l-yl, 2-ethyl-but-2-en-l-yl, 2-ethyl- but-3-en-l-yl, 1, 1, 2-trimethyl-prop-2-en-l-yl, l-ethyl-1-methyl-prop-2-en-l-yl, l-ethyl- 2-methyl-prop-1-en-l-yl and l-ethyl-2-methyl-prop-2-en-l-yl; C2-C6-alkynyl: ethynyl, propylene-1-yl, prop-2-yl-yl, but-1-yl-yl, but-1-in-3-yl, but -l-in-4-yl, but-2-in-l -yl, pent-1-in-l-yl, pent-l-in-3-yl, pent-l-in-4-yl, pent-l-in-5-yl, pent-2-yn-l-yl, pent-2-yn-4-yl , pent-2-in-5-yl, 3-methyl-but-l-in-3-yl, 3-methyl-but-l-in-4-yl, hex-1-yn-l-yl , hex-l-in-3-yl, hex-l-in-4-yl, hex-l-in-5-yl, hex-l-in-6-yl, hex-2-yn-l-yl , hex-2-in-4-yl, hex-2-yn-5-yl, hex-2-yn-6-yl, hex-3-yn-yl, hex-3-yn-2-yl , 3-methyl-pent-l-in-l-yl, 3-methyl-pent-l-in-3-yl, 3-methyl-pent-l-in-4-yl, 3-methyl pent-l- in-5-yl, 4-methyl-pent-l-in-l-yl, 4-methyl-10 pent-2-yn-4-yl and 4-methyl-pent-2-yn-5-yl; C3-C6-cycloalkyl: skypropyl, cyclobutyl, cyclopentyl and cyclohexyl; A 5 or 6 membered heterocycle, saturated or unsaturated, optionally substituted, which may contain up to 4 nitrogen atoms and / or up to 2 oxygen or sulfur atoms as ring members, such as, for example, 2-tetrahydrofuranyl, - tetrahydrofuranyl, 2-tetrahydrothienyl, 3-etrahydro-thienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3- pyrazoin, lidinyl, -pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4- thiazolidinyl, 5-aiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1, 2, 4-oxadiazolidin-3-yl, 1,2,4-oxa-diazolidin-5-yl, 1, 2,4-thiadiazolidin -3-yl, 1, 2, 4-thiadi-zolidin-5-yl, 1, 2, 4-triazolidin-3-yl, 1, 3, 4-oxadiazoli-din-2-yl, 1, 3, 4-thiadiazolidin -2-yl, 1, 3, 4-triazolin-30 din-2-yl, 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl 2,3-dihydrofuran-4-yl, 2 , 3-dihydrofuran-5-yl, 2,5-dihi drofuran-2-yl, 2,5-dihydrofuran-3-yl, 2,3-dihydro- thien-2-yl, 2,3-dihydrothien-3-yl, 2,3-dihydrothien-4-yl 2,3-dihydrothien-5-yl, 2,5-dihydrothien-2-yl, 2.5- dihyd thien-3-yl, 2,3-dihydropyrrol-2-yl, 2,3-dihydropyrrol-3-yl, 2,3-dihydropyrrol-4-yl, 2,3-dihydropyrrol-5-yl 2, 5-dihydropyrrol-2-yl, 2,5-dihydropyrrol-3-yl, 2,3-dihydroisoxazol-3-yl, 2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazole -5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl, 4,5-dihydroisoxazol-5-yl, 2,5-dihydroisoxazol-3-yl, 2 , 5-dihydroisoxa-10-zol-4-yl, 2,5-dihydroxazol-5-yl, 2,3-dihydroisothia-c-zol-3-yl, 2,3-dihydroisothiazol-4-yl, 2,3-dihydroisothi zol-5-yl, 4,5-dihydroisothiazol-3-yl, 4,5-dih.-idroisothi zol-4-yl, 4,5-dihydroisothiazol-5-yl, 2,5-dihydroisothiol-3-yl, 2,5-dihydroisothiazol-4-yl, 2,5-dihydroisothi -zol-5-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 4,5-dihydropyrazol-3-yl , 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,5-dihydropyrazol-3-yl, 2,5-dihydropyrazol-4-yl, 2,5-dihydropyrazole -5-yl, 2,3-dihydrooxa- 20-zol-2-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 4,5-dihydrooxazol-2-yl, 4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl ?, 2,5-dihydrooxazol-2-yl, 2,5-dihydrooxazol-4-yl, 2,5-dihydrooxa - zol-5-yl, 2,3-dihydrothiazol-2-yl, 2,3-dihydrothia-25-yl-4-yl, 2,3-dihydrothiazol-5-yl, 4,5-dihydrothiazol-2 ilo, 4, 5-dihydrothiazol-4-yl, 4,5-dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl, 2, 5- dihydrothiazol-5-yl, 2,3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-4-yl, 2,3-dihydroimide-30-yl-5-yl, 4,5-dihydroimidazol-2-yl , 4,5-dihydroimidazol-4-yl, 4,5-dihydroimidazol-5-yl, 2,5-dihydroimidazol-2-yl, 2,5-dihydroimidazole -4 -yl, 2,5-dihydroimide- zol-5-yl, 2-morpholinyl, 3-morpholinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-tetrahydropyridazinyl 4-etrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-t-trahydropyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetra dropiracinyl, 1, 3, 5-tetrahydrotriacin-2-yl, 1,2,4-tet, hydrotriazin-3-yl, 1,3-dihydrooxacin-2-yl, 1,3-di-tian-2-yl, 2 -tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-etrahydrothiopyranyl, 3-tetrahi-thothiopyranyl, 4-tetrahydrothiopyranyl, 1,3-dioxo-10-lane-2-yl, 3, 4, 5, 6-tetrahydropyridin-2-yl , 4H-1, 3-thia-cin-2-yl, 4H-, 1, 1-dioxo-2, 3, 4, 5-tetrahydrothien-2-yl, 1,3-dihydroxacin-2-yl, 2 -furyl, 3-furyl, 2-thienyl, 3 -thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4 -is xazolyl, 5 -isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, -isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl-2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, tet zol-5-yl, tetrazol-1-yl, 4-thiazolyl, -thiazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2, 4-oxadiazol-3-yl, 1, 2, 4-oxadiazo'l-5-yl, 1, 2, 4-diazodiazol-3-yl, 2,4-thia-20-diazol-5-yl, 1, 2, 4-triazol-3-yl, 1, 3, 4-oxadiazol-2-yl 1, 3, 4-thiadiazol-2-yl, 1 , 3,4-triazol-2-yl, 2-pyridinyl 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, , 3, 5- triazin-2-yl, 1, 2, 4-triazin-3-yl, , 1,2,4, 5- tetracin-3-yl.

With regard to the herbicidal action of the benzylidene diazole I, the following meanings are especially preferred for the substituents, each time alone or in combination tion: R1 C? -C "4-alkyl or C? -C4-halogenoalkyl; R2 C? -C4-alkyl, C? -C4-haloalkyl, C? -C4-alkoxy, C? -C4-haloalkoxy, halogen, nitro, cyano; R3 hydrogen, halogen, nitro, cyano, NR5R6 group one, OCOR5 N 5COR6, C02R5, -COSR5, -CONR5R6, C? -C4-alcoxiiminoalquil C? -C4-alkylcarbonyl, C? -C4 alkyl optionally Susti tuted by halogen, C? -C4? Alkoxy or phenyl, the phenyl ring being in turn substituted by halogen, C? -C2-alkyl or C? -C-alkoxy, C? -C4-alkoxy optionally substituted by halogen, C? C4-alkoxy or phenyl, the phenyl ring itself being able to be substituted by halogen, C? -C2-alkyl or C? -C2-alkoxy, C? -C4-alkylthio optionally substituted by halogen, C? -C4-alkoxy or phenyl, wherein phenyl ring may in turn be substituted by halogen, C? -C2-alkyl or C? -C2-alkoxy, C? -Cg-alkenyl or C2-C6-alkynyl optionally substituted by C? -C4-alkyl or halogen, phenyl or phenoxy optionally substituted by C? -C4-alkyl, C? -C4-alkoxy, C? -C-haloalkyl, C? -C4-halogenoalkoxy, halogen, phenyl, cyano, alkoxycarbonyl or nitro, a heterocyclic 5 or 6 members, saturated or unsaturated, eventually their substituted by C? -C4-alkyl, C? -C4-alkoxy, C? -C4-haloalkyl, C? -C4-halogen, alkoxy, halogen, phenyl, cyano or nitro, and which can contain up to 4 carbon atoms. nitrogen and / or up to 2 oxygen atoms or sulfur atoms as ring members, seleccionad group: tetrahydrofuranyl, tetrahydrothienyl, dinilo pirro, isoxazolidinyl, isothiazolidinyl, oxazolidinyl pirazolidini, thiazolidinyl, imidazolidinyl, 1,2,4-ox diazolidinyl, 1, 2 , 4-thiadiazolidinyl, 1, 2,4-triazolidinyl, 1,3,4-oxadiazolidinyl, 1,3,4-thiadiazolidinyl. 1, 3, 4-triazolidinyl, 2,3-dihydrofuranyl, 2,5-dihydrofu ranyl, 2,3-dihydrothienyl, 2,5-dihydrothienyl, 2,3-dihydropyrrolyl, 2,5-dihydropyrrolyl, 2,3- dihydroisoxazolyl, 4, 5-dihydroisoxazolyl, 2, 5-dihydroisoxazolyl, 2,5-dihydroxazolyl, 2,3-dihydroisothiazolyl, 4,5-dihydroisothiazolyl, 2, 5-dihydroisothiazolyl, 2, 3 zolilo -dihidropir, 4 , 5-dihydropyrazolyl, 2, 5 -dihidropirazolilo, 2, 3-dihydro-oxazolyl, 4, 5 -dihidrooxazolilo, 2, 5 xazolilo -dihidroo, 2, 3 -dihidrotiazolilo, 4, 5-dihydrothiazolyl 10 2, 5-dihydrothiazolyl, 2 3 -dihidroimidazolilo, 4,5-dihi-c- droimidazolilo, 2, 5 -dihidroimidazolilo, morpholinyl, ridinilo pip, tetrahidropiridacinilo, tetrahydropyrimidinyl tetrahidropiracinilo, 1, 3, 5- etrahidrotriacinilo, 1, 2, 4- tetrahidrotriacinilo, 1, 3 -dihydrooxacinyl, 1,3-di tianilo, tetrahydropyranyl, tetrahydrothiopyranyl, 1, 3-dioxolanyl, 1, 1-dioxo-2, 3, 4, 5 - tetrahydrothienyl, 1, 3 -dihidrooxacinilo, furyl, thienyl, pyrrolyl, Lilo isoxaz, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, im-dazolyl, 1,2,4-oxadiazolyl, 1, 2,4-thiadiazolyl, 1, 2, 4-triazolyl, tetrazolyl, 1,3,4-oxadiazolyl, 1,3-, 4-thiadiazolyl, 1, 3,4-triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-triazinyl, c. 1,2,4-triazinyl, 1,2,4,5-tetracinyl; R4 Ci-Cβ-alkyl, C? -C4-haloalkyl; R3 'R4 means a bridge of 2 or 3 members, saturated or without Saturate, which may contain a sulfur atom, which is oxidized to sulfoxide or sulfone; R5 hydrogen, C? -C4-alkyl, which may be unsubstituted substituted by halogen, C? -C4-alkoxy or phenyl, the phenyl ring being capable of carrying from one to five substituents selected from the group: halogen, C? -C2- alkyl or C? -C2-a coxy; R6 C? -C4 alkyl, which is unsubstituted or substituted by halogen, C? -C4-alkoxy or phenyl, the phenyl ring being able to carry from one to five substituents selected from the group: halogen, C? -C2-alkyl or C C2-alkoxy; R7 hydrogen, Ci-Q-alkyl or Ci-Cj-haloalkyl; n 0, 1 or 2; X hydrogen, chlorine or bromine; Whose claimed compounds may be present in either the trans form or in the cis form, or as mixtures of these isomers.

Preferred are phenyl rings and heterocycles, which may be unsubstituted or carry one to three halogen atoms and / or one or two radicals selected from the group: nitro, cyan methyl, ethyl, trifluoromethyl, methoxy, ethoxy or trifluorome-toxin.

Especially preferred are the compounds of the formula I in Table 1, in which the substituents have the following meanings, either by themselves or in combination.

R1 methyl, ethyl; R2 chloro, methyl, methoxy; R3 hydrogen, methyl, optionally substituted on the phenyl part by fluoro, chloro, methyl or methoxy substituents benzyl, allyl, propin-3-yl, methoxy, ethoxy, 2-methoxyethoxy, methylthio, methylcarbonyl, methoxycarbonyl, dimethyl minocarbonyl, cyano; preferably phenyl event. Substituted by fluoro, chloro, methyl or methoxy, 2-furyl, 3-fluoro, 2-thienyl, 3-thienyl, 4,5-dihydroisoxazol-3-yl, isoxazol-5-yl, isoxaz l-3-yl , pyrazol-1-yl, pyrazol-5-yl, oxazol-2-yl, 4,5-dihydrooxazol-2-yl, 1,3-di xolan-2-yl, 1,3-dithiolan-2- ilo, thiazol-2-yl, thiazol-5-yl, thiazol-4-yl, [1, 2, 4] -triazol-1-yl, [1,4] -oxadiazol-2-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidin-2-yl, pyrimidin-4-yl, 1,3-dioxan-2-yl, 1,3-dithian-2-yl; R4 methyl; R7 hydrogen; n 2; X chlorine.

The benzoylpyrazoles of the formula II, in which R3 means a 5- or 6-membered heterocycle, saturated or unsaturated, optionally subsituted, are new. As intermediate products for obtaining the active herbicidal substances described in the German patent registration application No. 19740494. 4, the benzoylpyrazoles of the formula II are particularly suitable, in which the substituents have the following types: R 1 C? -C 4 alkyl or C? -C 4 -haloalkyl; R2 C? -C4-alkyl, C1-C4-haloalkyl, C? -C4-alkoxy, C1-C4 haloalkoxy, halogen; R3 a 5- or 6-membered, saturated or unsaturated heterocycle unsubstituted or substituted by C? -C4-alkyl, C? -C4-C? -C4-haloalkyl,? C? -C4-halogenoalkoxy or halogen, or selected of the group: tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl, isothiazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl, imidazolidyl, 1,2,4-oxadiazolidinyl, 1, 2, 4-thiadiazolidinyl, 1, 2, 4-triazolidinyl, 1, 3,4-oxadiazolidinyl, 1,3,4-thiazodiazolidinyl, 1,3-triazolidinyl, 2,3-dihydrofuranyl, 2,5-dihydrofuranyl, 2,3-dihydrothienyl, 2,5-dihydrothienyl, 2, 3 dihydropyrrolyl, 2,5-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 4,5-dihydroisoxazolyl, 2,5-dihydroisoxazolyl, 2,5-dihydroxazolyl, 2,3-dihydroisothiazolyl, 4,5-dihydroisothiazolyl, 2, 5 -dihydroisothiazolyl, 2,3-dihydropyrazolyl, 4,5-dihydropyrazolyl, 2,5-dihydropyrazolyl, 2,3-dihydrooxazolyl, 4,5-dihydrooxazolyl, 2,5-dihydrooxazolyl, 2,3-dihydrothiazolyl, 4, 5-dihi Drothiazolinyl, 2,5-dihydrothiazolyl, 2,3-dihydroimidazolyl, 4,5-dihydroimidazolyl, 2,5-dihydroimidazolyl, morpholinyl, piperidinyl, tetrahydropyridazinyl, tetrahydropyrimidinyl, tetrahydropyrazinyl, 1, 3, 5-tetrahydrotriacyl nyl, 1,2,4-tetrahydrotriazinyl, 1,3-dihydrooxacinyl, 1,3-dithynyl, tetrahydropyranyl, tetrahydrothiopyranyl 1,3-dioxolanyl, 1, l-dioxo-2, 3,4,5-tetrahydrothienyl, 1,3-dihydrooxacinyl , furyl, thienyl, pyrrolyl, isoxa lyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, dazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl, 1, 2, 4-triazolyl, tetrazolyl, 1,3 , 4-oxadiazolyl, 1,3, 4-thiadiazolyl, 1,3-triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1, 3, 5-triazinyl, 1, 2, 4-triazinyl, 1, 2, 4,5-tetrathinyl, insbesondere bevo zugt sind: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 10 4, 5-dihydroisoxazol-3-yl, isoxazol-5-yl, isoxazol-3-yl pyrazol-1-yl, pyrazol-5-yl, oxazol-2-yl, 4, 5-dihydro xazol-2-yl, 1,3-dioxolan-2-yl, 1,3-dithiolan-2-yl, thiol-2-yl, thiazol-5-yl, thiazol-4-yl, [1, 2, 4] -triazol-1-yl, [1, 3, 4] -oxadiazol-2-yl, 2-pyridyl, 3-pyridyl-15-diol, 4-pyridyl, pyrimidin-2-yl , pyrimidin-4-yl, 1,3-dioxan-2-yl, 1,3-dithian-2-yl; R 4 C 4 -C 4 alkyl or C 1 -C 4 -haloalkyl; R7 hydrogen, C? ~ C4-alkyl or C? -C4-halogenoalkyl; n 0, 1, 2; C Chlorine, Bromine, 25 Compounds II of Table 2 are especially preferred.

Examples of obtaining: 1) Cis-4- [chloro (2-chloro-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonylphenyl) methylene] -2-methyl-2,4-dihydro-pyrazole-3-on (Tab.l No. 1.20): .0 g of (2-chloro-3- (4,5-dihydroisoxazol-3-yl) -4-methylsu fonylphenyl) (5-hydroxy-l-methyl-lH-pyrazol-4-yl) -methanone 15 ml of toluene are mixed with 2.0 g of phosphoric oxychloride and two drops of dimethylformamide and heated to reflux. Another 1.0 g of phosphoric oxychloride is added and another veu is boiled for 7 h. Then, reaction mixture is introduced into 125 ml of ice water and extracted with methyl tere. -butyl ether. The crude product was purified chromatographically on silica gel with cyclohexane / ethyl acetate / methanol. Yield: 1.3 g of colorless solid (cis isomer). iH-NMR (CDC13): d = 3.27 (s); 3.31 (s); 3.45 (t); 4.57 (t); 7.65 (d); 7.73 (s); 8.15 (d). In addition, the benzoylpyrazole isomer is isolated in the chromatographic purification of the reaction mixture: (5-chloro-l-methyl-pyrazol-4-yl) - (2-chloro-3- (4,5-dihydro-xazol-3-yl) -4-methylsulfonyl-phenyl) -methanone (Tab.2 No. 11.17): 1 H-NMR (CDC13): d = 3.30 (s); 3.45 (t); 3.93 (s), 4.63 (t); 7.61 (d); 7.75 (s); 8.17 (d). 2) Cis-4- [chloro (2-chloro-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonylphenyl) methylene] -2-ethyl-2,4-dihydro-pyrazole-3-on (Tab.l No. 1,119): The compound can be prepared in analogy to example 1. Colorless solid (cis isomer); i-H-NMR (CDC13): d = 1.28 (t); 3.27 (s) 3.46 (t); 3.72 (q), 4.62 (t); 7.64 (d); 7, (s); 8.16 (d). In addition, the benzoylpyrazole isomer is isolated in the chromatographic purification of the reaction mixture: (5-Chloro-1-ethyl-pyrazol-4-yl) - (2-chloro-3- (4,5-dihydroiso xazol-3-yl) -4-methylsulfonyl-phenyl) -methanone (Tab.2 No. 11.56): iH-NMR (CDC13): d = 1.50 (t); 3.28 (s); 3.45 (t); 4.28 (q), 4.63 (t); 7.63 (d); 7.74 (s); 8.18 (d).

) Cis-4- [bromo (2-chloro-3- (4,5-dihydroisoxazol-3-yl) -4-methylsulfonylphenyl) methylene] -2-methyl-2,4-dihydro-pyrazol-3-on ( Tab.l No. 1,466) :: 2.5 g of (2-chloro-3- (4,5-dihydroisoxazol-3-yl) -4-methylsu fonylphenyl) (5-hydroxy-l-methyl-lH-pyrazol-4-yl) -methanone 20 ml of toluene are mixed with 1.87 g of phosphoric oxybromide and two drops of dimethylformamide and boiled for 13 h at reflux. The reaction mixture is then introduced into 50 ° C soda solution and extracted with methyl tere, -butyl ether. The crude product is chromatographically purified in silica gel with cyclohexane / ethyl acetate / methanol. ^ -NMR (CDCI3): d = 3.25 (s); 3.31 (s); 3.43 (m); 4.59 (t); 7.57 (d); 7.63 (s); 8.15 (d).

The benzylidene diazolones of the formula I and the benzoylpyrazes of the formula II indicated in tables 1 and 2 below can be prepared in analogy to the prescriptions indicated in the above synthesis examples. c fifteen twenty o - s.

Table 1: n co or t? i n to r. to t 00 - \ t LO O n LO t or r co co r > co co in p co O? r * or r or OO co r OR to or OR C r s.

Table 2: l CO or r, vo or, cp o cp The compounds I and their salts useful for agriculture are suitable, both in the form of isomeric mixtures, and also in the form of pure isomers, and as herbicides. The herbicidal products containing I are well suited for combating the growth of unwanted plants in areas not intended for cultivation, especially in high amounts of application. In crops, such as wheat, rice, corn, soybeans and cotton are active against harmful grasses and gammas, without causing damage worthy of mention in the cultivation plants This effect occurs mainly with low amounts of application.

Depending on the respective application method, you can use the compounds i or the products containing them in other additional plant crops to eliminate the unwanted plants therein. For example, the following crops come into consideration: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var.

C napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Cartha us 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 herbaceum Gossypium vitifolium), Helianthus annuus. Hevea brasiliensis Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativ Musa spec., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus co munis, Ribes sylestre, Ricinus communis , Saccharum officinarum, Sécale cereale, Solanum tuberosum, So 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 compounds I or the herbicidal products that they contain can be applied before or after the emergency. When the active substances are less tolerated by the crop plants, then application methods can be used in which the herbicidal products are sprayed with the aid of spraying apparatuses in such a way that they do not fall on the leaves of the plants. sensitive cultivation, without only on the leaves of unwanted plants that grow below the first 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 sprayable suspensions, also in the form of suspensions, dispersions or emulsions aqueous, oleic or otherwise, dispersions of oil, pastes, Spray, dusting or granulating agents, by spraying, fogging, spraying, sprinkling or watering. 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 as inert auxiliaries are mineral oil fractions ranging from medium to high boiling point, such as kerosene or diesel oil, in addition, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, such as paraffin, tetrahydronaphthaline. alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, methanol, ethane propanol, butanol, cyclohexanol, cyclohexanone or strongly polar solvents, such as * N-methylpyrrolidone or water.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders or large water dispersible sides by the addition of water. For the obtention of emulsions, pastes or oil dispersions the substances can be homogenized as such or dissolved in an oil or solvent, by means of humectants, adherents, dispersants or emulsifiers, in water. However, it is also possible to prepare, from the active substance, a humectant, adhering agent, dispersant or emulsifier and, optionally, a solvent or an oil, concentrates which can be diluted with water.

Suitable surfactants are alkali metal, alkaline earth metal, ammonium salts of aromatic sulphonic acids, eg lignin sulphonic acid, phenolsulfonic acid, talisulfonic acid and dibutylnaphthalenesulfonic acid, as well as fatty acid, alkyl and alkylaryl sulphonates, alkyether, lauryl ether and fatty alcohol, as well as salts of sulphonated hexa, hepta and octadecanols, as well as fatty alcohol ethers, naphthalene condensates, their fonnation and its derivatives with formaldehyde, naphthalene or acid condensates naphthalenesulfonic acids with phenol and fo maldehyde, polyoxyethylenectylphenol ethers, isooctylphenol, octylphenol or nonylphenol ethoxylates, alkylphenol polyglycols ethers, tributylphenyl polyglycol ethers, alkylaryl polyethylene glycols, isotridecyl alcohol, condensates of fatty alcohol-ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ethers, polyoxypropylene, po-li acetal glycol ether lauryl alcohol, sor bitol 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 soils, such as silica gel, silicic acids, silicic gins, talc, kaolin, limestone, lime, chalk, bolus, clay loess, dolomite, diatomaceous earth, calcium sulfate and magnesium, magnesium oxide, plastics ground, fertilizers, such as ammonium sulphate, ammonium phosphate, ammonium nitrate ureas and vegetable products, such as stone powders, bark powders of trees, wood and nuts, cellulose powders or other solid supports .

The concentrations of the active substances I in the ready formulations can vary widely. The formulations generally contain from 0.001 to 98% by weight, preferably from 0.01 to 95% by weight of at least one active substance. The active substances are used in a purity of 90 bis 100%, preferably 95% up to 100% (according to NMR spectrum).

The compounds I of the invention can be formulated, for example in the following manner: parts by weight of compound No. 1.20 are dissolved in a mixture containing 80 parts by weight of alkylated benzene, 10 parts by weight of the addition product 8 to 10 moles of ethylene oxide to 1 mole of N-monoethanol acid lamide oleic acid, 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 finely distributing therein, an aqueous dispersion containing 0.02% by weight of the active substance is obtained.

II. 20 parts by weight of compound No. 1119 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 oxide of leno to 1 mole. of isooctylphenol and 10 parts by weight of the addition product of 40 moles of ethylene oxide to mol 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 the active substance No. 1466 are dissolved in a mixture consisting of 25 parts in pe cyclohexanone, 65 parts by weight of a mineral oil fraction of the boiling point of 210 to ° C and 10 parts by weight of the addition product of 40 me of ethylene oxide to 1 mole of castor oil. By pouring the solution in 100 000 parts by weight of ag 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. 21.20 are intimately mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene sulfonic acid, 17 parts by weight the sodium salt of a lignin sulphonic acid of a sulphite residual salt and 60 parts by weight of silica gel p. and ground in a hammer mill. By distributing the mixture finely in 20,000 parts by weight water, a spray mixture containing 0.1% by weight of the active substance is obtained V. 3 parts by weight of the active substance No. 1119 are mixed with 97 parts by weight of finely divided kaolin. In this way, a spray agent containing 3% by weight of the active substance is obtained.

SAW. 20 parts by weight of the active substance No. 1466 are intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol-polyglycol ether, 2 parts by weight of the sodium salt of a condensate of phenol sulfonic acid-urea-formaldehyde and 68 parts by weight of a paraffinic mineral oil. A stable oleic dispersion is obtained.

VII. 1 part by weight of compound No. 1.20 is dissolved in a mixture consisting of 70 parts by weight of cyclohexone, 20 parts by weight of ethoxylated isooctylphenol and 1 part by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained.

VIII. 1 part by weight of compound No. 1119 is dissolved in a mixture consisting of 80 parts by weight of cyclohexone and 20 parts by weight of Wettol ® EM 31 (nonionic emulsifier based on ethoxylated castor oil). A stable emulsion concentrate is obtained.

To broaden the spectrum of action and to achieve synergistic effects, the compounds I can be mixed with numerous representatives of other active herbicide and growth regulator groups and applied in conjunction therewith. Examples of suitable mixing components are 1, 2-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anuides, xalkanoic acid (het) aryl and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-aroyl. -l, 3-cyclohexandiones, hetaryl-aryl-ketones, benzylisoxazolidinones, derivatives of rae-ta-CF-phenyl, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexane-1,3-dione derivatives, diacines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanil nas, dinitrophenols, diphenyl ethers, dipyridyls, halogenated carboxylic acids and their derivatives, ureas, 3-phenyluracil imidazoles, imidazolinones, N-phenyl-3, 4, 5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and heteroarylox phenoxypropionates, phenylacetic acid and its derivatives, phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid Ilic and its derivatives, pirim dil ethers, sulfonamides, sulfonylureas, triazines, triazines, triazolinones, triazolecarboxamides and uracils.

Furthermore, it may be useful to apply the compounds I alone in combination with other herbicides also mixed with other plant protection products, for example products for controlling pests or phytopathogenic fungi or bacteria. It is also interesting the miscibility with solutions of mineral salts, which are used to alleviate nutritional deficiencies or d microelements. Non-phytotoxic oils can also be used and oil concentrates.

The amounts of application in active substance I amount depending on the respective application end, the time of year, the target plants and their growth state, to 0.00 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (s.a.).

C Application examples The herbicidal effect of benzylidene diazolones of formula I can be demonstrated by tests in the greenhouse: Plastic pots filled with clayey sand with approx. 3.0% humus as sus¬ deal. The seeds of the test plants are seeded according to the species.

In the pre-emergency treatment, actibas substances suspended or emulsified in water are applied directly after sowing by means of fine distribution nozzles. The containers are irrigated slightly to promote germination and growth, and then the pots are covered with bags of water. Clear plastic until the plants have taken root. With this covering a uniform germination of the test plants is reached, as this is not counteracted by the active substances.

For the treatment after the emergence, the test rooms are cultivated until. they have reached a height of growth of 3 to 15 cm, depending on their growth form, then they are treated with 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 separated germination containers and the seedlings are planted some days before the treatment in the test vessels. The amount of application in the treatments after emergence amount to 0.125 or 0.0625 kg / ha of s.a.

The plants were maintained according to their species at temperatures of 10 to 25 ° C or 20 to 35 ° C. The trial period amounted to 2 to 4 weeks. During this time the plants were taken care of and their reaction to the different treatments was evaluated.

The evaluation is based on a scale of 0 to 100, where 10 means no emergence or total destruction of at least the parts of the plants surfaced, and means no damage or normal development of growth.

In trials in the greenhouse the following plants are used in treatments after emergence: The result shows that, with compound No. 1,119, the harmful plants mentioned above (98% of plant damage) can be combed very effectively, while the useful plant, maize, does not suffer any visible damage (0%). Of damage) The comparative test indicated in Table A shows the improved herbicidal action of compounds 1119 according to the invention, compared to the compound A known from JP-A 61268670 (CA, 106: 209479).

Table A - Tests in the greenhouse with treatments after the emergency 15 20

Claims (6)

1. CLAIMS A benzylidene diazolone of the formula I, where the substituents and the index n have the following meanings: X R is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; R is C1-C4 alkyl, C1-C4 haloalkyl, alkoxy C? -C4, C? -C4 haloalkoxy, halogen, nitro or cyano; 3 R is hydrogen, halogen, nitro, cyano, a group NR5R6, OCOR5, NR5COR6, C02R5, -COSR5, CONR5R6, (C? -C4) alkoxyiminioalkyl, (C? -C4) alkylcarbonyl; the following radicals are unsubstituted or substituted by halogen, C-C4 alkoxy or phenyl, wherein the phenyl ring can carry from 1 to 5 substituents selected from the group consisting of: C1-C2 alkyl and C1-C2 alkoxy; C1-C4 alkyl, C1-C4 alkoxy, C-C4 alkylthio, C2-C6 alkenyl, C2-C6 alkynyl; the following radicals are unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, halogen, phenyl, cyano, C 4 -C 4 alkoxycarbonyl or nitro: phenyl, phenoxy, a saturated or unsaturated 5 or 6 membered heterocycle which may contain up to 4 nitrogen atoms and / or up to 2 oxygen or sulfur atoms as ring members; R4 is C? -C? Alkyl or C? -C haloalkyl; or R 3 and R 4 form a saturated or unsaturated, optionally substituted, two or three membered bridge which may contain a sulfur atom, which may be oxidized to obtain sulfoxide or sulfone; R is hydrogen, C? -C alkyl, which is unsubstituted or substituted by halogen, C? -C4 alkoxy or phenyl, where the phenyl ring can carry from 1 to 5 substituents selected from the group consisting of halogen, alkyl of C? -C2 and C? -C2 alkoxy; R is C -C alkyl which is unsubstituted or substituted by halogen, C? -C4 alkoxy or phenyl, where the phenyl ring can carry from 1 to 5 substituents selected from the group consisting of halogen, C? -C2 alkyl and C1-C2 alkoxy; R is hydrogen, C? -Cg alkyl or C? -C4 haloalkyl; n is 0, 1 or 2; X is hydrogen, chlorine or bromine; wherein the claimed compounds may be present in the trans form and in the cis form or as a mixture of these isomers. A benzylidenepyrazolone of formula I, as claimed in claim 1 wherein X is chloro. A benzylidenepyrazolone of the formula I, as claimed in claim 1, in which 7R is hydrogen. A benzylidenepyrazolone of formula I, as claimed in claim 1 wherein 2 R "is C -C4 alkyl, C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy or halogen; a 5- or 6-membered heterocycle, saturated or unsaturated, unsubstituted or substituted by C-C4 alkyl, C? -C4 alkoxy, C? -C4 haloalkyl, C? -C4 haloalkoxy or halogen selected from the group consisting of in: tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl, isothiazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, 1,2,4-oxadiazolidinyl, 1, 2, 4-thiadiazolidinyl, 1,2,4-triazolidinyl, 1, 3, 4 oxadiazolidinyl, 1,3,4-thiadiazolidinyl, 1,3-triazolidinyl, 2,3-dihydrofuranyl, 2,5-dihydrofuranyl, 2,3-dihydrothienyl, 2,5-dihydrothienyl, 2,3-10-dihydropyrrolyl, , 5-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 4,5-dihydroisoxazolyl, 2,5-dihydroisoxazolyl, 2,5-dihydroxazolyl, 2,3-dihydroisothiazolyl, 4,5-dihydroisothiaz olyl, 2,5-dihydroisothiazolyl, 2,3-dihydropyrazolyl, 4,5-15 dihydropyrazolyl, 2,5-dihydropyrazolyl, 2,3-dihydrooxazolyl, 4,5-dihydrooxazolyl, 2,5-dihydrooxazolyl, 2,3-dihydrothiazolyl 4,5-dihydrothiazolyl, 2,5-dihydrothiazolyl, 2,3-dihydroimidazolyl, 4,5-dihydroimidazolyl, 2,5-20-dihydroimidazolyl, morpholinyl, piperidinyl, tetrahydropyridazinyl, tetrahydropyrimidinyl, tetrahydropyrazinyl, 1,3,5-tetrahydrotriazinyl, 1, 2, 4-tetrahydrotriazinyl, 1,3-dihydrooxazinyl, 1,3-dithianyl, tetrahydropyranyl, Tetrahydrothiopyranyl, 1,3-dioxolanyl, 1,1-dioxo-2,3, 5-tetrahydrothienyl, 1,3-dihydrooxazinyl, furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, 1, 2,4-oxadiazolyl, 1,2,4-thiadiazolyl, 1,2-triazolyl, tetrazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,3-triazolyl, pyridyl, pyridazinyl , pyrimidinyl, pyrazinyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,4,5-tetrazinyl; R 'is C? -C4 alkyl; R is hydrogen or C?-C 4 alkyl which is unsubstituted or substituted by halogen or C?-C 4 alkoxy; R is C 1 -C 4 alkyl which is unsubstituted or substituted by halogen or C 1 -C 4 alkoxy; R is hydrogen; n is 2; X is hydrogen or chlorine. A composition containing an herbicidally effective amount of at least one benzylidenepyrazolone of the formula I, as mentioned in claim 1, and auxiliaries commonly used in the formulation of crop protection agents. A process for preparing active compositions as herbicides as mentioned in claim 5, which consists of mixing an herbicidally effective amount of at least one benzylidene pyrazolone I, as mentioned in claim 1, and the auxiliaries commonly used in the formulation of agents for crop protection. A method for controlling unwanted vegetation, which consists of allowing an herbicidally effective amount of at least one benzylidene pyrazolone I, as mentioned in claim 1, to act on plants, their habitat and / or on the seeds. A benzoylpyrazole of the formula II: wherein the substituents have the following meanings: R is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; R is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C alkoxy, C 1 -C haloalkoxy or halogen; R ° is a 5- or 6-membered, saturated or unsaturated heterocycle, unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 4 -C haloalkoxy or halogen selected from the group it consists of: tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl, isothiazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, 1,2,4-oxadiazolidinyl, 1, 2,4-thiadiazolidinyl, 1,2,4-triazolidinyl, 1, 3, 4 -oxadiazolidinyl, 1,3,4-10-thiadiazolidinyl, 1,3-triazolidinyl, 2,3-dihydrofuranyl, 2,5-dihydrofuranyl, 2,3-dihydrothienyl, 2,5-dihydrothienyl, 2,3-dihydropyrrolyl, 2,5-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 4,5-dihydroisoxazolyl, 2,5-dihydroisoxazolyl, 2,5-dihydroxazolyl, 2,3-dihydroisothiazolyl, 4,5-dihydroisothiazolyl, 2,5-dihydroisothiazolyl, 2 , 3-dihydropyrazolyl, 4,5-dihydropyrazolyl, 2,5-dihydropyrazolyl, 2,3-dihydrooxazolyl, 4,5-dihydrooxazolyl, 2,5-20-dihydrooxazolyl, 2,3-dihydrothi azolyl, 4,5-dihydrothiazolyl, 2,5-dihydrothiazolyl, 2,3-dihydroimidazolyl, 4,5-dihydroimidazolyl, 2,5-dihydroimidazolyl, orpholinyl, piperidinyl, tetrahydropyridazinyl, tetrahydropyrimidinyl, 25-tetrahydropyrazinyl, 1, 3, 5-tetrahydrotriazinyl, 1, 2,4-tetrahydrotriazinyl, 1,3-dihydrooxazinyl, 1,3-dithianyl, tetrahydropyranyl, tetrahydrothiopyranyl, 1,3-dioxolanyl, 1,1-dioxo- 2,3 , 4,5-tetrahydrothienyl, 1,3-dihydrooxazinyl, furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl, 1,2 , 4-triazolyl, tetrazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,3-triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-triazinyl, 1,2 , 4-triazinyl, 1,2,4,5-tetrazinyl; 4 R is C -C alkyl or C 1 -C 4 haloalkyl; 7 R is hydrogen, C1-C4 alkyl or haloalkyl of C? C4; n is 0, 1, 2; X 'is chlorine or bromine. A process for preparing benzylidenepyrazones of the formula I as mentioned in claim 1 and benzoylpyrazoles of the formula II, as mentioned in claim 8, which comprises reacting the benzoylpyrazolones of the formula V, wherein the substituents are as defined in claim 1 or claim 8 with acyl halides. SUMMARY OF THE INVENTION. Benzylidene diazolones of the formula I 15 in which the substituents and the index have the following meanings: R1 C? -C6-alkyl event. sust R2 C? -C6 ~ alkyl event. sust., C? -C6-alkoxy event. Substance, halogen, nitro, cyano; R3 hydrogen, halogen, nitro, cyano, a group NR5R6, OCOR NR5COR6, C02R5, -COSR5, -CONR5R6, C? -C4-alkoxyiminoalqui 25 Cx-Cg-alkylcarbonyl, C? -C6-alkyl event. sust., Cx-Cg-alkoxy event. sust., C? -C6-alkylthio event. sust., C2-C6-alkenyl event. .sub.
2. 2, C2-C6-alkynyl event. your phenyl event. sust., phenoxy event. sust., a heterocyclic of 5 or 6 members, saturated or unsaturated, event. sust Which may contain up to 4 nitrogen atoms, and / or sulfur atom as ring members; R4 C? -Cg-alkyl, C? -C4-halogenoalkyl; O well R3 'R4 a bridge of 2 or 3 members, saturated or unsaturated, event. sust, which may contain a sulfur atom, which can be oxidized in sulphoxide or sulfone; 5 hydrogen C? -Cg-alkyl event. sust .; R6 C? -Cg-alkyl event. sust .; R7 hydrogen, C? -Cg-alkyl or C? -C4-halogenoalkyl; n 0.1 or 2; X hydrogen, chlorine or bromine; Whose claimed compounds may be present in either the trans form, or in the cis form, or represent a mixture of these isomers.