EP1181297A1 - Derives de cyclohexenondioxothiochromanoyle - Google Patents

Derives de cyclohexenondioxothiochromanoyle

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Publication number
EP1181297A1
EP1181297A1 EP00936705A EP00936705A EP1181297A1 EP 1181297 A1 EP1181297 A1 EP 1181297A1 EP 00936705 A EP00936705 A EP 00936705A EP 00936705 A EP00936705 A EP 00936705A EP 1181297 A1 EP1181297 A1 EP 1181297A1
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European Patent Office
Prior art keywords
alkyl
methyl
formula
alkoxy
hydrogen
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EP00936705A
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German (de)
English (en)
Inventor
Klaus Langemann
Matthias Witschel
Ernst Baumann
Wolfgang Von Deyn
Steffen Kudis
Guido Mayer
Ulf Misslitz
Ulf Neidlein
Martina Otten
Karl-Otto Westphalen
Helmut Walter
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems

Definitions

  • the present invention relates to new cyclohexenone dioxothio-chromanoyl derivatives of the formula I,
  • R i is hydrogen, nitro, halogen, cyano, C 1 -C 6 -alkyl, Ci-C ⁇ -haloalkyl, C ⁇ -C 6 -alkoxy, Ci-C ⁇ -haloalkoxy, C ⁇ -C 6 -alkylthio, Ci-C ⁇ - Haloalkylthio, -C-C 6 alkyl sulfinyl, Ci-C ⁇ -haloalkyl sulfinyl, Ci-C ö alkyl sulfonyl, Ci-Cg-haloalkyl sulfonyl, aminosulfonyl, N- (-C 6 alkyl) aminosulfonyl, N, N-Di- (-C-C 6 -alkyl) - aminosulfonyl, N- (Ci-C ⁇ -alkylsulfonyl) -amino, N- (Ci-C
  • R 3 is hydrogen, -CC 6 alkyl or halogen
  • X is a -O- (CH) n chain which may be substituted from the following group by one to three radicals: halogen, cyano, C 4 -alkyl, C 4 haloalkyl or Ci-C 4 alkoxycarbonyl , -
  • a - (CH) p chain which can be interrupted by an oxygen or sulfur and / or can be substituted by one to four radicals from the following group: Halogen, cyano, C 4 -C 4 alkyl, C 4 -C 4 haloalkyl or Ci - C 4 alkoxycarbonyl;
  • R 4 , R 8 are hydrogen, -CC 4 alkyl or C 1 -C 4 alkoxycarbonyl
  • R 5 , R 7 , R 9 are hydrogen or -CC alkyl
  • R 6 is hydrogen, halogen, hydroxy, Ci-C ö -alkyl, C 6 -haloalkyl, di- (C ⁇ -C 6 -alkoxy) methyl, (C ⁇ -C 6 -alk- oxy) - (C ⁇ -C 6 -alkylthio) -methyl, di- (-C-C 6 -alkyl-thio) methyl, -C-C 6 -alkoxy, Ci-C ö -haloalkoxy, -C-C 6 -alkylthio, -C-C 6 -haloalkylthio, C ⁇ -C 6 -alkyl-sulfinyl, -C-C 6 -haloalkylsulfinyl, -C-C 6 -alkyl-sulfonyl, Ci-C ⁇ -haloalkylsulfonyl, Ci-C ⁇ -alkoxycarbonyl, Ci-C 6 -halo
  • Radicals can be substituted by one to three C 1 -C 4 -alkyl radicals
  • R 5 and R 6 or R 6 and R 9 together form a ⁇ bond or a Ci-Cs-alkyl chain which can carry one to three radicals from the following group: halogen, cyano, -CC alkyl, C,-C 4th -Halogenalkyl or C 1 -C 4 alkoxycarbonyl, from;
  • R 5 and R 9 together form a C ⁇ . -C 4 alkyl chain, which can carry one to three radicals from the following group: halogen, cyano, -C-C 4 alkyl, -C-C 4 haloalkyl or C 1 -C 4 alkoxycarbonyl, from;
  • R 6 and R 7 together form a -0- (CH) q -O-, -0- (CH) q -S-, -S- (CH) q -S-, -O- (CH 2 ) r - or -S- (CH 2) r chain which can be substituted from the following group by one to three radicals: halogen, cyano, C -alkyl, C 4 haloalkyl or C 1 -C 4 alkoxycarbonyl;
  • R 6 and R 7 together with the carbon to which they are attached form a carbonyl group
  • the invention relates to processes and intermediates for the preparation of compounds of the formula I, compositions which contain them and the use of these derivatives or compositions containing them for combating harmful plants.
  • dioxothiochroman derivatives are those which are substituted with an optionally substituted (1-hydroxy-3-oxo-cyclohex-1-en-2-yl) carbonyl Rest are known.
  • the herbicidal properties of the compounds known hitherto and the tolerances to crop plants can only satisfy to a limited extent. It was therefore the object of this invention to find new, biologically, in particular herbicidally active, compounds with improved properties.
  • herbicidal compositions which contain the compounds I and have a very good herbicidal action.
  • processes for the preparation of these compositions and processes for controlling unwanted vegetation using the compounds I have been found.
  • the compounds of the formula I can contain one or more centers of chirality and are then present as enantiomers or mixtures of diastereomers.
  • the invention relates both to the pure enantiomers or diastereomers and to their mixtures.
  • the compounds of the formula I can also be in the form of their tautomers, where I represents the tautomeric forms I 'and I ".
  • the compounds of the formula I can also be present in the form of their agriculturally useful salts, the type of salt generally not being important. In general, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the herbicidal activity of the compounds I
  • the cations used are in particular ions of the alkali metals, preferably lithium, sodium and potassium, the alkaline earth metals, preferably calcium and magnesium, and the transition metals, preferably manganese, copper, zinc and iron, and ammonium, where one to four hydrogen atoms by C ⁇ - C 4 alkyl, hydroxy -CC 4 alkyl, -C 4 alkoxy -CC-C 4 - alkyl, hydroxy-C 4 -C 4 alkoxy-C ⁇ -C 4 alkyl, phenyl or benzyl replaced can be, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2 - (2-hydroxyeth-1-oxy) eth-1-ylammonium, di (2-hydroxyeth-1-yl) ammonium, trimethylbenzylammonium , further phosphonium ions, sulfonium ions, preferably
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C 1 -C 4 alkane acids, preferably formate, Acetate, propionate and butyrate.
  • C ⁇ -C 4 alkyl and the alkyl moieties of hydroxy-C ⁇ -C * 4 alkyl, tri (C 1 -C 4 -alkyl) sulfonium and tri (C ⁇ -C4-alkyl) sulfoxonium: for example, methyl, ethyl, Propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl;
  • C ⁇ -C 6 alkyl and the alkyl moieties of N- (Ci-C 6 alkyl) -N- (C ⁇ -C 6 alkylsulfonyl) amino, N- (Ci-C ⁇ -alkyl) -N- (C.
  • C 1 -C 4 haloalkyl a C ⁇ -C 4 alkyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, Trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorofluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2, 2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2- Chloro-2, 2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 2, 2, 2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoro
  • -C-C 6 haloalkyl and the haloalkyl parts of N-Ci-C ⁇ -haloalkylamino: -C-C-haloalkyl, as mentioned above, and for example 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl or dodecafluorohexyl;
  • Ci-C ⁇ - alkoxy as well as the alkoxy parts of di- (Ci-C ⁇ -alkoxy) methyl and (C I -C ⁇ -alkoxy) - (Ci-C ⁇ -alkylthio) methyl: e.g.
  • Ci-C ⁇ alkoxy radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethoxy,
  • Ci-C ⁇ -haloalkylthio a Ci-C ⁇ -alkylthio radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, Bromodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio,
  • Ci-C ⁇ -haloalkylsulfinyl C ⁇ -C 6 -alkylsulfinyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethyl-sulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethylsulfi- 2-fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2, 2-difluoroethylsulfinyl, 2,2, 2-trifluoroethylsulfinyl, 2,2, 2-trichloroethylsulfinyl, 2-chloro-2-fluoroe
  • 3-methylpentylsulfonyl 4-methylpentylsulfonyl, 1, 1-dimethylbutylsulfonyl, 1, 2-dimethylbutylsulfonyl, 1, 3-dimethylbutyl- sulfonyl, 2, 2-dimethylbutylsulfonyl, 2, 3-dimethylbutylsulfonyl, 3, 3-dimethylbutylsulfonyl, 1- ⁇ thylbutylsulfonyl, 2-ethylbutylsulfonyl, 1, 1, 2-trimethylpropylsulfonyl,
  • Ci-C ⁇ -haloalkylsulfonyl and the haloalkyl radicals of N- (Ci-C ⁇ -haloalkylsulfonyl) -amino and N- (C ⁇ -C 6 -alkyl) -N- (Ci-C ⁇ -haloalkylsulfonyl) -amino: a Ci C ⁇ -alkylsulfonyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonylsulfonylsulfonylsulfonylsulfonylsul
  • (Ci-C ö -alkylamino) sulfonyl for example methylaminosulfonyl, ethylaminosulfonyl, propylaminosulfonyl, 1-methylethylaminosulfonyl, B tylminosulfonyl, 1-methylpropylaminosulfonyl,
  • 2-methylpropylaminosulfonyl 1, 1-dimethylethylaminosulfonyl, pentylaminosulfonyl, 1-methylb tylaminosulfonyl, 2-methylbutylaminosulfonyl, 3-methylbutylaminosulfonyl, 2, 2-dimethylpropylaminosulfonyl, 1-ethylpropylylamosulfonyl, 1-methylylamosulfonyl, 1-methylylosulfonyl, 1-hexylaminosulfonyl , 2-dimethylpropylaminosulfonyl, 1-methylpentylaminosulfonyl, 2-methylpentylaminosulfonyl, 3-methylpentylaminosulfonyl, 4-methylpentylaminosulfonyl, 1, 1-dimethylbutylaminosulfonyl, 1,2-dimethylbutylaminosulfonyl, 1, 3
  • Di- (-C 6 -alkyl) -aminosulfonyl for example N, N-dimethylaminosulfonyl, N, N-diethylaminosulfonyl, N, N-di- (1-methylethyl) aminosulfonyl, N, N-dipropylaminosulfonyl, N, N -Dibuylaminosulfonyl, N, N-Di- (1-methylpropyl) -aminosulfonyl, N, N-Di- (2-methyl ⁇ propyl) -aminosulfonyl, N, N-Di- (1, 1-dimethylethyl) - aminosulfonyl, N-ethyl-N-methylaminosulfonyl, N-methyl-N-propylaminosulfonyl, N-methyl-N- (1-methylethyl) aminosulfonyl, N-butyl-N-
  • C 1 -C 4 alkoxycarbonyl methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1-methylethoxycarbonyl, butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl or 1, 1-dimethylethoxycarbonyl;
  • (C ⁇ -C 6 -alkoxy) carbonyl (C 1 -C 4 -alkoxy) carbonyl, as mentioned above, and for example pentoxycarbonyl, 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2, 2-dimethylprooxycarbonyl, 1 -Ethylpropoxycarbonyl, Hexoxycarbonyl, 1, 1-Dimethylpropoxycarbonyl, 1, 2-Dimethylpropoxycarbonyl, 1-Methylpentoxycarbonyl, 2-Methylpentoxycarbonyl, 3-Methyl-pentoxycarbonyl, 4-Methylpentoxycarbonyl, 1, 1-Dimethylbutoxycarbonyl, 1,2-Dimethylbutoxycarbonyl, 1 , 3-dimethylbutoxycarbonyl, 2, 2-dimethylbutoxycarbonyl, 2, 3-dimethylb toxycarbonyl, 3, 3-dimethylbutoxycarbonyl, 1-ethylbutoxycarbonyl, 2-
  • C 1 -C 4 -alkoxy-C 4 -alkyl and the alkoxyalkyl parts of hydroxy-C 1 -C 4 -alkoxy-C 4 -C 4 -alkyl: C 1 -C 4 -alkoxy, as mentioned above, substituted C ⁇ -C 4 alkyl, for example for methoxymethyl, ethoxymethyl, propoxymethyl, (1-methylethoxy) methyl, butoxymethyl, (1-methylpropoxy) methyl, (2-methylpropoxy) methyl, (1, 1-dimethylethoxy) methyl, 2- (methoxy) ethyl, 2- (ethoxy) ethyl, 2- (propoxy) ethyl, 2- (l-methylethoxy) ethyl, 2- (butoxy) ethyl, 2- (l-methylprooxy) ethyl, 2- (2-methylpropoxy) ethyl, 2- (1, 1-dimethylethoxy) ethyl, 2- (
  • the variables preferably have the following meanings, in each case individually or in combination:
  • R 1 nitro, halogen, Ci-C ⁇ -alkyl, Ci-C ö -haloalkyl,
  • R 3 is hydrogen
  • X forms a -0- (CH 2 ) n chain, which can be substituted by one to three radicals from the following group: halogen, C1 . -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxycarbonyl;
  • a - (CH) P chain which can be interrupted by oxygen or sulfur and / or can be substituted by one to four radicals from the following group:
  • R 4 , R 8 are hydrogen or C1 . -C 4 alkyl, such as methyl, ethyl or
  • Propyl preferably hydrogen or methyl
  • R 5 , R 7 , R 9 are hydrogen or -CC alkyl, such as methyl, ethyl or
  • Propyl preferably hydrogen or methyl
  • R 6 is hydrogen, hydroxy, -CC 6 alkyl, di- (-C 6 alkoxy) -methyl, (-C 6 alkoxy) (-C 6 alkylthio) methyl, di- ( C ⁇ -C 6 -alkylthio) methyl, C ⁇ -C6 alkoxy, Ci-C alkyl ⁇ thio, Ci-C ⁇ haloalkylthio, C ⁇ -C 6 alkylsulfinyl, C. 3-C 6 haloalkylsulfinyl, C ⁇ -C 6 alkylsulfonyl or C 6 haloalkylsulfonyl;
  • R 5 and R 6 or R 6 and R 9 together form a ⁇ bond or a C 3 -C 5 alkyl chain which can carry one to three radicals from the following group: halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or Ci -C alkoxycarbonyl, from;
  • R 5 and R 9 together form a C ⁇ -C alkyl chain, which can carry one to three radicals from the following group: halogen, cyano, C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 - Alkoxycarbonyl, from;
  • R 6 and R 7 together form a -O- (CH 2 ) q -O-, -O- (CH 2 ) q -S- or - S- (CH 2 ) q -S chain, which is represented by one to three Residues from the following group can be substituted: halogen, cyano, -CC 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxycarbonyl; preferably R 6 and R 7 together form a -0- (CH) q -0-, -0- (CH) q -S- or -S- (CH 2 ) q -S chain, which by one to three of the Radicals from the following groups can be substituted: C1-C4-haloalkyl or C 1 -C 4 -alkoxycarbonyl;
  • R 6 and R 7 together with the carbon to which they are attached form a carbonyl group
  • R 1 is halogen, Ci-C ⁇ -alkyl, C ⁇ -C 6 haloalkyl, C ⁇ -C 6 -alkoxy, C 6 alkylthio, or C ⁇ -C 6 alkylsulfonyl; in particular halogen such as chlorine or bromine, -C 6 alkyl such as methyl or ethyl, -C 6 alkoxy such as methoxy or ethoxy or -C 6 alkylsulfonyl such as methylsulfonyl or ethylsulfonyl; particularly preferably chlorine, methyl, methoxy or methylsulfonyl;
  • R 3 is hydrogen
  • X forms a -0- (CH 2 ) n chain, which can be substituted by one to three radicals from the following group: -C-alkyl or Ci -C -haloalkyl;
  • a - (CH 2 ) p chain which can be substituted by one to four radicals from the following group: halogen, C 1 -C 4 alkyl or Ci -C 4 haloalkyl;
  • n 1 to 4 especially 1,3 or 4;
  • R 4 , R 8 are hydrogen or C 1 -C 4 alkyl, such as methyl, ethyl or propyl; preferably hydrogen or methyl;
  • R 5 , R 7 , R 9 are hydrogen or C 1 -C 4 alkyl, such as methyl, ethyl or propyl; preferably hydrogen or methyl;
  • R 6 is hydrogen, hydroxy, C ⁇ -C6 alkyl, di- (C ⁇ -C 6 -alk- oxy) methyl, (C C6 alkoxy) (C ⁇ -C 6 -alkylthio) methyl, di- ( CI-C ⁇ alkylthio) methyl, C ⁇ -C 6 alkylsulfonyl or C ⁇ -C6 haloalkylsulfonyl; preferably hydrogen, hydroxy or C 1 -C alkyl, such as methyl, ethyl or propyl;
  • R 6 and R 7 together with the carbon to which they are attached form a carbonyl group
  • R 1 halogen, C 1 -C 4 alkyl, -C -C alkoxy or C 1 -C 4 alkylsulfonyl;
  • R 3 is hydrogen
  • X is a -0- (CH 2) - (CH 2) p chain forms, with the latter by one to three halogen atoms, C 1 -C 4 alkyl - - or haloalkyl radicals may be substituted or C ⁇ -C 4 ;
  • p 2 to 5 especially 2, 4 or 5;
  • X forms a - (CH 2 ) 2 chain, which has 1 to 3 halogen atoms, such as fluorine or chlorine, -CC 4 -alkyl radicals such as methyl or ethyl or C ⁇ . -C 4 haloalkyl radicals such as trifluoromethyl, may be substituted.
  • R 6 is hydrogen, hydroxy, -CC 6 alkyl, di- (-C 6 alkoxy-oxy) methyl, (-C 6 alkoxy) (-C 6 alkylthio) methyl, di (-C- C 6 alkylthio) methyl or Ci -C 6 alkoxy;
  • R 7 is hydrogen or Ci-C 4 alkyl
  • R 1 is halogen or Ci -C 6 alkyl; especially chlorine or methyl; especially methyl;
  • X is an -O- (CH 2 ) - or a - (CH 2 ) s- or a
  • R 6 is hydrogen or -CC alkyl
  • R 7 is hydrogen or Ci-C 4 alkyl
  • R 6 and R 7 together with the carbon to which they are attached form a carbonyl group
  • the compounds of the formula Ia2 in particular the compounds Ia2.1 to Ia2.85, which differ from the compounds Ial.l to Ial.85 in that R 6 and R 7 are methyl.
  • the compounds of the formula Ia4 in particular the compounds Ia4.1 to Ia4.85, which differ from the compounds Ial.l to Ial.85 in that R 8 and R 9 are methyl.
  • cyclohexenone dioxothiochromanoyl derivatives of the formula I can be obtained in various ways, for example by the following process:
  • L 1 stands for a nucleophilically displaceable leaving group, such as halogen, for example bromine or chlorine, hetaryl, for example imidazolyl or pyridyl, carboxylate, for example acetate or trifluoroacetate, etc.
  • halogen for example bromine or chlorine
  • hetaryl for example imidazolyl or pyridyl
  • carboxylate for example acetate or trifluoroacetate, etc.
  • the activated benzoic acid Ila can be used directly, as in the case of the benzoyl halides or generated in situ, for example with dicyclohexylcarbodiimide, triphenylphosphine / azodicarboxylic acid. ester, 2-pyridine disulfide / triphenylphosphine, carbonyldiimidazole etc.
  • auxiliary base it may be advantageous to carry out the acylation reaction in the presence of a base.
  • the reactants and the auxiliary base are expediently used in equimolar amounts.
  • a slight excess of the auxiliary base e.g. 1.2 to 1.5 molar equivalents, based on II, can be advantageous under certain circumstances.
  • Tertiary alkyl amines, pyridine or alkali metal carbonates are suitable as auxiliary bases.
  • a solvent e.g. chlorinated hydrocarbons, such as methylene chloride or 1,2-dichloroethane, aromatic hydrocarbons, such as toluene, xylene or chlorobenzene, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, polar aprotic solvents, such as acetonitrile, dimethylformamide or dimethyl sulfoxide or esters such as ethyl acetate or mixtures thereof.
  • benzoyl halides are used as the activated carboxylic acid component, it may be expedient to cool the reaction mixture to 0-10 ° C. when this reactant is added. The mixture is then stirred at 20-100 ° C., preferably at 25-50 ° C., until the reaction is complete. The processing takes place in the usual way, e.g. the reaction mixture is poured onto water and the product of value is extracted. Methylene chloride, diethyl ether and ethyl acetate are particularly suitable as solvents for this. After drying the organic phase and removing the solvent, the crude ester can be used for rearrangement without further purification.
  • the rearrangement of the esters to the compounds of the formula I is advantageously carried out at from 20 to 100 ° C. in a solvent and in the presence of a base and, if appropriate, using a cyano compound as a catalyst.
  • solvent e.g. Acetonitrile, methylene chloride, 1, 2-dichloroethane, dioxane, ethyl acetate, toluene or mixtures thereof can be used.
  • Preferred solvents are acetonitrile and dioxane.
  • Suitable bases are tertiary amines such as triethylamine, aromatic amines such as pyridine or alkali carbonates such as sodium carbonate or potassium carbonate, which are preferably used in an equimolar amount or up to a fourfold excess, based on the ester. Triethylamine or alkali carbonate are preferred used, preferably in double equimolar ratio with respect to the ester.
  • Inorganic cyanides such as sodium cyanide or potassium cyanide and organic cyano compounds such as acetone cyanohydrin or trimethylsilyl cyanide are suitable as cyano compounds. They are used in an amount of 1 to 50 mole percent, based on the ester. Preferably acetone cyanohydrin or trimethylsilyl cyanide, e.g. in an amount of 5 to 15, preferably 10 10 mol percent, based on the ester.
  • the reaction mixture is e.g. with dilute mineral acid, such as
  • solvents e.g. Extracted methylene chloride or ethyl acetate.
  • the organic extract can be mixed with 5-10% alkali carbonate solution, e.g. Sodium carbonate or potassium carbonate solution are extracted.
  • the aqueous phase is acidified and the precipitate that forms is filtered off with suction and / or with methylene
  • halogenating reagents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride and oxalyl bromide.
  • the benzoic acids of the formula IIb can be prepared in a manner known per se from the corresponding esters by acidic or basic hydrolysis.
  • Suitable epoxidation reagents are, for example, organic peracids such as peroxyacetic acid or m-chloroperbenzoic acid, hydrogen peroxide (in alkaline) or alkyl peroxides, if appropriate in the presence of a transition metal catalyst such as e.g. Oxides of vanadium, molybdenum or cobalt.
  • organic peracids such as peroxyacetic acid or m-chloroperbenzoic acid
  • hydrogen peroxide (in alkaline) or alkyl peroxides if appropriate in the presence of a transition metal catalyst such as e.g. Oxides of vanadium, molybdenum or cobalt.
  • methylidenthiochromanoyl derivatives of the formula VI used as starting materials can be obtained by Wittig or related reactions from the corresponding thiochromanoyl derivatives of the formula IV (cf. for example J. March, "Advanced Organic Chemistry", 4th edition, Wiley, New York p. 956 ff.)
  • the methylidenthiochromanoyl derivatives of the formula VI can also be obtained by a McMurry reaction on corresponding thiochromanoyl derivatives of the formula IV (see, for example, A. Mostner, Angew. Chem. 105, 171 (1993)).
  • Mono- and di-halogen carbenes can e.g. by reaction of di- or trihalomethanes with bases such as e.g. n-butyl lithium, potassium hydroxide or potassium tert. -butanolate are obtained (cf. e.g. Houben-Weyl, "Methods of Organic Chemistry, Vol. E 17a)
  • Alkyl-substituted carbenes are obtained, for example, from sulfur ylides (see, for example, Kennwell et al., Chem. Soc. Rev. 4, 189 (1975); B. Trost et al., Acc. Chem. Res. 7, 85 ( 1974)). Furthermore, carbenes, in particular alkoxycarbonyl-substituted ones, can be obtained from corresponding diazo compounds with rhodium acetate.
  • Suitable oxidizing agents are organic peroxides such as m-chloroperbenzoic acid, peroxyacetic acid and tri-fluoroperoxyacetic acid, or hydrogen peroxide, if appropriate in the presence of a transition metal catalyst such as tungstate.
  • the compounds of the formula VII are obtained by alkylation of the mercapto compounds VIII, if appropriate in the presence of a base (cf. e.g. Karrer et al., Helv. Chim. Acta (1942) 25, 29).
  • Suitable bases are, for example, alkali metal carbonates, such as sodium carbonate or potassium carbonate, alkali metal hydrogen carbonates, such as sodium hydrogen carbonate or potassium hydrogen carbonate, or tertiary amines such as triethylamine or pyridine.
  • the compounds of the formula X are then cyclized to the compounds of the formula VII by Friedie-Kraft alkylation (cf., for example, Can. J. Chem. 59, 199 (1981); Chem. Ber. 58, 1625 (1925 ); Phosp. And Sulf. 19, 31 (1984)). This cyclization takes place in the presence of strong acids.
  • the above-mentioned process routes A to D represent synthesis principles. They also include the synthesis of the compounds of the formula IIc, where X is a -0- (CH) n chain, which can be substituted by one to three radicals from the following group: halogen, Cyano, -CC 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxycarbonyl; or a - (CH 2 ) p chain which can be interrupted by an oxygen or sulfur and / or one to four radicals from the following group can be substituted: halogen, cyano, C -C 4 alkyl, C 1 - C 4 haloalkyl or C 1 -C 4 alkoxycarbonyl.
  • This means that the starting materials V, VI, VII, IV and X and the ylides, carbenes used can be substituted accordingly.
  • R 1 is hydrogen, nitro, halogen, cyano, C ⁇ -C 6 alkyl
  • R 2 C ⁇ -C6 alkyl, Ci-C6 haloalkyl, C ⁇ -C 6 alkoxy or Ci-C -haloalkoxy ß;
  • R 3 is hydrogen, -CC 6 alkyl or halogen
  • X forms a -0- (CH) n chain, which can be substituted by one to three radicals from the following group: halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or Ci -C 4 -Alkoxycarbonyl;
  • a - (CH 2 ) p chain which can be interrupted by an oxygen or sulfur and / or can be substituted by one to four radicals from the following group:
  • R 10 is hydroxy or a hydrolyzable radical
  • residues which can be hydrolyzed are alkoxy, phenoxy, alkylthio, phenylthio residues, which may optionally be substituted, halides, hetaryl residues which are bonded via nitrogen, amino, imino residues which may be substituted can etc.
  • Benzoic acid esters of the formula IIc are likewise preferred
  • Step f) (2,2-difluorocyclopropane-l-spiro-4) -8-methyl -1,1-dioxothiochroman-7-carboxylic acid (compound 3.5)
  • Step g) 1 -hydroxy-2 - ⁇ [(2,2-difluorocyclopropane-l-spiro-4) -8-methyl-1,1-dioxothiochroman-7-yl] carbonyl ⁇ cyclohex -l-en-3-one (connection 2.9)
  • Step b) (Oxiran-2-spiro-4) - 8-methyl-l, 1-dioxo-thiochroman-7 -yl-carboxylic acid (compound 3.2)
  • Step c) 1 -hydroxy-4, 4, 6, 6 - tetramethyl -2 - ⁇ [(oxiran-2-spiro-4) - 8 -methyl -1, 1 -dioxothiochroman-7 -yl] carbonyl ⁇ - cyclohex-1-en-3,5-dione (compound 2.6)
  • the compounds of formula I and their agriculturally useful salts are suitable both as isomer mixtures and in the form of the pure isomers - as herbicides.
  • the herbicidal compositions which contain compounds of the formula I control vegetation very well on non-cultivated areas, especially when high amounts are applied. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. This effect occurs above all at low application rates.
  • the compounds of the formula I or herbicidal compositions comprising them can also be used in a further number of crop plants for eliminating undesired plants.
  • the following crops are considered, for example:
  • the compounds of the formula I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • the compounds of formula I or the herbicidal compositions containing them can be sprayed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, oldispersions, pastes, dusts, sprinkling agents or granules , Atomizing, dusting, scattering or pouring can be used.
  • the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • the herbicidal compositions comprise a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I and auxiliaries customary for the formulation of crop protection agents.
  • Mineral oil fractions from medium to high boiling point such as kerosene and diesel oil, also coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, e.g. Amines such as N-methylpyrrolidone and water.
  • Paraffin Paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes or their derivatives
  • alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol
  • ketones such as cyclo
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • the cyclohexenone dioxothiochromanoyl derivatives of the formula I as such can be used to prepare emulsions, pastes or oldispersions or dissolved in an oil or solvent, homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • the surfactants are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols as well as of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives Formaldehyde, condensation products of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, al
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are mineral soils such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the concentrations of the compounds of the formula I in the ready-to-use preparations can be varied within a wide range.
  • the formulations contain from about 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • the following formulation examples illustrate the preparation of such preparations:
  • Benzene 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide in 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide in 1 mole of castor oil.
  • an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
  • Wettol R EM 31 nonionic emulsifier based on ethoxylated castor oil.
  • the compounds of the formula I or the herbicidal compositions can be applied pre- or post-emergence. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit as far as possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (post-directed, lay-by).
  • the application rates of the compound of the formula I are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (as specified), depending on the control target, the season, the target plants and the growth stage.
  • cyclohexenone dioxothiochromanoyl derivatives of the formula I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
  • Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels.
  • the seeds of the test plants were sown separately according to species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles.
  • the tubes were lightly sprinkled to promote germination and growth, and then covered with clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, provided that this has not been impaired by the active ingredients.
  • test plants were first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water.
  • the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and some Planted into the test tubes days before treatment.
  • the application rate for post-emergence treatment was 0.5, 0.25, 0.125 and 0.0625 kg / ha aS (active substance).
  • the plants were kept in a species-specific manner at temperatures of 10 to 25 ° C and 20 to 35 ° C.
  • the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated.
  • Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
  • the plants used in the greenhouse experiments are composed of the following types:
  • Compound 2.9 combats the harmful plants field foxtail, wild oats at a rate of 0.25 or 0.125 kg / ha.
  • Chinese hemp, white goose foot and white mustard very good, as well as the compound 2.12 excellent effect against Chicken millet, Chinese hemp, white goosefoot, black nightshade and knotweed at 125 and 62.5 g / ha in the post-emergence shows.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

L'invention concerne des dérivés de cyclohexénondioxothiochromanoyle de la formule (I) dans laquelle, X forme une chaîne -O-(CH2)n qui peut être substituée ; ou une chaîne -(CH2)p qui peut être substituée et/ou être interrompue par un oxygène ou soufre ; n = entre 1 et 5 ; p = entre 2 et 6. L'invention concerne également les sels utilisables sur le plan agricole desdits dérivés. L'invention concerne par ailleurs des procédés et des produits intermédiaires pour préparer ces dérivés de cyclohexenondioxothiochromanoyle ou des agents les contenant pour lutter contre des plantes indésirables.
EP00936705A 1999-05-07 2000-05-03 Derives de cyclohexenondioxothiochromanoyle Withdrawn EP1181297A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19920953 1999-05-07
DE19920953 1999-05-07
PCT/EP2000/003964 WO2000068233A1 (fr) 1999-05-07 2000-05-03 Derives de cyclohexenondioxothiochromanoyle

Publications (1)

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EP1181297A1 true EP1181297A1 (fr) 2002-02-27

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EP00936705A Withdrawn EP1181297A1 (fr) 1999-05-07 2000-05-03 Derives de cyclohexenondioxothiochromanoyle

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EP (1) EP1181297A1 (fr)
JP (1) JP2002544134A (fr)
AU (1) AU5210900A (fr)
CA (1) CA2373165A1 (fr)
WO (1) WO2000068233A1 (fr)

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CN115010687B (zh) * 2022-06-14 2024-06-25 万华化学集团股份有限公司 一种破乳剂及其制备方法、香兰素的萃取工艺

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JPH11509192A (ja) * 1995-06-29 1999-08-17 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー 除草性ケタール類およびスピロ環類
DE19532311A1 (de) * 1995-09-01 1997-03-06 Basf Ag Benzoylderivate
BR9910070A (pt) * 1998-04-30 2000-12-26 Basf Ag Derivado de ciclo-hexenonadioxotiocromanoìla, composição processo para preparar compostos e uma, composição, método para controlar vegetação indesejável, e, uso de derivados da ciclo-hexenonadioxotiocromanoìla

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Title
See references of WO0068233A1 *

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AU5210900A (en) 2000-11-21
JP2002544134A (ja) 2002-12-24
WO2000068233A1 (fr) 2000-11-16
CA2373165A1 (fr) 2000-11-16

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