WO2000068233A1

WO2000068233A1 - Cyclohexenone dioxothiochromanoyl derivatives

Info

Publication number: WO2000068233A1
Application number: PCT/EP2000/003964
Authority: WO
Inventors: Klaus Langemann; Matthias Witschel; Ernst Baumann; Wolfgang Von Deyn; Steffen Kudis; Guido Mayer; Ulf Misslitz; Ulf Neidlein; Martina Otten; Karl-Otto Westphalen; Helmut Walter
Original assignee: Basf Aktiengesellschaft
Priority date: 1999-05-07
Filing date: 2000-05-03
Publication date: 2000-11-16
Also published as: EP1181297A1; JP2002544134A; AU5210900A; CA2373165A1

Abstract

The invention relates to cyclohexenone dioxothiochromanoyl derivatives of formula (I), in which: X forms an -O-(CH2)n -chain that can be substituted, or forms a -(CH2)p - chain that can be substituted and/or interrupted by an oxygen or sulfur; n ranges from 1 to 5, and; p ranges from 2 to 6. The invention also relates to the salts of said cyclohexenone dioxothiochromanoyl derivatives that can be used for agricultural purposes, to methods and intermediate products for producing said cyclohexenone dioxothiochromanoyl derivatives, to agents which contain the same, as well as to the use of these derivatives or of agents which contain these derivatives for controlling unwanted plants.

Description

Cyclohexenone dioxothiochromanoyl derivatives

description

The present invention relates to new cyclohexenone dioxothio-chromanoyl derivatives of the formula I,

in which the variables have the following meanings:

R ^{i is} hydrogen, nitro, halogen, cyano, C ₁ -C ₆ -alkyl, Ci-C _δ -haloalkyl, Cι-C ₆ -alkoxy, Ci-C _δ -haloalkoxy, Cι-C ₆ -alkylthio, Ci-C _δ - Haloalkylthio, -C-C ₆ alkyl sulfinyl, Ci-C _δ -haloalkyl sulfinyl, Ci-C _ö alkyl sulfonyl, Ci-Cg-haloalkyl sulfonyl, aminosulfonyl, N- (-C ₆ alkyl) aminosulfonyl, N, N-Di- (-C-C ₆ -alkyl) - aminosulfonyl, N- (Ci-C _δ -alkylsulfonyl) -amino, N- (Ci-C _ö -haloalkylsulfonyl) -amino, N- (Ci-Cβ-alkyl) - N- (-C-C ₆ alkylsulfonyl) amino or N- (-C-C ₆ alkyl) -N- (Ci-Cβ-haloalkylsulfonyl) amino;

R2 Ci-Ce alkyl, -C - C ₆ haloalkyl, -C -C ₆ alkoxy or Ci - C _Ö - haloalkoxy;

R ^{3 is} hydrogen, -CC ₆ alkyl or halogen;

X is a -O- (CH) _n chain which may be substituted from the following group by one to three radicals: halogen, cyano, C ₄ -alkyl, C ₄ haloalkyl or Ci-C ₄ alkoxycarbonyl , -

or

a - (CH) _p chain which can be interrupted by an oxygen or sulfur and / or can be substituted by one to four radicals from the following group: Halogen, cyano, C ₄ -C ₄ alkyl, C ₄ -C ₄ haloalkyl or Ci - C ₄ alkoxycarbonyl;

m 0 to 4;

n 1 to 5;

p 2 to 6;

R ⁴ , R ^{8 are} hydrogen, -CC ₄ alkyl or C ₁ -C ₄ alkoxycarbonyl;

R ⁵ , R ⁷ , R ^{9 are} hydrogen or -CC alkyl;

R ⁶ is hydrogen, halogen, hydroxy, Ci-C _ö -alkyl, C ₆ -haloalkyl, di- (Cι-C ₆ -alkoxy) methyl, (Cι-C ₆ -alk- oxy) - (Cι-C ₆ -alkylthio) -methyl, di- (-C-C ₆ -alkyl-thio) methyl, -C-C ₆ -alkoxy, Ci-C _ö -haloalkoxy, -C-C ₆ -alkylthio, -C-C ₆ -haloalkylthio, Cι -C ₆ -alkyl-sulfinyl, -C-C ₆ -haloalkylsulfinyl, -C-C ₆ -alkyl-sulfonyl, Ci-Cβ-haloalkylsulfonyl, Ci-Cβ-alkoxycarbonyl, Ci-C ₆ -haloalkoxycarbonyl;

1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3 oxathian-2-yl, 1,3-dithiolan-2-yl or 1, 3-dithian-2-yl, the latter six

Radicals can be substituted by one to three C 1 -C ₄ -alkyl radicals;

or

R ⁵ and R ⁶ or R ⁶ and R ⁹ together form a π bond or a Ci-Cs-alkyl chain which can carry one to three radicals from the following group: halogen, cyano, -CC alkyl, C,-C _4th -Halogenalkyl or C ₁ -C ₄ alkoxycarbonyl, from;

or

R ⁵ and R ⁹ together form a Cτ _. -C ₄ alkyl chain, which can carry one to three radicals from the following group: halogen, cyano, -C-C ₄ alkyl, -C-C ₄ haloalkyl or C ₁ -C ₄ alkoxycarbonyl, from;

or R ⁶ and R ⁷ together form a -0- (CH) _q -O-, -0- (CH) _q -S-, -S- (CH) _q -S-, -O- (CH ₂ ) _r - or -S- (CH ₂₎ _r chain which can be substituted from the following group by one to three radicals: halogen, cyano, C -alkyl, C ₄ haloalkyl or C ₁ -C ₄ alkoxycarbonyl;

or

R ⁶ and R ⁷ together with the carbon to which they are attached form a carbonyl group;

q 2 to 4;

r 1 to 5;

and their agriculturally useful salts.

In addition, the invention relates to processes and intermediates for the preparation of compounds of the formula I, compositions which contain them and the use of these derivatives or compositions containing them for combating harmful plants.

From the literature, for example from DE-A 19 532 311 and WO 97/08164, dioxothiochroman derivatives are those which are substituted with an optionally substituted (1-hydroxy-3-oxo-cyclohex-1-en-2-yl) carbonyl Rest are known. However, the herbicidal properties of the compounds known hitherto and the tolerances to crop plants can only satisfy to a limited extent. It was therefore the object of this invention to find new, biologically, in particular herbicidally active, compounds with improved properties.

Accordingly, the cyclohexenone dioxothiochromanoyl derivatives of the formula I and their herbicidal activity have been found.

Furthermore, herbicidal compositions have been found which contain the compounds I and have a very good herbicidal action. In addition, processes for the preparation of these compositions and processes for controlling unwanted vegetation using the compounds I have been found.

Depending on the substitution pattern, the compounds of the formula I can contain one or more centers of chirality and are then present as enantiomers or mixtures of diastereomers. The invention relates both to the pure enantiomers or diastereomers and to their mixtures. The compounds of the formula I can also be in the form of their tautomers, where I represents the tautomeric forms I 'and I ".

The compounds of the formula I can also be present in the form of their agriculturally useful salts, the type of salt generally not being important. In general, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the herbicidal activity of the compounds I

The cations used are in particular ions of the alkali metals, preferably lithium, sodium and potassium, the alkaline earth metals, preferably calcium and magnesium, and the transition metals, preferably manganese, copper, zinc and iron, and ammonium, where one to four hydrogen atoms by Cχ- C ₄ alkyl, hydroxy -CC ₄ alkyl, -C ₄ alkoxy -CC-C ₄ - alkyl, hydroxy-C ₄ -C ₄ alkoxy-Cχ-C ₄ alkyl, phenyl or benzyl replaced can be, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2 - (2-hydroxyeth-1-oxy) eth-1-ylammonium, di (2-hydroxyeth-1-yl) ammonium, trimethylbenzylammonium , further phosphonium ions, sulfonium ions, preferably tri (C 1 -C ₄ -alkyl) sulfonium and sulfoxonium ions, preferably tri (C 1 -C ₄ alkyl) sulfoxonium, into consideration. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C ₁ -C ₄ alkane acids, preferably formate, Acetate, propionate and butyrate.

The organic molecule parts mentioned for the substituents R ^ —R ⁹ and all other radicals listed in this application represent collective terms for individual lists of the individual group members. All hydrocarbon chains, ie all alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio -, Haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, N-alkylaminosulfonyl, N, N-dialkylaminosulfonyl, N-alkylsulfonylamino, N-haloalkylsulfonylamino, N-alkyl-N-alkylsulfon -, N-Alkyl-N-haloalkylsulfonylamino, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkyl, dialkoxymethyl, dialkylthiomethyl, (alkoxy) (alkylthio) methyl, trialkylsulfonium and trialkylsulfoxonium radicals can be straight-chain or branched. Unless stated otherwise, halogenated substituents preferably carry one to five identical or different halogen atoms. Halogen is fluorine, chlorine, bromine or iodine.

Furthermore, for example:

Cι-C ₄ alkyl, and the alkyl moieties of hydroxy-Cι-C * ₄ alkyl, tri (C ₁ -C ₄ -alkyl) sulfonium and tri _{(Cι-C4-alkyl)} sulfoxonium: for example, methyl, ethyl, Propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl;

Cι-C ₆ alkyl, and the alkyl moieties of N- (Ci-C ₆ alkyl) -N- (Cι-C ₆ alkylsulfonyl) amino, N- (Ci-Cβ-alkyl) -N- _(C. -C ₆ -haloalkylsulfonyl) amino: -C-C ₄ -Al yl, as mentioned above, and for example pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl , 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl , 2, 2-dimethylb tyl, 2, 3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1,2-trimethylpropyl, 1-ethyl-l-methylpropyl or l-ethyl- 3-methylpropyl;

C ₁ -C ₄ haloalkyl: a Cχ-C ₄ alkyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, Trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorofluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2, 2-difluoroethyl, 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-bromopropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl, 3, 3, 3-trichloropropyl, 2, 2, 3, 3, 3-pentafluoropropyl, Heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;

-C-C ₆ haloalkyl, and the haloalkyl parts of N-Ci-C _δ -haloalkylamino: -C-C-haloalkyl, as mentioned above, and for example 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl or dodecafluorohexyl;

Ci-C _δ- alkoxy, as well as the alkoxy parts of di- (Ci-Cβ-alkoxy) methyl and (C _I -C _Ö -alkoxy) - (Ci-Cβ-alkylthio) methyl: e.g. methoxy, ethoxy, propoxy, 1- Methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1, 1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2, 2- Dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2, 2-dimethylbutoxy, 2, 3-dimethylbutoxy, 3, 3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1, 2, 2-trimethylpropoxy, 1-ethyl-l-methylpropoxy or l-ethyl- 2-methylpropoxy;

Cχ-C ₆ haloalkoxy: a Ci-C _δ alkoxy radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethoxy,

Difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2, 2-difluoroethoxy, 2, 2, 2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2- Chloro-2, 2-difluoroethoxy, 2,2-di-chloro-2-fluoroethoxy, 2, 2, 2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2- Bromopropoxy, 3-Bromopropoxy, 2, 2-Difluorpropoxy, 2, 3-Difluorpropoxy, 2, 3-Dichlorpropoxy, 3, 3, 3-Trifluorpropoxy, 3,3,3-Trichlorpropoxy, 2, 2, 3, 3, 3- Pentafluoropropoxy, heptafluoropropoxy, 1- (fluoromethyl) -2-fluoroethoxy, 1- (chloromethyl) -2-chloroethoxy, 1- (bromomethyl) -2-bromethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy, nonafluorobutoxy, 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy;

- C ₆ -C ₆ -alkylthio and the alkyl hioreste of (-C -C ₆ -alkoxy) -

(Ci-C ₆ -alkylthio) methyl and di- (-C-C ₆ -alkylthio) methyl: e.g.

Methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1, 1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2, 2-dimethylpropyl 1-Ethylpropylthio, Hexylthio, 1, 1-Dirnethylpropylthio, 1, 2-Dirnethylpropylthio, 1-Methylpentylthio, 2-Methylpentylthio, 3-Methylpentylthio, 4-Methylpentylthio, 1, 1-Dimethylbutylthio, 1, 2-Dimethylb tylthio , 3-dimethylbutylthio, 2, 2-dimethylbutylthio, 2,3-dimethylbutylthio, 3, 3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1, 1, 2-trimethylpropylthio, 1,2,2-trimethylpropylthio , 1-ethyl-l-methylpropylthio or l-ethyl-2-methylpropylthio;

Ci-C _δ -haloalkylthio: a Ci-Cβ-alkylthio radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, Bromodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio,

2, 2-difluoroethylthio, 2, 2, 2-trifluoroethylthio, 2,2,2-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2, 2-di-fluoroethylthio, 2, 2-dichloro 2-fluoroethylthio, pentafluoroethylthio, 2-fluoropropylthio, 3-fluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 2, 2-difluoropropylthio, 2, 3-difluoropropylthio 3-dichloropropylthio, 3, 3, 3-trifluoropropylthio, 3,3,3-trichloropropylthio, 2, 2, 3, 3, 3-pentafluoropropylthio, heptafluoropropylthio, 1- (fluoromethyl) -2-fluoroethylthio, l- (Chloromethyl) -2-chloroethylthio, 1- (bromomethyl) -2-bromethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio, non-fluorobutylthio, 5-fluoropentylthio, 5-chloropentylthio, 5-bromopentylthio, 5-iodopentylthio, undecafluoropentylthio, 6-fluoro-hexylthio, 6-chlorohexylthio, 6-bromohexylthio, 6-iodohexylthio or dodecafluorhexylthio;

C ₁ -C ₆ alkylsulfinyl (C ₁ -C ₆ alkyl-S (= 0) -): for example methylsulfinyl, ethylsulfinyl, propylsulfinyl, 1-methylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1, 1-dimethylethylsulfinyl , Pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, 1, 1-dirnethylpro- pylsulfinyl, 1, 2-dimethylpropylsulfinyl, hexylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1, 1-dimethylbutylsulfinyl, 1, 2-dimethylbutylsulfinyl, 1, 3-dimethyl 2-dimethylbutylsulfinyl, 2, 3-dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1, 1, 2-trimethylpropylsulfinyl, 1, 2, 2-trimethylpropylsulfonyl, 1-ethyl l-methylpropylsulfinyl or l-ethyl-2-methylpropylsulfinyl;

Ci-Cβ-haloalkylsulfinyl: Cχ-C ₆ -alkylsulfinyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethyl-sulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethylsulfi- 2-fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2, 2-difluoroethylsulfinyl, 2,2, 2-trifluoroethylsulfinyl, 2,2, 2-trichloroethylsulfinyl, 2-chloro-2-fluoroethylsulfinyl, 2- Chloro-2, 2-difluoroethylsulfinyl, 2, 2-dichloro-2-fluoroethylsulfinyl, pentafluoroethylsulfinyl, 2-fluoropropylsulfinyl, 3-fluoropropylsulfinyl, 2-chloropropylsulfinyl, 3-chloropropylsulfinyl, 2-bromopropylsulfinyl, 3-bromopropyl 2, 2-difluoropropylsulfinyl, 2, 3-difluoropropylsulfinyl, 2,3-dichloropropylsulfinyl, 3, 3, 3-trifluoropropylsulfinyl, 3, 3, 3-trichloropropylsulfinyl, 2, 2, 3, 3, 3-pentafluoropropylsulfinyl, Heptafluoropropylsulfinyl, 1- (fluoromethyl) -2-fluoroethylsulfine yl, 1- (chloromethyl) -2-chloroethylsulfinyl, 1- (bromomethyl) -2-bromomethylsulfinyl, 4-fluorobutylsulfinyl, 4-chlorobutylsulfinyl, 4-bromobutylsulfinyl, non-fluorobutylsulfinyl, 5-fluoropentylsulfinyl, 5-chloropentylsulfinyl finyl, 5-bromopentylsulfinyl, 5-iodopentylsulfinyl, undecafluoropentylsulfinyl, 6-fluorohexylsulfinyl, 6-chlorohexylsulfinyl, 6-bromohexylsulfinyl, 6-iodohexylsulfinyl or dodecafluorohexylsulfinyl;

Cι-C ₆ alkylsulfonyl (Cι-C ₆ alkyl-S (= 0) ₂ -), and the alkyl - sulfonyl radicals of N- (Ci-C _δ alkylsulfonyl) amino and N- (Cι-C ₆ - Alkyl) -N- (Ci-Cβ-alkylsulfonyl) amino: for example methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1, 1-dimethylethylsulfonyl, pentylsulfonyl, pentylsulfonyl, pentylsulfonyl, pentylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 1, 1-dimethylpropylsulfonyl, 1, 2-dimethylpropylsulfonyl, 2, 2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpenton

3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1, 1-dimethylbutylsulfonyl, 1, 2-dimethylbutylsulfonyl, 1, 3-dimethylbutyl- sulfonyl, 2, 2-dimethylbutylsulfonyl, 2, 3-dimethylbutylsulfonyl, 3, 3-dimethylbutylsulfonyl, 1-Ξthylbutylsulfonyl, 2-ethylbutylsulfonyl, 1, 1, 2-trimethylpropylsulfonyl,

1,2, 2-trimethylpropylsulfonyl, 1-ethyl-l-methylpropylsulfonyl or l-ethyl-2-methylpropylsulfonyl;

Ci-Cβ-haloalkylsulfonyl, and the haloalkyl radicals of N- (Ci-C _δ -haloalkylsulfonyl) -amino and N- (Cι-C ₆ -alkyl) -N- (Ci-C _δ -haloalkylsulfonyl) -amino: a Ci Cε-alkylsulfonyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonyl, 2-fluoroethylsulfonylsulfonyl, 2-fluoroethylsulfonyl, , 2-iodoethylsulfonyl, 2, 2-difluoroethylsulfonyl, 2, 2, 2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2, 2-dichloro-2-fluoroethylsulfonyl , 2, 2, 2-trichloroethylsulfonyl, pentafluoroethylsulfonyl, 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 2, 2-propylsulfonyl, 2, 2-propylsulfonyl , 2, 3-dichloropropylsulfonyl,

3.3, 3-trifluoropropylsulfonyl, 3,3, 3-trichloropropylsulfonyl, 2,2,3,3, 3-pentafluoropropylsulfonyl, heptafluoropropylsulfonyl, 1- (fluoromethyl) -2-fluoroethylsulfonyl, 1- (chloromethyl) -2-chloroethylsulfonyl, 1- (Bromomethyl) -2-bromomethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl, nonafluorobutylsulfonyl, 5-fluoropentylsulfonyl, 5-chloropentylsulfonyl, 5-bromopentylsulfonylsulfonylsulfonyl, 5-iodonylsulfonyl, 5-iodonylsulfonyl 6-iodohexylsulfonyl or dodecafluorohexylsulfonyl;

(Ci-C _ö -alkylamino) sulfonyl: for example methylaminosulfonyl, ethylaminosulfonyl, propylaminosulfonyl, 1-methylethylaminosulfonyl, B tylminosulfonyl, 1-methylpropylaminosulfonyl,

2-methylpropylaminosulfonyl, 1, 1-dimethylethylaminosulfonyl, pentylaminosulfonyl, 1-methylb tylaminosulfonyl, 2-methylbutylaminosulfonyl, 3-methylbutylaminosulfonyl, 2, 2-dimethylpropylaminosulfonyl, 1-ethylpropylylamosulfonyl, 1-methylylamosulfonyl, 1-methylylosulfonyl, 1-hexylaminosulfonyl , 2-dimethylpropylaminosulfonyl, 1-methylpentylaminosulfonyl, 2-methylpentylaminosulfonyl, 3-methylpentylaminosulfonyl, 4-methylpentylaminosulfonyl, 1, 1-dimethylbutylaminosulfonyl, 1,2-dimethylbutylaminosulfonyl, 1, 3 -Dimethylbutylaminosulfonyl, 2, 3-dimethylbutylaminosulfonyl, 3, 3-dimethylbutylaminosulfonyl, 1-ethylbutylaminosulfonyl, 2-ethylbutylaminosulfonyl, 1, 1, 2-trimethylpropylamino- sulfonyl, 1, 2, 2-trimethylpropylaminosulfonyl, 1-ethyl-l-methylpropylaminosulfonyl or l-ethyl-2-methylpropylaminosulfonyl;

Di- (-C ₆ -alkyl) -aminosulfonyl: for example N, N-dimethylaminosulfonyl, N, N-diethylaminosulfonyl, N, N-di- (1-methylethyl) aminosulfonyl, N, N-dipropylaminosulfonyl, N, N -Dibuylaminosulfonyl, N, N-Di- (1-methylpropyl) -aminosulfonyl, N, N-Di- (2-methyl ^■ propyl) -aminosulfonyl, N, N-Di- (1, 1-dimethylethyl) - aminosulfonyl, N-ethyl-N-methylaminosulfonyl, N-methyl-N-propylaminosulfonyl, N-methyl-N- (1-methylethyl) aminosulfonyl, N-butyl-N-methylaminosulfonyl, N-methyl-N- (1-methyl-propyl) -aminosulfonyl, N-methyl-N- (2-methylpropyl) -aminosulfonyl, N- (1, 1-dimethylethyl) -N-methylaminosulfonyl, N-ethyl-N-propylaminosulfonyl, N-ethyl- N- (1-methylethyl) aminosulfonyl, N-butyl-N-ethylaminosulfonyl, N- ethyl-N- (1-methylpropyl) aminosulfonyl, N-ethyl-N- (2-methylpropyl) aminosulfonyl, N- Ethyl-N- (1,1-dimethylethyl) aminosulfonyl, N- (1-methylethyl) -N-propylaminosulfonyl, N-butyl-N-propylaminosulfonyl, N- (1-methylpropyl) -N-propylaminosulfonyl, N- (2-methylpropyl) -N-propyl aminosulfonyl, N- (1, 1-dimethylethyl) -N-propylaminosulfonyl, N-butyl-N- (1-methylethyl) -aminosulfonyl, N- (1-methylethyl) -N- (1-methyl-propyl) -aminosulfonyl, N- (1-Methylethyl) -N- (2-methylpropyl) aminosulfonyl, N- (1, 1-dimethylethyl) -N- (1-methylethyl) aminosulfonyl, N-butyl-N- (1-methylpropyl ) -aminosulfonyl, N-butyl-N- (2-methylpropyl) -aminosulfonyl, N-butyl-N- (1, 1-dimethylethyl) -aminosulfonyl, N- (1-methylpropyl) -N- (2-methylpropyl ) -aminosulfonyl, N- (1, 1-dimethyl-ethyl) -N- (1-methylpropyl) -aminosulfonyl, N- (1, 1-dimethylethyl) -N- (2-methylpropyl) -aminosulfonyl, N-methyl- N-pentyl-aminosulfonyl, N-methyl-N- (1-methylb tyl) -aminosulfonyl, N-methyl-N- (2-methylbutyl) -aminosulfonyl, N-methyl-N- (3-methyl-butyl) -aminosulfonyl , N-methyl-N- (2,2-dimethylpropyl) aminosulfonyl, N-methyl-N- (1-ethylpropyl) aminosulfonyl, N-methyl-N-hexylaminosulfonyl, N-methyl-N- (1, 1-dimethylpropyl) amino sulfonyl, N-methyl-N- (1, 2-dimethylpropyl) amino sulf onyl, N-methyl-N- (1-methylpentyl) aminosulfonyl, N-methyl-N- (2-methylpentyl) aminosulfonyl, N-methyl-N- (3-methylpentyl) aminosulfonyl, N- Methyl-N- (4-methylpentyl) aminosulfonyl, N-methyl-N- (1,1-dimethylbutyl) aminosulfonyl, N-methyl-N- (1,2-dimethylb tyl) aminosulfonyl, N-methyl -N- (1, 3-dimethylbutyl) -aminosulfonyl, N-methyl-N- (2, 2-dimethylbutyl) -aminosulfonyl, N-methyl-N- (2, 3-dimethylbutyl) -aminosulfonyl, N-methyl -N- (3, 3-dimethylbutyl) aminosulfonyl, N-methyl-N- (1-ethylbutyl) aminosulfonyl, N-methyl-N- (2-ethylbutyl) aminosulfonyl, N-methyl-N- (1, 1, 2-trimethylpropyl) aminosulfonyl, N-methyl-N- (1,2,2-trimethylpropyl) aminosulfonyl, N-methyl-N- (1-ethyl-l-methylpropyl) aminosulfonyl, N-methyl-N- (l-ethyl-2-methylpropyl ) aminosulfonyl, N-ethyl-N-pentiaminesulfonyl, N-ethyl-N- (1-methylb tyl) aminosulfonyl, N-ethyl-N- (2-methylbutyl) aminosulfonyl, N-ethyl-N- ( 3-methyl-b tyl) -aminosulfonyl, N-ethyl-N- (2,2-dimethylpropyl) -aminosulfonyl, N-ethyl-N- (1-ethylpropyl) -aminosulfonyl, N-ethyl-N-hexylaminosulfonyl, N- Ethyl-N- (1, 1-dimethylpropyl) aminosulfonyl, N-ethyl-N- (1, 2-dimethylpropyl) aminosulfonyl, N-ethyl-N- (1-methylpentyl) aminosulfonyl, N-ethyl-N- (2-methyl-pentyl) aminosulfonyl, N-ethyl-N- (3-methylpentyl) aminosulfonyl, N-ethyl-N- (4-methylpentyl) aminosulfonyl, N-ethyl-N- (1, 1-dimethylbutyl ) -aminosulfonyl, N-ethyl-N- (1, 2-dimethylbutyl) -aminosulfonyl, N-ethyl-N- (1, 3-dimethylbutyl) -aminosulfonyl, N-ethyl-N- (2, 2-dimethylbutyl ) -aminosulfonyl, N-

Ethyl-N- (2,3-dimethylbutyl) -aminosulfonyl, N-ethyl-N- (3,3-dimethylbutyl) -aminosulfonyl, N-ethyl-N- (1-ethylbutyl) -aminosulfonyl, N-ethyl-N- (2-ethylbutyl) aminosulfonyl, N-ethyl-N- (1, 1, 2-trimethylpropyl) aminosulfonyl, N-ethyl-N- (1,2, 2-ri-methylpropyl) aminosulfonyl, N-ethyl- N- (1-ethyl-1-methyl-propyl) aminosulfonyl, N-ethyl-N- (l-ethyl-2-methylpropyl) aminosulfonyl, N-propyl-N-pentylaminosulfonyl, N-butyl-N-pen- tylaminosulfonyl, N, N-dipentylaminosulfonyl, N-propyl-N-hexylaminosulfonyl, N-butyl-N-hexylaminosulfonyl, N-pentyl-N-hexylaminosulfonyl or N, N-dihexylaminosulfonyl;

C ₁ -C ₄ alkoxycarbonyl: methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1-methylethoxycarbonyl, butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl or 1, 1-dimethylethoxycarbonyl;

(Cχ-C ₆ -alkoxy) carbonyl: (C ₁ -C ₄ -alkoxy) carbonyl, as mentioned above, and for example pentoxycarbonyl, 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2, 2-dimethylprooxycarbonyl, 1 -Ethylpropoxycarbonyl, Hexoxycarbonyl, 1, 1-Dimethylpropoxycarbonyl, 1, 2-Dimethylpropoxycarbonyl, 1-Methylpentoxycarbonyl, 2-Methylpentoxycarbonyl, 3-Methyl-pentoxycarbonyl, 4-Methylpentoxycarbonyl, 1, 1-Dimethylbutoxycarbonyl, 1,2-Dimethylbutoxycarbonyl, 1 , 3-dimethylbutoxycarbonyl, 2, 2-dimethylbutoxycarbonyl, 2, 3-dimethylb toxycarbonyl, 3, 3-dimethylbutoxycarbonyl, 1-ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl, 1,1, 2-trimethylpropoxycarbonyl, 1,2, 2-trimethylpropoxycarbonyl, 1-ethyl-l-methyl-propoxycarbonyl or l-ethyl-2-methyl-propoxycarbonyl; Ci-C _δ -haloalkoxycarbonyl: a Cχ-C ₄ alkoxycarbonyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethoxycarbonyl, difluoromethoxycarbonyl, trifluoromethoxycarbonyl, chlorodifluoromethoxycarbonyl, bromodifluoromethyl 2-fluoroethoxycarbonyl, 2-chloroethoxycarbonyl, 2-bromoethoxycarbonyl, 2-iodoethoxycarbonyl, 2,2-di-fluoroethoxycarbonyl, 2, 2, 2-trifluoroethoxycarbonyl, 2-chloro-2-fluoroethoxycarbonyl, 2-chloro-2, 2- difluoroethoxycarbonyl, 2, 2-dichloro-2-fluoroethoxycarbonyl, 2,2, 2-trichloroethoxycarbonyl, pentafluoroethoxycarbonyl, 2-fluoropropoxycarbonyl, 3-fluoropropoxycarbonyl, 2-chloropropoxycarbonyl, 3-chloropropoxycarbonony1, 2-bromopropoxycarbonyloxy, 3-bromopropoxycarbony1, 3- 2, 2-difluoropropoxycarbonyl, 2, 3-difluoropropoxycarbonyl, 2, 3-dichloropropoxycarbonyl, 3, 3, 3-trifluoropropoxycarbonyl, 3,3, 3-trichloropropoxycarbonyl, 2,2,3,3, 3-pentafluoropropoxycarbonyl, heptafluoropropoxycarbonyl, 1- (fluoromethyl) -2-fluoroethoxycarbonyl, 1- (chloromethyl) -2-chloroethoxycarbonyl, 1- (bromomethyl) -2-bromethoxycarbonyl, 4-fluorobutoxycarbonyl, 4-chlorobutoxycarbonyl, 4-bromobutoxycarbonyl, 4-iodobutoxycarbonyl, 5- Fluoropentoxycarbonyl, 5-chloropentoxycarbonyl, 5-bromopentoxycarbonyl, 6-fluorohexoxycarbonyl, 6-chlorohexoxycarbonyl or 6-bromohexoxycarbonyl;

C 1 -C ₄ -alkoxy-C ₄ -alkyl, and the alkoxyalkyl parts of hydroxy-C 1 -C ₄ -alkoxy-C ₄ -C ₄ -alkyl: C 1 -C ₄ -alkoxy, as mentioned above, substituted Cι -C ₄ alkyl, for example for methoxymethyl, ethoxymethyl, propoxymethyl, (1-methylethoxy) methyl, butoxymethyl, (1-methylpropoxy) methyl, (2-methylpropoxy) methyl, (1, 1-dimethylethoxy) methyl, 2- (methoxy) ethyl, 2- (ethoxy) ethyl, 2- (propoxy) ethyl, 2- (l-methylethoxy) ethyl, 2- (butoxy) ethyl, 2- (l-methylprooxy) ethyl, 2- (2-methylpropoxy) ethyl, 2- (1, 1-dimethylethoxy) ethyl, 2- (methoxy) propyl, 2- (ethoxy) propyl, 2- (propoxy) propyl, 2- (1-methylethoxy) - propyl, 2- (butoxy) propyl, 2- (1-methylpropoxy) propyl, 2- (2-methylpropoxy) propyl, 2- (1, 1-dimethylethoxy) propyl, 3- (methoxy) propyl, 3- (ethoxy) propyl, 3- (propoxy) propyl, 3- (1-methylethoxy) propyl, 3- (butoxy) propyl, 3- (1-methylpropoxy) propyl, 3- (2-methylpropoxy) propyl, 3- (1 , 1-dimethylethoxy) propyl, 2- (methoxy) butyl, 2- (ethoxy) b utyl, 2- (propoxy) butyl, 2- (l-methylethoxy) butyl, 2- (butoxy) butyl, 2- (1-methylpropoxy) butyl, 2- (2-methylpropoxy) butyl, 2- (1, 1-dimethylethoxy) butyl, 3- (methoxy) butyl, 3- (ethoxy) butyl, 3- (propoxy) butyl, 3- (1-methylethoxy) butyl, 3- (butoxy) butyl, 3- (l-methyl propoxy) butyl, 3- (2-methylpropoxy) butyl, 3- (1, 1-dimethylethoxy) butyl, 4- (methoxy) butyl, 4- (ethoxy) butyl, 4- (prop- oxy) butyl, 4- (1-methylethoxy) butyl, 4- (butoxy) butyl, 4- (1-methylpropoxy) butyl, 4- (2-methylpropoxy) butyl or 4- (1, 1-dimethylethoxy) b tyl;

With regard to the use of the compounds of the formula I according to the invention as herbicides, the variables preferably have the following meanings, in each case individually or in combination:

R ¹ nitro, halogen, Ci-Cβ-alkyl, Ci-C _ö -haloalkyl,

Ci-C _ö alkoxy, -C-C ₆ -haloalkoxy, Cχ-C ₆ -alkylthio, Ci-Cβ-haloalkylthio, Ci-Cβ-alkylsulfonyl or Cι-C ₆ -haloalkylsulfonyl;

R ^{3 is} hydrogen;

X forms a -0- (CH ₂ ) _n chain, which can be substituted by one to three radicals from the following group: halogen, C1 _. -C ₄ alkyl, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ alkoxycarbonyl;

or

a - (CH) _P chain which can be interrupted by oxygen or sulfur and / or can be substituted by one to four radicals from the following group:

Halogen, -CC ₄ alkyl, C ₁ -C ₄ haloalkyl or Ci-C ₄ alkoxycarbonyl;

m 0;

n 1 to 5;

p 2 to 6;

R ⁴ , R ^{8 are} hydrogen or C1 _. -C ₄ alkyl, such as methyl, ethyl or

Propyl; preferably hydrogen or methyl;

R ⁵ , R ⁷ , R ^{9 are} hydrogen or -CC alkyl, such as methyl, ethyl or

Propyl; preferably hydrogen or methyl;

R ^{6 is} hydrogen, hydroxy, -CC ₆ alkyl, di- (-C ₆ alkoxy) -methyl, (-C ₆ alkoxy) (-C ₆ alkylthio) methyl, di- ( Cι-C ₆ -alkylthio) methyl, _Cι-C6 alkoxy, Ci-C alkyl _δ thio, Ci-Cε haloalkylthio, Cι-C ₆ alkylsulfinyl, C. _3-C ₆ haloalkylsulfinyl, Cι-C ₆ alkylsulfonyl or C ₆ haloalkylsulfonyl;

1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithiolan-2- yl or 1, 3-dithian-2-yl, where the latter six radicals can be substituted by one to three C ₁ -C ₄ alkyl radicals;

preferably hydrogen, hydroxy or C ₁ -C ₄ alkyl, such as methyl, ethyl or propyl;

or

R ⁵ and R ⁶ or R ⁶ and R ⁹ together form a π bond or a C ₃ -C ₅ alkyl chain which can carry one to three radicals from the following group: halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or Ci -C alkoxycarbonyl, from;

or

R ⁵ and R ⁹ together form a Cι-C alkyl chain, which can carry one to three radicals from the following group: halogen, cyano, C ₄ alkyl, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ - Alkoxycarbonyl, from;

or

R ⁶ and R ⁷ together form a -O- (CH ₂ ) _q -O-, -O- (CH ₂ ) _q -S- or - S- (CH ₂ ) _q -S chain, which is represented by one to three Residues from the following group can be substituted: halogen, cyano, -CC ₄ alkyl, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ alkoxycarbonyl; preferably R ⁶ and R ⁷ together form a -0- (CH) _q -0-, -0- (CH) _q -S- or -S- (CH ₂ ) _q -S chain, which by one to three of the Radicals from the following groups can be substituted: C1-C4-haloalkyl or C ₁ -C ₄ -alkoxycarbonyl;

or

q 2 to 4; Compounds of the formula I are particularly preferred, the variables having the following meanings, individually or in combination:

R ^{1 is} halogen, Ci-Cβ-alkyl, Cι-C ₆ haloalkyl, Cι-C ₆ -alkoxy, C ₆ alkylthio, or Cι-C ₆ alkylsulfonyl; in particular halogen such as chlorine or bromine, -C ₆ alkyl such as methyl or ethyl, -C ₆ alkoxy such as methoxy or ethoxy or -C ₆ alkylsulfonyl such as methylsulfonyl or ethylsulfonyl; particularly preferably chlorine, methyl, methoxy or methylsulfonyl;

R ^{3 is} hydrogen;

X forms a -0- (CH ₂ ) _n chain, which can be substituted by one to three radicals from the following group: -C-alkyl or Ci -C -haloalkyl;

or

a - (CH ₂ ) _p chain, which can be substituted by one to four radicals from the following group: halogen, C ₁ -C ₄ alkyl or Ci -C ₄ haloalkyl;

m 0;

n 1 to 4; especially 1,3 or 4;

p 2 to 6;

R ⁴ , R ^{8 are} hydrogen or C ₁ -C ₄ alkyl, such as methyl, ethyl or propyl; preferably hydrogen or methyl;

R ⁵ , R ⁷ , R ^{9 are} hydrogen or C ₁ -C ₄ alkyl, such as methyl, ethyl or propyl; preferably hydrogen or methyl;

R ⁶ is hydrogen, hydroxy, _Cι-C6 alkyl, di- (Cι-C ₆ -alk- oxy) methyl, (C _C6 alkoxy) (Cι-C ₆ -alkylthio) methyl, di- ( CI-C _Ö alkylthio) methyl, Cι-C ₆ alkylsulfonyl or _Cι-C6 haloalkylsulfonyl; preferably hydrogen, hydroxy or C ₁ -C alkyl, such as methyl, ethyl or propyl;

or

The compounds of the formula I are particularly preferred, where

R ¹ halogen, C ₁ -C ₄ alkyl, -C -C alkoxy or C ₁ -C ₄ alkylsulfonyl;

R ^{3 is} hydrogen;

mean.

Likewise particularly preferred are compounds of formula I, wherein

X is a -0- (CH ₂₎ - (CH ₂₎ _p chain forms, with the latter by one to three halogen atoms, C ₁ -C ₄ alkyl - - or haloalkyl radicals may be substituted or Cι-C ₄ ;

p 2 to 5; especially 2, 4 or 5;

mean.

The compounds of the formula I are particularly preferred, where

X forms a - (CH ₂ ) ₂ chain, which has 1 to 3 halogen atoms, such as fluorine or chlorine, -CC ₄ -alkyl radicals such as methyl or ethyl or Cτ _. -C ₄ haloalkyl radicals such as trifluoromethyl, may be substituted.

Likewise particularly preferred are the compounds of formula I, wherein

R ^{6 is} hydrogen, hydroxy, -CC ₆ alkyl, di- (-C ₆ alkoxy-oxy) methyl, (-C ₆ alkoxy) (-C ₆ alkylthio) methyl, di (-C- C ₆ alkylthio) methyl or Ci -C ₆ alkoxy;

R ^{7 is} hydrogen or Ci-C ₄ alkyl;

or R ⁶ and R ⁷ together with the carbon to which they are attached form a carbonyl group;

mean.

Also particularly preferred are the compounds of formula I, wherein

R ^{1 is} halogen or Ci -C ₆ alkyl; especially chlorine or methyl; especially methyl;

X is an -O- (CH ₂ ) - or a - (CH ₂ ) s- or a

- (CH) ₂ chain, the latter being substituted by one to three halogen atoms;

R ^{6 is} hydrogen or -CC alkyl;

R ^{7 is} hydrogen or Ci-C ₄ alkyl;

or

mean.

The compounds of the formula Ial (≡ I with m = O; R ⁴ to R ⁹ = H) are extraordinarily preferred, in particular the compounds Ial.l to Ial.85, the radical definitions R ¹ to R ⁹ , m and X not only in combination with one another, but also in each case viewed individually, are of particular importance for the compounds according to the invention.

Table 1:

The following cyclohexenone dioxothiochromanoyl derivatives of the formula I are also extremely preferred:

The compounds of the formula Ia2, in particular the compounds Ia2.1 to Ia2.85, which differ from the compounds Ial.l to Ial.85 in that R ⁶ and R ^{7 are} methyl.

- The compounds of formula Ia3, especially the

Compounds Ia3.1 to Ia3.85, which differ from the compounds Ial.l to Ial.85 in that R ^{6 is} methyl.

The compounds of the formula Ia4, in particular the compounds Ia4.1 to Ia4.85, which differ from the compounds Ial.l to Ial.85 in that R ⁸ and R ^{9 are} methyl.

The compounds of the formula Ia5, in particular the compounds Ia5.1 to Ia5.85, which differ from the compounds Ial.l to Ial.85 in that R ^{8 is} methyl.

The compounds of the formula Ia6, in particular the compounds Ia6.1 to Ia6.85, which differ from the compounds Ial.l to Ial.85 in that R ⁴ , R ⁵ , R ⁸ and R ^{9 are} methyl and R ⁶ and R ⁷ together with the carbon to which they are attached form a carbonyl group.

The compounds of formula Ia7, especially those

Compounds Ia7.1 to Ia7.85, which differ from the compounds Ial.l to Ial.85 in that R ⁴ , R ⁵ , R ⁸ and R ^{9 are} methyl and R ^{6 is} hydroxy.

The cyclohexenone dioxothiochromanoyl derivatives of the formula I can be obtained in various ways, for example by the following process:

Preparation of compounds of the formula I by reacting an activated benzoic acid Ila or a benzoic acid Ilb, which is preferably activated in situ, with a cyclohexanedione of the formula III to give the acylation product and subsequent rearrangement.

L ¹ stands for a nucleophilically displaceable leaving group, such as halogen, for example bromine or chlorine, hetaryl, for example imidazolyl or pyridyl, carboxylate, for example acetate or trifluoroacetate, etc.

The activated benzoic acid Ila can be used directly, as in the case of the benzoyl halides or generated in situ, for example with dicyclohexylcarbodiimide, triphenylphosphine / azodicarboxylic acid. ester, 2-pyridine disulfide / triphenylphosphine, carbonyldiimidazole etc.

It may be advantageous to carry out the acylation reaction in the presence of a base. The reactants and the auxiliary base are expediently used in equimolar amounts. A slight excess of the auxiliary base e.g. 1.2 to 1.5 molar equivalents, based on II, can be advantageous under certain circumstances.

Tertiary alkyl amines, pyridine or alkali metal carbonates are suitable as auxiliary bases. As a solvent e.g. chlorinated hydrocarbons, such as methylene chloride or 1,2-dichloroethane, aromatic hydrocarbons, such as toluene, xylene or chlorobenzene, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, polar aprotic solvents, such as acetonitrile, dimethylformamide or dimethyl sulfoxide or esters such as ethyl acetate or mixtures thereof.

If benzoyl halides are used as the activated carboxylic acid component, it may be expedient to cool the reaction mixture to 0-10 ° C. when this reactant is added. The mixture is then stirred at 20-100 ° C., preferably at 25-50 ° C., until the reaction is complete. The processing takes place in the usual way, e.g. the reaction mixture is poured onto water and the product of value is extracted. Methylene chloride, diethyl ether and ethyl acetate are particularly suitable as solvents for this. After drying the organic phase and removing the solvent, the crude ester can be used for rearrangement without further purification.

The rearrangement of the esters to the compounds of the formula I is advantageously carried out at from 20 to 100 ° C. in a solvent and in the presence of a base and, if appropriate, using a cyano compound as a catalyst.

As a solvent e.g. Acetonitrile, methylene chloride, 1, 2-dichloroethane, dioxane, ethyl acetate, toluene or mixtures thereof can be used. Preferred solvents are acetonitrile and dioxane.

Suitable bases are tertiary amines such as triethylamine, aromatic amines such as pyridine or alkali carbonates such as sodium carbonate or potassium carbonate, which are preferably used in an equimolar amount or up to a fourfold excess, based on the ester. Triethylamine or alkali carbonate are preferred used, preferably in double equimolar ratio with respect to the ester.

Inorganic cyanides such as sodium cyanide or potassium cyanide and organic cyano compounds such as acetone cyanohydrin or trimethylsilyl cyanide are suitable as cyano compounds. They are used in an amount of 1 to 50 mole percent, based on the ester. Preferably acetone cyanohydrin or trimethylsilyl cyanide, e.g. in an amount of 5 to 15, preferably 10 10 mol percent, based on the ester.

Working up can be carried out in a manner known per se. The

The reaction mixture is e.g. with dilute mineral acid, such as

5% hydrochloric acid or sulfuric acid, acidified, with an organic

15 solvents, e.g. Extracted methylene chloride or ethyl acetate. The organic extract can be mixed with 5-10% alkali carbonate solution, e.g. Sodium carbonate or potassium carbonate solution are extracted. The aqueous phase is acidified and the precipitate that forms is filtered off with suction and / or with methylene

20 chloride or ethyl acetate extracted, dried and concentrated.

The benzoyl halides of the formula Ila (with L ¹ = CI, Br) can be prepared in a manner known per se by reacting the benzoic acids 25 of the formula IIb with halogenating reagents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride and oxalyl bromide.

The benzoic acids of the formula IIb can be prepared in a manner known per se from the corresponding esters by acidic or basic hydrolysis.

The benzoic acid esters of formula IIc (with T = Cχ-C ₆ alkoxy) can be obtained, for example, by the following methods.

35

-Alkoxy)

A. Preparation of benzoic acid ester of the formula IIc with 5 X = -0- (CH ₂ ) _n ". N = 3 to 5 by reacting thiochromanoyl ^■ derivatives of the formula IV with α-halogen-ω-metal-alkyl compounds of the formula V (with Hai = CI, Br; M = Li, M = Li, Mg, Zn) (g1, e.g. M. Nöel et al., Comptes Rend. 268, 1152 (1969)).

IV V IIc with X = -0- (CH ₂ ) _n - n = 3 to 5

Representation of benzoic acid ester of formula IIc with

X = -O- (CH ₂ ) - by expoxidation of methylidenthiochromanoyl ^■ derivatives of the formula VI

Epoxidation

VI IIc with X = -0- (CH ₂ ) -

Suitable epoxidation reagents are, for example, organic peracids such as peroxyacetic acid or m-chloroperbenzoic acid, hydrogen peroxide (in alkaline) or alkyl peroxides, if appropriate in the presence of a transition metal catalyst such as e.g. Oxides of vanadium, molybdenum or cobalt.

The methylidenthiochromanoyl derivatives of the formula VI used as starting materials can be obtained by Wittig or related reactions from the corresponding thiochromanoyl derivatives of the formula IV (cf. for example J. March, "Advanced Organic Chemistry", 4th edition, Wiley, New York p. 956 ff.)

IV VI

The methylidenthiochromanoyl derivatives of the formula VI can also be obtained by a McMurry reaction on corresponding thiochromanoyl derivatives of the formula IV (see, for example, A. Fürstner, Angew. Chem. 105, 171 (1993)).

Preparation of benzoic acid esters of the formula IIc with X = - (CH ₂ ) ₂ - by reacting methylidenthiochromanoyl derivatives of the formula VI with carbenes or carbene equivalents (see, for example, J. Maren, "Advanced Organic Chemistry", 4th edition, Wiley, New York pp. 866 ff.)

R ² n ⁺ "carbene"

VI IIC with X = - (CH ₂ ) ₂ -

Mono- and di-halogen carbenes can e.g. by reaction of di- or trihalomethanes with bases such as e.g. n-butyl lithium, potassium hydroxide or potassium tert. -butanolate are obtained (cf. e.g. Houben-Weyl, "Methods of Organic Chemistry, Vol. E 17a)

Alkyl-substituted carbenes are obtained, for example, from sulfur ylides (see, for example, Kennwell et al., Chem. Soc. Rev. 4, 189 (1975); B. Trost et al., Acc. Chem. Res. 7, 85 ( 1974)). Furthermore, carbenes, in particular alkoxycarbonyl-substituted ones, can be obtained from corresponding diazo compounds with rhodium acetate.

D. Preparation of benzoic acid ester of the formula IIc with X = - (CH ₂ ) _p - and p = 4 to 6 by reacting compounds of the formula VII with an oxidizing agent.

Oxidizing agent

VII IIc with X = - (CH ₂ ) ₄ _ ₆ -

Examples of suitable oxidizing agents are organic peroxides such as m-chloroperbenzoic acid, peroxyacetic acid and tri-fluoroperoxyacetic acid, or hydrogen peroxide, if appropriate in the presence of a transition metal catalyst such as tungstate.

The compounds of the formula VII are obtained by alkylation of the mercapto compounds VIII, if appropriate in the presence of a base (cf. e.g. Karrer et al., Helv. Chim. Acta (1942) 25, 29).

VIII IX X

Suitable bases are, for example, alkali metal carbonates, such as sodium carbonate or potassium carbonate, alkali metal hydrogen carbonates, such as sodium hydrogen carbonate or potassium hydrogen carbonate, or tertiary amines such as triethylamine or pyridine. The compounds of the formula X are then cyclized to the compounds of the formula VII by Friedie-Kraft alkylation (cf., for example, Can. J. Chem. 59, 199 (1981); Chem. Ber. 58, 1625 (1925 ); Phosp. And Sulf. 19, 31 (1984)). This cyclization takes place in the presence of strong acids.

X VII

The above-mentioned process routes A to D represent synthesis principles. They also include the synthesis of the compounds of the formula IIc, where X is a -0- (CH) _n chain, which can be substituted by one to three radicals from the following group: halogen, Cyano, -CC ₄ alkyl, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ alkoxycarbonyl; or a - (CH ₂ ) _p chain which can be interrupted by an oxygen or sulfur and / or one to four radicals from the following group can be substituted: halogen, cyano, C -C ₄ alkyl, C ₁ - C ₄ haloalkyl or C ₁ -C ₄ alkoxycarbonyl. This means that the starting materials V, VI, VII, IV and X and the ylides, carbenes used can be substituted accordingly.

Benzoic acid derivatives of the formula II are new,

where the variables have the following meaning:

R ^{1 is} hydrogen, nitro, halogen, cyano, Cχ-C ₆ alkyl,

Ci-C _δ -haloalkyl, Cι-C ₆ -alkoxy, Ci-Cς-haloalkoxy, Cι-C ₆ -alkylthio, Cι-C ₆ -haloalkylthio, Cι-C ₆ -alkylsulfinyl, Cχ-C ₆ -haloalkylsulfinyl, Ci- C _δ- alkylsulfonyl, Cι-C ₆ -haloalkylsulfonyl, aminosulfonyl, N- (Cχ-C ₆ ~ alkyl) -aminosulfonyl, N, N-di- (-C-C ₆ -alkyl) -aminosulfonyl, N- (-Cι -C ₆ alkyl- sulfonyl) amino, N- (Ci-Cε-haloalkylsulfonyl) - amino, N- (-C-C ₆ -alkyl) -N- (-C-C ₆ -alkylsulfonyl) - amino or N- (Cχ-C ₆ -alky ) -N- (-C -C ₆ haloalkylsulfonyl) amino;

R ² _Cι-C6 alkyl, _Ci-C6 haloalkyl, Cι-C ₆ alkoxy or Ci-C -haloalkoxy _ß;

R ^{3 is} hydrogen, -CC ₆ alkyl or halogen;

X forms a -0- (CH) _n chain, which can be substituted by one to three radicals from the following group: halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or Ci -C ₄ -Alkoxycarbonyl;

or

a - (CH ₂ ) _p chain which can be interrupted by an oxygen or sulfur and / or can be substituted by one to four radicals from the following group:

Halogen, cyano, C1 _. -C ₄ alkyl, C ₁ -C ₄ haloalkyl or Ci -C alkoxycarbonyl;

m 0 to 4;

n 1 to 5;

p 2 to 6;

R ^{10 is} hydroxy or a hydrolyzable radical;

Examples of residues which can be hydrolyzed are alkoxy, phenoxy, alkylthio, phenylthio residues, which may optionally be substituted, halides, hetaryl residues which are bonded via nitrogen, amino, imino residues which may be substituted can etc.

Benzoic acid halides of the formula Ila with R ¹⁰ = halogen are preferred

where the variables R ¹ to R ³ , X and m have the meaning given under formula II and

Shark halogen, especially chloride or bromide.

Benzoic acids of the formula IIb are likewise preferred

Ilb

where the variables R ¹ to R ³ , X and m have the meaning given under formula II.

Benzoic acid esters of the formula IIc are likewise preferred

IIC

T Cι-C ₆ alkoxy.

The particularly preferred embodiments of the benzoic acid derivatives of the formula II Deri ^■ in respect to the variables R ¹ to R ^3, X and m which correspond to the Cyclohexenondioxothiochromanoyl derivatives of formula I. Manufacturing examples:

1-Hydroxy-5, 5-dimethyl-2 - {[(cyclohexane-1-spiro-4) -8 -methyl -1, 1-dioxothiochroman-7-yl] carbonyl} -cyclohex-1-en-3 -on (connection 2.2)

Step a) 3 - (2-Cyclohexylidene-ethylthio) -2-methyl-benzoic acid methyl ester

7.6 g (55 mmol) of potassium carbonate were added to 10.0 g (55 mmol) of methyl 3-mercapto-2-methylbenzoate in 100 ml of acetone, and a solution of (2-bromoethylidene) cyclohexane in 20 was added at room temperature ml of acetone was added dropwise. After 4 hours the solvent was removed, the residue was taken up in water and extracted with methylene chloride. The organic phases were dried and the solvent was removed. The residue was chromatographed on silica gel with ethyl acetate / cyclohexane as the eluent. Yield: 16.3 g ⁱ H-NMR (CDC1 ₃ ): δ = 7.60 (d, 1H); 7.42 (d, 1H), 7.15 (t, lH); 5.22 (t, lH); 3.88 (s, 3H); 3.50 (d. 2H); 2.55 (s, 3H); 2.04 (m, 4H); 1.60-1.34 (m, 6H).

Step b) (Cyclohexane-1-spiro -4) -8-methyl-thiochroman-7-carbonic acid methyl ester

20 g (69 mmol) of 3 - (2-cyclohexylide-ethylthio) -2-methyl-benzoic acid methyl ester was dissolved in 200 ml of methylene chloride and 27.6 g (276 mmol) of concentrated sulfuric acid were added at -10 ° C. After stirring for one hour at -10 ° C., the reaction mixture was poured onto ice water and the phases which formed were separated. The organic phase was washed successively with sodium hydrogen carbonate solution and water, dried and concentrated. Yield: 17.4 g (colorless oil) 1H-NMR (CDCI ₃ ): δ = 7.45 (d, 1H); 7.34 (d, 1H), 3.85 (s, 3H); 3.00 (t. 2H); 2.45 (s, 3H); 2.12 (t, 2H) 1.80-1.15 (m, 10H).

Step c) (Cyclohexane-l-spiro-4) -8-methyl-hiochroman-7-carboxylic acid

17.4 g (60 mmol) of (cyclohexane-1-spiro-4) -8-methyl-thiochro-man-7-carboxylic acid methyl ester were dissolved in 200 ml of a 1: 1 mixture of methanol and water, with 3.6 g (80 mmol) sodium hydroxide was added and the mixture was heated under reflux for 3 hours. The organic solvent was then removed, the aqueous phase was extracted with diethyl ether and acidified with 2N hydrochloric acid. The precipitate was filtered off, washed with water and dried. Yield: 13.8 g (80%) (colorless solid) Melting point: 238 ° C

Stage d) (cyclohexane-1-spiro -4) - 1,1-dioxo-8-methyl-thiochro-5 man-7-carboxylic acid (compound 3.1)

12.8 g (46 mmol) (cyclohexane-1-spiro-4) -8 -methyl-thiochromane-7-carboxylic acid and a spatula tip of sodium tungstate were added

100 ml of glacial acetic acid and 11.6 g (102 mmol) of one at 50 ° C.

10 30% hydrogen peroxide solution added dropwise. After another

The reaction mixture was stirred into ice water for 4 hours at this temperature, the precipitate formed was suction filtered, washed with water and dried. Yield: 11.3 g (79%) (colorless solid)

15 Melting point: 242 ° C

Stage e) 1 -hydroxy-5, 5 -dimethyl-2 - {[(cyclohexane-1-spiro-4) -8 -methyl-1, 1-dioxothiochroman-7-yl] carbonyl} -cyclo-hex- 1 -en-3-one (connection 2.2)

20th

To a solution of 0.8 g (2.6 mmol) (cyclohexane-spiro-4) - 8-methyl-1, 1-dioxothiochroman-7-carboxylic acid and 0.36 g (2.6 mmol) Dimedone in 20 ml acetonitrile was added 0.54 g (2.6 mmol) N, N-dicyclohexylcarbodiimide and stirring was continued for 6 hours at room temperature.

25 Then 0.52 g (5.2 mmol) of triethylamine and 0.05 ml of trimethylsilyl cyanide were added. After stirring for a further 2 hours at room temperature, the reaction mixture was partitioned between 2% sodium carbonate solution and ethyl acetate and the precipitate formed was suction filtered. The aqueous phase was washed with diethyl ether and with

30 hydrochloric acid adjusted to pH 2. The precipitate was filtered off, washed with water and dried. Yield: 0.55 g melting point: 122 ° C

35 1 -hydroxy- 2- {[(2,2-difluorocyclopropan-1-spiro-4 -) - 8 -methyl -1, 1 -dioxothiochroman-7-yl) -carbonyl] -cyclohex-l- en-3 -on (compound 2.9)

Step a) 3- (Hydroxycarbonyl-1-yl-ethyl-thio) -2-methyl-benzoic acid 0-remethyl ester

37.9 g (275 mmol) of potassium carbonate were added to a solution of 50.0 g (275 mmol) of methyl 3-mercapto-2-methylbenzoate in 100 ml of acetone, and 42.0 g (275 mmol) of 3 -bromopropionic acid ( 5 Aldrich) in 100 ml acetone. After 4 hours of stirring at room temperature, the solvent was removed and the residue in water taken up and acidified with concentrated hydrochloric acid. The precipitate was filtered off, washed with water and dried.

Yield: 68.8 g (99%) melting point: 113 ° C

Step b) 8-methyl-4-oxothiochroman-7-carboxylic acid methyl ester

34.4 g (135 mmol) of 3- (2-hydroxycarbonyl-eth-1-yl-thio) -2-methylbenzoic acid methyl ester were added to 350.0 g of polyphosphoric acid at 70 ° C. and the mixture was stirred for one hour at this temperature. It was then poured onto ice water and the resulting precipitate was filtered off with suction. This was chromatographed on silica gel with ethyl acetate / cyclohexane (1: 4) as the eluent. Yield: 20.7 g (62%) (colorless solid) Melting point: 97 ° C

Step c) 8-methyl-4-methylidene-thiochroman-7-carboxylic acid methyl ester

44.6 g (125 mmol) of triphenylmethylphosphonium bromide were dissolved in 150 ml of tetrahydrofuran, and 14.0 g (125 mmol) of potassium tert-butoxide were added. After stirring for 30 minutes at room temperature, the mixture was cooled to -20 ° C. and 24.7 g (105 mmol) of 8-methyl-4-oxothiochroman-7-carboxylic acid methyl ester in 150 ml of tetrahydrofuran were added. The mixture was left to stir at 0 ° C. for a further 30 minutes before the mixture was stirred into ice water. The aqueous phase was extracted with ethyl acetate, the resulting organic phase was dried and concentrated. The residue was chromatographed on silica gel with ethyl acetate / cyclohexane as the eluent. Yield: 9.8 g (38%) (yellow oil)

^! H-NMR (CDC1 ₃ ): δ = 7.44 (d, 1H); 7.40 (d, lH), 5.54 (s, lH); 5.06 (s, 1H); 3.88 (s, 3H), 3.10 (m, 2H); 2.80 (m, 2H); 2.46 (s, 3H).

Step d) (2,2-difluoro-cyclopropane-l-spiro-4) -8-methyl-thiochroman-7-carboxylic acid methyl ester

1.0 g (4.3 mmol) of 8-methyl-4-methylidene-thiochroman-7-carboxylic acid methyl ester were dissolved in 20 ml of diethylene glycol dimethyl ether and heated to reflux temperature. At this temperature, a solution of 6.5 g (43.0 mmol) of sodium chlorodifluoroacetate in 30 ml of diethylene glycol dimethyl ether was added dropwise and the mixture was stirred at this temperature for a further 15 minutes. After cooling, the mixture was stirred into ice water and extra- was with diethyl ether. The ethereal phase was dried and concentrated. The residue was chromatographed on silica gel with ethyl acetate / cyclohexane as the eluent. Yield: 0.9 g (74%) (colorless solid) Melting point: 104-105 ° C

Stage e) (2,2-difluoro-cyclopropane-l-spiro-4) -8-methyl-thiochroman-7-carboxylic acid

To a solution of 3.3 g (11.6 mmol) (2,2-difluoro-cyclopropan-l-spiro-4) -8-methyl-thiochroman-7-carboxylic acid methyl ester in 60 ml of a 1: 1 mixture of Methanol and water were added 0.7 g (17.4 mmol) of sodium hydroxide and heated under reflux for 2 hours. After cooling and removing the solvent, the residue was taken up in water and acidified with 2N hydrochloric acid. The precipitate was filtered off, washed with water and dried. Yield: 3.1 g (99%) melting point: 200-203 ° C

Step f) (2,2-difluorocyclopropane-l-spiro-4) -8-methyl -1,1-dioxothiochroman-7-carboxylic acid (compound 3.5)

To a solution of 2.9 g (10.7 mmol) (2,2-difluoro-cyclopropan-l-spiro-4) -8-methyl-thiochroman-7-carboxylic acid and a spatula tip of sodium tungstate in 30 ml of glacial acetic acid dripped 2.7 g (23.6 mmol) of 30% hydrogen peroxide solution were stirred at 50 ° C. and the mixture was stirred at this temperature for a further 1 hour. The mixture was stirred into ice water, the precipitate which had separated out was filtered off with suction and dried.

Yield: 3.0 g (93%) (colorless solid) Melting point: 250-253 ° C

Step g) 1 -hydroxy-2 - {[(2,2-difluorocyclopropane-l-spiro-4) -8-methyl-1,1-dioxothiochroman-7-yl] carbonyl} cyclohex -l-en-3-one (connection 2.9)

To a solution of 0.5 g (1.7 mmol) (2, 2-difluoro-cyclopropan-1-spiro-4) -8 -methyl -1, 1-dioxothiochroman-7-carboxylic acid and 0, 19 g (1.7 mmol) of 1,3-cyclohexanedione in 20 ml of acetonitrile was added to 0.34 g (1.7 mmol) of N, N-dicyclohexylcarbodiimide and stirred for 12 hours at room temperature. Then 0.33 g (3.3 mmol) of triethylamine and 0.05 ml of trimethylsilyl cyanide were added and the mixture was stirred for a further 4 hours. The reaction mixture was stirred into 2% sodium carbonate solution and ethyl acetate and the precipitate was removed. sucks. The aqueous phase was washed with diethyl ether and adjusted to pH 3 with hydrochloric acid. The precipitate was filtered off and dried. Yield: 0.5 g (colorless solid) Melting point: 225-227 ° C

1 -hydroxy- 4, 4,6, 6 - etramethyl- 2 - {[(oxiran-2-spiro-4) -8 -methyl -1, 1-dioxo -thiochroman-7 -yl] -carbonyl} -cyclohex- 1-en- 3, 5-dione (compound 2.6)

Step a) (0xiran-2-spiro-4) -8-methyl-l, 1 -dioxothiochroman-7 -yl] -carboxylic acid methyl ester (compound 3.2)

To a solution of 1.0 g (4.3 mmol) of 8-methyl-4-methyl-iden-1, 1-dioxothiochroman-7-yl-carboxylic acid methyl ester in 20 ml of methylene chloride was added 4.0 g (12.8 mmol) added m-chloroperbenzoic acid and stirred for 12 hours at room temperature. After 150 ml of ethyl acetate had been added, the resulting organic phase was washed with sodium bisulfite solution and sodium carbonate solution, then dried and the solvent removed. Yield: 0.9 g

Step b) (Oxiran-2-spiro-4) - 8-methyl-l, 1-dioxo-thiochroman-7 -yl-carboxylic acid (compound 3.2)

85 g of a 0.5 molar lithium hydroxide solution were added dropwise to 6.0 g (21 mmol) of (oxirane-2-spiro-4) - 8-methyl-l, 1-dioxothiochroman-7-yl-carboxylic acid methyl ester in 85 ml of tetrahydrofuran and stirred for 2 hours. The organic solvent was then removed and the pH was adjusted to 3 using hydrochloric acid. The precipitate was filtered off and dried. Yield: 4.5 g (79%) (beige solid) Melting point: 164 ° C

Step c) 1 -hydroxy-4, 4, 6, 6 - tetramethyl -2 - {[(oxiran-2-spiro-4) - 8 -methyl -1, 1 -dioxothiochroman-7 -yl] carbonyl} - cyclohex-1-en-3,5-dione (compound 2.6)

To a solution of 0.8 g (3.0 mmol) (oxiran-2-spiro-4) - 8-methyl-1, 1 -dioxothiochroman-7-carboxylic acid and 0.54 g (3.0 mmol) 2, 2, 4, 4-tetramethylcyclohexane-1,3,5-trione in 20 ml acetonitrile, 0.62 g (3.0 mmol) N, N-dicyclohexylcarbodiimide was added and the mixture was stirred for 12 hours at room temperature. Then 0.6 g (6.0 mmol) of triethylamine and 0.05 ml of trimethylsilyl cyanide were added and the mixture was stirred for a further 4 hours. Then 2% soda solution and ethyl acetate were added, the precipitate was filtered off with suction and the aqueous phase was extracted with diethyl ether. The mixture was acidified to pH 3 with hydrochloric acid and the precipitate formed was filtered off with suction. Yield: 0.7 g (54%) (beige solid) Melting point: 214 ° C. (dec.)

Tables 2 and 3 below list further compounds of the formula I and of the benzoic acid derivatives II which were prepared in an analogous manner.

Table 3

The compounds of formula I and their agriculturally useful salts are suitable both as isomer mixtures and in the form of the pure isomers - as herbicides. The herbicidal compositions which contain compounds of the formula I control vegetation very well on non-cultivated areas, especially when high amounts are applied. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. This effect occurs above all at low application rates.

Depending on the particular application method, the compounds of the formula I or herbicidal compositions comprising them can also be used in a further number of crop plants for eliminating undesired plants. The following crops are considered, for example:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea libericaus), Cucumodison , Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirs tum,

(Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec, Manihot esculenta, Medicago sativa, Musa spec, Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus vulgaris, phaseolus vulgaris, phaseolus vulgaris abies, Pinus spec, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (see vulgar), Theobroma cacao, Trifolitic aestiv , Triticum durum, Vicia faba, Vitis vinifera and Zea mays.

In addition, the compounds of the formula I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.

The compounds of formula I or the herbicidal compositions containing them can be sprayed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, oldispersions, pastes, dusts, sprinkling agents or granules , Atomizing, dusting, scattering or pouring can be used. The application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

The herbicidal compositions comprise a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I and auxiliaries customary for the formulation of crop protection agents.

The following are essentially considered as inert auxiliaries:

Mineral oil fractions from medium to high boiling point such as kerosene and diesel oil, also coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, e.g. Amines such as N-methylpyrrolidone and water.

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

The surfactants (adjuvants) are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols as well as of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives Formaldehyde, condensation products of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, isotridecyl ethoxylated, polyethylenethoxy alcohol, fatty alcohol alcohol, fatty alcohol Polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin sulfite waste liquor or methyl cellulose.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

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

The concentrations of the compounds of the formula I in the ready-to-use preparations can be varied within a wide range. In general, the formulations contain from about 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum). The following formulation examples illustrate the preparation of such preparations:

I. 20 parts by weight of compound no. 2.9 are dissolved in a mixture which is alkylated from 80 parts by weight

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

II. 20 parts by weight of compound no. 2.9 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 adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide on 1 Mole of castor oil consists. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

III. 20 parts by weight of compound no. 2.9 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

IV. 20 parts by weight of compound no. 2.9 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalenesulfonic acid, 17 parts by weight of the sodium salt of lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient.

V. 3 parts by weight of compound no. 2.9 are with

97 parts by weight of finely divided kaolin mixed. In this way, a dust is obtained which contains 3% by weight of the active ingredient. VI. 20 parts by weight of compound no

2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic

Mineral oil mixed intimately. A stable oily dispersion is obtained.

VII. 1 part by weight of compound no. 2.9 is dissolved in a mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained.

VIII. 1 part by weight of compound no. 2.9 is in a

Dissolved mixture, which consists of 80 parts by weight of cyclohexanone and 20 parts by weight Wettol ^R EM 31 (= nonionic emulsifier based on ethoxylated castor oil). A stable emulsion concentrate is obtained.

The compounds of the formula I or the herbicidal compositions can be applied pre- or post-emergence. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit as far as possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (post-directed, lay-by).

The application rates of the compound of the formula I are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (as specified), depending on the control target, the season, the target plants and the growth stage.

To widen the spectrum of activity and to achieve synergistic effects, the cyclohexenone dioxothiochromanoyl derivatives of the formula I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together. For example, 1, 2, 4-thiadiazoles, 1, 3, 4-thiadiazoles, amides, aminophosphoric acid and their derivatives, aminotriazoles, anilides, aryloxy- / heteroaryloxyalkanoic acids and their derivatives, benzoic acid and their derivatives, benzothiadiazinones, 2-aroyl-l, 3-cyclohexanediones, heteroaryl aryl ketones, benzylisoxazolidinones, meta-CF ₃ phenyl derivatives, carbamates, quinolinecarboxylic acid and their derivatives, Chloroacetanilides, cyclohexenone oxime ether derivatives, diazines, dichloropropionic acid and their derivatives, dihydrobenzofurans, dihydrofran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, urine substances, 3-phenidylazole, imid-azoleazole, imid-azoleazole, imid-azidazoles - nyl-3, 4, 5, 6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy and heteroaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, and pyridinecarboxylic acid , Pyrimidyl ether, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.

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

Examples of use

The herbicidal activity of the cyclohexenone dioxothiochromanoyl derivatives of the formula I was demonstrated by the following greenhouse experiments:

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

In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles. The tubes were lightly sprinkled to promote germination and growth, and then covered with clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, provided that this has not been impaired by the active ingredients.

For the purpose of post-emergence treatment, depending on the growth habit, the test plants were first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and some Planted into the test tubes days before treatment. The application rate for post-emergence treatment was 0.5, 0.25, 0.125 and 0.0625 kg / ha aS (active substance).

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

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

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

At application rates of 0.5 or 0.25 kg / ha, compound 2.3 has a very good post-emergence effect against the harmful plants mentioned above. Large bristle millet, white goose foot and

Black nightshade while the wheat crop is not affected.

Compound 2.9 combats the harmful plants field foxtail, wild oats at a rate of 0.25 or 0.125 kg / ha. Chinese hemp, white goose foot and white mustard very good, as well as the compound 2.12 excellent effect against Chicken millet, Chinese hemp, white goosefoot, black nightshade and knotweed at 125 and 62.5 g / ha in the post-emergence shows.

Claims

claims

Cyclohexenone dioxothiochromanoyl derivatives of the formula I.

in which the variables have the following meanings:

Rl is hydrogen, nitro, halogen, cyano, C ₆ alkyl, Ci-C _ß haloalkyl, Cι-C ₆ -alkoxy, halo-C ₆ alkoxy, Ci-Cβ alkylthio, Cι-C ₆ - Haloalkylthio, Ci-Cβ-alkylsulfinyl, Cι-C ₆ -haloalkylsulfinyl, Cι-C ₆ -alkylsulfonyl, Cι-C ₆ -haloalkylsulfonyl, aminosulfonyl, N- (Cχ-C ₆ -alkyl) -aminosulfonyl, N, N-di- (Cι-C ₆ -alkyl) aminosulfonyl, N- _(Cι-C6 alkyl sulfonyl) amino, N- _(Cι-C6 haloalkylsulfonyl) - amino, N- _(Cι-C6 alkyl) - N- (-C ₆ alkylsulfonyl) amino or N- (-C ₆ alkyl) -N- (-C ₆ haloalkylsulfonyl) amino;

R ² Ci -Cε alkyl, Ci -Ce haloalkyl, -C - C ₆ alkoxy or Ci -C _ö haloalkoxy;

R ³ hydrogen f, -CC ₆ alkyl or halogen;

X forms an -O- (CH ₂ ) _n chain, which can be substituted by one to three radicals from the following group:

Halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ alkoxycarbonyl;

or

a - (CH) _p chain which can be interrupted by an oxygen or sulfur and / or can be substituted by one to four radicals from the following group:

Halogen, cyano, C ₁ -C ₄ alkyl, C1 _. -C ₄ haloalkyl or C ₁ -C ₄ alkoxycarbonyl; m 0 to 4;

n 1 to 5;

p 2 to 6;

R ⁴ , R ^{8 are} hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxycarbonyl;

R ⁵ , R ⁷ , R ^{9 are} hydrogen or C ₁ -C 4 alkyl;

R ⁶ is hydrogen, halogen, hydroxy, Cι-C ₆ -alkyl, C ₆ -haloalkyl, di- (Cι-C ₆ - alkoxy) methyl, (Cι-C ₆ alkoxy) - (Ci-C ₆ - alkyl-thio) -methyl, di- (-C-C ₆ -alkylthio) methyl, C,-C ₆ -alkoxy, Cι-C ₆ -haloalkoxy, Cj-Cβ-alkylthio,

Ci-Cβ-haloalkylthio, C1.-C6-alkylsulfinyl, Ci -C ₆ haloalkylsulfinyl, Ci -C _δ- alkylsulfonyl, Ci -Cζ -haloalkylsulfonyl, Ci-C ₆ -alkoxycarbonyl, Ci-C ₆ -haloalkoxycarbonyl, -

1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithiolane 2-yl or 1, 3-dithian-2-yl, it being possible for the six latter radicals to be substituted by one to three C 1 -C ₄ -alkyl radicals;

or

R ⁵ and R ⁶ or R ⁶ and R ⁹ together form a π bond or a Cτ _. -C ₅ alkyl chain which can carry one to three radicals from the following group: halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ alkoxycarbonyl, from;

or

R ⁵ and R ⁹ together form a Cι-C ₄ -alkyl chain which may carry one to three radicals from the following group: halogen, cyano, C ₄ alkyl, C ₁ -C ₄ haloalkyl or Cι-C ₄ - Alkoxycarbonyl, from;

or

R ⁶ and R ⁷ together form a -0- (CH ₂ ) _q -0-, -0- (CH ₂ ) _q -S-, -S- (CH ₂ ) _q -S-, -0- (CH ₂ ) _r - or -S- (CH ₂ ) _r chain, which can be substituted by one to three radicals from the following group: Halogen, cyano, C ₁ -C ₄ alkyl, C1 _. -C ₄ haloalkyl or ^c ₁ " ^c ₄ alkoxycarbonyl;

or

q 2 to 4;

r 1 to 5;

2. Cyclohexenone dioxothiochromanoyl derivatives of the formula I according to claim 1, wherein

R ¹ halogen, C1.-C ₄ alkyl, -C-C ₄ alkoxy or Ci -C ₄ alkylsulfonyl;

R ^{3 is} hydrogen;

mean.

3. Cyclohexenone dioxothiochromanoyl derivatives of the formula I according to claims 1 or 2, wherein

X forms an -O- (CH ₂ ) - or a - (CH ₂ ) _p chain, the latter being able to be substituted by one to three halogen atoms, C ₁ -C -alkyl or C -C ₄ -haloalkyl radicals;

p 2 to 5;

mean.

4. Cyclohexenone dioxothiochromanoyl derivatives of the formula I according to claims 1 to 3, wherein

R ^{6 is} hydrogen, hydroxy, -CC ₆ alkyl,

Di- (Ci-Cβ-alkoxy) methyl, (-C-C ₆ -alkoxy) (Cι-C ₆ -alkyl-thio) methyl, di (Cι-C ₆ -alkylthio) methyl or

Ci -C ₆ alkoxy;

R ^{7 is} hydrogen or C1 _. -C ₄ alkyl;

mean.

A process for the preparation of compounds of formula I according to claim 1, characterized in that an activated benzoic acid Ila or a benzoic acid Ilb,

Ila Ilb

where the variables R ¹ to R ³ , X and m have the meanings given in claim 1 and L ^{1 represents} a nucleophilically displaceable leaving group, with a cyclohexanedione of the formula III

reacted and rearranged the acylation product in the presence of a catalyst to the compounds of formula I.

Agent containing a herbicidally effective amount of at least one cyclohexenone dioxothiochromanoyl derivative of the formula I or an agriculturally useful salt of I according to claim 1 and auxiliaries customary for the formulation of crop protection agents.

A process for the preparation of agents according to claim 6, characterized in that a herbicidally effective amount of at least one cyclohexenone dioxothiochromanoyl derivative of the formula I or an agriculturally useful salt of I according to claim 1 and for the formulation of crop protection agents customary auxiliaries.

Process for combating undesirable plant growth, characterized in that a herbicidally effective amount of at least one cyclohexenone dioxothiochromanoyl derivative of the formula I or an agriculturally useful salt of I according to claim 1 is allowed to act on plants, their habitat and / or on seeds.

Use of cyclohexenone dioxothiochromanoyl derivatives of the formula I or their agriculturally useful salts according to claim 1 as herbicides.

Benzoic acid derivatives of the formula II

where R ^{10 is} hydroxy or a hydrolyzable radical and the variables R ¹ to R ³ , X and m have the meaning given in claim 1.

Cyclohexenone dioxothiochromanoyl derivatives

Summary

Cyclohexenone dioxothiochromanoyl derivatives of the formula I,

in which the variables have the following meanings:

Ri hydrogen, nitro, halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, optionally sub. Aminosulfonyl, or optionally sub. Sulfonylamino;

R ² alkyl, haloalkyl, alkoxy or haloalkoxy,

R ^{3 is} hydrogen, alkyl or halogen;

or

X forms a -0- (CH) _n chain, which can be substituted; or a - (CH ₂ ) chain which can be substituted and / or interrupted by an oxygen or sulfur;

m 0 to 4;

n 1 to 5;

p 2 to 6;

R ⁴ , R ^{8 are} hydrogen, alkyl or alkoxycarbonyl;

R ⁵ , R ⁷ , R ^{9 are} hydrogen or alkyl; R ^{6 is} hydrogen, halogen, hydroxyl, alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or alkoxycarbonyl, it being possible for the alkyl radicals of the substituents mentioned to be substituted;

and their agriculturally useful salts;

Processes and intermediates for the preparation of the cyclohexenone dioxothiochromanoyl derivatives; Agents containing them, as well as the use of these derivatives or agents containing them for controlling unwanted plants.