TREA

2-benzoyl-cyclohexane-1,3-diones

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Information

  • Patent Grant
  • 6559100
  • Patent Number
    6,559,100
  • Date Filed
    Monday, February 7, 2000
    24 years ago
  • Date Issued
    Tuesday, May 6, 2003
    21 years ago
Information
Abstract
Substituted 2-benzoylcyclohexane-1,3-diones of the formula I where:R1 and R2 are each hydrogen, mercapto, nitro, halogen, cyano, thiocyanato, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, —OR3, —OCOR3, —OSO2R3, —S(O)nR3, —SO2OR3, —SO2N(R3)2, —NR3SO2R3 or —NR3COR3;R3 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, phenyl or phenyl-C1-C6-alkyl; where the abovementioned alkyl radicals may be partially or fully halogenated and/or may carry one to three of the following groups:hydroxyl, mercapto, amino, cyano, R3, —OR3, —SR3, —N(R3)2, ═NOR3, —OCOR3, —SCOR3, —NR3COR3, —CO2R3, —COSR3, —CON(R3)2, C1-C4-alkyliminooxy, C1-C4-alkoxyamino, C1-C4-alkylcarbonyl, C1-C4-alkoxy-C2-C6-alkoxycarbonyl, C1-C4-alkylsulfonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy and hetaryloxy, where the eight last mentioned radicals may in turn be substituted;n is 0, 1 or 2;Q is a cyclohexane-1,3-dione ring with or without substitution which is attached in position 2;X1 is a straight-chain or branched C1-C6-alkylene, a C2-C6-alkenylene or a C2-C6-alkynylene chain, where the abovementioned alkylene, alkenylene or alkynylene radicals may be partially halogenated and/or may carry one to three of the following groups:—OR4, —OCOR4, —OCONHR4 or —OSO2R4;except for those of the abovementioned alkenylene radicals where the double bond is α,β to the phenyl ring and where Het is linked to the double bond via the β position;R4 is hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, phenyl, phenyl-C1-C6-alkyl, where the abovementioned alkyl, alkenyl or alkynyl radicals may be partially or fully halogenated and/or may be substituted by one or more of the following radicals:hydroxyl, mercapto, amino, cyano, nitro, formyl, C1-C4-alkylamino, C1-C4-dialkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, C1-C4-alkylcarbonyloxy, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkoxy, C1-C4-haloalkoxy;Het is a three- to six-membered partially or fully saturated heterocyclic group or a three- to six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of:nitrogen, oxygen or sulfur,where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R5;R5 is hydrogen, hydroxyl, mercapto, amino, cyano, nitro, formyl, C1-C4-alkylamino, C1-C4-dialkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, C1-C4-alkylcarbonyloxy, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkoxy, C1-C4-haloalkoxy, where the alkyl radicals may in each case be substituted by in each case one or more of the following radicals:cyano, formyl, C1-C4-alkylamino, C1-C4-dialkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, C1-C4-alkylcarbonyloxy, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkoxy, C1-C4-haloalkoxy;and agriculturally useful salts thereof, processes and intermediates for preparing compounds of the formula I, compositions comprising them, and the use of the compounds of the formula I and compositions comprising them for controlling harmful plants are described.
Description




The present invention relates to substituted 2-benzoylcyclohexane-1,3-diones of the formula I











where:




R


1


and R


2


are each hydrogen, mercapto, nitro, halogen, cyano, thiocyanato, C


1


-C


6


-alkyl, C


1


-C


6


-haloalkyl, C


1


-C


6


-alkoxy, C


2


-C


6


-alkenyl, C


2


-C


6


-alkynyl, —OR


3


, —OCOR


3


, —OSO


2


R


3


, —S(O)


n


R


3


, —SO


2


OR


3


, —SO


2


N(R


3


)


2


, —NR


3


SO


2


R


3


or —NR


3


COR


3


;




R


3


is hydrogen, C


1


-C


6


-alkyl, C


1


-C


6


-haloalkyl, C


2


-C


6


-alkenyl, C


2


-C


6


-alkynyl, phenyl or phenyl-C


1


-C


6


-alkyl; where the abovementioned alkyl radicals may be partially or fully halogenated and/or may carry one to three of the following groups:




hydroxyl, mercapto, amino, cyano, R


3


, —OR


3


, —SR


3


, —N(R


3


)


2


, ═NOR


3


, —OCOR


3


, —SCOR


3


, —NR


3


COR


3


, —CO


2


R


3


, —COSR


3


, —CON(R


3


)


2


, C


1


-C


4


-alkyliminooxy, C


1


-C


4


-alkoxyamino, C


1


-C


4


-alkylcarbonyl, C


1


-C


4


-alkoxy-C


2


-C


6


-alkoxycarbonyl, C


1


-C


4


-alkylsulfonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy and hetaryloxy, where the eight last mentioned radicals may in turn be substituted;




n is 0, 1 or 2;




Q is a cyclohexane-1,3-dione ring with or without substitution which is attached in position 2;




X


1


is a straight-chain or branched C


1


-C


6


-alkylene, a C


2


-C


6


-alkenylene or a C


2


-C


6


-alkynylene chain, where the abovementioned alkylene, alkenylene or alkynylene radicals may be partially halogenated and/or may carry one to three of the following groups:




—OR


4


, —OCOR


4


, —OCONHR


4


or —OSO


2


R


4


;




except for those of the abovementioned alkenylene radicals where the double bond is α,β to the phenyl ring and where Het is linked to the double bond via the β position;




R


4


is hydrogen, C


1


-C


6


-alkyl, C


2


-C


6


-alkenyl, C


2


-C


6


-alkynyl, phenyl, phenyl-C


1


-C


6


-alkyl, where the abovementioned alkyl, alkenyl or alkynyl radicals may be partially or fully halogenated and/or may be substituted by one or more of the following radicals:




hydroxyl, mercapto, amino, cyano, nitro, formyl, C


1


-C


4


-alkylamino, C


1


-C


4


-dialkylamino, C


1


-C


4


-alkoxycarbonyl, C


1


-C


4


-alkylcarbonyl, C


1


-C


4


-alkylcarbonyloxy, C


1


-C


4


-alkyl, C


1


-C


4


-haloalkyl, C


1


-C


4


-alkylthio, C


1


-C


4


-haloalkylthio, C


1


-C


4


-alkoxy, C


1


-C


4


-haloalkoxy;




Het is a three- to six-membered partially or fully saturated heterocyclic group or a three- to six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of:




nitrogen, oxygen and sulfur,




where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R


5


;




R


5


is hydrogen, hydroxyl, mercapto, amino, cyano, nitro, formyl, C


1


-C


4


-alkylamino, C


1


-C


4


-dialkylamino, C


1


-C


4


-alkoxycarbonyl, C


1


-C


4


-alkylcarbonyl, C


1


-C


4


-alkylcarbonyloxy, C


1


-C


4


-alkyl, C


1


-C


4


-haloalkyl, C


1


-C


4


-alkylthio, C


1


-C


4


-haloalkylthio, C


1


-C


4


-alkoxy, C


1


-C


4


-haloalkoxy, where the alkyl radicals may in each case be substituted by in each case one or more of the following radicals:




cyano, formyl, C


1


-C


4


-alkylamino, C


1


-C


4


-dialkylamino, C


1


-C


4


-alkoxycarbonyl, C


1


-C


4


-alkylcarbonyl, C


1


-C


4


-alkylcarbonyloxy, C


1


-C


4


-alkyl, C


1


-C


4


-haloalkyl, C


1


-C


4


-alkylthio, C


1


-C


4


-haloalkylthio, C


1


-C


4


-alkoxy, C


1


-C


4


-haloalkoxy;




and agriculturally useful salts thereof.




In addition, the invention relates to processes and intermediates for preparing compounds of the formula I, to compositions comprising them and to the use of the compounds of the formula I and to compositions comprising them for controlling harmful plants.




2-Benzoylcyclohexane-1,3-diones are disclosed in the literature, for example in EP-A 278 742, EP-A 298 680, EP-A 320 864 and is WO 96/14285.




However, the herbicidal properties of the prior art compounds and their crop plant safety are not entirely satisfactory.




It is an object of the present invention to provide novel, in particular herbicidally active, compounds having improved properties.




We have found that this object is achieved by the 2-benzoylcyclohexane-1,3-diones of the formula I and their herbicidal activity.




Furthermore, we have found herbicidal compositions which comprise the compounds I and have very good herbicidal activity. Moreover, we have found processes for preparing these compositions and methods for controlling unwanted vegetation using the compounds I.




The present invention also provides stereoisomers of the compounds of the formula I. Pure stereoisomers and also mixtures thereof are included.




Depending on the substitution pattern, the compounds of the formula I may contain one or more chiral centers and, if this is the case, are present as mixtures of enantiomers or diastereomers. The invention provides the pure enantiomers or diastereomers and also mixtures thereof.




The compounds of the formula I may also be present in the form of their agriculturally useful salts, the kind of salt generally not being important. The salts of those cations or the acid addition salts of those acids whose cations or anions, respectively, do not adversely affect the herbicidal activity of the compounds I are generally suitable.




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 ammonium, where, if desired, one to four hydrogen atoms may be replaced by C


1


-C


4


-alkyl or hydroxy-C


1


-C


4


-alkyl and/or one phenyl or benzyl, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C


1


-C


4


-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C


1


C


4


-alkyl)sulfoxonium.




Anions of usable 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


-alkanoic acids, preferably formate, acetate, propionate and butyrate.




Emphasis is given to the compounds of the formula I according to the invention where the variable Q is a cyclohexane-1,3-dione ring of the formula II











which is attached in position 2, where II may also represent the tautomeric formulae II′ and II″,











where




R


6


, R


7


, R


9


and R


11


are each hydrogen or C


1


-C


4


-alkyl;




R


8


is hydrogen, C


1


-C


4


-alkyl or C


3


-C


4


-cycloalkyl, where the two last mentioned groups may carry one to three of the following substituents:




halogen, C


1


-C


4


-alkylthio or C


1


-C


4


-alkoxy; or




is tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-dioxolan-2-yl, 1,3ioxan-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 6 last mentioned radicals may be substituted by one to three C


1


-C


4


-alkyl radicals;




R


10


is hydrogen, C


1


-C


4


-alkyl or C


1


-C


6


-alkoxycarbonyl; or




R


8


and R


11


together form a a bond or a three- to six-membered carbocyclic ring; or




the CR


8


R


9


unit may be replaced by C═O.




Process A:




Reactions of the cyclohexane-1,3-dione of the formula II with an activated carboxylic acid IIIa or a carboxylic acid IIIb, which is preferably activated in situ, to give the acylation product IV, and subsequent rearrangement to the compounds of the formula I according to the invention











L


1


is a nucleophilically replaceable leaving group such as halogen, for example bromine or chlorine, hetaryl, for example imidazolyl or pyridyl, or carboxylate, for example acetate, trifluoroacetate, etc.




The activated carboxylic acid can be employed directly, as in the case of acyl halides, or be generated in situ, for example by using dicyclohexylcarbodiimide, triphenylphosphine/azodicarboxylic esters, 2-pyridine disulfite/triphenylphosphine, carbonyldiimidazole, etc.




It may be advantageous to carry out the acylation reaction in the presence of a base. Starting materials and auxiliary base are advantageously employed in equimolar amounts. A slight excess of auxiliary base, for example 1.R to 1.5 molar equivalents, based on II, may be advantageous under certain circumstances.




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, 1,2-dichloroethane, aromatic hydrocarbons, such as toluene, xylene, chlorobenzene, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, polar aprotic solvents, such as acetonitrile, dimethylformamide, dimethyl sulfoxide, or esters such as ethyl acetate or mixtures of these.




If acyl halides are employed as activated carboxylic acid component, it may be advantageous to cool the reaction mixture to 0-10° C. when adding this reaction partner. The mixture is subsequently stirred at 20-100° C., preferably at 25-50° C., until the reaction is complete. Work-up is carried out in a customary manner, for example by pouring the reaction mixture into water and extracting the product of value. 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 enol ester of the formula IV is purified, preferably by chromatography. Alternatively, it is possible to employ the crude enol ester of the formula IV without further purification for the rearrangement reaction.




The rearrangement of the enol esters of the formula IV to the compounds of the formula I is advantageously carried out at from 20 to 40° C. in a solvent and in the presence of a base and, if appropriate, in the presence of a cyano compound.




Examples of solvents which can be used 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, pyridine or alkali metal carbonates such as sodium carbonate, potassium carbonate, which are preferably employed in equimolar amounts or up to a four-fold excess, based on the ester. Preference is given to using triethylamine or alkali metal carbonates.




Suitable cyano compounds are inorganic cyanides such as sodium cyanide, potassium cyanide and organic cyano compounds such as acetone cyanohydrin, trimethylsilyl cyanide. They are employed in an amount of 1 to 50 mol percent, based on the ester. Preference is given to using acetone cyanohydrin or trimethylsilyl cyanide, for example in an amount of 5 to 15, preferably 10, mol percent, based on the ester.




Particular preference is given to employing alkali metal carbonates, such as potassium carbonate, in acetonitrile or dioxane.




Work-up can be carried out in a manner known per se. For example, the reaction mixture is acidified with dilute mineral acid, such as 5% strength hydrochloric acid or sulfuric acid, and extracted with an organic solvent, for example methylene chloride, ethyl acetate. The organic phase can be extracted with 5-10% strength 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 concentrated.




(Examples of the synthesis of esters of hydroxypyrazoles and the rearrangement of the esters are mentioned for example in EP-A 282 944 or U.S. Pat. No. 4,643,757).




The benzoic acids of the formula III are novel,











where:




R


1


and R


2


are each hydrogen, mercapto, nitro, halogen, cyano, thiocyanato, C


1


-C


6


-alkyl, C


1


-C


6


-haloalkyl, C


1


-C


6


-alkoxy, C


2


-C


6


-alkenyl, C


2


-C


6


-alkynyl, —OR


3


, —OCOR


3


, —OSO


2


R


3


, —S(O)


n


R


3


, —SO


2


OR


3


, —SO


2


N(R


3


)


2


, —NR


3


SO


2


R


3


or —NR


3


COR


3


;




R


3


is hydrogen, C


1


-C


6


-alkyl, C


1


-C


6


-haloalkyl, C


2


-C


6


-alkenyl, C


2


-C


6


-alkynyl, phenyl or phenyl-C


1


-C


6


-alkyl; where the abovementioned alkyl radicals may be partially or fully halogenated and/or may carry one to three of the following groups:




hydroxyl, mercapto, amino, cyano, R


3


, —OR


3


, —SR


3


, —N(R


3


)


2


, ═NOR


3


, —OCOR


3


, —SCOR


3


, —NR


3


COR


3


, —CO


2


R


3


, —COSR


3


, —CON(R


3


)


2


, C


1


-C


4


-alkyliminooxy, C


1


-C


4


-alkoxyamino, C


1


-C


4


-alkylcarbonyl, C


1


-C


4


-alkoxy-C


2


-C


6


-alkoxycarbonyl, C


1


-C


4


-alkylsulfonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy and hetaryloxy, where the eight last mentioned radicals may in turn be substituted;




n is 0, 1 or 2;




X


1


is a straight-chain or branched C


1


-C


6


-alkylene, a C


2


-C


6


-alkenylene or a C


2


-C


6


-alkynylene chain, where the abovementioned alkylene, alkenylene or alkynylene radicals may be partially halogenated and/or may carry one to three of the following groups:




—OR


4


, —OCOR


4


, —OCONHR


4


or —OSO


2


R


4


;




except for those of the abovementioned alkenylene radicals where the double bond is α,β to the phenyl ring and where Het is linked to the double bond via the β position;




R


4


is hydrogen, C


1


-C


6


-alkyl, C


2


-C


6


-alkenyl, C


2


-C


6


-alkynyl, phenyl, phenyl-C


1


-C


6


-alkyl, where the abovementioned alkyl, alkenyl or alkynyl radicals may be partially or fully halogenated and/or may be substituted by one or more of the following radicals:




hydroxyl, mercapto, amino, cyano, nitro, formyl, C


1


-C


4


-alkylamino, C


1


-C


4


-dialkylamino, C


1


-C


4


-alkoxycarbonyl, C


1


-C


4


-alkylcarbonyl, C


1


-C


4


-alkylcarbonyloxy, C


1


-C


4


-alkyl, C


1


-C


4


-haloalkyl, C


1


-C


4


-alkylthio, C


1


-C


4


-haloalkylthio, C


1


-C


4


-alkoxy, C


1


-C


4


-haloalkoxy;




Het is a three- to six-membered partially or fully saturated heterocyclic group or a three- to six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of:




nitrogen, oxygen and sulfur,




where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R


5


;




R


5


is hydrogen, hydroxyl, mercapto, amino, cyano, nitro, formyl, C


1


-C


4


-alkylamino, C


1


-C


4


-dialkylamino, C


1


-C


4


-alkoxycarbonyl, C


1


-C


4


-alkylcarbonyl, C


1


-C


4


-alkylcarbonyloxy, C


1


-C


4


-alkyl, C


1


-C


4


-haloalkyl, C


1


-C


4


-alkylthio, C


1


-C


4


-haloalkylthio, C


1


-C


4


-alkoxy, C


1


-C


4


-haloalkoxy, where the alkyl radicals may in each case be substituted by in each case one or more of the following radicals:




cyano, formyl, C


1


-C


4


-alkylamino, C


1


-C


4


-dialkylamino, C


1


-C


4


-alkoxycarbonyl, C


1


-C


4


-alkylcarbonyl, C


1


-C


4


-alkylcarbonyloxy, C


1


-C


4


-alkyl, C


1


-C


4


-haloalkyl, C


1


-C


4


-alkylthio, C


1


-C


4


-haloalkylthio, C


1


-C


4


-alkoxy, C


1


-C


4


-haloalkoxy;




R


12


is hydroxyl or a hydrolyzable radical.




Examples of hydrolyzable radicals are alkoxy, phenoxy, alkylthio and phenylthio radicals which possibly are substituted, halides, hetaryl radicals which are bonded via nitrogen, amino and imino radicals which possibly are substituted, etc.




Preference is given to benzoyl halides IIIa where L


1


=halogen ({circumflex over (=)} III where R


12


=halogen),











where the variables R


1


, R


2


, X


1


and Het are each as defined under formula III and




L


1


is halogen, in particular chlorine or bromine.




Preference is also given to benzoic acids of the formula IIIb ({circumflex over (=)} III where R


12


=hydroxyl),











where the variables R


1


, R


2


, X


1


and Het are each as defined under formula III.




Preference is also given to benzoic esters of the formula IIIc ({circumflex over (=)} III where R


12


=C


1


-C


6


-alkoxy),











where the variables R


1


, R


2


, X


1


and Het are each as defined under formula III and




M is C


1


-C


6


-alkoxy.




The compounds of the formula IIIa (where L


1


=halogen) can be synthesized by methods similar to those known from the literature (cf. L.G. Fieser, M. Fieser “Reagents for Organic Synthesis”, Vol. I, pp. 767-769 (1967)) by reacting benzoic acids of the formula IIIb with halogenating agents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride and oxalyl bromide.




The benzoic acids of the formula IIIb can be obtained, inter alia, by hydrolyzing the benzoic esters of the formula IIIc (where M=C


1


-C


6


-alkoxy).




The benzoic esters of the formula IIIc according to the invention are preparable by various methods known from the literature (for example a: G. Dittus in Houben-Weyl, Methoden der Organischen Chemie, Volume VI/3, Oxygen compounds I, 4th edition, p. 493 ff., Georg Thieme Verlag, 1965; b: T. L. Gilchrist, Heterocyclenchemie, 2nd edition, Verlag Chemie, 1995) as illustrated in the examples that follow.




Process B:




Metallation of appropriate benzoic esters IIIc ortho to the ester function using strong organometallic bases and subsequent 1,2-addition of a carbonyl compound V yields the benzoic esters IIIe according to the invention,











where R


13


is a substituent R


1


suitable for ortho-metallation (for example V. Snieckus,


Chem. Rev


. 90, (1990), 879), preferably halogen and C


1


-C


6


-alkoxy, and




X


2


is a straight-chain or branched C


1


-C


5


-alkylene, a C


2


-C


5


-alkenylene or a C


2


-C


5


-alkynylene chain where the abovementioned alkylene, alkenylene or alkynylene radicals may be partially halogenated and/or may carry one to three of the following groups:




—OR


4


, —OCOR


4


, —OCONHR


4


or —OSO


2


R


4


,




except for those of the abovementioned alkenylene radicals where the double bond is α,β to the phenyl ring and where Het is linked to the double bond via the β position.




Suitable organometallic bases for ortho-metallation of the benzoic esters IIId, which are known from the literature, include, for example, alkyllithium compounds, preferably n-butyllithium or sec-butyllithium, lithium dialkylamides, preferably lithium diisopropylamide or sodium hexamethyldisilazide.




Suitable inert solvents for the direct ortho-metallation are, for example, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane or 1,4-dioxane, dimethylformamide, dimethyl sulfoxide, methyl tert-butyl ether, or else mixtures of these.




The reaction temperatures can be from −80 to 100° C., preferably from −80 to 40° C.




The reaction of the ortho-metallated benzoic esters IIId, generated in situ, with the aldehydes V is carried out at reaction temperatures of from −80 to 100° C.




The products IIIe according to the invention contain a hydroxymethylene group which is suitable for further derivatizations by methods known from the literature. Thus, the hydroxymethylene group can for example be methylated to give the methoxy group.











Process C:




1,3-Dipolar cycloaddition of the benzoic esters IIIg with substituted or unsubstituted olefins or acetylenes under dehydrating conditions gives the benzoic esters according to the invention such as, for example, IIIh.











For dehydration by the method of Mukaiyama, preference is given to employing aromatic isocyanates (for example T. Mukaiyama et al.,


J. Am. Chem. Soc


. 82 (1960) 5339), for example phenyl isocyanate or 4-chlorophenyl isocyanate.




For the Shimizu variant, aliphatic chloroformates (for example T. Shimizu et al.,


Bull. Chem. Soc. Jpn


. 59 (1986), 2827), preferably ethyl chloroformate, are also suitable.




More recent developments show that it is also possible to employ for example N,N-diethylaminosulfur trifluoride (DAST), (methoxycarbonylsulfamoyl) triethylammonium hydroxide (Burgess reagent), phosphoryl chloride (for example C. Mioskowski et al.,


Tetrahedron Letters


38 (1997) 1547) or else a combination of di-tert-butyl dicarbonate (Boc


2


O) and 4-dimethylaminopyridine (DMAP) (A. Hassner et al.,


Synthesis


1997, 309) successfully as dehydrating agents for generating nitrile oxides.




At room temperature up to the boiling point of the solvent employed, the nitrile oxides generated in situ in this manner can be reacted with acetylenes or olefins having any desired substitution to give the benzoic esters hIIc according to the invention, X


1


here being for example a methylene group and Het an isoxazoline or isoxazole skeleton with or without substitution.




The cycloaddition is carried out in inert solvents such as, for example, toluene, chloroform or acetonitrile.




The benzoic ester IIIg can be obtained from IIIj by reduction according to methods known from the literature, IIIj being obtainable by nitroolefination (for example a: V. V. Perekalin et al., Nitroalkenes, John Wiley & Sons Ltd., New York 1994, b: A. G. M. Barrett et al.,


Chem. Rev


. 86 (1986), 751) of the corresponding aldehyde IIIi.











Emphasis is given to the compounds of the formula I according to the invention where the group X


1


is either a C


1


-C


2


-alkylene or a C


2


-alkenylene chain and




Het is a three- to six-membered partially or fully saturated heterocyclic group or a three- to six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of:




nitrogen, oxygen and sulfur,




where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R


5


.




Additionally, emphasis is given to the compounds of the formula I according to the invention where the group Het is a five- or six-membered partially or fully saturated heterocyclic or a five- or six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R


5


;




R


5


is hydrogen, hydroxyl, mercapto, amino, cyano, nitro, formyl, C


1


-C


4


-alkylamino, C


1


-C


4


-dialkylamino, C


1


-C


4


-alkoxycarbonyl, C


1


-C


4


-alkylcarbonyl, C


1


-C


4


-alkylcarbonyloxy, C


1


-C


4


-alkyl, C


1


-C


4


-haloalkyl, C


1


-C


4


-alkylthio, C


1


-C


4


-haloalkylthio, C


1


-C


4


-alkoxy, C


1


-C


4


-haloalkoxy, where the alkyl radicals may in each case be substituted by in each case one or more of the following radicals:




cyano, formyl, C


1


-C


4


-alkylamino, C


1


-C


4


-dialkylamino, C


1


-C


4


-alkoxycarbonyl, C


1


-C


4


-alkylcarbonyl, C


1


-C


4


-alkylcarbonyloxy, C


1


-C


4


-alkyl, C


1


-C


4


-haloalkyl, C


1


-C


4


-alkylthio, C


1


-C


4


-haloalkylthio, C


1


-C


4


-alkoxy, C


1


-C


4


-haloalkoxy.




The organic moieties mentioned for the substituents R


1


-R


13


or as radicals on phenyl, hetaryl and heterocyclyl rings are collective terms for individual enumerations of the individual group members. All hydrocarbon chains, ie. all alkyl, haloalkyl, cycloalkyl, alkoxyalkyl, alkoxy, haloalkoxy, alkyliminooxy, alkoxyamino, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkoxyalkoxycarbonyl, alkenyl, cycloalkenyl, alkynyl moieties can be straight-chain or branched. Unless otherwise specified, halogenated substituents preferably carry one to five identical or different halogen atoms, the meaning of halogen being in each case fluorine, chlorine, bromine or iodine.




Examples of other meanings are:




C


1


-C


4


-alkyl and the alkyl moieties of C


1


-C


4


-alkylcarbonyl: methyl, ethyl, n-propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;




C


1


-C


6


-alkyl and the alkyl moieties of C


1


-C


6


-alkoxy-C


1


-C


6


-alkyl and C


1


-C


6


-alkylcarbonyl: C


1


-C


4


-alkyl as mentioned above, and also 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 and 1-ethyl-3-methylpropyl;




C


1


-C


4


-haloalkyl: a C


1


-C


4


-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 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-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl;




C


1


-C


6


-haloalkyl and the haloalkyl moieties of C


1


-C


6


-haloalkylcarbonyl: C


1


-C


4


-haloalkyl as mentioned above, and also 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl and dodecafluorohexyl;




C


1


-C


4


-alkoxy and the alkoxy moieties of C


1


-C


4


-alkoxyamino, C


1


-C


4


-alkoxy-C


2


-C


6


-alkoxycarbonyl and C


1


-C


4


-alkoxycarbonyl: methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy; C


1


-C


6


-alkoxy and the alkoxy moieties of C


1


-C


6


-alkoxy-C


1


-C


6


-alkyl, C


1


-C


6


-alkoxy-C


2


-C


6


-alkyl, C


1


-C


4


-alkoxy-C


2


-C


6


-alkoxycarbonyl and C


1


-C


6


-alkoxycarbonyl: C


1


-C


4


-alkoxy as mentioned above, and also pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methoxylbutoxy, 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 and 1-ethyl-2-methylpropoxy;




C


1


-C


4


-haloalkoxy: a C


1


-C


4


-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-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-chloroethoxy, 1-(bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and nonafluorobutoxy;




C


1


-C


4


-alkylsulfonyl (C


1


-C


4


-alkyl-S(═O)


2


—): methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and 1,1-dimethylethylsulfonyl;




C


1


-C


6


-alkylsulfonyl: C


1


-C


4


-alkylsulfonyl as mentioned above, and also pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, 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 and 1-ethyl-2-methylpropylsulfonyl;




C


1


-C


6


-haloalkylsulfonyl: a C


1


-C


6


-alkylsulfonyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, 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-fluoropentylsulfonyl, 5-chloropentylsulfonyl, 5-bromopentylsulfonyl, 5-iodopentylsulfonyl, 6-fluorohexylsulfonyl, 6-bromohexylsulfonyl, 6-iodohexylsulfonyl and dodecafluorohexylsulfonyl;




C


1


-C


4


-alkyliminooxy: methyliminooxy, ethyliminooxy, 1-propyliminooxy, 2-propyliminooxy, 1-butyliminooxy and 2-butyliminooxy;




C


3


-C


6


-alkenyl: prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl, 1-ethylprop-2-en-1-yl, hex-1-en-1-yl, hex-2-en-1-yl, hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl, 1-ethyl-2-methylprop-1-en-1-yl and 1-ethyl-2-methylprop-2-en-1-yl;




C


2


-C


6


-alkenyl: C


3


-C


6


-alkenyl as mentioned above, and also ethenyl;




C


3


-C


6


-alkynyl: prop-1-yn-1-yl, prop-2-yn-1-yl, but-1-yn-1-yl, but-1-yn-3-yl, but-1-yn-4-yl, but-2-yn-1-yl, pent-1-yn-1-yl, pent-1-yn-3-yl, pent-1-yn-4-yl, pent-1-yn-5-yl, pent-2-yn-1-yl, pent-2-yn-4-yl, pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, hex-1-yn-1-yl, hex-1-yn-3-yl, hex-1-yn-4-yl, hex-1-yn-5-yl, hex-1-yn-6-yl, hex-2-yn-1-yl, hex-2-yn-4-yl, hex-2-yn-5-yl, hex-2-yn-6-yl, hex-3-yn-1-yl, hex-3-yn-2-yl, 3-methylpent-1-yn-1-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl and 4-methylpent-2-yn-5-yl;




C


2


-C


6


-alkynyl: C


3


-C


6


-alkynyl as mentioned above, and also ethynyl:




C


3


-C


6


-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;




C


4


-C


6


-cycloalkenyl: cyclobuten-1-yl, cyclobuten-3-yl, cyclopenten-1-yl, cyclopenten-3-yl, cyclopenten-4-yl, cyclohexen-1-yl, cyclohexen-3-yl and cyclohexen-4-yl;




heterocyclyl, and also the heterocyclyl radicals in heterocyclyloxy: three- to seven-membered saturated or partially unsaturated mono- or polycyclic heterocycles which contain one to three hetero atoms selected from a group consisting of oxygen, nitrogen and sulfur, such as oxiranyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,3-dihydrofuran-4-yl, 2,3-dihydrofuran-5-yl, 2,5-dihydrofuran-2-yl, 2,5-dihydrofuran-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,3-dihydrothien-4-yl, 2,3-dihydrothien-5-yl, 2,5-dihydrothien-2-yl, 2,5-dihydrothien-3-yl, 2,3-dihydropyrrol-2-yl, 2,3-dihydropyrrol-3-yl, 2,3-dihydropyrrol-4-yl, 2,3-dihydropyrrol-5-yl, 2,5-dihydropyrrol-2-yl, 2,5-dihydropyrrol-3-yl, 2,3-dihydroisoxazol-3-yl, 2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl, 4,5-dihydroisoxazol-5-yl, 2,5-dihydroisoxazol-3-yl, 2,5-dihydroisoxazol-4-yl, 2,5-dihydroisoxazol-5-yl, 2,3-dihydroisothiazol-3-yl, 2,3-dihydroisothiazol-4-yl, 2,3-dihydroisothiazol-5-yl, 4,5-dihydroisothiazol-3-yl, 4,5-dihydroisothiazol-4-yl, 4,5-dihydroisothiazol-5-yl, 2,5-dihydroisothiazol-3-yl, 2,5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol-5-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,5-dihydropyrazol-3-yl, 2,5-dihydropyrazol-4-yl, 2,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 4,5-dihydrooxazol-2-yl, 4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-2-yl, 2,5-dihydrooxazol-4-yl, 2,5-dihydrooxazol-5-yl, 2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl, 2,3-dihydrothiazol-5-yl, 4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazol-4-yl, 4,5-dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl, 2,3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4,5-dihydroimidazol-2-yl, 4,5-dihydroimidazol-4-yl, 4,5-dihydroimidazol-5-yl, 2,5-dihydroimidazol-2-yl, 2,5-dihydroimidazol-4-yl, 2,5-dihydroimidazol-5-yl, 2-morpholinyl, 3-morpholinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-tetrahydropyridazinyl, 4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetrahydropyrazinyl, 1,3,5-tetrahydrotriazin-2-yl, 1,2,4-tetrahydrotriazin-3-yl, 1,3-dihydrooxazin-2-yl, 1,3-dithian-2-yl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothiopyranyl, 3-tetrahydrothiopyranyl, 4-tetrahydrothiopyranyl, 1,3-dioxolan-2-yl, 3,4,5,6-tetrahydropyridin-2-yl, 4H-1,3-thiazin-2-yl, 4H-3,1-benzothiazin-2-yl, 1,1-dioxo-2,3,4,5-tetrahydrothien-2-yl, 2H-1,4-benzothiazin-3-yl, 2H-1,4-benzoxazin-3-yl, 1,3-dihydrooxazin-2-yl,




hetaryl, and also the hetaryl radicals in hetaryloxy: aromatic mono- or polycyclic radicals which, besides carbon ring members, may additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen and one sulfur atom, eg. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4,5-tetrazin-3-yl, and also the corresponding benzo-fused derivatives.




All phenyl, hetaryl and heterocyclyl rings are preferably unsubstituted or carry one to three halogen atoms and/or one or two radicals selected from the following group: nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy or methoxycarbonyl.




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, viz. in each case alone or in combination:




R


1


is nitro, halogen, cyano, thiocyanato, C


1


-C


6


-alkyl, C


1


-C


6


-haloalkyl, C


1


-C


6


-alkoxy-C


1


-C


6


-alkyl, C


2


-C


6


-alkenyl, C


2


-C


6


-alkynyl, —OR


3


or —S(O)


n


R


3


;




particularly preferably nitro, halogen such as, for example, fluorine, chlorine or bromine, C


1


-C


6


-haloalkyl, —OR


3


or —SO


2


R


3


;




R


2


is hydrogen, nitro, halogen, cyano, thiocyanato, C


1


-C


6


-alkyl, C


1


-C


6


-haloalkyl, C


1


-C


6


-alkoxy-C


1


-C


6


-alkyl, C


2


-C


6


-alkenyl, C


2


-C


6


-alkynyl, —OR


3


or —S(O)


n


R


3


;




particularly preferably hydrogen, nitro, halogen such as, for example, fluorine, chlorine or bromine, C


1


-C


6


-alkyl, C


1


-C


6


-haloalkyl, —OR


3


or —SO


2


R


3


;




R


3


is hydrogen, C


1


-C


6


-alkyl, C


1


-C


6


-haloalkyl, C


2


-C


6


-alkenyl, C


2


-C


6


-alkynyl, phenyl or phenyl-C


1


-C


6


-alkyl;




particularly preferably hydrogen, C


1


-C


4


-alkyl, C


1


-C


4


-haloalkyl, C


2


-C


3


-alkenyl, C


2


-C


3


-alkynyl or phenyl; where the abovementioned alkyl radicals may be partially or fully halogenated and/or may carry one to three of the following groups:




hydroxyl, mercapto, amino, cyano, R


3


, —OR


3


, —SR


3


, —N(R


3


)


2


, ═NOR


3


, —OCOR


3


, —SCOR


3


, —NR


3


COR


3


, —CO


2


R


3


, —COSR


3


, —CON(R


3


)


2


, C


1


-C


4


-alkyliminooxy, C


1


-C


4


-alkoxyamino, C


1


-C


4


-alkylcarbonyl, C


1


-C


4


-alkoxy-C


2


-C


6


-alkoxycarbonyl, C


1


-C


4


-alkylsulfonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy and hetaryloxy, where the eight last mentioned radicals may in turn be substituted;




n is 0, 1 or 2, particularly preferably 0 or 2;




X


1


is a straight-chain or branched C


1


-C


4


-alkylene, a propylene or butenylene or a C


2


-C


4


-alkynylene chain, particularly preferably a methylene, ethylene, propylene, propenylene, ethynylene or propynylene chain, where the abovementioned alkylene, alkenylene or alkynylene radicals may be partially halogenated and/or may carry one to three of the following groups:




—OR


4


, —OCOR


4


, —OCONHR


4


or —OSO


2


R


4


;




except for those of the abovementioned alkenylene radicals where the double bond is α,β to the phenyl ring and where Het is linked to the double bond via the β position;




R


4


is hydrogen, C


1


-C


6


-alkyl or C


1


-C


6


-haloalkyl; particularly preferably hydrogen, methyl, ethyl or trifluoromethyl;




R


5


is C


1


-C


6


-alkyl or C


1


-C


6


-haloalkyl; particularly preferably methyl, ethyl, propyl, isopropyl, butyl or isobutyl;




R


6


, R


7


, R


9


and R


11


are each hydrogen or C


1


-C


4


-alkyl;




particularly preferably hydrogen, methyl or ethyl;




R


8


is hydrogen, C


1


-C


4


-alkyl, C


3


-C


4


-cycloalkyl, where the two last mentioned groups may carry one to three of the following substituents: halogen, C


1


-C


4


-alkoxy or C


1


-C


4


-alkylthio;




or is tetrahydropyran2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-dioxolant2-yl, 1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithian-2-yl or 1,3-dithiolan-2-yl, where the six last mentioned groups may in each case carry one to three C


1


-C


4


-alkyl radicals;




particularly preferably hydrogen, methyl, ethyl, cyclopropyl, di(methoxy)methyl, di(ethoxy)methyl, 2-ethylthiopropyl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 5,5-dimethyl-1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithiolan-2-yl, 5,5-dimethyl-1,3-dithian-2-yl or 1-methylthiocyclopropyl; R


10


is hydrogen, C


1


-C


4


-alkyl or C


1


-C


4


-alkoxycarbonyl;




particularly preferably hydrogen, methyl or methoxycarbonyl.




Likewise, it may be advantageous for R


8


and R


11


to form a π bond, thus giving rise to a double bond system.




Alternatively, the CR


8


R


9


unit may be replaced by C═O.




Particular preference is given to the compounds of the formula Ia, where R


1


is attached in position 2 and R


2


is attached in position 4 of the phenyl ring.











Most particular preference is given to the compounds of the formula Ia in which the substituents R


1


, R


2


and Q are each as defined above, X


1


is a C


1


-C


2


-alkylene or a C


2


-alkynylene chain and




Het is a three- to six-membered, partially or fully saturated heterocyclic group or a three- to six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of:




nitrogen, oxygen and sulfur,




where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R


5


.




Particular preference is given to the compounds of the formula Ia where R


1


is attached in position 2 and R


2


is attached in position 4 of the phenyl ring.











Very particular preference is given to the compounds of the formula Ia in which the substituents R


1


, R


2


und Q are each as defined above, X


1


is a C


1


-C


2


-alkylene or a C


2


-alkynylene chain and




Het is a three- to six-membered partially or fully saturated heterocyclic group or a three- to six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of:




nitrogen, oxygen and sulfur,




where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R


5


.




Furthermore, very particular preference is given to the compounds of the formula Ia according to the invention in which the substituents R


1


, R


2


and X


1


are each as defined above and Het is a five- or six-membered partially or fully saturated heterocyclic or a five- or six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of




nitrogen, oxygen and sulfur.




Particular preference is given to the compounds Ib of Tables 1 to 36.














TABLE A









No.




X


1






Het

























1




CH


2






oxiranyl






2




CH


2






3-methyl-2-oxiranyl






3




CH


2






2-oxetanyl






4




CH


2






3-hydroxy-3-methyl-2-oxetanyl






5




CH


2






3-hydroxy-3-ethyl-2-oxetanyl






6




CH


2






3-hydroxy-3-propyl-2-oxetanyl






7




CH


2






3-hydroxy-3-butyl-2-oxetanyl






8




CH


2






3-methoxy-3-methyl-2-oxetanyl






9




CH


2






3-methoxy-3-ethyl-2-oxetanyl






10




CH


2






3-methoxy-3-propyl-2-oxetanyl






11




CH


2






3-methoxy-3-butyl-2-oxetanyl






12




CH


2






3-trimethylsilyloxy-3-ethyl-2-oxetanyl






13




CH


2






3-trimethylsilyloxy-3-ethyl-2-oxetanyl






14




CH


2






3-trimethylsilyloxy-3-propyl-2-oxetanyl






15




CH


2






3-trimethylsilyloxy-3-butyl-2-oxetanyl






16




CH


2






3-oxetanyl






17




CH


2






2-furyl






18




CH


2






4,5-dihydro-2-furyl






19




CH


2






2,3-dihydro-2-furyl






20




CH


2






3-furyl






21




CH


2






4,5-dihydro-3-furyl






22




CH


2






2,3-dihydro-3-furyl






23




CH


2






2-thienyl






24




CH


2






4,5-dihydro-2-thienyl






25




CH


2






2,3-dihydro-2-thienyl






26




CH


2






5-chloro-2-thienyl






27




CH


2






5-methyl-2-thienyl






28




CH


2






3-thienyl






29




CH


2






4,5-dihydro-3-thienyl






30




CH


2






2,3-dihydro-3-thienyl






31




CH


2






2-pyrrolyl






32




CH


2






2,5-dihydro-2-pyrrolyl






33




CH


2






3-pyrrolyl






34




CH


2






2,5-dihydro-3-pyrrolyl






35




CH


2






3-isoxazolyl






36




CH


2






4-methyl-3-isoxazolyl






37




CH


2






5-methyl-3-isoxazolyl






38




CH


2






4,5-dimethyl-3-isoxazolyl






39




CH


2






4,5-dihydro-3-isoxazolyl






40




CH


2






4-methyl-4,5-dihydro-3-isoxazolyl






41




CH


2






5-methyl-4,5-dihydro-3-isoxazolyl






42




CH


2






4,5-dimethyl-4,5-dihydro-3-isoxazolyl






43




CH


2






4-isoxazolyl






44




CH


2






3-methyl-4-isoxazolyl






45




CH


2






5-methyl-4-isoxazolyl






46




CH


2






5-cyclopropyl-4-isoxazolyl






47




CH


2






5-phenyl-4-isoxazolyl






48




CH


2






3,5-dimethyl-4-isoxazolyl






49




CH


2






4,5-dihydro-4-isoxazolyl






50




CH


2






3-methyl-4,5-dihydro-4-isoxazolyl






51




CH


2






5-methyl-4,5-dihydro-4-isoxazolyl






52




CH


2






3,5-dimethyl-4,5-dihydro-4-isoxazolyl






53




CH


2






5-isoxazolyl






54




CH


2






3-methyl-5-isoxazolyl






55




CH


2






4-methyl-5-isoxazolyl






56




CH


2






3,4-dimethyl-5-isoxazolyl






57




CH


2






4,5-dihydro-5-isoxazolyl






58




CH


2






3-methyl-4,5-dihydro-5-isoxazolyl






59




CH


2






4-methyl-4,5-dihydro-5-isoxazolyl






60




CH


2






3,4-dimethyl-4,5-dihydro-5-isoxazolyl






61




CH


2






3-isothiazolyl






62




CH


2






4-methyl-3-isothiazolyl






63




CH


2






5-methyl-3-isothiazolyl






64




CH


2






4-isothiazolyl






65




CH


2






3-methyl-4-isothiazolyl






66




CH


2






5-methyl-4-isothiazolyl






67




CH


2






5-isothiazolyl






68




CH


2






3-methyl-5-isothiazolyl






69




CH


2






4-methyl-5-isothiazolyl






70




CH


2






2-oxazolyl






71




CH


2






4-oxazolyl






72




CH


2






5-oxazolyl






73




CH


2






2-thiazolyl






74




CH


2






4-thiazolyl






75




CH


2






5-thiazolyl






76




CH


2






3-pyrazolyl






77




CH


2






4-pyrazolyl






78




CH


2






1-methyl-3-pyrazolyl






79




CH


2






1-methyl-4-pyrazolyl






80




CH


2






1-methyl-5-pyrazolyl






81




CH


2






2-imidazolyl






82




CH


2






1-methyl-2-imidazolyl






83




CH


2






5-methyl-[1,3,4]-2-oxadiazolyl






84




CH


2






5-methyl-[1,2,4]-3-oxadiazolyl






85




CH


2






5-methyl-[1,3,4]-2-thiadiazolyl






86




CH


2






5 methyl-[1,2,4]-3-thiadiazolyl






87




CH


2






[1,2,4]-3-triazolyl






88




CH


2






[1,2,3]-4-triazolyl






89




CH


2






2-pyridyl






90




CH


2






6-chloro-2-pyridyl






91




CH


2






6-methoxy-2-pyridyl






92




CH


2






6-trifluoromethyl-2-pyridyl






93




CH


2






3-pyridyl






94




CH


2






2-chloro-3-pyridyl






95




CH


2






2-methoxy-3-pyridyl






96




CH


2






4-pyridyl






97




CH


2






2-chloro-4-pyridyl






98




CH


2






2-methoxy-4-pyridyl






99




CH


2






2-ethoxy-4-pyridyl






100




CH


2






2-methylthio-4-pyridyl






101




CH


2






2-trifluoromethyl-5-pyridyl






102




CH


2






2-pyrimidinyl






103




CH


2






3-pyrimidinyl






104




CH


2






4-pyrimidinyl






105




CH


2






2-pyrazinyl






106




CH


2






3-pyridazinyl






107




CH


2






4-pyridazinyl






108




CH


2






2-(2H-1,3-oxazinyl)






109




CH


2






2-(6H-1,3-oxazinyl)






110




CH


2






4-(6H-1,3-oxazinyl)






111




CH


2






6-(6H-1,3-oxazinyl)






112




CH


2






[1,3,5]-2-triazinyl






113




CH


2






[1,2,4]-3-triazinyl






114




CH


2






[1,2,4]-5-triazinyl






115




CH


2






[1,2,4]-6-triazinyl






116




CHCH


3






oxiranyl






117




CHCH


3






3-methyl-2-oxiranyl






118




CHCH


3






2-oxetanyl






119




CHCH


3






3-hydroxy-3-methyl-2-oxetanyl






120




CHCH


3






3-hydroxy-3-ethyl-2-oxetanyl






121




CHCH


3






3-hydroxy-3-propyl-2-oxetanyl






122




CHCH


3






3-hydroxy-3-butyl-2-oxetanyl






123




CHCH


3






3-methoxy-3-methyl-2-oxetanyl






124




CHCH


3






3-methoxy-3-ethyl-2-oxetanyl






125




CHCH


3






3-methoxy-3-propyl-2-oxetanyl






126




CHCH


3






3-methoxy-3-butyl-2-oxetanyl






127




CHCH


3






3-trimethylsilyloxy-3-methyl-2-oxetanyl






128




CHCH


3






3-trimethylsilyloxy-3-ethyl-2-oxetanyl






129




CHCH


3






3-trimethylsilyloxy-3-propyl-2-oxetanyl






130




CHCH


3






3-trimethylsilyloxy-3-butyl-2-oxetanyl






131




CHCH


3






3-oxetanyl






132




CHCH


3






2-furyl






133




CHCH


3






4,5-dihydro-2-furyl






134




CHCH


3






2,3-dihydro-2-furyl






135




CHCH


3






3-furyl






136




CHCH


3






4,5-dihydro-3-furyl






137




CHCH


3






2,3-dihydro-3-furyl






138




CHCH


3






2-thienyl






139




CHCH


3






4,5-dihydro-2-thienyl






140




CHCH


3






2,3-dihydro-2-thienyl






141




CHCH


3






5-chloro-2-thienyl






142




CHCH


3






5-methyl-2-thienyl






143




CHCH


3






3-thienyl






144




CHCH


3






4,5-dihydro-3-thienyl






145




CHCH


3






2,3-dihydro-3-thienyl






146




CHCH


3






2-pyrrolyl






147




CHCH


3






2,5-dihydro-2-pyrrolyl






148




CHCH


3






3-pyrrolyl






149




CHCH


3






2,5-dihydro-3-pyrrolyl






150




CHCH


3






3-isoxazolyl






151




CHCH


3






4-methyl-3-isoxazolyl






152




CHCH


3






5-methyl-3-isoxazolyl






153




CHCH


3






4,5-dimethyl-3-isoxazolyl






154




CHCH


3






4,5-dihydro-3-isoxazolyl






155




CHCH


3






4-methyl-4,5-dihydro-3-isoxazolyl






156




CHCH


3






5-methyl-4,5-dihydro-3-isoxazolyl






157




CHCH


3






4,5-dimethyl-4,5-dihydro-3-isoxazolyl






158




CHCH


3






4-isoxazolyl






159




CHCH


3






3-methyl-4-isoxazolyl






160




CHCH


3






5-methyl-4-isoxazolyl






161




CHCH


3






5-cyclopropyl-4-isoxazolyl






162




CHCH


3






5-phenyl-4-isoxazolyl






163




CHCH


3






3,5-dimethyl-4-isoxazolyl






164




CHCH


3






4,5-dihydro-4-isoxazolyl






165




CHCH


3






3-methyl-4,5-dihydro-4-isoxazolyl






166




CHCH


3






5-methyl-4,5-dihydro-4-isoxazolyl






167




CHCH


3






3,5-dimethyl-4,5-dihydro-4-isoxazolyl






168




CHCH


3






5-isoxazolyl






169




CHCH


3






3-methyl-5-isoxazolyl






170




CHCH


3






4-methyl-5-isoxazolyl






171




CHCH


3






3,4-dimethyl-5-isoxazolyl






172




CHCH


3






4,5-dihydro-3-isoxazolyl






173




CHCH


3






3-methyl-4,5-dihydro-5-isoxazolyl






174




CHCH


3






4-methyl-4,5-dihydro-5-isoxazolyl






175




CHCH


3






3,4-dimethyl-4,5-dihydro-5-isoxazolyl






176




CHCH


3






3-isothiazolyl






177




CHCH


3






4-methyl-3-isothiazolyl






178




CHCH


3






5-methyl-3-isothiazolyl






179




CHCH


3






4-isothiazolyl






180




CHCH


3






3-methyl-4-isothiazolyl






181




CHCH


3






5-methyl-4-isothiazolyl






182




CHCH


3






5-isothiazolyl






183




CHCH


3






3-methyl-5-isothiazolyl






184




CHCH


3






4-methyl-5-isothiazolyl






185




CHCH


3






2-oxazolyl






186




CHCH


3






4-oxazolyl






187




CHCH


3






5-oxazolyl






188




CHCH


3






2-thiazolyl






189




CHCH


3






4-thiazolyl






190




CHCH


3






5-thiazolyl






191




CHCH


3






3-pyrazolyl






192




CHCH


3






4-pyrazolyl






193




CHCH


3






1-methyl-3-pyrazolyl






194




CHCH


3






1-methyl-4-pyrazolyl






195




CHCH


3






1-methyl-5-pyrazolyl






196




CHCH


3






2-imidazolyl






197




CHCH


3






1-methyl-2-imidazolyl






198




CHCH


3






5-methyl-[1,3,4]-2-oxadiazolyl






199




CHCH


3






5-methyl-[1,2,4]-3-oxadiazolyl






200




CHCH


3






5-methyl-[1,3,4]-2-thiadiazolyl






201




CHCH


3






5-methyl-[1,2,4]-3-thiadiazolyl






202




CHCH


3






[1,2,4]-3-triazolyl






203




CHCH


3






[1,2,3]-4-triazolyl






204




CHCH


3






2-pyridyl






205




CHCH


3






6-chloro-2-pyridyl






206




CHCH


3






6-methoxy-2-pyridyl






207




CHCH


3






6-trifluoromethyl-2-pyridyl






208




CHCH


3






3-pyridyl






209




CHCH


3






2-chloro-3-pyridyl






210




CHCH


3






2-methoxy-3-pyridyl






211




CHCH


3






4-pyridyl






212




CHCH


3






2-chloro-4-pyridyl






213




CHCH


3






2-methoxy-4-pyridyl






214




CHCH


3






2-ethoxy-4-pyridyl






215




CHCH


3






2-methylthio-4-pyridyl






216




CHCH


3






2-trifluoromethyl-5-pyridyl






217




CHCH


3






2-pyrimidinyl






218




CHCH


3






3-pyrimidinyl






219




CHCH


3






4-pyrimidinyl






220




CHCH


3






2-pyrazinyl






221




CHCH


3






3-pyridazinyl






222




CHCH


3






4-pyridazinyl






223




CHCH


3






2-(2H-1,3-oxazinyl)






224




CHCH


3






2-(6H-1,3-oxazinyl)






225




CHCH


3






4-(6H-1,3-oxazinyl)






226




CHCH


3






6-(6H-1,3-oxazinyl)






227




CHCH


3






[1,3,5]-2-triazinyl






228




CHCH


3






[1,2,4]-3-triazinyl






229




CHCH


3






[1,2,4]-5-triazinyl






230




CHCH


3






[1,2,4]-6-triazinyl






231




CHOH




oxiranyl






232




CHOH




3-methyl-2-oxiranyl






233




CHOH




2-oxetanyl






234




CHOH




3-hydroxy-3-methyl-2-oxetanyl






235




CHOH




3-hydroxy-3-ethyl-2-oxetanyl






236




CHOH




3-hydroxy-3-propyl-2-oxetanyl






237




CHOH




3-hydroxy-3-butyl-2-oxetanyl






238




CHOH




3-methoxy-3-methyl-2-oxetanyl






239




CHOH




3-methoxy-3-ethyl-2-oxetanyl






240




CHOH




3-methoxy-3-propyl-2-oxetanyl






241




CHOH




3-methoxy-3-butyl-2-oxetanyl






242




CHOH




3-trimethylsilyloxy-3-methyl-2-oxetanyl






243




CHOH




3-trimethylsilyloxy-3-ethyl-2-oxetanyl






244




CHOH




3-trimethylsilyloxy-3-propyl-2-oxetanyl






245




CHOH




3-trimethylsilyloxy-3-butyl-2-oxetanyl






246




CHOH




3-oxetanyl






247




CHOH




2-furyl






248




CHOH




4,5-dihydro-2-furyl






249




CHOH




2,3-dihydro-2-furyl






250




CHOH




3-furyl






251




CHOH




4,5-dihydro-3-furyl






252




CHOH




2,3-dihydro-3-furyl






253




CHOH




2-thienyl






254




CHOH




4,5-dihydro-2-thienyl






255




CHOH




2,3-dihydro-2-thienyl






256




CHOH




5-chloro-2-thienyl






257




CHOH




5-methyl-2-thienyl






258




CHOH




3-thienyl






259




CHOH




4,5-dihydro-3-thienyl






260




CHOH




2,3-dihydro-3-thienyl






261




CHOH




2-pyrrolyl






262




CHOH




2,5-dihydro-2-pyrrolyl






263




CHOH




3-pyrrolyl






264




CHOH




2,5-dihydro-3-pyrrolyl






265




CHOH




3-isoxazolyl






266




CHOH




4-methyl-3-isoxazolyl






267




CHOH




5-methyl-3-isoxazolyl






268




CHOH




4,5-dimethyl-3-isoxazolyl






269




CHOH




4,5-dihydro-3-isoxazolyl






270




CHOH




4-methyl-4,5-dihydro-3-isoxazolyl






271




CHOH




5-methyl-4,5-dihydro-3-isoxazolyl






272




CHOH




4,5-dimethyl-4,5-dihydro-3-isoxazolyl






273




CHOH




4-isoxazolyl






274




CHOH




3-methyl-4-isoxazolyl






275




CHOH




5-methyl-4-isoxazolyl






276




CHOH




5-cyclopropyl-4-isoxazolyl






277




CHOH




5-phenyl-4-isoxazolyl






278




CHOH




3,5-dimethyl-4-isoxazolyl






279




CHOH




4,5-dihydro-4-isoxazolyl






280




CHOH




3-methyl-4,5-dihydro-4-isoxazolyl






281




CHOH




5-methyl-4,5-dihydro-4-isoxazolyl






282




CHOH




3,5-dimethyl-4,5-dihydro-4-isoxazolyl






283




CHOH




5-isoxazolyl






284




CHOH




3-methyl-5-isoxazolyl






285




CHOH




4-methyl-5-isoxazolyl






286




CHOH




3,4-dimethyl-5-isoxazolyl






287




CHOH




4,5-dihydro-3-isoxazolyl






288




CHOH




3-methyl-4,5-dihydro-5-isoxazolyl






289




CHOH




4-methyl-4,5-dihydro-5-isoxazolyl






290




CHOH




3,4-dimethyl-4,5-dihydro-5-isoxazolyl






291




CHOH




3-isothiazolyl






292




CHOH




4-methyl-3-isothiazolyl






293




CHOH




5-methyl-3-isothiazolyl






294




CHOH




4-isothiazolyl






295




CHOH




3-methyl-4-isothiazolyl






296




CHOH




5-methyl-4-isothiazolyl






297




CHOH




5-isothiazolyl






298




CHOH




3-methyl-5-isothiazolyl






299




CHOH




4-methyl-5-isothiazolyl






300




CHOH




2-oxazolyl






301




CHOH




4-oxazolyl






302




CHOH




5-oxazolyl






303




CHOH




2-thiazolyl






304




CHOH




4-thiazolyl






305




CHOH




5-thiazolyl






306




CHOH




3-pyrazolyl






307




CHOH




4-pyrazolyl






308




CHOH




1-methyl-3-pyrazolyl






309




CHOH




1-methyl-4-pyrazolyl






310




CHOH




1-methyl-5-pyrazolyl






311




CHOH




2-imidazolyl






312




CHOH




1-methyl-2-imidazolyl






313




CHOH




5-methyl-[1,3,4]-2-oxadiazolyl






314




CHOH




5-methyl-[1,2,4]-3-oxadiazolyl






315




CHOH




5-methyl-[1,3,4]-2-thiadiazolyl






316




CHOH




5-methyl-[1,2,4]-3-thiadiazolyl






317




CHOH




[1,2,4]-3-triazolyl






318




CHOH




[1,2,3]-4-triazolyl






319




CHOH




2-pyridyl






320




CHOH




6-chloro-2-pyridyl






321




CHOH




6-methoxy-2-pyridyl






322




CHOH




6-trifluoromethyl-2-pyridyl






323




CHOH




3-pyridyl






324




CHOH




2-chloro-3-pyridyl






325




CHOH




2-methoxy-3-pyridyl






326




CHOH




4-pyridyl






327




CHOH




2-chloro-4-pyridyl






328




CHOH




2-methoxy-4-pyridyl






329




CHOH




2-ethoxy-4-pyridyl






330




CHOH




2-methylthio-4-pyridyl






331




CHOH




2-trifluoromethyl-5-pyridyl






332




CHOH




2-pyrimidinyl






333




CHOH




3-pyrimidinyl






334




CHOH




4-pyrimidinyl






335




CHOH




2-pyrazinyl






336




CHOH




3-pyridazinyl






337




CHOH




4-pyridazinyl






338




CHOH




2-(2H-1,3-oxazinyl)






339




CHOH




2-(6H-1,3-oxazinyl)






340




CHOH




4-(6H-1,3-oxazinyl)






341




CHOH




6-(6H-1,3-oxazinyl)






342




CHOH




[1,3,5]-2-triazinyl






343




CHOH




[1,2,4]-3-triazinyl






344




CHOH




[1,2,4]-5-triazinyl






345




CHOH




[1,2,4]-6-triazinyl






346




CHOCH


3






oxiranyl






347




CHOCH


3






3-methyl-2-oxiranyl






348




CHOCH


3






2-oxetanyl






349




CHOCH


3






3-hydroxy-3-methyl-2-oxetanyl






350




CHOCH


3






3-hydroxy-3-ethyl-2-oxetanyl






351




CHOCH


3






3-hydroxy-3-propyl-2-oxetanyl






352




CHOCH


3






3-hydroxy-3-butyl-2-oxetanyl






353




CHOCH


3






3-methoxy-3-methyl-2-oxetanyl






354




CHOCH


3






3-methoxy-3-ethyl-2-oxetanyl






355




CHOCH


3






3-methoxy-3-propyl-2-oxetanyl






356




CHOCH


3






3-methoxy-3-butyl-2-oxetanyl






357




CHOCH


3






3-trimethylsilyloxy-3-methyl-2-oxetanyl






358




CHOCH


3






3-trimethylsilyloxy-3-ethyl-2-oxetanyl






359




CHOCH


3






3-trimethylsilyloxy-3-propyl-2-oxetanyl






360




CHOCH


3






3-trimethylsilyloxy-3-butyl-2-oxetanyl






361




CHOCH


3






3-oxetanyl






362




CHOCH


3






2-furyl






363




CHOCH


3






4,5-dihydro-2-furyl






364




CHOCH


3






2,3-dihydro-2-furyl






365




CHOCH


3






3-furyl






366




CHOCH


3






4,5-dihydro-3-furyl






367




CHOCH


3






2,3-dihydro-3-furyl






368




CHOCH


3






2-thienyl






369




CHOCH


3






4,5-dihydro-2-thienyl






370




CHOCH


3






2,3-dihydro-2-thienyl






371




CHOCH


3






5-chloro-2-thienyl






372




CHOCH


3






5-methyl-2-thienyl






373




CHOCH


3






3-thienyl






374




CHOCH


3






4,5-dihydro-3-thienyl






375




CHOCH


3






2,3-dihydro-3-thienyl






376




CHOCH


3






2-pyrrolyl






377




CHOCH


3






2,5-dihydro-2-pyrrolyl






378




CHOCH


3






3-pyrrolyl






379




CHOCH


3






2,5-dihydro-3-pyrrolyl






380




CHOCH


3






3-isoxazolyl






381




CHOCH


3






4-methyl-3-isoxazolyl






382




CHOCH


3






5-methyl-3-isoxazolyl






383




CHOCH


3






4,5-dimethyl-3-isoxazolyl






384




CHOCH


3






4,5-dihydro-3-isoxazolyl






385




CHOCH


3






4-methyl-4,5-dihydro-3-isoxazolyl






386




CHOCH


3






5-methyl-4,5-dihydro-3-isoxazolyl






387




CHOCH


3






4,5-dimethyl-4,5-dihydro-3-isoxazolyl






388




CHOCH


3






4-isoxazolyl






389




CHOCH


3






3-methyl-4-isoxazolyl






390




CHOCH


3






5-methyl-4-isoxazolyl






391




CHOCH


3






5-cyclopropyl-4-isoxazolyl






392




CHOCH


3






5-phenyl-4-isoxazolyl






393




CHOCH


3






3,5-dimethyl-4-isoxazolyl






394




CHOCH


3






4,5-dihydro-4-isoxazolyl






395




CHOCH


3






3-methyl-4,5-dihydro-4-isoxazolyl






396




CHOCH


3






5-methyl-4,5-dihydro-4-isoxazolyl






397




CHOCH


3






3,5-dimethyl-4,5-dihydro-4-isoxazolyl






398




CHOCH


3






5-isoxazolyl






399




CHOCH


3






3-methyl-5-isoxazolyl






400




CHOCH


3






4-methyl-5-isoxazolyl






401




CHOCH


3






3,4-dimethyl-5-isoxazolyl






402




CHOCH


3






4,5-dihydro-5-isoxazolyl






403




CHOCH


3






3-methyl-4,5-dihydro-5-isoxazolyl






404




CHOCH


3






4-methyl-4,5-dihydro-5-isoxazolyl






405




CHOCH


3






3,4-dimethyl-4,5-dihydro-5-isoxazolyl






406




CHOCH


3






3-isothiazolyl






407




CHOCH


3






4-methyl-3-isothiazolyl






408




CHOCH


3






5-methyl-3-isothiazolyl






409




CHOCH


3






4-isothiazolyl






410




CHOCH


3






3-methyl-4-isothiazolyl






411




CHOCH


3






5-methyl-4-isothiazolyl






412




CHOCH


3






5-isothiazolyl






413




CHOCH


3






3-methyl-5-isothiazolyl






414




CHOCH


3






4-methyl-5-isothiazolyl






415




CHOCH


3






2-oxazolyl






416




CHOCH


3






4-oxazolyl






417




CHOCH


3






5-oxazolyl






418




CHOCH


3






2-thiazolyl






419




CHOCH


3






4-thiazolyl






420




CHOCH


3






5-thiazolyl






421




CHOCH


3






3-pyrazolyl






422




CHOCH


3






4-pyrazolyl






423




CHOCH


3






1-methyl-3-pyrazolyl






424




CHOCH


3






1-methyl-4-pyrazolyl






425




CHOCH


3






1-methyl-5-pyrazolyl






426




CHOCH


3






2-imidazolyl






427




CHOCH


3






1-methyl-2-imidazolyl






428




CHOCH


3






5-methyl-[1,3,4]-2-oxadiazolyl






429




CHOCH


3






5-methyl-[1,2,4]-3-oxadiazolyl






430




CHOCH


3






5-methyl-[1,3,4]-2-thiadiazolyl






431




CHOCH


3






5-methyl-[1,2,4]-3-thiadiazolyl






432




CHOCH


3






[1,2,4]-3-triazolyl






433




CHOCH


3






[1,2,3]-4-triazolyl






434




CHOCH


3






2-pyridyl






435




CHOCH


3






6-chloro-2-pyridyl






436




CHOCH


3






6-methoxy-2-pyridyl






437




CHOCH


3






6-trifluoromethyl-2-pyridyl






438




CHOCH


3






3-pyridyl






439




CHOCH


3






2-chloro-3-pyridyl






440




CHOCH


3






2-methoxy-3-pyridyl






441




CHOCH


3






4-pyridyl






442




CHOCH


3






2-chloro-4-pyridyl






443




CHOCH


3






2-methoxy-4-pyridyl






444




CHOCH


3






2-ethoxy-4-pyridyl






445




CHOCH


3






2-methylthio-4-pyridyl






446




CHOCH


3






2-trifluoromethyl-5-pyridyl






447




CHOCH


3






2-pyrimidinyl






448




CHOCH


3






3-pyrimidinyl






449




CHOCH


3






4-pyrimidinyl






450




CHOCH


3






2-pyrazinyl






451




CHOCH


3






3-pyridazinyl






452




CHOCH


3






4-pyridazinyl






453




CHOCH


3






2-(2H-1,3-oxazinyl)






454




CHOCH


3






2-(6H-1,3-oxazinyl)






455




CHOCH


3






4-(6H-1,3-oxazinyl)






456




CHOCH


3






6-(6H-1,3-oxazinyl)






457




CHOCH


3






[1,3,5]-2-triazinyl






458




CHOCH


3






[1,2,4]-3-triazinyl






459




CHOCH


3






[1,2,4]-5-triazinyl






460




CHOCH


3






[1,2,4]-6-triazinyl






461




CHOCOCH


3






oxiranyl






462




CHOCOCH


3






3-methyl-2-oxiranyl






463




CHOCOCH


3






2-oxetanyl






464




CHOCOCH


3






3-hydroxy-3-methyl-2-oxetanyl






465




CHOCOCH


3






3-hydroxy-3-ethyl-2-oxetanyl






466




CHOCOCH


3






3-hydroxy-3-propyl-2-oxetanyl






467




CHOCOCH


3






3-hydroxy-3-butyl-2-oxetanyl






468




CHOCOCH


3






3-methoxy-3-methyl-2-oxetanyl






469




CHOCOCH


3






3-methoxy-3-ethyl-2-oxetanyl






470




CHOCOCH


3






3-methoxy-3-propyl-2-oxetanyl






471




CHOCOCH


3






3-methoxy-3-butyl-2-oxetanyl






472




CHOCOCH


3






3-trimethylsilyloxy-3-methyl-2-oxetanyl






473




CHOCOCH


3






3-trimethylsilyloxy-3-ethyl-2-oxetanyl






474




CHOCOCH


3






3-trimethylsilyloxy-3-propyl-2-oxetanyl






475




CHOCOCH


3






3-trimethylsilyloxy-3-butyl-2-oxetanyl






476




CHOCOCH


3






3-oxetanyl






477




CHOCOCH


3






2-furyl






478




CHOCOCH


3






4,5-dihydro-2-furyl






479




CHOCOCH


3






2,3-dihydro-2-furyl






480




CHOCOCH


3






3-furyl






481




CHOCOCH


3






4,5-dihydro-3-furyl






482




CHOCOCH


3






2,3-dihydro-3-furyl






483




CHOCOCH


3






2-thienyl






484




CHOCOCH


3






4,5-dihydro-2-thienyl






485




CHOCOCH


3






2,3-dihydro-2-thienyl






486




CHOCOCH


3






5-chloro-2-thienyl






487




CHOCOCH


3






5-methyl-2-thienyl






488




CHOCOCH


3






3-thienyl






489




CHOCOCH


3






4,5-dihydro-3-thienyl






490




CHOCOCH


3






2,3-dihydro-3-thienyl






491




CHOCOCH


3






2-pyrrolyl






492




CHOCOCH


3






2,5-dihydro-2-pyrrolyl






493




CHOCOCH


3






3- pyrrolyl






494




CHOCOCH


3






2,5-dihydro-3-pyrrolyl






495




CHOCOCH


3






3-isoxazolyl






496




CHOCOCH


3






4-methyl-3-isoxazolyl






497




CHOCOCH


3






5-methyl-3-isoxazolyl






498




CHOCOCH


3






4,5-dimethyl-3-isoxazolyl






499




CHOCOCH


3






4,5-dihydro-3-isoxazolyl






500




CHOCOCH


3






4-methyl-4,5-dihydro-3-isoxazolyl






501




CHOCOCH


3






5-methyl-4,5-dihydro-3-isoxazolyl






502




CHOCOCH


3






4,5-dimethyl-4,5-dihydro-3-isoxazolyl






503




CHOCOCH


3






4-isoxazolyl






504




CHOCOCH


3






3-methyl-4-isoxazolyl






505




CHOCOCH


3






5-methyl-4-isoxazolyl






506




CHOCOCH


3






5-cyclopropyl-4-isoxazolyl






507




CHOCOCH


3






5-phenyl-4-isoxazolyl






508




CHOCOCH


3






3,5-dimethyl-4-isoxazolyl






509




CHOCOCH


3






4,5-dihydro-4-isoxazolyl






510




CHOCOCH


3






3-methyl-4,5-dihydro-4-isoxazolyl






511




CHOCOCH


3






5-methyl-4,5-dihydro-4-isoxazolyl






512




CHOCOCH


3






3,5-dimethyl-4,5-dihydro-4-isoxazolyl






513




CHOCOCH


3






5-isoxazolyl






514




CHOCOCH


3






3-methyl-5-isoxazolyl






515




CHOCOCH


3






4-methyl-5-isoxazolyl






516




CHOCOCH


3






3,4-dimethyl-5-isoxazolyl






517




CHOCOCH


3






4,5-dihydro-5-isoxazolyl






518




CHOCOCH


3






3-methyl-4,5-dihydro-5-isoxazolyl






519




CHOCOCH


3






4-methyl-4,5-dihydro-5-isoxazolyl






520




CHOCOCH


3






3,4-dimethyl-4,5-dihydro-5-isoxazolyl






521




CHOCOCH


3






3-isothiazolyl






522




CHOCOCH


3






4-methyl-3-isothiazolyl






523




CHOCOCH


3






5-methyl-3-isothiazolyl






524




CHOCOCH


3






4-isothiazolyl






525




CHOCOCH


3






3-methyl-4-isothiazolyl






526




CHOCOCH


3






5-methyl-4-isothiazolyl






527




CHOCOCH


3






5-isothiazolyl






528




CHOCOCH


3






3-methyl-5-isothiazolyl






529




CHOCOCH


3






4-methyl-5-isothiazolyl






530




CHOCOCH


3






2-oxazolyl






531




CHOCOCH


3






4-oxazolyl






532




CHOCOCH


3






5-oxazolyl






533




CHOCOCH


3






2-thiazolyl






534




CHOCOCH


3






4-thiazolyl






535




CHOCOCH


3






5-thiazolyl






536




CHOCOCH


3






3-pyrazolyl






537




CHOCOCH


3






4-pyrazolyl






538




CHOCOCH


3






1-methyl-3-pyrazolyl






539




CHOCOCH


3






1-methyl-4-pyrazolyl






540




CHOCOCH


3






1-methyl-5-pyrazolyl






541




CHOCOCH


3






2-imidazolyl






542




CHOCOCH


3






1-methyl-2-imidazolyl






543




CHOCOCH


3






5-methyl-[1,3,4]-2-oxadiazolyl






544




CHOCOCH


3






5-methyl-[1,2,4]-3-oxadiazolyl






545




CHOCOCH


3






5-methyl-[1,3,4]-2-oxadiazolyl






546




CHOCOCH


3






5-methyl-[1,2,4]-3-thiadiazolyl






547




CHOCOCH


3






[1,2,4]-3-triazolyl






548




CHOCOCH


3






[1,2,3]-4-triazolyl






549




CHOCOCH


3






2-pyridyl






550




CHOCOCH


3






6-chloro-2-pyridyl






551




CHOCOCH


3






6-methoxy-2-pyridyl






552




CHOCOCH


3






6-trifluoromethyl-2-pyridyl






553




CHOCOCH


3






3-pyridyl






554




CHOCOCH


3






2-chloro-3-pyridyl






555




CHOCOCH


3






2-methoxy-3-pyridyl






556




CHOCOCH


3






4-pyridyl






557




CHOCOCH


3






2-chloro-4-pyridyl






558




CHOCOCH


3






2-methoxy-4-pyridyl






559




CHOCOCH


3






2-ethoxy-4-pyridyl






560




CHOCOCH


3






2-methylthio-4-pyridyl






561




CHOCOCH


3






2-trifluoromethyl-5-pyridyl






562




CHOCOCH


3






2-pyrimidinyl






563




CHOCOCH


3






3-pyrimidinyl






564




CHOCOCH


3






4-pyrimidinyl






565




CHOCOCH


3






2-pyrazinyl






566




CHOCOCH


3






3-pyridazinyl






567




CHOCOCH


3






4-pyridazinyl






568




CHOCOCH


3






2-(2H-1,3-oxazinyl)






569




CHOCOCH


3






2-(6H-1,3-oxazinyl)






570




CHOCOCH


3






4-(6H-1,3-oxazinyl)






571




CHOCOCH


3






6-(6H-1,3-oxazinyl)






572




CHOCOCH


3






[1,3,5]-2-triazinyl






573




CHOCOCH


3






[1,2,4]-3-triazinyl






574




CHOCOCH


3






[1,2,4]-5-triazinyl






575




CHOCOCH


3






[1,2,4]-6-triazinyl






576




CHOSO


2


CH


3






oxiranyl






577




CHOSO


2


CH


3






3-methyl-2-oxiranyl






578




CHOSO


2


CH


3






2-oxetanyl






579




CHOSO


2


CH


3






3-hydroxy-3-methyl-2-oxetanyl






580




CHOSO


2


CH


3






3-hydroxy-3-ethyl-2-oxetanyl






581




CHOSO


2


CH


3






3-hydroxy-3-propyl-2-oxetanyl






582




CHOSO


2


CH


3






3-hydroxy-3-butyl-2-oxetanyl






583




CHOSO


2


CH


3






3-methoxy-3-methyl-2-oxetanyl






584




CHOSO


2


CH


3






3-methoxy-3-ethyl-2-oxetanyl






585




CHOSO


2


CH


3






3-methoxy-3-propyl-2-oxetanyl






586




CHOSO


2


CH


3






3-methoxy-3-butyl-2-oxetanyl






587




CHOSO


2


CH


3






3-trimethylsilyloxy-3-methyl-2-oxetanyl






588




CHOSO


2


CH


3






3-trimethylsilyloxy-3-ethyl-2-oxetanyl






589




CHOSO


2


CH


3






3-trimethylsilyloxy-3-propyl-2-oxetanyl






590




CHOSO


2


CH


3






3-trimethylsilyloxy-3-butyl-2-oxetanyl






591




CHOSO


2


CH


3






3-oxetanyl






592




CHOSO


2


CH


3






2-furyl






593




CHOSO


2


CH


3






4,5-dihydro-2-furyl






594




CHOSO


2


CH


3






2,3-dihydro-2-furyl






595




CHOSO


2


CH


3






3-furyl






596




CHOSO


2


CH


3






4,5-dihydro-3-furyl






597




CHOSO


2


CH


3






2,3-dihydro-3-furyl






598




CHOSO


2


CH


3






2-thienyl






599




CHOSO


2


CH


3






4,5-dihydro-2-thienyl






600




CHOSO


2


CH


3






2,3-dihydro-2-thienyl






601




CHOSO


2


CH


3






5-chloro-2-thienyl






602




CHOSO


2


CH


3






5-methyl-2-thienyl






603




CHOSO


2


CH


3






3-thienyl






604




CHOSO


2


CH


3






4,5-dihydro-3-thienyl






605




CHOSO


2


CH


3






2,3-dihydro-3-thienyl






606




CHOSO


2


CH


3






2-pyrrolyl






607




CHOSO


2


CH


3






2,5-dihydro-2-pyrrolyl






608




CHOSO


2


CH


3






3-pyrrolyl






609




CHOSO


2


CH


3






2,5-dihydro-3-pyrrolyl






610




CHOSO


2


CH


3






3-isoxazolyl






611




CHOSO


2


CH


3






4-methyl-3-isoxazolyl






612




CHOSO


2


CH


3






5-methyl-3-isoxazolyl






613




CHOSO


2


CH


3






4,5-dimethyl-3-isoxazolyl






614




CHOSO


2


CH


3






4,5-dihydro-3-isoxazolyl






615




CHOSO


2


CH


3






4-methyl-4,5-dihydro-3-isoxazolyl






616




CHOSO


2


CH


3






5-methyl-4,5-dihydro-3-isoxazolyl






617




CHOSO


2


CH


3






4,5-dimethyl-4,5-dihydro-3-isoxazolyl






618




CHOSO


2


CH


3






4-isoxazolyl






619




CHOSO


2


CH


3






3-methyl-4-isoxazolyl






620




CHOSO


2


CH


3






5-methyl-4-isoxazolyl






621




CHOSO


2


CH


3






5-cyclopropyl-4-isoxazolyl






622




CHOSO


2


CH


3






5-phenyl-4-isoxazolyl






623




CHOSO


2


CH


3






3,5-dimethyl-4-isoxazolyl






624




CHOSO


2


CH


3






4,5-dihydro-4-isoxazolyl






625




CHOSO


2


CH


3






3-methyl-4,5-dihydro-4-isoxazolyl






626




CHOSO


2


CH


3






5-methyl-4,5-dihydro-4-isoxazolyl






627




CHOSO


2


CH


3






3,5-dimethyl-4,5-dihydro-4-isoxazolyl






628




CHOSO


2


CH


3






5-isoxazolyl






629




CHOSO


2


CH


3






3-methyl-5-isoxazolyl






630




CHOSO


2


CH


3






4-methyl-5-isoxazolyl






631




CHOSO


2


CH


3






3,4-dimethyl-5-isoxazolyl






632




CHOSO


2


CH


3






4,5-dihydro-5-isoxazolyl






633




CHOSO


2


CH


3






3-methyl-4,5-dihydro-5-isoxazolyl






634




CHOSO


2


CH


3






4-methyl-4,5-dihydro-5-isoxazolyl






635




CHOSO


2


CH


3






3,4-dimethyl-4,5-dihydro-5-isoxazolyl






636




CHOSO


2


CH


3






3-isothiazolyl






637




CHOSO


2


CH


3






4-methyl-3-isothiazolyl






638




CHOSO


2


CH


3






5-methyl-3-isothiazolyl






639




CHOSO


2


CH


3






4-isothiazolyl






640




CHOSO


2


CH


3






3-methyl-4-isothiazolyl






641




CHOSO


2


CH


3






5-methyl-4-isothiazolyl






642




CHOSO


2


CH


3






5-isothiazolyl






643




CHOSO


2


CH


3






3-methyl-5-isothiazolyl






644




CHOSO


2


CH


3






4-methyl-5-isothiazolyl






645




CHOSO


2


CH


3






2-oxazolyl






646




CHOSO


2


CH


3






4-oxazolyl






647




CHOSO


2


CH


3






5-oxazolyl






648




CHOSO


2


CH


3






2-thiazolyl






649




CHOSO


2


CH


3






4-thiazolyl






650




CHOSO


2


CH


3






5-thiazolyl






651




CHOSO


2


CH


3






3-pyrazolyl






652




CHOSO


2


CH


3






4-pyrazolyl






653




CHOSO


2


CH


3






1-methyl-3-pyrazolyl






654




CHOSO


2


CH


3






1-methyl-4-pyrazolyl






655




CHOSO


2


CH


3






1-methyl-5-pyrazolyl






656




CHOSO


2


CH


3






2-imidazolyl






657




CHOSO


2


CH


3






1-methyl-2-imidazolyl






658




CHOSO


2


CH


3






5-methyl-[1,3,4]-2-oxadiazolyl






659




CHOSO


2


CH


3






5-methyl-[1,2,4]-3-oxadiazolyl






660




CHOSO


2


CH


3






5-methyl-[1,3,4]-2-thiadiazolyl






661




CHOSO


2


CH


3






5-methyl-[1,2,4]-3-thiadiazolyl






662




CHOSO


2


CH


3






[1,2,4]-3-triazolyl






663




CHOSO


2


CH


3






[1,2,3]-4-triazolyl






664




CHOSO


2


CH


3






2-pyridyl






665




CHOSO


2


CH


3






6-chloro-2-pyridyl






666




CHOSO


2


CH


3






6-methoxy-2-pyridyl






667




CHOSO


2


CH


3






6-trifluoromethyl-2-pyridyl






668




CHOSO


2


CH


3






3-pyridyl






669




CHOSO


2


CH


3






2-chloro-3-pyridyl






670




CHOSO


2


CH


3






2-methoxy-3-pyridyl






671




CHOSO


2


CH


3






4-pyridyl






672




CHOSO


2


CH


3






2-chlor-4-pyridyl






673




CHOSO


2


CH


3






2-methoxy-4-pyridyl






674




CHOSO


2


CH


3






2-ethoxy-4-pyridyl






675




CHOSO


2


CH


3






2-methylthio-4-pyridyl






676




CHOSO


2


CH


3






2-trifluoromethyl-5-pyridyl






677




CHOSO


2


CH


3






2-pyrimidinyl






678




CHOSO


2


CH


3






3-pyrimidinyl






679




CHOSO


2


CH


3






4-pyrimidinyl






680




CHOSO


2


CH


3






2-pyrazinyl






681




CHOSO


2


CH


3






3-pyridazinyl






682




CHOSO


2


CH


3






4-pyridazinyl






683




CHOSO


2


CH


3






2-(2H-1,3-oxazinyl)






684




CHOSO


2


CH


3






2-(6H-1,3-oxazinyl)






685




CHOSO


2


CH


3






4-(6H-1,3-oxazinyl)






686




CHOSO


2


CH


3






6-(6H-1,3-oxazinyl)






687




CHOSO


2


CH


3






[1,3,5]-2-triazinyl






688




CHOSO


2


CH


3






[1,2,4]-3-triazinyl






689




CHOSO


2


CH


3






[1,2,4]-5-triazinyl






690




CHOSO


2


CH


3






[1,2,4]-6-triazinyl






691




CH


2


CH


2






oxiranyl






692




CH


2


CH


2






3-methyl-2-oxiranyl






693




CH


2


CH


2






2-oxetanyl






694




CH


2


CH


2






3-hydroxy-3-methyl-2-oxetanyl






695




CH


2


CH


2






3-hydroxy-3-ethyl-2-oxetanyl






696




CH


2


CH


2






3-hydroxy-3-propyl-2-oxetanyl






697




CH


2


CH


2






3-hydroxy-3-butyl-2-oxetanyl






698




CH


2


CH


2






3-methoxy-3-methyl-2-oxetanyl






699




CH


2


CH


2






3-methoxy-3-ethyl-2-oxetanyl






700




CH


2


CH


2






3-methoxy-3-propyl-2-oxetanyl






701




CH


2


CH


2






3-methoxy-3-butyl-2-oxetanyl






702




CH


2


CH


2






3-trimethylsilyloxy-3-methyl-2-oxetanyl






703




CH


2


CH


2






3-trimethylsilyloxy-3-ethyl-2-oxetanyl






704




CH


2


CH


2






3-trimethylsilyloxy-3-propyl-2-oxetanyl






705




CH


2


CH


2






3-trimethylsilyloxy-3-butyl-2-oxetanyl






706




CH


2


CH


2






3-oxetanyl






707




CH


2


CH


2






2-furyl






708




CH


2


CH


2






4,5-dihydro-2-furyl






709




CH


2


CH


2






2,3-dihydro-2-furyl






710




CH


2


CH


2






3-furyl






711




CH


2


CH


2






4,5-dihydro-3-furyl






712




CH


2


CH


2






2,3-dihydro-3-furyl






713




CH


2


CH


2






2-thienyl






714




CH


2


CH


2






4,5-dihydro-2-thienyl






715




CH


2


CH


2






2,3-dihydro-2-thienyl






716




CH


2


CH


2






5-chloro-2-thienyl






717




CH


2


CH


2






5-methyl-2-thienyl






718




CH


2


CH


2






3-thienyl






719




CH


2


CH


2






4,5-dihydro-3-thienyl






720




CH


2


CH


2






2,3-dihydro-3-thienyl






721




CH


2


CH


2






2-pyrrolyl






722




CH


2


CH


2






2,5-dihydro-2-pyrrolyl






723




CH


2


CH


2






3-pyrrolyl






724




CH


2


CH


2






2,5-dihydro-3-pyrrolyl






725




CH


2


CH


2






3-isoxazolyl






726




CH


2


CH


2






4-methyl-3-isoxazolyl






727




CH


2


CH


2






5-methyl-3-isoxazolyl






728




CH


2


CH


2






4,5-dimethyl-3-isoxazolyl






729




CH


2


CH


2






4,5-dihydro-3-isoxazolyl






730




CH


2


CH


2






4-methyl-4,5-dihydro-3-isoxazolyl






731




CH


2


CH


2






5-methyl-4,5-dihydro-3-isoxazolyl






732




CH


2


CH


2






4,5-dimethyl-4,5-dihydro-3-isoxazolyl






733




CH


2


CH


2






4-isoxazolyl






734




CH


2


CH


2






3-methyl-4-isoxazolyl






735




CH


2


CH


2






5-methyl-4-isoxazolyl






736




CH


2


CH


2






5-cyclopropyl-4-isoxazolyl






737




CH


2


CH


2






5-phenyl-4-isoxazolyl






738




CH


2


CH


2






3,5-dimethyl-4-isoxazolyl






739




CH


2


CH


2






4,5-dihydro-4-isoxazolyl






740




CH


2


CH


2






3-methyl-4,5-dihydro-4-isoxazolyl






741




CH


2


CH


2






5-methyl-4,5-dihydro-4-isoxazolyl






742




CH


2


CH


2






3,5-dimethyl-4,5-dihydro-4-isoxazolyl






743




CH


2


CH


2






5-isoxazolyl






744




CH


2


CH


2






3-methyl-5-isoxazolyl






745




CH


2


CH


2






4-methyl-5-isoxazolyl






746




CH


2


CH


2






3,4-dimethyl-5-isoxazolyl






747




CH


2


CH


2






4,5-dihydro-5-isoxazolyl






748




CH


2


CH


2






3-methyl-4,5-dihydro-5-isoxazolyl






749




CH


2


CH


2






4-methyl-4,5-dihydro-5-isoxazolyl






750




CH


2


CH


2






3,4-dimethyl-4,5-dihydro-5-isoxazolyl






751




CH


2


CH


2






3-isothiazolyl






752




CH


2


CH


2






4-methyl-3-isothiazolyl






753




CH


2


CH


2






5-methyl-3-isothiazolyl






754




CH


2


CH


2






4-isothiazolyl






755




CH


2


CH


2






3-methyl-4-isothiazolyl






756




CH


2


CH


2






5-methyl-4-isothiazolyl






757




CH


2


CH


2






5-isothiazolyl






758




CH


2


CH


2






3-methyl-5-isothiazolyl






759




CH


2


CH


2






4-methyl-5-isothiazolyl






760




CH


2


CH


2






2-oxazolyl






761




CH


2


CH


2






4-oxazolyl






762




CH


2


CH


2






5-oxazolyl






763




CH


2


CH


2






2-thiazolyl






764




CH


2


CH


2






4-thiazolyl






765




CH


2


CH


2






5-thiazolyl






766




CH


2


CH


2






3-pyrazolyl






767




CH


2


CH


2






4-pyrazolyl






768




CH


2


CH


2






1-methyl-3-pyrazolyl






769




CH


2


CH


2






1-methyl-4-pyrazolyl






770




CH


2


CH


2






1-methyl-5-pyrazolyl






771




CH


2


CH


2






2-imidazolyl






772




CH


2


CH


2






1-methyl-2-imidazolyl






773




CH


2


CH


2






5-methyl-[1,3,4]-2-oxadiazolyl






774




CH


2


CH


2






5-methyl-[1,2,4]-3-oxadiazolyl






775




CH


2


CH


2






5-methyl-[1,3,4]-2-thiadiazolyl






776




CH


2


CH


2






5-methyl-[1,2,4]-3-thiadiazolyl






777




CH


2


CH


2






[1,2,4]-3-triazolyl






778




CH


2


CH


2






[1,2,3]-3-triazolyl






779




CH


2


CH


2






2-pyridyl






780




CH


2


CH


2






6-chloro-2-pyridyl






781




CH


2


CH


2






6-methoxy-2-pyridyl






782




CH


2


CH


2






6-trifluoromethyl-2-pyridyl






783




CH


2


CH


2






3-pyridyl






784




CH


2


CH


2






2-chloro-3-pyridyl






785




CH


2


CH


2






2-methoxy-3-pyridyl






786




CH


2


CH


2






4-pyridyl






787




CH


2


CH


2






2-chloro-4-pyridyl






788




CH


2


CH


2






2-methoxy-4-pyridyl






789




CH


2


CH


2






2-ethoxy-4-pyridyl






790




CH


2


CH


2






2-methylthio-4-pyridyl






791




CH


2


CH


2






2-trifluoromethyl-5-pyridyl






792




CH


2


CH


2






2-pyrimidinyl






793




CH


2


CH


2






3-pyrimidinyl






794




CH


2


CH


2






4-pyrimidinyl






795




CH


2


CH


2






2-pyrazinyl






796




CH


2


CH


2






3-pyridazinyl






797




CH


2


CH


2






4-pyridazinyl






798




CH


2


CH


2






2-(2H-1,3-oxazinyl)






799




CH


2


CH


2






2-(6H-1,3-oxazinyl)






800




CH


2


CH


2






4-(6H-1,3-oxazinyl)






801




CH


2


CH


2






6-(6H-1,3-oxazinyl)






802




CH


2


CH


2






[1,3,5]-2-triazinyl






803




CH


2


CH


2






[1,2,4]-3-triazinyl






804




CH


2


CH


2






[1,2,4]-5-triazinyl






805




CH


2


CH


2






[1,2,4]-6-triazinyl






806




—C≡C—




oxiranyl






807




—C≡C—




3-methyl-2-oxiranyl






808




—C≡C—




2-oxetanyl






809




—C≡C—




3-hydroxy-3-methyl-2-oxetanyl






810




—C≡C—




3-hydroxy-3-ethyl-2-oxetanyl






811




—C≡C—




3-hydroxy-3-propyl-2-oxetanyl






812




—C≡C—




3-hydroxy-3-butyl-2-oxetanyl






813




—C≡C—




3-methoxy-3-methyl-2-oxetanyl






814




—C≡C—




3-methoxy-3-ethyl-2-oxetanyl






815




—C≡C—




3-methoxy-3-propyl-2-oxetanyl






816




—C≡C—




3-methoxy-3-butyl-2-oxetanyl






817




—C≡C—




3-trimethylsilyloxy-3-methyl-2-oxetanyl






818




—C≡C—




3-trimethylsilyloxy-3-ethyl-2-oxetanyl






819




—C≡C—




3-trimethylsilyloxy-3-propyl-2-oxetanyl






820




—C≡C—




3-trimethylsilyloxy-3-butyl-2-oxetanyl






821




—C≡C—




3-oxetanyl






822




—C≡C—




2-furyl






823




—C≡C—




4,5-dihydro-2-furyl






824




—C≡C—




2,3-dihydro-2-furyl






825




—C≡C—




3-furyl






826




—C≡C—




4,5-dihydro-3-furyl






827




—C≡C—




2,3-dihydro-3-furyl






828




—C≡C—




2-thienyl






829




—C≡C—




4,5-dihydro-2-thienyl






830




—C≡C—




2,3-dihydro-2-thienyl






831




—C≡C—




5-chlor-2-thienyl






832




—C≡C—




5-methyl-2-thienyl






833




—C≡C—




3-thienyl






834




—C≡C—




4,5-dihydro-3-thienyl






835




—C≡C—




2,3-dihydro-3-thienyl






836




—C≡C—




2-pyrrolyl






837




—C≡C—




2,5-dihydro-2-pyrrolyl






838




—C≡C—




3-pyrrolyl






839




—C≡C—




2,5-dihydro-3-pyrrolyl






840




—C≡C—




3-isoxazolyl






841




—C≡C—




4-methyl-3-isoxazolyl






842




—C≡C—




5-methyl-3-isoxazolyl






843




—C≡C—




4,5-dimethyl-3-isoxazolyl






844




—C≡C—




4,5-dihydro-3-isoxazolyl






845




—C≡C—




4-methyl-4,5-dihydro-3-isoxazolyl






846




—C≡C—




5-methyl-4,5-dihydro-3-isoxazolyl






847




—C≡C—




4,5-dimethyl-4,5-dihydro-3-isoxazolyl






848




—C≡C—




4-isoxazolyl






849




—C≡C—




3-methyl-4-isoxazolyl






850




—C≡C—




5-methyl-4-isoxazolyl






851




—C≡C—




5-cyclopropyl-4-isoxazolyl






852




—C≡C—




5-phenyl-4-isoxazolyl






853




—C≡C—




3,5-dimethyl-4-isoxazolyl






854




—C≡C—




4,5-dihydro-4-isoxazolyl






855




—C≡C—




3-methyl-4,5-dihydro-4-isoxazolyl






856




—C≡C—




5-methyl-4,5-dihydro-4-isoxazolyl






857




—C≡C—




3,5-dimethyl-4,5-dihydro-4-isoxazolyl






858




—C≡C—




5-isoxazolyl






859




—C≡C—




3-methyl-5-isoxazolyl






860




—C≡C—




4-methyl-5-isoxazolyl






861




—C≡C—




3,4-dimethyl-5-isoxazolyl






862




—C≡C—




4,5-dihydro-5-isoxazolyl






863




—C≡C—




3-methyl-4,5-dihydro-5-isoxazolyl






864




—C≡C—




4-methyl-4,5-dihydro-5-isoxazolyl






865




—C≡C—




3,4-dimethyl-4,5-dihydro-5-isoxazolyl






866




—C≡C—




3-isothiazolyl






867




—C≡C—




4-methyl-3-isothiazolyl






868




—C≡C—




5-methyl-3-isothiazolyl






869




—C≡C—




4-isothiazolyl






870




—C≡C—




3-methyl-4-isothiazolyl






871




—C≡C—




5-methyl-4-isothiazolyl






872




—C≡C—




5-isothiazolyl






873




—C≡C—




3-methyl-5-isothiazolyl






874




—C≡C—




4-methyl-5-isothiazolyl






875




—C≡C—




2-oxazolyl






876




—C≡C—




4-oxazolyl






877




—C≡C—




5-oxazolyl






878




—C≡C—




2-thiazolyl






879




—C≡C—




4-thiazolyl






880




—C≡C—




5-thiazolyl






881




—C≡C—




3-pyrazolyl






882




—C≡C—




4-pyrazolyl






883




—C≡C—




1-methyl-3-pyrazolyl






884




—C≡C—




1-methyl-4-pyrazolyl






885




—C≡C—




1-methyl-5-pyrazolyl






886




—C≡C—




2-imidazolyl






887




—C≡C—




1-methyl-2-imidazolyl






888




—C≡C—




5-methyl-[1,3,4]-2-oxadiazolyl






889




—C≡C—




5-methyl-[1,2,4]-3-oxadiazolyl






890




—C≡C—




5-methyl-[1,3,4]-2-thiadiazolyl






891




—C≡C—




5-methyl-[1,2,4]-3-thiadiazolyl






892




—C≡C—




[1,2,4]-3-triazolyl






893




—C≡C—




[1,2,3]-4-triazolyl






894




—C≡C—




2-pyridyl






895




—C≡C—




6-chloro-2-pyridyl






896




—C≡C—




6-methoxy-2-pyridyl






897




—C≡C—




6-trifluoromethyl-2-pyridyl






898




—C≡C—




3-pyridyl






899




—C≡C—




2-chloro-3-pyridyl






900




—C≡C—




2-methoxy-3-pyridyl






901




—C≡C—




4-pyridyl






902




—C≡C—




2-chloro-4-pyridyl






903




—C≡C—




2-methoxy-4-pyridyl






904




—C≡C—




2-ethoxy-4-pyridyl






905




—C≡C—




2-methylthio-4-pyridyl






906




—C≡C—




2-trifluoromethyl-5-pyridyl






907




—C≡C—




2-pyrimidinyl






908




—C≡C—




3-pyrimidinyl






909




—C≡C—




4-pyrimidinyl






910




—C≡C—




2-pyrazinyl






911




—C≡C—




3-pyridazinyl






912




—C≡C—




4-pyridazinyl






913




—C≡C—




2-(2H-1,3-oxazinyl)






914




—C≡C—




2-(6H-1,3-oxazinyl)






915




—C≡C—




4-(6H-1,3-oxazinyl)






916




—C≡C—




6-(6H-1,3-oxazinyl)






917




—C≡C—




[1,3,5]-2-triazinyl






918




—C≡C—




[1,2,4]-3-triazinyl






919




—C≡C—




[1,2,4]-5-triazinyl






920




—C≡C—




[1,2,4]-6-triazinyl














Tables 1-36 below are based on the 2-benzoylcyclohexane-1,3-diones of the formula Ib











Table 1: Compounds 1.1-1.920




Compounds of the formula Ib where R


1


is chlorine, R


2


is methylsulfonyl, R


6


, R


7


, R


8


, R


9


, R


10


and R


11


are each hydrogen and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 2: Compounds 2.1-2.920




Compounds of the formula Ib where R


1


and R


2


are each chlorine, R


6


, R


7


, R


8


, R


9


, R


10


and R


11


are each hydrogen and where for each individual compounds the substituents X


1


and Het corresponds to one line of Table A.




Table 3: Compounds 3.1-3.920




Compounds of the formula Ib where R


1


is chlorine, R


2


is trifluoromethyl, R


6


, R


7


, R


8


, R


9


, R


10


and R


11


are each hydrogen and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 4: Compounds 4.1-4.920




Compounds of the formula Ib where R


1


is methyl, R


2


is chlorine, R


6


, R


7


, R


8


, R


9


, R


10


and R


11


are each hydrogen and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 5: Compounds 5.1-5.920




Compounds of the formula Ib where R


1


is methyl, R


2


is methylsulfonyl, R


6


, R


7


, R


8


, R


9


, R


10


and R


11


are each hydrogen and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 6: Compounds 6.1-6.920




Compounds of the formula Ib where R


1


is methyl, R


2


is trifluoromethyl, R


6


, R


7


, R


8


, R


9


, R


10


and R


11


are each hydrogen and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 7: Compounds 7.1-7.920




Compounds of the formula Ib where R


1


is chlorine, R


2


is methylsulfonyl, R


6


, R


7


, R


10


and R


11


are each hydrogen, R


8


and R


9


are each methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 8: Compounds 8.1-8.920




Compounds of the formula Ib where R


1


and R


2


are each chlorine, R


6


, R


7


, R


10


and R


11


are each hydrogen, R


8


and R


9


are each methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 9: Compounds 9.1-9.920




Compounds of the formula Ib where R


1


is chlorine, R


2


is trifluoromethyl, R


6


, R


7


, R


10


and R


11


are each hydrogen, R


8


and R


9


are each methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 10: Compounds 10.1-10.920




Compounds of the formula Ib where R


1


is methyl, R


2


is chlorine, R


6


, R


7


, R


10


and R


11


are each hydrogen, R


8


and R


9


are each methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 11: Compounds 11.1-11.920




Compounds of the formula Ib where R


1


is methyl, R


2


is methylsulfonyl, R


6


, R


7


, R


10


and R


11


are each hydrogen, R


8


and R


9


are each methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 12: Compounds 12.1-12.920




Compounds of the formula Ib where R


1


is methyl, R


2


is trifluoromethyl, R


6


, R


7


, R


10


and R


11


are each hydrogen, R


8


and R


9


is methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 13: Compounds 13.1-13.920




Compounds of the formula Ib where R


1


is chlorine, R


2


is methylsulfonyl, R


6


, R


7


, R


8


and R


9


are each hydrogen, R


10


and R


11


are each methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 14: Compounds 14.1-14.920




Compounds of the formula Ib where R


1


and R


2


is chlorine, R


6


, R


7


, R


8


and R


9


are each hydrogen, R


10


and R


11


are each methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 15: Compounds 15.1-15.920




Compounds of the formula Ib where R


1


is chlorine, R


2


is trifluoromethyl, R


6


, R


7


, R


8


and R


9


are each hydrogen, R


10


and R


11


are each methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 16: Compounds 16.1-16.920




Compounds of the formula Ib where R


1


is methyl, R


2


is chlorine, R


6


, R


7


, R


8


and R


9


are each hydrogen, R


10


and R


11


are each methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 17: Compounds 17.1-17.920




Compounds of the formula Ib where R


1


is methyl, R


2


is methylsulfonyl, R


6


, R


7


, R


8


and R


9


are each hydrogen, R


10


and R


11


are each methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 18: Compounds 18.1-18.920




Compounds of the formula Ib where R


1


is methyl, R


2


is trifluoromethyl, R


6


, R


7


, R


8


and R


9


are each hydrogen, R


10


and R


11


are each methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 19: Compounds 19.1-19.920




Compounds of the formula Ib where R


1


is chlorine, R


2


is methylsulfonyl, R


6


, R


7


, R


10


and R


11


are each methyl, the CR


8


R


9


unit forms a group C═O and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 20: Compounds 20.1-20.920




Compounds of the formula Ib where R


1


and R


2


are each chlorine, R


6


, R


7


, R


10


and R


11


are each methyl, the CR


8


R


9


unit forms a group C═O and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 21: Compounds 21.1-21.920




Compounds of the formula Ib where R


1


is chlorine, R


2


is trifluoromethyl, R


6


, R


7


, R


10


and R


11


are each methyl, the CR


8


R


9


unit forms a group C═O and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 22: Compounds 22.1-22.920




Compounds of the formula Ib where R


1


is methyl, R


2


is chlorine, R


6


, R


7


, R


10


and R


11


are each methyl, the CR


8


R


9


unit forms a group C═O and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 23: Compounds 23.1-23.920




Compounds of the formula Ib where R


1


is methyl, R


2


is methylsulfonyl, R


6


, R


7


, R


10


and R


11


are each methyl, the CR


8


R


9


unit forms a group C═O and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 24: Compounds 24.1-24.920




Compounds of the formula Ib where R


1


is methyl, R


2


is trifluoromethyl, R


6


, R


7


, R


10


and R


11


are each methyl, the CR


8


R


9


unit forms a group C═O and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 25: Compounds 25.1-25.920




Compounds of the formula Ib where R


1


is methylsulfonyl, R


6


, R


7


, R


8


, R


10


and R


11


are each hydrogen, R


9


is methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 26: Compounds 26.1-26.920




Compounds of the formula Ib where R


1


and R


2


are each chlorine, R


6


, R


7


, R


8


, R


10


and R


1


. are each hydrogen, R


9


is methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 27: Compounds 27.1-27.920




Compounds of the formula Ib where R


1


is chlorine, R


2


is trifluoromethyl, R


6


, R


7


, R


8


, R


10


and R


11


are each hydrogen, R


9


is methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 28: Compounds 28.1-28.920




Compounds of the formula Ib where R


1


is methyl, R


2


is chlorine, R


6


, R


7


, R


8


, R


10


and R


11


are each hydrogen, R


9


is methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 29: Compounds 29.1-29.920




Compounds of the formula Ib where R


1


is methyl, R


2


is methylsulfonyl, R


6


, R


7


, R


8


, R


10


and R


11


are each hydrogen, R


9


is methyl and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 30: Compounds 30.1-30.920




Compounds of the formula Ib where R


1


is methyl, R


2


is trifluoromethyl, R


6


, R


7


, R


8


, R


10


and R


11


are each hydrogen, R


9


is methyl and where for each individual compound the substituents XI and Het correspond to one line of Table A.




Table 31: Compounds 31.1-31.920




Compounds of the formula Ib where R


1


is chlorine, R


2


is methylsulfonyl, R


6


, R


7


, R


9


and R


10


are each hydrogen, R


8


and R


11


together form a methylene group and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 32: Compounds 32.1-32.920




Compounds of the formula Ib where R


1


and R


2


are each chlorine, R


6


, R


7


, R


9


and R


10


are each hydrogen, R


8


and R


11


together form a methylene group and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 33: Compounds 33.1-33.920




Compounds of the formula Ib where R


1


is chlorine, R


2


is trifluoromethyl, R


6


, R


7


, R


9


and R


10


are each hydrogen, R


8


and R


11


together form a methylene group and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 34: Compounds 34.1-34.920




Compounds of the formula Ib where R


1


is methyl, R


2


is chlorine, R


6


, R


7


, R


9


and R


10


are each hydrogen, R


8


and R


11


together form a methylene group and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 35: Compounds 35.1-35.920




Compounds of the formula Ib where R


1


is methyl, R


2


is methylsulfonyl, R


6


, R


7


, R


9


and R


10


are each hydrogen, R


8


and R


11


together form a methylene group and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




Table 36: Compounds 36.1-36.920




Compounds of the formula Ib where R


1


is methyl, R


2


is trifluoromethyl, R


6


, R


7


, R


9


and R


10


are each hydrogen, R


8


and R


11


together form a methylene group and where for each individual compound the substituents X


1


and Het correspond to one line of Table A.




The compounds I and their agriculturally useful salts are suitable, both in the form of isomer mixtures and in the form of the pure isomers, as herbicides. The herbicidal compositions comprising I control vegetation on non-crop areas very efficiently, especially at high rates of application. They act against broad-leaved weeds and grass weeds in crops such as wheat, rice, maize, soya and cotton without causing any significant damage to the crop plants. This effect is mainly observed at low rates of application.




Depending on the application method used, the compounds I, or the compositions comprising them, can additionally be employed in a further number of crop plants for eliminating undesirable plants.




Examples of suitable crops are the following:






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 liberica


),


Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum


, (


Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium


),


Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus


spec.,


Manihot esculenta, Medicago 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.






In addition, the compounds I may also be used in crops which tolerate the action of herbicides owing to breeding, including genetic engineering methods.




The herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active compounds are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are 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 compounds reach the leaves of undesirable plants growing underneath, or the bare soil surface (post-directed, lay-by).




The compounds I, or the herbicidal compositions comprising them, can be used for example in the form of ready-to-spray aqueous solutions, powders, suspensions, including highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting, or granules, by means of spraying, atomizing, dusting, broadcasting or watering. The application forms depend on the intended uses; in any case, they should guarantee a very fine distribution of the active compounds according to the invention.




Essentially, suitable inert auxiliaries include: mineral oil fractions of medium to high boiling point, such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, eg. 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 substituted 2-benzoylcyclohexane-1,3-diones, either as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetting agent, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates comprising active compound, wetting agent, tackifier, dispersant or emulsifier and, if desired, solvent or oil, which are suitable for dilution with water.




Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, eg. 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 or 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 broadcasting and dusts can be prepared by mixing or grinding the active compounds together with a solid carrier.




Granules, eg. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds 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 and 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 concentration of the active compounds I in the ready-to-use preparations can be varied within wide ranges. In general, the formulations comprise from 0.001 to 98% by weight, preferably 0.01 to 95% by weight of at least one active compound. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).




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




I 20 parts by weight of the compound No. 20.39 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 with 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 with 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 compound.




II 20 parts by weight of the compound No. 20.39 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 with 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide with 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 compound.




III 20 parts by weight of the compound No. 20.39 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 with 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 compound.




IV 20 parts by weight of the compound No. 20.39 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 which comprises 0.1% by weight of the active compound.




V 3 parts by weight of the compound No. 20.39 are mixed with 97 parts by weight of finely divided kaolin. This gives a dust which comprises 3% by weight of the active compound.




VI 20 parts by weight of the compound No. 20.39 are mixed intimately with 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycol 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 the compound No. 20.39 is dissolved in a mixture composed of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. This gives a stable emulsion concentrate.




VIII 1 part by weight of the compound No. 20.39 is dissolved in a mixture composed of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol® EM 31 (nonionic emulsifier based on ethoxylated castor oil). This gives a stable emulsion concentrate.




To widen the activity spectrum and to achieve synergistic effects, the substituted 2-benzoylcyclohexane-1,3-diones may be mixed with a large number of representatives of other herbicidal or growth-regulating active compound groups and then applied concomitantly. Suitable components for mixtures are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, (het)aryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-aroyl-1,3-cyclohexanediones, hetaryl aryl ketones, benzylisooxazolidinones, meta-CF


3


-phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, bipyridyls, halocarboxylic acids 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, phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.




It may furthermore be advantageous to apply the compounds I, alone or else concomitantly in combination with other herbicides and/or in the form of a mixture with other crop protection agents, for example together with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are employed for treating nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.




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




The syntheses of some starting materials and products are described below.




2-Chloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-4-sulfonylmethyl-(5,5-dimethylcyclohexane-1,3-dione)methanone




Step a: Methyl 2-Chloro-3-(2-nitroethenyl)-4-sulfonylmethylbenzoate




With the exclusion of atmospheric moisture, 50 g (0.18 mol) of methyl 2-chloro-3-formyl-4-sulfonylmethylbenzoate, 220 g (3.6 mol) of nitromethane, 216 g (3.6 mol) acetic acid and 7 g (91 mmol) of ammonium acetate are stirred at 85° C. The reaction mixture is poured into 2 l of distilled water and extracted with diethyl ether. The organic phase is washed with saturated aqueous sodium bicarbonate solution, dried with sodium sulfate, filtered and freed from the solvent under reduced pressure. The crude product is recrystallized from n-hexane/ethyl acetate. Yield: 13.1 g, m.p. 147-150° C.




Step b: Methyl 2-Chloro-3-(2-nitroethyl)-4-sulfonylmethylbenzoate




19.4 g (61 mmol) of methyl 2-chloro-3-(2-nitroethenyl)-4-sulfonylmethylbenzoate and 121 g of silica gel 60 are suspended in 180 ml of 2-propanol and 970 ml of chloroform and treated at room temperature with 3.5 g (94 mmol) of sodium borohydride. The reaction mixture is filtered, the filtrate is washed with dichloromethane/methanol 1:1 (v/v) and the organic phase is freed from the solvent under reduced pressure. Yield: 19.5 g;


1


H NMR, δ [ppm], CDCl


3


; 3.2 (s), 3.9 (m), 4.0 (s), 4.7 (m), 7.8 (d), 8.1 (d).




Step c: Methyl 2-Chloro-3-((4,5-dihydro-3-isoxazolylmethyl)-4-sulfonylmethylbenzoate




At room temperature, a solution of 2.8 g (23 mmol) of phenyl isocyanate in 50 ml of toluene is gassed with ethylene. A solution of 3.7 g (11 mmol) of methyl 2-chloro-3-(2-nitroethyl)-4-sulfonylmethylbenzoate and 0.5 ml of triethylamine in 100 ml of toluene is added to this mixture. The reaction mixture is taken up in 300 ml of diethyl ether and the organic phase is extracted with distilled water, and dried with sodium sulfate and filtered and the filtrate is freed from the solvent under reduced pressure. The crude product is purified over silica gel 60 using cyclohexane/ethyl acetate. Yield: 1.0 g;


1


H NMR, δ [ppm], CDCl


3


; 3.1 (t), 3.2 (s), 4.0 (s), 4.4 (t), 4.5 (s), 7.7 (d), 8.1 (d).




Step d: 2-Chloro-3-(4,5-dihydro-3-isoxazolylmethyl)-4-sulfonylmethylbenzoic Acid




At 5° C., a solution of 2.3 g (7 mmol) of methyl 2-chloro-3-(4,5-dihydro-3-isoxazolylmethyl)-4-sulfonylmethylbenzoate in 40 ml of tetrahydrofuran is treated with 0.3 g (13 mmol) of lithium hydroxide. The reaction mixture is taken up in 300 ml of diethyl ether and adjusted to pH 1 using 10% strength aqueous hydrochloric acid. The aqueous phase is extracted with diethyl ether. The combined organic phases are dried over sodium sulfate, filtered and freed from the solvent under reduced pressure. Yield: 1.7 g;


1


H NMR, δ [ppm], DMSO-d


6


; 3.0 (t), 3.3 (s), 4.2 (t), 4.3 (s), 7.8 (d), 8.1 (d).




Step e: 2-Chloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-4-sulfonylmethyl-(5,5-dimethylcyclohexane-1,3-dione)methanone (Table 7, Example 39)




At 40° C., a solution of 1.0 g (3 mmol) of 2-chloro-3-(4,5-dihydro-3-isoxazolylmethyl)-4-sulfonylmethylbenzoic acid and 440 mg (3 mmol) of dimedone in 50 ml of acetonitrile is treated with 0.8 g (3.8 mmol) of N,N-dicyclohexylcarbodiimide. After the reaction has ended (monitoring by tlc), 310 mg (3 mmol) of trimethylsilyl cyanide and 950 mg (9 mmol) of triethylamine are added. The reaction mixture is filtered and freed from the solvent under reduced pressure. The crude product is purified over silica gel 60 using toluene/tetrahydrofuran or dichloromethane/toluene. Yield: 600 mg; m.p. 168-173° C.




The compounds described below were prepared in a manner similar to the procedures given above.




2-Chloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-4-sulfonylmethyl(cyclohexane-1,3-dione)methanone (Table 1, Example 39)




m.p. 70-74° C.




2-Chloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-4-sulfonylmethyl-(3,3,6,6-tetramethylcyclohexane-1,3,5-trione)methanone (Table 19, Example 39)




40 m.p. 168-173° C.




2,4-Dichloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)(5,5-dimethylcyclohexane-1,3-dione)methanone (Table 8, Example 39)




m.p. 56-64° C.




2,4-Dichloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)(3,3,6,6-tetramethylcyclohexane-1,3,5-trione)methanone (Table 20, Example 39)




m.p. 196-202° C.




2,4-Dichloro-3-((3-(5H-furanone)methyl)phenyl)-(2,2,4,4-tetramethyl-1,3,5-cyclohexanetrione)methanone




Step a: 2,4-Dichloro-3-(3-(5H-furanone)methyl)benzoic Acid




The solution of 13 g (0.038 mol) of tert-butyl 2,4-dichloro-3-(3-furyl)hydroxymethylbenzoate and 1.8 g of p-toluenesulfonic acid in 370 ml of toluene is refluxed for 6 h. The mixture is subsequently poured into 100 ml of 10% strength aqueous sodium hydroxide solution and extracted with ethyl acetate. The aqueous phase is acidified with hydrochloric acid and extracted repeatedly with ethyl acetate. The combined organic phases are washed with water, dried and concentrated. This gives 4.8 g (45%) of the title compound, m.p. 196° C.




Step b: 2,4-Dichloro-3-((3-(5H-furanone)methyl)phenyl)(2,2,4,4-tetramethyl-1,3,5-cyclohexanetrione)methanone











1.6 g (0.0056 mol) of the resulting acid, 1.0 g (0.0056 mol) of 2,2,4,4-tetramethyl-1,3,5-cyclohexanetrione and 1.15 g (0.0056 mol) of dicyclohexylcarbodiimide are stirred in ml of acetonitrile at room temperature. 1.13 g (0.012 mol) of triethylamine and 0.1 ml of trimethylsilyl cyanide are subsequently added, and the mixture is left at room temperature for a further 12 h.




The reaction mixture is diluted with 50 ml of ethyl acetate and mixed with 50 ml of sodium carbonate solution, and the resulting precipitate is discarded. The organic phase is separated off, dried and concentrated.




The resulting residue is chromatographed using a silica gel column (cyclohexane/ethyl acetate 1:10). This gives 120 mg (5%) of the title compound. (Characteristic 13-C NMR data: 209.1, 197.6, 195.9, 195.1, 173.4, 145.6, 137.7, 136.2, 134.7, 131.3, 130.6, 128.6, 126.2, 110.2, 70.5, 27.7.




The following compound was prepared in a similar manner: 2,4-Dichloro-3-((3-(5H-furanone)methyl)phenyl)(1,3-cyclohexanedion-2-yl)methanone




Melting point: 119-121° C.












TABLE 37

























































1


H














m.p.




NMR






No.




R


6






R


7






R


8






R


9






R


10






R


11






Het




[° C.]




[ppm]























37.1




H




H




CH


3






CH


3






H




H




4,5-dihydro-




64














3-isoxazolyl



















37.2




CH


3






CH


3






C═O




CH


3






CH


3






4,5-dihydro-




202













3-isoxazolyl






















TABLE 38

























































1


H














m.p.




NMR






No.




R


6






R


7






R


8






R


9






R


10






R


11






Het




[° C.]




[ppm]























38.1




H




H




H




H




H




H




4,5-dihydro-




74














3-isoxazolyl






38.2




H




H




CH


3






CH


3






H




H




4,5-dihydro-




96













3-isoxazolyl






38.3




H




H




CH


3






CH


3






H




H




4,5-dihydro-




119













5-methyl-3-













isoxazolyl






38.4




H




H




CH


3






CH


3






H




H




3-isoxazolyl




92




















38.5




CH


3






CH


3






C═O





CH


3






CH


3






4,5-dihydro-




173














3-isoxazolyl






38.6




CH


3






CH


3






C═O





CH


3






CH


3






4,5-dihydro-




84













5-chloro-













methyl-3-













isoxazolyl





















USE EXAMPLES




The herbicidal activity of the substituted 2-benzoylcyclohexane-1,3-diones of the formula I was demonstrated by greenhouse experiments:




The culture containers used were plastic pots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.




For the pre-emergence treatment, the active compounds, which had been emulsified or suspended in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with translucent plastic hoods until the plants had started growing. This cover caused uniform germination of the test plants, unless this was adversely affected by the active compounds.




For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active compounds which had been emulsified or suspended in water. The test plants were for this purpose either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment. The application rate for the post-emergence treatment was 0.5 or 0.25 kg/ha of a.s.




Depending on the species, the plants were kept at 10-25° C. or 20-35° 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.




The evaluation was carried out using 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 course of growth.




The plants used in the greenhouse trials were from the following species:



















Scientific Name




Common Name















Chenopodium album






lambsquarters








(goosefoot)









Setaria viridis






green foxtail









Sinapis alba






white mustard









Solanum nigrum






black nightshade















Herbicidal activity when employed by the post-emergence method (greenhouse)











The compound 37.2, applied post-emergence at application rates of 0.5 or 0.25 kg/ha of a.s., allows very efficient control of the abovementioned weeds.



Claims
  • 1. A 2-benzoylcyclohexane-1,3-dione of the formula I where:R1 and R2 are each hydrogen, mercapto, nitro, halogen, cyano, thiocyanato, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, —OR3, —OCOR3, —OSO2R3, —S(O)nR3, —SO2OR3, —SO2N(R3)2, —NR3SO2R3 or —NR3COR3; R3 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, phenyl or phenyl-C1-C6-alkyl; where the abovementioned alkyl radicals may be partially or fully halogenated and/or may carry one to three of the following groups: hydroxyl, mercapto, amino, cyano, R3, —OR3, —SR3, —N(R3)2, ═NOR3, —OCOR3, —SCOR3, —NR3COR3, —CO2R3, —COSR3, —CON(R3)2, C1-C4-alkyliminooxy, C1-C4-alkoxyamino, C1-C4-alkylcarbonyl, C1-C4-alkoxy-C2-C6-alkoxycarbonyl, C1-C4-alkylsulfonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy and hetaryloxy, where the eight last mentioned radicals may in turn be substituted; n is 0, 1 or 2; Q is a cyclohexane-1,3-dione ring with or without substitution which is attached in position 2; X1 is a straight-chain or branched C1-C6-alkylene, a C2-C6-alkenylene or a C2-C6-alkynylene chain, where the abovementioned alkylene, alkenylene or alkynylene radicals may be partially halogenated and/or may carry one to three of the following groups: —OR4, —OCOR4, —OCONHR4 or —OSO2R4; except for those of the abovementioned alkenylene radicals where the double bond is α,β to the phenyl ring and where Het is linked to the double bond via the β position; R4 is hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, phenyl, phenyl-C1-C6-alkyl, where the abovementioned alkyl, alkenyl or alkynyl radicals may be partially or fully halogenated and/or may be substituted by one or more of the following radicals: hydroxyl, mercapto, amino, cyano, nitro, formyl, C1-C4-alkylamino, C1-C4-dialkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, C1-C4-alkylcarbonyloxy, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkoxy, C1-C4-haloalkoxy; Het is a three- to six-membered partially or fully saturated heterocyclic group or a three- to six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of: nitrogen, oxygen and sulfur, where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R5; R5 is hydrogen, hydroxyl, mercapto, amino, cyano, nitro, formyl, C1-C4-alkylamino, C1-C4-dialkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, C1-C4-alkylcarbonyloxy, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkoxy, C1-C4-haloalkoxy, where the alkyl radicals may in each case be substituted by in each case one or more of the following radicals: cyano, formyl, C1-C4-alkylamino, C1-C4-dialkylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, C1-C4-alkylcarbonyloxy, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkoxy, C1-C4-haloalkoxy; or an agriculturally useful salt thereof.
  • 2. A 2-benzoylcyclohexane-1,3-dione of the formula I as claimed in claim 1 in which Q is a cyclohexane-1,3-dione ring of the formula II which is attached in position 2, where R6, R7, R9 and R11 are each hydrogen or C1-C4-alkyl;R8 is hydrogen, C1-C4-alkyl or C3-C4-cycloalkyl, where the two last mentioned groups may carry one to three of the following substituents: halogen, C1-C4-alkylthio or C1-C4-alkoxy; or is tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 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 6 last mentioned radicals may be substituted by one to three C1-C4-alkyl radicals; R10 is hydrogen, C1-C4-alkyl or C1-C6-alkoxycarbonyl; or R8 and R11 together form a nc bond or a three- to six-membered carbocyclic ring; or the CR8R9 unit may be replaced by C═O.
  • 3. A 2-benzoylcyclohexane-1,3-dione of the formula I as claimed in claim 1, in whichR1 is nitro, halogen, cyano, thiocyanato, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy-C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, —OR3 or —S(O)nR3; R2 is hydrogen or one of the radicals mentioned above under R1.
  • 4. A 2-benzoylcyclohexane-1,3-dione of the formula Ia as claimed in claim 1, where the substituents R1, R2, Q, X1 and Het are each as defined in claim 1.
  • 5. A 2-benzoylcyclohexane-1,3-dione of the formula Ia as claimed in claim 4 where X1 is a C1-C2-alkylene or C2-alkynylene chain.
  • 6. A 2-benzoylcyclohexane-1,3-dione of the formula Ia as claimed in claim 1 where Het is a five- or six-membered partially or fully saturated heterocyclic or a five- or six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of:nitrogen, oxygen and sulfur.
  • 7. A composition comprising a herbicidally effective amount of at least one 2-benzoylcyclohexane-1,3-dione of the formula I or an agriculturally useful salt of I as claimed in claim 1 and auxiliaries which are customarily used for formulating crop protection agents.
  • 8. A method for controlling undesirable vegetation, which I comprises allowing a herbicidally effective amount of at least one 2-benzoylcyclohexane-1,3-dione of the formula I or an agriculturally useful salt of I as claimed in claim 1 to act on plants, their habitat and/or on seeds.
  • 9. A process for preparing a 2-benzoylcyclohexane-1,3-dione of the formula I as claimed in claim 1, which comprises acylating a substituted or unsubstituted cyclohexane-1,3-dione Q with an activated carboxylic acid IIIa or with a carboxylic acid IIIb, where the substituents R1, R2, X1 and Het are each as defined in claim 1 and L1 is a nucleophilically replaceable leaving group and rearranging the acylation product, if appropriate in the presence of a catalyst, to a compound I.
  • 10. A process for preparing a herbicidally active composition, which comprises mixing a herbicidally effective amount of at least one 2-benzoylcyclohexane-1,3-dione of the formula I or an agriculturally useful salt of I as claimed in claim 1 and auxiliaries which are customarily used for formulating crop protection agents.
  • 11. An activated carboxylic acid of the formula IIIa and a carboxylic acid of the formula IIIb as defined in claim 9.
  • 12. A 2-benzoyloyclohexane-1,3-dione of the formula I as claimed in claim 1 in whichX1 is CH2, CHCH3, CHOH, CHOCH3, CHOCOCH3, CHOSO2CH3, CH2CH2 or C≡C; Het is selected from the group consisting of oxiranyl, 3-methyl-2-oxiranyl, 2-oxetanyl, 3-hydroxy-3-methyl-2-oxetanyl, 3-hydroxy-3-ethyl-2-oxetanyl, 3-hydroxy-3-propyl-2-oxetanyl, 3-hydroxy-3-butyl-2-oxetanyl, 3-methoxy-3-methyl-2-oxetanyl, 3-methoxy-3-ethyl-2-oxotanyl, 3-methoxy-3-propyl-2-oxetanyl, 3-methoxy-3-butyl-2-oxetanyl, 3-trimethylsilyloxy-3-methyl-2-oxetanyl, 3-trimethylsilyloxy-3-ethyl-2-oxetanyl, 3-oxetanyl, 3-trimethylsilyloxy-3-propyl-2-oxetanyl, 3-trimethylsilyloxy-3-butyl-2-oxetanyl, 3-oxetanyl, 2-furyl, 4,5-dihydro-2-furyl, 2,3-dihydro-2-furyl, 3-furyl, 4,5-dihydro-3-furyl, 2,3-dihydro-3-furyl, 2-thienyl, 4,5-dihydro -2-thienyl, 2,3-dihydro-2-thienyl, 5-chloro-2-thienyl, 5-methyl-2-thienyl, 3-thienyl, 4,5-dihydro-3-thienyl, 2,3-dihydro -3-thienyl, 2-pyrrolyl, 2,5-dihydro-2-pyrrolyl, 3-pyrrolyl, 2,5-dihydro-3-pyrrolyl, 3-isoxazolyl, 4-methyl-3isoxazolyl, 5-methyl-3-isoxazolyl, 4,5-dimethyl-3-isoxazolyl, 4,5-dihydro-3-isoxazolyl, 4-methyl-4,5- dihydro-3- isoxazolyl, 5-methyl-4,5-dihydro-3-isoxazolyl, 4,5-dimethyl-4,5-dihydro-3-isoxazolyl, 4- isoxazolyl, 3-methyl-4-isoxazolyl, 5-methyl-4-isoxazolyl, 5-cyolopropyl-4-isoxazolyl, 5-phenyl-4-isoxazolyl, 3,5-dimethyl-4-isoxazolyl, 4,5-dihydro-4-isoxazolyl, 3-methyl-4,5-dihydro-4-isoxazolyl, 5-methyl-4,5-dihydro-4-isoxazolyl, 3,5-dimethyl-4,5-dihydro-4-isoxazolyl, 5-isoxazolyl, 3-methyl-5-isoxazolyl, 4-methyl-5-isozazolyl, 3,4-dimethyl-5-isoxazolyl, 4,5-dihydro-5-isoxazolyl, 3-methyl-4, 5-dihydro-5-isoxazolyl, 4-methyl-4,5-dihydro-5-isoxazolyl, 3,4-dimethyl-4,5-dihydro-5-isoxazolyl, 3-isothiazolyl, 4-methyl-3-isoxazolyl, 5-methyl-3-isothiazolyl, 4-isothiazolyl, 3-methyl-4-isothiazolyl, 5-methyl-4-isothiazolyl, 5-isothiazolyl, 3-methyl-5-isothiazolyl, 4methyl-5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-pyrazolyl, 4-pyrazolyl, 1-methyl-3-pyrazolyl-1-methyl-4-pyrazolyl-1-methyl-5-pyrazolyl, 2-imidazolyl, 1-methyl-2-imidazolyl, 5-methyl-[1,3,4]-2-oxadiazolyl, 5-methyl-[1,2,4]-3-oxadiazolyl, 5-methyl-[1,3,4]-2-thiaiazolyl, 5-methyl-[1,2,4]-3-thiadiazolyl, [1,2,4]-3-triazolyl, [1,2,3]-4-triazolyl, 2-pyridyl, 6-chloro-2-pyridyl, 6-methoxy-2-pyridyl, 6-trifluoromethyl-2-pyridyl, 3-pyridyl, 2-chloro-3-pyridyl, 2-methoxy-3-pyridyl, 4-pyridyl, 2-chloro-4-pyridyl, 2-methoxy-4-pyridyl, 2-ethoxy-4-pyridyl, 2-methylthio-4-pyridyl, 2-trifluoromethyl-5-pyridyl, 2-pyrimidinyl, 3-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl, 3-pyridazinyl, 4-pyridazinyl, 2-(2H-1,3-oxazinyl), 2(6H-1,3-oxazinyl), 4-(6H-1,3-oxazinyl), 6-(6H-1,3-oxazinyl), [1,3,5]-2-triaziayl, [1,2,4]-3-triazinyl, [1,2,4]-5-triazinyl and [1,2,4]-6-triazinyl.
  • 13. A 2-benzoylcyclohexane-1,3-dione of the formula I as claimed in claim 2, in whichX1 is CH2, CHCH3, CHOH, CHOCH3, CHOSO2CH3, CH2CH2 or C≡C; Het is selected from the group consisting of oxiranyl, 3-methyl-2-oxiranyl, 2-oxetanyl, 3-hydroxy-3-methyl-2-oxetanyl, 3-hydroxy-3-ethyl-2-oxetanyl, 3-hydroxy-3-propyl-2-oxetanyl, 3-hydroxy-3-butyl-2-oxetanyl, 3-methoxy-3-methyl-2-oxetanyl, 3-methoxy-3-ethyl-2-oxetanyl, 3-methoxy-3-propyl-2-oxetanyl, 3-methoxy-3-butyl-2-oxetanyl, 3-trimethylsilyloxy-3-methyl-2-oxetanyl, 3-trimethylsilyloxy-3-ethyl-2-oxetanyl, 3-trimethylsilyloxy-3-propyl-2-oxetanyl, 3-trimethylsilyloxy-3-butyl-2-oxetanyl, 3-oxetanyl, 2-furyl, 4,5-dihydro-2-furyl, 2,3-dihydro-2-furyl, 3-furyl, 4,5-dihydro-3-furyl, 2,3-dihydro-3-furyl, 2-thienyl, 4,5-dihydro-2-thienyl, 2,3-dihydro-2-thienyl, 5-chloro-2-thienyl, 5-methyl-2-thienyl, 3-thienyl, 4,5-dihydro-3-thienyl, 2,3-dihydro-3-thienyl, 2-pyrrolyl, 2,5-dihydro-2-pyrrolyl, 3-pyrrolyl, 2,5-dihydro-3-pyrrolyl, 3-isoxazolyl, 4-methyl-3-isoxazolyl, 5-methyl-3-isoxazolyl, 4,5-dimethyl-3-isonzolyl, 4,5-dihydro-3-isoxazolyl, 4-methyl-4,5-dihydro-3-isoxazolyl, 5-methyl-4,5-dihydro-3-isoxazolyl, 4,5-dimethyl-4,5-dihydro-3-isoxazolyl, 4-isoxazolyl, 3-methyl-4-isoxazolyl, 5-methyl-4-isoxazolyl, 5-cyclopropyl-4-isoxazolyl, 5-phenyl-4-isoxasolyl, 3,5-dimethyl-4-isoxazolyl, 4,5-dihydro-4-isoxasolyl, 3-methyl-4,5-dihydro-4-isoxazolyl, 5-methyl-4,5-dihydro-4-isoxazolyl, 3,5-dimethyl-4,5-dihydrol-4-isoxazolyl, 5-isoxazolyl, 3-methyl-5-isoxazolyl, 4-methyl-5-isoxazolyl, 3,4-dimethyl-5-isoxazolyl, 4,5-dihydro-5-isoxazolyl, 3-methyl-4,5-dihydro-5-isoxazolyl, 4-methyl-4,5-dihydro-5-isoxarolyl, 3,4-dimethyl-4,5-dihydro-5-isoxazolyl, 3-isothiazolyl, 4-methyl-3-isothiazolyl, 5-methyl-3-isothiazolyl, 4-isothiatolyl, 3-methyl-4-isothiazolyl, 5-methyl-4-isothiazolyl, 5-isothiazolyl, 3-methyl-5-isothiazolyl, 4-methyl-5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiatolyl, 4-thiatolyl, 5-thiazolyl, 3-pyrazolyl, 4-pyrasolyl, 1-methyl-3-pyrazolyl, 1-methyl-4-pyrazolyl, 1-methyl-5-pyrazolyl, 2-imidazolyl, 1-methyl-2-imidazolyl, 5-methyl-[1,3,4]-2-oxadiazolyl, 5-methyl-[1,2,4]-3-oxadiazolyl, 5-methyl-[1,3,4]-2-thiadiazolyl, 5-methyl-[1,2,4]-3-thiadiazolyl, [1,2,4]-3-triazolyl, [1,2,3]-4-triazolyl, 2-pyridyl, 6-chloro-2-pyridyl-6-methoxy-2-pyridyl, 6-trifluoromethyl-2-pyridyl, 3-pyridyl, 2-chloro-3-pyridyl, 2-methoxy-3-pyridyl-4-pyridyl, 2-chloro-4-pyridyl, 2-methoxy-4-pyridyl, 2-ethoxy-4-pyridyl, 2-methylthio-4-pyridyl, 2-trifluoromethyl-5- pyridyl, 2-pyrimidinyl, 3-pyrimidinyl, 4-pyrimidiayl, 2-pyrazinyl, 3-pyridazinyl, 4-pyridazinyl, 2-(2H-1,3-oxazinyl), 2-(6H-1,3-oxazinyl), 4-(6H-1,3-oxazinyl), 6-(6H-1,3-oxazinyl), [1,3,5]-2-triazinyl, [1,2,4]-3-triazinyl, [1,2,4]-5-triazinyl and [1,2,4]-6-triazinyl.
  • 14. A 2-benzoylcyclohexane-1,3-dione of the formula I as claimed in claim 1, which is selected from the group consisting of 2-chloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-4-sulfonylmethyl-(5,5-dimethylcyclohexane-1,3-dione)methanone, 2-chloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-4-sulfonylmethyl(cyclohexane-1,3-dione)methanone, 2-chloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-4-sulfonylmethyl-(3,3,6,6-tetramethylcyclohexane-1,3,5-trione)methanone, 2,4-dichloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-5,5-dimethylcyclohexane-1,3-dione)methanone, 2,4-dichloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl-3,3,6,6-tetramethylcyclohexane-1,3,5-trione)methanone, 2,4-dichloro-3-((3-(5H-furanone)methyl)phenyl)-(2,2,4,4-tetramethyl-1,3,5-cyclohexanetrione)methanone, 2,4-dichloro-3{[3-(5H-furanone)methyl]phenyl}-(1,3-cyclohexanetrione)methanone, 2-chloro-3-[(4,5-dihydro-5-methyl-3-isoxazolylmethyl)phenyl]-4-sulfonylmethyl-(5,5-dimethylcyclohexane-1,3-dione)methanone, 2-chloro-3-[(3-isoxazolylmethyl)phenyl]-4-sulfonylmethyl-(5,5-dimethylcyclohexane-1,3-dione)methanone and 2-chloro-3-[(4,5-dihydro-5-chloromethyl-3-isoxazolylmethyl)phenyl]-4-sulfonylmethyl-(5,5-dimethylcyclohexane-1,3-dione)methanone.
Priority Claims (1)
Number Date Country Kind
197 34 201 Aug 1997 DE
PCT Information
Filing Document Filing Date Country Kind
PCT/EP98/04636 WO 00
Publishing Document Publishing Date Country Kind
WO99/07688 2/18/1999 WO A
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4780127 Michaely et al. Oct 1988 A
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4954165 Baba et al. Sep 1990 A
5114461 Geach et al. May 1992 A
5834404 Sagae et al. Nov 1998 A
6004903 Von Deyn et al. Dec 1999 A
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Entry
Patent Abst. JP, 06173122, 0/020554A Jan. 23, 1996.