CA2373165A1 - Cyclohexenone dioxothiochromanoyl derivatives - Google Patents

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
The present invention relates to novel cyclohexenonedioxothiochromanoyl derivatives of the formula I

S
R I I \ R2m I

R
in which the variables have the following meanings:
R1 is hydrogen, nitro, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, N-(C1-C6-alkyl)aminosulfonyl, N,N-di(C1-C6-alkyl)aminosulfonyl, N-(C1-C6-alkylsulfonyl)amino, N-(C1-C6-haloalkylsulfonyl)amino, N-(C1-C6-alkyl)-N-(C1-C6-alkylsulfonyl)amino or N-(C1-C6-alkyl)-N-(C1-C6-haloalkylsulfonyl)amino;
R2 is C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
R3 is hydrogen, C1-C6-alkyl or halogen;
X forms an -O-(CHZ)n- chain which can be substituted by one to three radicals selected from the following group:
halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxycarbonyl;
or a -(CH2)~- chain which can be interrupted by an oxygen or sulfur and/or can be substituted by one to four radicals selected from the following group:
halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxycarbonyl;

'. 0050/49977 a m is 0 to 4;
n is 1 to 5;
p is 2 to 6 ;
Rq, R8 are hydrogen, C1-Cq-alkyl or C1-Cq-alkoxycarbonyl;
R5, R7, R9 are hydrogen or C1-Cq-alkyl;
R6 is hydrogen, halogen, hydroxyl, C1-C6-alkyl, C1-C6-haloalkyl, di(C1-C6-alkoxy)methyl, (C1-C6-alkoxy)-(C1-C6-alkylthio)methyl, di(C1-C6-alkylthio)methyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, Cl-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, C1-C6-alkoxycarbonyl, C1-C6-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, it being possible for the six last-mentioned radicals to be substituted by one to three C1-Cq-alkyl radicals;
a5 or R5 and R6 or R6 and R9 together form a ~ bond or a C1-C5-alkyl chain which can have attached to it one to three radicals selected from the following group: halogen, cyano, C1-Cq-alkyl, C1-Cq-haloalkyl or C1-Cq-alkoxycarbonyl;
or R5 and R9 together form a C1-Cq-alkyl chain which can have attached to it one to three radicals selected from the following group: halogen, cyano, C1-Cq-alkyl, C1-Cq-haloalkyl or C1-Cq-alkoxycarbonyl;
or R6 and R7 together form an -O-(CH2)Q-0-, -O-(CH2)q-S-, -S-(CH2)q-S-, -O-(CH2)r- or -S-(CH2)r chain which can be substituted by one to three radicals selected from the following group: halogen, cyano, C1-Cq-alkyl, C1-Cq-haloalkyl or C1-Cq-alkoxycarbonyl;

'~ 0050/49977 or R6 and R7 together with the carbon to which they are bonded form a carbonyl group;
q is 2 to 4;
r is 1 to 5;
and to their agriculturally useful salts.
Moreover, the invention relates to processes and intermediates for the preparation of compounds of the formula I, to compositions comprising them, and to the use of these derivatives or compositions comprising them for the control of harmful plants.
The literature, for example DE-A 19 532 311 and WO 97/08164 discloses dioxothiochromane derivatives which are linked to a substituted or unsubstituted (1-hydroxy-3-oxocyclohex-1-en-2-yl)carbonyl radical. However, the herbicidal properties of the compounds known to date, and the tolerances with respect to crop plants are only moderately satisfactory.
It is an object of the present invention to find novel biologically, in particular, herbicidally, active compounds with improved properties.
We have found that this object is achieved by the cyclohexenonedioxothiochromanoyl derivatives of the formula I and their herbicidal action.
There have furthermore been found herbicidal compositions which comprise the compounds I and which have a very good herbicidal action. Moreover, there have been found processes for the preparation of these compositions and methods of controlling undesired vegetation using the compounds I.
Depending on the substitution pattern, the compounds of the formula I may contain one or more chiral centers, in which case they exist as enantiomer or diastereomer mixtures. The invention relates not only to the pure enantiomers or diastereomers, but also to their mixtures.
The compounds of the formula I may also exist in the form of their tautomers, where I represents the tautomeric forms I' and ' - 0050/49977 I".
R9 0 0 R1 ~ ~ R9 0 O R1 Rs \ S S
R8 \
R2m ~ I / R2m R7 OH / ~ R7 \ O
R
R R5 R4 R3 < ~ R5 R4 R3 I I' Rg OH O R1 S
R8 ~ \
R2m R7 \ 0 R R5 R4 R3 'XJ
I"
The compounds of the formula I may also exist in the form of their agriculturally useful salts, the nature of the salt generally not being decisive. In general, suitable salts are salts of those cations, or the acid addition salts of those acids, whose cations, or anions, respectively, do not adversely affect the herbicidal action of the compounds I.
Suitable cations are, in particular, ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium, it being preferable here, if desired, for one to four hydrogen atoms to be replaced by C1-C4-alkyl, hydroxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C~-alkyl, hydroxy-C1-C4-alkoxy-Cl-C4-alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2-(2-hydroxyeth-1-oxy)eth-1-ylammonium, di(2-hydroxyeth-1-yl)ammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.
Anions of useful acid addition salts are mainly chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate.
5 The organic moieties mentioned for the substituents R1-R9 and all the other radicals given in the present application are collective terms for individual enumerations of the individual group members. All hydrocarbon chains, that is to say all alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, N-alkylaminosulfonyl, N,N-dialkylaminosulfonyl, N-alkylsulfonylamino, N-haloalkylsulfonylamino, N-alkyl-N-alkylsulfonylamino, N-alkyl-N-haloalkylsulfonylamino, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkyl, dialkoxymethyl, dialkylthiomethyl, (alkoxy)(alkylthio)methyl, trialkylsulfonium and trialkylsulfoxonium radicals, can be straight-chain or branched. Unless otherwise specified, halogenated substituents preferably have attached to them one to five identical or different halogen atoms. The meaning halogen is in each case fluorine, chlorine, bromine or iodine.
Examples of other meanings are:
- C1-C4-alkyl, and the alkyl moieties of hydroxy-C1-C4-alkyl, tri(C1-C4-alkyl)sulfonium and tri(C1-C4-alkyl)sulfoxonium: for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl;
- C1-C6-alkyl, and the alkyl moieties of N-(C1-C6-alkyl)-N-(C1-C6-alkylsulfonyl)amino, N-(C1-C6-alkyl)-N-(C1-C6-halo-alkylsulfonyl)amino, C1-CQ-alkyl, 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-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-3-methylpropyl;
- C1-C4-haloalkyl: a C1-C4-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, v ~ 0050/49977 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-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;
- C1-C6-haloalkyl and the haloalkyl moieties of N-C1-C6-haloalkylamino: C1-C4-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;
- C1-C6-alkoxy and the alkoxy moieties of di(C1-C6-alkoxy)methyl and (C1-C6-alkoxy)-(C1-C6-alkylthio)methyl: for example 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-1-methylpropoxy or 1-ethyl-2-methylpropoxy;
- C1-C6-haloalkoxy: a C1-C6-alkoxy radical as mentioned above which is partially or fully 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-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloro-ethoxy, 1-(bromomethyl)-2-bromoethoxy, 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;
- C1-C6-alkylthio and the alkylthio radicals of (C1-C6-alkoxy)-(C1-C6-alkylthio)methyl and di(C1-C6-alkylthio)methyl: for example methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio or 1-ethyl-2-methylpropylthio;
- Cl-C6-haloalkylthio: a C1-C6-alkylthio radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, 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-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, pentafluoroethylthio, 2-fluoropropylthio, 3-fluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio, 2,3-dichloropropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio, heptafluoropropylthio, 1-(fluoromethyl)-2-fluoroethylthio, 1-(chloromethyl)-2-chloroethylthio, 1-(bromomethyl)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio, nonafluorobutylthio, 5-fluoropentylthio, 5-chloropentylthio, 5-bromopentylthio, 5-iodopentylthio, undecafluoropentylthio, 6-fluorohexylthio, 6-chlorohexylthio, 6-bromohexylthio, 6-iodohexylthio or dodecafluorohexylthio;
- C1-C6-alkylsulfinyl (C1-C6-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-dimethylpropylsulfinyl, 1,2-dimethylpropylsulfinyl, hexylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1,1-dimethylbutylsulfinyl, 1,2-dimethylbutylsulfinyl, 1,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1,1,2-trimethylpropylsulfinyl, 1,2,2-trimethylpropylsulfinyl, 1-ethyl-1-methylpropylsulfinyl or 1-ethyl-2-methylpropylsulfinyl;
C1-C6-haloalkylsulfinyl: C1-C6-alkylsulfinyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethylsulfinyl, 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-bromopropylsulfinyl, 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-fluoroethylsulfinyl, 1-(chloromethyl)-2-chloroethylsulfinyl, 1-(bromomethyl)-2-bromoethylsulfinyl, 4-fluorobutylsulfinyl, 4-chlorobutylsulfinyl, 4-bromobutylsulfinyl, nonafluorobutylsulfinyl, 5-fluoropentylsulfinyl, 5-chloropentylsulfinyl, 5-bromopentylsulfinyl, ' ' 0050/49977 CA 02373165 2001-11-06 5-iodopentylsulfinyl, undecafluoropentylsulfinyl, 6-fluorohexylsulfinyl, 6-chlorohexylsulfinyl, 6-bromohexylsulfinyl, 6-iodohexylsulfinyl or dodecafluorohexylsulfinyl;
- C1-C6-alkylsulfonyl (C1-C6-alkyl-S(=0)z-), and the alkylsulfonyl radicals of N-(C1-C6-alkylsulfonyl)amino and N- (C1-C6-alkyl)-N-(Cl-C6-alkylsulfonyl)amino: for example methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-ethyl-1-methylpropylsulfonyl or 1-ethyl-2-methylpropylsulfonyl;
- C1-C6-haloalkylsulfonyl and the haloalkyl radicals of N-(C1-C6-haloalkylsulfonyl)amino and N-(C1-C6-alkyl)-N-(C1-C6-haloalkylsulfonyl)amino: a C1-C6-alkylsulfonyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 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-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl, 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-bromoethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl, nonafluorobutylsulfonyl, 5 5-fluoropentylsulfonyl, 5-chloropentylsulfonyl, 5-bromopentylsulfonyl, 5-iodopentylsulfonyl, 6-fluorohexylsulfonyl, 6-bromohexylsulfonyl, 6-iodohexylsulfonyl or dodecafluorohexylsulfonyl;

10 - (C1-C6-alkylamino)sulfonyl: for example methylaminosulfonyl, ethylaminosulfonyl, propylaminosulfonyl, 1-methylethylaminosulfonyl, butylaminosulfonyl, 1-methylpropylaminosulfonyl, 2-methylpropylaminosulfonyl, 1,1-dimethylethylaminosulfonyl, pentylaminosulfonyl, 1-methylbutylaminosulfonyl, 2-methylbutylaminosulfonyl, 3-methylbutylaminosulfonyl, 2,2-dimethylpropylaminosulfonyl, 1-ethylpropylaminosulfonyl, hexylaminosulfonyl, 1,1-dimethylpropylaminosulfonyl, 1,2-dimethylpropylaminosulfonyl, 1-methylpentylaminosulfonyl, 2-methylpentylaminosulfonyl, 3-methylpentylaminosulfonyl, 4-methylpentylaminosulfonyl, 1,1-dimethylbutylaminosulfonyl, 1,2-dimethylbutylaminosulfonyl, 1,3-dimethylbutylaminosulfonyl, 2,2-dimethylbutylaminosulfonyl, 2,3-dimethylbutylaminosulfonyl, 3,3-dimethylbutylaminosulfonyl, 1-ethylbutylaminosulfonyl, 2-ethylbutylaminosulfonyl, 1,1,2-trimethylpropylaminosulfonyl, 1,2,2-trimethylpropylaminosulfonyl, 1-ethyl-1-methylpropylaminosulfonyl or 1-ethyl-2-methylpropylaminosulfonyl;
- di(C1-C6-alkyl)aminosulfonyl: for example N,N-dimethylaminosulfonyl, N,N-diethylaminosulfonyl, N,N-di(1-methylethyl)aminosulfonyl, N,N-dipropylaminosulfonyl, N,N-dibutylaminosulfonyl, N,N-di(1-methylpropyl)aminosulfonyl, N,N-di(2-methylpropyl)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-methylpropyl)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-propylaminosulfonyl, N-(1,1-dimethylethyl)-N-propylaminosulfonyl, N-butyl-N-(1-methylethyl)aminosulfonyl, N-(1-methylethyl)-N-(1-methylpropyl)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,l-dimethylethyl)aminosulfonyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminosulfonyl, N-(1,1-dimethylethyl)-N-(1-methylpropyl)aminosulfonyl, N-(1,1-dimethylethyl)-N-(2-methylpropyl)aminosulfonyl, N-methyl-N-pentylaminosulfonyl, N-methyl-N-(1-methylbutyl)aminosulfonyl, N-methyl-N-(2-methylbutyl)aminosulfonyl, N-methyl-N-(3-methylbutyl)aminosulfonyl, N-methyl-N-(2,2-dimethylpropyl)aminosulfonyl, N-methyl-N-(1-ethylpropyl)aminosulfonyl, N-methyl-N-hexylaminosulfonyl, N-methyl-N-(1,1-dimethylpropyl)aminosulfonyl, N-methyl-N-(1,2-dimethylpropyl)aminosulfonyl, 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-dimethylbutyl)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-1-methylpropyl)aminosulfonyl, N-methyl-N-(1-ethyl-2-methylpropyl)aminosulfonyl, N-ethyl-N-pentylaminosulfonyl, N-ethyl-N-(1-methylbutyl)aminosulfonyl, N-ethyl-N-(2-methylbutyl)aminosulfonyl, N-ethyl-N-(3-methylbutyl)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-methylpentyl)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-trimethylpropyl)aminosulfonyl, N-ethyl-N-(1-ethyl-1-methylpropyl)aminosulfonyl, N-ethyl-N-(1-ethyl-2-methylpropyl)aminosulfonyl, N-propyl-N-pentylaminosulfonyl, N-butyl-N-pentylaminosulfonyl, N,N-dipentylaminosulfonyl, N-propyl-N-hexylaminosulfonyl, N-butyl-N-hexylaminosulfonyl, N-pentyl-N-hexylaminosulfonyl or N,N-dihexylaminosulfonyl;
- C1-C4-alkoxycarbonyl: methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1-methylethoxycarbonyl, butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl or 1,1-dimethylethoxycarbonyl;
- (C1-C6-alkoxy)carbonyl: (C1-C4-alkoxy)carbonyl as mentioned above and, for example, pentoxycarbonyl, 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2,2-dimethylpropoxycarbonyl, 1-ethylpropoxycarbonyl, hexoxycarbonyl, 1,1-dimethylpropoxycarbonyl, 1,2-dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4-methylpentoxycarbonyl, 1,1-dimethylbutoxycarbonyl, 1,2-dimethylbutoxycarbonyl, 1,3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 2,3-dimethylbutoxycarbonyl, 3,3-dimethylbutoxycarbonyl, 1-ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl, 1,1,2-trimethylpropoxycarbonyl, 1,2,2-trimethylpropoxycarbonyl, ~~5U~49977 CA 02373165 2001-11-06 1-ethyl-1-methylpropoxycarbonyl or 1-ethyl-2-methylpropoxycarbonyl;
- C1-C6-haloalkoxycarbonyl: a C1-C4-alkoxycarbonyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example fluoromethoxycarbonyl, difluoromethoxycarbonyl, trifluoromethoxycarbonyl, chlorodifluoromethoxycarbonyl, bromodifluoromethoxycarbonyl, 2-fluoroethoxycarbonyl, 2-chloroethoxycarbonyl, 2-bromoethoxycarbonyl, 2-iodoethoxycarbonyl, 2,2-difluoroethoxycarbonyl, 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-chloropropoxycarbonyl, 2-bromopropoxycarbonyl, 3-bromopropoxycarbonyl, 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-bromoethoxycarbonyl, 4-fluorobutoxycarbonyl, 4-chlorobutoxycarbonyl, 4-bromobutoxycarbonyl, 4-iodobutoxycarbonyl, 5-fluoropentoxycarbonyl, 5-chloropentoxycarbonyl, 5-bromopentoxycarbonyl, 6-fluorohexoxycarbonyl, 6-chlorohexoxycarbonyl or 6-bromohexoxycarbonyl;
- C1-C4-alkoxy-C1-C4-alkyl and the alkoxyalkyl moieties of hydroxy-C1-C4-alkoxy-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-alkoxy as mentioned above, for example 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-(1-methylethoxy)ethyl, 2-(butoxy)ethyl, 2-(1-methylpropoxy)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)butyl, 2-(propoxy)butyl, 5 2-(1-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-(1-methylpropoxy)butyl, 10 3-(2-methylpropoxy)butyl, 3-(1,1-dimethylethoxy)butyl, 4-(methoxy)butyl, 4-(ethoxy)butyl, 4-(propoxy)butyl, 4-(1-methylethoxy)butyl, 4-(butoxy)butyl, 4-(1-methylpropoxy)butyl, 4-(2-methylpropoxy)butyl or 4-(1,1-dimethylethoxy)butyl.
With a view to the use of the compounds of the formula I
according to the invention as herbicides, the variables preferably have the following meanings, either alone or in combination:
R1 is nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-Cs-haloalkylthio, C1-C6-alkylsulfonyl or C1-C6-haloalkylsulfonyl;
R3 is hydrogen;
X forms an -0-(CH2)n- chain which can be substituted by one to three radicals selected from the following group: halogen, C1-Cq-alkyl, C1-Cq-haloalkyl or C1-Cq-alkoxycarbonyl;
or 35 a -(CH2)p-chain which can be interrupted by an oxygen or sulfur and/or can be substituted by one to four radicals selected from the following group:
halogen, C1-Cq-alkyl, C1-Cq-haloalkyl or 40 C1-Cq-alkoxycarbonyl;
m is 0;
n is 1 to 5;
p is 2 to 6;

w - 0050/49977 R4, R8 are hydrogen or C1-Cq-alkyl such as methyl, ethyl or propyl;
preferably hydrogen or methyl;
5 R5, R7, R9 are hydrogen or C1-C4-alkyl such as methyl, ethyl or propyl;
preferably hydrogen or methyl;
R6 is hydrogen, hydroxyl, C1-C6-alkyl, 10 di(C1-C6-alkoxy)methyl, (C1-C6-alkoxy)(C1-C6-alkylthio)methyl, di(C1-C6-alkylthio)methyl, C1-C6-alkoxy, C1-Cs-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, 15 C1-C6-alkylsulfonyl or C1-C6-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, it being possible for the six last-mentioned radicals to be substituted by one to three C1-C4-alkyl radicals;
preferably hydrogen, hydroxyl or C1-C4-alkyl such as methyl, ethyl or propyl;
or R5 and R6 or R6 and R9 together form a n bond or a C3-C5-alkyl chain which can have attached to it one to three radicals selected from the following group: halogen, cyano, C1-CQ-alkyl, C1-C4-haloalkyl or Cl-CQ-alkoxycarbonyl;
or R5 and R9 together form a C1-C4-alkyl chain which can have attached to it one to three radicals selected from the following group: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxycarbonyl;
or R6 and R7 together from an -0-(CH2)q-0-, -0-(CH2)q-S- or -S-(CH2)q-S- chain which can be substituted by one to three radicals selected from the following group: halogen, cyano, C1-CQ-alkyl, C1-C4-haloalkyl or C1-C4-alkoxycarbonyl;
preferably, R6 and R7 together form an -O-(CH2)q-0-, -0-(CHZ)q-S-or -S-(CH2)q-S chain which can be substituted by one to three of the radicals selected from the following group: C1-C4-haloalkyl or C1-C4-alkoxycarbonyl;
or R6 and R7 together with the carbon to which they are bonded form a carbonyl group;
q is 2 to 4.
Especially preferred compounds of the formula I are those where the variables have the following meanings, either alone or in combination:
R1 is halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-alkylthio or C1-C6-alkylsulfonyl;
in particular halogen such as chlorine or bromine, C1-C6-alkyl such as methyl or ethyl, C1-C6-alkoxy such as methoxy or ethoxy or C1-C6-alkylsulfonyl such as methylsulfonyl or ethylsulfonyl;
particularly preferably chlorine, methyl, methoxy or methylsulfonyl;
R3 is hydrogen;
X forms an -0-(CH2)n- chain which can be substituted by one to three radicals selected from the following group:
C1-C4-alkyl or C1-C4-haloalkyl;
or a -(CH2)p- chain which can be substituted by one to four radicals selected from the following group:
halogen, C1-C4-alkyl or C1-C4-haloalkyl;
m is 0;
n is 1 to 4 ;
in particular 1, 3 or 4;
p is 2 to 6;
R4, R8 are hydrogen or C1-C4-alkyl such as methyl, ethyl or propyl;
preferably hydrogen or methyl;

' 0050/49977 CA 02373165 2001-11-06 R5, R7, R9 are hydrogen or C1-C4-alkyl such as methyl, ethyl or propyl;
preferably hydrogen or methyl;
5 R6 is hydrogen, hydroxyl, C1-C6-alkyl, di(C1-C6-alkoxy)methyl, (C1-C6-alkoxy)(C1-C6-alkylthio)methyl, di(C1-C6-alkylthio)methyl, C1-C6-alkylsulfonyl or C1-C6-haloalkylsulfonyl;
preferably hydrogen, hydroxyl or C1-C4-alkyl such as methyl, ethyl or propyl;
or R6 and R7 together with the carbon atom to which they are bonded form a carbonyl group.
Particularly preferred compounds of the formula I are those where R1 is halogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkyl-sulfonyl;
R3 is hydrogen.
Equally particularly preferred compounds of the formula I are those where X forms an -0-(CH2)- or a -(CH2)p- chain, it being possible for the latter to be substituted by one to three halogen atoms, C1-C4-alkyl or C1-C4-haloalkyl radicals;
p is 2 to 5;
in particular 2, 4 or 5.
Most particularly preferred compounds of the formula I are those where X forms a -(CH2)2- chain which can be substituted by 1 to 3 halogen atoms such as fluorine or chlorine, C1-C4-alkyl radicals such as methyl or ethyl or C1-C4-haloalkyl radicals such as trifluoromethyl.
Equally particularly preferred compounds of the formula I are those where R6 is hydrogen, hydroxyl, C1-C6-alkyl, di(C1-C6-alkoxy)-methyl, (C1-C6-alkoxy)(C1-C6-alkylthio)methyl, di(C1-C6-alkylthio)methyl or C1-C6-alkoxy;
R7 is hydrogen or C1-C4-alkyl;
or R6 and R7 together with the carbon to which they are bonded form a carbonyl group.
Also particularly preferred are the compounds of the formula I
where R1 is halogen or C1-C6-alkyl;
in particular chlorine or methyl;
most particularly methyl;
x is an -0-(CH2)- or a -(CHz)5- or a -(CH2)2 chain, it being possible for the latter to be substituted by one to three halogen atoms;
R6 is hydrogen or C1-Cq-alkyl;
R7 is hydrogen or C1-C4-alkyl;
or R6 and R7 together with the carbon to which they are bonded form a carbonyl group.
Extraordinarily preferred compounds are those of the formula Ial (= I where m=0; R4 to R9=H), in particular the compounds Ial.1 to Ia1.85, where the definitions of the radicals R1 to R9, m and X
have a particular meaning for the compounds according to the invention, not only in combination with each other, but also in each case alone.

Table 1:
O O R1 ~~
S
Ia1 OH

No. R R X

Ial.1 C1 H -OCH2-Ial.2 C1 H -0(CH2)3-Ial.3 C1 H -0(CH2)a-15Ial.4 C1 H -(CH2)2-Ial.5 C1 H -(CH2)3-Ial.6 C1 H -(CH2)a-Ial.7 C1 H -(CH2)5-Ial.8 C1 H -CHF-CH2-Ial.9 C1 H -CHCl-CH2-20Ia1.10 C1 H -CHBr-CH2-Ial.11 C1 H _=CF2=CH2=-___ Ia1.12 C1 H -CC12-CHZ-Ia1.13 C1 H -CBr2-CH2-Ia1.14 C1 H -CFCI-CHZ-25Ia1.15 C1 H -CFBr-CH2-Ia1.16 C1 H -CClBr-CH2-Ia1.17 C1 H -(CH2)Z-C(CH3)2-(CHz)2-Ial.l8 CH3 H -OCH2-Ia1. CH3 H -0 (CH2 ) 3-Ia1.20 CH3 H -0(CH2)4-30Ia1.21 CH3 H _ (CH2~Z= _ Ia1.22 CH3 H -(CHz)3-Ia1.23 CH3 H -(CH2)c-Ia1.24 CH3 H -(CH2)5-Ia1.25 CH3 H -CHF-CH2-35Ia1.26 CH3 H -CHC1-CH2-Ia1.27 CH3 H -CHBr-CH2-Ia1.28 CH3 H -CF2-CH2-Ia1.29 CH3 H -CClz-CHZ-Ia1.30 CH3 H -CBr2-CH2-Ia1.31 CH3 H -CFC1-CH2-40Ia1.32 CH3 H -CFBr-CH2-Ia1.33 CH3 H -CClBr-CH2-Ia1.34 CH3 H -(CH2)2-C(CH3)2-(CH2)2-Ia1.35 OCH3 H -OCH2-Ia1.36 OCH3 H -0(CH2)3-45Ia1. OCH3 H -0 (CH2 ) q,-Ia1.38 OCH3 H -(CH2)2-Ia1.39 OCH3 H -(CH2)3-Ia1.40 OCH3 H -(CH2)4-No. R R X

Ia1.41 OCH3 H -(CH2)5-Ia1.42 OCH3 H -CHF-CH2-Ia1.43 OCH3 H -CHC1-CH2-5 Ia1.44 OCH3 H -CHBr-CH2-Ia1.45 OCH3 H -CF2-CH2-Ia1.46 OCH3 H -CC12-CH2-Ia1.47 OCH3 H -CBr2-CH2-Ia1.48 OCH3 H -CFCl-CH2-Ia1.49 OCH3 H -CFBr-CH2-10 Ia1.50 OCH3 H -CClBr-CH2-Ia1.51 OCH3 H -(CH2)2-C(CH3)2-(CH2)2-Ia1.52 SCH3 H -OCH2-Ia1.53 SCH3 H -O(CH2)3-Ia1.54 SCH3 H -O(CH2)4-15 Ia1.55 SCH3 H -(CH2)2-Ia1.56 SCH3 H -(CH2)3-Ia1.57 SCH3 H -(CH2)a-Ia1.58 SCH3 H -(CH2)5-Ia1.59 SCH3 H -CHF-CH2-Ia1.60 SCH3 H -CHC1-CH2-20 Ia1.61 SCH3 H -CHBr-CH2-Ia1.62 SCH3 H -CF2-CH2-Ia1.63 SCH3 H -CC12-CH2-Ia1.64 SCH3 H -CBr2-CH2-Ia1.65 SCH3 H -CFCl-CH2-Ia1.66 SCH3 H -CFBr-CH2-Ia1.67 SCH3 H -CClBr-CH2-Ia1.68 SCH3 H -(CH2)2-C(CH3)2-(CH2)2-Ia1.69 S02CH3 H -OCH2-Ia1.70 S02CH3 H -O(CH2)3-Ia1.71 S02CH3 H -0(CH2)4-Ia1.72 S02CH3 H -(CH2)2-Ia1.73 S02CH3 - H _. __ (CH2) 3_ _ Ia1.74 S02CH3 H. -(CH2)4-Ia1.75 S02CH3-__ - H... - -(CH2)5_ Ia1. S02CH3 H - -CHF-CH2_ Ia1.77 S02CH3 H -CHC1-CH2-Ia1.78 S02CH3 H -CHBr-CH2-Ia1.79 S02CH3 H -CF2-CH2-Ia1.80 S02CH3 H -CC12-CH2-Ia1.81 S02CH3 H -CBr2-CH2-Ia1.82 S02CH3 H -CFC1-CH2-Ia1.83 S02CH3 H -CFBr-CH2-Ia1.84 S02CH3 _. H ___._ _CClBr-CH2_ Ia1.85 S02CH3 H ~ -(CH2)2-C(CH3)2-(CH2)2-Further extraordinarily preferred cyclohexenonedioxo-thiochromanoyl derivatives of the formula I are those which follow:

- The compounds of the formula Ia2, in particular the compounds Ia2.1 to Ia2.85, which differ from the compounds Ial.1 to Ia1.85 by the fact that R6 and R7 are methyl.

S
Ia2 ~OH

- The compounds of the formula Ia3, in particular the compounds Ia3.1 to Ia3.85, which differ from the compounds Ial.1 to Ia1.85 by the fact that R6 is methyl.
0 0 R1 ~ //
S
Ia3 ~ off I /
LXJ

- The compounds of the formula Ia4, in particular the compounds Ia4.1 to Ia4.85, which differ from the compounds Ial.l to Ia1.85 by the fact that R8 and R9 are methyl.

S
Ia4 OH

- The compounds of the formula IaS, in particular the compounds Ia5.1 to Ia5.85, which differ from the compounds Ial.l to Ia1.85 by the fact that R8 is methyl.

S
Ia5 OH

~~rJ~~49977 CA 02373165 2001-11-06 2~
The compounds of the formula Ia6, in particular the compounds Ia6.1 to Ia6.85, which differ from the compounds Ial.1 to Ia1.85 by the fact that R4, R5, R8 and R9 are methyl and R6 and R7 together with the carbon to which they are bonded form a carbonyl group.
O O R~ O O
S
Ia6 ~ OH

- The compounds of the formula Ia7, in particular the compounds Ia7.1 to Ia7.85, which differ from the compounds Ial.1 to Ia1.85 by the fact that R4, R5, R8 and R9 are methyl and R6 is hydroxyl.
O 0 R~ 0 O
S
ao Ia7 HO OH
Rs X
The cyclohexenonedioxothiochromanoyl derivatives of the formula I
can be obtained by various routes, for example by the following process:
Synthesis of compounds of the formula I by reacting an activated benzoic acid IIa or a benzoic acid IIb, which is preferably activated in situ, with a cyclohexanedione of the formula III to give the acylation product, followed by a rearrangement reaction.

s HO I \ R2m IIb R9 O R1 ~ ~ R8 0 R1 R8 + S I S
I ~ 7 \ R O \
R7 OH L1 I / R2m R6 R5 R4 I / R2m R3 ~ R3 X
III IIa S

R I I \ R2m OH

I
L1 represents 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, and the like.
The activated benzoic acid IIa can be employed directly, as in the case of the benzoyl halides, or it can be prepared in situ, for example with dicyclohexylcarbodiimide, triphenylphosphine/azodicarboxylic acid ester, 2-pyridine disulfide/triphenylphosphine, carbonyldiimidazole and the like.
Occasionally, it may be advantageous to carry out the acylation reaction in the presence of a base. The reactants and the auxiliary base are expediently employed in equimolar amounts.
Under certain circumstances, a small excess of the auxiliary base, for example 1.2 to 1.5 mole equivalents, based on II, may be advantageous.

0~50~49977 CA 02373165 2001-11-06 Suitable auxiliary bases are tertiary alkylamines, pyridine or alkali metal carbonates. Examples of solvents which can be used are 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 of these.
If a benzoyl halide is employed as the activated carboxylic acid component, it may be advantageous to cool the reaction mixture to 0-10°C when this reactant is added. Then, the mixture is stirred at 20 - 100°C, preferably at 25 - 50°C, until the reaction is complete. Work-up is carried out in the customary manner, for example the reaction mixture is poured into water and the product of interest is extracted. Solvents which are particularly suitable for this purpose are methylene chloride, diethyl ether and ethyl acetate. After the organic phase has been dried and the solvent has been removed, the crude ester can be employed in the rearrangement reaction without further purification.
The rearrangement reaction of the esters to give the compounds of the formula I is expediently carried out at temperatures from 20 to 100°C in a solvent and in the presence of a base, without or with the aid of a cyano compound as catalyst.
Examples of solvents which can be employed are acetonitrile, methylene chloride, 1,2-dichloroethane, dioxane, ethyl acetate, toluene or mixtures of these. Preferred solvents are acetonitrile and dioxane.
Suitable bases are tertiary amines such as triethylamine, aromatic amines such as pyridine or alkali metal carbonates such as sodium carbonate or potassium carbonate, all of which are preferably employed in equimolar amounts or up to a four-fold excess based on the ester. Substances which are preferably used are triethylamine or alkali metal carbonate, preferably in twice the equimolar amount based on the ester.
Suitable cyano compounds are inorganic cyanides such as sodium cyanide or potassium cyanide, and organic cyano compounds such as acetone cyanohydrin or trimethylsilyl cyanide. They are employed in an amount of 1 to 50 mole percent based on the ester. It is preferred to employ acetone cyanohydrin or trimethylsilyl cyanide, for example in an amount of 5 to 15, preferably 10, mole percent based on the ester.

Work-up can be carried out in a manner known per se. The reaction mixture is acidified with, for example, dilute mineral acid, such as 5~ hydrochloric acid or sulfuric acid, and extracted with an organic solvent, for example methylene chloride or ethyl acetate.
5 The organic extract can be extracted with a 5-10~ alkali metal carbonate solution, for example sodium carbonate or potassium carbonate solution. The aqueous phase is acidified, and the precipitate which forms is filtered off with suction and/or extracted with methylene chloride or ethyl acetate, dried and 10 concentrated.
The benzoyl halides of the formula IIa (where L1 = C1, Br) can be prepared in a manner known per se by reacting the benzoic acids of the formula IIb with halogenating reagents such as thionyl 15 chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride or oxalyl bromide.
The benzoic acids of the formula IIb can be prepared in a manner known per se by subjecting the corresponding esters to acid or 20 basic hydrolysis.
The benzoic esters of the formula IIc (where T = C1-C6-alkoxy) can be obtained, for example, by the following processes.

S
T I \
R2m IIc (where T=C1-C6-alkoxy) A. Synthesis of the benzoic esters of the formula IIc where X=-O-(CH2)n-, n = 3 to 5 by reacting thiochromanoyl derivatives of the formula IV with a-halo-w-metal-alkyl compounds of the formula V (where Hal = C1, Br; M = Li, M =
Li, Mg, Zn) (cf., for example, M. Noel et al., Comptes Rend.
268, 1152 (1969)).

0~5~~49977 CA 02373165 2001-11-06 as 0 R1 ~ ~ 0 R1 ~ //0 S S
' / R2m + Hal- ( CH2 ) n-M -~' Z' ~ / Rzm R3 0 R3 0-(CHZ)n IV V IIc where X=-0-(CH2)n-%
n= 3 to 5 B. Synthesis of the benzoic acid esters of the formula IIc where X=-0-(CH2)- by epoxidizing methylidenethiochromanoyl derivatives of the formula VI
0 R1 ~~ ~ 0 R1 S epoxidation ~ S
I R2m T ~ R2m / /

a5 VI IIc where X=-0-(CH2)-Examples of suitable epoxidizing reagents are organic peracids such as peroxyacetic acid, or m-chloroperbenzoic acid, hydrogen peroxide (in alkaline medium) or alkyl peroxides, in the presence or absence of a transition metal catalyst such as, for example, oxides of vanadium, molybdenum or cobalt.
The methylidenethiochromanoyl derivatives of the formula VI
which are used as starting materials can be obtained from the corresponding thiochromanoyl derivatives of the formula IV by Wittig reactions or similar reactions (cf., for example, J.
March, "Advanced Organic Chemistry", 4th edition, Wiley, New York p. 956 et seq.) O R1 ~ ~ O R1 S Ph3 P=CH2 \ S
/ Rzm ~' T ~ / R2m IV VI
The methylidenethiochromanoyl derivatives of the formula VI
can also be obtained by subjecting corresponding thiochromanoyl derivatives of the formula IV to a McMurry reaction (cf., for example, A. Fiirstner, Angew. Chem. 105, 171 (1993)).
C. Synthesis of the benzoic esters of the formula IIc where X=-(CH2)2- by reacting methylidenethiochromanoyl derivatives of the formula VI with carbenes or carbene equivalents (cf., for example, J. March, "Advanced Organic Chemistry", 4th edition, Wiley, New York p. 866 et seq.) O R 0 ~~O O R1 0 ~~O
1 ~S~ S//
\ \
R2m + "carbene" ~--~ T ( R2m / /

VI IIc where X=-(CH2)2-Mono- and dihalocarbenes can be obtained, for example, by reacting di- or trihalomethanes with bases such as, for example, n-butyllithium, potassium hydroxide or potassium tert-butoxide (cf., for example, Houben-Weyl, "Methoden der Organischen Chemie" [Methods in Organic Chemistry], Vol. E
17a).
Alkyl-substituted carbenes are obtained, for example, from sulfur glides (cf., 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 carbenes, can be obtained from corresponding diazo compounds, using rhodium acetate.
D. Synthesis of the benzoic acid esters of the formula IIc where X=-(CH2)p- and p = 4 to 6 by reacting compounds of the formula VII with an oxidant.

S S
R2m oxidant ~ T ~ ~ R2m R3 (CH2)4-6 R3 (CH2)4_6 VII IIc where X=-(CH2)4-6-Examples of suitable oxidants are organic peroxides such as m-chloroperbenzoic acid, peroxyacetic acid and trifluoroperoxyacetic acid, or hydrogen peroxide, in the presence or absence of a transition metal catalyst such as tungstate.
The compounds of the formula VII are obtained by alkylating the mercapto compounds VIII in the presence or absence of a base (cf., for example, Karrer et al., Helv. Chim. Acta (1942) 25, 29).

SH R2m S
~ + L2 ~ ~ H2 ) 4-6 '-'~ T I \ ~ R2m / /

(CH2) 4-6 VIII IX X
Examples of suitable bases are 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.

' 0050/49977 CA 02373165 2001-11-06 as The compounds of the formula X are subsequently cyclized by Friedel-Craft alkylation to give the compounds of the formula VII (cf., for example, Can. J. Chem. 59, 199 (1981); Chem.
Ber. 58, 1625 (1925); Phosp. and Sulf. 19, 31 (1984)). This cyclization is carried out in the presence of strong acids.

S S
\ H+ \
T I R2m ~ R2m / ~ /

(CH2) 4-6 ( CH2 ) 4-6 X VII
The abovementioned process routes A to D constitute synthesis principles. They also encompass the synthesis of the compounds of the formula IIc where X is an -O-(CH2)n- chain which can be substituted by one to three radicals selected from the following group: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxycarbonyl; or a -(CH2)p- chain which can be interrupted by an oxygen or sulfur and/or can be substituted by one to four radicals selected from the following group: halogen, cyano, a5 C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxycarbonyl. This means that the starting materials V, VI, VII, IV and X and the glides and carbenes used can be suitably substituted.
Benzoic acid derivatives of the formula II are novel, S
R1~ I \ R2m II
/

the variables having the following meanings:
R1 is hydrogen, nitro, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, N-(C1-C6-alkyl)aminosulfonyl, N,N-di(C1-C6-alkyl)aminosulfonyl, N-(C1-C6-alkylsulfonyl)amino, N-(C1-C6-haloalkylsulfonyl)amino, N-(C1-C6-alkyl)-N-(C1-C6-alkylsulfonyl)amino or N-(C1-C6-alkyl)-N-(C1-C6-haloalkylsulfonyl)amino;

R2 is C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
R3 is hydrogen, C1-C6-alkyl or halogen;
X forms an -0-(CH2)n- chain which can be substituted by one to three radicals selected from the following group:
halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxycarbonyl;
or a -(CH2)p- chain which can be interrupted by an oxygen or sulfur and/or can be substituted by one to four radicals selected from the following group:
halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxycarbonyl;
m is 0 to 4;
n is 1 to 5;
p is 2 to 6;
R1~ is hydroxyl or a hydrolytically removable radical;
Examples of hydrolytically removable radicals are alkoxy, phenoxy, alkylthio, phenylthio radicals which can be unsubstituted or substituted, halides, hetaryl radicals which are bonded via nitrogen, amino or imino radicals which can be unsubstituted or substituted, and the like.
Preferred are benzoic acid halides of the formula IIa where R1~=halogen S
Hal I \ R2m IIa where the variables R1 to R3, X and m have the meanings given under formula II and Hal is halogen, in particular chloride or bromide.
Equally preferred are benzoic acids of the formula IIb S
HO
R2m IIb where the variables R1 to R3, X and m have the meanings given under formula II.
Equally preferred are benzoic esters of the formula IIc S
T ~ /~ ~ RZm IIc where the variables R1 to R3, X and m have the meanings given under formula II and T is C1-C6-alkoxy.
The especially preferred embodiments of the benzoic acid derivatives of the formula II with regard to the variables R1 to R3, X and m correspond to those of the cyclohexenonedioxo-thiochromanoyl derivatives of the formula I.

- 3a Preparation Examples:
1-Hydroxy-5,5-dimethyl-2-{((cyclohexane-1-spiro-4)-8-methyl-1,1-dioxothiochroman-7-yl]carbonyl)cyclohex-1-en-3-one (compound 2.2) Step a) Methyl 3-(2-cyclohexylideneethylthio)-2-methylbenzoate 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 ml of acetone was added dropwise at room temperature. After 4 hours, the solvent was removed, and 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 15 chromatographed on silica gel with ethyl acetate/cyclohexane as the eluent.
Yield: 16.3 g 1H NMR (CDC13): 8=7.60 (d,lH); 7.42 (d,lH), 7.15 (t,lH); 5.22 (t,lH); 3.88 (s,3H); 3.50 (d,2H); 2.55 (s,3H); 2.04 (m,4H);
a0 1.60-1.34 (m,6H).
Step b) Methyl (cyclohexane-1-spiro-4)-8-methylthiochromane-7-carboxylate 20 g (69 mmol) of methyl 3-(2-cyclohexylideneethylthio)-2-methylbenzoate were dissolved in 200 ml of methylene chloride, and 27.6 g (276 mmol) of concentrated sulfuric acid were added at -10°C. After the reaction mixture had been stirred for one hour at -10°C, it was poured into ice-water, and the phases which formed were separated. The organic phase was washed in succession with sodium hydrogen carbonate solution and water, dried and concentrated.
Yield: 17.4 g (colorless oil) 1H NN~ (CDC13): b=7.45 (d,lH); 7.34 (d,lH), 3.85 (s,3H); 3.00 (t,2H); 2.45 (s,3H); 2.12 (t,2H) 1.80-1.15 (m,lOH).
Step c) (Cyclohexane-1-spiro-4)-8-methylthiochromane-7-carboxylic acid 17.4 g (60 mmol) of methyl (cyclohexane-1-spiro-4)-8-methyl-thiochromane-7-carboxylate were dissolved in 200 ml of a 1:1 mixture of methanol and water, treated with 3.6 g (80 mmol) of sodium hydroxide and refluxed for 3 hours. The organic solvent was subsequently removed, the aqueous phase was extracted with diethyl ether and acidified with 2 N hydrochloric acid. The precipitate which had formed was filtered off with suction, washed with water and dried.

0050/4997'7 CA 02373165 2001-11-06 Yield: 13.8 g (80~) (colorless solid) Melting point: 238°C
Step d) (Cyclohexane-1-spiro-4)-1,1-dioxo-8-methylthiochromane-7-carboxylic acid (compound 3.1) 12.8 g (46 mmol) of (cyclohexane-1-spiro-4)-8-methylthiochromane-7-carboxylic acid and a spatula-tipful of sodium tungstate were introduced into 100 ml of glacial acetic acid, and 11.6 g (102 mmol) of a 30~ hydrogen peroxide solution were added dropwise at 50°C. After the reaction mixture had been stirred for 4 more hours at this temperature, it was stirred into ice-water, and the precipitate formed was filtered off with suction, washed with water and dried.
Yield: 11.3 g (79~) (colorless solid) Melting point: 242°C
Step e) 1-Hydroxy-5,5-dimethyl-2-{[(cyclohexane-1-spiro-4)-8 methyl-1,1-dioxothiochroman-7-yl]carbonyl)cyclohex-1 en-3-one (compound 2.2) 0.54 g (2.6 mmol) of N,N-dicyclohexylcarbodiimide was added to a solution of 0.8 g (2.6 mmol) of (cyclohexane-1-spiro-4)-8-methyl-1,1-dioxothiochromane-7-carboxylic acid and 0.36 g (2.6 mmol) of dimedone in 20 ml of acetonitrile, and stirring was continued for 6 hours at room temperature. 0.52 g (5.2 mmol) of triethylamine and 0.05 ml of trimethylsilylcyanide were then added. After the reaction mixture had been stirred for 2 more hours at room temperature, it was partitioned between a 2~ soda solution and ethyl acetate, and the precipitate which formed was filtered off with suction. The aqueous phase was washed with diethyl ether and brought to pH 2 with hydrochloric acid. The precipitate formed was filtered off with suction, washed with water and dried.
Yield: 0.55 g Melting point: 122°C
1-Hydroxy-2-{[(2,2-difluorocyclopropane-1-spiro-4)-8-methyl-1,1-dioxothiochroman-7-yl)carbonyl]cyclohex-1-en-3-one (compound 2.9) Step a) Methyl 3-(hydroxycarbonyl-1-ylethylthio)-2-methylbenzoate 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, 42.0 g (275 mmol) of 3-bromopropionic acid (Aldrich) in 100 ml of acetone were added dropwise. After the mixture had been stirred for 4 hours at room temperature, the solvent was removed, the residue was taken up in water and the mixture was acidified with concentrated hydrochloric acid. The precipitate formed was filtered off with suction, washed with water and dried.
Yield: 68.8 g (99~) Melting point: 113°C
Step b) Methyl 8-methyl-4-oxothiochromane-7-carboxylate 34.4 g (135 mmol) of methyl 3-(2-hydroxycarbonyleth-1-ylthio)-2-methylbenzoate were added to 350.0 g of polyphosphoric acid at 70°C, and the mixture was stirred for one hour at this temperature. The mixture was subsequently poured into ice-water, and the precipitate formed was filtered off with suction. The precipitate 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) Methyl 8-methyl-4-methylidenethiochromane-7-carboxylate 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 the mixture had been stirred for 30 minutes at room temperature, it was cooled to 20°C, and 24.7 g (105 mmol) of methyl 8-methyl-4-oxothiochromane-7-carboxylate in 150 ml of tetrahydrofuran were added. The batch was then stirred for a further 30 minutes at 0°C and then stirred into ice-water. The aqueous phase was extracted with ethyl acetate, and 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) 1H NMR (CDC13): 8=7.44 (d,lH); 7.40 (d,lH), 5.54 (s,lH); 5.06 (s,lH); 3.88 (s,3H), 3.10 (m,2H); 2.80 (m,2H); 2.46 (s,3H).
Step d) Methyl (2,2-difluorocyclopropane-1-spiro-4)-8-methyl-thiochromane-7-carboxylate 1.0 g (4.3 mmol) of methyl 8-methyl-4-methylidenethiochromane-7-carboxylate were dissolved in 20 ml of diethylene glycol dimethyl ether and the solution was heated to reflux temperature.
A solution of 6.5 g (43.0 mmol) of sodium chlorodifluoroacetate in 30 ml of diethylene glycol dimethyl ether was added dropwise at this temperature in the course of 30 minutes, and the mixture was stirred for a further 15 minutes at this temperature. When cold, the batch was stirred into ice-water and extracted with diethyl ether. The ether phase was dried and concentrated. The 5 residue was chromatographed on silica gel using ethyl acetate/cyclohexane as the eluent.
Yield: 0.9 g (74~) (colorless solid) Melting point: 104-105°C
10 Step e) (2,2-Difluorocyclopropane-1-spiro-4)-8-methyl-thio-chromane-7-carboxylic acid 0.7 g (17.4 mmol) of sodium hydroxide was added to a solution of 3.3 g (11.6 mmol) of methyl (2,2-difluorocyclopropane-1-spiro-15 4)-8-methylthiochromane-7-carboxylate in 60 ml of a 1:1 mixture of methanol and water, and the mixture was refluxed for 2 hours.
When cold, the solvent was removed and the residue was then taken up in water and acidifed with 2 N hydrochloric acid. The precipitate formed was filtered off with suction, washed with 20 water and dried.
Yield: 3.1 g (99$) Melting point: 200-203°C
Step f) (2,2-Difluorocyclopropane-1-spiro-4)-8-methyl-1,1-25 dioxothiochromane-7-carboxylic acid (compound 3.5) 2.7 g (23.6 mmol) of a 30~ strength hydrogen peroxide solution were added dropwise at 50°C to a solution of 2.9 g (10.7 mmol) of (2,2-difluorocyclopropane-1-spiro-4)-8-methylthiochromane-7-30 carboxylic acid and a spatula-tipful of sodium tungstate in 30 ml of glacial acetic acid, and stirring was continued for 1 hour at this temperature. The batch was stirred into ice-water, and the precipitate formed was filtered off with suction and dried.
Yield: 3.0 g (93~) (colorless solid) 35 Melting point: 250-253°C
Step g) 1-Hydroxy-2-{((2,2-difluorocyclopropane-1-spiro-4)-8-methyl-1,1-dioxothiochroman-7-yl]carbonyl]cyclohex-1-en-3-one (compound 2.9) 0.34 g (1.7 mmol) of N,N-dicyclohexylcarbodiimide were added to a solution of 0.5 g (1.7 mmol) of (2,2-difluorocyclopropane-1-spiro-4)-8-methyl-I,1-dioxothiochromane-7-carboxylic acid and 0.19 g (1.7 mmol) of 1,3-cyclohexanedione in 20 ml of acetonitrile, and the mixture was 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 a 2~
soda solution and ethyl acetate, and the precipitate was filtered off with suction. The aqueous phase was washed with diethyl ether and brought to pH 3 using hydrochloric acid. The precipitate formed was filtered off with suction and dried.
Yield: 0.5 g (colorless solid) Melting point: 225-227°C
1-Hydroxy-4,4,6,6-tetramethyl-2-{[(oxirane-2-spiro-4)-8-methyl-1,1-dioxothiochroman-7-yl]carbonyl}cyclohex-1-ene-3,5-dione (compound 2.6) Step a) Methyl (oxirane-2-spiro-4)-8-methyl-1,1-dioxo-thiochroman-7-yl]carboxylate (compound 3.2) ' 4.0 g (12.8 mmol) of m-chloroperbenzoic acid were added to a solution of 1.0 g (4.3 mmol) of methyl 8-methyl-4-methylidene-1,1-dioxothiochroman-7-yl-carboxylate in ml of methylene chloride, and the mixture was stirred for 20 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 soda solution and then dried, and the solvent was removed.
Yield: 0.9 g Step b) (Oxirane-2-spiro-4)-8-methyl-1,1-dioxothiochroman-7-ylcarboxylic acid (compound 3.2) 85 ml of a 0.5 molar lithium hydroxide solution were added dropwise to 6.0 g (21 mmol) of methyl (oxirane-2-spiro-4)-8-methyl-1,1-dioxothiochroman-7-yl-carboxylate in 85 ml of tetrahydrofuran, and the mixture was stirred for 2 hours. The organic solvent was then removed, and the pH was brought to 3 using hydrochloric acid. The precipitate was filtered off with suction and dried.
Yield: 4.5 g (79~) (beige solid) Melting point: 164°C
Step c) 1-Hydroxy-4,4,6,6-tetramethyl-2-{[(oxirane-2-spiro-4)-8-methyl-1,1-dioxothiochroman-7-yl]carbonyl}cyclohex-1-ene-3,5-dione (compound 2.6) 0.62 g (3.0 mmol) of N,N-dicyclohexylcarbodiimide was added to a solution of 0.8 g (3.0 mmol) of (oxirane-2-spiro-4)-8-methyl-1,1-dioxothiochromane-7-carboxylic acid and 0.54 g (3.0 mmol) of 2,2,4,4-tetramethylcyclohexane-1,3,5-trione in 20 ml of acetonitrile, and the mixture was stirred for 12 hours at room ao temperature. 0.6 g (6.0 mmol) of triethylamine and 0.05 ml of trimethylsilyl cyanide were subsequently added, and stirring was continued for 4 hours. Then, a 2~ soda solution and ethyl acetate were added, and the precipitate was filtered off with suction, 5 and the aqueous phase was extracted with diethyl ether. The mixture was acidified with hydrochloric acid to pH 3, and the precipitate which forms is filtered off with suction.
Yield: 0.7 g (54~) (beige solid) Melting point: 214°C (decomposition) Other compounds of the formula I and of the benzoic acid derivatives II which were prepared in a similar manner are listed in Tables 2 and 3 below.

s~
.r., x ~ ~ ~ .u m ~n x v ~ v v ro~ ro e-IN ~i I I I
p a O N c-1d~O d~M d~ Il1l0 M
v-IN r-10000 e-iM N N 00 O

II ~'N ri v-Ir-1c-IN r1e-IN v-ir1 ~r ~ x x ~ x x ~ x x x x H

x x ~ x x ~ x x x x x x x x x x x x x U U U U

O O O

v ~ M fr1 M M
x x v x ~ x v x v x / ~ x x ~ x x ~ x x ~ x x x x x wx ~ x x ~ x x ~ x x x x ao r I I I I I
w w w O O O U U U U U
x I I 1 U U U U U U N N x x x _ _ ~ I I I U U U U U

M M 1"1M M f'1P'1M c"1('1f'~1 x x x x x x x x x x x U U U U U U U U U U U

N

r1N M 'd~II1l0I~00 a1~ r1 ~ N N N N N N N N N N N

a a .r., .r., .r., x " "

O QJ N N
b b N
I
a l0 O 00 O1 O tf1 ',~,'" ~-I r-1 N
x x x x x x v II
v x x x x I I I
N N N
x x x U U U

N N N
x x x U U U
I
Y~) M (~1 U U U
N M d~
O ri r-1 r1 z -N N N

Table 3 S
Rlo ~ \~ ~ II where m = 0, R3 = H
No. R X R M.p. (C) 3 .1 CH3 -CH2 ) 5- OH - 242 3.2 CH3 -CHzO- OCH3 198 (decomposi-tion) 3.3 CH3 -CH20- OH 164 3.4 CH3 -CH2-CC12- OH 239-240 3.5 CH3 -CH2-CF2- OH 250-253 3.6 CH3 -CH2-CH2- OH 260-262 ao The compounds of the formula I and their agriculturally useful salts, both as isomer mixtures and in the form of the pure isomers, are suitable for use as herbicides. The herbicidal compositions which comprise the compounds of the formula I are capable of effecting very efficient control of vegetation on non-crop areas, in particular at high application rates. In crops such as wheat, rice, corn, soya and cotton, they act against broad-leaved weeds and grass weeds without harming the crop plants to a significant extent. This effect is particularly pronounced at low application rates.
Depending on the method of application in question, the compounds of the formula I, or herbicidal compositions comprising them, can also be employed in a further number of crop plants for eliminating undesirable plants. The following are examples of suitable crops:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec.
rapa, grassica 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 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 ' ' 0050/49977 CA 02373165 2001-11-06 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 lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s, vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.
Moreover, the compounds of the formula I can also be employed in crops which have been made resistant to the action of herbicides by means of breeding including genetic engineering methods.
The compounds of the forniula I, or the herbicidal compositions comprising them, can be used, for example, in the form of ready-to-spray aqueous solutions, powders, suspensions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend on the intended aims, in any case, they should guarantee the finest possible distribution of the active ingredients according to the invention.
The herbicidal compositions comprise a herbicidally active amount of at least one compound of the formula I or of an agriculturally useful salt of I, and auxiliaries conventionally used for the formulation of crop protection products.
Suitable inert auxiliaries are essentially:
Mineral oil fractions of medium to high boiling point, such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable and animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example 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, for example 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. To prepare emulsions, pastes or oil dispersions, the cyclohexenonedioxothiochromanoyl derivatives of the formula I, either as such or dissolved in an oil or solvent, can be homogenized in water by means of wetters, tackifiers, dispersants or emulsifiers. Alternatively, it is possible to prepare concentrates comprising active ingredient, wetter, tackifier, dispersant or emulsifier and, if desired, solvent or oil, which are suitable for dilution with water.
Suitable surface-active substances (adjuvants) are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, e.g. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and also of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl-or nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.
Powders, materials for spreading and dusts can be prepared by mixing or grinding the active ingredients together with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous granules can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree-bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.
The concentrations of the compounds of the formula I in the ready-to-use products can be varied within wide ranges. In general, the formulations comprise approximately 0.001 to 98~ by weight, preferably 0.01 to 95~ by weight, of at least one active ingredient. The active ingredients are employed in a purity of 90$ to 100, preferably 95~ to 100 (according to NMR spectrum).

4~
The formulation examples which follow illustrate the preparation of such products:
I. 20 parts by weight of compound No. 2.9 are dissolved in a mixture composed of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide to 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonate and 5 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol 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.
II. 20 parts by weight of compound No. 2.9 are dissolved in a mixture composed 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 to 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol 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.
III. 20 parts by weight of compound No. 2.9 are dissolved in a mixture composed of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280°C and 10 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol 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 thoroughly with 3 parts by weight of sodium diisobutylnaphthalenesulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture comprising 0.1~ by weight of the active ingredient.
V. 3 parts by weight of compound No. 2.9 are mixed with 97 parts by weight of finely divided kaolin. This gives a dust which comprises 3~ by weight of the active ingredient.

VI. 20 parts by weight of compound No. 2.9 are mixed intimately with 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol palyglycol ether, 2 parts by weight of the sodium salt of a phenol/urea/
formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. This gives a stable oily dispersion.
VII. 1 part by weight of compound No. 2.9 is dissolved in a mixture composed of 70 parts by weight of cyclohexanone, parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. This gives a stable emulsion concentrate.
15 VIII. 1 part by weight of compound No. 2.9 is dissolved in a mixture composed of 80 parts by weight of cyclohexanone and 20 parts by weight of WettolR EM 31 (= nonionic emulsifier based on ethoxylated castor oil). This gives a stable emulsion concentrate.
ao The compounds of the formula I, or the herbicidal compositions, can be applied pre- or post-emergence. If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are Z5 sprayed, with the aid of the spraying equipment, in such a way that they come into contact as little as possible, if at all, with the leaves of the sensitive crop plants, while the active ingredients reach the leaves of undesirable plants growing underneath, or the naked soil surface (post-directed, lay-by).
The application rates of the compound of the formula I are from 0.001 to 3.0, preferably 0.01 to 1.0, kg of active ingredient (a.i.) per ha, depending on the control target, the season, the type of plants and the growth stage.
To broaden the spectrum of action and to achieve synergistic effects, the cyclohexenonedioxothiochromanoyl derivatives of the formula I may be mixed with a large number of representatives of other groups of herbicidal or growth-regulating active ingredients and then applied concomitantly. Examples of suitable components for mixtures are 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy/hetaryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-aroyl-1,3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, ' i 0050/49977 CA 02373165 2001-11-06 chloroacetanilides, cyclohexenone oxime ether derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ether, dipyridyls, halocarboxylic acids 5 and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and hetaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, 10 pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.
15 It may also be useful to apply the compounds of the formula I
alone or in combination with other herbicides, as a mixture together with other crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt 20 solutions which are employed for treating nutrient and trace element deficiencies. Nonphytotoxic oils and oil concentrates may also be added.
Use Examples The herbicidal action of the cyclohexenonedioxothiochromanoyl derivatives of the formula I was demonstrated by the following greenhouse experiments:
The culture containers used were plastic flowerpots with loamy sand containing approximately 3.0~ humus as the substrate. The seeds of the test plants were sown separately for each species.
For the pre-emergence treatment, the active ingredients, which were suspended or emulsified in water, were applied immediately after sowing using finely distributing nozzles. The containers were irrigated gently to promote germination and growth and then covered with translucent plastic hoods until the plants had rooted. This cover causes uniform germination of the test plants, unless this was adversely affected by the active ingredients.
To carry out the post-emergence treatment, the test plants, depending on their habit, were first grown to a height of 3 to 15 cm and only then treated with the active ingredients, which were suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown on in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to '' 0050/49977 CA 02373165 2001-11-06 treatment. The application rate for the post-emergence treatment was 0.5, 0.25, 0.125 or 0.0625 kg of a.i. (active ingredient) per ha.
Depending on the species, the plants were kept at temperatures from 10 to 25°C or 20 to 35°C. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.
Evaluation was carried out using a scale from 0 to 100. 100 means no plant emergence, or complete destruction of at least the aerial parts, and 0 means no damage, or normal course of growth.
The plants used in the greenhouse experiments consisted of the following species:
Latin name English name Triticum aestivum winter wheat Abutilon theophrasti velvetleaf Aleopecurus myosuroidesblackgrass Avena fatua wild oat Chenopodium album lambsquarters (goosefoot) Echinochloa crus-galli barnyardgrass Polygonum persicaria ladysthumb Setaria faberi giant foxtail Sinapis alba white mustard Solanum nigrum black nightshade When applied post-emergence at application rates of 0.5 and 0.25 kg/ha, the compound 2.3 is very active against the abovementioned harmful plants giant foxtail, lambsquarters and black nightshade while the crop plant wheat is not adversely affected.
When applied post-emergence at application rates of 0.25 or 0.125 kg/ha, the compound 2.9 is very effective against the harmful Plants blackgrass, wild oat, velvetleaf, lambsquarters and white mustard, and the compound 2.12 is outstandingly effective against barnyardgrass, velvetleaf, lambsquarters, black nightshade and ladysthumb when applied post-emergence at 125 or 62.5 g/ha.

Claims

We claim:

1. Cyclohexenonedioxothiochromanoyl derivatives of the formula I

in which the variables have the following meanings:
R1 is hydrogen, nitro, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, N-(C1-C6-alkyl)aminosulfonyl, N,N-di(C1-C6-alkyl)aminosulfonyl, N-(C1-C6-alkylsulfonyl)amino, N-(C1-C6-haloalkylsulfonyl)amino, N-(C1-C6-alkyl)-N-(C1-C6-alkylsulfonyl)amino or N-(C1-C6-alkyl)-N-(C1-C6-haloalkylsulfonyl)amino;
R2 is C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
R3 is hydrogen, C1-C6-alkyl or halogen;
X forms an -0-(CH2)n- chain which can be substituted by one to three radicals selected from the following group:
halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxycarbonyl;
or a -(CH2)p- chain which can be interrupted by an oxygen or sulfur and/or can be substituted by one to four radicals selected from the following group:
halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxycarbonyl;

m is 0 to 4;
n is 1 to 5;
p is 2 to 6;
R4, R8 are hydrogen, C1-C4-alkyl or C1-C4-alkoxycarbonyl;
R5, R7, R9 are hydrogen or C1-C4-alkyl;
R6 is hydrogen, halogen, hydroxyl, C1-C6-alkyl, C1-C6-haloalkyl, di(C1-C6-alkoxy)methyl, (C1-C6-alkoxy)-(C1-C6-alkylthio)methyl, di(C1-C6-alkylthio)methyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, C1-C6-alkoxycarbonyl, C1-C6-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, it being possible for the six last-mentioned radicals to be substituted by one to three C1-C4-alkyl radicals;
or R5 and R6 or R6 and R9 together form a n bond or a C1-C5-alkyl chain which can have attached to it one to three radicals selected from the following group: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxycarbonyl;
or R5 and R9 together form a C1-C4-alkyl chain which can have attached to it one to three radicals selected from the following group: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxycarbonyl;
or R6 and R7 together form an -O-(CH2)q-O-, -O-(CH2)q-S-, -S-(CH2)q-S-, -O-(CH2)r- or -S-(CH2)r chain which can be substituted by one to three radicals selected from the following group: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxycarbonyl;

or R6 and R7 together with the carbon to which they are bonded form a carbonyl group;
q is 2 to 4;
r is 1 to 5.

2. A cyclohexenonedioxothiochromanoyl derivative of the formula I as claimed in claim 1, where R1 is halogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylsulfonyl;
R3 is hydrogen.

3. A cyclohexenonedioxothiochromanoyl derivative of the formula I as claimed in claim 1 or 2, where X forms an -O-(CH2)- or a -(CH2)p- chain, it being possible for the latter to be substituted by one to three halogen atoms, C1-C4-alkyl or C1-C4-haloalkyl radicals;
p is 2 to 5.

4. A cyclohexenonedioxothiochromanoyl derivative of the formula I as claimed in any of claims 1 to 3, where R6 is hydrogen, hydroxyl, C1-C6-alkyl, di(C1-C6-alkoxy)methyl, (C1-C6-alkoxy)(C1-C6-alkyl-thio)methyl, di(C1-C6-alkylthio)methyl or C1-C6-alkoxy;
R7 is hydrogen or C1-C4-alkyl;
or R6 and R7 together with the carbon to which they are bonded form a carbonyl group.

5. A process for the preparation of a compound of the formula I
as claimed in claim 1, which comprises reacting an activated benzoic acid IIa or a benzoic acid IIb, where the variables R1 to R3, X and m have the meanings given in claim 1 and L1 is a nucleophilically displaceable leaving group, with a cyclohexanedione of the formula III

and subjecting the acylation product to a rearrangement reaction in the presence of a catalyst to give a compound of the formula I.

6. A composition comprising a herbicidally active amount of at least one cyclohexenonedioxothiochromanoyl derivative of the formula I or of an agriculturally useful salt of I as claimed in claim 1, and auxiliaries conventionally used for the formulation of crop protection products.

7. A process for the preparation of a composition as claimed in claim 6, wherein a herbicidally active amount of at least one cyclohexenonedioxothiochromanoyl derivative of the formula I
or of an agriculturally useful salt of I as claimed in claim 1, and auxiliaries conventionally used for the formulation of, crop protection products are mixed.

8. A method of controlling undesired vegetation, which comprises allowing a herbicidally active amount of at least one cyclohexenonedioxothiochromanoyl derivative of the formula I
or of an agriculturally useful salt of I as claimed in claim 1 to act on plants, their environment and/or on seeds.

9. Use of a cyclohexenonedioxothiochromanoyl derivative of the formula I or of an agriculturally useful salt thereof as claimed in claim 1 as herbicides.

10. A benzoic derivative of the formula II

where R10 is hydroxyl or a hydrolytically removable radical and the variables R1 to R3, X and m have the meaning given in

claim 1.