WO1997019071A1 - 2-cyano-1,3-dione derivatives, the production of same and their use as herbicides - Google Patents

2-cyano-1,3-dione derivatives, the production of same and their use as herbicides Download PDF

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WO1997019071A1
WO1997019071A1 PCT/EP1996/005065 EP9605065W WO9719071A1 WO 1997019071 A1 WO1997019071 A1 WO 1997019071A1 EP 9605065 W EP9605065 W EP 9605065W WO 9719071 A1 WO9719071 A1 WO 9719071A1
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alkyl
alkoxy
haloalkyl
haloalkoxy
nitro
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PCT/EP1996/005065
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German (de)
French (fr)
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Martina Otten
Wolfgang Von Deyn
Stefan Engel
Regina Luise Hill
Uwe Kardorff
Marcus Vossen
Peter Plath
Helmut Walter
Karl-Otto Westphalen
Ulf Misslitz
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Basf Aktiengesellschaft
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Priority to AU76269/96A priority Critical patent/AU7626996A/en
Publication of WO1997019071A1 publication Critical patent/WO1997019071A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D275/06—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/18—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with sulfur as the ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/64—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/66—Nitrogen atoms not forming part of a nitro radical
    • 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
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans

Definitions

  • the present invention relates to novel phenyldiketone derivatives with herbicidal activity, processes for the preparation of the phenyldiketone derivatives, agents which contain them and the use of these derivatives or agents containing them for grass weeding /
  • Herbicidal phenyldiketone derivatives are known from the literature, for example from EP 625505. However, the herbicidal properties of the known compounds and the compatibility with crop plants can only give satisfactory results to a limited extent.
  • the task was to find new phenyldiketone derivatives with improved properties.
  • L, M is hydrogen, C 1 -C 3 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl,
  • CR 10 R 11 CR 7 -SR 8 ; 1,3-dioxanyl or 1,3-dioxolanyl substituted with hydrogen or C 1 -C 4 alkyl; a heteroatom selected from the group consisting of oxygen, sulfur and nitrogen;
  • R 1 C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or NR 14 ;
  • R 2 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or NR 14 ;
  • R 3 is hydrogen, -NR 9 R 4 ; C 1 -C 6 alkyl, C 1 -C 6 haloalkyl,
  • R 4 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl,
  • R 3 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl,
  • R 7 is hydrogen, C 1 -C 6 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl,
  • C 1 -C 4 haloalkoxy optionally substituted phenyl, where the substituents can consist of one to three halogens, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, nitro; R 7 and R 21 or R 7 and R 23 or R 7 and R 12 can form a bond; R 8 is hydrogen, C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, substituted phenyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 - Haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; substituted benzyl where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloal
  • R 10 , R 11 independently of one another are hydrogen, C 1 -C 6 alkyl; Phenyl optionally substituted with one to three halogens, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, nitro;
  • R 10 and R 12 or R 10 and R 23 or R 10 and R 21 may form a bond;
  • R 12 , R 13 independently of one another are hydrogen, C 1 -C 6 alkyl,
  • C 1 -C 6 haloalkyl C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy; optionally substituted phenyl where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
  • R 14 C 1 -C 4 alkyl
  • R 21 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy,
  • C 1 -C 6 haloalkoxy optionally substituted phenyl where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
  • R 22 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy,
  • C 1 -C 6 haloalkoxy optionally substituted phenyl where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
  • R 23 is hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy;
  • phenyl or benzyl optionally substituted with C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
  • phenyldiketone derivatives can exist in the following tautomeric forms:
  • L, M, X, Y, n and R 15 have the meaning given at the outset and T stands for halogen.
  • the first step of the reaction sequence is such that magnesium and a small amount of CCl 4 are added to a methanolic solution of a cyanoketone of the formula AI and this is allowed to react to the magnesium enolate.
  • Analog C-acylations of cyanoketones are described, for example, in EP-A 496 630 and EP-A 496 631.
  • the magnesium enolate of the formula A2 obtained is dissolved in toluene or acetonitrile, with acetonitrile being preferred, and the amount of the acid chloride of the formula III equivalent to AI is then added dropwise as an acetonitrile solution.
  • the reaction is complete.
  • the mixture is concentrated in vacuo, the remaining residue is taken up in a solvent such as ethyl acetate or methylene chloride and 10%.
  • HCl washed to break down the magnesium salt.
  • the product is precipitated from the remaining residue by rubbing with a hydrocarbon such as petroleum ether, cyclohexane or n-pentane.
  • the cyanoketones of the formula AI used as starting materials are generally known compounds. They can be obtained, for example, by reacting cyanoacetic acid with butyllithium and then with an acid chloride R 15 -COCl.
  • the acid chlorides R 15 -COCl are obtained in a manner known per se from the corresponding carboxylic acids R 15 -COOH by reaction with thionyl chloride.
  • the carboxylic acids R 15 -COOH are compounds known from the literature: pivalic acid and cyclopropanecarboxylic acid are commercial compounds.
  • DMethylcyclopropanecarboxylic acid is either obtained by saponification from the commercially available ethyl ester or obtained in a known manner by methylation of the lithium ⁇ -lithiocylopropanecarboxylate [Warner + Le, JOC 47, 893 (1982)].
  • 1-methylthiocyclopropanecarboxylic acid is obtained in a known manner from the 1-methylthiocyclopropanecarboxylic acid nitrile, which in turn can be prepared from methylmercaptoacetonitrile and ethylene dibromide in the presence of sodium amide
  • AlCl 3 or SnCl 4 are preferred as Lewis acids and polyphosphoric acid and sulfuric acid are preferred as protonic acids according to Can. J. Chem. 1981, 59, 199; Chem. Ber. 1925, 58, 1625; Chem. Ber. 1926, 59, 1074; Phosp. and sulf. 1984, 19, 31.
  • Thiochromenonic acids can continue to be e.g. Elimination of hydrogen halide from 3-halothiochromanonic acids or e.g. by reacting the substituted thiophenolic acids with substituted ⁇ -alkylacetoacetic esters in the presence of phosphorus pentoxide according to Ann. Chem. 1964, 680, 40.
  • the arylthio compounds IV can be obtained, for example, by a Sandmeyer reaction from corresponding anilines, which in turn are synthesized by reducing suitable nitro compounds in accordance with Organikum 19th edition 1992, 552ff.
  • the reactants and the base are expediently used in equimolar amounts.
  • the reaction mixture is preferably stirred at 20-100 ° C., in particular at 20-40 ° C.
  • Working up is carried out, for example, by pouring the reaction mixture onto water, acidifying the aqueous phase with mineral acids such as hydrochloric acid or sulfuric acid and suctioning off the product of value or by extraction with methylene chloride or Extracted ethyl acetate, dried and freed from the solvent.
  • the ester can be reacted without further purification.
  • the thiochromenone ester can be reacted, for example, by reacting an arylthio compound with an acetylenecarboxylic acid derivative in water or solvent at a temperature of 0-140 ° Implement C.
  • Working up is carried out in a manner known per se by adding water and dilute mineral acid such as hydrochloric acid. The product of value is either suctioned off or by extraction with methylene chloride or ethyl acetate, followed by
  • the intermediates of formula III can be obtained by reactions known from the literature, such as reduction according to Jerry March "Advanced Organic Chemistry, Fourth Ed., E.g. S.910ff, oximation according to Jerry March” Advanced Organic Chemistry, Fourth Ed., E.g. P.934, 935, 1039, 1226, 405ff, conversion into imines and amines according to Jerry March "Advanced Organic Chemistry, Fourth Ed., Ketalization, alkylation, halogenation, elimination and oxidation according to Jerry March” Advanced Organic Chemistry, Fourth Ed. be further functionalized.
  • 3-alkoxy-1,2-benzisothiazoles can be obtained starting from corresponding saccharin derivatives or 1,2-benzisothiazoles by, for example, reaction with PCl 5 , POCI 3 or chlorine and alcohol, optionally in the presence of an auxiliary base such as, for example, triethylamine, which is described, for example, in US 4,571,429, Arch. Pharm. 1984, 317, 807, US 4461901, US 450916, J. Med. Chem. 1986, 29, 359.
  • Saccharin carboxylic acids can be described by literature methods according to Ann. Chem. 427, 231, 1922, Chem. Ber. 13, 1554, 1980, Chem. Ber. 25, 1740, 1892, DE-OS 3607343, German patent application P 44 27 995.7 can be obtained.
  • the benzoic acids of formula III can also be obtained by the corresponding bromo or iodo substituted compound of formula VII
  • Y, L, M, X and n have the meaning described above, in the presence of a palladium, nickel, cobalt or rhodium transition metal catalyst and a base with carbon monoxide and water under elevated pressure.
  • Palladium can be metallic or in the form of customary salts such as in the form of halogen compounds, for example PdCl 2 , RhCl 3 -H 2 O, acetates, for example Pd (OAc) 2 , cyanides etc. in the known valence levels.
  • phosphine ligand is widely variable. For example, they can be represented by the following formulas: or
  • n 1, 2, 3 or 4 and the radicals R 24 to R 26 are low molecular weight alkyl, for example C 1 -C 6 alkyl, aryl, C 1 -C 4 alkylaryl, for example benzyl, phenethyl or aryloxy .
  • Aryl is, for example, naphthyl, anthryl and preferably optionally substituted phenyl, the substituents only having to be considered for their inertness to the carboxylation reaction, otherwise they can be varied widely and include all inert C-organic radicals such as C 1 -C 6 -alkyl radicals , e.g. methyl, carboxyl residues such as COOH, COOM (M is for example a
  • the phosphine complexes can be prepared in a manner known per se, for example as described in the documents mentioned at the outset. For example, one starts from customary commercially available metal salts such as PdCl 2 or Pd (OCOCH 3 ) 2 and adds the phosphine, for example P (C 6 H 5 ) 3 , P (nC 4 H 9 ) 3 , PCH 3 (C 6 H 5 ) 2 ,
  • the amount of phosphine, based on the transition metal is usually 0 to 20, in particular 0.1 to 10 mol equivalents, particularly preferably 1 to 5 mol equivalents.
  • the amount of transition metal is not critical. Of course, for reasons of cost, you will rather get a small amount, e.g. from 0.1 to 10 mol%, in particular 1 to 5 mol%, based on the starting material II or III.
  • the reaction is carried out with carbon monoxide and at least equimolar amounts of water, based on the starting materials VI.
  • the reactant water can also serve as a solvent, i.e. the maximum amount is not critical.
  • Inert solvents which are customary for carboxylation reactions, such as hydrocarbons, for example toluene, xylene, hexane, pentane, cyclohexane, ethers, for example methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted amides such as dimethylformamide, per-substituted ureas such as tetra-C 1 -C 4 alkylureas or nitriles such as benzonitrile or acetonitrile.
  • one of the reactants, in particular the base is used in excess, so that no additional solvent is required.
  • Bases suitable for the process are all inert bases which are able to bind the hydrogen iodide or hydrogen bromide released during the reaction.
  • tertiary amines such as tert-alkylamines, for example trialkylamines such as triethylamine, cyclic amines such as N-methylpiperidine or N, N'-dimethylpiperazine, pyridine, alkali metal or hydrogen carbonates, or tetraalkyl-substituted urea derivatives such as tetra-C 1 -C 4 - alkyl urea, for example tetramethyl urea.
  • the amount of base is not critical, usually 1 to 10, in particular 1 to 5, moles are used.
  • the amount is usually measured so that the reactants are dissolved, avoiding unnecessarily high excesses for reasons of practicality in order to save costs, to use small reaction vessels and to ensure maximum contact for the reactants.
  • the carbon monoxide pressure at room temperature is preferably 1 to 250 bar, in particular 5 to 150 bar CO.
  • the carbonylation is generally carried out continuously or batchwise at temperatures from 20 to 250 ° C., in particular at 30 to 150 ° C.
  • carbon monoxide is expediently pressed continuously onto the reaction mixture in order to maintain a constant pressure.
  • aryl halogen compounds VII used as starting compounds are known or can easily be prepared by a suitable combination of known syntheses and reaction sequences described above.
  • L M hydrogen, C 1 -C 6 -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3 -Methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1 , 2-dimethylbutyl, 1,3-dimethylbutyl,
  • C 2 -C 6 alkynyl such as propargyl, 2-butynyl, 3-butenyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl- 2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3 pentynyl, 1-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl,
  • C 1 -C 4 alkoxy such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy, in particular C 1 -C 3 alkoxy such as methoxy, ethoxy , i-Propoxy, where these groups can optionally be substituted by one to five halogen atoms such as fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine or C 1 -C 4 alkoxy as mentioned above.
  • halogen atoms such as fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine or C 1 -C 4 alkoxy as mentioned above.
  • the group defined above - (A) m -S (O) n R 1 represents , for example, C 1 -C 4 -alkylthio such as methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1-methylpropylthio, 2- Methylpropylthio and 1,1-dimethylethylthio, especially methylthio; C 1 -C 4 alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl and 1,1-dimethylethylsulfinyl, especially methylsulfinyl; C 1 -C 4
  • NC 1 -C 4 alkylsulfamoyl such as N-methylsulfamoyl, N-ethylsulfamoyl, Nn-propylsulfamoyl, N-1-methylethylsulfamoyl, Nn-butylsulfamoyl, N-1-methylpropylsulfamoyl, N-2-methylpropylsulfamoyl, N-2-methylpropylsulfamoyl especially N-methylsulfamoyl;
  • NC 1 -C 4 alkylsulfinamoyl such as N-methylsulfinamoyl, N-ethylsulfinamoyl, Nn-propylsulfinamoyl, N-1-methylethylsulfinamoyl, Nn-butylsulfinamoyl, N-1-methylpropylsulfinamoyl, N-2-methylproylmoylmethylsulfinamoyl especially N-methylsulfinamoyl; Di-C 1 -C 4 alkylsulfamoyl such as dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl, N-methyl-N-ethylsulfamoyl, N-methyl-N-propylsulfamoyl, N-methyl-N-1-methylethy
  • C 1 -C 4 alkylsulfinyloxy such as methylsulfinyloxy, ethylsulfinyloxy, n-propylsulfinyloxy, 1-methylethylsulfinyloxy, n-butylsulfinyloxy, 1-methylpropylsulfinyloxy, 2-methylpropylsulfinyloxy and 1,1-dimethylethylsulfinyloxy, especially methylsulfinyloxy;
  • C 1 -C 4 alkylsulfonyloxy such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, 1-methylethylsulfonyloxy, n-butylsulfonyloxy, 1-methylpropylsulfonyloxy, 2-methylpropylsulfonyloxy and 1,1-dimethylethylsulfonyloxy, especially methylsulfonyloxy;
  • C 1 -C 4 alkylsulfinylamino such as methylsulfinylamino, ethylsulfinylamino, n-propylsulfinylamino, 1-methylethylsulfinylamino, n-butylsulfinylamino, 1-methylpropylsulfinylamino, 2-methylpropylsulfinylamino and 1, 1-dimethylethylsulfinylamino, in particular;
  • C 1 -C 4 alkylsulfonylamino such as methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, 1-methylethylsulfonylamino, n-butylsulfonylamino, 1-methylpropylsulfonylamino, 2-methylpropylsulfonylamino and 1,1-dimethylamino, especially 1,1-dimethylamino; NC 1 -C 4 alkylsulfinyl-N-methyl-amino such as N-methylsulfinyl-N-methyl-amino, N-ethylsulfinyl-N-methyl-amino, Nn-propylsulfinylN-methyl-amino, N-1-methylethylsulfinyl-N- methyl-amino,
  • N-n-butylsulfinyl-N-methyl-amino N-1-methylpropylsulfinyl-N-methyl-amino, N-2-methylpropylsulfinyl-N-methyl-amino and
  • NC 1 -C 4 alkylsulfinyl-N-ethylamino such as N-methylsulfinyl-N-ethylamino, N-ethylsulfinyl-N-ethylamino, Nn-propylsulfinyl-N-ethylamino, N-1-methylethylsulfinyl-N-ethylamino amino, Nn-butylsulfinylN-ethyl-amino, N-1-methylpropylsulfinyl-N-ethyl-amino,
  • NC 1 -C 4 alkylsulfonyl-N-methyl-amino such as N-methylsulfonyl-N-methyl-amino, N-ethylsulfonyl-N-methyl-amino, Nn-propylsulfonylN-methyl-amino, N-1-methylethylsulfonyl-N- methyl-amino,
  • N-n-butylsulfonyl-N-methyl-amino N-1-methylpropylsulfonyl-N-methyl-amino, N-2-methylpropylsulfonyl-N-methyl-amino and
  • NC 1 -C 4 alkylsulfonyl-N-ethylamino such as N-methylsulfonyl-N-ethylamino, N-ethylsulfonyl-N-ethylamino, Nn-propylsulfonyl-N-ethylamino, N-1-methylethylsulfonyl-N-ethylamino amino, Nn-butylsulfonyl-N-ethyl-amino, N-1-methylpropylsulfonyl-N-ethyl-amino,
  • C 1 -C 4 haloalkylthio such as chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, chlorodifluoromethylthio,
  • Pentafluoroethylthio especially trifluoromethylthio.
  • the group - (A) m -CO-R 2 defined above stands for example for C 1 -C 4 alkylcarbonyl such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl and 1 , 1-dimethylethylcarbonyl, especially methylcarbonyl;
  • C 1 -C 4 alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, 1-methylethoxycarbonyl, n-butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl and 1,1-dimethylethoxycarbonyl, especially methoxycarbonyl;
  • NC 1 -C 4 alkylcarbamoyl such as N-methylcarbamoyl, N-ethylcarbamoyl, Nn-propylcarbamoyl, N-1-methylethylcarbamoyl, Nn-butylcarbamoyl, N-1-methylpropylcarbamoyl, N-2-methylpropylcarbamoyl and N-1,1-dimethylethylcarbamoyl especially N-methylcarbamoyl; Di-C 1 -C 4 alkylcarbamoyl such as dimethylcarbamoyl, diethylcarbamoyl, dipropylcarbamoyl, dibutylcarbamoyl, N-methyl-N-ethylcarbamoyl, N-methyl-N-propylcarbamoyl, N-methyl-N-1-methylethylcarbamoyl, N-methyl
  • C 1 -C 4 alkylcarbonyloxy such as methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, 1-methylethylcarbonyloxy, n-butylcarbonyloxy, 1-methylpropylcarbonyloxy, 2-methylpropylcarbonyloxy and 1,1-dimethylethylcarbonyloxy, especially methylcarbonyloxy;
  • C 1 -C 4 alkylcarbonylamino such as methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, 1-methylethylcarbonylamino,
  • n-butylcarbonylamino 1-methylpropylcarbonylamino, 2-methylpropylcarbonylamino and 1,1-dimethylethylcarbonylamino, especially methylcarbonylamino;
  • NC 1 -C 4 -alkylcarbonyl-N-methyl-amino such as N-methylcarbonyl- 1 -N-methyl-amino, N-ethylcarbonyl-N-methyl-amino, Nn-propylcarbonyl-N-methyl-amino, N-1-methylethylcarbonyl- N-methylamino,
  • N-n-butylcarbonyl-N-methyl-amino N-1-methylpropylcarbonyl-N-methyl-amino, N-2-methylpropylcarbonyl-N-methyl-amino and
  • X stands for:
  • C N-OCH 2 C ⁇ CH
  • C N-OCH 2 C ⁇ CCH3
  • C N-OCH 2 C 6 H 5 , CH-NH (OCH 3 ), CH-NH (OC 2 H 5 ),
  • C NN ((C 2 H 5 ) 2 ), CH-SCH 3 , CH-SC 2 H 5 , CH-SC 3 H 7 , CH-SC 4 H 9 , CH-SPr, CH-SiBu, CH-SH , C (CH 3 ) -SCH 3 , C (CH 3 ) -SC 2 H 5 , C (CH 3 ) -SC 3 H 7 ,
  • Phenyldiketone derivatives of the formula Ia are preferred,
  • L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl
  • L is C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl,
  • phenyldiketone derivatives of the formula I in which the radicals L and M are hydrogen, methyl, methoxy, chlorine,
  • Phenyldiketone derivatives of the formula Ic are preferred,
  • L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl
  • Cyano is and R 15 , n, Y and R 22 , R 21 , R 12 and R 13 have the meanings given above.
  • L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl
  • Cyano is and R 15 , n, Y and R 12 and R 13 have the meanings given above.
  • Phenyldiketone derivatives of the formula Ie are also preferred.
  • L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl
  • M is hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy,
  • C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, halogen, nitro or cyano and R 15 , n, Y and R 12 and R 13 have the meanings given above.
  • phenyldiketone derivatives of the formula I in which n is one or two and Y is CR 7 -OR 8 , where R 7 and R 8 have the meaning given above. Examples of particularly preferred compounds of the general formula I are compiled in the following tables.
  • Diazonium solution is carefully added dropwise. It is stirred for 1 hour. Then 106 g (2.65 mol) of sodium hydroxide in 270 ml of water are added, the mixture is stirred for a further 2 hours, the solution is acidified with hydrochloric acid and the precipitate formed is filtered off with suction. The solid is washed with water and dried.
  • the resulting precipitate is filtered off, washed with water and dried.
  • reaction solution is poured onto ice water and extracted with ethyl acetate.
  • organic phase is dried and then concentrated.
  • the product is purified by chromatography.
  • the compounds 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 containing I control vegetation very well on non-cultivated areas, particularly 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 especially at low application rates.
  • the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants.
  • the following crops are considered, for example:
  • 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
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • the herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less contractual for certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers, that the leaves of the sensitive crops are not hit, if possible, while the active ingredients reach the leaves of unwanted plants growing underneath or the uncovered area of the soil (post-directed, lay-by).
  • the compounds I or the herbicidal compositions comprising them can be sprayed or atomized, for example in the form of directly sprayable aqueous solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusting agents, scattering agents or granules , Dusting, scattering or pouring.
  • 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.
  • mineral oil fractions such as kerosene or diesel oil, also coal tarols and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol,
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • the substrates as such or dissolved in an oil or solvent can be 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.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin-,
  • Powders, materials for spreading and dusting can be produced by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. Coated granules, impregnated granules and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carrier materials are mineral earths such as silica, 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, Urea and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range.
  • the formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of active ingredient.
  • the active ingredients are used in a purity of 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:
  • Dissolved mixture consisting of 40 parts by weight of cyclohexanone
  • Dissolved mixture which consists of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of ricinusol. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient. IV 20 parts by weight of active ingredient No. 1.92 are with
  • Dissolved mixture which consists of 80 parts by weight of cyclohexanone and 20 parts by weight of Emulphor EL.
  • a stable emulsion concentrate is obtained.
  • the phenyldiketone derivatives I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
  • the application rates of active ingredient are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance depending on the aim of the control, the season, the target plants and the growth stage (a.s.)
  • Plastic flower pots with loamy sand with about 3.0% humus as a 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 vessels were lightly sprinkled, to encourage germination and growth, and then covered with clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.
  • test plants For the purpose of post-emergence treatment, the test plants, depending on the growth habit, are 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 are either sown directly and grown in the same containers, or they are first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
  • the application rate for post-emergence treatment was 0.5 or
  • the plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species.
  • the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to the individual treatments was evaluated.
  • the plants used in the greenhouse experiments are composed of the following types:

Abstract

The disclosure relates to phenyl diketone derivatives of formula I in which the substituents have the following meanings: L, M - hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy (these groups being optionally substituted by one to five halogen atoms or C1-C4 alkoxy), halogen, cyano, nitro, a -(A)m-S(O)nR1 group or a -(A)¿m-CO-R?2 group; Y - a group consisting of C=O, C=N-R?3, CR7-NR5R6, CR7-OR8, CR10R11, CR7-OR8¿, hydrogen- or C¿1?-C4-alkyl-substituted 1,3-dioxanyl or 1,3-dioxolanyl, a heteroatom selected from the group comprising oxygen, sulphur and nitrogen; X consists of a chain (-CR?12R13¿-), (-CR?12R13-CR21R22¿-), (-CR?12=CR13-), (CR12R13-CR12=CR13¿-), or NR23; the bond between X and Y can be saturated or unsaturated; A - O, NR14; m is 0 or 1; n is 0, 1 or 2; R15 is cyclopropyl, 1-methylcyclopropyl; 1-méthylthiocyclopropyl or tert. butyl; when Y = C=O, X is different from NR?23. R1 to R14 and R16 to R23¿ have the meanings indicated in claim 1. Also disclosed are processes for producing these phenyl diketone derivatives, agents containing them and the use of the derivatives or agents containing them for weed control.

Description

2-CYANO-1,3-DION DERIVATE, DEREN HERSTELLUNG UND DEREN VERWENDUNG ALS HERBIZIDE. 2-CYANO-1,3-DION DERIVATIVES, THEIR PRODUCTION AND THE USE THEREOF AS HERBICIDES.
Beschreibung  description
Die vorliegende Erfindung betrifft neue Phenyldiketonderivate mit herbizider Wirkung, Verfahren zur Herstellung der Phenyldiketonderivate, Mittel welche diese enthalten sowie die Verwendung dieser Derivate oder diese enthaltende Mittel zur Ungraser/ The present invention relates to novel phenyldiketone derivatives with herbicidal activity, processes for the preparation of the phenyldiketone derivatives, agents which contain them and the use of these derivatives or agents containing them for grass weeding /
Unkrautbekämpfung. Weed control.
Aus der Literatur sind herbizidwirksame Phenyldiketonderivate bekannt, beispielsweise aus EP 625505. Die herbiziden Eigenschaften der bekannten Verbindungen sowie die Verträglichkeit gegenüber Kulturpflanzen können jedoch nur bedingt befriedigen. Herbicidal phenyldiketone derivatives are known from the literature, for example from EP 625505. However, the herbicidal properties of the known compounds and the compatibility with crop plants can only give satisfactory results to a limited extent.
Die Aufgabe bestand darin, neue Phenyldiketonderivate mit ver- besserten Eigenschaften zu finden. The task was to find new phenyldiketone derivatives with improved properties.
Es wurden Phenyldiketonderivate der Formel I gefunden, Phenyldiketone derivatives of the formula I were found
Figure imgf000003_0001
Figure imgf000003_0001
in der die Substituenten folgende Bedeutung haben: in which the substituents have the following meaning:
L,M Wasserstoff, C1-C3-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, L, M is hydrogen, C 1 -C 3 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl,
C1-C4-Alkoxy, wobei diese Gruppen gegebenenfalls durch ein bis fünf Halogenatome oder C1-C4-Alkoxy substituiert sein können; Halogen, Cyano, Nitro, eine Gruppe -(A)m-S(O)nR1 oder eine Gruppe-(A)m-CO-R2; C 1 -C 4 alkoxy, where these groups may optionally be substituted by one to five halogen atoms or C 1 -C 4 alkoxy; Halogen, cyano, nitro, a group - (A) m -S (O) n R 1 or a group - (A) m -CO-R 2 ;
Y eine Gruppe bestehend aus C=O, C=N-R3, CR7-NR5R6, CR7-OR8, Y is a group consisting of C = O, C = NR 3 , CR 7 -NR 5 R 6 , CR 7 -OR 8 ,
CR10R11, CR7-SR8; mit Wasserstoff oder C1-C4-Alkyl substituiertes 1,3-Dioxanyl oder 1,3-Dioxolanyl; ein Heteroatom ausgewählt aus der Gruppe Sauerstoff, Schwefel und Stickstoff; CR 10 R 11 , CR 7 -SR 8 ; 1,3-dioxanyl or 1,3-dioxolanyl substituted with hydrogen or C 1 -C 4 alkyl; a heteroatom selected from the group consisting of oxygen, sulfur and nitrogen;
X bestehend aus einer Kette (-CR12R13-), (-CR12R13-CR21R22-), X consisting of a chain (-CR 12 R 13 -), (-CR 12 R 13 -CR 21 R 22 -),
(-CR12=CR13-), (-CR12R13-CR12=CR13-); NR23 die Bindung zwischen X und Y kann gesattigt oder ungesättigt sein; A O , NR14 ; m nul l oder eins ; n nul l , eins oder zwei ; (-CR 12 = CR 13 -), (-CR 12 R 13 -CR 12 = CR 13 -); NR 23 the bond between X and Y can be saturated or unsaturated; AO, NR 14 ; m zero or one; n zero, one or two;
R1 C1-C4-Alkyl , C1-C4-Haloalkyl oder NR14 ; R 1 C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or NR 14 ;
R2 C1-C4 Alkyl , C1-C4 -Haloalkyl , C1-C4-Alkoxy oder NR14 ; R 2 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or NR 14 ;
R3 Wasserstoff, -NR9R4; C1-C6-Alkyl, C1-C6-Haloalkyl, R 3 is hydrogen, -NR 9 R 4 ; C 1 -C 6 alkyl, C 1 -C 6 haloalkyl,
C1-C6-Alkoxy, C1-C6-Haloalkoxy, C2-C6-Alkenyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 2 -C 6 alkenyl,
C2-C6-Haloalkenyl, C2-C6 Alkinyl; C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl;
einfach bis mehrfach substituiertes Phenyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, mono- to polysubstituted phenyl, where the substituents can consist of C 1 -C 4 alkyl,
C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; ein- bis mehrfach substituiertes Benzyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; mono- to polysubstituted benzyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro ;
ein bis mehrfach substituiertes Benzyloxy wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; R4 Wasserstoff, C1-C6-Alkyl, C1-C6-Haloalkyl, C2-C6-Alkenyl, mono- to polysubstituted benzyloxy, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; R 4 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl,
C2-C6-Alkinyl, C=O-NR14; C 2 -C 6 alkynyl, C = O-NR 14 ;
einfach bis mehrfach substituiertes Phenyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; ein- bis mehrfach substituiertes Benzyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; R3 Wasserstoff, C1-C6-Alkyl, C1-C6-Haloalkyl, C2-C6-Alkenyl, mono- to polysubstituted phenyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; mono- to polysubstituted benzyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro ; R 3 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl,
C2-C6-Alkinyl, C=O-NR14; C 2 -C 6 alkynyl, C = O-NR 14 ;
einfach bis mehrfach substituiertes Phenyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; ein- bis mehrfach substituiertes Benzyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; R5,R6 unabhängig voneinander Wasserstoff, C1-C6-Alkyl, mono- to polysubstituted phenyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; mono- to polysubstituted benzyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro ; R 5 , R 6 independently of one another are hydrogen, C 1 -C 6 alkyl,
C2-C6-Alkenyl, C1-C4 Haloalkyl, C2-C6 Haloalkenyl, C 2 -C 6 alkenyl, C 1 -C 4 haloalkyl, C 2 -C 6 haloalkenyl,
C1-C6-Alkoxy, C1-C6-Haloalkoxy; einfach bis mehrfach substituiertes Phenyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; ein- bis mehrfach substituiertes Benzyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy; mono- to polysubstituted phenyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; mono- to polysubstituted benzyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro ;
R7 Wasserstoff, C1-C6-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkyl, R 7 is hydrogen, C 1 -C 6 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl,
C1-C4-Haloalkoxy; gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus ein bis drei Halogenen, C1-C4 Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, Nitro; R7 und R21 oder R7 und R23 oder R7 und R12 können eine Bindung bilden; R8 Wasserstoff, C1-C6 Alkyl, C1-C4-Halogenalkyl, substituiertes Phenyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; substituiertes Benzyl wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; C 1 -C 4 haloalkoxy; optionally substituted phenyl, where the substituents can consist of one to three halogens, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, nitro; R 7 and R 21 or R 7 and R 23 or R 7 and R 12 can form a bond; R 8 is hydrogen, C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, substituted phenyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 - Haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; substituted benzyl where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
R10,R11 unabhängig voneinander Wasserstoff, C1-C6-Alkyl; Phenyl gegebenenfalls substituiert mit ein bis drei Halogenen, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, Nitro; R 10 , R 11 independently of one another are hydrogen, C 1 -C 6 alkyl; Phenyl optionally substituted with one to three halogens, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, nitro;
R10 und R12 oder R10 und R23 oder R10 und R21 können eine Bindung bilden; R12,R13 unabhängig voneinander Wasserstoff, C1-C6-Alkyl, R 10 and R 12 or R 10 and R 23 or R 10 and R 21 may form a bond; R 12 , R 13 independently of one another are hydrogen, C 1 -C 6 alkyl,
C1-C6-Haloalkyl, C1-C6-Alkoxy, C1-C6-Haloalkoxy; gegebenenfalls substituiertes Phenyl wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy; optionally substituted phenyl where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
R14 C1-C4-Alkyl; R 14 C 1 -C 4 alkyl;
R21 Wasserstoff, C1-C6-Alkyl, C1-C6-Haloalkyl, C1-C6-Alkoxy, R 21 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy,
C1-C6-Haloalkoxy; gegebenenfalls substituiertes Phenyl wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; C 1 -C 6 haloalkoxy; optionally substituted phenyl where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
R22 Wasserstoff, C1-C6-Alkyl, C1-C6-Haloalkyl, C1-C6-Alkoxy, R 22 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy,
C1-C6-Haloalkoxy; gegebenenfalls substituiertes Phenyl wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; C 1 -C 6 haloalkoxy; optionally substituted phenyl where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
R23 Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, C1-C6 Alkoxy; R 23 is hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy;
gegebenenfalls mit C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro substituiertes Phenyl oder Benzyl; phenyl or benzyl optionally substituted with C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
R15 Cyclopropyl, 1-Methylcyclopropyl, 1-Methylthiocyclopropyl oder tert. -Butyl; wobei für den Fall, daß Y = C=O ist, X ungleich NR23 ist, sowie landwirtschaftliche übliche Salze der Verbindung I. R 15 cyclopropyl, 1-methylcyclopropyl, 1-methylthiocyclopropyl or tert. Butyl; where, if Y = C = O, X is not equal to NR 23 , and customary agricultural salts of the compound I.
Die Phenyldiketonderivate können in folgenden tautomeren Formen vorliegen: The phenyldiketone derivatives can exist in the following tautomeric forms:
Figure imgf000006_0001
Verbindungen der Formel I erhalt man dadurch, daß man das
Figure imgf000006_0001
Compounds of the formula I are obtained by
Magnesiumenolat A2 eines Cyanoketons der Formel A1
Figure imgf000006_0002
Magnesium enolate A2 of a cyanoketone of the formula A1
Figure imgf000006_0002
mit einem Benzoesaurederivat der Formel III (T = Cl) zu der enolisierten Verbindung I acyliert. acylated with a benzoic acid derivative of the formula III (T = Cl) to give the enolized compound I.
Figure imgf000007_0001
Figure imgf000007_0001
In den oben genannten Formeln haben L, M, X, Y, n und R15 die eingangs angegebene Bedeutung und T steht für Halogen. In the above formulas, L, M, X, Y, n and R 15 have the meaning given at the outset and T stands for halogen.
Der erste Schritt der Reaktionsabfolge erfolgt in der Weise, daß man eine methanolische Losung eines Cyanoketons der Formel AI mit Magnesium und einer geringen Menge CCl4 versetzt und dieses zum Magnesiumenolat abreagieren laßt. Analoge C-Acylierungen von Cyanoketonen sind z.B. in den EP-A 496 630 und EP-A 496 631 beschrieben. The first step of the reaction sequence is such that magnesium and a small amount of CCl 4 are added to a methanolic solution of a cyanoketone of the formula AI and this is allowed to react to the magnesium enolate. Analog C-acylations of cyanoketones are described, for example, in EP-A 496 630 and EP-A 496 631.
Nach Entfernen des Methanols wird das erhaltene Magnesiumenolat der Formel A2 in Toluol oder Acetonitril gelost, wobei Acetonitril bevorzugt wird, und dann die zu AI äquivalente Menge des Saurechlorids der Formel III als Acetonitrillosung zugetropft. Nach 1 - 16 Stunden Ruhren bei 25°C bis 50°C ist die Umsetzung abgeschlossen. Zur Aufarbeitung wird im Vakuum eingeengt, der verbleibende Ruckstand in einem Losungsmittel wie Essigsaureethylester oder Methylenchlorid aufgenommen und mit 10 proz. HCl gewaschen, um das Magnesiumsalz zu zerlegen. Nach Waschen der organischen Phase mit Wasser wird mit einem Trockenmittel wie Natriumsulfat getrocknet und eingeengt. Aus dem verbleibenden Ruckstand wird das Produkt durch Anreiben mit einem Kohlenwasserstoff wie Petrolether, Cyclohexan oder n-Pentan ausgefallt. After removal of the methanol, the magnesium enolate of the formula A2 obtained is dissolved in toluene or acetonitrile, with acetonitrile being preferred, and the amount of the acid chloride of the formula III equivalent to AI is then added dropwise as an acetonitrile solution. After 1 to 16 hours of stirring at 25 ° C to 50 ° C, the reaction is complete. For working up, the mixture is concentrated in vacuo, the remaining residue is taken up in a solvent such as ethyl acetate or methylene chloride and 10%. HCl washed to break down the magnesium salt. After washing the organic phase with water, it is dried with a drying agent such as sodium sulfate and concentrated. The product is precipitated from the remaining residue by rubbing with a hydrocarbon such as petroleum ether, cyclohexane or n-pentane.
Die als Ausgangsstoffe verwendeten Cyanoketone der Formel AI sind allgemein bekannte Verbindungen. Sie können beispielsweise durch Umsetzung von Cyanessigsaure mit Butyllithium und anschließend mit einem Saurechlorid R15-COCl erhalten werden. Die Saurechloride R15-COCl werden in an sich bekannter Weise aus den entsprechenden Carbonsauren R15-COOH durch Umsetzung mit Thionylchlorid erhalten. Die Carbonsauren R15-COOH sind literaturbekannte Verbindungen: Pivalinsaure und Cyclopropancarbonsaure sind kaufliehe Verbindungen. DMethylcyclopropancarbonsaure wird entweder durch Verseifung aus dem kauflichen Ethylester erhalten oder in bekannter Weise durch Methylierung des Lithium-α-lithiocylopropancarboxylates [Warner + Le, JOC 47, 893 (1982)] erhalten. 1-Methylthiocyclopropancarbonsaure wird in bekannter Weise aus dem 1-Methyl-thiocyclopropancarbonsaurenitril erhalten, das seinerseits aus Methylmercaptoacetonitril und Ethylendibromid in Gegenwart von Natriumamid hergestellt werden kann The cyanoketones of the formula AI used as starting materials are generally known compounds. They can be obtained, for example, by reacting cyanoacetic acid with butyllithium and then with an acid chloride R 15 -COCl. The acid chlorides R 15 -COCl are obtained in a manner known per se from the corresponding carboxylic acids R 15 -COOH by reaction with thionyl chloride. The carboxylic acids R 15 -COOH are compounds known from the literature: pivalic acid and cyclopropanecarboxylic acid are commercial compounds. DMethylcyclopropanecarboxylic acid is either obtained by saponification from the commercially available ethyl ester or obtained in a known manner by methylation of the lithium α-lithiocylopropanecarboxylate [Warner + Le, JOC 47, 893 (1982)]. 1-methylthiocyclopropanecarboxylic acid is obtained in a known manner from the 1-methylthiocyclopropanecarboxylic acid nitrile, which in turn can be prepared from methylmercaptoacetonitrile and ethylene dibromide in the presence of sodium amide
[DE-OS 21 20 908 = CA 76: 72099]. Benzoesauren der Formel III lassen sich folgendermaßen herstellen: [DE-OS 21 20 908 = CA 76: 72099]. Benzoic acids of formula III can be prepared as follows:
Benzoylhalogenide wie beispielsweise Benzoylchloride der Formel III (T = Cl) werden in an sich bekannter Weise durch Umsetzung der Benzoesauren der Formel III (T = OH) mit Thionylchlorid hergestellt. Benzoyl halides such as benzoyl chlorides of the formula III (T = Cl) are prepared in a manner known per se by reacting the benzoic acids of the formula III (T = OH) with thionyl chloride.
Die Benzoesauren der Formel III (T = OH) können in bekannter Weise durch saure oder basische Hydrolyse aus den entsprechenden Estern der Formel III (T = C1-C4-Alkoxy) hergestellt werden. The benzoic acids of the formula III (T = OH) can be prepared in a known manner by acidic or basic hydrolysis from the corresponding esters of the formula III (T = C 1 -C 4 alkoxy).
Die Zwischenprodukte der Formel III sind teilweise bekannt oder lassen sich nach literaturbekannten Verfahren darstellen. Some of the intermediates of the formula III are known or can be prepared by processes known from the literature.
Figure imgf000008_0001
Figure imgf000009_0001
Figure imgf000008_0001
Figure imgf000009_0001
Danach lassen sich z.B. wie in Schema 2 dargestellt Arylthioverbindungen IV mit substituierten Haloalkenyl gemäß J. Med. Chem. 1984, 27, 1516, substituierten Alkinylcarbonsauren gemäß J. Org. Chem. 1980, 45, 4611 oder J. Am. Chem. Soc. 1983, 105, 883, substituierten Haloalkylcarbonsauren gemäß Chem. Ber. 1925, 58, 1612 in Gegenwart einer Base wie Alkalihydroxid, Alkalihydrid oder Alkalicarbonat umsetzen. Die entstehenden Verbindungen V werden unter Friedel-Crafts Bedingungen unter Zusatz einer Lewissaure oder einer Protonensaure zu VI cyclisiert. Als Lewissauren werden AlCl3 oder SnCl4 und als Protonensaure Polyphoshorsaure und Schwefelsaure bevorzugt gemäß Can. J. Chem. 1981, 59, 199; Chem. Ber. 1925, 58, 1625; Chem. Ber. 1926, 59, 1074; Phosp. and Sulf. 1984, 19, 31. Thereafter, for example, as shown in Scheme 2, arylthio compounds IV with substituted haloalkenyl according to J. Med. Chem. 1984, 27, 1516, substituted alkynyl carboxylic acids according to J. Org. Chem. 1980, 45, 4611 or J. Am. Chem. Soc. 1983, 105, 883, substituted haloalkyl carboxylic acids according to Chem. Ber. 1925, 58, 1612 in the presence of a base such as alkali metal hydroxide, alkali metal hydroxide or alkali metal carbonate. The resulting compounds V are cyclized to VI under Friedel-Crafts conditions with the addition of a Lewis acid or a protonic acid. AlCl 3 or SnCl 4 are preferred as Lewis acids and polyphosphoric acid and sulfuric acid are preferred as protonic acids according to Can. J. Chem. 1981, 59, 199; Chem. Ber. 1925, 58, 1625; Chem. Ber. 1926, 59, 1074; Phosp. and sulf. 1984, 19, 31.
Thiochromenonsauren lassen sich weiterhin durch z.B. Abspaltung von Halogenwasserstoff von 3-Halothiochromanonsauren oder z.B. durch Umsetzung der substituierten Thiophenolsauren mit substituierten α-Alkylacetessigestern in Gegenwart von Phosphorpentoxid gemäß Ann. Chem. 1964, 680, 40 darstellen. Thiochromenonic acids can continue to be e.g. Elimination of hydrogen halide from 3-halothiochromanonic acids or e.g. by reacting the substituted thiophenolic acids with substituted α-alkylacetoacetic esters in the presence of phosphorus pentoxide according to Ann. Chem. 1964, 680, 40.
Die Arylthioverbindungen IV können beispielsweise durch Sandmeyer-Reaktion aus entsprechenden Anilinen erhalten werden, die ihrerseits durch Reduktion von geeigneten Nitroverbindungen gemäß Organikum 19.Auflage 1992, 552ff synthetisiert werden. The arylthio compounds IV can be obtained, for example, by a Sandmeyer reaction from corresponding anilines, which in turn are synthesized by reducing suitable nitro compounds in accordance with Organikum 19th edition 1992, 552ff.
Für den Fall, daß z.B. X gleich (-CR12R13-) bzw. (-CR12R13CR21R22-), Y gleich C=O und T gleich C1-C4-Alkoxy ist, laßt sich der In the event that, for example, X is (-CR 12 R 13 -) or (-CR 12 R 13 CR 21 R 22 -), Y is C = O and T is C 1 -C 4 alkoxy, the
Thiochromanonester bzw. Dihydrobenzothiophenester wie in Schema 2 beschrieben durch Alkylierung der Arylthioverbindung IV in Gegenwart einer der obengenannten Basen in Lösungsmittel oder Wasser mit Halogenpropionsäure bzw. Halogenessigsaure herstellen und cyclisieren zu VI. Prepare thiochromanone esters or dihydrobenzothiophene esters as described in Scheme 2 by alkylating the arylthio compound IV in the presence of one of the bases mentioned in solvent or water with halopropionic acid or haloacetic acid and cyclize to VI.
Die Reaktanden und die Base werden dabei zweckmäßig in aquimolaren Mengen eingesetzt. Die Reaktionsmischung wird vorzugsweise bei 20-100°C, insbesondere bei 20-40°C, gerührt. Die Aufarbeitung erfolgt beispielsweise so, daß das Reaktionsgemisch auf Wasser gegossen wird, die wäßrige Phase mit Mineralsauren wie Salzsaure oder Schwefelsaure sauer gestellt und das Wertprodukt abgesaugt wird oder durch Extraktion mit Methylenchlorid oder Essigsaureethylester extrahiert, getrocknet und vom Losungsmittel befreit wird. Der Ester kann ohne weitere Reinigung umgesetzt werden. Durch Ruhren von V in z.B. Polyphosphorsaure bei 40-140°C, insbesondere bei 70-100°C, oder durch Aktivierung der Carbonsaure durch Überführung ins Saurechlorid und Ruhren mit 2-6, insbesondere 3.5 bis 4.5, Molaquivalenten einer Lewissaure wie z.B. AICI3 oder SnCl4 in einem Losungsmittel oder durch Ruhren mit oder in Schwefelsaure, erhalt man nach an sich bekannter Aufarbeitung, d.h. Zugabe von Eiswasser und Absaugen des Wertproduktes oder Extraktion der wäßrigen Phase mit Essigsaureethylester oder The reactants and the base are expediently used in equimolar amounts. The reaction mixture is preferably stirred at 20-100 ° C., in particular at 20-40 ° C. Working up is carried out, for example, by pouring the reaction mixture onto water, acidifying the aqueous phase with mineral acids such as hydrochloric acid or sulfuric acid and suctioning off the product of value or by extraction with methylene chloride or Extracted ethyl acetate, dried and freed from the solvent. The ester can be reacted without further purification. By stirring V in, for example, polyphosphoric acid at 40-140 ° C, in particular at 70-100 ° C, or by activating the carboxylic acid by converting it into acid chloride and stirring with 2-6, in particular 3.5 to 4.5, molar equivalents of a Lewis acid such as, for example, AICI 3 or SnCl 4 in a solvent or by stirring with or in sulfuric acid, is obtained after working up known per se, ie adding ice water and suctioning off the product of value or extraction of the aqueous phase with ethyl acetate or
Methylenchlorid, Trocknen und Entfernen des Losungsmittel eine Zwischenstufe der Formel III. Methylene chloride, drying and removal of the solvent an intermediate of formula III.
Für den Fall, daß z.B. X gleich einer Ethylengruppierung In the event that e.g. X is an ethylene grouping
(-CR12=CR13-), Y gleich C=O und T gleich C1-C4-Alkoxy laßt sich der Thiochromenonester durch z.B. Umsetzung von einer Arylthioverbindung mit einem Acetylencarbonsaurederivat in Wasser oder Losungsmittel bei einer Temperatur von 0-140°C umsetzen. Die Aufarbeitung erfolgt nach an sich bekannter Weise durch Zugabe von Wasser und verdünnter Mineralsaure wie z.B. Salzsaure. Das Wertprodukt wird entweder abgesaugt oder durch Extraktion mit Methylenchlorid oder Essigsaureethylester, anschließendem (-CR 12 = CR 13- ), Y equal to C = O and T equal to C 1 -C 4 alkoxy, the thiochromenone ester can be reacted, for example, by reacting an arylthio compound with an acetylenecarboxylic acid derivative in water or solvent at a temperature of 0-140 ° Implement C. Working up is carried out in a manner known per se by adding water and dilute mineral acid such as hydrochloric acid. The product of value is either suctioned off or by extraction with methylene chloride or ethyl acetate, followed by
Trocknen und Entfernen des Losungsmittel erhalten. Obtain drying and solvent removal.
Die Zwischenprodukte der Formel III können durch literaturbekannte Reaktionen wie Reduktion gemäß Jerry March " Advanced Organic Chemistry, Fourth Ed., z.B. S.910ff, Oximierung gemäß Jerry March " Advanced Organic Chemistry, Fourth Ed., z.B. S.934, 935, 1039, 1226, 405ff, Überführung in Imine und Amine gemäß Jerry March " Advanced Organic Chemistry, Fourth Ed., Ketalisierung, Alkylierung, Halogenierung, Eliminierung und Oxidation gemäß Jerry March " Advanced Organic Chemistry, Fourth Ed. weiter funktionalisiert werden. The intermediates of formula III can be obtained by reactions known from the literature, such as reduction according to Jerry March "Advanced Organic Chemistry, Fourth Ed., E.g. S.910ff, oximation according to Jerry March" Advanced Organic Chemistry, Fourth Ed., E.g. P.934, 935, 1039, 1226, 405ff, conversion into imines and amines according to Jerry March "Advanced Organic Chemistry, Fourth Ed., Ketalization, alkylation, halogenation, elimination and oxidation according to Jerry March" Advanced Organic Chemistry, Fourth Ed. be further functionalized.
Die Sauren der 3-Alkoxy-1,2-benzisothiazol-1,1-dioxide oder The acids of 3-alkoxy-1,2-benzisothiazol-1,1-dioxide or
3-Alkoxy-1,2-benzisothiazole können ausgehend von entsprechenden Saccharinderivaten oder 1,2-Benzisothiazolen durch z.B. Umsetzung mit PCl5, POCI3 oder Chlor und Alkohol gegebenenfalls in Gegenwart einer Hilfsbase wie z.B. Triethylamin erhalten werden, was beispielsweise beschrieben ist in US 4,571,429, Arch. Pharm. 1984, 317, 807, US 4461901, US 450916, J. Med. Chem. 1986, 29, 359. Saccharincarbonsauren können durch Literatur bekannte Verfahren gemäß Ann. Chem. 427, 231, 1922, Chem. Ber. 13, 1554, 1980, Chem. Ber. 25, 1740, 1892, DE-OS 3607343, deutsche Patentanmeldung P 44 27 995.7 erhalten werden. 3-alkoxy-1,2-benzisothiazoles can be obtained starting from corresponding saccharin derivatives or 1,2-benzisothiazoles by, for example, reaction with PCl 5 , POCI 3 or chlorine and alcohol, optionally in the presence of an auxiliary base such as, for example, triethylamine, which is described, for example, in US 4,571,429, Arch. Pharm. 1984, 317, 807, US 4461901, US 450916, J. Med. Chem. 1986, 29, 359. Saccharin carboxylic acids can be described by literature methods according to Ann. Chem. 427, 231, 1922, Chem. Ber. 13, 1554, 1980, Chem. Ber. 25, 1740, 1892, DE-OS 3607343, German patent application P 44 27 995.7 can be obtained.
Die Derivate der Benzo-1,4-oxathiinsauren sind teilweise bekannt, z.B. aus J. Org. Chem. 1968, 33, 456 oder lassen sich z.B. The derivatives of benzo-1,4-oxathiic acids are partially known, e.g. from J. Org. Chem. 1968, 33, 456 or e.g.
durch Reaktion aus den entsprechenden Phenolderivaten gemäß Chem. Comm., 1975, 451, J. Org. Chem. 1974, 39, 1811, J. Am. by reaction from the corresponding phenol derivatives according to Chem. Comm., 1975, 451, J. Org. Chem. 1974, 39, 1811, J. Am.
Chem. Soc. 1954, 76, 1068 oder durch Kombination von z.B. Substitutionsreaktion an Halogen-substituierten Thiophenolderivaten und weiterfuhrende Reaktionen wie z.B Oxidation, Reduktion oder Addition gemäß J. Het. Chem. 1983, 20, 867 aufbauen. Chem. Soc. 1954, 76, 1068 or by combining e.g. Substitution reaction on halogen-substituted thiophenol derivatives and further reactions such as oxidation, reduction or addition according to J. Het. Chem. 1983, 20, 867.
Die Benzoesauren der Formel III können auch erhalten werden, indem man die entsprechende brom- oder iodsubstituierte Verbindung der Formel VII The benzoic acids of formula III can also be obtained by the corresponding bromo or iodo substituted compound of formula VII
Figure imgf000011_0001
in der die Substituenten die folgende Bedeutung haben:
Figure imgf000011_0001
in which the substituents have the following meaning:
T OH, C1-C4-Alkoxy, T OH, C 1 -C 4 alkoxy,
Y,L,M,X und n die oben beschriebene Bedeutung haben, in Gegenwart eines Palladium-, Nickel-, Cobalt- oder RhodiumUbergangsmetallkatalysators und einer Base mit Kohlenmonoxid und Wasser unter erhöhtem Druck umsetzt.  Y, L, M, X and n have the meaning described above, in the presence of a palladium, nickel, cobalt or rhodium transition metal catalyst and a base with carbon monoxide and water under elevated pressure.
Die Katalysatoren Nickel, Cobalt, Rhodium und insbesondere The catalysts nickel, cobalt, rhodium and in particular
Palladium können metallisch oder in Form üblicher Salze wie in Form von Halogenverbindungen, z.B. PdCl2, RhCl3-H2O, Acetaten, z.B. Pd(OAc)2, Cyaniden usw. in den bekannten Wertigkeitsstufen vorliegen. Ferner können Metallkomplexe mit tertiären Phosphinen, Metallalkylcarbonyle, Metallcarbonyle, z.B. CO2(CO)8, Ni(CO)4, Metallcarbonyl-Komplexe mit tertiären Phosphinen, z.B. Palladium can be metallic or in the form of customary salts such as in the form of halogen compounds, for example PdCl 2 , RhCl 3 -H 2 O, acetates, for example Pd (OAc) 2 , cyanides etc. in the known valence levels. Furthermore, metal complexes with tertiary phosphines, metal alkylcarbonyls, metal carbonyls, for example CO 2 (CO) 8 , Ni (CO) 4 , metal carbonyl complexes with tertiary phosphines, for example
(PPh3)2Ni(CO)2, oder mit tertiären Phosphinen komplexierte Ubergangsmetallsalze vorliegen. Die letztgenannte Ausfuhrungsform ist insbesondere im Fall von Palladium als Katalysator bevorzugt. Dabei ist die Art der Phosphinliganden breit variabel. Beispielsweise lassen sie sich durch folgende Formeln wiedergeben: oder(PPh 3 ) 2 Ni (CO) 2 , or transition metal salts complexed with tertiary phosphines. The latter embodiment is preferred in particular in the case of palladium as a catalyst. The type of phosphine ligand is widely variable. For example, they can be represented by the following formulas: or
Figure imgf000012_0001
Figure imgf000012_0002
Figure imgf000012_0001
Figure imgf000012_0002
wobei n die Zahlen 1, 2, 3 oder 4 bedeutet und die Reste R24 bis R26 für niedermolekulares Alkyl, z.B. C1-C6-Alkyl, Aryl, C1-C4-Alkylaryl, z.B. Benzyl, Phenethyl oder Aryloxy stehen. where n is 1, 2, 3 or 4 and the radicals R 24 to R 26 are low molecular weight alkyl, for example C 1 -C 6 alkyl, aryl, C 1 -C 4 alkylaryl, for example benzyl, phenethyl or aryloxy .
Aryl ist z.B. Naphthyl, Anthryl und vorzugsweise gegebenenfalls substituiertes Phenyl, wobei man hinsichtlich der Substituenten nur auf deren Inertheit gegenüber der Carboxylierungsreaktion zu achten hat, ansonsten können sie breit variiert werden und umfassen alle inerten C-organischen Reste wie C1-C6-Alkylreste, z.B. Methyl, Carboxylreste wie COOH, COOM (M ist z.B. ein Aryl is, for example, naphthyl, anthryl and preferably optionally substituted phenyl, the substituents only having to be considered for their inertness to the carboxylation reaction, otherwise they can be varied widely and include all inert C-organic radicals such as C 1 -C 6 -alkyl radicals , e.g. methyl, carboxyl residues such as COOH, COOM (M is for example a
Alkali-, Erdalkalimetall oder Ammoniumsalz), oder C-organische Reste über Sauerstoff gebunden wie C1-C6-Alkoxyreste. Alkali, alkaline earth metal or ammonium salt), or C-organic radicals bound via oxygen, such as C 1 -C 6 alkoxy radicals.
Die Herstellung der Phosphinkomplexe kann in an sich bekannter Weise, z.B. wie in den eingangs genannten Dokumenten beschrieben, erfolgen. Beispielsweise geht man von üblichen kommerziell erwerblichen Metallsalzen wie PdCl2 oder Pd(OCOCH3)2 aus und fugt das Phosphin z.B. P(C6H5)3, P(n-C4H9)3, PCH3(C6H5)2, The phosphine complexes can be prepared in a manner known per se, for example as described in the documents mentioned at the outset. For example, one starts from customary commercially available metal salts such as PdCl 2 or Pd (OCOCH 3 ) 2 and adds the phosphine, for example P (C 6 H 5 ) 3 , P (nC 4 H 9 ) 3 , PCH 3 (C 6 H 5 ) 2 ,
1,2-Bis(diphenylphosphino)ethan hinzu. 1,2-bis (diphenylphosphino) ethane added.
Die Menge an Phosphin, bezogen auf das Ubergangsmetall, betragt üblicherweise 0 bis 20, insbesondere 0,1 bis 10 Molaquivalente, besonders bevorzugt 1 bis 5 Molaquivalente. The amount of phosphine, based on the transition metal, is usually 0 to 20, in particular 0.1 to 10 mol equivalents, particularly preferably 1 to 5 mol equivalents.
Die Menge an Ubergangsmetall ist nicht kritisch. Natürlich wird man aus Kostengrunden eher eine geringe Menge, z.B. von 0,1 bis 10 Mol.-%, insbesondere 1 bis 5 Mol.-%, bezogen auf den Ausgangsstoff II bzw. III verwenden. The amount of transition metal is not critical. Of course, for reasons of cost, you will rather get a small amount, e.g. from 0.1 to 10 mol%, in particular 1 to 5 mol%, based on the starting material II or III.
Zur Herstellung der Benzoesauren III (T = OH) fuhrt man die Umsetzung mit Kohlenmonoxid und mindestens aquimolaren Mengen an Wasser, bezogen auf die Ausgangsstoffe VI durch. Der Reaktionspartner Wasser kann gleichzeitig auch als Losungsmittel dienen, d.h. die maximale Menge ist nicht kritisch. To prepare the benzoic acids III (T = OH), the reaction is carried out with carbon monoxide and at least equimolar amounts of water, based on the starting materials VI. The reactant water can also serve as a solvent, i.e. the maximum amount is not critical.
Es kann aber auch je nach Art der AusgangsStoffe und der verwendeten Katalysatoren von Vorteil sein, anstelle des Reaktionspartners ein anderes inertes Losungsmittel oder die für die Carboxylierung verwendete Base als Losungsmittel zu verwenden. However, depending on the type of starting materials and the catalysts used, it may also be advantageous to use another inert solvent or the base used for the carboxylation as the solvent instead of the reaction partner.
Als inerte Losungsmittel kommen für Carboxylierungsreaktionen übliche Losungsmittel wie Kohlenwasserstoffe, z.B. Toluol, Xylol, Hexan, Pentan, Cyclohexan, Ether z.B. Methyl-tert.butylether, Tetrahydrofuran, Dioxan, Dimethoxyethan, substituierte Amide wie Dimethylformamid, persubstituierte Harnstoffe wie Tetra-C1-C4-alkylharnstoffe oder Nitrile wie Benzonitril oder Acetonitril in Betracht. In einer bevorzugten Ausfuhrungsform des Verfahrens verwendet man einen der Reaktionspartner, insbesondere die Base, im Überschuß, so daß kein zusätzliches Losungsmittel erforderlich ist. Inert solvents which are customary for carboxylation reactions, such as hydrocarbons, for example toluene, xylene, hexane, pentane, cyclohexane, ethers, for example methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted amides such as dimethylformamide, per-substituted ureas such as tetra-C 1 -C 4 alkylureas or nitriles such as benzonitrile or acetonitrile. In a preferred embodiment of the process, one of the reactants, in particular the base, is used in excess, so that no additional solvent is required.
Für das Verfahren geeignete Basen sind alle inerten Basen, die den bei der Umsetzung freiwerdenden Jodwasserstoff bzw. Bromwasserstoff zu binden vermögen. Beispielsweise sind hier tertiäre Amine wie tert.-Alkylamine, z.B. Trialkylamine wie Triethylamin, cyclische Amine wie N-Methylpiperidin oder N,N'-Dimethylpiperazin, Pyridin, Alkali- oder -hydrogencarbonate, oder tetraalkylsubstituierte Harnstoffderivate wie Tetra-C1-C4-alkylharnstoff, z.B. Tetramethylharnstoff, zu nennen. Bases suitable for the process are all inert bases which are able to bind the hydrogen iodide or hydrogen bromide released during the reaction. For example, tertiary amines such as tert-alkylamines, for example trialkylamines such as triethylamine, cyclic amines such as N-methylpiperidine or N, N'-dimethylpiperazine, pyridine, alkali metal or hydrogen carbonates, or tetraalkyl-substituted urea derivatives such as tetra-C 1 -C 4 - alkyl urea, for example tetramethyl urea.
Die Menge an Base ist nicht kritisch, üblicherweise werden 1 bis 10, insbesondere 1 bis 5 Mol verwendet. Bei gleichzeitiger Verwendung der Base als Losungsmittel, wird die Menge in der Regel so bemessen, daß die Reaktionspartner gelost sind, wobei man aus Praktikabilitatsgrunden unnötig hohe Überschüsse vermeidet, um Kosten zu sparen, kleine Reaktionsgefaße einsetzen zu können und den Reaktionspartnern maximalen Kontakt zu gewahrleisten. The amount of base is not critical, usually 1 to 10, in particular 1 to 5, moles are used. When using the base as a solvent, the amount is usually measured so that the reactants are dissolved, avoiding unnecessarily high excesses for reasons of practicality in order to save costs, to use small reaction vessels and to ensure maximum contact for the reactants.
Wahrend der Umsetzung wird der Kohlenmonoxiddruck so eingestellt, daß immer ein Überschuß an CO, bezogen auf VI vorliegt. Vorzugsweise liegt der Kohlenmonoxiddruck bei Raumtemperatur bei 1 bis 250 bar, insbesondere 5 bis 150 bar CO. During the reaction, the carbon monoxide pressure is adjusted so that there is always an excess of CO, based on VI. The carbon monoxide pressure at room temperature is preferably 1 to 250 bar, in particular 5 to 150 bar CO.
Die Carbonylierung wird in der Regel bei Temperaturen von 20 bis 250°C, insbesondere bei 30 bis 150°C kontinuierlich oder diskontinuierlich durchgeführt. Bei diskontinuierlichem Betrieb wird zweckmaßigerweise zur Aufrechterhaltung eines konstanten Druckes kontinuierlich Kohlenmonoxid auf das Umsetzungsgemisch aufgepreßt. The carbonylation is generally carried out continuously or batchwise at temperatures from 20 to 250 ° C., in particular at 30 to 150 ° C. In the case of discontinuous operation, carbon monoxide is expediently pressed continuously onto the reaction mixture in order to maintain a constant pressure.
Die als Ausgangsverbindungen benutzten ArylhalogenVerbindungen VII sind bekannt oder können leicht durch geeignete Kombination bekannter Synthesen und nach oben beschriebenen Reaktionsfolgen hergestellt werden. The aryl halogen compounds VII used as starting compounds are known or can easily be prepared by a suitable combination of known syntheses and reaction sequences described above.
Im Hinblick auf die bestimmungsgemaße Verwendung der Phenyldiketonderivate der allgemeinen Formel I kommen als Substituenten folgende Reste in Betracht: L,M Wasserstoff, C1-C6-Alkyl wie Methyl, Ethyl, Propyl, 1-Methylethyl, Butyl, 1-Methylpropyl, 2-Methylpropyl, 1,1-Dimethylethyl, Pentyl, 1-Methylbutyl, 2-Methylbutyl, 3-Methylbutyl, 1,1-Dimethylpropyl, 1,2-Dimethylpropyl, 2,2-Dimethylpropyl, 1-Ethylpropyl, Hexyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylbutyl, 1,2-Dimethylbutyl, 1,3-Dimethylbutyl, With regard to the intended use of the phenyldiketone derivatives of the general formula I, the following radicals are suitable as substituents: L, M hydrogen, C 1 -C 6 -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3 -Methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 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, 2,2-dimethylbutyl, 2, 3-dimethylbutyl, 3,3-dimethylbutyl,
1-Ethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2-Trimethylpropyl, 1-Ethyl-1-methylpropyl oder 1-Ethyl-2-methyl-propyl, insbesondere Methyl, Ethyl, 1-Methylethyl, 1-Methylpropyl, 2-Methylpropyl, 1,1-Dimethylethyl und 1,1-Dimethylpropyl; 1-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl, especially methyl, ethyl, 1-methylethyl, 1-methylpropyl , 2-methylpropyl, 1,1-dimethylethyl and 1,1-dimethylpropyl;
C2-C6-Alkenyl wie 2-Propenyl, 2-Butenyl, 3-Butenyl, C 2 -C 6 alkenyl such as 2-propenyl, 2-butenyl, 3-butenyl,
1-Methyl-2-propenyl, 2-Methyl-2-propenyl, 2-Pentenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl,
3-Pentenyl, 4-Pentenyl, 3-Methyl-2-butenyl, 1-Methyl-2-butenyl, 2-Methyl-2-butenyl, 1-Methyl-3-butenyl, 2-Methyl-4-butenyl, 3-Methyl-3 butenyl, 1,1-Dimethyl-2-propenyl, 1,2-Dimethyl-3-pentenyl, 4-pentenyl, 3-methyl-2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-4-butenyl, 3- Methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-
2-propenyl, 1-Ethyl-2-propenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-Hexenyl, 1-Methyl-2-pentenyl, 2-Methyl-2-pentenyl, 2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,
3-Methyl-2-pentenyl, 4-Methyl-2-pentenyl, 1-Methyl-3 pentenyl, 2-Methyl-3-pentenyl, 3-Methyl-3-pentenyl, 4-Methyl-3-pentenyl, 1-Methyl-4-pentenyl, 2-Methyl-4-pentenyl, 3-Methyl-4-pentenyl, 4-Methyl-4-pentenyl, 1,1-Dimethyl-2-butenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3 pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl -4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl,
1,1-Dimethyl-3-butenyl, 1,2-Dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl,
1,3-Dimethyl-3-butenyl, 2,2-Dimethyl-3-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl,
2,3-Dimethyl-2-butenyl, 2,3-Dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,
1-Ethyl-2-butenyl, 1-Ethyl-3 butenyl, 2-Ethyl-2-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl,
2-Ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,
1-Ethyl-1-methyl-2-propenyl und Ethyl-2-methyl-2-propenyl, insbesondere 1-Methyl-2-propenyl, 1-Methyl-2-butenyl, 1-ethyl-1-methyl-2-propenyl and ethyl-2-methyl-2-propenyl, in particular 1-methyl-2-propenyl, 1-methyl-2-butenyl,
1,1-Dimethyl-2-propenyl und 1,1-Dimethyl-2-butenyl;  1,1-dimethyl-2-propenyl and 1,1-dimethyl-2-butenyl;
C2-C6-Alkinyl wie Propargyl, 2-Butinyl, 3-Butenyl, 2-Pentinyl, 3-Pentinyl, 4-Pentinyl, 1-Methyl-3-butinyl, 2-Methyl-3-butinyl, 1-Methyl-2-butinyl, 1,1-Dimethyl-2 propinyl, 1-Ethyl-2-propinyl, 2-Hexinyl, 3-Hexinyl, 4-Hexinyl, 5-Hexinyl, 1-Methyl-2-pentinyl, 1-Methyl-3-pentinyl, 1-Methyl-4-pentinyl, 3-Methyl-4-pentinyl, 4-Methyl-2-pentinyl, 1,1-Dimethyl-2-butinyl, C 2 -C 6 alkynyl such as propargyl, 2-butynyl, 3-butenyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl- 2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3 pentynyl, 1-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl,
1,1-Dimethyl-3-butinyl, 1,2-Dimethyl-3-butinyl,  1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,
2,2-Dimethyl-3-butinyl, 1-Ethyl-2-butinyl, 1-Ethyl-3-butinyl, 2-Ethyl-3-butinyl und 1-Ethyl-1-methyl-2-propinyl; C1-C4-Alkoxy wie Methoxy, Ethoxy, n-Propoxy, 1-Methylethoxy, n-Butoxy, 1-Methylpropoxy, 2-Methylpropoxy und 1,1-Dimethylethoxy, insbesondere C1-C3-Alkoxy wie Methoxy, Ethoxy, i-Propoxy, wobei diese Gruppen gegebenenfalls durch ein bis fünf Halogenatome wie Fluor, Chlor, Brom und Iod, vorzugsweise Fluor und Chlor oder C1-C4-Alkoxy wie vorstehend genannt substituiert sein können. 2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl; C 1 -C 4 alkoxy such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy, in particular C 1 -C 3 alkoxy such as methoxy, ethoxy , i-Propoxy, where these groups can optionally be substituted by one to five halogen atoms such as fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine or C 1 -C 4 alkoxy as mentioned above.
Die vorstehend definierte Gruppe -(A)m-S(O)nR1 steht beispielsweise für C1-C4-Alkylthio wie Methylthio, Ethylthio, n-Propylthio, 1-Methylethylthio, n-Butylthio, 1-Methylpropylthio, 2-Methylpropylthio und 1,1-Dimethylethylthio, insbesondere Methylthio; C1-C4-Alkylsulfinyl wie Methylsulfinyl, Ethylsulfinyl, n-Propylsulfinyl, 1-Methylethylsulfinyl, n-Butylsulfinyl, 1-Methylpropylsulfinyl, 2-Methylpropylsulfinyl und 1,1-Dimethylethylsulfinyl, insbesondere Methylsulfinyl; C1-C4-Alkylsulfonyl wie Methylsulfonyl, Ethylsulfonyl, n-Propylsulfonyl, 1-Methylethylsulfonyl, n-Butylsulfonyl, 1-Methylpropylsulfonyl, 2-Methylpropylsulfonyl und 1,1-Dimethylethylsulfonyl, insbesondere Methylsulfonyl; C1-C4-Alkoxysulfonyl wie Methoxysulfonyl, Ethoxysulfonyl, n-Propoxysulfonyl, 1-Methylethoxysulfonyl, n-Butoxysulfonyl, 1-Methylpropoxysulfonyl, 2-Methylpropoxysulfonyl und 1,1-Dimethylethoxysulfonyl, insbesondere Methoxysulfonyl; The group defined above - (A) m -S (O) n R 1 represents , for example, C 1 -C 4 -alkylthio such as methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1-methylpropylthio, 2- Methylpropylthio and 1,1-dimethylethylthio, especially methylthio; C 1 -C 4 alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl and 1,1-dimethylethylsulfinyl, especially methylsulfinyl; C 1 -C 4 alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1-methylethylsulfonyl, n-butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and 1,1-dimethylethylsulfonyl, especially methylsulfonyl; C 1 -C 4 alkoxysulfonyl such as methoxysulfonyl, ethoxysulfonyl, n-propoxysulfonyl, 1-methylethoxysulfonyl, n-butoxysulfonyl, 1-methylpropoxysulfonyl, 2-methylpropoxysulfonyl and 1,1-dimethylethoxysulfonyl, especially methoxysulfonyl;
N-C1-C4-Alkylsulfamoyl wie N-Methylsulfamoyl, N-Ethylsulfamoyl, N-n-Propylsulfamoyl, N-1-Methylethylsulfamoyl, N-n-Butylsulfamoyl, N-1-Methylpropylsulfamoyl, N-2-Methylpropylsulfamoyl und N-1,1-Dimethylethylsulfamoyl, insbesondere N-Methylsulfamoyl; NC 1 -C 4 alkylsulfamoyl such as N-methylsulfamoyl, N-ethylsulfamoyl, Nn-propylsulfamoyl, N-1-methylethylsulfamoyl, Nn-butylsulfamoyl, N-1-methylpropylsulfamoyl, N-2-methylpropylsulfamoyl, N-2-methylpropylsulfamoyl especially N-methylsulfamoyl;
N-C1-C4-Alkylsulfinamoyl wie N-Methylsulfinamoyl, N-Ethylsulfinamoyl, N-n-Propylsulfinamoyl, N-1-Methylethylsulfinamoyl, N-n-Butylsulfinamoyl, N-1-Methylpropylsulfinamoyl, N-2-Methylpropylsulfinamoyl und N-1,1-Dimethylethylsulfinamoyl, insbesondere N-Methylsulfinamoyl; Di-C1-C4-Alkylsulfamoyl wie Dimethylsulfamoyl, Diethylsulfamoyl, Dipropylsulfamoyl, Dibutylsulfamoyl, N-Methyl-N-ethylsulfamoyl, N-Methyl-N-propylsulfamoyl, N-Methyl-N-1-methylethylsulfamoyl, N-Methyl-N-1,1-Dimethylethylsulfamoyl, Di-1-Methylethylsulfamoyl, N-Ethyl-N-1-Methylethylsulfamoyl und N-Ethyl-N-1,1-dimethyl ethylsulfamoyl; insbesondere Dimethylsulfamoyl; Di-C1-C4-Alkylsulfinamoyl wie Dimethylsulfinamoyl, Diethylsulfinamoyl, Dipropylsulfinamoyl, Dibutylsulfinamoyl, N-MethylN-ethylsulfinamoyl, N-Methyl-N-propylsulfinamoyl, N-Methyl-N-1-methylethylsulfinamoyl, N-Methyl-N-1,1-Dimethylethylsulfinamoyl, Di-1-Methylethylsulfinamoyl, N-Ethyl-N-1-Methylethylsulfinamoyl und N-Ethyl-N-1,1-dimethylethylsulfinamoyl; insbesondere NC 1 -C 4 alkylsulfinamoyl such as N-methylsulfinamoyl, N-ethylsulfinamoyl, Nn-propylsulfinamoyl, N-1-methylethylsulfinamoyl, Nn-butylsulfinamoyl, N-1-methylpropylsulfinamoyl, N-2-methylproylmoylmethylsulfinamoyl especially N-methylsulfinamoyl; Di-C 1 -C 4 alkylsulfamoyl such as dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl, N-methyl-N-ethylsulfamoyl, N-methyl-N-propylsulfamoyl, N-methyl-N-1-methylethylsulfamoyl, N-methyl-N-1,1-dimethylethylsulfamoyl, di-1-methylethylsulfamoyl, N-ethyl-N-1-methylethylsulfamoyl and N-ethyl-N-1,1-dimethylethylsulfamoyl; especially dimethylsulfamoyl; Di-C 1 -C 4 alkylsulfinamoyl such as dimethylsulfinamoyl, diethylsulfinamoyl, dipropylsulfinamoyl, dibutylsulfinamoyl, N-methylN-ethylsulfinamoyl, N-methyl-N-propylsulfinamoyl, N-methyl-N-1-methyll-1-methyl-1-sulfinamoyl 1-dimethylethylsulfinamoyl, di-1-methylethylsulfinamoyl, N-ethyl-N-1-methylethylsulfinamoyl and N-ethyl-N-1,1-dimethylethylsulfinamoyl; in particular
Dimethylsulfinamoyl, Dimethylsulfinamoyl,
C1-C4-Alkylsulfinyloxy wie Methylsulfinyloxy, Ethylsulfinyloxy, n-Propylsulfinyloxy, 1-Methylethylsulfinyloxy, n-Butylsulfinyloxy, 1-Methylpropylsulfinyloxy, 2-Methylpropylsulfinyloxy und 1,1-Dimethylethylsulfinyloxy, insbesondere Methylsulfinyloxy; C 1 -C 4 alkylsulfinyloxy such as methylsulfinyloxy, ethylsulfinyloxy, n-propylsulfinyloxy, 1-methylethylsulfinyloxy, n-butylsulfinyloxy, 1-methylpropylsulfinyloxy, 2-methylpropylsulfinyloxy and 1,1-dimethylethylsulfinyloxy, especially methylsulfinyloxy;
C1-C4-Alkylsulfonyloxy wie Methylsulfonyloxy, Ethylsulfonyloxy, n-Propylsulfonyloxy, 1-Methylethylsulfonyloxy, n-Butylsulfonyloxy, 1-Methylpropylsulfonyloxy, 2-Methylpropylsulfonyloxy und 1,1-Dimethylethylsulfonyloxy, insbesondere Methylsulfonyloxy; C 1 -C 4 alkylsulfonyloxy such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, 1-methylethylsulfonyloxy, n-butylsulfonyloxy, 1-methylpropylsulfonyloxy, 2-methylpropylsulfonyloxy and 1,1-dimethylethylsulfonyloxy, especially methylsulfonyloxy;
C1-C4-Alkylsulfinylamino wie Methylsulfinylamino, Ethylsulfinylamino, n-Propylsulfinylamino, 1-Methylethylsulfinylamino, n-Butylsulfinylamino, 1-Methylpropylsulfinylamino, 2-Methylpropylsulfinylamino und 1, 1-Dimethylethylsulfinylamino, insbesondere Methylsulfinylamino; C 1 -C 4 alkylsulfinylamino such as methylsulfinylamino, ethylsulfinylamino, n-propylsulfinylamino, 1-methylethylsulfinylamino, n-butylsulfinylamino, 1-methylpropylsulfinylamino, 2-methylpropylsulfinylamino and 1, 1-dimethylethylsulfinylamino, in particular;
C1-C4-Alkylsulfonylamino wie Methylsulfonylamino, Ethylsulfonylamino, n-Propylsulfonylamino, 1-Methylethylsulfonylamino, n-Butylsulfonylamino, 1-Methylpropylsulfonylamino, 2-Methylpropylsulfonylamino und 1,1-Dimethylethylsulfonylamino, insbesondere Methylsulfonylamino; N-C1-C4-Alkylsulfinyl-N-methyl-amino wie N-Methylsulfinyl-N-methyl-amino, N-Ethylsulfinyl-N-methyl-amino, N-n-PropylsulfinylN-methyl-amino, N-1-Methylethylsulfinyl-N-methyl-amino, C 1 -C 4 alkylsulfonylamino such as methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, 1-methylethylsulfonylamino, n-butylsulfonylamino, 1-methylpropylsulfonylamino, 2-methylpropylsulfonylamino and 1,1-dimethylamino, especially 1,1-dimethylamino; NC 1 -C 4 alkylsulfinyl-N-methyl-amino such as N-methylsulfinyl-N-methyl-amino, N-ethylsulfinyl-N-methyl-amino, Nn-propylsulfinylN-methyl-amino, N-1-methylethylsulfinyl-N- methyl-amino,
N-n-Butylsulfinyl-N-methyl-amino, N-1-Methylpropylsulfinyl-N-methyl-amino, N-2-Methylpropylsulfinyl-N-methyl-amino und N-n-butylsulfinyl-N-methyl-amino, N-1-methylpropylsulfinyl-N-methyl-amino, N-2-methylpropylsulfinyl-N-methyl-amino and
N-1,1-Dimethylethylsulfinyl-N-methyl-amino, insbesondere N-1,1-dimethylethylsulfinyl-N-methylamino, in particular
N-Methylsulfinyl-N-methyl-amino; N-methylsulfinyl-N-methyl-amino;
N-C1-C4-Alkylsulfinyl-N-ethyl-amino wie N-Methylsulfinyl-N-ethylamino, N-Ethylsulfinyl-N-ethyl-amino, N-n-Propylsulfinyl-N-ethylamino, N-1-Methylethylsulfinyl-N-ethyl-amino, N-n-ButylsulfinylN-ethyl-amino, N-1-Methylpropylsulfinyl-N-ethyl-amino, NC 1 -C 4 alkylsulfinyl-N-ethylamino such as N-methylsulfinyl-N-ethylamino, N-ethylsulfinyl-N-ethylamino, Nn-propylsulfinyl-N-ethylamino, N-1-methylethylsulfinyl-N-ethylamino amino, Nn-butylsulfinylN-ethyl-amino, N-1-methylpropylsulfinyl-N-ethyl-amino,
N-2-Methylpropylsulfinyl-N-ethyl-amino und N-1,1-Dimethylethyl sulfinyl-N-ethyl-amino, insbesondere N-Methylsulfinyl-N-ethylamino; N-2-methylpropylsulfinyl-N-ethyl-amino and N-1,1-dimethylethyl sulfinyl-N-ethylamino, especially N-methylsulfinyl-N-ethylamino;
N-C1-C4-Alkylsulfonyl-N-methyl-amino wie N-Methylsulfonyl-N-methyl-amino, N-Ethylsulfonyl-N-methyl-amino, N-n-PropylsulfonylN-methyl-amino, N-1-Methylethylsulfonyl-N-methyl-amino, NC 1 -C 4 alkylsulfonyl-N-methyl-amino such as N-methylsulfonyl-N-methyl-amino, N-ethylsulfonyl-N-methyl-amino, Nn-propylsulfonylN-methyl-amino, N-1-methylethylsulfonyl-N- methyl-amino,
N-n-Butylsulfonyl-N-methyl-amino, N-1-Methylpropylsulfonyl-N-methyl-amino, N-2-Methylpropylsulfonyl-N-methyl-amino und N-n-butylsulfonyl-N-methyl-amino, N-1-methylpropylsulfonyl-N-methyl-amino, N-2-methylpropylsulfonyl-N-methyl-amino and
N-1,1-Dimethylethylsulfonyl-N-methyl-amino, insbesondere N-1,1-dimethylethylsulfonyl-N-methylamino, in particular
N-Methylsulfonyl-N-methyl-amino; N-methylsulfonyl-N-methylamino;
N-C1-C4-Alkylsulfonyl-N-ethyl-amino wie N-Methylsulfonyl-N-ethylamino, N-Ethylsulfonyl-N-ethyl-amino, N-n-Propylsulfonyl-N-ethylamino, N-1-Methylethy1sulfonyl-N-ethyl-amino, N-n-Butylsulfonyl-N-ethyl-amino, N-1-Methylpropylsulfonyl-N-ethyl-amino, NC 1 -C 4 alkylsulfonyl-N-ethylamino such as N-methylsulfonyl-N-ethylamino, N-ethylsulfonyl-N-ethylamino, Nn-propylsulfonyl-N-ethylamino, N-1-methylethylsulfonyl-N-ethylamino amino, Nn-butylsulfonyl-N-ethyl-amino, N-1-methylpropylsulfonyl-N-ethyl-amino,
N-2-Methylpropylsulfonyl-N-ethyl-amino und N-1,1-Dimethylethylsulfonyl-N-ethyl-amino, insbesondere N-Methylsulfonyl-N-ethyl-amino; C1-C4-Halogenalkylthio wie Chlormethylthio, Dichlormethylthio, Trichlormethylthio, Fluormethylthio, Difluormethylthio, Trifluormethylthio, Chlorfluormethylthio, Chlordifluormethylthio, N-2-methylpropylsulfonyl-N-ethyl-amino and N-1,1-dimethylethylsulfonyl-N-ethyl-amino, especially N-methylsulfonyl-N-ethyl-amino; C 1 -C 4 haloalkylthio such as chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, chlorodifluoromethylthio,
1-Fluorethylthio, 2-Fluorethylthio, 2,2-Difluorethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio,
2,2,2-Trifluorethylthio, 2-Chlor-2,2-difluorethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2,2-difluoroethylthio,
2,2-Dichlor-2 fluorethylthio, 2,2,2-Trichlorethylthio und 2,2-dichloro-2 fluoroethylthio, 2,2,2-trichloroethylthio and
Pentafluorethylthio, insbesondere Trifluormethylthio. Pentafluoroethylthio, especially trifluoromethylthio.
Die vorstehend definierte Gruppe -(A)m-CO-R2 steht beispielsweise für C1-C4-Alkylcarbonyl wie Methylcarbonyl, Ethylcarbonyl, n-Propylcarbonyl, 1-Methylethylcarbonyl, n-Butylcarbonyl, 1-Methylpropylcarbonyl, 2-Methylpropylcarbonyl und 1,1-Dimethylethylcarbonyl, insbesondere Methylcarbonyl; The group - (A) m -CO-R 2 defined above stands for example for C 1 -C 4 alkylcarbonyl such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl and 1 , 1-dimethylethylcarbonyl, especially methylcarbonyl;
C1-C4-Alkoxycarbonyl wie Methoxycarbonyl, Ethoxycarbonyl, n-Propoxycarbonyl, 1-Methylethoxycarbonyl, n-Butoxycarbonyl, 1-Methylpropoxycarbonyl, 2-Methylpropoxycarbonyl und 1,1-Dimethylethoxycarbonyl, insbesondere Methoxycarbonyl; C 1 -C 4 alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, 1-methylethoxycarbonyl, n-butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl and 1,1-dimethylethoxycarbonyl, especially methoxycarbonyl;
N-C1-C4-Alkylcarbamoyl wie N-Methylcarbamoyl, N-Ethylcarbamoyl, N-n-Propylcarbamoyl, N-1-Methylethylcarbamoyl, N-n-Butylcarbamoyl, N-1-Methylpropylcarbamoyl, N-2-Methylpropylcarbamoyl und N-1,1-Dimethylethylcarbamoyl, insbesondere N-Methylcarbamoyl; Di-C1-C4-Alkylcarbamoyl wie Dimethylcarbamoyl, Diethylcarbamoyl, Dipropylcarbamoyl, Dibutylcarbamoyl, N-Methyl-N-ethylcarbamoyl, N-Methyl-N-propylcarbamoyl, N-Methyl-N-1-methylethylcarbamoyl, N-Methyl-N-1,1-Dimethylethylcarbamoyl, Di-1-Methylethylcarbamoyl, N-Ethyl-N-1-Methylethylcarbamoyl und N-Ethyl-N-1,1-dimethylethylcarbamoyl; insbesondere Dimethylcarbamoyl; NC 1 -C 4 alkylcarbamoyl such as N-methylcarbamoyl, N-ethylcarbamoyl, Nn-propylcarbamoyl, N-1-methylethylcarbamoyl, Nn-butylcarbamoyl, N-1-methylpropylcarbamoyl, N-2-methylpropylcarbamoyl and N-1,1-dimethylethylcarbamoyl especially N-methylcarbamoyl; Di-C 1 -C 4 alkylcarbamoyl such as dimethylcarbamoyl, diethylcarbamoyl, dipropylcarbamoyl, dibutylcarbamoyl, N-methyl-N-ethylcarbamoyl, N-methyl-N-propylcarbamoyl, N-methyl-N-1-methylethylcarbamoyl, N-methyl-N- 1,1-dimethylethylcarbamoyl, di-1-methylethylcarbamoyl, N-ethyl-N-1-methylethylcarbamoyl and N-ethyl-N-1,1-dimethylethylcarbamoyl; especially dimethylcarbamoyl;
C1-C4-Alkylcarbonyloxy wie Methylcarbonyloxy, Ethylcarbonyloxy, n-Propylcarbonyloxy, 1-Methylethylcarbonyloxy, n-Butylcarbonyloxy, 1-Methylpropylcarbonyloxy, 2-Methylpropylcarbonyloxy und 1,1-Dimethylethylcarbonyloxy, insbesondere Methylcarbonyloxy; C 1 -C 4 alkylcarbonyloxy such as methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, 1-methylethylcarbonyloxy, n-butylcarbonyloxy, 1-methylpropylcarbonyloxy, 2-methylpropylcarbonyloxy and 1,1-dimethylethylcarbonyloxy, especially methylcarbonyloxy;
C1-C4-Alkylcarbonylamino wie Methylcarbonylamino, Ethylcarbonylamino, n-Propylcarbonylamino, 1-Methylethylcarbonylamino, C 1 -C 4 alkylcarbonylamino such as methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, 1-methylethylcarbonylamino,
n-Butylcarbonylamino, 1-Methylpropylcarbonylamino, 2-Methylpropylcarbonylamino und 1,1-Dimethylethylcarbonylamino, insbesondere Methylcarbonylamino; n-butylcarbonylamino, 1-methylpropylcarbonylamino, 2-methylpropylcarbonylamino and 1,1-dimethylethylcarbonylamino, especially methylcarbonylamino;
N-C1-C4-Alkylcarbonyl-N-methyl-amino wie N-Methylcarbony1-N-methyl-amino, N-Ethylcarbonyl-N-methyl-amino, N-n-Propylcarbonyl-N-methyl-amino, N-1-Methylethylcarbonyl-N-methyl-amino, NC 1 -C 4 -alkylcarbonyl-N-methyl-amino such as N-methylcarbonyl- 1 -N-methyl-amino, N-ethylcarbonyl-N-methyl-amino, Nn-propylcarbonyl-N-methyl-amino, N-1-methylethylcarbonyl- N-methylamino,
N-n-Butylcarbonyl-N-methyl-amino, N-1-Methylpropylcarbonyl-N-methyl-amino, N-2-Methylpropylcarbonyl-N-methyl-amino und  N-n-butylcarbonyl-N-methyl-amino, N-1-methylpropylcarbonyl-N-methyl-amino, N-2-methylpropylcarbonyl-N-methyl-amino and
N-1,1-Dimethylethylcarbonyl-N-methyl-amino, insbesondere N-1,1-dimethylethylcarbonyl-N-methylamino, in particular
N-Methylcarbonyl-N-methyl-amino. N-methylcarbonyl-N-methyl-amino.
X steht beispielsweise für: For example, X stands for:
CH2, CH(CH3), C((CH3)2), CH(C2H5), C((C2H5)2), CH(C6H5), CH2-CH2, CH2-CH(CH3), CH2-C((CH3)2), CH(CH3)-CH(CH3), CH(CH3)-C((CH3)2), C((CH3)2)-C((CH3)2), CH 2, CH (CH 3 ), C ((CH 3 ) 2 ), CH (C 2 H 5 ), C ((C 2 H 5 ) 2 ), CH (C 6 H 5 ), CH 2 -CH 2 , CH 2 -CH (CH 3 ), CH 2 -C ((CH 3 ) 2 ), CH (CH 3 ) -CH (CH 3 ), CH (CH 3 ) -C ((CH 3 ) 2 ), C ((CH 3 ) 2 ) -C ((CH 3 ) 2 ),
CH2-CH(C2H5), CH2-C((C2H5)2), CH(C2H5)-CH(C2H5), CH(C2H5)-C((C2H5)2), C((C2H5)2)-C((C2H5)2), CH2-CH(C3H7), CH2-CH(iC3H7), CH2-CH(C4H9), CH2-CH(iC4H9), CH 2 -CH (C 2 H 5 ), CH 2 -C ((C 2 H 5 ) 2 ), CH (C 2 H 5 ) -CH (C 2 H 5 ), CH (C 2 H 5 ) -C ((C 2 H 5 ) 2 ), C ((C 2 H 5 ) 2 ) -C ((C 2 H 5 ) 2 ), CH 2 -CH (C 3 H 7 ), CH 2 -CH (iC 3 H 7 ), CH 2 -CH (C 4 H 9 ), CH 2 -CH (iC 4 H 9 ),
CH2-CH(Br), CH2-C((Br)2), CH(Br)-CH{Br), C((Br)2)-C((Br)2), CH 2 -CH (Br), CH 2 -C ((Br) 2 ), CH (Br) -CH {Br), C ((Br) 2 ) -C ((Br) 2 ),
CH2-CH(Cl), CH2-C((Cl)2), CH(Cl)-C((Cl2), C((Cl)2)-C((Cl)2), CH 2 -CH (Cl), CH 2 -C ((Cl) 2 ), CH (Cl) -C ((Cl 2 ), C ((Cl) 2 ) -C ((Cl) 2),
CH2-CH(C6H5), CH(C6H5)-CH(C6H5), CH2-CH(p-NO2C5H5)] CH 2 -CH (C 6 H 5 ), CH (C 6 H 5 ) -CH (C 6 H 5 ), CH 2 -CH (p-NO 2 C 5 H 5 )]
CH=CH, C(CH3)=CH, C(CH3)=CCH3, CH=CBr, CH=CCl, CBr=CBr, CCl=CCl, CH=C(OCH3), CH=C(C6H5), C(C6H5)=C(C6H5), C(C2H5)=CH, CH = CH, C (CH 3 ) = CH, C (CH 3 ) = CCH 3 , CH = CBr, CH = CCl, CBr = CBr, CCl = CCl, CH = C (OCH 3 ), CH = C (C 6 H 5 ), C (C 6 H 5 ) = C (C 6 H 5 ), C (C 2 H 5 ) = CH,
C(C2H5)=C(C2H5), CH=C(C3H5), CH=C(C4H7), CH2-CH=CH, CH(CH3)-CH=CH, C( (CH3)2)-CH=CH, CH2-CH=C(CH3), CH2-C(CH3)=CH, CH2-C(CH3)=C(CH3), CH(CH3)-C(CH3)=C(CH3), C((CH3)2)-C(CH3)=C(CH3), N-H, N-CH3, N-C2H5, N-C3H7, N-C4H9, N-iCH3H7, N-OCH3, N-OC2H5, N-CH2C6H5, N-C6H5; C (C 2 H 5 ) = C (C 2 H 5 ), CH = C (C 3 H 5 ), CH = C (C 4 H 7 ), CH 2 -CH = CH, CH (CH 3 ) -CH = CH, C ((CH 3 ) 2 ) -CH = CH, CH 2 -CH = C (CH 3 ), CH 2 -C (CH 3 ) = CH, CH 2 -C (CH 3 ) = C (CH 3 ), CH (CH 3 ) -C (CH 3 ) = C (CH 3 ), C ((CH 3 ) 2 ) -C (CH 3 ) = C (CH 3 ), NH, N-CH 3 , NC 2 H 5 , NC 3 H 7 , NC 4 H 9 , N-iCH 3 H 7 , N-OCH 3 , N-OC 2 H 5 , N-CH 2 C 6 H 5 , NC 6 H 5 ;
Y steht beispielsweise für: C=O, CH-OH, CH-OCH3, CH-OC2H5, CH-OC3H7, CH-OiPr, CH-OC4H9, Y stands for example for: C = O, CH-OH, CH-OCH 3 , CH-OC 2 H 5 , CH-OC 3 H 7 , CH-OiPr, CH-OC 4 H 9 ,
CH-OiBu, CH-OC5H11, CH-OC6H13, CH-OC6H5, C(CH3)-OCH3, C(CH3)-OC2H5, C(CH3)-OC3H7, C(CH3)-OC4H9, C(CH3)-OiPr, C(CH3)-OiBu, C(CH3)-OtBu, C(CH3)-OPh, CH2, CH(CH3), C( (CH3)2), C=N-CH3, C=N-C2H5, C=N-C3H7, C=N-C4H9, C=N-iC4H9, C=N-tC4H9, C=N-iPr, C=N-OCH3, C=N-OC2H5, C=N-OC3H7, C=N-OC4H9, C=N-OiC4H9, C=N-OtC4H9, C=N-OCH2CH=CH2, CH-OiBu, CH-OC 5 H 11 , CH-OC 6 H 13 , CH-OC 6 H 5 , C (CH 3 ) -OCH 3, C (CH 3) - OC 2 H 5 , C (CH 3) - OC 3 H 7 , C (CH 3 ) -OC 4 H 9 , C (CH 3 ) -OiPr, C (CH 3 ) -OiBu, C (CH 3 ) -OtBu, C (CH 3 ) -OPh, CH 2 , CH (CH 3 ), C ((CH 3 ) 2), C = N-CH 3 , C = NC 2 H 5 , C = NC 3 H 7 , C = NC 4 H 9 , C = N-iC 4 H 9 , C = N-tC 4 H 9 , C = N-iPr, C = N-OCH 3 , C = N-OC 2 H 5 , C = N-OC 3 H 7 , C = N-OC 4 H 9 , C = N-OiC 4 H 9 , C = N-OtC 4 H 9 , C = N-OCH 2 CH = CH 2 ,
C=N-OCH(CH3)CH=CH2, C=N-OCH2CH=CHCH3, C=N-OCH2CH=C(CH3)2, C = N-OCH (CH 3) CH = CH 2 , C = N-OCH 2 CH = CHCH 3 , C = N-OCH 2 CH = C (CH 3 ) 2 ,
C=N-OCH2CH=CHBr, C=N-OCH2CH=CHCl, C=N-OCH2CH=CHC2H5, C=N-OCH2C≡CH, C=N-OCH2C≡CCH3 , C=N-OCH2C6H5, CH-NH(OCH3), CH-NH(OC2H5), C = N-OCH 2 CH = CHBr, C = N-OCH 2 CH = CHCl, C = N-OCH 2 CH = CHC 2 H 5 , C = N-OCH 2 C≡CH, C = N-OCH 2 C ≡CCH3, C = N-OCH 2 C 6 H 5 , CH-NH (OCH 3 ), CH-NH (OC 2 H 5 ),
CH-NH(OiPr), CH-NH(OnPr), CH-NH(OC6H5), CH-NCH3(OCH3), CH-NH (OiPr), CH-NH (OnPr), CH-NH (OC 6 H 5 ), CH-NCH 3 (OCH 3 ),
CH-NCH3(OC2H5), CH-NCH3(OiPr), CH-NCH3(OnPr), CH-NCH3(OC6H5), CH-NH(CH3), CH-NH(C2H5), CH-NH(C3H7), CH-NH(C4H9), CH-NH(iPr), CH-NH(iBu), CH-NH (tBu), CH-NH(C6H5), CH-N(CH3)2, CH-NCH3(C2H5), CH-NCH3(C3H7), CH-NCH3(C4H9), CH-NCH3(iPr), CH-NCH3(iBu), C=N-NH2, C=N-NHCH3, C=N-N( (CH3)2), C=N-NH (C2H5 ), C=N-NCH3 (C2H5 ), CH-NCH 3 (OC 2 H 5 ), CH-NCH 3 (OiPr), CH-NCH 3 (OnPr), CH-NCH 3 (OC 6 H 5 ), CH-NH (CH 3 ), CH-NH ( C 2 H 5 ), CH-NH (C 3 H 7 ), CH-NH (C 4 H 9 ), CH-NH (iPr), CH-NH (iBu), CH-NH (tBu), CH-NH (C 6 H 5 ), CH-N (CH 3 ) 2 , CH-NCH 3 (C 2 H 5 ), CH-NCH 3 (C 3 H 7 ), CH-NCH 3 (C 4 H 9 ), CH -NCH 3 (iPr), CH-NCH 3 (iBu), C = N-NH 2 , C = N-NHCH 3 , C = NN ((CH 3 ) 2 ), C = N-NH (C 2 H 5 ), C = N-NCH 3 (C 2 H 5 ),
C=N-N((C2H5)2), CH-SCH3, CH-SC2H5, CH-SC3H7, CH-SC4H9, CH-SPr, CH-SiBu, CH-SH, C(CH3)-SCH3, C(CH3)-SC2H5, C(CH3)-SC3H7, C = NN ((C 2 H 5 ) 2 ), CH-SCH 3 , CH-SC 2 H 5 , CH-SC 3 H 7 , CH-SC 4 H 9 , CH-SPr, CH-SiBu, CH-SH , C (CH 3 ) -SCH 3 , C (CH 3 ) -SC 2 H 5 , C (CH 3 ) -SC 3 H 7 ,
1,3-Dioxanyl, 1,3-Dioxolanyl, 5,5-Dimethyl-1,3-dioxanyl 1,3-dioxanyl, 1,3-dioxolanyl, 5,5-dimethyl-1,3-dioxanyl
Bevorzugt sind Phenyldiketonderivate der Formel Ia, Phenyldiketone derivatives of the formula Ia are preferred,
Figure imgf000019_0001
Figure imgf000019_0001
in der L für Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, in which L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl,
C2-C6-Alkinyl, C1-C4-Alkoxy, C1-C4-Alkylthio, C1-C4-Halogenalkyl, C1 -C4-Halogenalkoxy, C1-C4-Halogenalkylthio, C1-C4-Alkylsulfonyl, Halogen, Nitro oder Cyano und M für Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C1-C4-Alkoxy, C1-C4-Alkylthio, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkyl, C 1 -C 4 -haloalkoxy, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylsulfonyl, halogen, nitro or cyano and M for hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio,
C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, C1-C4-Halogenalkoxy, C1-C4-Halogenalkylthio, C1-C4-Alkylsulfonyl, Halogen, Nitro oder Cyano steht und R15, X, n und Y die oben angegebenen Bedeutungen haben, wobei für den Fall, daß Y = C=O ist, X ungleich NR23 ist. Weiterhin bevorzugt sind Phenyldiketonderivate der Formel Ib, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylsulfonyl, halogen, nitro or cyano and R 15 , X, n and Y have the meanings given above, where if Y = C = O, X is not equal to NR 23 . Phenyldiketone derivatives of the formula Ib are also preferred,
Figure imgf000019_0002
Figure imgf000019_0002
in der L für C1-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, in which L is C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl,
C1-C4-Alkoxy, C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro oder Cyano und M für Wasserstoff C1-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C1-C4-Alkoxy, C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro oder Cyano steht und R15, X, n und Y die oben angegebenen Bedeutungen haben, wobei für den Fall, daß Y = C=O ist, X ungleich NR23 ist. C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, halogen, nitro or cyano and M for hydrogen C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 -haloalkoxy, halogen, nitro or cyano and R 15, X, n and Y have the meanings given above, where in the case that Y = C = O, X is not equal to NR 23 .
Bevorzugt sind auch Phenyldiketonderivate der Formel I, in der die Reste L bzw. M für Wasserstoff, Methyl, Methoxy, Chlor, Also preferred are phenyldiketone derivatives of the formula I in which the radicals L and M are hydrogen, methyl, methoxy, chlorine,
Cyano, Nitro, Trifluormethyl stehen. Cyano, nitro, trifluoromethyl are available.
Bevorzugt sind Phenyldiketonderivate der Formel Ic, Phenyldiketone derivatives of the formula Ic are preferred,
Figure imgf000020_0001
Figure imgf000020_0001
in der L für Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, in which L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl,
C2-C6-Alkinyl, C1 -C4-Alkoxy, C1 -C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro oder Cyano und M für Wasserstoff, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 -haloalkoxy, halogen, nitro or cyano and M is hydrogen,
C1-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C1-C4-Alkoxy, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy,
C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro oder C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, halogen, nitro or
Cyano steht und R15, n, Y sowie R22, R21 , R12 und R13 die oben angegebenen Bedeutungen haben. Cyano is and R 15 , n, Y and R 22 , R 21 , R 12 and R 13 have the meanings given above.
Ebenfalls bevorzugt sind Phenyldiketonderivate der Formel Id, Also preferred are phenyldiketone derivatives of the formula Id
Figure imgf000020_0002
Figure imgf000020_0002
in der L für Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, in which L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl,
C2-C6-Alkinyl, C1-C4-Alkoxy, C1-C4-Halogenalkyl, C1 -C4-Halogealkoxy, Halogen, Nitro oder Cyano und M für Wasserstoff, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, halogen, nitro or cyano and M for hydrogen,
C1-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C1-C4-Alkoxy, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy,
C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro oder C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, halogen, nitro or
Cyano steht und R15, n, Y sowie R12 und R13 die oben angegebenen Bedeutungen haben. Cyano is and R 15 , n, Y and R 12 and R 13 have the meanings given above.
Auch bevorzugt sind Phenyldiketonderivate der Formel Ie, Phenyldiketone derivatives of the formula Ie are also preferred,
Figure imgf000020_0003
Figure imgf000020_0003
in der L für Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, in which L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl,
C2-C6-Alkinyl, C1-C4-Alkoxy, C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro oder Cyano und M für Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C1-C4-Alkoxy, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 -haloalkoxy, halogen, nitro or cyano and M is hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy,
C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro oder Cyano steht und R15, n, Y sowie R12 und R13 die oben angegebenen Bedeutungen haben. C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, halogen, nitro or cyano and R 15 , n, Y and R 12 and R 13 have the meanings given above.
Bevorzugt sind ebenfalls Phenyldiketonderivate der Formel I, in der n für eins oder zwei steht und Y für CR7-OR8, wobei R7 und R8 die oben angegebene Bedeutung haben. Beispiele für besonders bevorzugte Verbindungen der allgemeinen Formel I sind in den folgenden Tabellen zusammengestellt. Also preferred are phenyldiketone derivatives of the formula I in which n is one or two and Y is CR 7 -OR 8 , where R 7 and R 8 have the meaning given above. Examples of particularly preferred compounds of the general formula I are compiled in the following tables.
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
HerStellungsbeispiele Manufacturing examples
A) Herstellung der Ausgangsmaterialien und Zwischenprodukte A) Preparation of the starting materials and intermediates
1. 3-Thio-2-methylbenzoesaure 1. 3-thio-2-methylbenzoic acid
100 g (0.66 mol) 3-Amino-2-methylbenzoesaure werden zusammen mit 270 g Eis und 127 ml konz. HCl vorgelegt. Bei 0-10°C werden dann 45.7 g (0.66 mol) Natriumnitrit in 270 ml Wasser zugetropft. 100 g (0.66 mol) of 3-amino-2-methylbenzoic acid together with 270 g of ice and 127 ml of conc. HCl submitted. 45.7 g (0.66 mol) of sodium nitrite in 270 ml of water are then added dropwise at 0-10 ° C.
In einem zweiten Gefäß werden 84.2 g (0.79 mol) Natriumcarbonat und 106 g (0.66 mol) Kaliummethylxanthogenat in 450 ml Wasser gelost und auf 60-70°C erhitzt. Die 84.2 g (0.79 mol) of sodium carbonate and 106 g (0.66 mol) of potassium methylxanthate are dissolved in 450 ml of water in a second vessel and heated to 60-70.degree. The
Diazoniumlosung wird vorsichtig zugetropft. Es wird 1 Stunde nachgeruhrt. Anschließend gibt man 106 g (2.65 mol) Natriumhydroxid in 270 ml Wasser hinzu, rührt weitere 2 Stunden, stellt die Losung mit Salzsaure sauer und saugt den entstehenden Niederschlag ab. Der Feststoff wird mit Wasser gewaschen und getrocknet.  Diazonium solution is carefully added dropwise. It is stirred for 1 hour. Then 106 g (2.65 mol) of sodium hydroxide in 270 ml of water are added, the mixture is stirred for a further 2 hours, the solution is acidified with hydrochloric acid and the precipitate formed is filtered off with suction. The solid is washed with water and dried.
Ausbeute: 110 g (100 % d.Th.) an 3-Thio-2-methylbenzoesaure; Schmelzpunkt: 155°C Yield: 110 g (100% of theory) of 3-thio-2-methylbenzoic acid; Melting point: 155 ° C
1H-NMR (d6-DMSO):  1H-NMR (d6-DMSO):
δ (ppm): 13.0 (1H, bs), 7.7 (2H, m), 7.3 (1H, tr),  δ (ppm): 13.0 (1H, bs), 7.7 (2H, m), 7.3 (1H, tr),
2.4 (3H, s)  2.4 (3H, s)
2. 3-Thio-2-methylbenzoesauremethylester 2. 3-Thio-2-methylbenzoic acid methyl ester
110 g (0.66 mol) 3-Thio-2-methylbenzoesaure werden in 1.6 1 Methanol, der 5 % Schwefelsaure enthalt, gelost und 5 Stunden unter Ruckfluß erhitzt. Anschließend wird der Alkohol abdestilliert, der Rückstand wird in Essigsaureethylester aufgenommen, die organische Phase mit Wasser und mit Natriumcarbonatlosung gewaschen, mit Natriumsulfat getrocknet und einrotiert. 110 g (0.66 mol) of 3-thio-2-methylbenzoic acid are dissolved in 1.6 liters of methanol containing 5% sulfuric acid and heated under reflux for 5 hours. The alcohol is then distilled off, the residue is taken up in ethyl acetate, the organic phase is washed with water and with sodium carbonate solution, dried with sodium sulfate and evaporated in a rotary evaporator.
Ausbeute: 104 g (87 % d.Th.) an 3-Thio-2-methylbenzoesauremethylester 1H-NMR (CDCI3): Yield: 104 g (87% of theory) of methyl 3-thio-2-methylbenzoate 1 H-NMR (CDCI 3 ):
δ (ppm): 7.6 (1H, d), 7.4 (1H, d), 7.1 (1H, d), 3.9 (3H, s), 3.4 (1H, s), 2.5 (3H, s) 3. 3-Thio(2'-propionsäure)-2-methylbenzoesauremethylester δ (ppm): 7.6 (1H, d), 7.4 (1H, d), 7.1 (1H, d), 3.9 (3H, s), 3.4 (1H, s), 2.5 (3H, s) 3. 3-Thio (2'-propionic acid) -2-methylbenzoic acid methyl ester
Figure imgf000042_0001
Figure imgf000042_0001
70 g (0.38 mol) 3-Thio-2-methylbenzoesauremethylester werden in 400 ml Wasser gelost und mit 30.8 g (0.77 mol) Natronlauge und 58.8 g (0.45 mol) Brompropionsäure 7 Stunden unter Rückfluß erhitzt. Nach dem Abkühlen wird die wäßrige Phase mit MTB-Ether gewaschen. Anschließend säuert man die wäßrige Phase mit 2N HCl an, saugt den entstandenen Niederschlag ab, wascht ihn mit Wasser und trocknet das Produkt.  70 g (0.38 mol) of 3-thio-2-methylbenzoic acid methyl ester are dissolved in 400 ml of water and refluxed with 30.8 g (0.77 mol) of sodium hydroxide solution and 58.8 g (0.45 mol) of bromopropionic acid for 7 hours. After cooling, the aqueous phase is washed with MTB ether. The aqueous phase is then acidified with 2N HCl, the precipitate formed is filtered off with suction, washed with water and the product is dried.
Ausbeute: 75.5 g (78 % d.Th.) an 3-Thiopropionsaure-2- methylbenzoesauremethylester; 1H-NMR (CDCl3): δ (ppm): 7.66 (1H, d), 7.51 (1H, d), 7.20 (1H, tr), 3.96 (3H, s), 3.18 (2H, tr), 2.70 (2H, tr), 2.63 (3H, s) Yield: 75.5 g (78% of theory) of methyl 3-thiopropionate-2-methylbenzoate; 1 H NMR (CDCl 3 ): δ (ppm): 7.66 (1H, d), 7.51 (1H, d), 7.20 (1H, tr), 3.96 (3H, s), 3.18 (2H, tr), 2.70 (2H, tr), 2.63 (3H, s)
4. 8-Methylthiochroman-4-on-7-carbonsauremethylester 4. 8-methylthiochroman-4-one, 7-carboxylic acid methyl ester
Figure imgf000042_0002
Figure imgf000042_0002
4 g (15.8 mmol) 3-Thiopropionsaure-2-methylbenzoesauremethylester werden in 40 g Polyphosphorsaure bei 70°C 15 Minuten gerührt. Danach gibt man die Reaktionslosung auf Eiswasser und saugt den entstandenen Niederschlag ab. Das Produkt wird mit Wasser gewaschen und im Trockenschrank getrocknet. Als Nebenprodukt der Cyclisierung kann 8-Methylthiochromen4-on-carbonsäuremethylester entstehen, der durch Chromatographie abgetrennt werden kann.  4 g (15.8 mmol) of methyl 3-thiopropionate-2-methylbenzoate are stirred in 40 g of polyphosphoric acid at 70 ° C. for 15 minutes. Then the reaction solution is poured onto ice water and the precipitate formed is filtered off with suction. The product is washed with water and dried in a drying cabinet. As a by-product of the cyclization, 8-methylthiochromen4-one-carboxylic acid methyl ester can be formed, which can be separated off by chromatography.
Ausbeute: 3.1 g (83 % d. Th.) an 8-Methylthiochroman- 4-on-7-carbonsauremethylester 1H-NMR (CDCI3): δ (ppm): Yield: 3.1 g (83% of theory) of 8-methylthiochroman-4-one-7-carboxylic acid methyl ester 1 H-NMR (CDCI 3 ): δ (ppm):
8.00 (1H, d), 7.30 (1H, d), 3.94 (3H, s), 3.15 (2H, m), 2.98 (2H, m), 2.50 (3H, s)  8.00 (1H, d), 7.30 (1H, d), 3.94 (3H, s), 3.15 (2H, m), 2.98 (2H, m), 2.50 (3H, s)
Nebenkomponente 8-Methylthiochromen-4-on-carbonsäuremethylester: 1H-NMR (CDCI3): δ (ppm): 8.4 (1H, d), 7.9 (1H, d), 7.8 (1H, d), 7.0 (1H, d), 4.0 (3H, s), 2.7 (3H, s) 5. 8-Methylthiochroman-4-on-7-carbonsaure Minor component 8-methylthiochromen-4-one-carboxylic acid methyl ester: 1 H-NMR (CDCI 3 ): δ (ppm): 8.4 (1H, d), 7.9 (1H, d), 7.8 (1H, d), 7.0 (1H, d), 4.0 (3H, s), 2.7 (3H, s) 5. 8-methylthiochroman-4-one-7-carboxylic acid
41.1 g (0.17 mol) 8-Methylthiochroman-4-on-7-carbonsauremethylester werden in einer Mischung aus 400 ml Wasser und Methanol mit 10.3 g (0.26 mol) NaOH bei Ruckflußtemperatur hydrolisiert. Anschließend wird das Methanol abdestilliert und der Ruckstand mit Wasser verdünnt und mit 2N Salzsaure angesäuert. Das Wertprodukt fallt aus und wird abgesaugt, mit Wasser gewaschen und getrocknet. 41.1 g (0.17 mol) of 8-methylthiochroman-4-one-7-carboxylic acid methyl ester are hydrolyzed in a mixture of 400 ml of water and methanol with 10.3 g (0.26 mol) of NaOH at the reflux temperature. The methanol is then distilled off and the residue is diluted with water and acidified with 2N hydrochloric acid. The valuable product precipitates and is filtered off, washed with water and dried.
Ausbeute: 34.4 g (89 % d.Th.) an 8-Methylthiochroman-4- on-7-carbonsaure, Schmelzpunkt: 243-246°C Yield: 34.4 g (89% of theory) of 8-methylthiochroman-4- on-7-carboxylic acid, melting point: 243-246 ° C
6. 8-Methyl-1,1-dioxothiochroman-4-on-7-carbonsaure 6. 8-methyl-1,1-dioxothiochroman-4-one-7-carboxylic acid
Figure imgf000043_0001
Figure imgf000043_0001
20 g (0.09 mol) 8-Methylthiochroman-4-on-7-carbonsaure werden in 100 ml Essigsaure gelost. Man gibt eine Spatelspitze Natriumwolframat hinzu. Bei 50°C werden dann 24.9 g 20 g (0.09 mol) of 8-methylthiochroman-4-one-7-carboxylic acid are dissolved in 100 ml of acetic acid. A spatula tip of sodium tungstate is added. At 50 ° C then 24.9 g
(0.22 mol) 30 %ige Wasserstoffperoxidlosung zugetropft. Es wird eine Stunde bei RT nachgeruhrt. Die Reaktionslosung wird danach auf Wasser gegeben, wobei ein Niederschlag entsteht der abgesaugt wird. Nach dem Waschen des Produktes mit Wasser wird dieses getrocknet.  (0.22 mol) 30% hydrogen peroxide solution was added dropwise. The mixture is stirred at RT for one hour. The reaction solution is then poured onto water, a precipitate being formed which is suctioned off. After washing the product with water, it is dried.
Ausbeute: 18.4 g (80 % d.Th.) 8-Methyl-1, 1-dioxothiochroman- 4-on-7-carbonsaure, Schmelzpunkt: 224-225°C 7. 4-Hydroxy-8-methylthiochroman-7-carbonsauremethylester Yield: 18.4 g (80% of theory) of 8-methyl-1, 1-dioxothiochroman-4-one-7-carboxylic acid, melting point: 224-225 ° C. 7. 4-Hydroxy-8-methylthiochroman-7-carboxylic acid, methyl ester
Figure imgf000043_0002
Figure imgf000043_0002
30 g (0.127 mol) 8-Methylthiochroman-4-on-7-carbonsauremethylester werden in einer Mischung aus 120 ml Methylenchlorid und 60 ml Methanol gelost und auf 0-5°C gekühlt.  30 g (0.127 mol) of 8-methylthiochroman-4-one-7-carboxylic acid methyl ester are dissolved in a mixture of 120 ml of methylene chloride and 60 ml of methanol and cooled to 0-5 ° C.
Portionsweise werden dann 2.4 g (0.064 mol) Natriumborhydrid hinzugefugt. Man laßt eine Stunde bei dieser Temperatur nach rühren. Zu der Reaktionslosung werden 200 ml 2N Salzsaure gegeben. Es bilden sich zwei Phasen. Die organische Phase wird abgetrennt getrocknet und das Losungsmittel abdestilliert. Das Rohprodukt wird ohne weitere Reinigung direkt weiter umgesetzt. 2.4 g (0.064 mol) of sodium borohydride are then added in portions. Let the temperature drop for an hour stir. 200 ml of 2N hydrochloric acid are added to the reaction solution. Two phases are formed. The organic phase is dried off and the solvent is distilled off. The raw product is directly implemented without further purification.
Ausbeute: 27.6 g (91 % d.Th.) an 4-Hydroxy-8-methylthiochroman-7-carbonsauremethylester 8. 4-Ethoxy-8-methylthiochroman-7-carbonsauremethylester Yield: 27.6 g (91% of theory) of 4-hydroxy-8-methylthiochroman-7-carboxylic acid, methyl ester 8. 4-Ethoxy-8-methylthiochroman-7-carboxylic acid, methyl ester
13.8 g (0.058 mol) 4-Hydroxy-8-methylthiochroman-7-carbonsauremethylester werden in 6O ml Ethanol unter Zusatz von 1 g Schwefelsaure 4 Stunden unter Siedetemperatur erhitzt. Danach wird das Solvens abdestilliert und der Ruckstand mit Wasser aufgenommen. Man extrahiert die wäßrige Phase mit Essigsaureethylester. Die organische Phase wird mit Natriumhydrogencarbonatlosung gewaschen, getrocknet und eingeengt. Das Produkt wird durch Chromatographie gereinigt. 13.8 g (0.058 mol) of 4-hydroxy-8-methylthiochroman-7-carboxylic acid methyl ester are heated in 6O ml of ethanol with the addition of 1 g of sulfuric acid for 4 hours at the boiling point. The solvent is then distilled off and the residue is taken up in water. The aqueous phase is extracted with ethyl acetate. The organic phase is washed with sodium bicarbonate solution, dried and concentrated. The product is purified by chromatography.
Ausbeute: 10.1 g (60 % d. Th.) an 4-Ethoxy-8-methylthiochroman-7-carbonsauremethylester 1H-NMR (CDCI3) δ (ppm): Yield: 10.1 g (60% of theory) of 4-ethoxy-8-methylthiochroman-7-carboxylic acid methyl ester 1 H-NMR (CDCI 3 ) δ (ppm):
7.44 (1H, d), 7.13 ( 1H , d), 4.40 (1H, m), 3.90 (3H, s), 3.60 (2H, m), 3.38 (1 H, dtr), 2.90 (1H, m), 2.50 (3H, s), 2.40 (1H, m ), 1.98 (1H, m) 1.10 (3H, tr)  7.44 (1H, d), 7.13 (1H, d), 4.40 (1H, m), 3.90 (3H, s), 3.60 (2H, m), 3.38 (1 H, dtr), 2.90 (1H, m), 2.50 (3H, s), 2.40 (1H, m), 1.98 (1H, m) 1.10 (3H, tr)
Die Umsetzung zu 4-Methoxy-8-methylthiochroman-4-on-7-carbonsauremethylester und 4-Isopropoxy-8-methylthiochroman-4-on-7-carbonsauremethylester erfolgt analog obiger Vorschrift, wobei im Fall von 4-Methoxy-8-methylthiochroman-4-on-7-carbonsauremethylester Ethanol durch Methanol und bei 4-Isopropoxy-8-methylthiochroman-4-on-7-carbonsauremethylester Ethanol durch Isopropanol ersetzt wurde. 9. 4-Ethoxy-8-methylthiochroman-7-carbonsaure The conversion to 4-methoxy-8-methylthiochroman-4-one-7-carboxylic acid methyl ester and 4-isopropoxy-8-methylthiochroman-4-one-7-carboxylic acid methyl ester is carried out analogously to the above procedure, in the case of 4-methoxy-8-methylthiochroman -4-one-7-carboxylic acid methyl ester ethanol was replaced by methanol and in the case of 4-isopropoxy-8-methylthiochroman-4-one-7-carboxylic acid methyl ester ethanol was replaced by isopropanol. 9. 4-ethoxy-8-methylthiochroman-7-carboxylic acid
2.1 g Natronlauge werden in 20 ml Wasser gelost. Bei RT tropft man 4-Ethoxy-8-methylthiochroman-4-on-7-carbonsauremethylester in 20 ml Methanol gelost zu. Man erhitzt 2 Stunden unter Ruckfluß. Anschließend destilliert man das Losungsmittel ab und gibt den Rückstand auf 2N Salzsaure. Die wäßrige Phase wird mit Methylenchlorid extrahiert. Die organische Phase wird getrocknet und eingeengt. Ausbeute: 9.3 g (100 % d.Th.) an 4-Ethoxy-8-methylthiochroman-7-carbonsäure, Schmelzpunkt: 89-98°C Die Hydrolyse der entsprechenden Ester zu 4-Methoxy-8-methylthiochroman-7-carbonsaure und 4-Isopropoxy-8-methylthiochroman-7-carbonsaure verlauft analog. Gleiches gilt für die Verseifung der entsprechenden unten aufgeführten Benzofb] thiophenderivate. 2.1 g of sodium hydroxide solution are dissolved in 20 ml of water. At RT, 4-ethoxy-8-methylthiochroman-4-one-7-carboxylic acid methyl ester is added dropwise in 20 ml of methanol. The mixture is heated under reflux for 2 hours. The solvent is then distilled off and the residue is poured into 2N hydrochloric acid. The aqueous phase is extracted with methylene chloride. The organic phase is dried and concentrated. Yield: 9.3 g (100% of theory) of 4-ethoxy-8-methylthiochroman-7-carboxylic acid, melting point: 89-98 ° C The hydrolysis of the corresponding esters to 4-methoxy-8-methylthiochroman-7-carboxylic acid and 4-isopropoxy-8-methylthiochroman-7-carboxylic acid proceeds analogously. The same applies to the saponification of the corresponding benzofb] thiophene derivatives listed below.
10. 8-Methyl-4-ethoxy-1,1-dioxothiochroman-7-carbonsaure 10. 8-methyl-4-ethoxy-1,1-dioxothiochroman-7-carboxylic acid
8.4 g (0.033 mol) 4-Ethoxy-8-methylthiochroman-7-carbonsaure werden in 60 ml Essigsaure vorgelegt. Man gibt eine Spatelspitze Natriumwolframat hinzu. Bei 50°C werden langsam 7.9 g (0.07 mol) 30 %ige Wasserstoffperoxidlosung zugetropft. Man rührt 2 Stunden nach. Der Reaktionsansatz wird dann in Wasser gegossen und die wäßrige Phase mit Essigsaureethylester extrahiert. Die organische Phase wird mit Bisulfitlosung gewaschen, dann getrocknet und eingeengt. 8.4 g (0.033 mol) of 4-ethoxy-8-methylthiochroman-7-carboxylic acid are placed in 60 ml of acetic acid. A spatula tip of sodium tungstate is added. At 50 ° C, 7.9 g (0.07 mol) of 30% hydrogen peroxide solution are slowly added dropwise. Stir for 2 hours. The reaction mixture is then poured into water and the aqueous phase is extracted with ethyl acetate. The organic phase is washed with bisulfite solution, then dried and concentrated.
Ausbeute: 9.5 g (100 % d.Th.) an 8-Methyl-4-ethoxy-1,1dioxothiochroman-7-carbonsaure, Schmelzpunkt: 150°C 11. 8-Methylthiochroman-4-on-7-carbonsaure-O-ethyloxim Yield: 9.5 g (100% of theory) of 8-methyl-4-ethoxy-1,1-dioxothiochroman-7-carboxylic acid, melting point: 150 ° C. 11. 8-methylthiochroman-4-one-7-carboxylic acid-O- ethyloxime
Figure imgf000045_0001
Figure imgf000045_0001
In 20 ml Methanol werden 0.88 g (9 mmol) Ethylhydroxylamin vorgelegt. Man gibt dann 0.62 g (4.5 mmol) Kaliumcarbonat hinzu. Anschließend werden 2.0 g (9 mmol) 8-Methylthiochroman-4-on-7-carbonsaure zugegeben. Die Reaktion wird 10 Tage bei RT gerührt. Aufgearbeitet wird durch Zugabe von Wasser und 2N HCl. Der entstehende Niederschlag wird abgesaugt und getrocknet.  0.88 g (9 mmol) of ethylhydroxylamine are placed in 20 ml of methanol. Then 0.62 g (4.5 mmol) of potassium carbonate is added. Then 2.0 g (9 mmol) of 8-methylthiochroman-4-one-7-carboxylic acid are added. The reaction is stirred for 10 days at RT. It is worked up by adding water and 2N HCl. The resulting precipitate is filtered off and dried.
Ausbeute: 2.2 g (92 % d.Th.) an 8-Methylthiochroman-4- on-7-carbonsaure-O-ethyloxim; Schmelzpunkt: 166°C 12. 8-Methyl-1,1-dioxothiochroman-4-on-7-carbonsaure-O-ethyloxim Yield: 2.2 g (92% of theory) of 8-methylthiochroman-4- on-7-carboxylic acid-O-ethyloxime; Melting point: 166 ° C 12. 8-methyl-1,1-dioxothiochroman-4-one-7-carboxylic acid-O-ethyloxime
3.0 g (0.011 mol) 8-Methylthiochroman-4-on-7-carbonsaure-O- ethyloxim werden zusammen mit einer Spatelspitze Natriumwolframat in 30 ml Essigsaure vorgelegt. Bei 50°C tropft man 2.8 g (0.024 mol) 30 %ige Wasserstoffperoxidlosung zu. Nach einstundigem Ruhren wird das Reaktionsgemisch in Eiswasser gegossen, der entstehende Niederschlag wird abgesaugt. Das Produkt wird mit Wasser gewaschen und getrocknet. 3.0 g (0.011 mol) of 8-methylthiochroman-4-one-7-carboxylic acid-O-ethyloxime are placed together with a spatula tip of sodium tungstate in 30 ml of acetic acid. 2.8 g (0.024 mol) of 30% hydrogen peroxide solution are added dropwise at 50 ° C. After stirring for one hour, the reaction mixture is poured into ice water poured, the resulting precipitate is suctioned off. The product is washed with water and dried.
Ausbeute: 2.5 g (74 % d.Th.) 8-Methyl-1,1-dioxothiochroman- 4-on-7-carbonsaure-O-ethyloxim, Schmelzpunkt 198°C Yield: 2.5 g (74% of theory) of 8-methyl-1,1-dioxothiochroman-4-one-7-carboxylic acid-O-ethyloxime, melting point 198 ° C.
13. 8-Methyl-1-oxothiochroman-4-on-7-carbonsaure 13. 8-methyl-1-oxothiochroman-4-one-7-carboxylic acid
7.0 g (31.5 mmol) 8-Methylthiochroman-4-on-7-carbonsaure werden zusammen mit einer Spatelspitze Natriumwolframat in7.0 g (31.5 mmol) of 8-methylthiochroman-4-one-7-carboxylic acid are mixed in with a spatula tip of sodium tungstate
70 ml Essigsaure vorgelegt. Bei 50°C werden 3.6 g (31.5 mmol) 30 %ige Wasserstoffperoxidlosung zugetropft. Man rührt 70 ml of acetic acid submitted. 3.6 g (31.5 mmol) of 30% strength hydrogen peroxide solution are added dropwise at 50 ° C. You stir
3 Stunden nach. Danach wird die Reaktionslösung in Wasser eingerührt. Man extrahiert mit Essigsaureethylester das Produkt. Die organische Phase wird getrocknet und das  3 hours after. The reaction solution is then stirred into water. The product is extracted with ethyl acetate. The organic phase is dried and that
Losungsmittel entfernt. Das Produkt wird durch Chromatographie gereinigt.  Solvent removed. The product is purified by chromatography.
Ausbeute: 5.4 g (72 % d. Th.) 8-Methyl-1-oxothiochroman- 4-on-7-carbonsäure 1H-NMR (d6-DMSO), δ (ppm): 8.0 (2H, m), 3.5 (3H, m), 2.8 (1H, m), 2.7 (3H,s) Yield: 5.4 g (72% of theory) of 8-methyl-1-oxothiochroman-4-one-7-carboxylic acid 1 H-NMR (d6-DMSO), δ (ppm): 8.0 (2H, m), 3.5 (3H, m), 2.8 (1H, m), 2.7 (3H, s)
14. 3-Thioessigsaure-2-methylbenzoesauremethylester 14. 3-Thioacetic acid-2-methylbenzoic acid methyl ester
Figure imgf000046_0001
Figure imgf000046_0001
Zu 1.6 g (0.068 mol) NaH in 40 ml DMF werden 12.4 g  12.4 g become 1.6 g (0.068 mol) NaH in 40 ml DMF
(0.068 mol) 3-Thio-2-methylbenzoesauremethylester in 80 ml DMF getropft. Es wird 60 min bei RT gerührt. Danach gibt man 8 g (0.068 mol) Chloressigsaure zu. Es wird 4 Stunden bei RT gerührt.  (0.068 mol) of 3-thio-2-methylbenzoic acid methyl ester in 80 ml of DMF. The mixture is stirred at RT for 60 min. Then 8 g (0.068 mol) of chloroacetic acid are added. The mixture is stirred at RT for 4 hours.
Aufgearbeitet wird durch Einrühren des Reaktionsgemisches in salzsaures Eiswasser.  It is worked up by stirring the reaction mixture into hydrochloric ice water.
Der entstehende Niederschlag wird abgesaugt, mit Wasser gewaschen und getrocknet. The resulting precipitate is filtered off, washed with water and dried.
Ausbeute: 14.6 g (89 % d.Th.) 3-Thioessigsäure-2- methylbenzoesauremethylester 1H-NMR (d6-DMSO) δ (ppm): Yield: 14.6 g (89% of theory) of methyl 3-thioacetic acid-2-methylbenzoate 1 H-NMR (d6-DMSO) δ (ppm):
7.55 (1H d), 7.45 (1H, d), 7.21 (1H, tr), 3.82 (2H,s), 2.50 (3H,s) 15. 7-Methyl-benzo[b]thiophen-3[2H]-on-6-carbonsauremethylester 7.55 (1H d), 7.45 (1H, d), 7.21 (1H, tr), 3.82 (2H, s), 2.50 (3H, s) 15. 7-Methyl-benzo [b] thiophene-3 [2H] -one-6-carboxylic acid methyl ester
Figure imgf000047_0001
Figure imgf000047_0001
14.3 g (0.06 mmol) 3-Thioessigsaure-2-methylbenzoesaure werden in 300 ml Methylenchlorid gelost. 13.1 g (0.11 mmol) Thionylchlorid werden zugetropft. Man erhitzt eine Stunde unter Ruckfluß. Danach wird das Losungsmittel sowie überschüssiges Thionylchlorid abdestilliert. Der Ruckstand wird in 100 ml Methylenchlorid aufgenommen und mit 31.8 g (0.24 mmol) Aluminiumtrichlorid versetzt. Die Reaktion wird 1 Stunde bei RT gerührt. Anschließend gibt man das Gemisch auf Eiswasser und trennt die organische Phase ab. Nach dem Waschen und Trocknen der organischen Phase wird das Losungsmittel entfernt. Das Produkt wird ohne Reinigung weiter umgesetzt.  14.3 g (0.06 mmol) of 3-thioacetic acid-2-methylbenzoic acid are dissolved in 300 ml of methylene chloride. 13.1 g (0.11 mmol) of thionyl chloride are added dropwise. The mixture is heated under reflux for one hour. The solvent and excess thionyl chloride are then distilled off. The residue is taken up in 100 ml of methylene chloride and 31.8 g (0.24 mmol) of aluminum trichloride are added. The reaction is stirred at RT for 1 hour. The mixture is then poured onto ice water and the organic phase is separated off. After washing and drying the organic phase, the solvent is removed. The product is implemented without cleaning.
Ausbeute: 12.9 g (97 % d.Th.) 7-Methyl-benzo[b]thiophen- 3[2H]-on-6-carbonsauremethylester 1H-NMR (CDCl3), δ (ppm): 7.65 (2H, m), 3.93 (3H, s), 3.88 (2H, s), 2.50 (3H, s) Yield: 12.9 g (97% of theory) of 7-methyl-benzo [b] thiophene-3 [2H] -one-6-carboxylic acid methyl ester 1 H-NMR (CDCl 3 ), δ (ppm): 7.65 (2H, m), 3.93 (3H, s), 3.88 (2H, s), 2.50 (3H, s)
16. 7-Methyl-3-hydroxybenzo[b]thiophen-[2H]-6-carbonsauremethylester 16. 7-Methyl-3-hydroxybenzo [b] thiophene- [2H] -6-carboxylic acid methyl ester
Figure imgf000047_0002
Figure imgf000047_0002
12.8 g (0.058 mol) 7-Methyl-benzo[b]thiophen-3[2H]-on-6- carbonsauremethylester werden in 120 ml Methylenchlorid und 60 ml Methanol gelost und auf 0°C gekühlt. 1.1 g (0.029 mol) Natriumborhydrid wird portionsweise zugegeben. Es wird 3 Stunden gerührt. Durch Zugabe von Wasser wird die Reaktion abgebrochen. Die Phasen werden getrennt und die wäßrige Phase wird mit Methylenchlorid extrahiert. Die vereinigten organischen Phasen werden getrocknet. Das Losungsmittel wird abdestilliert. Das Rohprodukt wird weiter umgesetzt.  12.8 g (0.058 mol) of 7-methyl-benzo [b] thiophene-3 [2H] -one-6-carboxylic acid methyl ester are dissolved in 120 ml of methylene chloride and 60 ml of methanol and cooled to 0 ° C. 1.1 g (0.029 mol) of sodium borohydride is added in portions. It is stirred for 3 hours. The reaction is stopped by adding water. The phases are separated and the aqueous phase is extracted with methylene chloride. The combined organic phases are dried. The solvent is distilled off. The raw product will continue to be implemented.
Ausbeute: 13.2 g (100 % d.Th.) 7-Methyl-3-hydroxybenzo[b]thiophen-[2H]-6-carbonsauremethylester 1H-NMR (CDCI3), δ (ppm): 7.6 (2H, m), 5.3 (1H, m), 3.9 (3H, s), 3.7 (1H, m), 3.3 (1H, m), 2.4 (3H, s) 17. 7-Methyl-3-methoxybenzo[b]thiophen-[2H]-6-carbonsauremethylester Yield: 13.2 g (100% of theory) of 7-methyl-3-hydroxybenzo [b] thiophene- [2H] -6-carboxylic acid methyl ester 1 H-NMR (CDCI 3 ), δ (ppm): 7.6 (2H, m ), 5.3 (1H, m), 3.9 (3H, s), 3.7 (1H, m), 3.3 (1H, m), 2.4 (3H, s) 17. 7-Methyl-3-methoxybenzo [b] thiophene- [2H] -6-carboxylic acid methyl ester
2.4 g (0.059 mol) NaH wird in 50 ml DMF gelost. 13.2 g 2.4 g (0.059 mol) NaH is dissolved in 50 ml DMF. 13.2 g
7-Methyl-3-hydroxybenzo[b]thiophen-[2H]-6-carbonsauremethylester gelost in 50 ml werden zugetropft. Anschließend wird 2 Stunden bei RT gerührt. Danach werden 8.4 g (0.059 mol) Iodmethan zugefugt und weitere 2 Stunden gerührt.  7-Methyl-3-hydroxybenzo [b] thiophene- [2H] -6-carboxylic acid methyl ester dissolved in 50 ml are added dropwise. The mixture is then stirred at RT for 2 hours. Then 8.4 g (0.059 mol) of iodomethane are added and the mixture is stirred for a further 2 hours.
Die Reaktionslosung wird auf Eiswasser gegeben und mit Essigsaureethylester extrahiert. Die organische Phase wird getrocknet und anschließend eingeengt. Das Produkt wird durch Chromatographie gereinigt.  The reaction solution is poured onto ice water and extracted with ethyl acetate. The organic phase is dried and then concentrated. The product is purified by chromatography.
Ausbeute: 3.5 g (25 % d. Th.) 7-Methyl-3-methoxybenzo[b]thiophen-[2H]-6-carbonsauremethylester 1H-NMR (CDCl3), δ (ppm): 7.60 (1H, d), 7.20 (1H, d), 5.04 (1H, m), 3.90 (3H, s),3.56 (1H, m), 3.40 (3H, s), 3.38 (1H, m), 2.50 (3H, s) Yield: 3.5 g (25% of theory) of 7-methyl-3-methoxybenzo [b] thiophene- [2H] -6-carboxylic acid methyl ester 1 H-NMR (CDCl3), δ (ppm): 7.60 (1H, d) , 7.20 (1H, d), 5.04 (1H, m), 3.90 (3H, s), 3.56 (1H, m), 3.40 (3H, s), 3.38 (1H, m), 2.50 (3H, s)
Analog der oben beschriebenen Verseifung der Thiochromanonester erhalt man auch die entsprechenden Benzothiophensauren. Analogously to the saponification of the thiochromanone esters described above, the corresponding benzothiophene acids are also obtained.
In analoger Weise werden die in den nachfolgenden Tabellen aufgeführten Verbindungen erhalten: The compounds listed in the tables below are obtained in an analogous manner:
Figure imgf000048_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0003
Figure imgf000049_0001
Figure imgf000050_0003
Herstellung der Endprodukte 1. Darstellung von Verbindung 1.92  Production of the end products 1. Preparation of compound 1.92
Figure imgf000050_0001
Figure imgf000050_0002
Figure imgf000050_0001
Figure imgf000050_0002
0.3 g (0.0125 mol) Magnesiumspane werden zusammen mit 1.13 g (0.0104 mol) Cyanomethylcyclopropylketon A3 in 40 ml Methanol gelost. 1 ml Tetrachlorkohlenstoff wird zugetropft. Man rührt 2 h bei RT und destilliert anschließend das Losungsmittel ab. 0.3 g (0.0125 mol) of magnesium shavings are dissolved together with 1.13 g (0.0104 mol) of cyanomethylcyclopropyl ketone A3 in 40 ml of methanol. 1 ml carbon tetrachloride is added dropwise. The mixture is stirred at RT for 2 h and then the solvent is distilled off.
Der Ruckstand wird dann in 20 ml Acetonitril aufgenommen und mit 3.0 g (0.0104 mol) 4-Methoxy-8-methyl-1,1-dioxothiochromancarbonsaurechlorid in 20 ml Acetonitril versetzt. Man rührt mehrere Stunden bei RT. Danach wird die Reaktionslosung in 2N HCl eingerührt und die wäßrige Phase mit Essigsaureethylester extrahiert. Das Produkt wird aus Pentan/Ether kristallisiert. The residue is then taken up in 20 ml of acetonitrile and mixed with 3.0 g (0.0104 mol) of 4-methoxy-8-methyl-1,1-dioxothiochromanecarboxylic acid chloride in 20 ml of acetonitrile. The mixture is stirred at RT for several hours. The reaction solution is then stirred into 2N HCl and the aqueous phase is extracted with ethyl acetate. The product is crystallized from pentane / ether.
Ausbeute: 0.5 g (1.38 mmol, 13 %) Schmelzp.: 177°C. Yield: 0.5 g (1.38 mmol, 13%) Melting point: 177 ° C.
Die Verbindungen I und deren landwirtschaftlich brauchbaren Salze eignen sich - sowohl als Isomerengemische als auch in Form der reinen Isomeren - als Herbizide. Die I enthaltenden herbiziden Mittel bekämpfen Pflanzenwuchs auf Nichtkulturflächen sehr gut, besonders bei hohen Aufwandmengen. In Kulturen wie Weizen, Reis, Mais, Soja und Baumwolle wirken sie gegen Unkräuter und Schadgraser, ohne die Kulturpflanzen nennenswert zu schadigen. Dieser Effekt tritt vor allem bei niedrigen Aufwandmengen auf. The compounds 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 containing I control vegetation very well on non-cultivated areas, particularly 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 especially at low application rates.
In Abhängigkeit von der jeweiligen Applikationsmethode können die Verbindungen I bzw. sie enthaltende Mittel noch in einer weiteren Zahl von Kulturpflanzen zur Beseitigung unerwünschter Pflanzen eingesetzt werden. In Betracht kommen beispielsweise folgende Kulturen: Depending on the particular application method, the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants. The following crops are considered, for example:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus Allium cepa, pineapple comosus, Arachis hypogaea, asparagus
officinalis, Beta vulgaris spp. altissima, Beta vulagris spp. rapa, Brassica napus var. napus, Brassica napus var. officinalis, Beta vulgaris spp. altissima, Beta vulagris spp. 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 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,guineensis, Fragaria vesca, glycine max. Gossypium hirsutum,
(Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp., Nicotiana tabacum (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Musushotppa, Manus Medici spp ., Nicotiana tabacum
(N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgäre), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.  (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, sorghum bicolor (see vulgar), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.
Darüber hinaus können die Verbindungen I auch in Kulturen, die durch Züchtung einschließlich gentechnischer Methoden gegen die Wirkung von Herbiziden tolerant sind, verwandt werden. In addition, the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
Die Applikation der herbiziden Mittel bzw. der Wirkstoffe kann im Vorauflauf- oder im Nachauflaufverfahren erfolgen. Sind die Wirkstoffe für gewisse Kulturpflanzen weniger vertraglich, so können Ausbringungstechniken angewandt werden, bei welchen die herbiziden Mittel mit Hilfe der Spritzgerate so gespritzt werden, daß die Blatter der empfindlichen Kulturpflanzen nach Möglichkeit nicht getroffen werden, wahrend die Wirkstoffe auf die Blatter darunter wachsender unerwünschter Pflanzen oder die unbedeckte Bodenflache gelangen (post-directed, lay-by). The herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less contractual for certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers, that the leaves of the sensitive crops are not hit, if possible, while the active ingredients reach the leaves of unwanted plants growing underneath or the uncovered area of the soil (post-directed, lay-by).
Die Verbindungen I bzw. die sie enthaltenden herbiziden Mittel können beispielsweise in Form von direkt verspruhbaren wäßrigen Losungen, Pulvern, Suspensionen, auch hochprozentigen wäßrigen, öligen oder sonstigen Suspensionen oder Dispersionen, Emulsionen, Öldispersionen, Pasten, Staubemitteln, Streumitteln oder Granulaten durch Versprühen, Vernebeln, Verstauben, Verstreuen oder Gießen angewendet werden. Die Anwendungsformen richten sich nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfindungsgemaßen Wirkstoffe gewahrleisten. The compounds I or the herbicidal compositions comprising them can be sprayed or atomized, for example in the form of directly sprayable aqueous solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusting agents, scattering agents or granules , Dusting, scattering or pouring. 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.
Als inerte Zusatzstoffe kommen im Wesentlichen in Betracht: The following are essentially considered as inert additives:
Mineralolfrakt ionen von mittlerem bis hohem Siedepunkt, wie Kerosin oder Dieselöl, ferner Kohlenteerole sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Paraffin, Tetrahydronaphthalin, alkylierte Naphthaline oder deren Derivate, alkylierte Benzole oder deren Derivate, Alkohole wie Methanol, Ethanol, Propanol, Medium to high boiling point mineral oil fractions such as kerosene or diesel oil, also coal tarols and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol,
Butanol, Cyclohexanol, Ketone wie Cyclohexanon oder stark polare Losungsmittel, z.B. Amine wie N-Methylpyrrolidon oder Wasser. Butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, e.g. Amines such as N-methylpyrrolidone or water.
Wäßrige Anwendungsformen können aus Emulsionskonzentraten, Suspensionen, Pasten, netzbaren Pulvern oder wasserdispergierbaren Granulaten durch Zusatz von Wasser bereitet werden. Zur HerStellung von Emulsionen, Pasten oder Öldispersionen können die Substrate als solche oder in einem Öl oder Losungsmittel gelost, mittels Netz-, Haft-, Dispergier- oder Emulgiermittel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz, Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Losungsmittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind. 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 substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
Als oberflächenaktive Stoffe kommen die Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsauren, z.B. Lignin-, The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin-,
Phenol-, Naphthalin- und Dibutylnaphthalinsulfonsaure, sowie von Fettsauren, Alkyl- und Alkylarylsulfonaten, Alkyl-, Lauryletherund Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Heptaund Octadecanolen sowie von Fettalkoholglykolether, Kondensationsprodukte von sulfoniertem Naphthalin und seiner Derivate mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsauren mit Phenol und Formaldehyd, Polyoxyethylenoctylphenolether, ethoxyliertes Isooctyl-, Octyl- oder Nonylphenol, Alkylphenyl-, Tributylphenylpolyglykolether, Alkylarylpolyetheralkohole, Isotridecylalkohol, Fettalkoholethylenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkylether oder Polyoxypropylenalkylether, Laurylalkoholpolyglykoletheracetat, Sorbitester, Lignin-Sulfitablaugen oder Methylcellulose in Betracht. Phenolic, 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 fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives and formaldehyde and its derivatives with formaldehyde of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or Nonylphenol, alkylphenyl, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin sulfite waste liquor or methyl lignin.
Pulver, Streu- und Staubemittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Tragerstoff hergestellt werden. Powders, materials for spreading and dusting can be produced by mixing or grinding the active substances together with a solid carrier.
Granulate, z.B. Umhullungs-, Impragnierungs- und Homogengranulate können durch Bindung der Wirkstoffe an feste Tragerstoffe hergestellt werden. Feste Tragerstoffe sind Mineralerden wie Kieselsauren, Kieselgele, Silikate, Talkum, Kaolin, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver oder andere feste Tragerstoffe. Granules, e.g. Coated granules, impregnated granules and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carrier materials are mineral earths such as silica, 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, Urea and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
Die Konzentrationen der Wirkstoffe I in den anwendungsfertigen Zubereitungen können in weiten Bereichen variiert werden. Die Formulierungen enthalten im allgemeinen 0,001 bis 98 Gew.-%, vorzugsweise 0,01 bis 95 Gew.-%, Wirkstoff. Die Wirkstoffe werden dabei in einer Reinheit von 90 % bis 100 %, vorzugsweise 95 % bis 100 % (nach NMR-Spektrum) eingesetzt. Die erfindungsgemaßen Verbindungen I können beispielsweise wie folgt formuliert werden: The concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range. The formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of active ingredient. The active ingredients are used in a purity of 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 Gewichtsteile der Verbindung Nr. 1.92 werden in einer I 20 parts by weight of compound no. 1.92 are in one
Mischung gelost, die aus 80 Gewichtsteilen alkyliertem  Blended mixture that alkylated from 80 parts by weight
Benzol, 10 Gewichtsteilen des Anlagerungsproduktes von  Benzene, 10 parts by weight of the adduct of
8 bis 10 Mol Ethylenoxid an 1 Mol Ölsaure-N-monoethanolamid, 5 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsaure und 5 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusol besteht. Durch Ausgießen und feines Verteilen der Losung in 100000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.-% des Wirkstoffs enthalt.  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 with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
II 20 Gewichtsteile der Verbindung Nr. 1.92 werden in einer II 20 parts by weight of compound no. 1.92 are in one
Mischung gelost, die aus 40 Gewichtsteilen Cyclohexanon, Dissolved mixture consisting of 40 parts by weight of cyclohexanone,
30 Gewichtsteilen Isobutanol, 20 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Isooctylphenol und 10 Gewichts teilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusol besteht. Durch Eingießen und feines Verteilen der Losung in 100000 Gewichtsteilen Wasser erhalt man eine wäßrige Dispersion, die 0,02 Gew.-% des Wirkstoffs enthalt. 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of isooctylphenol and 10 parts by weight divide the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.
III 20 Gewichtsteile des Wirkstoffs Nr. 1.92 werden in einer III 20 parts by weight of active ingredient no. 1.92 are in a
Mischung gelost, die aus 25 Gewichtsteilen Cyclohexanon, 65 Gewichtsteilen einer Mineralolfraktion vom Siedepunkt 210 bis 280°C und 10 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusol besteht. Durch Eingießen und feines Verteilen der Losung in 100000 Gewichtsteilen Wasser erhalt man eine wäßrige Dispersion, die 0,02 Gew.-% des Wirkstoffs enthalt. IV 20 Gewichtsteile des Wirkstoffs Nr. 1.92 werden mit  Dissolved mixture, which consists of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of ricinusol. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient. IV 20 parts by weight of active ingredient No. 1.92 are with
3 Gewichtsteilen des Natriumsalzes der Dusobutylnaphthalinsulfonsaure, 17 Gewichtsteilen des Natriumsalzes einer  3 parts by weight of the sodium salt of dusobutylnaphthalenesulfonic acid, 17 parts by weight of the sodium salt one
Ligninsulfonsaure aus einer Sulfit-Ablauge und 60 Gewichtsteilen pulverformigem Kieselsauregel gut vermischt und in einer Hammermuhle vermählen. Durch feines Verteilen der Mischung in 20000 Gewichtsteilen Wasser enthalt man eine Spritzbruhe, die 0,1 Gew.-% des Wirkstoffs enthalt.  Lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel mixed well and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray broth is obtained which contains 0.1% by weight of the active ingredient.
V 3 Gewichtsteile des Wirkstoffs Nr. 1.92 werden mit V 3 parts by weight of active ingredient No. 1.92 are with
97 Gewichtsteilen feinteiligem Kaolin vermischt. Man erhalt auf diese Weise ein Staubemittel, das 3 Gew -% des Wirkstoffs enthalt.  97 parts by weight of finely divided kaolin mixed. In this way, a dusting agent is obtained which contains 3% by weight of the active ingredient.
VI 20 Gewichtsteile des Wirkstoffs Nr. 1.92 werden mit VI 20 parts by weight of active ingredient No. 1.92 are with
2 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsaure, 8 Gewichtsteilen Fettalkohol-polyglykolether, 2 Gewichtsteilen Natriumsalz eines Phenol-Harnstoff-Formaldehyd-Kondensates und 68 Gewichtsteilen eines paraffinischen Mineralöls innig vermischt. Man erhalt eine stabile ölige Dispersion.  2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
VII 1 Gewichtsteil der Verbindung Nr. 1.92 wird in einer Mischung gelost, die aus 70 Gewichtsteilen Cyclohexanon, 20 Gewichtsteilen ethoxyliertem Isooctylphenol und 10 Gewichtsteilen ethoxyliertem Rizinusöl besteht. Man erhalt ein stabiles Emulsionskonzentrat. VII 1 part by weight of compound no. 1.92 is dissolved in a mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained.
VIII 1 Gewichtsteil der Verbindung Nr. 1.92 wird in einer VIII 1 part by weight of compound no. 1.92 is in a
Mischung gelost, die aus 80 Gewichtsteilen Cyclohexanon und 20 Gewichtsteilen Emulphor EL besteht. Man erhalt ein stabiles Emulsionskonzentrat. Zur Verbreiterung des Wirkungsspektrums und zur Erzielung synergistischer Effekte können die Phenyldiketonderivate I mit zahlreichen Vertretern anderer herbizider oder wachstumsregulierender Wirkstoffgruppen gemischt und gemeinsam ausgebracht werden. Dissolved mixture, which consists of 80 parts by weight of cyclohexanone and 20 parts by weight of Emulphor EL. A stable emulsion concentrate is obtained. In order to broaden the spectrum of activity and to achieve synergistic effects, the phenyldiketone derivatives I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
Beispielsweise kommen als Mischungspartner 1,2,4-Thiadiazole, 1,3,4-Thiadiazole, Amide, Aminophosphorsaure und deren Derivate, Aminotriazole, Anilide, (Het)-Aryloxyalkansaure und deren For example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and their derivatives, aminotriazoles, anilides, (het) -aryloxyalkanoic acid and their come as mixing partners
Derivate, Benzoesaure und deren Derivate, Benzothiadiazinone, Triketone, Hetaryl-Aryl-Ketone, Benzylisoxazolidinone, MetaCF3-phenylderivate, Carbamate, Chinolinsaure und deren Derivate, Chloracetanilide, Cyclohexandione, Diazine, Dichlorpropionsaure und deren Derivate, Dihydrobenzofurane, Dihydrofuran-3-one, Dinitroaniline, Dinitrophenole, Diphenylether, Dipyridyle, Derivatives, benzoic acid and its derivatives, benzothiadiazinones, triketones, hetaryl aryl ketones, benzylisoxazolidinones, metaCF 3 phenyl derivatives, carbamates, quinoline acids and their derivatives, chloroacetanilides, cyclohexanediones, diazines, dichloropropane dihydrobenzofluorodehydroane, and 3 Dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls,
Halogencarbonsauren und deren Derivate, Harnstoffe, N-Phenyluracile, Imidazole, Imidazolinone, Isoindoldione, Oxadiazole, Oxirane, Phenole, Aryloxy- oder Heteroaryloxyphenoxypropionsaureester, Phenylessigsaure und deren Derivate, Phenylpropionsaure und deren Derivate, Pyrazole, Phenylpyrazole, Pyridazine, Pyridincarbonsaure und deren Derivate, Pyrimidylether, Sulfonamide, Sulfonylharnstoffe, Triazine, Triazinone, Triazolinone, Triazolcarboxamide, Uracile und andere in Betracht. Halogenated carboxylic acids and their derivatives, ureas, N-phenyluracils, imidazoles, imidazolinones, isoindoldiones, oxadiazoles, oxiranes, phenols, aryloxy- or heteroaryloxyphenoxypropionic acid esters, phenylacetic acid and their derivatives, phenylpropionic acid and their derivatives, pyrazole, pyrazole, pyrazidene, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, pyrazole, and pyridine, pyrazole, pyrazole, pyrazole, and pyrazole, pyrazole, pyrazole, and pyrazoles , Sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides, uraciles and others.
Außerdem kann es von Nutzen sein, die Verbindungen I allein oder in Kombination mit anderen herbiziden auch noch mit weiteren Pflanzenschutzmitteln gemischt, gemeinsam auszubringen, beispielsweise mit Mitteln zur Bekämpfung von Schädlingen oder phytopathogenen Pilzen bzw. Bakterien. Von Interesse ist ferner die Mischbarkeit mit Mineralsalzlösungen, welche zur Behebung von Ernahrungs- und Spurenelementmangeln eingesetzt werden. Es können auch nichtphytotoxische Öle und Ölkonzentrate zugesetzt werden. It may also be useful to apply the compounds I alone or in combination with other herbicides, mixed with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.
Die Aufwandmengen an Wirkstoff betragen je nach Bekampfungsziel, Jahreszeit, Zielpflanzen und Wachstumsstadium 0.001 bis 3.0, vorzugsweise 0.01 bis 1.0 kg/ha aktive Substanz (a. S.) The application rates of active ingredient are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance depending on the aim of the control, the season, the target plants and the growth stage (a.s.)
AnwendungsbeIspIele APPLICATION EXAMPLES
Die herbizide Wirkung der Phenyldiketonderivate der Formel I ließ sich durch Gewachshausversuche zeigen: The herbicidal activity of the phenyldiketone derivatives of the formula I was demonstrated by greenhouse tests:
Als Kulturgefaße dienten Plastikblumentopfe mit lehmigem Sand mit etwa 3,0 % Humus als Substrat. Die Samen der Testpflanzen wurden nach Arten getrennt eingesät. Bei Vorauflaufbehandlung wurden die in Wasser suspendierten oder emulgierten Wirkstoffe direkt nach Einsaat mittels fein verteilender Düsen aufgebracht. Die Gefäße wurden leicht beregnet, um Keimung und Wachstum zu fordern, und anschließend mit durchsichtigen Plastikhauben abgedeckt, bis die Pflanzen angewachsen waren. Diese Abdeckung bewirkt ein gleichmaßiges Keimen der Testpflanzen, sofern dies nicht durch die Wirkstoffe beeinträchtigt wurde. Plastic flower pots with loamy sand with about 3.0% humus as a substrate served as culture vessels. The seeds of the test plants were sown separately according to species. In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles. The vessels were lightly sprinkled, to encourage germination and growth, and then covered with clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.
Zum Zweck der Nachauflaufbehandlung werden die Testpflanzen je nach Wuchsform erst bis zu einer Wuchshohe von 3 bis 15 cm angezogen und erst dann mit den in Wasser suspendierten oder emulgierten Wirkstoffen behandelt. Die Testpflanzen werden dafür entweder direkt gesät und in den gleichen Gefäßen aufgezogen oder sie werden erst als Keimpflanzen getrennt angezogen und einige Tage vor der Behandlung in die Versuchsgefaße verpflanzt. Die Aufwandmenge für die Nachauflaufbehandlung betrug 0.5 bzw. For the purpose of post-emergence treatment, the test plants, depending on the growth habit, are 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 are either sown directly and grown in the same containers, or they are first grown separately as seedlings and transplanted into the test containers a few days before the treatment. The application rate for post-emergence treatment was 0.5 or
0.25 kg/ha a.S. 0.25 kg / ha a.S.
Die Pflanzen wurden artenspezifisch bei Temperaturen von 10 - 25°C bzw. 20 - 35°C gehalten. Die Versuchsperiode erstreckte sich über 2 bis 4 Wochen. Wahrend dieser Zeit wurden die Pflanzen gepflegt, und ihre Reaktion auf die einzelnen Behandlungen wurde ausgewertet. The plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species. The trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to the individual treatments was evaluated.
Bewertet wurde nach einer Skala von 0 bis 100. Dabei bedeutet 100 kein Aufgang der Pflanzen bzw. völlige Zerstörung zumindest der oberirdischen Teile und 0 keine Schädigung oder normaler It was rated 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
Wachstumsverlauf. Growth course.
Die in den Gewachshausversuchen verwendeten Pflanzen setzten sich aus folgenden Arten zusammen: The plants used in the greenhouse experiments are composed of the following types:
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000056_0001
Figure imgf000057_0001

Claims

Patentansprüche claims
1. Phenyldiketonderivate der Formel I, 1. phenyldiketone derivatives of the formula I,
Figure imgf000058_0001
Figure imgf000058_0001
in der die Substituenten folgende Bedeutung haben:  in which the substituents have the following meaning:
L,M Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, C2-C6- Alkinyl, C1-C4-Alkoxy, wobei diese Gruppen gegebenenfalls durch ein bis fünf Halogenatome oder C1-C4- Alkoxy substituiert sein können; Halogen, Cyano, Nitro, eine Gruppe -(A)m-S(O)nR1 oder eine Gruppe- (A)m-CO-R2; Y eine Gruppe bestehend aus C=O, C=N-R3 , CR7-NR5R6, L, M is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy, these groups optionally being substituted by one to five halogen atoms or C 1 - C 4 - alkoxy may be substituted; Halogen, cyano, nitro, a group - (A) m -S (O) n R 1 or a group - (A) m -CO-R 2 ; Y is a group consisting of C = O, C = NR 3 , CR 7 -NR 5 R 6 ,
CR7-OR8, CR10R11, CR7-SR8; mit Wasserstoff oder CR 7 -OR 8 , CR 10 R 11 , CR 7 -SR 8 ; with hydrogen or
C1-C4-Alkyl substituiertes 1,3-Dioxanyl oder C 1 -C 4 alkyl substituted 1,3-dioxanyl or
1,3-Dioxolanyl; ein Heteroatom ausgewählt aus der Gruppe Sauerstoff, Schwefel und Stickstoff;  1,3-dioxolanyl; a heteroatom selected from the group consisting of oxygen, sulfur and nitrogen;
X bestehend aus einer Kette (-CR12R12-), X consisting of a chain (-CR 12 R 12 -),
(-CR12R13-CR21R22-) , (-CR12=CR13-) , (-CR 12 R 13 -CR 21 R 22 -), (-CR 12 = CR 13 -),
(-CR12R13-CR12=CR13-); NR23 die Bindung zwischen X und Y kann gesattigt oder ungesättigt sein; (-CR 12 R 13 -CR 12 = CR 13 -); NR 23 the bond between X and Y can be saturated or unsaturated;
A O, NR14; m null oder eins ; n null , eins oder zwei ; AO, NR 14 ; m zero or one; n zero, one or two;
R1 C1-C4-Alkyl , C1-C4 Haloalkyl oder NR1 4 ; R 1 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or NR 1 4 ;
R2 C1-C4 Alkyl , C1-C4 Haloalkyl , C1-C4-Alkoxy oder NR14 ; R 2 C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or NR 14 ;
R3 Wasserstoff , -NR9R4 ; C1-C6-Alkyl , C1-C6-Haloalkyl , R 3 is hydrogen, -NR 9 R 4 ; C 1 -C 6 alkyl, C 1 -C 6 haloalkyl,
C1-C6-Alkoxy , C1-C6-Haloalkoxy , C2-C6-Alkenyl , C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 2 -C 6 alkenyl,
C2-C6-Haloalkenyl , C2-C6-Alkinyl ; gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; gegebenenfalls substituiertes Benzyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl; optionally substituted phenyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; optionally substituted benzyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
gegebenenfalls substituiertes Benzyloxy wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl,optionally substituted benzyloxy where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl,
Halogen, Cyano, Nitro; Halogen, cyano, nitro;
R4 Wasserstoff, C1-C6-Alkyl, C1-C6-Haloalkyl, R 4 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl,
C2-C6-Alkenyl, C2-C6-Alkinyl, C=O-NR14; C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C = O-NR 14 ;
gegebenenfalls substituiertes Phenyl, wobei die optionally substituted phenyl, the
Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1 -C4-Haloalkyl,Substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl,
Halogen, Cyano, Nitro; Halogen, cyano, nitro;
gegebenenfalls substituiertes Benzyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl,optionally substituted benzyl, where the substituents can consist of C 1 -C 4 alkyl,
C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl,C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl,
Halogen, Cyano, Nitro; Halogen, cyano, nitro;
R9 Wasserstoff, C1-C6-Alkyl, C1-C6-Haloalkyl, R 9 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl,
C2-C6-Alkenyl, C2-C6-Alkinyl, C=O-NR14; C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C = O-NR 14 ;
gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; optionally substituted phenyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
gegebenenfalls substituiertes Benzyl, wobei die optionally substituted benzyl, the
Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; R5,R6 unabhängig voneinander Wasserstoff, C1-C6-Alkyl, Substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; R 5 , R 6 independently of one another are hydrogen, C 1 -C 6 alkyl,
C2-C6 Alkenyl, C1-C4 Haloalkyl, C2-C6 Haloalkenyl, C1-C6 Alkoxy, C1-C6-Haloalkoxy; C 2 -C 6 alkenyl, C 1 -C 4 haloalkyl, C 2 -C 6 haloalkenyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy;
gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl,optionally substituted phenyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl,
Halogen, Cyano, Nitro; Halogen, cyano, nitro;
gegebenenfalls substituiertes Benzyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; R7 Wasserstoff, C1-C6 Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkyl, C1-C4-Haloalkoxy; gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus ein bis drei Halogenen, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, Nitro; R7 und R21 oderoptionally substituted benzyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; R 7 is hydrogen, C 1 -C 6 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy; optionally substituted phenyl, where the substituents can consist of one to three halogens, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, nitro; R 7 and R 21 or
R7 und R23 oder R7 und R12 können eine Bindung bilden; R 7 and R 23 or R 7 and R 12 can form a bond;
R8 Wasserstoff, C1-C6-Alkyl, C1-C4-Halogenalkyl, gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; R 8 is hydrogen, C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, optionally substituted phenyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4- haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano, nitro;
gegebenenfalls substituiertes Benzyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl,optionally substituted benzyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl,
Halogen, Cyano, Nitro; Halogen, cyano, nitro;
R10,R11 unabhängig voneinander Wasserstoff, C1-C6-Alkyl; R 10 , R 11 independently of one another are hydrogen, C 1 -C 6 alkyl;
gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus ein bis drei  optionally substituted phenyl, where the substituents can consist of one to three
Halogenen, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, Nitro; R10 und R12 oder R10 und R21 oder R10 und R23 können eine Bildung bilden; Halogens, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, nitro; R 10 and R 12 or R 10 and R 21 or R 10 and R 23 may form;
R12,R13 unabhängig voneinander Wasserstoff, C1-C6-Alkyl, R 12 , R 13 independently of one another are hydrogen, C 1 -C 6 alkyl,
C1-C6-Haloalkyl, C1-C6-Alkoxy, C1-C6-Haloalkoxy; C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy;
gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; optionally substituted phenyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
R14 C1-C4-Alkyl; R 14 C 1 -C 4 alkyl;
R21 Wasserstoff, C1-C6-Alkyl, C1-C6-Haloalkyl, R 21 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl,
C1-C6-Alkoxy, C1-C6-Haloalkoxy; gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; R22 Wasserstoff, C1-C6 Alkyl, C1-C6 Haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy; optionally substituted phenyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; R 22 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl,
C1-C6-Alkoxy, C1-C6-Haloalkoxy; gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; R23 Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, C1-C6-Alkoxy; gegebenenfalls mit C1-C4-Alkyl, C1-C4-Alkoxy, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy; optionally substituted phenyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; R 23 is hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy; optionally with C 1 -C 4 alkyl, C 1 -C 4 alkoxy,
C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro substituiertes Phenyl oder Benzyl; C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro substituted phenyl or benzyl;
R15 Cyclopropyl, 1-Methylcyclopropyl, 1-Methylthiocyclopropyl oder tert.-Butyl; wobei für den Fall, daß Y = C=O ist, X ungleich NR23 ist, sowie landwirtschaftlich brauchbare Salze. R 15 cyclopropyl, 1-methylcyclopropyl, 1-methylthiocyclopropyl or tert-butyl; where, if Y = C = O, X is not equal to NR 23 , and agriculturally useful salts.
2. Phenyldiketonderivate der Formel Ia, 2. phenyldiketone derivatives of the formula Ia,
Figure imgf000061_0001
Figure imgf000061_0001
in der L für Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, in which L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl,
C2-C6-Alkinyl, C1-C4-Alkoxy, C1-C4-Alkylthio, C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, C1-C4-Halogenalkylthio, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkyl, C 1 -C 4 -haloalkoxy, C 1 -C 4 haloalkylthio,
C1-C4-Alkylsulfonyl, Halogen, Nitro oder Cyano und M für Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C 1 -C 4 alkylsulfonyl, halogen, nitro or cyano and M for hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl,
C1-C4-Alkoxy, C1-C4-Alkylthio, C1-C4-Halogenalkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkyl,
C1-C4-Halogenalkoxy, C1-C4-Halogenalkoxy, C1-C4-Halogenalkylthio, C1-C4-Alkylsulfonyl, Halogen, Nitro oder Cyano steht und R15, X, n und Y die in Anspruch 1 angegebenen Bedeutungen haben, wobei für den Fall, daß Y = C=O ist, X ungleich NR23 ist. C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylsulfonyl, halogen, nitro or cyano and R 15 , X, n and Y are the claims 1 have meanings given, where Y = C = O, X is not equal to NR 23 .
3. Phenyldiketonderivate der Formel Ib, 3. phenyldiketone derivatives of the formula Ib,
Figure imgf000061_0002
Figure imgf000061_0002
in der L für C1-C6 Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, in the L for C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl,
C1-C4-Alkoxy, C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro oder Cyano und M für Wasserstoff, C1-C6 Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C1-C4-Alkoxy, C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro oder Cyano steht und R15, X, n und Y die in Anspruch 1 angegebenen Bedeutungen haben, wobei für den Fall, daß Y = C=O ist, X ungleich NR23 ist. C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, halogen, nitro or cyano and M for hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 -haloalkoxy, halogen, nitro or cyano and R 15, X, n and Y are as in claim 1 have the meanings given, where, if Y = C = O, X is not equal to NR 23 .
4. Phenyldiketonderivate der Formel I gemäß Anspruch 1 in der die Reste L bzw. M für Wasserstoff, Methyl, Methoxy, Chlor, Cyano, Nitro, Trifluormethyl stehen. 4. phenyldiketone derivatives of the formula I according to claim 1 in which the radicals L and M are hydrogen, methyl, methoxy, chlorine, cyano, nitro, trifluoromethyl.
5. Phenyldiketonderivate der Formel Ic, 5. phenyldiketone derivatives of the formula Ic,
Figure imgf000062_0001
Figure imgf000062_0001
in der L für Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, in which L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl,
C2-C6-Alkinyl, C1-C4-Alkoxy, C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro oder Cyano und M für Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C1-C4-Alkoxy, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 -haloalkoxy, halogen, nitro or cyano and M is hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy,
C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro oder Cyano steht und R15, n, Y sowie R22, R21 , R12 und R13 die in Anspruch 1 angegebenen Bedeutungen haben. C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, halogen, nitro or cyano and R 15 , n, Y and R 22 , R 21 , R 12 and R 13 have the meanings given in claim 1.
6. Phenyldiketonderivate der Formel Id, 6. phenyldiketone derivatives of the formula Id,
Figure imgf000062_0002
Figure imgf000062_0002
in der L für Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, in which L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl,
C2-C6-Alkinyl, C1-C4-Alkoxy, C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro oder Cyano und M für Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C1-C4-Alkoxy, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 -haloalkoxy, halogen, nitro or cyano and M is hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy,
C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro oder Cyano steht und R15, n, Y sowie R12 und R13 die in Anspruch 1 angegebenen Bedeutungen haben. C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, halogen, nitro or cyano and R 15 , n, Y and R 12 and R 13 have the meanings given in Claim 1.
7. Phenyldiketonderivate der Formel Ie 7. Phenyldiketone derivatives of the formula Ie
Figure imgf000062_0003
Figure imgf000062_0003
in der L für Wasserstoff, C1-C6 Alkyl, C2-C6-Alkenyl, in which L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl,
C2-C6-Alkinyl, C1-C4-Alkoxy, C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen Nitro oder Cyano und M für Wasserstoff, C1-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C1-C4-Alkoxy, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 -haloalkoxy, halogen, nitro or cyano and M is hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy,
C1-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen Nitro oder Cyano steht und R15, n, Y sowie R12 und R13 die in Anspruch 1 angegebenen Bedeutungen haben. C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, halogen nitro or Cyano is and R 15 , n, Y and R 12 and R 13 have the meanings given in claim 1.
8. Phenyldiketonderivate der Formel I gemäß Anspruch 1 in der n für eins oder zwei steht und Y für CR7-OR8, wobei R7 und R8 die in Anspruch 1 angegebene Bedeutung haben. 8. phenyldiketone derivatives of the formula I according to claim 1 in which n is one or two and Y is CR 7 -OR 8 , where R 7 and R 8 have the meaning given in claim 1.
9. Verfahren zur Herstellung der Phenyldiketonderivate der 9. Process for the preparation of the phenyldiketone derivatives
Formel I gemäß Anspruch 1, dadurch gekennzeichnet, daß man Verbindungen der Formel A2  Formula I according to claim 1, characterized in that compounds of the formula A2
Figure imgf000063_0001
Figure imgf000063_0002
Figure imgf000063_0001
Figure imgf000063_0002
wobei T = Halogen bedeutet und L, M, X, n und Y die in Anspruch 1 genannte Bedeutung haben, umsetzt.  where T = halogen and L, M, X, n and Y have the meaning given in claim 1.
10. Herbizides Mittel, enthaltend mindestens ein Phenyldiketonderivat der Formel I gemäß Anspruch I und übliche inerte Zusatzstoffe. 10. Herbicidal composition containing at least one phenyldiketone derivative of the formula I according to claim I and customary inert additives.
11. Verfahren zur Bekämpfung unerwünschten Pflanzenwuchses, 11. methods for controlling undesirable plant growth,
dadurch gekennzeichnet, daß man eine herbizid wirksame Menge eines Phenyldiketonderivates der Formel 1 gemäß Anspruch 1 auf die Pflanzen oder deren Lebensraum einwirken laßt.  characterized in that a herbicidally effective amount of a phenyldiketone derivative of the formula 1 according to Claim 1 is allowed to act on the plants or their habitat.
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