EP1311469A1 - Method for producing beta- ketoenol esters - Google Patents

Method for producing beta- ketoenol esters

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Publication number
EP1311469A1
EP1311469A1 EP01967292A EP01967292A EP1311469A1 EP 1311469 A1 EP1311469 A1 EP 1311469A1 EP 01967292 A EP01967292 A EP 01967292A EP 01967292 A EP01967292 A EP 01967292A EP 1311469 A1 EP1311469 A1 EP 1311469A1
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EP
European Patent Office
Prior art keywords
alkyl
alkoxy
iii
haloalkyl
general formula
Prior art date
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EP01967292A
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German (de)
French (fr)
Inventor
Steffen Kudis
Ulf Misslitz
Ernst Baumann
Wolfgang Von Deyn
Klaus Langemann
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BASF SE
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BASF SE
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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member

Definitions

  • the present invention relates to a process for the preparation of ⁇ -ketoenol esters of the general formula Ia and Ib
  • R a , R b independently of one another are Ci-C ⁇ -alkyl or C 3 -C 8 -cycloalkyl, or
  • R a and R b together represent C 2 -C alkanediyl or C 5 -C 7 cycloalkanediyl, where the three aforementioned groups may be substituted or unsubstituted, and / or a fused 3, 4, 5 or 6 membered saturated carbocycle, a spiro-linked 3-, 4-, 5-, 6- or 7-membered saturated carbocycle, a spiro-linked 3-, 4-, 5-, 6- or 7-membered saturated heterocycle with 1 or 2 chalcogen atoms, selected from oxygen and sulfur, and / or may have a carbonyl or thiocarbonyl group;
  • Ar phenyl or pyridyl each of which may have 1, 2, 3 or 4 substituents, two substituents bonded to adjacent carbon atoms with these atoms also having a 5- or 6-membered saturated or unsaturated carbocycle or a 5- or 6-membered saturated or can form unsaturated heterocycle which has 1, 2 or 3 heteroatoms selected from 0, N and S and which in turn can be substituted or unsubstituted.
  • R a , R b and Ar have the meanings mentioned above.
  • Herbicidally active 2-aroyl-1,3-diketones are known, for example, from EP-A 90262, EP-A 135191, EP-A 162166, EP-A 186118, EP-A 186119, EP-A 283261, EP-A 319075, WO 90/05712, WO 94/04524, WO 94/08988, JP 3052862, JP 3120202, WO 96/04182, WO 97/09324, WO 99/03845 and Weed Science, 45, 1997, 601-609 and the literature cited therein - knows.
  • the 2-aroyl-1,3-diketones are generally prepared starting from an aromatic carboxylic acid of the formula Ar-COOH or its acid chloride Ar-CO-Cl, which is reacted with a 1,3-diketone of the formula III
  • R a -C (OH) CH-C (0) -R b (III ")
  • R a and R b have the meanings given above, in the presence of a dehydrating agent, for example an anhydride or a carbodiimide, is converted to ⁇ -ketoenol esters of the formula I defined above.
  • a dehydrating agent for example an anhydride or a carbodiimide
  • the ⁇ -ketoenol esters I are then rearranged with a base and preferably in the presence of a catalytically effective amount of a compound containing cyanide groups to give the herbicidally active 2-aroyl-1,3-diketones of the formula X defined above.
  • a catalytically effective amount of a compound containing cyanide groups to give the herbicidally active 2-aroyl-1,3-diketones of the formula X defined above.
  • an activated arylcarboxylic acid derivative for example carboxylic acid halide Ar-COL, in which L represents a halogen atom such as chlorine, can also be used to prepare ⁇ -ketoenol esters I.
  • the conversion of the acid halide with III to I preferably takes place in the presence of a base (cf.
  • the present invention is therefore based on the object of providing a more economical process for the preparation of ⁇ -ketoenol esters of the general formula I.
  • Ar has the meanings mentioned above and Hai represents a halogen atom which is selected from chlorine, bromine and iodine, with a 1,3-diketone of the general formula III or its tautomers III 'or III "in a carbon monoxide atmosphere in the presence a base and a catalyst which contains at least one transition metal from Group VIII of the Periodic Table leads in good yields to the ⁇ -ketoenol esters of the general formula I defined above.
  • the present invention relates to a process for the preparation of ⁇ -ketoenol esters of the general formula Ia or Ib defined at the outset, which is characterized in that an aryl halide of the general formula II defined above with a 1,3-diketone of the general formula III or its Tautomers III 'or III "in a carbon monoxide atmosphere in the presence of a base and a catalyst which contains at least one transition metal from group VIII of the periodic table.
  • the present invention also relates to a process in which an aryl halide of the formula II is first used with a 1,3-diketone of the general formula III or its tautomers III 'or III "in a carbon monoxide atmosphere in the presence of a base and a catalyst , which contains at least one transition metal from group VIII of the periodic table, to a ⁇ -ketoenol ester of the general formula Ia or defined at the outset Ib and this is then converted into 2-aroyl-substituted 1,3-diketones of the formula X or their tautomers Xa, Xb or Xc by treatment with a base and a catalytically active amount of at least one cyanide compound
  • halogenated substituents preferably carry one to five identical or different halogen atoms.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Ci-C 6 -alkylcarbonyl Ci-C ⁇ -alkoxycarbonyl
  • Ci-C 6 -alkyloxycarbonyl Ci-C 6 -alkylaminocarbonyl
  • Ci-C ⁇ -alkylcarbonylamino for: Ci-C 4 -alkyl, as mentioned above , and for example pentyl, 1-ethylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-d
  • C 1 -C 4 alkoxy for example methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy;
  • Ci-C -haloalkoxy ß a Ci-C 6 alkoxy group as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine;
  • Ci-C ⁇ alkylcarbonyl and alkylcarbonyl of C ⁇ -C 6 alkylcarbonyl-C ⁇ -C 6 -alkyl, C 6 alkylcarbonyloxy,
  • Ci-Cg-alkylcarbonylamino an alkyl radical bonded via a carbonyl group, e.g. Methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl, 1-ethylpropylcarbonyl, 2-methylpropylcarbonyl, 1, 1-dimethylethylcarbonyl;
  • Ci-C-alkoxycarbonyl e.g. Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1-methylethoxycarbonyl, butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl or 1, 1-dimethylethoxycarbonyl;
  • - (-C 1 -C 4 -alkyl) carbonyloxy acetyloxy, ethyl carbonyloxy, propyl carbonyloxy, 1-methyl ethyl carbonyloxy, butyl carbonyloxy, 1-meth propyl carbonyloxy, 2-methyl propyl carbonyloxy or 1,1-dimethyl ethyl carbonyloxy;
  • Ci-C ⁇ -alkyl substituted by one to three OH groups, for example hydroxymeth 1, 1-hydroxyethyl, 2-hydroxyethyl, 1,2-bishydroxyethyl, 1-hydroxypropyl, 2-hydroxypro - pyl, 3-hydroxypropy1, 4-hydroxybutyl, 2,2-dimethyl-3-hydroxypropyl;
  • Ci-C ⁇ -alkoxy substituted by one to three OH groups, for example hydroxymethoxy, 1-hydroxyethoxy, 2-hydroxyethoxy, 1,2-bishydroxyethoxy, 1-hydroxypropoxy, 2-hydroxypropoxy, 3-hydroxypropoxy , 4-hydroxybutoxy, 2,2-dimethyl 1-3 hydroxypropoxy;
  • Phenyl-C 1 -C 6 -alkyl Ci-C ß- alkyl substituted by a phenyl radical, for example benzyl, 1-phenylethyl and 2-phenylethyl, where the phenyl radical can be partially or completely halogenated in the manner indicated or one to three of those for Phenyl may have substituents given above;
  • Heterocyclyl-Ci-Cg-alkyl accordingly represents a Ci-C ⁇ -alkyl substituted by a heterocyclyl radical
  • C 1 -C 6 -alkoxy-C 6 -C 6 -alkyl C 1 -C 6 -alkoxy, as mentioned above, substituted C 1 -C 6 -alkyl, for example methoxymethyl,
  • Ci-C ß alkoxy-Ci-Cg-alkoxy by C ö alkoxy as mentioned above, substituted Ci-C ⁇ -alkoxy, eg for
  • C 3 -C 6 alkenyl and the alkenyl parts of C 3 -C 6 alkenylcarbonyl, C 3 -Cg alkenyloxy, C 3 -C 6 alkenyloxycarbonyl, C 3 -C 6 alkenylaminocarbonyl, N— (C 3 -Cg —Alkenyl) —N— (C ⁇ -Cg-alkyl) aminocarbonyl, N— (C 3 —Cg-Alkenyl) —W— (C ⁇ — Cg-alkox) aminocarbonyl: eg prop-2-ene-1-y1, but— 1-ene-4-y1, 1-methyl-rop-2-ene-1-y1, 2-methyl-prop-2-ene-1, 1.2, butene-1-yl, 1-pentene-3 yl, l-penten-4-yl, 2-penten-4-y1, 1-methyl-but-2-en-l-y1, 2-methyl-but-2-en-l-yl
  • C 2 -C 6 alkenyl and the alkenyl parts of C 2 -C 6 alkenylcarbonyl, phenyl C 2 -Cg alkenylcarbonyl and heterocyclyl C 2 -C 6 alkenylcarbonyl: C 3 -Cg alkenyl as mentioned above as well as ethenyl;
  • C 2 -C 4 alkanediyl for R a and R b ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1, 3-diyl, butane-l, 4-diyl, especially propane-l, 3-diyl;
  • Ci-Cg-alkanediyl methanediyl, ethane-1, 1-diyl, ethane-l, 2-diyl, propane-1, 1-diyl, propane-l, 2-diyl, propane-l, 3-diyl, propane 2,2-diyl, butane-1, 1-diyl, but nl, 2-diyl, but nl, 3-diyl, butane-l, 4-diyl, 2-methyl-propane-l, 3-diyl, 2- Methy1-propane-1,2-diy1, 2-methyl-propane-1,1-diyl, 1-methyl-propane-1,2-diyl, 1-methyl-propane-2,2-diyl, 1-meth 1 -propan-l, 1-diyl, pentane-1, 1-diyl, pentane-1,2-diyl, pentane-l, 3-diyl
  • C 5 -C 7 cycloalkanediyl in the case of R a and R b a divalent cycloaliphatic radical having 5 to 7 ring carbon atoms, for example cyclopentane-1,2-diyl or -1,3-diyl, cyclohexane-1,2 -diyl, -1,3-diyl or -1,4-diyl, cycloheptane-1,2-diyl, -1,3-diyl or -1,4-diyl;
  • N-linked 5-membered rings such as:
  • N-linked 6-membered rings such as:
  • N-linked cyclic imides such as:
  • 6-membered heterocycle can form a bicyclic ring system
  • Residues can be partially or completely halogenated and / or can carry one to three substituents selected from C 1 -C 4 alkoxy or hydroxy.
  • transition metal catalysts whose active metal component comprises at least one platinum metal and in particular one transition metal selected from palladium, platinum, nickel, cobalt, ruthenium and rhodium.
  • active metal component comprises at least one platinum metal and in particular one transition metal selected from palladium, platinum, nickel, cobalt, ruthenium and rhodium.
  • catalysts which comprise palladium as metal of group VIII of the periodic table are particularly preferred.
  • the catalysts in particular those which contain platinum, nickel, cobalt, ruthenium and rhodium and in particular palladium as catalytically active metal, can be in the form of metals or in the form of customary salts, for example in the form of halogen compounds such as PdCl 2 , NiCl 2 , CoCl 2 , RhCl 3 -H 2 0, acetates such as Pd (OAc) 2 , Co (OAc) 2 , acetylacetonates or cyanides can be used in the known valence levels.
  • halogen compounds such as PdCl 2 , NiCl 2 , CoCl 2 , RhCl 3 -H 2
  • acetates such as Pd (OAc) 2 , Co (OAc) 2 , acetylacetonates or cyanides can be used in the known valence levels.
  • the catalytically active metals can be in the form of metal complexes, e.g. complexes mixed with tertiary phosphines, as metal alkylcarbonyls, which contain at least two different ligands, preferably at least one tertiary phosphine and at least one different ligand, e.g. CO, comprise, or transition metal salts complexed with tertiary phosphines can be used.
  • metal complexes e.g. complexes mixed with tertiary phosphines, as metal alkylcarbonyls, which contain at least two different ligands, preferably at least one tertiary phosphine and at least one different ligand, e.g. CO, comprise, or transition metal salts complexed with tertiary phosphines can be used.
  • the catalyst system comprises a tertiary phosphine in addition to the transition metal of group VIII of the periodic table, the tertiary phosphine being present separately or together with the transition metal Form of a transition metal complex can be added to the reaction mixture.
  • Suitable phosphine ligands can be represented, for example, by the following formulas:
  • A is a divalent organic radical, for example for C 1 -C 6 - preferably C 1 -C 4 -alkanediyl, in particular 1,2-ethylene or 1,3-propylene, for 1,2-cycloalkanediyl, for example 1,2-cyclohexanediyl, 1,2-cyclopentanediyl, for ferrocendiyl, a polycyclic aromatic radical such as 1,8-anthracenediyl or for a 2,2-biphenyl structure.
  • R x , RY, R X ', RY' independently of one another represent Ci-Cg-alkyl, C 5 -C 8 cycloalkyl such as cyclohexyl, aryl, especially phenyl or p-tolyl, -C-C 4 alkylaryl, for example Benzyl, phenethyl or aryloxy such as phenoxy.
  • R x , RY, R x ', RY' are preferably aryl.
  • Aryl is, for example, phenyl, naphthyl, anthryl, which are optionally substituted, and in particular unsubstituted or substituted phenyl such as tolyl.
  • Suitable residues are all inert C-organic residues such as Ci-Cg-alkyl residues, for example methyl, sulfone or carboxyl residues such as COOH, COOM (M is for example an alkali, alkaline earth metal or ammonium salt), or C-organic residues bound via oxygen such as C. ! -C 6 alkoxy radicals.
  • Examples of such complexes are P (C 6 H 5 ) 3 , P (C 6 H 4 CH 3 ) 3 , P (n-CH 9 ) 3 , P (cyclo-C 6 H u ) 3 , PCH 3 (C 6 H 5 ) 2 , 1,2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 8-bis (diphenylphosphino) anthracene and ⁇ , ⁇ '-bis (diphenylphosphino) ferrocene.
  • a particularly preferred tertiary phosphine is triarylphosphine and in particular triphenylphosphine, which can be substituted on the phenyl ring.
  • Examples of complex compounds preferred according to the invention are (PPh 3 ) 2 Ni (CO) 2 , Pt (CO) 2 (PPh 3 ) 2 , in particular Pd (CO) (PPh 3 ) 3 , (PPh 3 ) 2 Pd (OAc) 2 , (PPh 3 ) 2 PdCl 2 .
  • the phosphine complexes can be prepared in a manner known per se. 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 (C 6 H 4 CH 3 ) 3 , P (n-CH 9 ) 3 , P (cyclo-CgHn) 3 , PCH 3 (C 6 H 5 ) 2 , 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,8-bis (diphenylphosphino) anthracene or ⁇ , ⁇ '-bis (diphenylphosphino) ferrocene, optionally in a solvent.
  • PdCl 2 or Pd (OCOCH 3 ) 2 adds the phosphine, for example P (C 6 H 5 ) 3 , P (C 6
  • the complexes will often also be generated in situ in the reaction mixture by adding at least one phosphine ligand and a precursor compound, that is to say a transition metal compound which contains the catalytically active metal, for example a metal salt or another complex of the metal, to the reaction mixture.
  • a precursor compound that is to say a transition metal compound which contains the catalytically active metal, for example a metal salt or another complex of the metal
  • the amount of phosphine, based on 1 mol of transition metal is at least 0.1 mol, preferably at least 0.5 mol and particularly preferably at least 1 mol.
  • the molar ratio of tertiary phosphine to transition metal does not exceed a value of 20, preferably 10 and in particular 5, not least in order to keep the entry of foreign substances into reaction components II and III as low as possible.
  • the catalysts can be used as such or on a support.
  • the type of carrier is of minor importance. Suitable carriers include inorganic oxides such as silicon dioxide, aluminum oxide, aluminosilicates, e.g. Zeolites, calcium carbonate, barium sulfate, also activated carbon, soot. Also suitable are organic polymers as carrier material, in particular those that can complex the transition metal, e.g. Polymers with tertiary amino groups, pyridine groups, imidazole groups or polymers with tertiary phosphine groups.
  • 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 20 mol%, in particular 0.5 to 10 mol%, based on the aryl halide II. Of course you can also use larger quantities, e.g. Use 50, 100 or 200 mol%, based on 1 mol aryl halide II.
  • inert bases which are able to bind the hydrogen halide released during the reaction, in particular hydrogen bromide, are suitable for the process according to the invention.
  • the amount of base is not critical, usually the base will be used in an amount of at least 1 mole per mole of aryl halide II, e.g. use in an amount of 1 to 10 mol, in particular 1 to 5 mol.
  • the base can also be used as a solvent or diluent for the reactants. If the base is simultaneously used as a solvent, the amount is generally such that the reactants are dissolved, unnecessarily high excesses being avoided for reasons of practicality in order to save costs, to be able to use small reaction vessels and to ensure maximum contact for the reactants.
  • Inert solvents include, for example, aromatic hydrocarbons such as toluene, xylenes, cumene, aliphatic hydrocarbons such as hexane, pentane or cyclohexane, halogenated aliphatic hydrocarbons such as di-, tri and tetrachloromethane, 1,2-dichloroethane and 1,1-dichloroethane, ethers such as methyl tert.
  • aromatic hydrocarbons such as toluene, xylenes, cumene
  • aliphatic hydrocarbons such as hexane, pentane or cyclohexane
  • halogenated aliphatic hydrocarbons such as di-, tri and tetrachloromethane, 1,2-dichloroethane and 1,1-dichloroethane
  • ethers such as methyl tert.
  • butyl ether tetrahydrofuran, dioxane, dimethoxyethane, substituted amides such as dimethylformamide or N-methylpyrrolidone, per-substituted ureas such as tetra-C 1 -C 8 -alkylureas or nitriles such as benzonitrile or acetonitrile and mixtures of the aforementioned solvents.
  • Preferred solvents are aromatic hydrocarbons or solvent mixtures with a high proportion of aromatic hydrocarbons.
  • lithium salts such as lithium halides, e.g. Lithium chloride, also basic lithium salts such as lithium carbonate, lithium acetate or lithium hydroxide.
  • 0.1 to 10 mol, in particular 0.2 to 5 mol and particularly preferably 0.5 to 2 mol, of lithium ions are generally used per mol of aryl halide.
  • aryl halide II and the compounds III or III 'or III are generally used in an approximately stoichiometric amount, with an excess of one component of up to 50 mol%, based on the amount available in the deficit. lying component usually has no disadvantages.
  • Diketone III or its tautomers III 'or III are preferably used in an approximately equi-olar amount or in excess.
  • the carbon monoxide pressure is adjusted so that there is always an excess of carbon monoxide, based on the aryl halide.
  • the carbon monoxide partial pressure at room temperature is preferably 1 to 250 bar, in particular 5 to 150 bar CO.
  • the process according to the invention is generally carried out continuously or batchwise at temperatures from room temperature to 300 ° C., preferably at 50 to 250 ° C., in particular at 100 to 200 ° C.
  • carbon monoxide is expediently pressed continuously onto the reaction mixture in order to maintain a constant pressure.
  • the method according to the invention can be applied to a large number of different substrate compounds II and III.
  • Preference for shark in formula II means bromine or iodine and in particular bromine.
  • Aryl halides II include, for example, those compounds which are represented by the general formula Ha
  • shark is chlorine, bromine or iodine, preferably bromine or iodine, and in particular bromine, shark is preferably adjacent to the radical R la , and
  • R la and R 4a independently of one another for hydrogen
  • Halogen especially fluorine or chlorine, cyano, Ci-Cg-alkyl, Ci-Cg-haloalkyl, Ci-C ⁇ - alkoxy, Ci-Cg-haloalkoxy, Ci-Cg-alkylthio, C ⁇ -Cg-haloalkylthio, hydroxy-Ci C ⁇ -alkyl, C ⁇ -C 6 alkylsulfonyl, Ci-Cg-haloalkylsulfonyl, C ⁇ -Cg-Alko- xy-Ci-Cg-alkyl, C-Cg-alkylthio-C-Cg-alkyl, C ⁇ -C 6 -halogenal- kylthio-Ci-Cg-alkyl, C ⁇ -Cg-alkylsulfonyl-C ⁇ -C 6 -alkyl, C ⁇ -C 6 -haloalkylsulfonyl-Ci-Cg-alkyl, C ⁇ -
  • Sulfur atoms in the heterocycle can also be present as sulfoxide or sulfone,
  • Nitrogen atoms and carbon atoms in the heterocycle have a hydrogen atom or a substituent which is selected from halogen, nitro, cyano, hydroxy, amino,
  • Carbon ring members can also be present as a carbonyl function, thiocarbonyl function, oxime or oxime ether function; or
  • R la and R 2a or R 3a and R 4a form an annellated 5- or 6-membered, saturated or unsaturated heterocycle which can have 1, 2 or 3 heteroatoms selected from N, S and 0, the ring atoms of the Heterocycle may be substituted in the manner described above;
  • R la , R 2a , R 3a and R 4a independently of one another have the meanings given for R la , or R 2a represents hydrogen or 5-, 6- or 7-membered heterocyclyl which has 1, 2 or 3 heteroatoms selected from N, S and 0, where the ring atoms of the heterocycle can be substituted in the manner described above; and
  • R la , R 3a and R 4a independently of one another have the meanings given above for R la .
  • fused 5- or 6-membered heterocycles are pyrrole, 2,3-dihydropyrrole, 2,5-dihydropyrrole, pyrazole, 2,3-dihydropyrazole, imidazole, 2,3-dihydroimidazole, triazole, furan, 2 , 3- and 2,5-dihydrofuran, oxazole, 2, 3-dihydrooxazole, isoxazole, 2,3-dihydroisoxazole, thiophene, 2,3- and 2,5-dihydrothiophene, thiazole, 2, 3-dihydrothiazole, isothiazole , 2,3-dihydroisothiazole, pyridine, 1,2-, 2,3- and 3, 4-dihydropyrimidine and tetrahydropyridine.
  • Fused carbocycles are, for example, cyclopentene, cyclopentadiene, cyclohexene, cycl
  • R la and R 2a or R 3a and R 4a together with the benzene ring to which they are attached form an indole, isoindole, benzofuran, isobenzofuran, benzo [a] thiophene, benzo [b ] -thiophene, benzimidazole, benzoxazole, benzthiazole, benzisothiazole, benztriazole, quinoline, isoquinoline, quinoxaline, chroman, thiochroman, chromium, thiochrome, indane, indene or naphthalene ring , or a derivative thereof partially hydrogenated on the fused ring.
  • heterocyclic structures can also be partially hydrogenated and the N and / or C ring atoms substituted in the manner described above.
  • Carbon ring members can also be present as carbonyl function, thiocarbonyl function, oxime or oximeter function as in chroman-4-one, thiochroman-4-one, benzoisothiazolone, and ring sulfur atoms as sulfoxide or sulfone, as in benzothiophene-S-oxide , Benzothiophene
  • aryl halides of the general formula IIb are used:
  • Hal is the meanings and R lb aforementioned previously have the meanings specified above for R 4a R a and R 4b, preferably Hai R lb is adjacent, R lb is preferably halogen, in particular fluorine or chlorine, C ⁇ -C 4 alkyl , C ⁇ -C 4 haloalkyl, CC 4 -alkoxy and CC is 4 -haloalkoxy, R 4b is preferably water serstoff, fluorine, chlorine, methyl or methoxy,
  • R5b fo r is hydrogen, C-Cg-alkyl, C ⁇ -C 6 haloalkyl, C ⁇ -Cg alkyl carbonyl, C ⁇ -C 6 -alkoxy-C ⁇ -C 6 alkyl, C 2 -CG-alkenyl, C 2 - C 6 -alkynyl, C ⁇ -Cg-hydroxyalkoxy, C ⁇ -Cg-alkoxy-C ⁇ -Cg-alkoxy, C 3 -C 8 -cycloalkyl, phenyl, phenyl-C ⁇ -C 6 -alkyl, where phenyl in the latter two groups have one, two or three substituents selected from halogen, nitro, cyano, hydroxy, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl, C ⁇ -C alkoxy and C ⁇ -C 4 haloalkoxy, can wear, and in particular C ⁇ -C 4 alkyl, phenyl or phenyl-
  • n 0, 1 or 2
  • X means oxygen or sulfur, in particular oxygen.
  • Hai has the meanings mentioned above and preferably R lc is adjacent, R lc has the meanings mentioned for R la , and preferably halogen, in particular fluorine or chlorine, C ⁇ -C 4 alkyl, in particular methyl, C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy and C ⁇ -C 4 haloalkoxy,
  • R 3c for halogen, C ⁇ -C 6 alkyl, Ci-Cg-haloalkyl, C -Cg-alkylthio, C ⁇ -Cg-alkylsulfinyl, C ⁇ -C 6 -alkylsulfonyl, C ⁇ -Cg-alkoxy or
  • C ⁇ -Cg-haloalkoxy and in particular C ⁇ -Cg-alkylsulfonyl and especially chlorine, fluorine, methyl, methoxy or methylsulfonyl means,
  • R 6c represents hydrogen or optionally substituted C ⁇ -C-alkyl.
  • Substituted C ⁇ -C 4 alkyl here is preferably haloalkyl as defined above, for example fluoromethyl, chloromethyl, difluoromethyl, chlorodifluoromethyl, trifluoromethyl, or C ⁇ -C 4 -alkoxy-C ⁇ -C 4 -alkyl as defined above, for example methoxymethyl.
  • Hai as defined above and preferably having R ld adjacent R ld as defined for R la has, and preferably halogen, in particular fluorine or chlorine, C ⁇ -C alkyl 4 -Al-, especially methyl, C ⁇ -C -haloalkyl , C ⁇ -C-alkoxy and C ⁇ -C 4 -haloalkoxy,
  • R3d represents halogen, Ci-Cg-alkyl, C -Cg-haloalkyl, CC 6 -alkylthio, C ⁇ -C 6 -alkylsulfinyl, C ⁇ -Cg-alkylsulfonyl, C ⁇ -Cg-alkoxy or C ⁇ -Cg-haloalkoxy, and in particular C ⁇ -C 6 -Alkylsulfonyl and especially chlorine, fluorine, methyl, methoxy or methylsulfonyl means.
  • an unsubstituted halobenzene such as bromobenzene or a halopyridine such as 2-, 3- or 4-bromopyridine can also be used as compound II in the process according to the invention.
  • Cyclic or bicyclic 1,3-diketones which obey the general formulas lilac or IIIb are preferably used in the process according to the invention as 1,3-diketones of the general formula III (or as tautomer III 'or III "):
  • R 1 , R 5 independently of one another are hydrogen, C ⁇ -C 4 -alkyl, in particular methyl, or C ⁇ -C 4 -alkoxycarbonyl;
  • R 2 , R 4 , R 6 independently of one another are hydrogen, CC 4 -alkyl, in particular methyl, C ⁇ -C 4 -alkoxy such as methoxy or C ⁇ -C-alkylthio such as methylthio;
  • R 3 is hydrogen, halogen, hydroxy, C ⁇ -Cg-alkyl, C ⁇ -Cg-haloalkyl, di- (C ⁇ -Cg-alkoxy) methyl,
  • R 5 and R 6 together form a C ⁇ -Cs alkanediyl chain which have a ⁇ bond and / or can carry one, two or three radicals from the following group: halogen,
  • R 2 and R 6 together form a C ⁇ -C 4 alkanediyl chain which have a ⁇ bond and / or can carry two or three radicals from the following group: halogen, cyano, C ⁇ -C 4 alkyl, C ⁇ -C- Haloalkyl or CC 4 alkoxycarbonyl, and which is preferably unsubstituted; or
  • R 3 and R 4 together with the carbon to which they are attached form a carbonyl or thiocarbonyl group.
  • Examples of preferred cyclic diketones of the formula purple or IIIb are the cyclohexane-1,3-diones of the formulas III-1 to 111-12:
  • the inventive reaction of aryl halide II with 1,3-diketone III can be worked up in a manner known per se.
  • the reaction mixture can be evaporated to dryness, preferably under reduced pressure.
  • the residue is then generally recrystallized from a suitable solvent and / or purified by chromatography, the solvent used for the recrystallization, the stationary phase used in the chromatography and the mobile phase (eluent), of course, being based on the type of starting compounds and by the person skilled in the art can be easily determined by routine experimentation.
  • silica gel or aluminum oxide will be suitable as the stationary phase.
  • eluents are aliphatic and cycloaliphatic hydrocarbons such as n-hexane or cyclohexane or their mixtures with polar solvents such as ethers or esters, for example acetic acid. acid ethyl ester, into consideration.
  • polar solvents such as ethers or esters, for example acetic acid. acid ethyl ester, into consideration.
  • the reaction mixture can also be worked up in an aqueous extractive manner in order to remove salts, for example the acid addition salts of hydrogen halide resulting from the reaction with the base or catalysts used.
  • the process according to the invention provides the ⁇ -ketoenol esters of the general formula I in good yields. Its great advantage can be seen in the fact that instead of the partially Ar-carboxylic acids Ar-COOH, which are difficult to prepare, and the more accessible aryl halides of the formula II can be used.
  • the ⁇ -ketoenol esters of the general formula I obtained by the process according to the invention are, as a rule, in a further reaction into the 2-aroyl-substituted 1,3-diketones of the formula X by treating I with a base and one catalytically rearranged active amount of at least one cyanide compound.
  • the ⁇ -ketoenol esters I can be used as isolated pure substance, as an isolated crude product of the above-described reaction or in the reaction mixture of the above reaction without prior isolation.
  • reaction mixture obtained by the process according to the invention can be mixed with a base and a catalytically active amount of at least one cyanide compound immediately after removal of the carbon monoxide, and the rearrangement of I into compound X can thus be initiated.
  • the rearrangement of the ⁇ -ketoenol esters I to the compounds of the formula X is generally carried out at from 20 to 100 ° C. in a solvent and in the presence of a base and, if appropriate, using a cyano compound as a catalyst.
  • solvent e.g. Acetonitrile, methylene chloride, 1,2-dichloroethane, dioxane, ethyl acetate, toluene or mixtures thereof can be used.
  • Preferred solvents are acetonitrile and dioxane and mixtures thereof.
  • Suitable bases are the above-mentioned tertiary amines such as triethylamine and pyridine, alkaline earth metal or alkali metal carbonates, such as sodium carbonate or potassium carbonate, which are preferably used in an equimolar amount or up to a fourfold excess, based on the ⁇ -ketoenol ester of the formula I.
  • Triethylamine or alkali carbonate are preferably used, preferably in a double equimolar ratio with respect to the ester.
  • Suitable cyano compounds are inorganic cyanides, such as sodium cyanide or potassium cyanide, and organic cyano compounds which can release cyanide ions, for example cyanohydrins of aliphatic ketones such as acetone cyanohydrin or trialkylsilyl cyanides such as trimethylsilyl cyanide. They are preferably used in an amount of 1 to 50 mol percent, in particular 5 to 25 mol%, based on the ⁇ -ketoenol ester I. Acetone cyanohydrin or trimethylsilyl cyanide are preferably used, for example in an amount of 5 to 25, preferably about 10 to 20, mol percent, based on the ⁇ -ketoenol ester I.
  • the rearrangement reaction mixture is, for example, diluted mineral acid, e.g. 5% hydrochloric acid or sulfuric acid, acidified, with an organic solvent, e.g. Extracted methylene chloride or ethyl acetate.
  • the organic extract can be used to remove contaminants with a base such as 5-10% alkali carbonate solution, e.g. Sodium carbonate or potassium carbonate solution can be extracted.
  • the aqueous phase is acidified and the precipitate formed is suction filtered and / or extracted with methylene chloride or ethyl acetate, dried and concentrated. If necessary, the residue is recrystallized and / or further purified by chromatography in the manner described above.
  • the residue was chromatographed on silica gel using a cyclohexane-ethyl acetate gradient (100/0 to 60/40 v / v).
  • the residue was taken up in ethyl acetate, 3 times with 5% by weight aqueous sodium carbonate, 2 times with 10% by weight hydrochloric acid and 2 times with
  • the respective ß-ketoenol ester of 2,4-dimethyl-saccharin-5-carboxylic acid was obtained as a viscous oil or as a white solid.
  • reaction mixture was washed 3 times with 5% by weight aqueous sodium carbonate, with 10% by weight hydrochloric acid and with water.
  • the organic phase was dried over sodium sulfate and left to dry in vacuo. geengt. 10.4 g of 5- [(bicyclo [3.2.1] -3-oxoocten-l-yl) oxycarbonyl] -2,4-dimethylsaccharin were obtained as a viscous oil.
  • Hex stands for one of the cyclohexenone radicals hex-1 to hex-5 defined below

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Abstract

The invention relates to a method for producing beta ketoenol esters of the general formula (Ia) or (Ib), wherein Ar, R<a> and R<b> are defined as in claim 1. The inventive method is characterized by reacting an arylhalogenide of the general formula (II) with a 1,3-diketone of the general formula (III) or the tautomers thereof in a carbon monoxide atmosphere in the presence of an alkali and a catalyst that contains at least one transition metal of group VIII of the periodic system.

Description

Verfahren zur Herstellung von ß-KetoenolesternProcess for the preparation of ß-ketoenol esters
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von ß-Ketoenolestern der allgemeinen Formel Ia und IbThe present invention relates to a process for the preparation of β-ketoenol esters of the general formula Ia and Ib
worin wherein
Ra, Rb unabhängig voneinander für Ci-Cβ-Alkyl oder C3-C8-Cycloalkyl stehen, oderR a , R b independently of one another are Ci-Cβ-alkyl or C 3 -C 8 -cycloalkyl, or
Ra und Rb zusammen für C2-C-Alkandiyl oder C5-C7-Cycloalkandiyl stehen, wobei die drei vorgenannten Gruppen substituiert oder unsubstituiert sein können, und/oder einen anellierten 3-, 4-, 5- oder 6-gliedrigen gesättigten Carbocyclus, einen spiro-verküpften 3-, 4-, 5-, 6- oder 7-gliedrigen gesättigten Carbocyclus, einen spiro-verküpften 3-, 4-, 5-, 6- oder 7-gliedrigen gesättigten Heterocyclus mit 1 oder 2 Chalkoge- natomen, ausgewählt unter Sauerstoff und Schwefel, und/oder eine Carbonyl- oder Thiocarbonylgruppe aufweisen können;R a and R b together represent C 2 -C alkanediyl or C 5 -C 7 cycloalkanediyl, where the three aforementioned groups may be substituted or unsubstituted, and / or a fused 3, 4, 5 or 6 membered saturated carbocycle, a spiro-linked 3-, 4-, 5-, 6- or 7-membered saturated carbocycle, a spiro-linked 3-, 4-, 5-, 6- or 7-membered saturated heterocycle with 1 or 2 chalcogen atoms, selected from oxygen and sulfur, and / or may have a carbonyl or thiocarbonyl group;
Ar Phenyl oder Pyridyl, die jeweils 1, 2, 3 oder 4 Substituenten aufweisen können, wobei zwei an benachbarte Kohlenstoffatome gebundene Substituenten mit diesen Atomen auch einen einen 5- oder 6-gliedrigen gesättigten oder ungesättigten Carbocyclus oder einen 5- oder 6-gliedrigen gesättigten oder ungesättigten Heterocyclus bilden können, der 1, 2 oder 3 Heteroatome, ausgewählt unter 0, N und S aufweist und der seinerseits substituiert oder unsubstituiert sein kann.Ar phenyl or pyridyl, each of which may have 1, 2, 3 or 4 substituents, two substituents bonded to adjacent carbon atoms with these atoms also having a 5- or 6-membered saturated or unsaturated carbocycle or a 5- or 6-membered saturated or can form unsaturated heterocycle which has 1, 2 or 3 heteroatoms selected from 0, N and S and which in turn can be substituted or unsubstituted.
ß-Ketoenolester von aromatischen Carbonsäuren, die der oben definierten allgemeinen Formel Ia und Ib gehorchen, sind interessante Vorstufen zur Herstellung von herbizid wirksamen 2-Aroyl-l,3-di- ketonen der allgemeinen Formel X: β-ketoenol esters of aromatic carboxylic acids which obey the general formula Ia and Ib defined above are interesting precursors for the preparation of herbicidally active 2-aroyl-1,3-di-ketones of the general formula X:
in der Ra, Rb und Ar die zuvor genannten Bedeutungen haben.in which R a , R b and Ar have the meanings mentioned above.
Herbizid wirksame 2-Aroyl-l,3-diketone sind beispielsweise aus EP-A 90262, EP-A 135191, EP-A 162166, EP-A 186118, EP-A 186119, EP-A 283261, EP-A 319075, WO 90/05712, WO 94/04524, WO 94/08988, JP 3052862, JP 3120202, WO 96/04182, WO 97/09324, WO 99/03845 und Weed Science, 45, 1997, 601-609 und darin zitierte Literatur be- kannt.Herbicidally active 2-aroyl-1,3-diketones are known, for example, from EP-A 90262, EP-A 135191, EP-A 162166, EP-A 186118, EP-A 186119, EP-A 283261, EP-A 319075, WO 90/05712, WO 94/04524, WO 94/08988, JP 3052862, JP 3120202, WO 96/04182, WO 97/09324, WO 99/03845 and Weed Science, 45, 1997, 601-609 and the literature cited therein - knows.
Die Herstellung der 2-Aroyl-l,3-diketone erfolgt in der Regel ausgehend von einer aromatischen Carbonsäure der Formel Ar-COOH oder ihrem Säurechlorid Ar-CO-Cl, die mit einem 1,3-Diketon der Formel IIIThe 2-aroyl-1,3-diketones are generally prepared starting from an aromatic carboxylic acid of the formula Ar-COOH or its acid chloride Ar-CO-Cl, which is reacted with a 1,3-diketone of the formula III
Ra-C(0)-CH2-C(0)-Rb (HI)R a -C (0) -CH 2 -C (0) -R b (HI)
oder seinen Tautomeren III' bzw. III"or its tautomers III 'or III "
Ra-C(0)-CH=C(OH)-R (III');R a -C (0) -CH = C (OH) -R (III ');
Ra-C(OH)=CH-C(0)-Rb (III")R a -C (OH) = CH-C (0) -R b (III ")
worin Ra und Rb die zuvor genannten Bedeutungen haben, in Gegenwart eines wasserentziehenden Mittels, z.B. eines Anhydrids oder eines Carbodiimids , zu ß-Ketoenolestern der oben definierten Formel I umgesetzt wird.wherein R a and R b have the meanings given above, in the presence of a dehydrating agent, for example an anhydride or a carbodiimide, is converted to β-ketoenol esters of the formula I defined above.
Die ß-Ketoenolester I werden anschliessend mit einer Base und vorzugsweise in Gegenwart einer katalytisch wirksamen Menge einer Cyanidgruppen-enthaltenden Verbindung zu den herbizid wirksamen 2-Aroyl-l,3-diketonen der oben definierten Formel X umgelagert. Auch kann man anstelle der Carbonsäure Ar-COOH ein aktiviertes Arylcarbonsäurederivat, z.B. Carbonsäurehalogenid Ar-COL, worin L ein Halogenatom wie Chlor bedeutet, zur Herstellung von ß-Ketoenolestern I einsetzen. Die Umsetzung des Säurehalogenids mit III zu I erfolgt vorzugsweise in Gegenwart einer Base (vgl. den oben genannten Stand der Technik insbesondere EP 283261 und WO 96/05182 sowie die darin genannte Literatur) . Dieses Verfahren hat den Nachteil, dass die aromatischen Carbonsäuren Ar-COOH aufwendig hergestellt werden müssen, beispielsweise aus den besser zugänglichen Arylhalogeniden, z.B. durch sukzessive Überführung in eine metallorganische Verbindung und anschliessende Umsetzung mit C02, oder durch Seitenkettenoxidation von Methyl-substuierten Aromaten.The β-ketoenol esters I are then rearranged with a base and preferably in the presence of a catalytically effective amount of a compound containing cyanide groups to give the herbicidally active 2-aroyl-1,3-diketones of the formula X defined above. Instead of the carboxylic acid Ar-COOH, an activated arylcarboxylic acid derivative, for example carboxylic acid halide Ar-COL, in which L represents a halogen atom such as chlorine, can also be used to prepare β-ketoenol esters I. The conversion of the acid halide with III to I preferably takes place in the presence of a base (cf. the abovementioned prior art, in particular EP 283261 and WO 96/05182 and the literature mentioned therein). This process has the disadvantage that the aromatic carboxylic acids Ar-COOH have to be prepared in a complex manner, for example from the more accessible aryl halides, for example by successive conversion into an organometallic compound and subsequent reaction with CO 2 , or by side chain oxidation of methyl-substituted aromatics.
Die Herstellung der Carbonsäuren Ar-COOH ist insbesondere bei Aromaten mit anellierten Heterocyclen nicht unproblematisch. Auch die anschliessende Umsetzung der Arylcarbonsäuren Ar-COOH bzw. ihrer aktivierten Derivate Ar-COL zu den ß-Ketoenolestern I lässt sich nicht immer mit zufriedenstellenden Ausbeuten realisieren.The production of the carboxylic acids Ar-COOH is not without problems, in particular in the case of aromatics with fused heterocycles. The subsequent conversion of the aryl carboxylic acids Ar-COOH or their activated derivatives Ar-COL to the β-ketoenol esters I cannot always be achieved with satisfactory yields.
Der vorliegenden Erfindung liegt somit die Aufgabe zugrunde, ein wirtschaftlicheres Verfahren zur Herstellung von ß-Ketoenolestern der allgemeinen Formel I bereitzustellen.The present invention is therefore based on the object of providing a more economical process for the preparation of β-ketoenol esters of the general formula I.
Es wurde überraschenderweise gefunden, dass die Umsetzung von Arylhalogeniden der allgemeinen Formel IIIt has surprisingly been found that the reaction of aryl halides of the general formula II
Ar-Hal (II)Ar-Hal (II)
worin Ar die zuvor genannten Bedeutungen hat und Hai für ein Halogenatom steht, das ausgewählt ist unter Chlor, Brom und Iod, mit einem 1,3-Diketon der allgemeinen Formel III oder seinen Tautomeren III' oder III" in einer Kohlenmonoxid-Atmosphäre in Gegenwart einer Base und eines Katalysators, der wenigstens ein Übergangsmetall der Gruppe VIII des Periodensystems enthält, in guten Ausbeuten zu den ß-Ketoenolestern der oben definierten all- gemeinen Formel I führt.wherein Ar has the meanings mentioned above and Hai represents a halogen atom which is selected from chlorine, bromine and iodine, with a 1,3-diketone of the general formula III or its tautomers III 'or III "in a carbon monoxide atmosphere in the presence a base and a catalyst which contains at least one transition metal from Group VIII of the Periodic Table leads in good yields to the β-ketoenol esters of the general formula I defined above.
Demnach betrifft die vorliegende Erfindung ein Verfahren zur Herstellung von ß-Ketoenolestern der eingangs definierten allgemeinen Formel Ia oder Ib, das dadurch gekennzeichnet ist, dass man ein Arylhalogenid der oben definierten allgemeinen Formel II mit einem 1,3-Diketon der allgemeinen Formel III oder seinen Tautomeren III' oder III" in einer Kohlenmonoxid-Atmosphäre in Gegenwart einer Base und eines Katalysators, der wenigstens ein Übergangsmetall der Gruppe VIII des Periodensystems enthält, umsetzt.Accordingly, the present invention relates to a process for the preparation of β-ketoenol esters of the general formula Ia or Ib defined at the outset, which is characterized in that an aryl halide of the general formula II defined above with a 1,3-diketone of the general formula III or its Tautomers III 'or III "in a carbon monoxide atmosphere in the presence of a base and a catalyst which contains at least one transition metal from group VIII of the periodic table.
Die vorliegende Erfindung betrifft ausserdem ein Verfahren, bei dem man zunächst ein Arylhalogenid der Formel II mit einem 1,3-Diketon der allgemeinen Formel III oder seinen Tautomeren III' oder III" in einer Kohlenmonoxid-Atmosphäre in Gegenwart ei- ner Base und eines Katalysators, der wenigstens ein Übergangsmetall der Gruppe VIII des Periodensystems enthält, zu einem ß-Ketoenolestern der eingangs definierten allgemeinen Formel Ia oder Ib umsetzt und diesen dann durch Behandlung mit einer Base und einer katalytisch aktiven Menge wenigstens einer Cyanid-Verbin- dung in 2-Aroyl-substituierte 1,3-Diketone der Formel X oder ihre Tautomere Xa, Xb oder XcThe present invention also relates to a process in which an aryl halide of the formula II is first used with a 1,3-diketone of the general formula III or its tautomers III 'or III "in a carbon monoxide atmosphere in the presence of a base and a catalyst , which contains at least one transition metal from group VIII of the periodic table, to a β-ketoenol ester of the general formula Ia or defined at the outset Ib and this is then converted into 2-aroyl-substituted 1,3-diketones of the formula X or their tautomers Xa, Xb or Xc by treatment with a base and a catalytically active amount of at least one cyanide compound
(Xa) (Xb) (XC) umlagert.(Xa) (Xb) (XC) rearranged.
Die für die Substituenten Ra, Rb und Ar oder im folgenden als Reste an Phenyl— und Heterocyclyl—Resten genannten organischen Molekülteile stellen Sammelbegriffe für individuelle Aufzählungen der einzelnen Gruppenmitglieder dar. Sämtliche Kohlenwasserstoffketten, also alle Alkyl—, Halogenalkyl—, Alkoxy—, Halogenalkoxy—, Alkylthio—, Halogenalkylthio—, Alkyls lfinyl—, Alkylsulfonyl—, N-Alkylamino-, N,N-Dialkylamino-, Alkylcarbonyl—, Alkoxycarbonyl—, Alkylcarbonyloxy—, Alkylaminocarbonyl—, Dialkylaminocarbonyl—, Alkoxyalkyl—, Alkoxyiminoalkyl-, Phenylalkyl, Heterocyclylalkyl, Alkenylcarbo- nyl—, Alkenyloxycarbonyl—, Alkenyl—, Alkinyl—, Halogenalkenyl—, Halogenalkinyl—, Alkenyloxy-, Alkinyloxy, Alkandiyl-, Alkendiyl-, Alkadiendiyl- oder Alkindiyl—eile können geradkettig oder verzweigt sein. Die Angabe Cn-Cm steht dabei für die Anzahl mögli- eher Kohlenstoffatome . Sofern nicht anders angegeben, tragen halogenierte Substituenten vorzugsweise ein bis fünf gleiche oder verschiedene Halogenatome. Die Bedeutung Halogen steht jeweils für Fluor, Chlor, Brom oder Iod.The organic molecule parts mentioned for the substituents R a , R b and Ar or in the following as residues on phenyl and heterocyclyl residues represent collective terms for individual lists of the individual group members. All hydrocarbon chains, that is to say all alkyl, haloalkyl, alkoxy, Haloalkoxy, alkylthio, haloalkylthio, alkylsfinyl, alkylsulfonyl, N-alkylamino, N, N-dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxyalkyl, alkoxyiminoalkyl, phenylalkyl , Heterocyclylalkyl, alkenylcarbonyl, alkenyloxycarbonyl, alkenyl, alkynyl, haloalkenyl, haloalkynyl, alkenyloxy, alkynyloxy, alkanediyl, alkenediyl, alkadienediyl or alkynediyl ropes can be straight-chain or branched. The specification C n -C m stands for the number of possible carbon atoms. Unless otherwise stated, halogenated substituents preferably carry one to five identical or different halogen atoms. Halogen is fluorine, chlorine, bromine or iodine.
Ferner bedeuten beispielsweise:Furthermore, for example:
Ci— C — Alkyl sowie die Alkylteile von (Di) -Cι— C4— Alkylamino, C1-C4- Alkoxy, C1-C4— Alk lthio , Cι-C -Alkylsulfinyl, Cι-C4— Alkylsulfonyl , C1-C — Alkylcarbonyl, Ci— C4— Alkoxycarbonyl, Ci— C4— Älkyloxycarbonyl , C1—C4— Alkylaminocarbonyl, Ci— C4— Alkyl- carbonylamino, für: z .B . Methyl, Ethyl, Propyl, 1— Methyl- ethyl, Butyl, 1—Methylpropy1, 2—Methylpropyl oder 1, 1—Dimethylethyl;Ci— C - alkyl and the alkyl parts of (di) -Cι— C 4 - alkylamino, C 1 -C 4 - alkoxy, C 1 -C 4 - alk lthio, Cι-C-alkylsulfinyl, Cι-C 4 - alkylsulfonyl, C1 - alkylcarbonyl, Ci- C 4 - alkoxycarbonyl, Ci- C 4 - Älkyloxycarbonyl, C 1 -C 4 - alkylaminocarbonyl, Ci- C 4 - alkyl carbonylamino, for: e .g. Methyl, ethyl, propyl, 1- methyl ethyl, butyl, 1-methylpropy1, 2-methylpropyl or 1, 1-dimethylethyl;
— Ci—C6—Alkyl, sowie die Alkylteile von (Di)-Cι—C6—Alkylamino, Cι-C6—Alkoxy, Cι-C6-Alkylthio, Cι-C6-Alkylsulfinyl, Cι-C6—Al- kylsulfonyl, Ci—C6—Alkylcarbonyl, Ci—Cε—Alkoxycarbonyl, Ci—C6—Alkyloxycarbonyl, Ci—C6—Alkylaminocarbonyl, Ci—Cβ—Alkyl- carbonylamino, für: Ci—C4—Alkyl, wie voranstehend genannt, sowie z.B. Pentyl, 1— ethylbutyl, 2—Methylbutyl, 3—Methylbutyl, 2 , 2—Dimethylpropyl, 1—Ethylpropyl, Hexyl, 1, 1—Dimethylpropyl, 1, 2—Dimethylpropyl, 1—Methylpenty1, 2—Methylpentyl, 3-Methylpentyl, 4-Methylpenty1, 1 , 1-Dimethylbutyl, 1, 2-Dimethylbutyl, 1, 3-Dimethylbutyl, 2 , 2—Dimethylbutyl, 2 , 3—Dimethylbutyl, 3 , 3—Dimethylbut 1, 1—Ethylbutyl, 2—Ethylbutyl, 1,1, 2—Trimethylpropyl, 1—Ethyl—1—methylpropyl oder 1—Ethyl—3—methylpropyl;- C 1 -C 6 -Alkyl, and the alkyl parts of (di) -C-C 6 -alkylamino, -C-C 6 -alkoxy, -C-C 6 -alkylthio, -C-C 6 -alkylsulfinyl, -C-C 6 -Al - Cylsulfonyl, Ci-C 6 -alkylcarbonyl, Ci-Cε-alkoxycarbonyl, Ci-C 6 -alkyloxycarbonyl, Ci-C 6 -alkylaminocarbonyl, Ci-Cβ-alkylcarbonylamino, for: Ci-C 4 -alkyl, as mentioned above , and for example pentyl, 1-ethylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpenty1, 2-methylpentyl, 3 -Methylpentyl, 4-methylpenty1, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3, 3-dimethylbut 1, 1-ethylbutyl, 2- Ethyl butyl, 1,1, 2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-3-methylpropyl;
— Ci—C4—Halogenalkyl sowie die Halogenalkylteile von (Di) ~Cχ—C4—Halogenalkylamino, Ci—C4—Halogenalkoxy, Ci—C4—Halogenalkylthio, Ci—C—Halogenalkylsulfinyl,Ci-C 4 -haloalkyl and the haloalkyl parts of (di) ~ Cχ-C 4 -haloalkylamino, Ci-C 4 -haloalkoxy, Ci-C 4 -haloalkylthio, Ci-C-haloalkylsulfinyl,
Ci—C4—Halogenalkylsulfonyl, Cι-C—Halogenalkylcarbonyl, Ci—C4—Halogenalkoxycarbonyl, Ci—C4—Halogenalkyloxycarbonyl, Ci—C4—Halogenalkylaminocarbonyl, Ci—C4—Halogenalkylcarbonyla- mino: einen Ci—C4—Alkylrest, wie vorstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder lod substituiert ist, also z.B. Chlormethyl, Dichlormethyl, Trichlormethyl, Fluormethyl, Difluormethyl, Trifluormethyl, Chlorfluormethyl, Dichlorfluormethyl, Chlordifluormethyl, 2-Fluorethyl, 2-Chlorethyl, 2-Bromethyl, 2-Iodethyl, 2,2-Difluorethyl, 2,2,2-Trifluorethyl, 2-Chlor-2-fluorethyl, 2-Chlor-2 , 2-difluorethyl, 2 , 2-Dichlor-2-fluorethyl, 2,2,2-Trichlorethyl, Pentafluorethyl, 2-Fluorpropyl, 3-Fluorpropyl, 2,2-Difluorpropyl, 2,3-Difluorpropyl, 2-Chlorpropyl, 3-Chlorpropyl, 2,3-Dichlorpropyl, 2-Brompropyl, 3-Brompropyl, 3, 3, 3-Trifluorpropyl, 3,3,3-Trichlorpropy1, 2,2,3,3,3-Pentafluorpropyl, Heptafluorpropyl, 1- (Fluormethyl)-2-fluorethyl, 1- (Chlormethyl) -2-chlorethyl, 1- (Brommethyl) -2-bromethyl, 4-Fluorbutyl, 4-Chlorbutyl, 4-Brombutyl oder Nonafluorbutyl;Ci — C 4 —haloalkylsulfonyl, Ci-C — haloalkylcarbonyl, Ci — C 4 —haloalkoxycarbonyl, Ci — C 4 —haloalkyloxycarbonyl, Ci — C 4 —haloalkylaminocarbonyl, Ci — C 4 —haloalkylcarbonylamino: a Ci — C 4 —alkyl radical , as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3- Bromopropyl, 3, 3, 3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) l) -2-chloroethyl, 1- (bromomethyl) -2-bromethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;
— Cι—C6—Halogenalkyl, sowie die Halogenalkylteile von (Di)-Cι—C6—Halogenalkylamino, Cι—C6—Halogenalkoxy, Ci—Cß—Halogenalkylthio, Ci—Cß—Halogenalkylsulfinyl, Ci—Cß—Halogenalkylsulfonyl, CI—CÖ—Halogenalkylcarbonyl, Ci— Cβ—Halogenalkoxycar- bonyl, Ci—C6—Halogenalkyloxycarbonyl, Ci-Cβ—Halogenalkylaminocarbonyl, Cι—C6—Halogenalkylcarbon lamino: Ci—C4—Halogenalkyl, wie voranstehend genannt, sowie z.B. 5—Fluorpentyl, 5—Chlorpentyl, 5—Brompentyl, 5—Iodpentyl, Undecafluorpentyl, 6—Fluorhexyl, 6—Chlorhexyl, 6—Bromhexyl, 6—Iodhexyl oder Dodecafluorhexyl;- C 1 -C 6 -Halogenalkyl, as well as the haloalkyl parts of (Di) -Cι-C 6 -Halogenalkylamino, Cι-C 6 -Halogenalkoxy, Ci-C ß -Halogenalkylthio, Ci-C ß -Halogenalkylsulfinyl, Ci-C ß -Halogenalkylsulfonyl , C I —C O —haloalkylcarbonyl, Ci— Cβ — haloalkoxycarbonyl, Ci — C 6 —haloalkyloxycarbonyl, Ci-Cβ — haloalkylaminocarbonyl, Cι — C 6 —haloalkylcarbonamino: Ci — C 4 —haloalkyl, as mentioned above, and eg 5 — fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodo-pentyl, undecafluoropentyl, 6-fluorohexyl, 6-chloro-hexyl, 6-bromohexyl, 6-iodo-hexyl or dodecafluoro-hexyl;
— Ci—C4—Alkoxy: z.B. Methoxy, Ethoxy, Propoxy, 1—Me hylethoxy, Butoxy, 1—Methylpropoxy, 2—Methylpropoxy oder 1 , 1—Dimethylethoxy;C 1 -C 4 alkoxy: for example methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy;
— Ci—C6—Alkoxy: Cι—C4—Alkoxy, wie voranstehend genannt, sowie z.B. Pentoxy, 1—Methylbutoxy, 2—Methylbutoxy, 3—Methylbutoxy,Ci — C 6 —alkoxy: —CC 4 —alkoxy, as mentioned above, and for example pentoxy, 1 — methylbutoxy, 2 — methylbutoxy, 3 — methylbutoxy,
1, 1—Dimethylpropox , 1, 2—Dimethylpropox ,1, 1-dimethylpropox, 1, 2-dimethylpropox,
2,2-Dimethylpropoxy, 1-Ethylpropoxy, Hexoxy, 1-Methylpentoxy, 2-Methylpentoxy, 3-Methylpentoxy, 4-Methylpentoxy, 1, 1-Dimethylbutoxy, 1,2-Dimethylbutoxy, 1,3-Dirnethylbutoxy, 2, 2-Dimethylbutoxy, 2, 3-Dimethylbutoxy, 3,3-Dimethylbutoxy, 1-Ethylbutoxy, 2-Ethylbutoxy, 1, 1,2-Trimethylpropoxy, 1,2, 2-Trimethylpropoxy, 1-Ethyl-l-methylpropoxy oder 1-Eth 1—2-meth lpropoxy;2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dirnethylbutoxy, 2, 2- Dimethylbutoxy, 2, 3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1,2-trimethylpropoxy, 1,2, 2-trimethylpropoxy, 1-ethyl-l-methylpropoxy or 1-eth 1 - 2-meth lpropoxy;
— Ci—Cß—Halogenalkoxy: einen Ci—C6—Alkoxyrest, wie voranstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder Iod substituiert ist;- Ci-C -haloalkoxy ß: a Ci-C 6 alkoxy group as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine;
— Ci—CÖ—Alkylcarbonyl, sowie die Alkylcarbonylreste von Cι-C6-Alkylcarbonyl-Cι-C6-alkyl, Cι-C6-Alkylcarbonyloxy,- Ci-C Ö alkylcarbonyl, and alkylcarbonyl of Cι-C 6 alkylcarbonyl-Cι-C 6 -alkyl, C 6 alkylcarbonyloxy,
Ci-Cg-Alkylcarbonylamino: einen über eine Carbonylgruppe gebundenen Alkylrest z.B. Methylcarbonyl, Ethylcarbonyl, Propylcarbonyl, 1—Methylethylcarbonyl, Butylcarbonyl, 1— ethylpropylcarbonyl, 2—Methylpropylcarbonyl, 1, 1—Dimethyl- ethylcarbonyl;Ci-Cg-alkylcarbonylamino: an alkyl radical bonded via a carbonyl group, e.g. Methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl, 1-ethylpropylcarbonyl, 2-methylpropylcarbonyl, 1, 1-dimethylethylcarbonyl;
— Ci—C—Alkoxycarbonyl: z.B. Methoxycarbonyl, Ethoxycarbonyl, Propoxycarbonyl, 1—Methylethoxycarbonyl, Butoxycarbonyl, 1—Methylpropoxycarbonyl, 2—Methylpropoxycarbonyl oder 1, 1—Dimethylethoxycarbonyl;Ci-C-alkoxycarbonyl: e.g. Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1-methylethoxycarbonyl, butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl or 1, 1-dimethylethoxycarbonyl;
— Cι-C6-Alkoxycarbonyl: Methoxycarbonyl, Ethoxycarbonyl, Propoxycarbonyl, 1—Methylethoxycarbonyl, Butoxycarbonyl,-C 6 -alkoxycarbonyl: methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1 — methylethoxycarbonyl, butoxycarbonyl,
1—Methylpropoxycarbonyl, 2—Meth lpropoxycarbonyl oder 1, 1—Di- methylethoxycarbonyl, Pentoxycarbonyl,1-methylpropoxycarbonyl, 2-meth lpropoxycarbonyl or 1, 1-dimethylethoxycarbonyl, pentoxycarbonyl,
1-Methylbutoxycarbonyl, 2-Methylbutoxycarbonyl,1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl,
3-Methylbutoxycarbonyl, 2,2-Dimethylpropoxycarbonyl,3-methylbutoxycarbonyl, 2,2-dimethylpropoxycarbonyl,
1-Ethylpropoxycarbony1, Hexoxycarbony1,1-ethylpropoxycarbony1, hexoxycarbony1,
1 , 1-Dimethylpropoxycarbonyl, 1, 2-Dimethylpropoxycarbonyl, 1-Methylpentoxycarbony1, 2-Methylpentoxycarbonyl,1, 1-dimethylpropoxycarbonyl, 1, 2-dimethylpropoxycarbonyl, 1-methylpentoxycarbony1, 2-methylpentoxycarbonyl,
3-Methylpentoxycarbonyl, 4-Methylpentoxycarbony1,3-methylpentoxycarbonyl, 4-methylpentoxycarbony1,
1, 1-Dimeth lbutoxycarbony1, 1, 2-Dimethylbutoxycarbonyl, 1,3-Dimethylbutoxycarbonyl, 2 ,2-Dimethylbutoxycarbonyl, 2 , 3-Dimethylbutoxycarbonyl, 3 , 3-Dimethylbutoxycarbonyl, 1-Ethylbutoxycarbonyl, 2-Ethylbutoxycarbonyl, 1,1, 2-Trimethylpropoxycarbonyl, 1> 2, 2-Trimethylpropoxycarbonyl,1, 1-dimeth-1-butoxycarbony1, 1, 2-dimethylbutoxycarbonyl, 1,3-dimethylbutoxycarbonyl, 2, 2-dimethylbutoxycarbonyl, 2, 3-dimethylbutoxycarbonyl, 3, 3-dimethylbutoxycarbonyl, 1-ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl, 1,1, 2-trimethylpropoxycarbonyl, 1 > 2, 2-trimethylpropoxycarbonyl,
1-Ethyl-l-methyl-propoxycarbonyl oder l-Ethyl-2-methyl-propoxycarbonyl;1-ethyl-l-methyl-propoxycarbonyl or l-ethyl-2-methyl-propoxycarbonyl;
— (Cι—C4—Alkyl)carbonyloxy: Acetyloxy, Eth lcarbonyloxy, Propylcarbonyloxy, 1—Methylethylcarbonyloxy, Butylcarbonyloxy, 1—Meth lpropylcarbonyloxy, 2—Methylpropylcarbonyloxy oder 1,1—Dimethylethylcarbonyloxy;- (-C 1 -C 4 -alkyl) carbonyloxy: acetyloxy, ethyl carbonyloxy, propyl carbonyloxy, 1-methyl ethyl carbonyloxy, butyl carbonyloxy, 1-meth propyl carbonyloxy, 2-methyl propyl carbonyloxy or 1,1-dimethyl ethyl carbonyloxy;
Cι-C6-Hydroxyalkyl: durch ein bis drei OH-Gruppen substituier- tes Ci-Cβ-Alkyl, z.B Hydroxymeth 1, 1-Hydroxyethyl, 2-Hydro- xyethyl, 1,2-Bishydroxyethyl, 1-Hydroxypropyl, 2-Hydroxypro- pyl, 3-Hydroxypropy1, 4-Hydroxybutyl, 2,2-Dimethyl-3-hydroxy- propyl;-C-C 6 -hydroxyalkyl: Ci-Cβ-alkyl substituted by one to three OH groups, for example hydroxymeth 1, 1-hydroxyethyl, 2-hydroxyethyl, 1,2-bishydroxyethyl, 1-hydroxypropyl, 2-hydroxypro - pyl, 3-hydroxypropy1, 4-hydroxybutyl, 2,2-dimethyl-3-hydroxypropyl;
- Cχ-C6-Hydroxyalkoxy: durch ein bis drei OH-Gruppen substituiertes Ci-Cβ-Alkoxy, z.B Hydroxymethoxy, 1-Hydroxyethoxy, 2-Hydroxyethoxy, 1,2-Bishydroxyethoxy, 1-Hydroxypropoxy, 2-Hydroxypropoxy, 3-Hydroxypropoxy, 4-Hydroxybutoxy, 2,2-Di- methy1-3-hydroxypropoxy;- Cχ-C 6 -hydroxyalkoxy: Ci-Cβ-alkoxy substituted by one to three OH groups, for example hydroxymethoxy, 1-hydroxyethoxy, 2-hydroxyethoxy, 1,2-bishydroxyethoxy, 1-hydroxypropoxy, 2-hydroxypropoxy, 3-hydroxypropoxy , 4-hydroxybutoxy, 2,2-dimethyl 1-3 hydroxypropoxy;
Phenyl-Cι-C6-alkyl: durch einen Phenylrest substituiertes Ci-Cß-Alkyl, z.B. Benzyl, 1-Phenylethyl und 2-Phenylethyl, wobei der Phenylrest in der angegebenen Weise teilweise oder vollständig halogeniert sein kann oder einen bis drei der für Phenyl oben angegebenen Substituenten aufweisen kann;Phenyl-C 1 -C 6 -alkyl: Ci-C ß- alkyl substituted by a phenyl radical, for example benzyl, 1-phenylethyl and 2-phenylethyl, where the phenyl radical can be partially or completely halogenated in the manner indicated or one to three of those for Phenyl may have substituents given above;
Heterocyclyl-Ci-Cg-alkyl steht dementsprechend für ein durch einen Heterocyclylrest substituiertes Ci-Cβ-Alkyl;Heterocyclyl-Ci-Cg-alkyl accordingly represents a Ci-Cβ-alkyl substituted by a heterocyclyl radical;
Cι-C6-Alkoxy-Cι-C6-alkyl: durch Cι-C6-Alkoxy, wie vorstehend genannt, substituiertes Cι-C6-Alkyl, also z.B. Methoxymethyl,C 1 -C 6 -alkoxy-C 6 -C 6 -alkyl: C 1 -C 6 -alkoxy, as mentioned above, substituted C 1 -C 6 -alkyl, for example methoxymethyl,
Ethoxymethyl, Propoxymeth 1, ( 1-Methylethoxy)methy1,Ethoxymethyl, propoxymeth 1, (1-methylethoxy) methy1,
Butoxymethy1, ( l-Methylpropoxy)methyl,Butoxymethy1, (l-methylpropoxy) methyl,
(2-Methylpropoxy)-methy1, ( 1, 1-DimethylethoxyJmethyl,(2-methylpropoxy) -methyl, (1, 1-dimethylethoxy-methyl,
2-(Methoxy)ethyl, 2-(Ethoxy)ethyl, 2-(Propoxy)ethyl, 2-(l-Methylethoxy)ethyl, 2-(Butoxy)ethyl,2- (methoxy) ethyl, 2- (ethoxy) ethyl, 2- (propoxy) ethyl, 2- (l-methylethoxy) ethyl, 2- (butoxy) ethyl,
2-( 1-Methylpropoxy)ethyl, 2-(2-Methylpropoxy)ethyl,2- (1-methylpropoxy) ethyl, 2- (2-methylpropoxy) ethyl,
2-(l, 1-Dimethylethoxy)ethyl, 2-(Methoxy)-propyl,2- (l, 1-dimethylethoxy) ethyl, 2- (methoxy) propyl,
2-(Ethoxy)propyl, 2-(Propoxy)propyl,2- (ethoxy) propyl, 2- (propoxy) propyl,
2- ( 1-Methylethoxy)—propy1, 2- (Butoxy) rop 1, 2- ( 1-Methylpropoxy)propy1, 2-(2-Methylpropoxy)propy1,2- (1-methylethoxy) propy1, 2- (butoxy) rop 1,2, (1-methylpropoxy) propy1, 2- (2-methylpropoxy) propy1,
2-(l, 1-Dimethylethoxy) rop 1, 3-(Methoxy)propyl,2- (l, 1-dimethylethoxy) rop 1,3, (methoxy) propyl,
3- (Ethoxy)—propy1, 3- (Propoxy) ropy1, 3- 1-Meth lethoxy)propy1, 3- (Butoxy)prop 1, 3- 1-Meth lpropoxy)propy1, 3- (2-Methylpropoxy)propy1, 3- 1, l-Dimethylethoxy)propyl, 2-(Methoxy)butyl, 2- Ethoxy)butyl, 2-(Prop—oxy)butyl, 2- (1-Meth lethoxy)butyl, 2- Butoxy)buty1, 2- ( 1-Methylpropoxy)buty1, 2- 2-Methylpropox )buty1, 2- ( 1, 1-Dimethylethoxy)buty1, 3- Methox )but 1, 3-(Ethoxy)butyl, 3-(Propoxy)butyl, 3- 1-Meth lethoxy)buty1, 3- (Butox )—buty1, 3- 1-Methylpropox )buty1, 3-( 2-Meth lpropoxy)buty1, 3- 1, l-Dimethylethoxy)butyl, 4- (Methox )butyl, 4- Ethoxy)—butyl, 4-(Propoxy)butyl, 4-(l-Methylethoxy)butyl, 4- Butoxy)—butyl, 4- ( 1-Methylpropoxy)butyl, 4- 2-Methylpropoxy)butyl oder 4-(l, 1-Dimethylethoxy)butyl;3- (ethoxy) -propy1, 3- (propoxy) ropy1, 3- 1-meth lethoxy) propy1, 3- (butoxy) prop 1, 3- 1-meth lpropoxy) propy1, 3- (2-methylpropoxy) propy1, 3- 1, l-dimethylethoxy) propyl, 2- (methoxy) butyl, 2-ethoxy) butyl, 2- (propoxy) butyl, 2- (1-methethoxy) butyl, 2-butoxy) buty1, 2- (1-methylpropoxy) buty1, 2- 2-methylpropox) buty1, 2- (1, 1-Dimethylethoxy) buty1, 3-methox) but 1, 3- (ethoxy) butyl, 3- (propoxy) butyl, 3- 1-methethoxy) buty1, 3- (butox) -buty1, 3rd - 1-methylpropox) buty1, 3- (2-meth lpropoxy) buty1, 3- 1, l-dimethylethoxy) butyl, 4- (methox) butyl, 4- ethoxy) butyl, 4- (propoxy) butyl, 4- (l-methylethoxy) butyl, 4-butoxy) butyl, 4- (1-methylpropoxy) butyl, 4- 2-methylpropoxy) butyl or 4- (l, 1-dimethylethoxy) butyl;
- Di-(Cι-C6-alkoxy)methyl: durch zwei Ci-Cß-Alkoxy-Gruppen substituiertes Methyl;- Di- (-C 6 alkoxy) methyl: methyl substituted by two Ci-C ß alkoxy groups;
Di-(Cι-C6-alkylthio)methyl: durch zwei Cι-C6-Alkylthio-Gruppen substituiertes Methyl;Di- (-C 6 alkylthio) methyl: methyl substituted by two -C 6 alkylthio groups;
(Ci-Cβ-Alkoxy) (Cι-C6-alkylthio)methyl: durch eine Ci-Cg-Alko- xy-Gruppe und eine Ci-Cß-Alkylthio-Gruppen substituiertes Methyl;(Ci-Cβ-alkoxy) (-CC 6 -alkylthio) methyl: methyl substituted by a Ci-Cg-alkoxy group and a Ci-C ß- alkylthio group;
- Cι-C6-(Halogen)alkylsulfonyl-C1-C6-alkyl, Ci-Cg- (Halogen)al- kylthio-Cι-C6-alkyl, Ci-Cö-Alkyla ino-Ci-Ce-alkyl, Di-Cι-C6-Al- kylamino-Ci-Ce-alkyl: Durch Cι-C6- (Halogen) alkylsulfonyl,- -C-C 6 - (Halogen) alkylsulfonyl-C 1 -C 6 alkyl, Ci-Cg- (halogen) alkyl-thio-Cι-C 6 alkyl, Ci-C ö -Alkla ino-Ci-Ce-alkyl , C 1 -C 6 -alkylamino-Ci-Ce-alkyl: C 1 -C 6 - (halogen) alkylsulfonyl,
Cι-C6-(Halogen)alkylthio, Ci-Cg-Alkylamino bzw. Di-Ci-Cß-Alky- lamino substituiertes Ci-Cδ-Alkyl;-C-C 6 - (Halogen) alkylthio, Ci-Cg-alkylamino or di-Ci-C ß -Alkylamino substituted Ci-C δ alkyl;
Ci-Cß-Alkoxy-Ci-Cg-alkoxy: durch Ci-Cö-Alkoxy, wie vorstehend genannt, substituiertes Ci-Cβ-Alkoxy, also z.B. fürCi-C ß alkoxy-Ci-Cg-alkoxy: by C ö alkoxy as mentioned above, substituted Ci-Cβ-alkoxy, eg for
Methoxymethoxy, Ethoxymethoxy, Propoxymethoxy,Methoxymethoxy, ethoxymethoxy, propoxymethoxy,
( 1—Methylethoxy)methoxy, Butoxymethoxy, ( 1—Methylpropoxy)methoxy, (2—Meth lpropoxy)methoxy,(1-methylethoxy) methoxy, butoxymethoxy, (1-methylpropoxy) methoxy, (2-methylpropoxy) methoxy,
(1, 1—Dimethylethoxy)methoxy, 2- (Methoxy)ethoxy,(1,1-dimethylethoxy) methoxy, 2- (methoxy) ethoxy,
2- (Ethoxy)ethoxy, 2-(Propoxy) ethox ,2- (ethoxy) ethoxy, 2- (propoxy) ethox,
2- ( 1-Methylethoxy)ethoxy, 2- (Butoxy)ethoxy,2- (1-methylethoxy) ethoxy, 2- (butoxy) ethoxy,
2- ( 1-Meth lpropoxy)ethoxy, 2- (2-Methylpropox )ethoxy, 2- ( 1, 1-Dimethylethoxy)ethoxy, 2-(Methoxy)propoxy,2- (1-methylpropoxy) ethoxy, 2- (2-methylpropox) ethoxy, 2- (1, 1-dimethylethoxy) ethoxy, 2- (methoxy) propoxy,
2- (Ethoxy)propoxy, 2-( ropoxy) ropoxy,2- (ethoxy) propoxy, 2- (ropoxy) ropoxy,
2- ( 1-Methylethox )propoxy, 2- (Butoxy)—propoxy,2- (1-methylethox) propoxy, 2- (butoxy) propoxy,
2- ( 1-Methylpropoxy) ropox , 2-(2-Methylpropoxy)propoxy,2- (1-methylpropoxy) ropox, 2- (2-methylpropoxy) propoxy,
2- (1,1-Dirnethylethoxy) ropoxy, 3- ( ethoxy)—ropoxy, 3- (Ethoxy)propoxy, 3- (Propoxy)propoxy,2- (1,1-dimethylethyloxy) ropoxy, 3- (ethoxy) -ropoxy, 3- (ethoxy) propoxy, 3- (propoxy) propoxy,
3- ( 1-Methylethoxy)propoxy, 3-(Butoxy)propoxy,3- (1-methylethoxy) propoxy, 3- (butoxy) propoxy,
3- ( 1-Methylpropoxy)— ropoxy, 3- (2-Methylpropoxy)propoxy, 3- 1, 1-Dimethylethoxy)propoxy, 2- (Methoxy)butoxy, 2- Ethoxy)butoxy, 2- (Propoxy)butoxy, 2- 1-Meth lethox )butoxy, 2- (Butox )—butox , 2- 1-Meth lpropoxy)butoxy, 2- ( 2-Methylpropox )butox , 2- 1, 1-Dimethylethoxy)butoxy, 3- (Methoxy)butoxy, 3- Ethoxy)—butoxy, 3- (Propoxy)butox , 3- 1-Methylethoxy)butoxy, 3-(Butoxy)butoxy, 3- 1-Methylpropoxy)butoxy, 3-(2-Methylpropox )butoxy, 3- 1, 1-Dimeth lethoxy)butoxy, 4- (Methoxy)—butoxy, 4- Ethoxy)butoxy, 4- (Propoxy)butox , 4- 1-Methylethoxy)butoxy, 4-(Butoxy)butoxy, 4- 1-Me hylpropoxy)butox , 4- ( 2-Methylpropoxy)butoxy oder 4- 1, 1-Dimethylethoxy)butoxy;3- (1-methylpropoxy) ropoxy, 3- (2-methylpropoxy) propoxy, 3- 1, 1-dimethylethoxy) propoxy, 2- (methoxy) butoxy, 2-ethoxy) butoxy, 2- (propoxy) butoxy, 2- 1-methethox) butoxy, 2- (butox) butox, 2- 1 -Meth lpropoxy) butoxy, 2- (2-methylpropox) butox, 2- 1, 1-dimethylethoxy) butoxy, 3- (methoxy) butoxy, 3-ethoxy) butoxy, 3- (propoxy) butox, 3- 1- Methylethoxy) butoxy, 3- (butoxy) butoxy, 3- 1-methylpropoxy) butoxy, 3- (2-methylpropox) butoxy, 3- 1, 1-dimethethoxy) butoxy, 4- (methoxy) butoxy, 4-ethoxy ) butoxy, 4- (propoxy) butox, 4- 1-methylethoxy) butoxy, 4- (butoxy) butoxy, 4- 1-methylpropoxy) butox, 4- (2-methylpropoxy) butoxy or 4- 1, 1-dimethylethoxy ) butoxy;
Cι-C6-Alkylcarbonyl-Cι-C6-alkyl: Durch eine-CC 6 -alkylcarbonyl -CC 6 -alkyl: by a
Ci-Cg-Alkylcarbonylgruppe substituiertes Ci-Cg-Alkyl, worin beide der Cχ-Cg-Alkylgruppen ein oder mehrere Substituenten, ausgewählt unter Cι-C-Alkoxy und/oder Hydroxy aufweisen können: z.B. Acetylmethyl (=2-Oxopropyl) , 2-(Acetyl)ethyl (=3-0xo-n-butyl) , 3-0xo-n-pentyl, 1, l-Dimethyl-2-oxopropyl, 3-Hydroxy-2-oxopropyl oder 3-Hydroxy-2-oxobutyl;Ci-Cg-alkylcarbonyl group substituted Ci-Cg-alkyl, in which both of the Cχ-Cg-alkyl groups may have one or more substituents selected from -C-C-alkoxy and / or hydroxy: e.g. Acetylmethyl (= 2-oxopropyl), 2- (acetyl) ethyl (= 3-0xo-n-butyl), 3-0xo-n-pentyl, 1, l-dimethyl-2-oxopropyl, 3-hydroxy-2-oxopropyl or 3-hydroxy-2-oxobutyl;
C3—C6—Alkenyl, sowie die Alkenylteile von C3—C6—Alkenylcarbonyl, C3-Cg-Alkenyloxy, C3—C6—Alkenyloxycarbonyl, C3—C6—Alkenylaminocarbonyl, N—(C3—Cg—Alkenyl)—N—(Cι—Cg-alkyl)aminocarbonyl, N—(C3—Cg—Alkenyl)—W—(Cι—Cg—alkox )aminocarbonyl: z.B. Prop—2—en—1—y1, But—1-en—4—y1, 1-Methy1—rop—2—en—1—y1, 2—Methyl—prop—2—en—1— l, 2—Buten—1—yl, 1—Penten—3—yl, l-Penten-4-yl, 2-Penten-4-y1, 1-Methyl-but-2-en-l-y1, 2-Methyl-but-2-en-l-yl, 3-Methyl-but-2-en-l-yl, 1-Methy1-but—3-en-l-yl, 2-Methyl-but-3-en-l-yl, 3— ethyl—but—3—en—1—yl, 1 , 1—Dimethy1—prop-2—en—1—yl, 1 , 2—Dimethy1—prop—2—en—1—yl, 1—Ethy1—prop-2—en—1—yl, Hex—3—en—1—y1, Hex—4—en—1—yl, Hex—5—en—1—y1,C 3 -C 6 alkenyl, and the alkenyl parts of C 3 -C 6 alkenylcarbonyl, C 3 -Cg alkenyloxy, C 3 -C 6 alkenyloxycarbonyl, C 3 -C 6 alkenylaminocarbonyl, N— (C 3 -Cg —Alkenyl) —N— (Cι-Cg-alkyl) aminocarbonyl, N— (C 3 —Cg-Alkenyl) —W— (Cι — Cg-alkox) aminocarbonyl: eg prop-2-ene-1-y1, but— 1-ene-4-y1, 1-methyl-rop-2-ene-1-y1, 2-methyl-prop-2-ene-1, 1.2, butene-1-yl, 1-pentene-3 yl, l-penten-4-yl, 2-penten-4-y1, 1-methyl-but-2-en-l-y1, 2-methyl-but-2-en-l-yl, 3-methyl but-2-en-l-yl, 1-methyl-but-3-en-l-yl, 2-methyl-but-3-en-l-yl, 3-ethyl-but-3-en-1 - yl, 1, 1-dimethy1-prop-2-ene-1-yl, 1, 2-dimethy1-prop-2-ene-1-yl, 1-ethy1-prop-2-ene-1-yl, hex 3-en-1-y1, hex-4-en-1-yl, hex-5-en-1-y1,
1—Methy1—pent—3—en—1—yl, 2—Methy1—pent—3—en—1—yl, 3—Methy1—pent—3—en—1—y1, 4—Methyl—pent—3—en—1—yl, 1—Methy1—pent—4—en—l—yl, 2—Methyl—pent—4—en—1—yl, 3— ethyl—pent—4—en—1— l, 4—Methy1—pent—4—en—l—yl, 1 , 1—Dimethy1—but—2—en—l—yl, 1 , 1—Dimethy1—but—3—en—l—yl, 1 , 2—Dimethy1—but—2—en—1— l, 1 , 2—Dimethy1—but—3—en—1—yl, 1 , 3—Dimethy1—but—2—en—1— l, 1, 3—Dimethy1—ut—3—en—1—yl, 2 , 2—Dimethy1—but—3—en—1—yl, 2 , 3—Dimethy1-but—2—en—1—yl, 2 , 3—Dimethy1—but—3—en—1—yl, 3 , 3—Dimethy1—but—2—en—1—yl, l-Ethyl-but-2-en-l-yl, 1-Ethyl-but-3-en-l-y1, 2-Ethyl-but-2-en-l-y1, 2-Ethyl-but-3-en-l-y1, 1,1, 2— rimethy1—prop—2-en—1—yl, 1—Ethyl—1— ethy1— rop—2—en—l—yl oder 1—Ethyl— 2—methy1-rop—2—en—l—yl;1 — methyl-pent-3-ene-1-yl, 2-methyl-1-pent-3-ene-1-yl, 3-methyl-1-pent-3-ene-1-yl, 4-methyl-pent-3— en-1-yl, 1-methyl-pent-4-en-1-yl, 2-methyl-pent-4-en-1-yl, 3-ethyl-pent-4-en-1-l, 4- Methy1-pent-4-en-l-yl, 1, 1-dimethy1-but-2-en-l-yl, 1, 1-dimethy1-but-3-en-l-yl, 1, 2-dimethy1- but — 2 — en — 1 — l, 1, 2 — dimethy1 — but — 3 — en — 1 — yl, 1, 3 — dimethy1 — but — 2 — en — 1— l, 1, 3 — dimethy1 — ut— 3-en-1-yl, 2, 2-dimethy1-but-3-en-1-yl, 2, 3-dimethy-1-but-2-en-1-yl, 2, 3-dimethy-1-but-3- en-1-yl, 3,3-dimethy1-but-2-en-1-yl, l-ethyl-but-2-en-l-yl, 1-ethyl-but-3-en-l-y1, 2-ethyl-but-2-en-l-y1, 2-ethyl-but-3-en-l-y1, 1,1, 2-rimethy1-prop-2-en-1-yl, 1 — ethyl — 1 — ethy1 — rop — 2 — en — l — yl or 1 — ethyl — 2 — methy1-rop — 2 — en — l — yl;
C2—C6—Alkenyl, sowie die Alkenylteile von C2—C6—Alkenylcarbonyl, Phenyl—C2-Cg—alkenylcarbonyl und Heterocyclyl—C2-C6—alkenylcarbonyl: C3—Cg—Alkenyl, wie voranstehend genannt, sowie Ethenyl;C 2 -C 6 alkenyl, and the alkenyl parts of C 2 -C 6 alkenylcarbonyl, phenyl C 2 -Cg alkenylcarbonyl and heterocyclyl C 2 -C 6 alkenylcarbonyl: C 3 -Cg alkenyl as mentioned above as well as ethenyl;
— C3—C6—Alkinyl, sowie die Alkinylteile von C3—C6—Alkinylcarbony1, C3-C6-Alkinyloxy, C3-C6—Alkinyloxy- carbonyl, C3—Cg—Alkinylaminocarbonyl, N—(C3—Cg—Alkinyl)—N—(Ci—Cg—alkyl)—aminocarbonyl, N—(C3—Cg—Alkinyl)—N—(Ci—Cg—alkoxy) aminocarbonyl : z.B. Propargyl, But—1—in—3—y1, But—1—in—4—yl, But—2—in—1—yl, Pent—1—in—3—yl, Pent—1—in—4—y1, Pent—1—in—5—yl, Pent—2-in-l-yl, Pent-2-in-4-y1, Pent-2-in-5-yl, 3-Methyl-but-l-in-3-yl, 3-Methy1-but—l-in-4-yl, Hex—1—in—3—yl, Hex—1—in—4— l, Hex—1—in—5—y1, Hex—1—in—6—y1, Hex—2—in—1—yl, Hex—2—in—4— l, Hex—2—in—5—y1, Hex—2—in—6—yl, Hex—3—in—1— l, Hex—3—in—2— l, 3—Methy1—pent—1—in—3—yl, 3—Methy1— ent—1—in—4—yl, 3—Methyl—pent—1—in—5—yl, 4—Methy1—pent—2—in—4—yl oder 4—Methyl—pent—2—in—5—yl;- C 3 -C 6 alkynyl, and the alkynyl parts of C 3 -C 6 alkynylcarbonyl, C 3 -C 6 alkynyloxy, C 3 -C 6 alkynyloxycarbonyl, C 3 -Cg alkynylaminocarbonyl, N - (C 3 —Cg — alkynyl) —N— (Ci-Cg-alkyl) aminocarbonyl, N— (C 3 —Cg-alkynyl) —N— (Ci-Cg-alkoxy) aminocarbonyl: eg propargyl, but — 1 — in— 3-y1, but-1-in-4-yl, but-2-in-1-yl, pent-1-in-3-yl, pent-1-in-4-y1, pent-1-in- 5-yl, pent-2-in-1-yl, pent-2-in-4-yl, pent-2-in-5-yl, 3-methyl-but-1-in-3-yl, 3- Methyl-but-l-in-4-yl, hex — 1-in-3-yl, hex-1-in-4-l, hex-1-in-5-y1, hex-1-in-6— y1, hex — 2 — in — 1 — yl, hex — 2 — in — 4 — l, hex — 2 — in — 5 — y1, hex — 2 — in — 6 — yl, hex — 3 — in — 1— l, hex — 3 — in — 2, 1, 3 — methyl-pent — 1 — in — 3-yl, 3 — methyl-ent — 1 — in — 4-yl, 3 — methyl-pent — 1 — in— 5-yl, 4-methyl-pent-2-in-4-yl or 4-methyl-pent-2-in-5-yl;
— C2—Cg—Alkinyl, sowie die Alkinylteile von C2—Cg—Alkinylcarbonyl: C3—Cg—Alkinyl, wie voranstehend genannt, sowie Ethinyl;C 2 -Cg alkynyl, and the alkynyl parts of C 2 -Cg alkynylcarbonyl: C 3 -Cg alkynyl, as mentioned above, and ethynyl;
C2-C4-Alkandiyl bei Ra und Rb: Ethan-l,2-diyl, Propan-l,2-diyl, Propan-l,3-diyl, Butan-l,2-diyl, Butan-l,3-diyl, Butan-l,4-diyl, insbesondere Propan-l,3-diyl;C 2 -C 4 alkanediyl for R a and R b : ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1, 3-diyl, butane-l, 4-diyl, especially propane-l, 3-diyl;
Ci-Cg-Alkandiyl: Methandiyl, Ethan-1, 1-diyl, Ethan-l,2-diyl, Propan-1, 1-diyl, Propan-l,2-diyl, Propan-l,3-diyl, Propan-2,2-diyl, Butan-1, 1-diyl, But n-l,2-diyl, But n-l,3-diyl, Butan-l,4-diyl, 2-Methyl-propan-l,3-diyl, 2-Methy1-propan-1 , 2-diy1, 2-Methy1-propan-1, 1-diyl, 1-Methyl-propan-l, 2-diyl, l-Methyl-propan-2, 2-diyl, 1-Meth 1-propan-l, 1-diyl, Pentan-1, 1-diyl, Pentan-1,2-diyl, Pentan-l,3-diyl, Pentan-1,5-diyl, Pentan-2,3-diyl, Pentan-2, 2-diyl, 1-Methyl-butan-l, 1-diyl,Ci-Cg-alkanediyl: methanediyl, ethane-1, 1-diyl, ethane-l, 2-diyl, propane-1, 1-diyl, propane-l, 2-diyl, propane-l, 3-diyl, propane 2,2-diyl, butane-1, 1-diyl, but nl, 2-diyl, but nl, 3-diyl, butane-l, 4-diyl, 2-methyl-propane-l, 3-diyl, 2- Methy1-propane-1,2-diy1, 2-methyl-propane-1,1-diyl, 1-methyl-propane-1,2-diyl, 1-methyl-propane-2,2-diyl, 1-meth 1 -propan-l, 1-diyl, pentane-1, 1-diyl, pentane-1,2-diyl, pentane-l, 3-diyl, pentane-1,5-diyl, pentane-2,3-diyl, pentane -2, 2-diyl, 1-methylbutane-l, 1-diyl,
1-Meth 1-butan-1 , 2-diyl, 1-Methy1-butan-1, 3-diyl, 1-Methy1-butan-1,4-diyl, 2-Methyl-butan-l , 1-diyl, 2-Meth l-butan-l, 2-diyl, 2-Meth 1-butan-1, 3-diyl, 2-Methy1-butan-1, 4-diyl, 2 , 2-Dimethy1-propan-1, 1-diyl, 2, 2-Dimethy1-propan-1,3-diyl, 1, l-Dimethyl-propan-l,3-diyl, 1, 1-Dimethyl-propan-l,2-diyl, 2, 3-Dimethy1-propan-1,3-diyl, 2 , 3-Dimethy1-propan-1 , 2-diyl, 1 , 3-Dimethy1-propan-l,3-diyl, Hexan-1, 1-diyl, Hexan-1, 2-diyl, Hexan-1,3-diyl, Hexan-1, 4-diyl, Hexan-1,5-diyl, Hexan-1,6-diyl, Hexan-2,5-diyl, 2-Methyl-pentan-l, 1-diyl, 1-Methy1-pentan-1 ,2-di l, 1-Methy1-pentan-1, 3-diyl, 1-Methyl-pentan-l, 4-diyl, 1-Methy1-pentan-1,5-diyl, 2-Methy1-pentan-1, 1-diyl, 2-Methy1-pentan-1, 2-diyl, 2-Methyl-pentan-l, 3-diyl, 2-Methyl-pentan-l, 4-diyl, 2-Methy1-pentan-1, 5-diyl, 3-Methy1-pentan-1, 1-diyl, 3-Methyl-pentan-1,2-diyl, 3-Methyl-pentan-1, 3-diyl, 3-Methy1-pentan-l, 4-diyl, 3-Methy1-pentan-1,5-diyl,1-meth 1-butane-1,2-diyl, 1-methyl-butane-1,3-diyl, 1-methyl-butane-1,4-diyl, 2-methyl-butane-1,1-diyl, 2nd -Meth 1-butane-l, 2-diyl, 2-meth 1-butane-1, 3-diyl, 2-methyl-1-butane, 4-diyl, 2, 2-dimethyl-propane-1, 1-diyl , 2, 2-Dimethy1-propane-1,3-diyl, 1, l-dimethyl-propane-l, 3-diyl, 1, 1-dimethyl-propane-l, 2-diyl, 2, 3-dimethyl-propane -1,3-diyl, 2,3-dimethy1-propane-1,2-diyl, 1,3-dimethy-1-propane-1,3-diyl, Hexane-1, 1-diyl, hexane-1, 2-diyl, hexane-1,3-diyl, hexane-1, 4-diyl, hexane-1,5-diyl, hexane-1,6-diyl, hexane 2,5-diyl, 2-methyl-pentane-1, 1-diyl, 1-methyl-1-pentane, 2-di 1, 1-methyl-1-pentane, 1,3-diyl, 1-methyl-1-pentane-1 , 4-diyl, 1-methyl-pentane-1,5-diyl, 2-methyl-1-pentane, 1-diyl, 2-methyl-1-pentane, 1,2-diyl, 2-methylpentane-1,3 -diyl, 2-methylpentan-l, 4-diyl, 2-methyl-1-pentane, 5-diyl, 3-methyl-1-pentane, 1-diyl, 3-methylpentane-1,2-diyl , 3-methyl-pentane-1,3-diyl, 3-methyl-1-pentane, 1,4-diyl, 3-methyl-1-pentane-1,5-diyl,
1, 1-Dimethyl-butan-1,2-diyl, 1, 1-Dimethyl-butan-l, 3-diyl, 1, 1-Dimethyl-butan-l, 4-diyl, 1, 2-Dimethy1-butan-1, 1-diyl, 1, 2-Dimethyl-butan-l,2-diyl, 1,2-Dimethy1-butan-l,3-diyl, 1, 2-Dimethyl-butan-1, 4-diyl, 1, 3-Dimethy1-butan-1 , 1-diyl, 1, 3-Dimethy1-butan-1, 2-diyl, 1,3-Dimethyl-butan-l, 3-diyl, 1 , 3-Dimethy1-butan-l, 4-diyl, 1-Ethyl-butan-l , 1-diyl, 1-Ethy1-butan-1,2-diyl, 1-Ethy1-butan-1 , 3-diyl, 1-Ethyl-butan-l,4-diyl, 2-Ethyl-butan-l, 1-diyl, 2-Ethy1-butan-1, 2-diyl, 2-Ethy1-butan-1, 3-diyl, 2-Ethy1-butan-l, 4-diyl, 2-Ethyl-butan-2, 3-diyl,1, 1-dimethylbutane-1,2-diyl, 1, 1-dimethylbutane-l, 3-diyl, 1, 1-dimethylbutane-l, 4-diyl, 1, 2-dimethy1-butane 1, 1-diyl, 1, 2-dimethylbutane-l, 2-diyl, 1,2-dimethy1-butane-l, 3-diyl, 1, 2-dimethylbutane-1, 4-diyl, 1, 3-Dimethy1-butan-1, 1-diyl, 1, 3-Dimethy1-butan-1, 2-diyl, 1,3-Dimethyl-butan-l, 3-diyl, 1, 3-Dimethy1-butan-l, 4-diyl, 1-ethyl-butane-l, 1-diyl, 1-ethyl-1-butane-1,2-diyl, 1-ethyl-1-butane, 1,3-diyl, 1-ethyl-butane-1, 4- diyl, 2-ethyl-butane-l, 1-diyl, 2-ethyl-1-butane-1, 2-diyl, 2-ethyl-1-butane, 1,3-diyl, 2-ethyl-1-butane, 1,4-diyl, 2-ethyl-butane-2,3-diyl,
2 , 2-Dimethy1-butan-1 , 1-diyl, 2 ,2-Dimethy1-butan-l, 3-diyl, 2 , 2-Dimethy1-butan—1 , 4-diyl, 1-Isopropyl-propan-l, 1-diyl, 1-Isopropyl-propan-l,2-diyl, 1-lsopropyl-propan-l,3-diyl, 2-lsopropyl-propan-l, 1-diyl, 2-Isopropyl-propan-l, 2-diyl, 2-Isopropyl-propan-l , 3-diyl, 1 , 2 ,3-Trimethy1-propan-l , 1-diyl, 1,2,3-Trimethy1-propan-1 , 2-diyl oder 1,2, 3-Trimethyl-propan-l, 3-diyl;2, 2-dimethy1-butane-1, 1-diyl, 2, 2-dimethy1-butane-l, 3-diyl, 2, 2-dimethy1-butane-1, 4-diyl, 1-isopropyl-propane-l, 1-diyl, 1-isopropyl-propane-l, 2-diyl, 1-isopropyl-propane-l, 3-diyl, 2-isopropyl-propane-l, 1-diyl, 2-isopropyl-propane-l, 2- diyl, 2-isopropyl-propane-l, 3-diyl, 1, 2, 3-trimethy-1-propane-l, 1-diyl, 1,2,3-trimethy-1-propane-1, 2-diyl or 1,2, 3-trimethyl-propane-1,3-diyl;
— c3—C8-Cycloalkyl, sowie die Cycloalkylteile von C3-C8-Cycloal- koxy, C3-C8-Cycloalkylamino und C3-C8-Cycloalkylcarbonyl: z.B.- C 3 -C 8 cycloalkyl, and the cycloalkyl parts of C 3 -C 8 cycloalkoxy, C 3 -C 8 cycloalkylamino and C 3 -C 8 cycloalkylcarbonyl: for example
Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cyclohep- tyl, Cyclooctyl, Norbornyl, [2.2.2]- oder [3.2.l]-Bicyclooc- tyl;Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, [2.2.2] - or [3.2.1] bicyclooc- tyl;
- C5-C7-Cycloalkandiyl bei Ra und Rb: ein zweiwertiger cycloali- phatischer Rest mit 5 bis 7 Ringkohlenstoffatomen, z.B. Cy- clopentan-1, 2-diyl oder -1,3-diyl, Cyclohexan-1, 2-diyl, -1,3-diyl oder -1,4-diyl, Cycloheptan-1,2-diyl, -1,3-diyl oder -1,4-diyl;C 5 -C 7 cycloalkanediyl in the case of R a and R b : a divalent cycloaliphatic radical having 5 to 7 ring carbon atoms, for example cyclopentane-1,2-diyl or -1,3-diyl, cyclohexane-1,2 -diyl, -1,3-diyl or -1,4-diyl, cycloheptane-1,2-diyl, -1,3-diyl or -1,4-diyl;
— 5- bis 7- gliedriges Heterocyclyl, sowie Heterocyclylteile und anellierte 5- oder 6-gliedrige Heterocyclen an Phenyl oder Pyridyl: ein gesättigter, partiell gesättigter oder ungesättigter 5—, 6— oder 7- gliedriger, heterocyclischer Ring, der ein, zwei, drei oder vier gleiche oder verschiedene Heteroatome, ausgewählt aus folgender Gruppe: Sauerstoff, Schwefel oder Stickstoff, enthält, und der im Falle der anel- lierten Heterocyclen wenigstens eine C=C-Doppelbindung aufweist, also z.B.5 to 7-membered heterocyclyl, as well as heterocyclyl parts and fused 5 or 6-membered heterocycles to phenyl or pyridyl: a saturated, partially saturated or unsaturated 5, 6 or 7-membered heterocyclic ring which has one, two, contains three or four identical or different heteroatoms, selected from the following group: oxygen, sulfur or nitrogen, and which in the case of the heterocycles has at least one C = C double bond, for example
C-gebundene 5—gliedrige Ringe wie:C-linked 5-membered rings such as:
Tetrahydrofuran—2—yl, Tetrahydro uran—3—y1, Tetrahydrothien—2— l, Tetrahydrothien—3— l, Tetrahydropyrrol—2— l, Tetrahydropyrrol—3—yl, 2 , 3—Dihydrofuran—2—yl, 2 , 3—Dihydrofuran—3—yl, 2 , 5—Dihydrofuran—2—yl, 2 , 5—Dihydrofuran—3—yl, 4, 5—Dihydrofuran—2—yl, 4, 5—Dihydrofuran—3—yl, 2 , 3—Dihydrothien—2—yl, 2 , 3—Dihydrothien—3—yl, 2 , 5—Dihydrothien—2— l, 2 , 5—Dihydrothien—3—yl, 4, 5—Dihydrothien—2—yl, 4 , 5—Dihydrothien—3—yl, 2 , 3-Dihydro-lH-pyrrol-2-yl, 2 , 3-Dihydro-lH-pyrrol-3-yl, 2 , 5—Dihydro—1H—pyrrol—2—yl, 2 , 5—Dihydro—1H—pyrrol—3— l, 4 , 5—Dihydro—1H—pyrrol—2—yl, 4 , 5—Dihydro—1H—pyrrol—3—yl, 3, 4-Dihydro-2H-pyrrol-2-yl, 3, 4-Dihydro-2H-pyrrol-3-yl, 3 , 4-Dihydro-5H-pyrrol-2-yl, 3 , 4-Dihydro-5H-pyrrol-3-yl, 2—Furyl, 3—Furyl, 2—Thienyl, 3—Thienyl, Pyrrol—2—yl,Tetrahydrofuran — 2-yl, tetrahydro uranium-3-y1, tetrahydrothiene-2-1, tetrahydrothiene-3-1, tetrahydropyrrole-2-1, tetrahydropyrrole-3-yl, 2,3- dihydrofuran-2-yl, 2,3 —Dihydrofuran — 3-yl, 2,5-dihydrofuran-2-yl, 2,5-dihydrofuran-3-yl, 4,5-dihydrofuran-2-yl, 4,5-dihydrofuran-3-yl, 2,3 —Dihydrothien — 2-yl, 2, 3 — dihydrothien — 3-yl, 2, 5 — dihydrothien — 2— l, 2, 5 — dihydrothien — 3-yl, 4, 5 — dihydrothien — 2-yl, 4, 5 Dihydrothiene-3-yl, 2,3-dihydro-1H-pyrrol-2-yl, 2,3-dihydro-1H-pyrrol-3-yl, 2,5-dihydro-1H-pyrrole-2-yl, 2 , 5-dihydro-1H-pyrrole-3-1, 4.5-dihydro-1H-pyrrole-2-yl, 4.5-dihydro-1H-pyrrole-3-yl, 3,4-dihydro-2H-pyrrole -2-yl, 3,4-dihydro-2H-pyrrol-3-yl, 3,4-dihydro-5H-pyrrol-2-yl, 3,4-dihydro-5H-pyrrol-3-yl, 2-furyl , 3-furyl, 2-thienyl, 3-thienyl, pyrrole-2-yl,
Pyrrol—3—yl, Tetrahydropyrazol—3—yl, Tetrahydropyrazol—4—yl, Tetrahydroisoxazol—3—yl, Tetrahydroisoxazol—4—yl, Tetrahydroisoxazol—5—y1, 1 , 2-Oxathiolan—3—yl, 1, 2—Oxathiolan—4—yl, 1 , 2—Oxathiolan—5—yl, Tetrahydroisothiazol—3—yl, Tetrahydro-isothiazol—4—yl, Tetrahydroisothiazol—5—yl, 1, 2—Dithiolan—3— l, 1, 2—Dithiolan—4— l, Tetrahydroimidazol—2— l, Tetrahydroimidazol—4— 1, Tetrahydrooxazol—2—yl, Tetrahydrooxazol—4—yl, Tetrahydrooxazol—5—yl, Tetrahydrothiazol—2— l, Tetrahydrothiazol—4— l, Tetrahydrothiazol—5—yl, 1 , 3—Dioxolan—2—yl,Pyrrole-3-yl, tetrahydropyrazole-3-yl, tetrahydropyrazole-4-yl, tetrahydroisoxazole-3-yl, tetrahydroisoxazole-4-yl, tetrahydroisoxazole-5-y1, 1, 2-oxathiolane-3-yl, 1 Oxathiolane-4-yl, 1, 2-oxathiolane-5-yl, tetrahydroisothiazole-3-yl, tetrahydro-isothiazole-4-yl, tetrahydroisothiazole-5-yl, 1, 2-dithiolane-3-l, 1, 2— Dithiolan-4-1, Tetrahydroimidazole-2-1, Tetrahydroimidazole-4-1, Tetrahydrooxazole-2-yl, Tetrahydrooxazole-4-yl, Tetrahydrooxazole-5-yl, Tetrahydrothiazole-2-1, Tetrahydroliazole 5-yl, 1, 3-dioxolane-2-yl,
1,3—Dioxolan—4—yl, 1,3—Oxathiolan—2—yl, 1, 3—Oxathiolan—4—yl, 1,3—Oxathiolan—5—yl, 1,3—Dithiolan—2— l, 1,3—Dithiolan—4—yl, 4 , 5—Dihydro—1H—pyrazol—3—yl, 4 , 5—Dihydro—1H—pyrazol—4—yl, 4 , 5—Dihydro—1H—pyrazol—5—yl, 2 , 5—Dihydro—1H—pyrazol—3—yl, 2, 5—Dihydro—1H—pyrazol—4—yl, 2 , 5—Dihydro—1H—pyrazol—5—yl, 4 , 5—Dihydroisoxazol—3—yl, 4 ,5—Dihydroisoxazol—4— l, 4, 5—Dihydroisoxazol—5—yl, 2, 5—Dihydroisoxazol—3—yl, 2 , 5—Dihydroisoxazol—4—yl, 2 , 5—Dihydroisoxazol—5—yl, 2,3—Dihydroisoxazol—3—yl, 2,3—Dihydroisoxazol—4—yl,1,3-dioxolane-4-yl, 1,3-oxathiolane-2-yl, 1,3-oxathiolane-4-yl, 1,3-oxathiolane-5-yl, 1,3-dithiolane-2-l, 1,3-dithiolane-4-yl, 4,5-dihydro-1H-pyrazole-3-yl, 4,5-dihydro-1H-pyrazole-4-yl, 4,5-dihydro-1H-pyrazole-5 yl, 2, 5-dihydro-1H-pyrazole-3-yl, 2, 5-dihydro-1H-pyrazole-4-yl, 2, 5-dihydro-1H-pyrazole-5-yl, 4, 5-dihydroisoxazole 3-yl, 4,5-dihydroisoxazole-4,1, 4,5-dihydroisoxazole-5-yl, 2,5-dihydroisoxazole-3-yl, 2,5-dihydroisoxazole-4-yl, 2,5-dihydroisoxazole 5-yl, 2,3-dihydroisoxazole-3-yl, 2,3-dihydroisoxazole-4-yl,
2 , 3—Dihydroisoxazol—5—yl, 4 , 5—Dihydroisothiazol—3—yl, 4 , 5—Dihydroisothiazol—4—yl, 4 , 5—Dihydroisothiazol—5— l, 2, 5—Dihydroisothiazol—3—yl, 2, 5—Dihydroisothiazol—4—yl, 2 , 5—Dihydroisothiazol—5—yl, 2 , 3—Dihydroisothiazol—3—yl, 2 , 3—Dihydroisothiazol—4—yl, 2 , 3—Dihydroisothiazol—5—yl, Δ3-l, 2-Dithiol-3-yl, Δ3-l , 2-Dithiol-4-yl, Δ3-l, 2-Dithiol-5-yl, 4, 5-Dihydro-lH-imidazol-2-yl, 4 , 5—Dihydro—IH—imidazol—4— l, 4 , 5—Dihydro—IH—imidazol—5—yl, 2 , 5—Dihydro—IH—imidazol—2— l, 2 , 5—Dihydro—IH—imidazol—4— l, 2 , 5—Dihydro—IH—imidazol—5— l, 2 , 3—Dihydro—IH—imidazol—2— l, 2, 3—Dihydro—IH—imidazol—4—yl, 4 , 5—Dihydrooxazol—2—yl, 4 , 5—Dihydrooxazol—4— l, 4 , 5—Dihydrooxazol—5— l, 2 , 5—Dihydrooxazol—2—yl, 2 , 5—Dihydrooxazol—4—yl, 2 , 5—Dihydrooxazol—5— l, 2, 3—Dihydrooxazol—2—yl, 2 , 3—Dihydrooxazol—4—yl, 2 , 3—Dihydrooxazol—5— l, 4, 5—Dihydrothiazol—2—yl, 4 , 5—Dihydrothiazol—4—yl, 4,5—Dihydrothiazol—5— l, 2 , 5—Dihydrothiazol—2—yl, 2 , 5—Dihydrothiazol—4—yl, 2 , 5—Dihydrothiazol—5—yl, 2,3—Dihydrothiazol—2— l, 2 ,3—Dihydrothiazol—4—yl, 2 , 3—Dihydrothiazol—5—yl, 1, 3—Dioxol—2—yl, 1,3—Dioxol—4—yl, l,3-Dithiol-2-yl, l,3-Dithiol-4-yl, 1, 3-Oxathiol-2-yl, 1,3—Oxathiol—4—yl, 1,3-Oxathiol—5—yl, Pyrazol—3—yl,2,3-dihydroisoxazole-5-yl, 4,5-dihydroisothiazole-3-yl, 4,5-dihydroisothiazole-4-yl, 4,5-dihydroisothiazole-5-1, 2,5-dihydroisothiazole-3-yl, 2,5-dihydroisothiazole-4-yl, 2,5-dihydroisothiazole-5-yl, 2,3-dihydroisothiazole-3-yl, 2,3-dihydroisothiazole-4-yl, 2,3-dihydroisothiazole-5-yl, Δ 3 -l, 2-dithiol-3-yl, Δ 3 -l, 2-dithiol-4-yl, Δ 3 -l, 2-dithiol-5-yl, 4, 5-dihydro-lH-imidazol-2 yl, 4,5-dihydro-IH-imidazole-4-1, 4,5-dihydro-IH-imidazole-5-yl, 2,5-dihydro-IH-imidazole-2-1, 2,5-dihydro-IH- imidazole-4-1, 2, 5-dihydro-IH-imidazole-5-1, 2, 3-dihydro-IH-imidazole-2-1, 2, 3-dihydro-IH-imidazole-4-yl, 4, 5-dihydrooxazole-2-yl, 4.5-dihydrooxazole-4-1, 4.5-dihydrooxazole-5.1-l, 2.5-dihydrooxazole-2-yl, 2.5-dihydrooxazole-4-yl, 2.2 5 — dihydrooxazole — 5, 1, 2, 3 — dihydrooxazole — 2 — yl, 2, 3 — dihydrooxazole — 4 — yl, 2, 3 — dihydrooxazole — 5, 1, 4, 5 — dihydrothiazole — 2-yl, 4, 5-dihydrothiazole-4-yl, 4.5-dihydrothiazole-5.1-l, 5-dihydrothiazole-2-yl, 2.5-dihydrothiazole-4-yl, 2.5-dihydrothiazole-5-yl, 2 3 — dihydrothiazole — 2, 1, 2, 3 — dihydrothiazole — 4-yl, 2, 3 — dihydrothiazole-5-yl, 1, 3 — dioxol-2-yl, 1,3-dioxol-4-yl, 1, 3-dithiol-2-yl, 1,3-dithiol-4-yl, 1,3-oxathiol-2-yl, 1,3-oxathiol-4-yl, 1 , 3-oxathiol-5-yl, pyrazole-3-yl,
Pyrazol—4—yl, Isoxazol—3—yl, Isoxazol—4—yl, Isoxazol—5—yl, Isothiazol—3—yl, Isothiazol—4—yl, Isothiazol—5—yl, Imidazol—2— l, Imidazol—4—yl, Oxazol—2—yl, Oxazol—4—yl, Oxazol—5—yl, Thiazol—2—yl, Thiazol—4—yl, Thiazol—5—yl, 1,2,3—Δ2-Oxadiazolin—4-yl, 1, 2 ,3-Δ2-Oxadiazolin—5-yl, 1,2, 4-Δ4-Oxadiazolin-3-yl, 1,2, 4-Δ4-Oxadiazolin-5-yl, 1,2, 4—Δ2-Oxadiazolin—3— l, 1,2, 4—Δ2-Oxadiazolin—5—yl, 1,2, 4—Δ3-Oxadiazolin—3-yl, 1,2, 4-Δ3-Oxadiazolin—5-yl, 1,3, 4—Δ2-Oxadiazolin—2— l, 1,3, 4—Δ2—Oxadiazolin—5—yl, 1,3,4—Δ3—Oxadiazolin—2—yl, 1, 3 , 4-0xadiazolin—2—yl,Pyrazole-4-yl, isoxazole-3-yl, isoxazole-4-yl, isoxazole-5-yl, isothiazole-3-yl, isothiazole-4-yl, isothiazole-5-yl, imidazole-2-l, imidazole 4-yl, oxazole-2-yl, oxazole-4-yl, oxazole-5-yl, thiazole-2-yl, thiazole-4-yl, thiazole-5-yl, 1,2,3-Δ 2 -oxadiazoline 4-yl, 1, 2, 3-Δ 2 -oxadiazolin-5-yl, 1,2, 4-Δ 4 -oxadiazolin-3-yl, 1,2, 4-Δ 4 -oxadiazolin-5-yl, 1,2, 4-Δ 2 -oxadiazoline-3-1, 1,2, 4-Δ 2 -oxadiazolin-5-yl, 1,2, 4-Δ 3 -oxadiazolin-3-yl, 1,2, 4 -Δ 3 -oxadiazolin-5-yl, 1,3, 4-Δ 2 -oxadiazolin- 2-1 , 1,3, 4-Δ 2 -oxadiazolin-5-yl, 1,3,4-Δ 3 -oxadiazoline -2-yl, 1, 3, 4-0xadiazolin-2-yl,
1,2, 4-Δ-Thiadiazolin-3-y1, 1,2, 4-Δ4-Thiadiazolin-5-yl, 1,2, 4—Δ3—Thiadiazolin—3—yl, 1,2, 4—Δ3—Thiadiazolin—5—yl, 1,2, 4—Δ2—Thiadiazolin—3—yl, 1,2, 4-Δ2—Thiadiazolin—5—yl, 1,3, 4—Δ2— hiadiazolin—2—y1, 1,3, 4—Δ2—Thiadiazolin—5—yl, 1,3,4-Δ3—Thiadiazolin-2—yl, 1,3,4-Thiadiazolin—2—yl, 1,3, 2—Dioxathiolan—4—yl, 1,2, 3—Δ2—riazolin—4—yl, 1,2, 3—Δ2—Triazolin—5—yl, 1,2, 4—Δ2—Triazolin—3—yl, 1,2, 4-Δ2-Triazolin-5-yl, 1,2, 4-Δ3-Triazolin-3-yl, 1,2, 4—Δ3—Triazolin—5— l, 1,2, 4-Δ1-Triazolin-2—yl, l,2,4-Triazolin-3-yl, 3H-l,2,4-Dithiazol-5-yl,1,2, 4-Δ-thiadiazoline-3-y1, 1,2, 4-Δ 4 -Thiadiazolin-5-yl, 1,2, 4-Δ 3 -Thiadiazolin-yl-3, 1,2, 4- Δ 3 —thiadiazoline — 5 — yl, 1,2, 4 — Δ 2 —thiadiazoline — 3 — yl, 1,2, 4-Δ 2 —thiadiazoline — 5 — yl, 1,3, 4 — Δ 2 - hiadiazolin— 2-y1, 1,3, 4-Δ 2 -thiadiazolin-5-yl, 1,3,4-Δ 3 -thiadiazolin-2-yl, 1,3,4-thiadiazolin-2-yl, 1,3, 2 — dioxathiolane-4-yl, 1,2, 3-Δ 2 -riazoline-4-yl, 1,2, 3-Δ 2 -triazoline-5-yl, 1,2, 4-Δ 2 -triazoline-3 —Yl, 1,2, 4-Δ 2 -triazolin-5-yl, 1,2, 4-Δ 3 -triazolin-3-yl, 1,2, 4 — Δ 3 -triazolin-5-1, 1, 2, 4-Δ 1 -Triazolin-2-yl, l, 2,4-triazoline-3-yl, 3H-l, 2,4-dithiazole-5-yl,
2H-1 , 3 , 4— Dithiazol-5-yl , 2H-1 , 3 , 4-Oxathiazol-5— yl , 1 , 2 , 3-Oxadiazol-4-y 1 , 1 , 2 , 3-Oxadiazol-5-yl , 1 , 2 , 4— Oxadiazol— 3— yl , 1 , 2 , 4— Oxadiazol— 5— yl , 1 , 3 , 4-Oxadiazol— 2-yl , 1, 2 , 3-Thiadiazol-4-yl , 1 , 2 , 3— Thiadiazol— 5— yl , 1 , 2 , 4— Thiadiazol— 3— yl,2H-1, 3, 4-dithiazol-5-yl, 2H-1, 3, 4-oxathiazol-5-yl, 1, 2, 3-oxadiazol-4-y 1, 1, 2, 3-oxadiazol-5 -yl, 1, 2, 4-oxadiazole-3-yl, 1, 2, 4-oxadiazole-5-yl, 1, 3, 4-oxadiazole-2-yl, 1, 2, 3-thiadiazol-4-yl , 1, 2, 3 - thiadiazole - 5 - yl, 1, 2, 4 - thiadiazole - 3 - yl,
1 , 2 , 4-Thiadiazol-5-y 1 , 1 , 3 , 4-Thiadiazol-2-yl , 1 , 2 , 3— Triazol— 4— yl, 1 , 2 , 4— Triazol— 3— y 1 , Tetrazol— 5— yl ;1, 2, 4-thiadiazol-5-y 1, 1, 3, 4-thiadiazol-2-yl, 1, 2, 3 - triazole - 4 - yl, 1, 2, 4 - triazole - 3 - y 1, Tetrazole-5-yl;
C-gebundene 6—gliedrige Ringe wie:C-linked 6-membered rings such as:
Tetrahydropyran— 2—yl, Tetrahydropyran—3— l, Tetrahydropyran—4—yl, Piperidin—2—yl, Piperidin—3—yl, Piperidin—4—yl, Tetrahydrothiopyran—2—yl, Tetrahydrothiopyran—3— l, Tetrahydrothiopyran—4—yl, 2H-3 , 4-Dihydropyran-6— l, 2H-3 , 4-Dihydropyran-5-yl, 2H—3 , 4—Dihydropyran—— l, 2H—3 , 4-Dihydropyran—3—yl, 2H-3 , 4-Dihydropyran-2-yl, 2H-3 , 4-Dihydropyran-6-yl,Tetrahydropyran-2-yl, tetrahydropyran-3-l, tetrahydropyran-4-yl, piperidine-2-yl, piperidine-3-yl, Piperidine-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-l, tetrahydrothiopyran-4-yl, 2H-3, 4-dihydropyran-6-l, 2H-3, 4-dihydropyran-5-yl, 2H— 3,4-dihydropyran-1,2H-3,4-dihydropyran-3-yl,2H-3,4,4-dihydropyran-2-yl,2H-3,4,4-dihydropyran-6-yl
2H—3 , 4—Dihydrothiopyran—5—yl, 2H—3 , 4—Dihydrothiopyran—4—yl, 2H—3 ,4—Dihydropyran—3—yl, 2H—3,4—Dihydropyran—2—yl, 1,2,3, 4—Tetrahydropyridin-6-yl, 1,2,3, 4—Tetrahydropyridin—5— l, 1,2,3, 4—Tetrahydropyridin—4—yl, 1,2,3, 4—Tetrahydropyridin—3—yl,2H-3, 4-dihydrothiopyran-5-yl, 2H-3,4, -dihydrothiopyran-4-yl, 2H-3,4, -dihydropyran-3-yl, 2H-3,4-dihydropyran-2-yl, 1,1 2,3,4-tetrahydropyridin-6-yl, 1,2,3,4-tetrahydropyridine-5-1, 1,2,3,4-tetrahydropyridine-4-yl, 1,2,3,4-tetrahydropyridine 3-yl,
1,2,3, 4—Tetrahydropyridin—2—y1, 2H—5, 6—Dihydropyran—2—yl, 2H—5 , 6—Dihydropyran—3—yl, 2H—5, 6—Dihydropyran—4—yl, 2H—5, 6—Dihydropyran—5—yl, 2H—5, 6—Dihydropyran—6—yl, 2H—5 , 6—Dihydrothiopyran—2—yl, 2H—5 , 6—Dihydrot iopyran—3—yl, 2H—5 , 6—Dihydrothiopyran—4—yl, 2H—5 , 6—Dihydrothiopyran—5—yl, 2H—5 , 6—Dihydrothiopyran—6—yl, 1,2,5, 6—Tetrahydropyridin—2—yl, 1,2,5, 6—etrahydropyridin—3—yl, 1,2,5, 6—Tetrahydropyridin—4—yl, 1,2,5, 6—Tetrahydropyridin—5—yl, 1,2,5, 6—Tetrahydropyridin—6—yl, 2,3,4, 5—Tetrahydropyridin—2— l, 2,3,4, 5—Tetrahydropyridin—3—yl, 2,3,4, 5—etrahydropyridin—4—yl, 2,3,4, 5—Tetrahydropyridin—5—yl,1,2,3,4-tetrahydropyridine-2-y1, 2H-5,6-dihydropyran-2-yl, 2H-5,6-dihydropyran-3-yl, 2H-5,6-dihydropyran-4-yl, 2H-5,6-dihydropyran-5-yl, 2H-5,6-dihydropyran-6-yl, 2H-5,6-dihydrothiopyran-2-yl, 2H-5,6-dihydro-iopyran-3-yl, 2H -5,6-dihydrothiopyran-4-yl, 2H-5,6-dihydrothiopyran-5-yl, 2H-5,6-dihydrothiopyran-6-yl, 1,2,5,6-tetrahydropyridine-2-yl, 1 , 2,5, 6-etrahydropyridine-3-yl, 1,2,5, 6-tetrahydropyridine-4-yl, 1,2,5, 6-tetrahydropyridine-5-yl, 1,2,5, 6-tetrahydropyridine -6-yl, 2,3,4,5-tetrahydropyridine-2-1, 2,3,4,5-tetrahydropyridine-3-yl, 2,3,4,5-etrahydropyridine-4-yl, 2,3 , 4, 5 — tetrahydropyridine — 5-yl,
2,3,4, 5—Tetrahydropyridin—6—yl, 4H—Pyran—2—yl, 4H—Pyran—3—yl,2,3,4,5-tetrahydropyridine-6-yl, 4H-pyran-2-yl, 4H-pyran-3-yl,
4H—yran—4— l, 4H—Thiopyran—2— l, 4H—Thiopyran—3—yl,4H-yran-4-1.4H-thiopyran-2-1.4H-thiopyran-3-yl,
4H—Thiopyran—4-yl, 1, 4-Dihydropyridin—2-yl,4H-thiopyran-4-yl, 1,4-dihydropyridine-2-yl,
1, 4—Dihydropyridin—3—yl, 1, 4—Dihydropyridin—4—yl, 2H-Pyran-2-yl, 2H-Pyran-3-yl, 2H-Pyran-4-yl, 2H—Pyran-5-yl, 2H—Pyran—6—yl, 2H—Thiopyran—2—yl, 2H—Thiopyran—3—yl, 2H—Thiopyran—4—yl, 2H—Thiopyran—5— l, 2H—Thiopyran—6—yl, 1 , 2—Dihydropyridin—2—yl, 1 , 2—Dihydropyridin—3—yl, 1, 2-Dihydropyridin-4—yl, 1, 2-Dihydropyridin-5—yl, 1 , 2—Dihydropyridin—6—yl, 3 , 4—Dihydropyridin—2—yl, 3, 4—Dihydropyridin—3— l, 3, 4—Dihydropyridin—4—yl, 3 , 4—Dihydropyridin—5—yl, 3 , 4—Dihydropyridin—6—yl, 2 , 5—Dihydropyridin—2—yl, 2 , 5—Dihydropyridin—3—yl, 2 , 5—Dihydropyridin—4—yl, 2 , 5—Dihydropyridin—5—yl, 2 , 5—Dihydropyridin—6—yl, 2 , 3—Dihydropyridin—2—yl, 2 , 3—Dihydropyridin—3—yl, 2 , 3—Dihydropyridin—4—yl, 2 , 3—Dihydropyridin—5—yl, 2 , 3—Dihydropyridin—6—yl, Pyridin—2—y1, Pyridin—3— l, Pyridin—4— l, 1 , 3—Dioxan—2—yl, 1, 3—Dioxan—4—yl, 1 , 3—Dioxan—5—yl, 1, 4—Dioxan—2—yl,1,4-dihydropyridine-3-yl, 1,4-dihydropyridine-4-yl, 2H-pyran-2-yl, 2H-pyran-3-yl, 2H-pyran-4-yl, 2H-pyran-5- yl, 2H-pyran-6-yl, 2H-thiopyran-2-yl, 2H-thiopyran-3-yl, 2H-thiopyran-4-yl, 2H-thiopyran-5-1, 2H-thiopyran-6-yl, 1,2-dihydropyridine-2-yl, 1,2-dihydropyridine-3-yl, 1,2-dihydropyridin-4-yl, 1,2-dihydropyridin-5-yl, 1,2-dihydropyridine-6-yl, 3,4-dihydropyridine-2-yl, 3,4-dihydropyridine-3-1, 3,4-dihydropyridine-4-yl, 3,4-dihydropyridine-5-yl, 3,4-dihydropyridine-6-yl, 2,5-dihydropyridine-2-yl, 2,5-dihydropyridine-3-yl, 2,5-dihydropyridine-4-yl, 2,5-dihydropyridine-5-yl, 2,5-dihydropyridine-6-yl, 2,3-dihydropyridine-2-yl, 2,3-dihydropyridine-3-yl, 2,3-dihydropyridine-4-yl, 2,3-dihydropyridine-5-yl, 2,3-dihydropyridine-6-yl, Pyridine-2-y1, pyridine-3-l, pyridine-4-l, 1, 3-dioxane-2-yl, 1 , 3-dioxane-4-yl, 1,3-dioxane-5-yl, 1,4-dioxane-2-yl,
1 , 3-Dithian-2-y1, 1, 3-Dithian-4-yl, 1, 3—Dithian—5—yl, 1, 4—Dithian—2—yl, 1, 3—Oxathian—2—yl, 1, 3—Oxathian—4—y1, 1, 3—Oxathian—5— l, 1 , 3—Oxathian—6— l, 1,4-Oxathian-2-yl, 1,4-Oxathian-3-yl, 1, 2-Dithian-3-yl, 1 , 2-Dithian-4-yl, Hexahydropyrimidin—2—yl, Hexahydropyrimidin—4—yl, Hexahydropyrimidin—5— l, Hexahydropyrazin—2— l, Hexahydropyridazin—3—yl, Hexahydropyridazin—4—yl, Tetrahydro—1,3—oxazin—2—yl, Tetrahydro—1, 3—oxazin—4—yl, Tetrahydro—1, 3—oxazin—5—yl, Tetrahydro—1 , 3—oxazin—6—yl, Tetrahydro—1, 3—thiazin—2—yl, Tetrahydro—1 , 3—thiazin—4—yl, Tetrahydro—1, 3—thiazin—5—yl, Tetrahydro—1, 3—thiazin—6—yl, Tetrahydro—1 , 4—thiazin—2— l, Tetrahydro—1, 4—thiazin—3—yl, Tetrahydro—1,4—oxazin—2—yl, Tetrahydro—1, 4—oxazin—3—yl, Tetrahydro—1,2—oxazin—3—yl, Tetrahydro—1, 2—oxazin—4—yl, Tetrahydro—1, 2—oxazin—5—yl, Tetrahydro—1, 2—oxazin—6—yl, 2H—5 , 6—Dihydro—1 , 2—oxazin—3—yl,1, 3-dithian-2-yl, 1, 3-dithian-4-yl, 1, 3-dithian-5-yl, 1, 4-dithian-2-yl, 1,3-oxathian-2-yl, 1,3-oxathian-4-y1,1,3-oxathian-5-1, 1,3-oxathian-6,1, 1,4-oxathian-2-yl, 1,4-oxathian-3-yl, 1,2-dithian-3-yl, 1,2-dithian-4-yl, hexahydropyrimidine-2-yl, hexahydropyrimidine-4-yl, hexahydropyrimidine-5-1, hexahydropyrazine 2-1, hexahydropyridazine-3-yl, hexahydropyridazine-4-yl, tetrahydro-1,3-oxazin-2-yl, tetrahydro-1,3, -oxazin-4-yl, tetrahydro-1,3, -oxazin-5— yl, tetrahydro-1, 3-oxazine-6-yl, tetrahydro-1, 3-thiazine-2-yl, tetrahydro-1, 3-thiazine-4-yl, tetrahydro-1, 3-thiazine-5-yl, Tetrahydro — 1,3-thiazine — 6-yl, tetrahydro — 1,4-thiazine — 2-1, tetrahydro — 1,4-thiazine-3-yl, tetrahydro — 1,4-oxazin — 2-yl, tetrahydro— 1,4-oxazin-3-yl, tetrahydro-1,2-oxazin-3-yl, tetrahydro-1,2-oxazin-4-yl, tetrahydro-1,2-oxazin-5-yl, tetrahydro-1, 2-oxazin-6-yl, 2H-5, 6-dihydro-1, 2-oxazin-3-yl,
2H-5 6—Dihydro—1 2—oxazin—4—yl, 2H-5 6—Dihydro—1 2—oxazin—5—yl, 2H-5 6—Dihydro—1 2—oxazin—6—yl, 2H-5 6—Dihydro—1 2—thiazin—3— l, 2H-5 6—Dihydro—1 2—thiazin—4—yl, 2H-5 6—Dihydro—1 2—thiazin—5—yl, 2H-5 6—Dihydro—1 2—thiazin—6—yl, 4H-5 6—Dihydro—1 2—oxazin—3—yl, 4H-5 6—Dihydro—1 2—oxazin—4—l, 4H-5 6—Dihydro—1 2—oxazin—5—yl, 4H-5 6—Dihydro—1 2—oxazin—6—yl, 4H-5 6—Dihydro—1 2—thiazin—3—yl, 4H-5 6—Dihydro—1 2—thiazin—4—yl, 4H-5 6—Dihydro—1 2—thiazin—5—yl, 4H-5 6—Dihydro—1 2—thiazin—6—yl, 2H-3 6—Dihydro—1 2—oxazin—3—yl, 2H-3 6—Dihydro—1 2—oxazin—4—yl, 2H-3 6—Dihydro—1 2—oxazin—5—yl, 2H-3 6—Dihydro—1 2—oxazin—6—yl, 2H-3 6—Dihydro—1 2—thiazin—3—yl, 2H-3 6—Dihydro—1 2—thiazin—4— l, 2H-3 6—Dihydro—1 2—thiazin—5— l, 2H-3 6—Dihydro—1 2—thiazin—6—yl, 2H-3 4—Dihydro—1 2—oxazin—3—yl, 2H-3 4—Dihydro—1 2—oxazin—4—yl, 2H-3 4—Dihydro—1 2—oxazin—5—yl, 2H-3 4—Dihydro—1 2—oxazin—6—yl, 2H-3 4—Dihydro—1 2—thiazin—3—yl, 2H-3 4—Dihydro—1 2—thiazin—4—yl, 2H-3 4—Dihydro—1 2—thiazin—5—yl, 2H-3 4—Dihydro-1 2—thiazin—6—yl, 2,3,4, 5—Tetrahydropyridazin—3—yl, 2,3,4, 5—Tetrahydropyridazin—4—yl, 2,3,4, 5—Tetrahydropyridazin—5—yl, 2,3,4, 5—etrahydropyridazin—6—yl, 3,4,5, 6—etrahydropyridazin—3—yl, 3,4,5, 6—Tetrahydropyridazin—4—yl, 1,2,5, 6—Tetrahydropyridazin—3—yl, 1,2,5, 6—Tetrahydropyridazin—4—yl, 1,2,5, 6—Tetrahydropyridazin—5—yl, 1,2,5, 6—Tetrahydropyridazin—6—yl, 1,2,3, 6—Tetrahydropyridazin—3—yl, 1,2,3, 6—Tetrahydropyridazin—4—yl, 4H—5 , 6—Dihydro—1, 3—oxazin—2—yl, 4H—5, 6—Dihydro—1 , 3—oxazin—4—yl, 4H—5 , 6—Dihydro—1 , 3—oxazin—5—yl, 4H—5, 6—Dihydro—1, 3—oxazin—6—yl", 4H-5 , 6-Dihydro-l , 3-thiazin-2-yl, 4H-5 , 6-Dihydro-l , 3-thiazin-4-yl, H—5, 6—Dihydro—1 , 3—thiazin—5— l, 4H-5, 6-Dihydro-l, 3-thiazin-6-yl, 3,4, 5—6—Tetrahydropyrimidin—2—yl, 3,4,5, 6—Tetrahydropyrimidin—4—yl, 3,4,5, 6—Tetrahydropyrimidin—5—yl, 3,4,5, 6—Tetrahydropyrimidin—6—yl, 1,2,3, 4—Tetrahydropyrazin—2—yl, 1,2,3, 4—Tetrahydropyrazin—5—yl, 1,2,3, 4—Tetrahydropyrimidin—2—yl, 1,2,3, 4—Tetrahydropyrimidin—4—yl, 1,2,3, 4—Tetrahydropyrimidin—5—yl, 1,2,3, 4—Tetrahydropyrimidin—6—yl,2H-5 6-dihydro-1 2-oxazin-4-yl, 2H-5 6-dihydro-1 2-oxazin-5-yl, 2H-5 6-dihydro-1 2-oxazin-6-yl, 2H- 5 6-Dihydro-1 2-thiazine-3-1, 2H-5 6-Dihydro-1 2-thiazine-4-yl, 2H-5 6-Dihydro-1 2-thiazine-5-yl, 2H-5 6 Dihydro-1 2-thiazine-6-yl, 4H-5 6-dihydro-1 2-oxazine-3-yl, 4H-5 6-dihydro-1 2-oxazine-4-l, 4H-5 6-dihydro -1 1-oxazin-5-yl, 4H-5 6-dihydro-1 2-oxazin-6-yl, 4H-5 6-dihydro-1 2-thiazine-3-yl, 4H-5 6-dihydro-1 2-thiazine-4-yl, 4H-5 6-dihydro-1 2-thiazine-5-yl, 4H-5 6-dihydro-1 2-thiazine-6-yl, 2H-3 6-dihydro-1 2— oxazin-3-yl, 2H-3 6-dihydro-1 2-oxazin-4-yl, 2H-3 6-dihydro-1 2-oxazin-5-yl, 2H-3 6-dihydro-1 2-oxazin- 6-yl, 2H-3 6-dihydro-1 2-thiazine-3-yl, 2H-3 6-dihydro-1 2-thiazine-4-l, 2H-3 6-dihydro-1 2-thiazine-5 - 1, 2H-3 6-dihydro-1 2-thiazine-6-yl, 2H-3 4-dihydro-1 2 oxazin-3-yl, 2H-3 4-dihydro-1 2-oxazin-4-yl, 2H-3 4-dihydro-1 2-oxazin-5-yl, 2H-3 4-dihydro-1 2-oxazin- 6-yl, 2H-3 4-dihydro-1 2-thiazine-3-yl, 2H-3 4-dihydro-1 2-thiazine-4-yl, 2H-3 4-dihydro-1 2-thiazine-5 - yl, 2H-3 4-dihydro-1 2-thiazine-6-yl, 2,3,4,5-tetrahydropyridazine-3-yl, 2,3,4,5-tetrahydropyridazine-4-yl, 2,3,4,5-tetrahydropyridazine-5-yl, 2,3,4,5- etrahydropyridazine-6-yl, 3,4,5,6-etrahydropyridazine-3-yl, 3,4,5,6-tetrahydropyridazine-4-yl, 1,2,5,6-tetrahydropyridazine-3-yl, 1,1 2,5,6-tetrahydropyridazine-4-yl, 1,2,5,6-tetrahydropyridazine-5-yl 1,2,5,6-tetrahydropyridazine-6-yl 1,2,3,6-tetrahydropyridazine 3-yl, 1,2,3,6-tetrahydropyridazine-4-yl, 4H-5,6-dihydro-1,3-oxazin-2-yl, 4H-5,6-dihydro-1,3-oxazine- 4-yl, 4H-5,6-dihydro-1,3-oxazin-5-yl, 4H-5,6-dihydro-1,3-oxazin-6-yl " , 4H-5,6-dihydro-1 , 3-thiazin-2-yl, 4H-5, 6-dihydro-l, 3-thiazin-4-yl, H-5,6-dihydro-1,3-thiazine-5-1, 4H-5,6 -Dihydro-1,3-thiazin-6-yl, 3,4,5-6-tetrahydropyrimidine-2-yl, 3,4,5,6-tetrahydropyrimidine-4-yl, 3,4,5,6-tetrahydropyrimidine -5-yl, 3,4,5,6-tetrahydropyrimidine-6-y l, 1,2,3, 4-tetrahydropyrazine-2-yl, 1,2,3, 4-tetrahydropyrazine-5-yl, 1,2,3, 4-tetrahydropyrimidine-2-yl, 1,2,3, 4-tetrahydropyrimidine-4-yl, 1,2,3, 4-tetrahydropyrimidine-5-yl, 1,2,3, 4-tetrahydropyrimidine-6-yl,
2 , 3—Dihydro—1, 4—thiazin—2—yl, 2 , 3—Dihydro—1, 4—thiazin—3—yl, 2, 3—Dihydro—1, 4—thiazin—5—yl, 2 ,3—Dihydro—1, 4—thiazin—6— l, 2H-1 , 2-Oxazin-3-yl, 2H-1, 2-Oxazin-4-yl,2,3-dihydro-1,4-thiazine-2-yl, 2,3-dihydro-1,4, -thiazine-3-yl, 2,3-dihydro-1,4-thiazine-5-yl,2, 3-dihydro-1,4-thiazine-6-1, 2H-1,2-oxazin-3-yl, 2H-1,2-oxazin-4-yl,
2H-1 2-Oxazin-5—yl, 2H—1, 2-Oxazin-6— l, 2H-1 2-Thiazin-3-yl, 2H-l,2-Thiazin-4-yl, 2H-1 2—Thiazin—5—yl, 2H—1, 2—Thiazin—6— l, 4H-1 2—Oxazin—3—yl, 4H—1,2-Oxazin—4—yl, 4H-1 2—Oxazin—5—yl, 4H—1,2—Oxazin—6—yl, 4H-1 2-Thiazin-3-yl, 4H-1, 2-Thiazin-4-yl, 4H-1 2-Thiazin-5-yl, 4H-1, 2-Thiazin-6-yl, 6H-1 2-Oxazin-3-yl, 6H-l,2-Oxazin-4—yl, 6H-1 2-Oxazin—5—y1, 6H—1, 2-Oxazin-6—y1, 6H-1 2-Thiazin-3-yl, 6H-1, 2-Thiazin-4-yl, 6H-1 2-Thiazin-5-yl, 6H-1,,2-Thiazin-6-yl, 2H-1 3-Oxazin-2-yl, 2H-l,3-Oxazin-4-yl, 2H-1 3-Oxazin-5-yl, 2H-l,3-Oxazin-6—yl, 2H-1 3—Thiazin-2-yl, 2H-1, 3-Thiazin-4-yl, 2H-1, 3-Thiazin-5-yl, 2H-1, 3-Thiazin-6-yl,2H-1 2-oxazin-5-yl, 2H-1, 2-oxazin-6-1, 2H-1 2-thiazin-3-yl, 2H-1, 2-thiazin-4-yl, 2H-1 2 -Thiazine-5-yl, 2H-1, 2-thiazine-6-l, 4H-1 2-oxazin-3-yl, 4H-1,2-oxazin-4-yl, 4H-1 2-oxazin-5 -Yl, 4H-1,2-oxazin-6-yl, 4H-1 2-thiazin-3-yl, 4H-1, 2-thiazin-4-yl, 4H-1 2-thiazin-5-yl, 4H -1, 2-thiazin-6-yl, 6H-1 2-oxazin-3-yl, 6H-1, 2-oxazin-4-yl, 6H-1 2-oxazin-5-y1, 6H-1, 2 -Oxazin-6-y1, 6H-1 2-thiazin-3-yl, 6H-1, 2-thiazin-4-yl, 6H-1 2-thiazin-5-yl, 6H-1,, 2-thiazine 6-yl, 2H-1 3-oxazin-2-yl, 2H-l, 3-oxazin-4-yl, 2H-1 3-oxazin-5-yl, 2H-l, 3-oxazin-6-yl, 2H-1 3-thiazin-2-yl, 2H-1, 3-thiazin-4-yl, 2H-1, 3-thiazin-5-yl, 2H-1, 3-thiazin-6-yl,
4H—1 , 3-Oxazin-2-yl, 4H-1,3-Oxazin-4—yl,4H-1,3-oxazin-2-yl, 4H-1,3-oxazin-4-yl,
4H-1 , 3-Oxazin-5-yl, 4H-1, 3-Oxazin-6-yl,4H-1, 3-oxazin-5-yl, 4H-1, 3-oxazin-6-yl,
4H-1 , 3-Thiazin-2-yl, 4H-1, 3-Thiazin-4-yl, 4H-l,3-Thiazin-5-yl, 4H-l,3-Thiazin-6-yl,4H-1, 3-thiazin-2-yl, 4H-1, 3-thiazin-4-yl, 4H-1, 3-thiazin-5-yl, 4H-1, 3-thiazin-6-yl,
6H-1, 3-Oxazin-2-yl, 6H-1, 3-Oxazin-4-yl,6H-1, 3-oxazin-2-yl, 6H-1, 3-oxazin-4-yl,
6H—1, 3-Oxazin-5-yl, 6H-1 , 3-Oxazin-6—yl,6H-1,3-oxazin-5-yl, 6H-1,3-oxazin-6-yl,
6H—1 , 3-Thiazin-2-yl, 6H-1, 3-Thiazin-4-yl,6H-1,3-thiazin-2-yl, 6H-1,3-thiazin-4-yl,
6H-1, 3-Thiazin-5-yl, 6H-1,3-Thiazin-6-yl, 2H-l,4-Oxazin-2-yl, 2H-l,4-Oxazin-3-yl,6H-1, 3-thiazin-5-yl, 6H-1,3-thiazin-6-yl, 2H-l, 4-oxazin-2-yl, 2H-l, 4-oxazin-3-yl,
2H—1 , 4-Oxazin-5-yl, 2H—1, 4-Oxazin-6—yl,2H-1,4-oxazin-5-yl, 2H-1,4-oxazin-6-yl,
2H—1, 4-Thiazin-2-yl, 2H-1, 4-Thiazin-3-yl,2H-1,4-thiazin-2-yl, 2H-1,4-thiazin-3-yl,
2H-1 , 4-Thiazin-5-yl, 2H-1 , 4-Thiazin-6-yl,2H-1, 4-thiazin-5-yl, 2H-1, 4-thiazin-6-yl,
4H-1 , 4-Oxazin-2-yl, 4H-1 , 4-Oxazin-3-yl, 4H-l,4-Thiazin-2-yl, 4H-l,4-Thiazin-3-yl,4H-1, 4-oxazin-2-yl, 4H-1, 4-oxazin-3-yl, 4H-1, 4-thiazin-2-yl, 4H-1, 4-thiazin-3-yl,
1 , 4—Dihydropyridazin—3—yl, 1, 4—Dihydropyridazin—4—yl,1,4-dihydropyridazine-3-yl, 1,4-dihydropyridazine-4-yl,
1, 4—Dihydropyridazin—5—yl, 1, 4—Dihydropyridazin—6—yl,1,4-dihydropyridazine-5-yl, 1,4-dihydropyridazine-6-yl,
1 , 4—Dihydropyrazin—2—y1, 1, 2—Dihydropyrazin—2—yl,1,4-dihydropyrazine-2-y1, 1,2-dihydropyrazine-2-yl,
1, 2—Dihydropyrazin—3— l, 1, 2—Dihydropyrazin—5—yl, 1,2—Dihydropyrazin—6—yl, 1, 4—Dihydropyrimidin—2— l,1,2-dihydropyrazine-3-1, 1,2-dihydropyrazine-5-yl, 1,2-dihydropyrazine-6-yl, 1,4-dihydropyrimidine-2-1,
1, 4—Dihydropyrimidin—4—yl, 1, 4—Dihydropyrimidin—5—yl,1,4-dihydropyrimidine-4-yl, 1,4-dihydropyrimidine-5-yl,
1, 4—Dihydropyrimidin—6—yl, 3, 4—Dihydropyrimidin—2—yl,1,4-dihydropyrimidine-6-yl, 3,4-dihydropyrimidine-2-yl,
3, 4—Dihydropyrimidin—4—yl, 3, 4—Dihydropyrimidin—5—yl,3,4-dihydropyrimidine-4-yl, 3,4-dihydropyrimidine-5-yl,
3 , 4—Dihydropyrimidin—6— l, Pyridazin—3— l, Pyridazin—4—yl, Pyrimidin—2—yl, Pyrimidin—4—yl, Pyrimidin—5—yl, Pyrazin—2—yl,3,4-dihydropyrimidine-6-1, pyridazine-3-1, pyridazine-4-yl, pyrimidine-2-yl, pyrimidine-4-yl, pyrimidine-5-yl, pyrazine-2-yl,
1,3,5—Triazin—2—yl, 1,2,4—Triazin—3—yl, 1,2,4—Triazin—5—yl,1,3,5-triazine-2-yl, 1,2,4-triazine-3-yl, 1,2,4-triazine-5-yl,
1,2,4— riazin—6—yl oder 1,2,4,5—Tetra-zin—3—yl;1,2,4-riazine-6-yl or 1,2,4,5-tetrazine-3-yl;
N-gebundene 5-gliedrige Ringe wie:N-linked 5-membered rings such as:
Tetrahydropyrrol—1—yl, 2 , 3—Dihydro—IH—pyrrol—1—yl, 2 , 5—Dihydro—IH—pyrrol—1— l, Pyrrol—1—yl, Tetrahydropyrazol—1—yl, Tetrahydroisoxazol—2—yl, Tetrahydroisothiazol—2—yl, Tetrahydroimidazol—1—yl, Tetrahydrooxazol—3—yl, Tetrahydrothiazol—3—yl,Tetrahydropyrrole — 1-yl, 2,3-dihydro-IH-pyrrole-1-yl, 2,5-dihydro-IH-pyrrole-1-1, pyrrole-1-yl, tetrahydropyrazole-1-yl, tetrahydroisoxazole — 2- yl, tetrahydroisothiazole-2-yl, tetrahydroimidazole-1-yl, tetrahydrooxazole-3-yl, tetrahydrothiazole-3-yl,
4 , 5—Dihydro—IH—pyrazol—1—yl, 2 , 5—Dihydro—IH—pyrazol—1—yl, 2 , 3—Dihydro—IH—pyrazol—1—yl, 2 , 5—Dihydroisoxazol—2—yl, 2, 3—Dihydroisoxazol—2—yl, 2 , 5—Dihydroisothiazol—2—yl, 2 , 3—Dihydroisoxazol—2—yl, 4 , 5—Dihydro—IH—imidazol—1—yl, 2 , 5—Dihydro—IH—imidazol—1—yl, 2 , 3—Dihydro—IH—imidazol—1—yl, 2 , 3—Dihydrooxazol—3—yl, 2 , 3—Dihydrothiazol—3—yl, Pyrazol—1—yl, Imidazol-1-yl, 1,2,4—Δ4-Oxadiazolin-2—yl, 1,2, 4-Δ2-Oxadiazolin—4-yl, 1,2, 4-Δ3-Oxadiazolin-2-yl, 1,3, 4—Δ2-Oxadiazolin—4—yl, 1,2, 4—Δ5—Thiadiazolin-2—yl, l,2,4-Δ3-Thiadiazolin-2-yl, 1,2,4-Δ2—Thiadiazolin-4-yl, 1,3, 4-Δ-Thiadiazolin-4-y1, 1,2, 3-Δ2-Triazolin-l-yl, 1,2, 4-Δ2-Triazolin-l-yl, 1,2, 4-Δ2-Triazolin-4-yl, 1,2, 4-Δ3-Triazolin-1-yl, 1,2, 4-Δ1-Triazolin-4-yl, 1,2,3-Triazol-l-yl, 1,2,4-Triazol-l-yl, Tetrazol-1—yl;4,5-dihydro-IH-pyrazole-1-yl, 2,5-dihydro-IH-pyrazole-1-yl, 2,3-dihydro-IH-pyrazole-1-yl, 2,5-dihydroisoxazole-2 yl, 2,3-dihydroisoxazole-2-yl, 2,5-dihydroisothiazole-2-yl, 2,3-dihydroisoxazole-2-yl, 4,5-dihydro-IH-imidazole-1-yl, 2,5- Dihydro-IH-imidazole-1-yl, 2,3-dihydro-IH-imidazole-1-yl, 2,3-dihydrooxazole-3-yl, 2,3-dihydrothiazole-3-yl, pyrazole-1-yl, Imidazol-1-yl, 1,2,4-Δ 4 -oxadiazolin-2-yl, 1,2, 4-Δ 2 -oxadiazolin-4-yl, 1,2, 4-Δ 3 -oxadiazolin-2-yl , 1,3, 4-Δ 2 -oxadiazolin-4-yl, 1,2, 4-Δ 5 -thiadiazolin-2-yl, l, 2,4-Δ 3 -thiadiazolin-2-yl, 1,2, 4-Δ 2 -thiadiazolin-4-yl, 1,3, 4-Δ-thiadiazolin-4-y1, 1,2, 3-Δ 2 -triazolin-l-yl, 1,2, 4-Δ 2 -triazolin -l-yl, 1,2,4-Δ 2 -triazolin-4-yl, 1,2, 4-Δ 3 -Triazolin-1-yl, 1,2, 4-Δ 1 -Triazolin-yl-4, 1,2,3-triazol-l-yl, 1,2,4-triazole l-yl, tetrazol-1-yl;
N—gebundene 6—gliedrige Ringe wie:N-linked 6-membered rings such as:
Piperidin—1—yl, 1,2,3, 4—Tetrahydropyridin—1—yl,Piperidine-1-yl, 1,2,3, 4-tetrahydropyridine-1-yl,
1,2,5, 6—Tetrahydropyridin—1—yl, 1, 4—Dihydropyridin—1— l,1,2,5,6-tetrahydropyridine-1-yl, 1,4-dihydropyridine-1-1,
1 , 2—Dihydropyridin—1—yl, Hexahydropyrimidin—1—yl,1,2-dihydropyridine-1-yl, hexahydropyrimidine-1-yl,
Hexahydropyrazin—1—yl, Hexahydropyridazin—1— l, Tetrahydro—1 , 3—oxazin—3—yl, Tetrahydro—1 , 3—thiazin—3— l,Hexahydropyrazine-1-yl, hexahydropyridazine-1-l, tetrahydro-1, 3-oxazine-3-yl, tetrahydro-1, 3-thiazine-3-l,
Tetrahydro—1 , 4—thiazin—4—yl, Tetrahydro—1 , 4—oxazin—4— lTetrahydro-1,4-thiazine-4-yl, tetrahydro-1,4-oxazin-4-1
(Morpholinyl) , Tetrahydro—1, 2—oxazin—2— l,(Morpholinyl), tetrahydro-1, 2-oxazine-2-l,
2H—5, 6—Dihydro—1, 2—oxazin—2—yl,2H-5,6-dihydro-1,2-oxazin-2-yl
2H—5 , 6-Dihydro-l, 2-thiazin-2-yl, 2H—3 , 6-Dihydro-l, 2-oxazin-2-yl,2H-5, 6-dihydro-l, 2-thiazin-2-yl, 2H-3, 6-dihydro-l, 2-oxazin-2-yl,
2H—3 , 6-Dihydro-l, 2-thiazin-2-yl,2H-3,6-dihydro-1,2-thiazin-2-yl
2H—3 , 4-Dihydro-l , 2-thiazin-2-yl,2H-3,4-dihydro-l, 2-thiazin-2-yl,
2,3,4, 5—Tetrahydropyridazin—2—yl,2,3,4,5-tetrahydropyridazin-2-yl,
1,2,5, 6—Tetrahydropyridazin—1—yl, 1,2,5, 6—Tetrahydropyridazin—2—yl,1,2,5,6-tetrahydropyridazine-1-yl, 1,2,5,6-tetrahydropyridazine-2-yl
1,2,3, 6—Tetrahydropyridazin—1— l,1,2,3,6-tetrahydropyridazine-1-1,
3,4,5, 6—etrahydropyrimidin—3—yl,3,4,5,6-etrahydropyrimidine-3-yl,
1,2,3, 4—Tetrahydropyrazin—1—yl,1,2,3,4-tetrahydropyrazine-1-yl,
1,2,3, 4—Tetrahydropyrimidin—1—yl, 1,2,3, 4—Tetrahydropyrimidin—3—yl,1,2,3,4-tetrahydropyrimidine-1-yl, 1,2,3,4-tetrahydropyrimidine-3-yl,
2 , 3—Dihydro—1 , 4—thiazin—4— l, 2H—1, 2-Oxazin—2—yl,2,3-dihydro-1,4-thiazine-4-1, 2H-1,2-oxazine-2-yl,
2H-l,2-Thiazin-2-yl, 4H-l,4-Oxazin-4-yl, 4H-l,4-Thiazin-4-yl,2H-l, 2-thiazin-2-yl, 4H-l, 4-oxazin-4-yl, 4H-l, 4-thiazin-4-yl,
1 , 4—Dihydropyridazin—1—yl, 1, 4—Dihydropyrazin—1—yl,1,4-dihydropyridazine-1-yl, 1,4-dihydropyrazine-1-yl,
1 , 2—Dihydropyrazin—1—yl, 1 , 4—Dihydropyrimidin—1—yl oder 3 , 4—Dihydropyrimidin—3—yl;1,2-dihydropyrazine-1-yl, 1,4-dihydropyrimidine-1-yl or 3,4-dihydropyrimidine-3-yl;
sowie N-gebundene cyclische Imide wie:as well as N-linked cyclic imides such as:
Phthalsäureimid, Tetrahydrophthalsäureimid, Succinimid, Maleinimid, Glutarimid, 5-0xo-triazolin-l-yl, 5-Oxo-l , 3 , 4-oxadiazolin-4-yl oder 2 , 4-Dioxo- ( IH, 3H) -pyrimidin-3-yl;Phthalimide, tetrahydrophthalimide, succinimide, maleimide, glutarimide, 5-0xo-triazolin-l-yl, 5-oxo-l, 3, 4-oxadiazolin-4-yl or 2,4-dioxo (IH, 3H) pyrimidine 3-yl;
wobei Heterocyclyl mit einem ankondensierten Phenylring oder mit einem C3-Cg-Carbocyclus oder einem weiteren 5- biswhere heterocyclyl with a fused phenyl ring or with a C 3 -Cg carbocycle or another 5- to
6-gliedrigen Heterocyclus ein bicyclisches Ringsystem ausbilden kann,6-membered heterocycle can form a bicyclic ring system,
wobei gegebenfalls ein Ring-Kohlenstoffatom in Heterocyclyl als Carbonyl oder Thiocarbonyl-Gruppe vorliegen kann, wobei gegebenenfalls der Schwefel der genannten Heterocyclen zu S=0 oder S(=0)2 oxidiert sein kann.where appropriate a ring carbon atom in heterocyclyl can be present as a carbonyl or thiocarbonyl group, where appropriate, the sulfur of the heterocycles mentioned can be oxidized to S = 0 or S (= 0) 2 .
Alle Phenylringe bzw. Heterocyclylreste sowie alle Phenylko ponenten in Phenoxy, Phenylalkyl, Phenylamino, Phenyl- carbonyl, Phenyloxycarbonyl, Phenylaminocarbonyl und N—Alkyl—N—phenylaminocarbonyl, sowie Heterocyclylkomponenten in Heterocyclyloxy, Heterocyclylalkyl, Heterocyclylcarbonyl, Hetero- cyclyloxycarbonyl, Heterocyclylcarbonyloxy, sind, soweit nicht anders angegeben, vorzugsweise unsubstituiert oder sind partiell oder vollständig halogeniert und/oder tragen einen, zwei oder drei Substituenten, ausgewählt unter Nitro, Cyano, Hydroxy, Cι-C-Alkyl, C!-C4-Halogenalkyl, Ci-C4-Alkoxy, Cι-C4-Halogenalkoxy, Ci-Cg-Alkylamino, Di-Ci-Cg-alkylamino, C3-C6-Cycloalkylamino, wobei die Alkyl- und Cycloalkylgruppen der drei letztgenannten Reste teilweise oder vollständig halogeniert sein können und/oder ein bis drei Substituenten, ausgewählt unter Cι-C4-Alkoxy oder Hydroxy tragen können.All phenyl rings or heterocyclyl residues and all phenyl components in phenoxy, phenylalkyl, phenylamino, phenylcarbonyl, phenyloxycarbonyl, phenylaminocarbonyl and N — alkyl — N — phenylaminocarbonyl, as well as heterocyclyl components in heterocyclyloxy, heterocyclylalkyl, heterocycyloxycarbonyl, heterocyclyloxycarbonyl, heterocycyloxycarbonyl, not stated otherwise, preferably unsubstituted or are partially or completely halogenated and / or carry one, two or three substituents selected from nitro, cyano, hydroxy, C 1 -C 4 alkyl, C ! -C4-Haloalkyl, Ci-C 4 -alkoxy, -C-C 4 -haloalkoxy, Ci-Cg-alkylamino, di-Ci-Cg-alkylamino, C 3 -C 6 cycloalkylamino, the alkyl and cycloalkyl groups of the latter three Residues can be partially or completely halogenated and / or can carry one to three substituents selected from C 1 -C 4 alkoxy or hydroxy.
Für die Umsetzung der Arylhalogenide II mit den Verbindungen III bzw. III' oder III" werden solche Übergangsmetallkatalysatoren bevorzugt, deren aktive Metallkomponente wenigstens ein Platinmetall und insbesondere ein Übergangsmetall ausgewählt unter Palladium, Platin, Nickel, Cobalt, Ruthenium und Rhodium umfasst. Be- sonders bevorzugt sind solche Katalysatoren, die Palladium als Metall der Gruppe VIII des Periodensystems umfassen.For the reaction of the aryl halides II with the compounds III or III 'or III ", preference is given to those transition metal catalysts whose active metal component comprises at least one platinum metal and in particular one transition metal selected from palladium, platinum, nickel, cobalt, ruthenium and rhodium. Especially preferred are those catalysts which comprise palladium as metal of group VIII of the periodic table.
Die Katalysatoren, insbesondere solche, die Platin, Nickel, Cobalt, Ruthenium und Rhodium und insbesondere Palladium als kata- lytisch aktives Metall enthalten, können als Metalle oder in Form üblicher Salze, z.B. in Form von Halogenverbindungen wie PdCl2, NiCl2, CoCl2, RhCl3-H20, Acetaten wie Pd(OAc)2, Co(OAc)2, Acetyla- cetonaten oder Cyaniden in den bekannten Wertigkeitsstufen eingesetzt werden.The catalysts, in particular those which contain platinum, nickel, cobalt, ruthenium and rhodium and in particular palladium as catalytically active metal, can be in the form of metals or in the form of customary salts, for example in the form of halogen compounds such as PdCl 2 , NiCl 2 , CoCl 2 , RhCl 3 -H 2 0, acetates such as Pd (OAc) 2 , Co (OAc) 2 , acetylacetonates or cyanides can be used in the known valence levels.
Ausserdem können die katalytisch aktiven Metalle in Form von Metallkomplexen, z.B. mit tertiären Phosphinen, als Metallalkylcar- bonyle, gemischte Komplexe, die wenigstens zwei verschiedene Liganden, vorzugsweise wenigstens ein tertiäres Phosphin und wenig- stens einen davon verschiedenen Liganden, z.B. CO, umfassen, oder mit tertiären Phosphinen komplexierte Übergangsmetallsalze eingesetzt werden.In addition, the catalytically active metals can be in the form of metal complexes, e.g. complexes mixed with tertiary phosphines, as metal alkylcarbonyls, which contain at least two different ligands, preferably at least one tertiary phosphine and at least one different ligand, e.g. CO, comprise, or transition metal salts complexed with tertiary phosphines can be used.
Für das erfindungsgemässe Verfahren hat es sich bewährt, wenn das Katalysatorsystem neben dem Übergangsmetall der Gruppe VIII des Periodensystems ein tertiäres Phosphin umfasst, wobei das Tertiäre Phosphin separat oder zusammen mit dem Übergangsmetall in Form eines Übergangsmetallkomplexes zur Reaktionsmischung gegeben werden kann.It has proven useful for the process according to the invention if the catalyst system comprises a tertiary phosphine in addition to the transition metal of group VIII of the periodic table, the tertiary phosphine being present separately or together with the transition metal Form of a transition metal complex can be added to the reaction mixture.
Geeignete Phosphinliganden lassen sie sich beispielsweise durch folgende Formeln wiedergeben:Suitable phosphine ligands can be represented, for example, by the following formulas:
^•Rx Rx \ ^Rx' p — RY oder , P —A— P^ • R x R x \ ^ R x 'p - RY or, P —A— P
^R* RY ^RY' worin A für einen zweiwertigen organischen Rest, z.B. für Cι-C6- vorzugsweise Cι-C4-Alkandiyl, insbesondere 1,2-Ethylen oder 1,3-Propylen, für 1,2-Cycloalkandiyl, z.B. 1,2-Cyclohexandiyl, 1,2-Cyclopentandiyl, für Ferrocendiyl, einen polycyclischen aromatischen Rest wie 1, 8-Anthracen-diyl oder für eine 2,2-Biphenyl- Struktur steht.^ R * RY ^ RY 'in which A is a divalent organic radical, for example for C 1 -C 6 - preferably C 1 -C 4 -alkanediyl, in particular 1,2-ethylene or 1,3-propylene, for 1,2-cycloalkanediyl, for example 1,2-cyclohexanediyl, 1,2-cyclopentanediyl, for ferrocendiyl, a polycyclic aromatic radical such as 1,8-anthracenediyl or for a 2,2-biphenyl structure.
Die Reste Rx, RY, RX', RY' stehen unabhängig voneinander für Ci-Cg-Alkyl, C5-C8-Cycloalkyl wie Cyclohexyl, Aryl, insbesondere Phenyl oder p-Tolyl, Cι-C4-Alkylaryl, z.B. Benzyl, Phenethyl oder Aryloxy wie Phenoxy. Bevorzugt stehen Rx, RY, Rx' , RY' für Aryl. Aryl ist z.B. Phenyl, Naphthyl, Anthryl, die gegebenenfalls substituiert sind, und insbesondere unsubstituiertes oder substituiertes Phenyl wie Tolyl. Hinsichtlich der Substituenten an Aryl hat man in erster Linie auf deren Inertheit gegenüber angewende- teten Reaktionsbedingungen zu achten. Geeignete Reste sind alle inerten C-organischen Reste wie Ci-Cg-Alkylreste, z.B. Methyl, Sulfon- oder Carboxylreste wie COOH, COOM (M ist z.B. ein Alkali-, Erdalkalimetall oder Ammoniumsalz), oder über Sauerstoff gebundene C-organische Reste wie C!-C6-Alkoxyreste .The radicals R x , RY, R X ', RY' independently of one another represent Ci-Cg-alkyl, C 5 -C 8 cycloalkyl such as cyclohexyl, aryl, especially phenyl or p-tolyl, -C-C 4 alkylaryl, for example Benzyl, phenethyl or aryloxy such as phenoxy. R x , RY, R x ', RY' are preferably aryl. Aryl is, for example, phenyl, naphthyl, anthryl, which are optionally substituted, and in particular unsubstituted or substituted phenyl such as tolyl. With regard to the substituents on aryl, the primary concern is their inertness to the reaction conditions used. Suitable residues are all inert C-organic residues such as Ci-Cg-alkyl residues, for example methyl, sulfone or carboxyl residues such as COOH, COOM (M is for example an alkali, alkaline earth metal or ammonium salt), or C-organic residues bound via oxygen such as C. ! -C 6 alkoxy radicals.
Beispiele für derartige Komplexe sind P(C6H5)3, P(C6H4CH3)3, P(n-CH9)3, P(cyclo-C6Hu)3, PCH3(C6H5)2, 1,2-Bis(diphenylphos- phino)ethan, 1, 3-Bis (diphenylphosphino)propan, 1, 8-Bis (dipheny1- phosphino)anthracen und α,α'-Bis(diphenylphosphino)ferrocen. Be- sonders bevorzugtes tertiäres Phosphin ist Triarylphosphin und insbesondere Triphenylphosphin, das am Phenylring substituiert sein kann.Examples of such complexes are P (C 6 H 5 ) 3 , P (C 6 H 4 CH 3 ) 3 , P (n-CH 9 ) 3 , P (cyclo-C 6 H u ) 3 , PCH 3 (C 6 H 5 ) 2 , 1,2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 8-bis (diphenylphosphino) anthracene and α, α'-bis (diphenylphosphino) ferrocene. A particularly preferred tertiary phosphine is triarylphosphine and in particular triphenylphosphine, which can be substituted on the phenyl ring.
Beispiele für erfindungsgemäss bevorzugte Komplexverbindungen sind (PPh3)2Ni(CO)2, Pt(CO)2(PPh3)2 , insbesondere Pd(CO) (PPh3)3, (PPh3)2Pd(OAc)2, (PPh3)2PdCl2.Examples of complex compounds preferred according to the invention are (PPh 3 ) 2 Ni (CO) 2 , Pt (CO) 2 (PPh 3 ) 2 , in particular Pd (CO) (PPh 3 ) 3 , (PPh 3 ) 2 Pd (OAc) 2 , (PPh 3 ) 2 PdCl 2 .
Die Herstellung der Phosphinkomplexe kann in an sich bekannter Weise erfolgen. Beispielsweise geht man von üblichen kommerziell erwerblichen Metallsalzen wie PdCl2 oder Pd(OCOCH3)2 aus und fügt das Phosphin z.B. P(C6H5)3, P(C6H4CH3)3, P(n-CH9)3, P(cyclo- CgHn)3, PCH3(C6H5)2, 1,2-Bis (diphenylphosphino)ethan, 1, 3-Bis (diphenylphosphino)propan, 1, 8-Bis (diphenylphosphino)an- thracen oder α,α'-Bis (diphenylphosphino)ferrocen, gegebenenfalls in einem Lösungsmittel hinzu. Häufig wird man die Komplexe auch in-situ im Reaktionsansatz generieren, indem man wenigstens einen Phosphinliganden und eine Precursorverbindung, also einer Übergangsmetallverbindung, die das katalytisch aktive Metall enthält, z.B. ein Metallsalz oder ein anderer Komplex des Metalls, zum Reaktionsansatz gibt.The phosphine complexes can be prepared in a manner known per se. 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 (C 6 H 4 CH 3 ) 3 , P (n-CH 9 ) 3 , P (cyclo-CgHn) 3 , PCH 3 (C 6 H 5 ) 2 , 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,8-bis (diphenylphosphino) anthracene or α, α'-bis (diphenylphosphino) ferrocene, optionally in a solvent. The complexes will often also be generated in situ in the reaction mixture by adding at least one phosphine ligand and a precursor compound, that is to say a transition metal compound which contains the catalytically active metal, for example a metal salt or another complex of the metal, to the reaction mixture.
Sofern im erfindungsgemässen Verfahren ein Phosphin als Ligand eingesetzt wird, beträgt die Menge an Phosphin, bezogen auf 1 Mol Übergangsmetall, wenigstens 0,1 Mol, vorzugsweise wenigstens 0,5 Mol und besonders bevorzugt wenigstens 1 Mol. In der Regel wird das molare Verhältnis von tertiärem Phosphin zu Übergangsmetall einen Wert von 20, vorzugsweise 10 und insbesondere 5 nicht überschreiten, nicht zuletzt um den Eintrag von Fremdsubstanzen in die Reaktionskomponenten II und III möglichst gering zu halten.If a phosphine is used as the ligand in the process according to the invention, the amount of phosphine, based on 1 mol of transition metal, is at least 0.1 mol, preferably at least 0.5 mol and particularly preferably at least 1 mol. As a rule, the molar ratio of tertiary phosphine to transition metal does not exceed a value of 20, preferably 10 and in particular 5, not least in order to keep the entry of foreign substances into reaction components II and III as low as possible.
Die Katalysatoren können als solche oder auf einem Träger einge- setzt werden. Die Art des Trägers ist von untergeordneter Bedeutung. Geeignete Träger umfassen anorganische Oxide wie Silicium- dioxid, Aluminiumoxid, Alumosilikate, z.B. Zeolithe, Calciumcar- bonat, Bariumsulfat, weiterhin Aktivkohle, Ruß. Ebenfalls geige- net sind organische Polymere als Trägermaterial, insbesondere solche, die das Übergangsmetall komplexieren können, z.B. Polymere mit tertiären Aminogruppen, Pyridin-Gruppen, Imidazol-Grup- pen oder Polymere mit tertiären Phosphin-Gruppen.The catalysts can be used as such or on a support. The type of carrier is of minor importance. Suitable carriers include inorganic oxides such as silicon dioxide, aluminum oxide, aluminosilicates, e.g. Zeolites, calcium carbonate, barium sulfate, also activated carbon, soot. Also suitable are organic polymers as carrier material, in particular those that can complex the transition metal, e.g. Polymers with tertiary amino groups, pyridine groups, imidazole groups or polymers with tertiary phosphine groups.
Die Menge an Übergangsmetall ist nicht kritisch. Natürlich wird man aus Kostengründen eher eine geringe Menge, z.B. von 0,1 bis 20 Mol-%, insbesondere 0,5 bis 10 Mol-%, bezogen auf das Arylhalogenid II einsetzen. Selbstverständlich kann man auch grössere Mengen, z.B. 50, 100 oder 200 Mol-%, bezogen auf 1 Mol Arylhalogenid II einsetzen.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 20 mol%, in particular 0.5 to 10 mol%, based on the aryl halide II. Of course you can also use larger quantities, e.g. Use 50, 100 or 200 mol%, based on 1 mol aryl halide II.
Für das erfindungsgemässe Verfahren sind alle inerten Basen geeignet, die den bei der Umsetzung freiwerdenden Halogenwasserstoff insbesondere Bromwasserstoff zu binden vermögen. Beispiele für geeignete Basen sind Amine, vorzugsweise tertiäre Amine, insbe- sondere Trialkylamine wie Triethylamin, Triethanolamin, cyclische Amine wie N-Methylpiperidin, Triethylendiamin (= 1,4-Diazabi- cyclo[2.2.2]octan) , l,5-Diazabicyclo[4.3.0]non-5-en, 1,8-Diazabi- cyclo[5.4.0]undec-7-en oder N,N'-Dimethylpiperazin, heteroaromatische Amine wie Pyridin und substituierte Pyridine, weiterhin Alkalicarbonate oder -hydrogencarbonate, oder tetraalkyl- substituierte Harnstoffderivate wie Tetra-Cι-C4-alkylharnstoff, z.B. Tetramethylharnstoff.All inert bases which are able to bind the hydrogen halide released during the reaction, in particular hydrogen bromide, are suitable for the process according to the invention. Examples of suitable bases are amines, preferably tertiary amines, in particular trialkylamines such as triethylamine, triethanolamine, cyclic amines such as N-methylpiperidine, triethylenediamine (= 1,4-diazabicyclo [2.2.2] octane), l, 5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene or N, N'-dimethylpiperazine, heteroaromatic amines such as pyridine and substituted pyridines, furthermore alkali metal carbonates or bicarbonates, or tetraalkyl Substituted urea derivatives such as tetra-C 4 alkyl urea, for example tetramethyl urea.
Die Menge an Base ist nicht kritisch, üblicherweise wird man die Base in einer Menge von wenigstens 1 Mol pro Mol Arylhalogenid II, z.B. in einer Menge von 1 bis 10 Mol, insbesondere 1 bis 5 Mol verwenden. Selbstverständlich kann man die Base auch als Lö- sungs oder Verdünnungsmittel für die Reaktanden verwenden. Bei gleichzeitiger Verwendung der Base als Lösungsmittel, wird die Menge in der Regel so bemessen, daß die Reaktionspartner gelöst sind, wobei man aus Praktikabilitätsgründen unnötig hohe Überschüsse vermeidet, um Kosten zu sparen, kleine Reaktionsgefäße einsetzen zu können und den Reaktionspartnern maximalen Kontakt zu gewährleisten.The amount of base is not critical, usually the base will be used in an amount of at least 1 mole per mole of aryl halide II, e.g. use in an amount of 1 to 10 mol, in particular 1 to 5 mol. Of course, the base can also be used as a solvent or diluent for the reactants. If the base is simultaneously used as a solvent, the amount is generally such that the reactants are dissolved, unnecessarily high excesses being avoided for reasons of practicality in order to save costs, to be able to use small reaction vessels and to ensure maximum contact for the reactants.
Es kann aber auch je nach Art der Ausgangsstoffe und der verwendeten Katalysatoren von Vorteil sein, anstelle des Reaktionspartners oder der Base ein anderes inertes Lösungsmittel zu verwenden.However, depending on the type of starting materials and the catalysts used, it may also be advantageous to use another inert solvent instead of the reactant or the base.
Als inerte Lösungsmittel kommen beispielsweise aromatische Kohlenwasserstoffe, wie Toluol, Xylole, Cumol, aliphatische Kohlenwasserstoffe wie Hexan, Pentan oder Cyclohexan, halogenierte aliphatische Kohlenwasserstoffe wie Di-, Tri und Tetrachlormethan, 1,2-Dichlorethan und 1, 1-Dichlorethan, Ether wie Methyl-tert .bu- tylether, Tetrahydrofuran, Dioxan, Dimethoxyethan, substituierte Amide wie Dimethylformamid oder N-Methylpyrrolidon, persubstituierte Harnstoffe wie Tetra-Cι-C-alkylharnstoffe oder Nitrile wie Benzonitril oder Acetonitril sowie Mischungen der vorgenann- ten Lösungsmittel in Betracht. Bevorzugte Lösungsmittel sind aromatische Kohlenwasserstoffe oder Lösungsmittelmischungen mit einem hohen Anteil an aromatischen Kohlenwasserstoffen.Inert solvents include, for example, aromatic hydrocarbons such as toluene, xylenes, cumene, aliphatic hydrocarbons such as hexane, pentane or cyclohexane, halogenated aliphatic hydrocarbons such as di-, tri and tetrachloromethane, 1,2-dichloroethane and 1,1-dichloroethane, ethers such as methyl tert. butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted amides such as dimethylformamide or N-methylpyrrolidone, per-substituted ureas such as tetra-C 1 -C 8 -alkylureas or nitriles such as benzonitrile or acetonitrile and mixtures of the aforementioned solvents. Preferred solvents are aromatic hydrocarbons or solvent mixtures with a high proportion of aromatic hydrocarbons.
Weiterhin hat es sich bewährt, wenn man das erfindungsgemässe Verfahren in Gegenwart von Lithiumionen durchführt. Als Lithiumquellen kommen insbesondere Lithiumsalze wie Lithiumhalogenide, z.B. Lithiumchlorid, weiterhin basische Lithiumsalze wie Lithium- carbonat, Lithiumacetat oder Lithiumhydroxid in Betracht. In diesen bevorzugten Ausführungsformen des erfindungsgemässen Verfah- rens verwendetet man in der Regel 0,1 bis 10 Mol, insbesondere 0,2 bis 5 Mol und besonders bevorzugt 0,5 bis 2 Mol Lithiumionen pro Mol Arylhalogenid.It has also proven useful if the process according to the invention is carried out in the presence of lithium ions. In particular, lithium salts such as lithium halides, e.g. Lithium chloride, also basic lithium salts such as lithium carbonate, lithium acetate or lithium hydroxide. In these preferred embodiments of the process according to the invention, 0.1 to 10 mol, in particular 0.2 to 5 mol and particularly preferably 0.5 to 2 mol, of lithium ions are generally used per mol of aryl halide.
Im erfindungsgemässen Verfahren werden Arylhalogenid II und die Verbindungen III bzw. III' oder III" in der Regel in etwa stö- chiometrischer Menge eingesetzt, wobei ein Überschuss einer Komponente von bis zu 50 Mol-%, bezogen auf die im Unterschuss vor- liegende Komponente in der Regel keine Nachteile mit sich bringt. Vorzugsweise setzt man das Diketon III bzw. seine Tautomeren III' oder III" in etwa equi olarer Menge oder im Überschuss ein.In the process according to the invention, aryl halide II and the compounds III or III 'or III "are generally used in an approximately stoichiometric amount, with an excess of one component of up to 50 mol%, based on the amount available in the deficit. lying component usually has no disadvantages. Diketone III or its tautomers III 'or III "are preferably used in an approximately equi-olar amount or in excess.
Während der Umsetzung wird der Kohlenmonoxiddruck so eingestellt, daß immer ein Überschuß an Kohlenmonoxid, bezogen auf das Arylhalogenid vorliegt. Vorzugsweise liegt der Kohlenmonoxidpartial- druck 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 carbon monoxide, based on the aryl halide. The carbon monoxide partial pressure at room temperature is preferably 1 to 250 bar, in particular 5 to 150 bar CO.
Das erfindungsgemässe Verfahren wird in der Regel bei Temperaturen von Raumtemperatur bis 300°C, vorzugsweise bei 50 bis 250°C insbesondere bei 100 bis 200°C kontinuierlich oder diskontinuierlich durchgeführt. Bei diskontinuierlichem Betrieb wird zweckmä- ßigerweise zur Aufrechterhaltung eines konstanten Druckes kontinuierlich Kohlenmonoxid auf das Umsetzungsgemisch aufgepreßt.The process according to the invention is generally carried out continuously or batchwise at temperatures from room temperature to 300 ° C., preferably at 50 to 250 ° C., in particular at 100 to 200 ° C. In the case of discontinuous operation, carbon monoxide is expediently pressed continuously onto the reaction mixture in order to maintain a constant pressure.
Das erfindungsgemässe Verfahren lässt sich auf eine Vielzahl unterschiedlicher Substratverbindungen II und III anwenden. Bevor- zugt bedeutet Hai in Formel II Brom oder Iod und insbesondere Brom.The method according to the invention can be applied to a large number of different substrate compounds II and III. Preference for shark in formula II means bromine or iodine and in particular bromine.
Als Arylhalogenide II sind beispielsweise solche Verbindungen zu nennen, die durch die allgemeine Formel HaAryl halides II include, for example, those compounds which are represented by the general formula Ha
repräsentiert wird, worin Hai für Chlor, Brom oder Iod, vorzugsweise Brom oder Iod, und insbesondere Brom steht, Hai vorzugs- weise dem Rest Rla benachbart ist, undis represented in which shark is chlorine, bromine or iodine, preferably bromine or iodine, and in particular bromine, shark is preferably adjacent to the radical R la , and
Rla und R4a unabhängig voneinander für Wasserstoff,R la and R 4a independently of one another for hydrogen,
Halogen, insbesondere Fluor oder Chlor, Cyano, Ci-Cg-Alkyl, Ci-Cg-Halogenalkyl, Ci-Cδ-Alkoxy, Ci-Cg-Halogenalkoxy, Ci-Cg-Alkylthio, Cχ-Cg-Halogenalkylthio, Hydroxy-Ci-Cβ-alkyl, Cι-C6-Alkylsulfonyl, Ci-Cg-Halogenalkylsulfonyl, Cχ-Cg-Alko- xy-Ci-Cg-alkyl, C-Cg-Alkylthio-C-Cg-alkyl, Cχ-C6-Halogenal- kylthio-Ci-Cg-alkyl, Cχ-Cg-Alkylsulfonyl-Cχ-C6-alkyl, Cι-C6-Halogenalkylsulfonyl-Ci-Cg-alkyl, Cχ-Cg-Alkylamino- Cι-C6-alkyl, oder Di-(Cχ-C6-alkyl)amino-Cι-C6-alkyl stehen und R2a und R3 einen anellierten 5- oder 6-gliedrigen, gesättigten oder ungesättigten Heterocyclus bilden, der 1, 2 oder 3 Hete- roatome, ausgewählt unter N, S und 0 aufweisen kann, wobeiHalogen, especially fluorine or chlorine, cyano, Ci-Cg-alkyl, Ci-Cg-haloalkyl, Ci-C δ- alkoxy, Ci-Cg-haloalkoxy, Ci-Cg-alkylthio, Cχ-Cg-haloalkylthio, hydroxy-Ci Cβ-alkyl, Cι-C 6 alkylsulfonyl, Ci-Cg-haloalkylsulfonyl, Cχ-Cg-Alko- xy-Ci-Cg-alkyl, C-Cg-alkylthio-C-Cg-alkyl, Cχ-C 6 -halogenal- kylthio-Ci-Cg-alkyl, Cχ-Cg-alkylsulfonyl-Cχ-C 6 -alkyl, Cι-C 6 -haloalkylsulfonyl-Ci-Cg-alkyl, Cχ-Cg-alkylamino- Cι-C 6 -alkyl, or di- (Cχ-C 6 -alkyl) amino -CC-C 6 alkyl and R 2a and R 3 form a fused 5- or 6-membered, saturated or unsaturated heterocycle which can have 1, 2 or 3 heteroatoms selected from N, S and 0, where
Schwefelatome im Heterocyclus auch als Sulfoxid oder Sulfon vorliegen können,Sulfur atoms in the heterocycle can also be present as sulfoxide or sulfone,
Stickstoffatome und Kohlenstoffatome im Heterocyclus ein Wasserstoffatom oder einen Substituenten aufweisen, der ausge- wählt ist unter Halogen, Nitro, Cyano, Hydroxy, Amino,Nitrogen atoms and carbon atoms in the heterocycle have a hydrogen atom or a substituent which is selected from halogen, nitro, cyano, hydroxy, amino,
Cχ-Cg-Alkyl, Ci-Cg-Halogenalkyl, Cχ-Cg-Aminoalkyl, Hydro- xy-Cχ-C6-alkyl, Cχ-C6-Alkylcarbonyl, Cχ-Cg-Alkylcarbonyloxy, Cχ-Cg-Alkyloxycarbonyl, Cχ-Cg-Alkoxy-Cχ-C6-alkyl, Cι-C6-Alkyl- carbonyl-Cχ-C6-alkyl, Cχ-C6-Alkoxy, Cχ-C6-Halogenalkoxy, C2-Cg-Alkenyl, C2-Cg-Alkinyl, Cχ-C6-Hydroxyalkoxy, Cχ-C6-Al- koxy-Cχ-Cg-alkoxy, C3-Cg-Cycloalkyl, C3-C8-Cycloalkoxy, Cχ-Cg-Alkylthio, Cχ-C6-Halogenalkylthio, Cχ-Cg-Hydroxyalkylt- hio, Cχ-C6-Alkoxy-Cχ-Cg-alkylthio,Cχ-Cg-alkyl, Ci-Cg-haloalkyl, Cχ-Cg-aminoalkyl, hydroxy- Cχ-C 6 -alkyl, Cχ-C 6 -alkylcarbonyl, Cχ-Cg-alkylcarbonyloxy, Cχ-Cg-alkyloxycarbonyl, Cχ- Cg-alkoxy-Cχ-C 6 -alkyl, Cι-C 6 -alkyl-carbonyl-Cχ-C 6 -alkyl, Cχ-C 6 -alkoxy, Cχ-C 6 -haloalkoxy, C 2 -Cg-alkenyl, C 2 -Cg-alkynyl, Cχ-C 6 -hydroxyalkoxy, Cχ-C 6 -alkoxy-Cχ-Cg-alkoxy, C 3 -Cg-cycloalkyl, C 3 -C 8 -cycloalkoxy, Cχ-Cg-alkylthio, Cχ- C 6 -haloalkylthio, Cχ-Cg-hydroxyalkyl-thio, Cχ-C 6 -alkoxy-Cχ-Cg-alkylthio,
Phenyl, Phenyl-Cχ-Cg-alkyl, Phenylcarbonyl, Phenylcarbonyloxy, Phenoxycarbonyl, 5-, 6- oder 7-gliedriges Heterocyclyl, Phe- noxy, Phenylamino, Diphenylamino, Heterocyclyl-Ci-Cg-alkyl, Heterocycl loxy, Heterocyclylcarbonyl, Heterocyclyloxycarbonyl, Heterocyclylcarbonyloxy, wobei die Phenyl- und Heterocy- clylgruppen der 14 letztgenannten Reste ihrerseits partiell oder vollständig halogeniert und/oder einen, zwei oder drei Substituenten, ausgewählt unter Nitro, Cyano, Hydroxy, Cχ-C4-Alkyl, Cχ-C-Halogenalkyl, Cχ-C4-Alkoxy und Cχ-C4-Haloge- nalkoxy, tragen können, Cχ-Cg-Alkylamino, Di-Ci-Cg-alkylamino, C3-Cg-Cycloalkylamino, wobei die Alkyl- und Cycloalkylgruppen der drei letztgenannten Reste teilweise oder vollständig halogeniert und/oder ein bis drei Substituenten, ausgewählt unter Cχ-C4-Alkoxy oder Hydroxy tragen können,Phenyl, phenyl-Cχ-Cg-alkyl, phenylcarbonyl, phenylcarbonyloxy, phenoxycarbonyl, 5-, 6- or 7-membered heterocyclyl, phenoxy, phenylamino, diphenylamino, heterocyclyl-Ci-Cg-alkyl, heterocycl loxy, heterocyclylcarbonloxy, heterocyclyl, heterocyclyl Heterocyclylcarbonyloxy, the phenyl and heterocyclyl groups of the 14 last-mentioned radicals in turn partially or completely halogenated and / or one, two or three substituents selected from nitro, cyano, hydroxy, Cχ-C 4 -alkyl, Cχ-C-haloalkyl, Cχ-C 4 alkoxy and Cχ-C 4 haloalkoxy, can carry, Cχ-Cg-alkylamino, di-Ci-Cg-alkylamino, C 3 -Cg-cycloalkylamino, the alkyl and cycloalkyl groups of the latter three radicals partially or fully halogenated and / or can carry one to three substituents selected from C C-C 4 alkoxy or hydroxy,
Kohlenstoffringlieder auch als Carbonylfunktion, Thiocarbo- nylfunktion, Oxim- oder Oximetherfunktion vorliegen können; oderCarbon ring members can also be present as a carbonyl function, thiocarbonyl function, oxime or oxime ether function; or
Rla und R2a oder R3a und R4a einen anellierten 5- oder 6-gliedri- gen, gesättigten oder ungesättigten Heterocyclus bilden, der 1, 2 oder 3 Heteroatome, ausgewählt unter N, S und 0 aufweisen kann, wobei die Ringatome des Heterocyclus in der oben beschriebenen Weise substituiert sein können; undR la and R 2a or R 3a and R 4a form an annellated 5- or 6-membered, saturated or unsaturated heterocycle which can have 1, 2 or 3 heteroatoms selected from N, S and 0, the ring atoms of the Heterocycle may be substituted in the manner described above; and
die verbleibenden Reste Rla, R2a, R3a und R4a unabhängig voneinander die für Rla genannten Bedeutungen aufweisen, oder R2a für Wasserstoff oder 5-, 6- oder 7-gliedriges Heterocyclyl steht, das 1, 2 oder 3 Heteroatome, ausgewählt unter N, S und 0 aufweist, wobei die Ringatome des Heterocyclus in der oben beschriebenen Weise substituiert sein können; undthe remaining radicals R la , R 2a , R 3a and R 4a independently of one another have the meanings given for R la , or R 2a represents hydrogen or 5-, 6- or 7-membered heterocyclyl which has 1, 2 or 3 heteroatoms selected from N, S and 0, where the ring atoms of the heterocycle can be substituted in the manner described above; and
Rla, R3a und R4a unabhängig voneinander die zuvor für Rla genannten Bedeutungen aufweisen.R la , R 3a and R 4a independently of one another have the meanings given above for R la .
Als anellierte 5- oder 6-gliedrige Heterocyclen sind beispiels- weise Pyrrol, 2,3-Dihydropyrrol, 2,5-Dihydropyrrol, Pyrazol, 2, 3-Dihydropyrazol, Imidazol, 2, 3-Dihydroimidazol, Triazol, Fu- ran, 2,3- und 2,5-Dihydrofuran, Oxazol, 2, 3-Dihydrooxazol, Isoxazol, 2,3-Dihydroisoxazol, Thiophen, 2,3- und 2,5-Dihydrothio- phen, Thiazol, 2, 3-Dihydrothiazol, Isothiazol, 2,3-Dihydroiso- thiazol, Pyridin, 1,2-, 2,3- und 3, 4-Dihydropyrimidin sowie Tetrahydropyridin zu nennen. Anellierte Carbocyclen sind beispielsweise Cyclopenten, Cyclopentadien, Cyclohexen, Cyclohexadien, Benzol, Cyclohepten.Examples of fused 5- or 6-membered heterocycles are pyrrole, 2,3-dihydropyrrole, 2,5-dihydropyrrole, pyrazole, 2,3-dihydropyrazole, imidazole, 2,3-dihydroimidazole, triazole, furan, 2 , 3- and 2,5-dihydrofuran, oxazole, 2, 3-dihydrooxazole, isoxazole, 2,3-dihydroisoxazole, thiophene, 2,3- and 2,5-dihydrothiophene, thiazole, 2, 3-dihydrothiazole, isothiazole , 2,3-dihydroisothiazole, pyridine, 1,2-, 2,3- and 3, 4-dihydropyrimidine and tetrahydropyridine. Fused carbocycles are, for example, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, benzene, cycloheptene.
Somit bilden beispielsweise Rla und R2a oder R3a und R4a mit dem Benzolring, an den sie gebunden sind, einen Indol-, Isoindol-, Benzofuran-, Isobenzofuran-, Benzo-[a]-thiophen-, Benzo-[b] -thiophen-, Benzimidazol-, Benzoxazol-, Benzthiazol-, Benzisothiazol-, Benztriazol-, Chinolin-, Isochinolin-, Chinoxalin-, Chroman-, Thiochroman-, Chromen-, Thiochromen-, Indan-, Inden- oder Naphthalin-Ring, oder ein partiell am anellierten Ring hydriertes Derivat davon.Thus, for example, R la and R 2a or R 3a and R 4a together with the benzene ring to which they are attached form an indole, isoindole, benzofuran, isobenzofuran, benzo [a] thiophene, benzo [b ] -thiophene, benzimidazole, benzoxazole, benzthiazole, benzisothiazole, benztriazole, quinoline, isoquinoline, quinoxaline, chroman, thiochroman, chromium, thiochrome, indane, indene or naphthalene ring , or a derivative thereof partially hydrogenated on the fused ring.
Selbstverständlich können die heterocyclischen Strukturen auch teilweise hydriert, die N- und/oder C-Ringatome in der oben beschriebenen Weise substituiert sein. Kohlenstoffringlieder können auch als Carbonylfunktion, Thiocarbonylfunktion, Oxim- oder Oxi- metherfunktion vorliegen wie in Chroman-4-on, Thiochroman-4-on, Benzoisothiazolon, und Ring-Schwefelatome als Sulfoxid oder Sul- fon vorliegen, wie in Benzothiophen-S-oxid, Benzothiophen-Of course, the heterocyclic structures can also be partially hydrogenated and the N and / or C ring atoms substituted in the manner described above. Carbon ring members can also be present as carbonyl function, thiocarbonyl function, oxime or oximeter function as in chroman-4-one, thiochroman-4-one, benzoisothiazolone, and ring sulfur atoms as sulfoxide or sulfone, as in benzothiophene-S-oxide , Benzothiophene
S,S-dioxid, Benzothiazol-S-oxid, Benzothiazol-S,S-dioxid, Thioch- roman-S-oxid und Thiochroman-S,S-dioxid.S, S-dioxide, benzothiazole-S-oxide, benzothiazole-S, S-dioxide, thiochroman-S-oxide and thiochroman-S, S-dioxide.
In einer bevorzugten Ausführungsform des erfindungsgemässen Ver- fahrens werden Arylhalogenide der allgemeinen Formel Ilb eingesetzt: In a preferred embodiment of the process according to the invention, aryl halides of the general formula IIb are used:
worin Hai die zuvor genannten Bedeutungen und Rlb die zuvor für Rla und R4b die zuvor für R4a genannten Bedeutungen aufweisen, Hai vorzugsweise Rlb benachbart ist, Rlb vorzugsweise für Halogen, insbesondere Fluor oder Chlor, Cχ-C4-Alkyl, Cχ-C4-Halogenalkyl, C-C4-Alkoxy und C-C4-Halogenalkoxy steht, R4b vorzugsweise Was- serstoff, Fluor, Chlor, Methyl oder Methoxy bedeutet,wherein Hal is the meanings and R lb aforementioned previously have the meanings specified above for R 4a R a and R 4b, preferably Hai R lb is adjacent, R lb is preferably halogen, in particular fluorine or chlorine, Cχ-C 4 alkyl , Cχ-C 4 haloalkyl, CC 4 -alkoxy and CC is 4 -haloalkoxy, R 4b is preferably water serstoff, fluorine, chlorine, methyl or methoxy,
R5b für Wasserstoff, C-Cg-Alkyl, Cχ-C6-Halogenalkyl, Cχ-Cg-Alkyl- carbonyl, Cι-C6-Alkoxy-Cχ-C6-alkyl, C2-Cg-Alkenyl, C2-C6-Alki- nyl, Cχ-Cg-Hydroxyalkoxy, Cχ-Cg-Alkoxy-Cχ-Cg-alkoxy, C3-C8-Cy- cloalkyl, Phenyl, Phenyl-Cχ-C6-alkyl steht, wobei Phenyl in den zwei letztgenannten Gruppen einen, zwei oder drei Substituenten, ausgewählt unter Halogen, Nitro, Cyano, Hydroxy, Cχ-C4-Alkyl, Cχ-C4-Halogenalkyl, Cχ-C -Alkoxy und Cχ-C4-Haloge- nalkoxy, tragen kann, und insbesondere Cχ-C4-Alkyl, Phenyl oder Phenyl-Cχ-C4-alkyl bedeutet, wobei Phenyl unsubstituiert oder in der zuvor beschriebenen Weise substituiert sein kann;R5b fo r is hydrogen, C-Cg-alkyl, Cχ-C 6 haloalkyl, Cχ-Cg alkyl carbonyl, Cι-C 6 -alkoxy-Cχ-C 6 alkyl, C 2 -CG-alkenyl, C 2 - C 6 -alkynyl, Cχ-Cg-hydroxyalkoxy, Cχ-Cg-alkoxy-Cχ-Cg-alkoxy, C 3 -C 8 -cycloalkyl, phenyl, phenyl-Cχ-C 6 -alkyl, where phenyl in the latter two groups have one, two or three substituents selected from halogen, nitro, cyano, hydroxy, Cχ-C 4 alkyl, Cχ-C 4 haloalkyl, Cχ-C alkoxy and Cχ-C 4 haloalkoxy, can wear, and in particular Cχ-C 4 alkyl, phenyl or phenyl-Cχ-C 4 alkyl means, where phenyl may be unsubstituted or substituted in the manner described above;
n für 0, 1 oder 2 steht undn stands for 0, 1 or 2 and
X Sauerstoff oder Schwefel, insbesondere Sauerstoff bedeutet.X means oxygen or sulfur, in particular oxygen.
In einer weiteren bevorzugten Ausführungsform des erfindungsge- mässen Verfahrens werden Arylhalogenide der allgemeinen Formel IIc eingesetzt, worinIn a further preferred embodiment of the process according to the invention, aryl halides of the general formula IIc are used, in which
Hai die zuvor genannten Bedeutungen aufweist und vorzugsweise Rlc benachbart ist, Rlc die für Rla genannten Bedeutungen hat, und vorzugsweise für Halogen, insbesondere Fluor oder Chlor, Cχ-C4-Alkyl, insbesondere Methyl, Cχ-C4-Halogenalkyl, Cχ-C4-Alkoxy und Cχ-C4-Halogenalkoxy steht,Hai has the meanings mentioned above and preferably R lc is adjacent, R lc has the meanings mentioned for R la , and preferably halogen, in particular fluorine or chlorine, Cχ-C 4 alkyl, in particular methyl, Cχ-C 4 haloalkyl, Cχ-C 4 alkoxy and Cχ-C 4 haloalkoxy,
R3c für Halogen, Cχ-C6-Alkyl, Ci-Cg-Halogenalkyl, C -Cg-Alkylthio, Cχ-Cg-Alkylsulfinyl, Cχ-C6-Alkylsulfonyl, Cχ-Cg-Alkoxy oderR 3c for halogen, Cχ-C 6 alkyl, Ci-Cg-haloalkyl, C -Cg-alkylthio, Cχ-Cg-alkylsulfinyl, Cχ-C 6 -alkylsulfonyl, Cχ-Cg-alkoxy or
Cχ-Cg-Halogenalkoxy steht, und insbesodere Cχ-Cg-Alkylsulfonyl und speziell Chlor, Fluor, Methyl, Methoxy oder Methylsulfo- nyl bedeutet,Cχ-Cg-haloalkoxy, and in particular Cχ-Cg-alkylsulfonyl and especially chlorine, fluorine, methyl, methoxy or methylsulfonyl means,
eine Doppelbindung oder vorzugsweise eine Einfachbindung bedeutet undis a double bond or preferably a single bond and
R6c für Wasserstoff oder gegebenenfalls substituiertes Cχ-C-Alkyl steht. Substituiertes Cχ-C4-Alkyl heisst hier vorzugsweise Ha- logenalkyl wie vorstehend definiert, z.B. Fluormethyl, Chlormethyl, Difluormethyl, Chlordifluormethyl, Trifluormethyl, oder Cχ-C4-Alkoxy-Cχ-C4-alkyl wie vorstehehend definiert, z.B. Methoxymethyl.R 6c represents hydrogen or optionally substituted Cχ-C-alkyl. Substituted Cχ-C 4 alkyl here is preferably haloalkyl as defined above, for example fluoromethyl, chloromethyl, difluoromethyl, chlorodifluoromethyl, trifluoromethyl, or Cχ-C 4 -alkoxy-Cχ-C 4 -alkyl as defined above, for example methoxymethyl.
In einer weiteren bevorzugten Ausfuhrungsform des erfindungsge- mässen Verfahrens werden Arylhalogenide der allgemeinen Formel Ild eingesetzt,In a further preferred embodiment of the process according to the invention, aryl halides of the general formula III are used,
worinwherein
Hai die zuvor genannten Bedeutungen aufweist und vorzugsweise Rld benachbart ist, Rld die für Rla genannten Bedeutungen hat, und vorzugsweise für Halogen, insbesondere Fluor oder Chlor, Cχ-C4-Al- kyl, insbesondere Methyl, Cχ-C-Halogenalkyl, Cχ-C-Alkoxy und Cχ-C4-Halogenalkoxy steht,Hai as defined above and preferably having R ld adjacent R ld as defined for R la has, and preferably halogen, in particular fluorine or chlorine, Cχ-C alkyl 4 -Al-, especially methyl, Cχ-C -haloalkyl , Cχ-C-alkoxy and Cχ-C 4 -haloalkoxy,
R3d für Halogen, Ci-Cg-Alkyl, C -Cg-Halogenalkyl, C-C6-Alkylthio, Cχ-C6-Alkylsulfinyl, Cχ-Cg-Alkylsulfonyl, Cχ-Cg-Alkoxy oder Cχ-Cg-Halogenalkoxy steht, und insbesodere Cχ-C6-Alkylsulfonyl und speziell Chlor, Fluor, Methyl, Methoxy oder Methylsulfo- nyl bedeutet. Selbstverständlich kann man im erfindungsgemässen Verfahren auch ein unsubstituiertes Halogenbenzol wie Brombenzol oder ein Halo- genpyridin wie 2-, 3- oder 4-Brompyridin als Verbindung II einsetzen.R3d represents halogen, Ci-Cg-alkyl, C -Cg-haloalkyl, CC 6 -alkylthio, Cχ-C 6 -alkylsulfinyl, Cχ-Cg-alkylsulfonyl, Cχ-Cg-alkoxy or Cχ-Cg-haloalkoxy, and in particular Cχ -C 6 -Alkylsulfonyl and especially chlorine, fluorine, methyl, methoxy or methylsulfonyl means. Of course, an unsubstituted halobenzene such as bromobenzene or a halopyridine such as 2-, 3- or 4-bromopyridine can also be used as compound II in the process according to the invention.
Vorzugsweise werden im erfindungsgemässen Verfahren als 1,3-Dike- ton der allgemeinen Formel III (bzw. als Tautomer III' oder III") cyclische oder bicyclische 1,3-Diketone eingesetzt, die den allgemeinen Formeln lila oder Illb gehorchen:Cyclic or bicyclic 1,3-diketones which obey the general formulas lilac or IIIb are preferably used in the process according to the invention as 1,3-diketones of the general formula III (or as tautomer III 'or III "):
worin k für 0, 1 oder 2 steht und vorzugsweise 1 bedeutet, und die Variablen R1 bis R6 folgende Bedeutung haben:wherein k stands for 0, 1 or 2 and preferably means 1, and the variables R 1 to R 6 have the following meaning:
R1, R5 unabhängig voneinander Wasserstoff, Cχ-C4-Alkyl, insbesondere Methyl, oder Cχ-C4-Alkoxycarbonyl;R 1 , R 5 independently of one another are hydrogen, Cχ-C 4 -alkyl, in particular methyl, or Cχ-C 4 -alkoxycarbonyl;
R2, R4, R6 unabhängig voneinander Wasserstoff, C-C4-Alkyl, insbesondere Methyl, Cχ-C4-Alkoxy wie Methoxy oder Cχ-C-Alkylthio wie Methylthio;R 2 , R 4 , R 6 independently of one another are hydrogen, CC 4 -alkyl, in particular methyl, Cχ-C 4 -alkoxy such as methoxy or Cχ-C-alkylthio such as methylthio;
R3 Wasserstoff, Halogen, Hydroxy, Cχ-Cg-Alkyl, Cχ-Cg-Halogenalkyl, Di-(Cχ-Cg-alkoxy)-methyl,R 3 is hydrogen, halogen, hydroxy, Cχ-Cg-alkyl, Cχ-Cg-haloalkyl, di- (Cχ-Cg-alkoxy) methyl,
(Cχ-Cg-Alkoxy) -(Cχ-C6-alkylthio)-methyl, Di- (Ci-Cg-alkylthioJmethyl, Cχ-Cg-Alkoxy, Cχ-Cg-Halogenalkoxy, Cχ-C6-Alkylthio, Cχ-Cg-Halogenalkylthio, Cχ-Cg-Alkylsulfinyl, Cχ-C6-Halogenalkylsulfinyl, Cχ-C6-Alkylsulfonyl,(Cχ-Cg-Alkoxy) - (Cχ-C 6 -alkylthio) -methyl, di- (Ci-Cg-alkylthioJmethyl, Cχ-Cg-alkoxy, Cχ-Cg-haloalkoxy, Cχ-C 6 -alkylthio, Cχ-Cg Haloalkylthio, Cχ-Cg-alkylsulfinyl, Cχ-C 6 -haloalkylsulfinyl, Cχ-C 6 -alkylsulfonyl,
Cχ-C6-Halogenalkylsulfonyl, Cχ-Cg-Alkoxycarbonyl, Cχ-Cg-Halogenalkoxycarbonyl; insbesondere Wasserstoff oder Methyl,Cχ-C 6 haloalkylsulfonyl, Cχ-Cg-alkoxycarbonyl, Cχ-Cg-haloalkoxycarbonyl; especially hydrogen or methyl,
l,3-Dioxolan-2-yl, l,3-Dioxan-2-yl,l, 3-dioxolan-2-yl, l, 3-dioxan-2-yl,
1 , 3-Oxathiolan-2-y1, 1,3-Oxathian-2-y1, l,3-Dithiolan-2-yl oder l,3-Dithian-2-yl, wobei die sechs letztgenannten Reste durch einen bis drei Cχ-C4-Alkylreste substituiert sein können; oder R2 und R4 oder R4 und R6 bilden gemeinsam eine π-Bindung oder eine Cχ-Cs-Alkandiylkette, die eine π-Bindung aufweisen und/oder einen, zwei oder drei Reste aus folgender Gruppe tragen kann: Halogen, Cyano, Cχ-C4-Alkyl, Cχ-C4-Halogenalkyl oder Cχ-C4-Alkoxy- carbonyl; oder1, 3-oxathiolan-2-y1, 1,3-oxathian-2-y1, l, 3-dithiolan-2-yl or l, 3-dithian-2-yl, the six last-mentioned radicals by one to three Cχ -C 4 alkyl radicals can be substituted; or R 2 and R 4 or R 4 and R 6 together form a π bond or a Cχ-Cs alkanediyl chain which have a π bond and / or can carry one, two or three radicals from the following group: halogen, cyano, Cχ-C 4 alkyl, Cχ-C 4 haloalkyl or Cχ-C 4 alkoxycarbonyl; or
R5 und R6 bilden gemeinsam eine Cχ-Cs-Alkandiylkette, die eine π-Bindung aufweisen und/oder einen, zwei oder drei Reste aus folgender Gruppe tragen kann: Halogen,R 5 and R 6 together form a Cχ-Cs alkanediyl chain which have a π bond and / or can carry one, two or three radicals from the following group: halogen,
Cyano, Cχ-C4-Alkyl, Cχ-C4-Halogenalkyl oder Cχ-C4-Alkoxycarbonyl; oderCyano, Cχ-C 4 alkyl, Cχ-C 4 haloalkyl or Cχ-C 4 alkoxycarbonyl; or
R2 und R6 bilden gemeinsam eine Cχ-C4-Alkandiylkette, die eine π-Bindung aufweisen und/oder einen zwei oder drei Reste aus folgender Gruppe tragen kann: Halogen, Cyano, Cχ-C4-Alkyl, Cχ-C-Halogenalkyl oder C-C4-Alkoxy- carbonyl, und die vorzugsweise unsubstituiert ist; oderR 2 and R 6 together form a Cχ-C 4 alkanediyl chain which have a π bond and / or can carry two or three radicals from the following group: halogen, cyano, Cχ-C 4 alkyl, Cχ-C- Haloalkyl or CC 4 alkoxycarbonyl, and which is preferably unsubstituted; or
R3 und R4 bilden gemeinsam eine Kette der FormelR 3 and R 4 together form a chain of the formula
-0-(CH2)p-0-, -0-(CH2)p-S-, -S-(CH2)p-S-, -0-(CH2)q- oder -S-(CH2)g-, worin p für 2, 3, 4 oder 5, vorzugsweise 2 oder 3, und q für 2, 3, 4, 5 oder 6 stehen, und die durch einen, zwei oder drei Reste aus folgender Gruppe substituiert sein kann: Halogen, Cyano, Cχ-C4-Alkyl, Cχ-C4-Halogenalkyl oder Cχ-C4-Alkoxy- carbonyl und vorzugsweise unsubstituiert ist; oder-0- (CH 2 ) p -0-, -0- (CH 2 ) p -S-, -S- (CH 2 ) p -S-, -0- (CH 2 ) q - or -S- ( CH 2 ) g -, where p is 2, 3, 4 or 5, preferably 2 or 3, and q is 2, 3, 4, 5 or 6, and which are substituted by one, two or three radicals from the following group can: halogen, cyano, Cχ-C 4 alkyl, Cχ-C 4 haloalkyl or Cχ-C 4 alkoxycarbonyl and is preferably unsubstituted; or
R3 und R4 bilden gemeinsam mit dem Kohlenstoff, an dem sie gebunden sind, eine Carbonyl- oder Thiocarbonylgruppe.R 3 and R 4 together with the carbon to which they are attached form a carbonyl or thiocarbonyl group.
Beispiele für bevorzugte cyclische Diketone der Formel lila bzw. Illb sind die Cyclohexan-l,3-dione der Formeln III-l bis 111-12: Examples of preferred cyclic diketones of the formula purple or IIIb are the cyclohexane-1,3-diones of the formulas III-1 to 111-12:
(III-4) (III-5) (III-6)(III-4) (III-5) (III-6)
(111-10) (III-ll) (111-12)(111-10) (III-ll) (111-12)
Y = X = O oder S n = 1, 2, 3 oder 4 m = 2, 3 oder 4Y = X = O or S n = 1, 2, 3 or 4 m = 2, 3 or 4
Die Aufarbeitung der erfindungsgemässen Umsetzung von Arylhalogenid II mit dem 1,3-Diketon III kann in an sich bekannter Weise erfolgen. Beispielsweise kann die Reaktionsmischung, vorzugsweise bei vermindertem Druck, zur Trockne eingeengt werden. Der Rückstand wird dann in der Regel aus einem geeigneten Lösungsmittel umkristallisiert und/oder chromatographisch gereinigt, wobei das zur Umkristallisation verwendete Lösungsmittel sowie die bei der Chromatographie eingesetzte stationäre Phase und die mobile Phase (Eluent) sich selbstverständlich nach Art der Ausgangsverbindungen richtet und vom Fachmann in einfacher Weise durch Routineversuche ermittelt werden können. Als stationäre Phase wird in vielen Fällen Kieselgel oder Aluminiumoxid geeignet sein. Als Eluent kommen beispielsweise aliphatische und cycloaliphatische Kohlenwasserstoffe wie n-Hexan oder Cyclohexan oder deren Mischungen mit polaren Lösungsmitteln wie Ethern, oder Estern, z.B. Essig- säureethylester, in Betracht. Selbstverständlich kann die Reaktionsmischung auch wässrig extraktiv aufgearbeitet werden um Salze, z.B. die bei der Umsetzung anfallenden Säureadditionssalze von Halogenwasserstoff mit der eingesetzten Base oder Katalysatoren, zu entfernen.The inventive reaction of aryl halide II with 1,3-diketone III can be worked up in a manner known per se. For example, the reaction mixture can be evaporated to dryness, preferably under reduced pressure. The residue is then generally recrystallized from a suitable solvent and / or purified by chromatography, the solvent used for the recrystallization, the stationary phase used in the chromatography and the mobile phase (eluent), of course, being based on the type of starting compounds and by the person skilled in the art can be easily determined by routine experimentation. In many cases, silica gel or aluminum oxide will be suitable as the stationary phase. Examples of suitable eluents are aliphatic and cycloaliphatic hydrocarbons such as n-hexane or cyclohexane or their mixtures with polar solvents such as ethers or esters, for example acetic acid. acid ethyl ester, into consideration. Of course, the reaction mixture can also be worked up in an aqueous extractive manner in order to remove salts, for example the acid addition salts of hydrogen halide resulting from the reaction with the base or catalysts used.
Das erfindungsgemässe Verfahren liefert die ß-Ketoenolester der allgemeinen Formel I in guten Ausbeuten. Sein grosser Vorteil ist insbesondere darin zu sehen, dass anstelle der z.T. aufwendig herzustellenden Arylcarbonsauren Ar-COOH die besser zugänglichen Arylhalogenide der Formel II eingesetzt werden können.The process according to the invention provides the β-ketoenol esters of the general formula I in good yields. Its great advantage can be seen in the fact that instead of the partially Ar-carboxylic acids Ar-COOH, which are difficult to prepare, and the more accessible aryl halides of the formula II can be used.
Die nach dem erfindungsgemässen Verfahren erhaltenen ß-Ketoenolester der allgemeinen Formel I werden in der Regel in einer wei- teren Reaktion in die 2-Aroyl-substituierten 1,3-Diketone der Formel X durch Behandlung von I mit einer Base und einer kataly- tisch aktiven Menge wenigstens einer Cyanid-Verbindung umgelagert. Hierzu können die ß-Ketoenolester I als isolierte Reinsubstanz, als isoliertes Rohprodukt der vorstehend beschrieben Um- Setzung oder in der Reaktionsmischung der vorstehenden Umsetzung ohne vorherige Isolierung eingesetzt werden. Beispielsweise kann man die nach dem erfindungsgemässen Verfahren erhaltene Reaktionsmischung direkt nach Entfernen des Kohlenmonoxids mit einer Base und einer katalytisch aktiven Menge wenigstens einer Cyanid- Verbindung versetzen und so die Umlagerung von I in die Verbindung X einleiten.The β-ketoenol esters of the general formula I obtained by the process according to the invention are, as a rule, in a further reaction into the 2-aroyl-substituted 1,3-diketones of the formula X by treating I with a base and one catalytically rearranged active amount of at least one cyanide compound. For this purpose, the β-ketoenol esters I can be used as isolated pure substance, as an isolated crude product of the above-described reaction or in the reaction mixture of the above reaction without prior isolation. For example, the reaction mixture obtained by the process according to the invention can be mixed with a base and a catalytically active amount of at least one cyanide compound immediately after removal of the carbon monoxide, and the rearrangement of I into compound X can thus be initiated.
Die Umlagerung der ß-Ketoenolester I zu den Verbindungen der Formel X erfolgt in der Regel bei Temperaturen von 20 bis 100°C in einem Lösungsmittel und in Gegenwart einer Base sowie gegebenenfalls mit Hilfe einer Cyanoverbindung als Katalysator.The rearrangement of the β-ketoenol esters I to the compounds of the formula X is generally carried out at from 20 to 100 ° C. in a solvent and in the presence of a base and, if appropriate, using a cyano compound as a catalyst.
Als Lösungsmittel können z.B. Acetonitril, Methylenchlorid, 1,2—Dichlorethan, Dioxan, Essigsäureethylester, Toluol oder Ge- mische hiervon verwendet werden. Bevorzugte Lösungsmittel sind Acetonitril und Dioxan und deren Mischungen.As a solvent e.g. Acetonitrile, methylene chloride, 1,2-dichloroethane, dioxane, ethyl acetate, toluene or mixtures thereof can be used. Preferred solvents are acetonitrile and dioxane and mixtures thereof.
Geeignete Basen sind die vorstehend genannten tertiären Amine wie Triethylamin und Pyridin, Erdalkali- oder Alkalicarbonate, wie Natriumcarbonat oder Kaliumcarbonat, die vorzugsweise in äquimolarer Menge oder bis zu einem vierfachen Überschuß, bezogen auf den ß-Ketoenolester der Formel I, eingesetzt werden. Bevorzugt werden Triethylamin oder Alkalicarbonat verwendet, vorzugsweise in doppelt äquimolaren Verhältnis in Bezug auf den Ester. Als Cyanoverbindungen sind beispielsweise anorganische Cyanide, wie Natriumcyanid oder Kaliumcyanid und organische Cyanoverbindungen, die Cyanidionen freisetzen können, z.B. Cyanhydrine aliphatischer Ketone wie Acetoncyanhydrin oder Trialkylsilylcya- nide wie Trimethylsilylcyanid geeignet. Sie werden vorzugsweise in einer Menge von 1 bis 50 Molprozent, insbesondere 5 bis 25 Mol-%, bezogen auf den ß-Ketoenolester I, eingesetzt. Vorzugsweise werden Acetoncyanhydrin oder Trimethylsilylcyanid, z.B. in einer Menge von 5 bis 25, vorzugsweise etwa 10 bis 20 Molprozent, bezogen auf den ß-Ketoenolester I, eingesetzt.Suitable bases are the above-mentioned tertiary amines such as triethylamine and pyridine, alkaline earth metal or alkali metal carbonates, such as sodium carbonate or potassium carbonate, which are preferably used in an equimolar amount or up to a fourfold excess, based on the β-ketoenol ester of the formula I. Triethylamine or alkali carbonate are preferably used, preferably in a double equimolar ratio with respect to the ester. Examples of suitable cyano compounds are inorganic cyanides, such as sodium cyanide or potassium cyanide, and organic cyano compounds which can release cyanide ions, for example cyanohydrins of aliphatic ketones such as acetone cyanohydrin or trialkylsilyl cyanides such as trimethylsilyl cyanide. They are preferably used in an amount of 1 to 50 mol percent, in particular 5 to 25 mol%, based on the β-ketoenol ester I. Acetone cyanohydrin or trimethylsilyl cyanide are preferably used, for example in an amount of 5 to 25, preferably about 10 to 20, mol percent, based on the β-ketoenol ester I.
Die Aufarbeitung kann in an sich bekannter Weise erfolgen. Das Reaktionsgemisch der Umlagerung wird beispielsweise mit verdünnter Mineralsäure, z.B. 5 %ige Salzsäure oder Schwefelsäure, ange- säuert, mit einem organischen Lösungsmittel, z.B. Methylenchlorid oder Essigsäureethylester extrahiert. Der organische Extrakt kann zur Entfernung von Verunreinigungen mit einer Base wie 5—10%iger Alkalicarbonatlösung, z.B. Natriumcarbonat— oder Kaliumcarbonat- lösung extrahiert werden. Die wäßrige Phase wird angesäuert und der sich bildende Niederschlag abgesaugt und/oder mit Methylenchlorid oder Essigsäureethylester extrahiert, getrocknet und eingeengt. Gegebenenfalls wird der Rückstand umkristallisiert und/ oder chromatographisch in der oben beschriebenen Weise weiter gereinigt.Working up can be carried out in a manner known per se. The rearrangement reaction mixture is, for example, diluted mineral acid, e.g. 5% hydrochloric acid or sulfuric acid, acidified, with an organic solvent, e.g. Extracted methylene chloride or ethyl acetate. The organic extract can be used to remove contaminants with a base such as 5-10% alkali carbonate solution, e.g. Sodium carbonate or potassium carbonate solution can be extracted. The aqueous phase is acidified and the precipitate formed is suction filtered and / or extracted with methylene chloride or ethyl acetate, dried and concentrated. If necessary, the residue is recrystallized and / or further purified by chromatography in the manner described above.
Die im folgenden angegebenen Beispiele dienen der weiteren Erläuterung der Erfindung.The examples given below serve to further explain the invention.
I . ß-KetonenolesterI. ß-Ketonenolester
Allgemeine Vorschrift für die Umsetzung von 5-Brom-2,4-dime- thylsaccharin ( 5-Brom-2 , 4-dimethyl-l, 2-benzoisothia- zol-3-(2H)-on-l,l-dioxid = Verbindung der Formel Ilb mit Rlb = R5b = Methyl, Rb = Wasserstoff, X = 0, n = 2 und Hai = Brom) mit Cyclohexan-l,3-dionen der Formel lila im Laborautoklaven (Beispiele 1 bis 3)General instructions for the reaction of 5-bromo-2,4-dimethylsaccharin (5-bromo-2, 4-dimethyl-l, 2-benzoisothiazole-3- (2H) -on-l, l-dioxide = Compound of the formula IIb with R lb = R 5b = methyl, R b = hydrogen, X = 0, n = 2 and Hai = bromine) with cyclohexane-1,3-dions of the formula purple in a laboratory autoclave (Examples 1 to 3)
1 g (3,6 mmol) 5-Brom-2,4-dimethylsaccharin, 4,3 mol (1,2 eq.) 1,3-Diketon, 0,1 g Bis(triphenylphosphin)palladiumdich- lorid, 0,15 g (3,6 mmol) Lithiumchlorid, 0,73 g (7,2 mmol) Triethylamin wurden in einem Laborautoklaven in 100 ml Lösungsmittel vorgelegt. Anschliessend spülte man den Gasraum des Autoklaven 1 bis 6 mal mit Kohlenmonoxid, erwärmte auf 140°C und stellte dann einen Kohlenmonoxid-Druck von 20 bar ein. Man behielt die Temperatur und Druck 12 h bis 24 h bei, kühlte ab, entspannte auf Normaldruck und engte die Reaktionsmischung zur Trockne ein.1 g (3.6 mmol) 5-bromo-2,4-dimethylsaccharin, 4.3 mol (1.2 eq.) 1,3-diketone, 0.1 g bis (triphenylphosphine) palladium dichloride, 0.15 g (3.6 mmol) of lithium chloride, 0.73 g (7.2 mmol) of triethylamine were placed in a laboratory autoclave in 100 ml of solvent. The gas space of the autoclave was then flushed 1 to 6 times with carbon monoxide, heated to 140 ° C. and then set to a carbon monoxide pressure of 20 bar. The temperature and pressure were maintained for 12 to 24 hours, cooled, relaxed to normal pressure and concentrated the reaction mixture to dryness.
Zur Aufarbeitung nach Methode A wurde der Rückstand an Kie- selgel mit einem Cyclohexan-Ethylacetat-Gradienten (100/0 bis 60/40 v/v) chromatographiert.For working up according to method A, the residue was chromatographed on silica gel using a cyclohexane-ethyl acetate gradient (100/0 to 60/40 v / v).
Zur Aufarbeitung nach Methode B wurde der Rückstand in Ethy- lacetat aufgenommen, 3 mal mit 5 gew.-%igem wässrigen Natri- umcarbonat, 2 mal mit 10 gew.-%iger Salzsäure und 2 mal mitFor working up by method B, the residue was taken up in ethyl acetate, 3 times with 5% by weight aqueous sodium carbonate, 2 times with 10% by weight hydrochloric acid and 2 times with
Wasser gewaschen. Die organische Phase wurde über Natriumcar- bonat getrocknet und zur Trockne im Vakuum eingeengt.Washed water. The organic phase was dried over sodium carbonate and concentrated to dryness in vacuo.
Man erhielt den jeweiligen ß-Ketoenolester der 2,4-Dimethyl- saccharin-5-carbonsäure als zähes Öl oder als weissen Feststoff.The respective ß-ketoenol ester of 2,4-dimethyl-saccharin-5-carboxylic acid was obtained as a viscous oil or as a white solid.
Die Authentizität der erhaltenen Verbindungen wurde mittels ^•H-NMR-Spektrum überprüft. Die Einsatzmaterialien und Ergebnisse der Umsetzung sind in Tabelle 1 angegeben:The authenticity of the compounds obtained was checked by means of a ^ • H-NMR spectrum. The feed materials and results of the implementation are given in Table 1:
Tabelle 1 :Table 1 :
1) bezogen auf 5-Brom-2,4-dimethylsaccharin1) based on 5-bromo-2,4-dimethylsaccharin
Beispiel 4 :Example 4:
10 g (36 mmol) 5-Brom-2,4-dimethylsaccharin, 5 g (36 mmol) Bicyclo[3.2.1]-l,3-dioxooctan (Diketon III-4), 1 g Bis(tri- phenylphosphin)palladiumdichlorid, 1,5 g (3,6 mmol) Lithiumchlorid und 7,3 g (72 mmol) Triethylamin wurden in einem 1-L Autoklaven in 700 ml Toluol vorgelegt und inertisiert. Anschliessend spülte man den Gasraum des Autoklaven mit Kohlenmonoxid, erwärmte auf 140°C und stellte dann einen Kohlen- monoxid-Druck von 20 bar ein. Man behielt die Temperatur und Druck 24 h bei, kühlte ab und entspannte auf Normaldruck.10 g (36 mmol) 5-bromo-2,4-dimethylsaccharin, 5 g (36 mmol) bicyclo [3.2.1] -l, 3-dioxooctane (diketone III-4), 1 g bis (triphenylphosphine) palladium dichloride , 1.5 g (3.6 mmol) of lithium chloride and 7.3 g (72 mmol) of triethylamine were placed in a 1 L autoclave in 700 ml of toluene and rendered inert. The gas space in the autoclave was then flushed with carbon monoxide, heated to 140 ° C. and then a carbon monoxide pressure of 20 bar was set. The temperature and pressure were maintained for 24 hours, cooled and let down to normal pressure.
Zur Aufarbeitung wurde die Reaktionsmischung je 3 mal mit 5 gew.-%igem wässrigen Natriumcarbonat, mit 10 gew.-%iger Salzsäure und mit Wasser gewaschen. Die organische Phase wurde über Natriumsulfat getrocknet und zur Trockne im Vakuum ein- geengt. Man erhielt 10,4 g 5-[ (Bicyclo[3.2. l]-3-oxooc- ten-l-yl)oxycarbonyl]-2,4-dimethylsaccharin als zähes Öl.For working up, the reaction mixture was washed 3 times with 5% by weight aqueous sodium carbonate, with 10% by weight hydrochloric acid and with water. The organic phase was dried over sodium sulfate and left to dry in vacuo. geengt. 10.4 g of 5- [(bicyclo [3.2.1] -3-oxoocten-l-yl) oxycarbonyl] -2,4-dimethylsaccharin were obtained as a viscous oil.
Beispiel 5 :Example 5:
l-Brom-2,4-dichlorbenzol und 4, 4, 6, 6-Tetramethyl-1,3,5-trio- xocyclohexan (Diketon III-2) wurden in Gegenwart von Bis(tri- phenylphosphin)palladiumdichlorid, Lithiumchlorid und Triethylamin auf die für Beispiel 4 beschriebene Weise in den dort angegebenen Mengenverhältnissen umgesetzt. Man erhielt nach Aufarbeitung (4,4,6, 6-Tetramethyl-3, 5-dioxo-cyclohe- xen-l-yl)-2,4-dichlorbenzoat in einer Ausbeute von 30 %.l-Bromo-2,4-dichlorobenzene and 4, 4, 6, 6-tetramethyl-1,3,5-trio-xocyclohexane (diketone III-2) were palladium dichloride, lithium chloride and triethylamine in the presence of bis (triphenylphosphine) implemented in the manner described for Example 4 in the proportions given there. After working up (4,4,6, 6-tetramethyl-3, 5-dioxo-cyclohexen-l-yl) -2,4-dichlorobenzoate was obtained in a yield of 30%.
Beispiel 6:Example 6:
l-Brom-2,4-dichlorbenzol und 4,6-Dimethyl-l,3-dioxocyclohexan (Diketon III-3) wurden in Gegenwart von Bis(triphenylphosp- hin)palladiumdichlorid, Lithiumchlorid und Triethylamin auf die für Beispiel 4 beschriebene Weise in den dort angegebenen Mengenverhältnissen umgesetzt. Man erhielt nach Aufarbeitung (4, 6-Dimethyl-3-dioxocyclohex-l-en-l-yl)-2 , 4-dichlorbenzoat in einer Ausbeute von 27 %.l-Bromo-2,4-dichlorobenzene and 4,6-dimethyl-1,3-dioxocyclohexane (diketone III-3) were in the presence of bis (triphenylphosphine) palladium dichloride, lithium chloride and triethylamine in the manner described for Example 4 in implemented the proportions given there. After working up (4, 6-dimethyl-3-dioxocyclohex-1-en-1-yl) -2, 4-dichlorobenzoate was obtained in a yield of 27%.
Beispiel 8:Example 8:
l-Brom-2-methyl-4-methylsulfonyl-3- ( 4 ' ,5 '-dihydrooxa- zol-3-yl)benzol wurde mit (36 mmol) 5,5-Dimethyl-l,3-dioxocy- clohexan (Diketon III-9) in Gegenwart von Bis(triphenylphosp- hin)palladiumdichlorid, Lithiumchlorid und Triethylamin auf die für Beispiel 4 beschriebene Weise in den dort angegebenen Mengenverhältnissen umgesetzt. Man erhielt nach Aufarbeitung 1- (5 , 5-Dimethy1-3-oxocyclohex-1-en-l-yl)oxycarbon l-2-me- thyl-4-methylsulfonyl-3-(4 ' ,5 '-dihydrooxazol-3-yl)benzol in einer Ausbeute von 35 %.l-Bromo-2-methyl-4-methylsulfonyl-3- (4 ', 5' -dihydrooxazol-3-yl) benzene was treated with (36 mmol) 5,5-dimethyl-1,3-dioxocyclohexane ( Diketone III-9) in the presence of bis (triphenylphosphine) palladium dichloride, lithium chloride and triethylamine in the manner described for Example 4 in the proportions given there. After working up, 1- (5, 5-dimethy1-3-oxocyclohex-1-en-l-yl) oxycarbon l-2-methyl-4-methylsulfonyl-3- (4 ', 5' -dihydrooxazol-3 -yl) benzene in a yield of 35%.
Beispiel 9 :Example 9:
l-Brom-2-methyl-4-methylsulfonyl-3- ( 4 ' , 5 ' -dihydrooxa- zol-3-yl)benzol wurde mit Cyclohexan-l,3-dion (Diketon III-l) in Gegenwart von Bis(triphenylphosphin)palladiumdichlorid, Lithiumchlorid und Triethylamin auf die für Beispiel 4 beschriebene Weise in den dort angegebenen Mengenverhältnissen umgesetzt. Man erhielt nach Aufarbeitung l-(3-0xocyclo- hex-l-en-l-yl)oxycarbonyl-2-methyl-4-methylsulfo- nyl-3- (4 ' ,5 '-dihydrooxazol-3-yl)benzol. Auf die in Beispiel 8 und 9 beschriebene Weise lassen sich ausserdem die ß-Ketoenolester der nachstehenden Formell-Bromo-2-methyl-4-methylsulfonyl-3- (4 ', 5' -dihydrooxazol-3-yl) benzene was treated with cyclohexan-1,3-dione (diketone III-l) in the presence of bis ( triphenylphosphine) palladium dichloride, lithium chloride and triethylamine in the manner described for Example 4 in the proportions given there. After working up, 1- (3-0xocyclo-hex-1-en-1-yl) oxycarbonyl-2-methyl-4-methylsulfonyl-3- (4 ', 5' -dihydrooxazol-3-yl) benzene was obtained. In the manner described in Examples 8 and 9, the β-ketoenol esters of the formula below can also be used
herstellen, worin Hex, Rlc und R3c jeweils die in Tabelle 2 angegebene Bedeutung haben. Hex steht dabei für einen der nachfolgend definierten Cyclohexenon-Reste Hex-1 bis Hex-5produce, wherein Hex, R lc and R 3c each have the meaning given in Table 2. Hex stands for one of the cyclohexenone radicals hex-1 to hex-5 defined below
Tabelle 2:Table 2:
I. 2-Aroyl-1,3-diketone I. 2-Aroyl-1,3-diketones
Die Umlagerung der nach den unter I hergestellten Verbindungen kann beispielsweise nach Beispiel C) 17, S. 19 der WO 96/05182 erfolgen, auf das hiermit Bezug genommen wird. The rearrangement of the compounds prepared under I can take place, for example, according to Example C) 17, p. 19 of WO 96/05182, to which reference is hereby made.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von ß—Ketoenolestern der allgemeinen Formel Ia oder Ib1. Process for the preparation of β-ketoenol esters of the general formula Ia or Ib
worin wherein
Ra, Rb unabhängig voneinander für Cχ-C6-Alkyl oder C3-C8-Cy- cloalkyl stehen, oderR a , R b independently of one another are Cχ-C 6 -alkyl or C 3 -C 8 -cycloalkyl, or
Ra und Rb zusammen für C-C4-Alkandiyl oder Cs-C7-Cycloalkan- diyl stehen, wobei die drei vorgenannten Gruppen substituiert oder unsubstituiert sein können, und/oder einen anellierten 3-, 4-, 5- oder 6-gliedrigen gesättigten Carbocyclus, einen spiro-verküpften 3-, 4-, 5-, 6- oder 7-gliedrigen gesättigten Carbocyclus, einen spiro-verküpften 3-, 4-, 5-, 6- oder 7-gliedrigen gesättigten Heterocyclus mit 1 oder 2 Chalkogenato en, ausgewählt unter Sauerstoff und Schwefel, und/oder eine Carbonyl- oder Thiocarbonylgruppe aufweisen können;R a and R b together represent CC 4 -alkanediyl or Cs-C 7 -cycloalkanedyl, where the three aforementioned groups may be substituted or unsubstituted, and / or a fused 3, 4, 5 or 6-membered group saturated carbocycle, a spiro-linked 3-, 4-, 5-, 6- or 7-membered saturated carbocycle, a spiro-linked 3-, 4-, 5-, 6- or 7-membered saturated heterocycle with 1 or 2 Chalcogenatos, selected from oxygen and sulfur, and / or may have a carbonyl or thiocarbonyl group;
Ar Phenyl oder Pyridyl, die jeweils 1, 2, 3 oder 4 Substituenten aufweisen können, wobei zwei an benachbarte Koh- lenstoffatome gebundene Substituenten mit diesen Atomen auch einen einen 5- oder 6-gliedrigen gesättigten oder ungesättigten Carbocyclus oder einen 5- oder 6-gliedrigen gesättigten oder ungesättigten Heterocyclus bilden können, der 1, 2 oder 3 Heteroatome, ausgewählt unter O, N und S aufweist und der seinerseits substituiert oder unsubstituiert sein kann;Ar phenyl or pyridyl, each of which may have 1, 2, 3 or 4 substituents, two substituents bonded to adjacent carbon atoms with these atoms also having a 5- or 6-membered saturated or unsaturated carbocycle or a 5- or 6- can form membered saturated or unsaturated heterocycle which has 1, 2 or 3 heteroatoms selected from O, N and S and which in turn can be substituted or unsubstituted;
dadurch gekennzeichnet, dass man ein Arylhalogenid der allgemeinen Formel IIcharacterized in that an aryl halide of the general formula II
Ar-Hal (II) worin Hai für ein Halogenatom, ausgewählt unter Chlor, Brom oder Iod, steht,Ar-Hal (II) wherein shark represents a halogen atom selected from chlorine, bromine or iodine,
mit einem 1,3-Diketon der allgemeinen Formel III oder seinen Tautomeren III' oder III"with a 1,3-diketone of the general formula III or its tautomers III 'or III "
0 00 0
X 1 (III) X 1 (III)
in einer Kohlenmonoxid-Atmosphäre in Gegenwart einer Base und eines Katalysators, der wenigstens ein Übergangsmetall der Gruppe VIII des Periodensystems enthält, umsetzt.in a carbon monoxide atmosphere in the presence of a base and a catalyst which contains at least one transition metal from Group VIII of the periodic table.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Katalysator als Übergangsmetall Palladium umfasst.2. The method according to claim 1, characterized in that the catalyst comprises palladium as the transition metal.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Katalysator zusätzlich ein tertiäres Phosphin um- fasst.3. The method according to claim 1 or 2, characterized in that the catalyst additionally comprises a tertiary phosphine.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass das tertiäre Phosphin ein Triarylphosphin ist.4. The method according to claim 3, characterized in that the tertiary phosphine is a triarylphosphine.
5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Base ausgewählt ist unter sekundären und tertiären Aminen.5. The method according to any one of the preceding claims, characterized in that the base is selected from secondary and tertiary amines.
6. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass man die Umsetzung bei einer Temperatur im Bereich von 50 bis 250°C durchführt.6. The method according to any one of the preceding claims, characterized in that one carries out the reaction at a temperature in the range of 50 to 250 ° C.
7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das 1,3-Diketon der allgemeinen Formel III bzw. seine Tautomer III' und III" den allgemeinen Formeln lila oder Illb gehorchen: 7. The method according to any one of the preceding claims, characterized in that the 1,3-diketone of the general formula III or its tautomer III 'and III "obey the general formulas purple or Illb:
worin k für 0, 1 oder 2 steht, die Variablen R1 bis R6 fol- gende Bedeutung haben:where k is 0, 1 or 2, the variables R 1 to R 6 have the following meaning:
R1, R5 unabhängig voneinander Wasserstoff, Cχ-C4-Alkyl oder Cχ-C4-Alkoxycarbonyl;R 1 , R 5 independently of one another are hydrogen, Cχ-C 4 -alkyl or Cχ-C 4 -alkoxycarbonyl;
R2, R4, R6 unabhängig voneinander Wasserstoff, Cχ-C4-Alkyl, Cχ-C4-Alkylthio oder Cχ-C4-Alkoxy;R 2 , R 4 , R 6 independently of one another are hydrogen, Cχ-C 4 -alkyl, Cχ-C 4 -alkylthio or Cχ-C 4 -alkoxy;
R3 Wasserstoff, Halogen, Hydroxy, Cχ-Cg-Alkyl, Cχ-Cg-Halogenalkyl, Di-(Cχ-Cg-alkoxy)-methyl, (Cχ-Cg-Alkoxy)-(Cχ-Cg-alkylthio) -methyl,R 3 is hydrogen, halogen, hydroxy, Cχ-Cg-alkyl, Cχ-Cg-haloalkyl, di- (Cχ-Cg-alkoxy) -methyl, (Cχ-Cg-alkoxy) - (Cχ-Cg-alkylthio) -methyl,
Di- (Cχ-Cg-alkylthio)methyl, Cχ-Cg-Alkoxy, Cχ-Cg-Halogenalkoxy, Cχ-Cg-Alkylthio, Cχ-Cg-Halogenalkylthio, Cχ-C6-Alkylsulfinyl, Cχ-Cg-Halogenalkylsulfinyl, Cχ-Cg-Alkylsulfonyl, Cχ-Cg-Halogenalkylsulfonyl, Cχ-Cg-Alkoxycarbonyl,Di- (Cχ-Cg-alkylthio) methyl, Cχ-Cg-alkoxy, Cχ-Cg-haloalkoxy, Cχ-Cg-alkylthio, Cχ-Cg-haloalkylthio, Cχ-C 6 -alkylsulfinyl, Cχ-Cg-haloalkylsulfinyl, Cχ- Cg-alkylsulfonyl, Cχ-Cg-haloalkylsulfonyl, Cχ-Cg-alkoxycarbonyl,
Cχ-Cg-Halogenalkoxycarbonyl;Cχ-Cg-halogenoalkoxycarbonyl;
1 , 3-Dioxolan-2-yl, 1 , 3-Dioxan-2-yl, 1 , 3-Oxathiolan-2-yl, 1, 3-Oxathian-2-yl, l,3-Dithiolan-2-yl oder l,3-Dithian-2-yl, wobei die sechs letztgenannten Reste durch einen bis drei Cχ-C4-Alkylreste substituiert sein können; oder1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithiolan-2-yl or l, 3-dithian-2-yl, where the latter six radicals can be substituted by one to three Cχ-C 4 alkyl radicals; or
R2 und R4 oder R4 und R6 bilden gemeinsam eine π-Bindung oder eine Cχ-C5-Alkandiylkette, die eine π-Bindung aufweisen und /oder einen, zwei oder drei Reste aus folgender Gruppe tragen kann: Halogen, Cyano, Cχ-C-Alkyl, Cχ-C4-Halogenalkyl oder Cχ-C4-Alkoxy- carbony1; oderR 2 and R 4 or R 4 and R 6 together form a π bond or a Cχ-C 5 alkanediyl chain which have a π bond and / or can carry one, two or three radicals from the following group: halogen, cyano , Cχ-C-alkyl, Cχ-C 4 -haloalkyl or Cχ-C 4 -alkoxy-carbony1; or
R5 und R6 bilden gemeinsam eine Cχ-Cs-Alkandiylkette, die eine π-Bindung aufweisen und /oder einen, zwei oder drei Reste aus folgender Gruppe tragen kann: Halogen, Cyano, Cχ-C4-Alkyl, Cχ-C-Halogenalkyl oder Cχ-C4-Alkoxycarbonyl; oder R2 und R6 bilden gemeinsam eine Cχ-C4-Alkandiylkette, die eine π-Bindung aufweisen und /oder einen, zwei oder drei Reste aus folgender Gruppe tragen kann: Halogen, Cyano, Cχ-C4-Alkyl, Cχ-C4-Halogenalkyl oder Cχ-C4-Alkoxycarbonyl; oderR 5 and R 6 together form a Cχ-Cs-alkanediyl chain which has a π bond and / or can carry one, two or three radicals from the following group: halogen, cyano, Cχ-C 4 alkyl, Cχ-C- Haloalkyl or Cχ-C 4 alkoxycarbonyl; or R 2 and R 6 together form a Cχ-C 4 alkanediyl chain which have a π bond and / or can carry one, two or three radicals from the following group: halogen, cyano, Cχ-C 4 alkyl, Cχ-C 4 -haloalkyl or Cχ-C 4 alkoxycarbonyl; or
R3 und R4 bilden gemeinsam eine Kette der FormelR 3 and R 4 together form a chain of the formula
-0-(CH2)p-0-, -0-(CH2)p-S-, _S-(CH2)p-S-, -0-(CH2)g- oder -S-(CH2)q-, worin p für 2, 3, 4 oder 5 und q für 2, 3, 4, 5 oder 6 stehen, und die durch einen, zwei oder drei Reste aus folgender Gruppe substituiert sein kann: Halogen, Cyano, Cχ-C4-Alkyl, Cχ-C4-Halogenalkyl oder Cχ-C4-Alkoxycarbonyl; oder-0- (CH 2 ) p -0-, -0- (CH 2 ) p -S-, _S- (CH 2 ) p -S-, -0- (CH 2 ) g - or -S- (CH 2 ) q -, where p is 2, 3, 4 or 5 and q is 2, 3, 4, 5 or 6, and which can be substituted by one, two or three radicals from the following group: halogen, cyano, Cχ -C 4 alkyl, Cχ-C 4 haloalkyl or Cχ-C 4 alkoxycarbonyl; or
R3 und R4 bilden gemeinsam mit dem Kohlenstoff, an dem sie gebunden sind, eine Carbonyl- oder Thiocarbonylgruppe .R 3 and R 4 together with the carbon to which they are attached form a carbonyl or thiocarbonyl group.
8. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, das das Arylhalogenid der allgemeinen Formel II durch die allgemeine Formel Ha repräsentiert wird:8. The method according to any one of the preceding claims, characterized in that the aryl halide of the general formula II is represented by the general formula Ha:
worinwherein
Rla und R4a unabhängig voneinander für Wasserstoff, Halogen, insbesondere Fluor oder Chlor, Cyano, Cχ-C6-Alkyl, C -C6-Halogenalkyl, Cχ-C6-Alkoxy, Cχ-Cg-Halogenalkoxy, Cχ-Cg-Alkylthio, Cχ-C6-Halogenalkylthio, Hydroxy-Cχ-C6-alkyl,R la and R 4a independently of one another for hydrogen, halogen, in particular fluorine or chlorine, cyano, Cχ-C 6 -alkyl, C -C 6 -haloalkyl, Cχ-C 6 -alkoxy, Cχ-Cg-haloalkoxy, Cχ-Cg- Alkylthio, Cχ-C 6 -haloalkylthio, hydroxy-Cχ-C 6 -alkyl,
Cχ-Cg-Alkylsulfonyl, Cχ-Cg-Halogenalkylsulfonyl, Cχ-Cg-Alkoxy-Cχ-Cg-alkyl, Cχ-C6-Alkylthio-Cι-Cg-alkyl, Cχ-Cg-Halogenalkylthio-Cχ-Cg-alkyl, Cχ-Cg-Alkylsulfonyl-Cχ-Cg-alkyl, Cχ-Cg-Halogenalkylsulfonyl-Cχ-C6-alkyl, Cχ-Cg-Alkylamino-Cχ-Cg-alkyl, oder Di-(Cχ-Cg-alkyl)amino-Cχ-Cg-alkyl stehen undCχ-Cg-alkylsulfonyl, Cχ-Cg-haloalkylsulfonyl, Cχ-Cg-alkoxy-Cχ-Cg-alkyl, Cχ-C 6 -alkylthio-Cι-Cg-alkyl, Cχ-Cg-haloalkylthio-Cχ-Cg-alkyl, Cχ -Cg-alkylsulfonyl-Cχ-Cg-alkyl, Cχ-Cg-haloalkylsulfonyl-Cχ-C 6 -alkyl, Cχ-Cg-alkylamino-Cχ-Cg-alkyl, or di- (Cχ-Cg-alkyl) amino-Cχ- Cg-alkyl stand and
R2a und R3a einen 5- oder 6-gliedrigen, gesättigten oder unge- sättigten Heterocyclus bilden, der 1, 2 oder 3 Heteroa- tome, ausgewählt unter N, S und O aufweisen kann, wobei Schwefelatome im Heterocyclus auch als Sulfoxid oder Sul- fon vorliegen können,R 2a and R 3a form a 5- or 6-membered, saturated or unsaturated heterocycle which can have 1, 2 or 3 heteroatoms selected from N, S and O, where Sulfur atoms in the heterocycle can also be present as sulfoxide or sulfone,
Stickstoffatome und Kohlenstoffatome im Heterocyclus ein Wasserstoff tom oder einen Substituenten aufweisen, der ausgewählt ist unter Halogen, Nitro, Cyano, Hydroxy, Amino, Cχ-Cg-Alkyl, Cχ-Cg-Halogenalkyl, Cχ-Cg-Aminoalkyl, Cχ-Cg-Alkylcarbonyl, Cχ-C6-Alkylcarbonyloxy, Cx-Cg-Alkylo- xycarbonyl, Cχ-C6-Alkoxy-Cχ-C6-alkyl, Cχ-C6-Alkylcarbo- nyl-Cχ-Cg-alkyl, Cχ-C6-Alkoxy, Cχ-C6-Halogenalkoxy, C2-C6-Alkenyl, C2-C6-Alkinyl, Cχ-Cg-Hydroxyalkoxy, Cχ-Cg-Alkoxy-Cχ-Cg-alkoxy, C3-C6-Cycloalkyl, C3-C8-Cyclo- alkoxy, Cχ-Cg-Alkylthio, Cχ-Cg-Halogenalkylthio, Cχ-Cg-Hydroxyalkylthio, Cχ-C6-Alkoxy-Cχ-Cg-alkylthio,Nitrogen atoms and carbon atoms in the heterocycle have a hydrogen atom or a substituent which is selected from halogen, nitro, cyano, hydroxy, amino, Cχ-Cg-alkyl, Cχ-Cg-haloalkyl, Cχ-Cg-aminoalkyl, Cχ-Cg-alkylcarbonyl , Cχ-C 6 -alkylcarbonyloxy, Cx-Cg-alkyloxycarbonyl, Cχ-C 6 -alkoxy-Cχ-C 6 -alkyl, Cχ-C 6 -alkylcarbonyl-Cχ-Cg-alkyl, Cχ-C 6 - Alkoxy, Cχ-C 6 haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Cχ-Cg-hydroxyalkoxy, Cχ-Cg-alkoxy-Cχ-Cg-alkoxy, C 3 -C 6 cycloalkyl , C 3 -C 8 cycloalkoxy, Cχ-Cg-alkylthio, Cχ-Cg-haloalkylthio, Cχ-Cg-hydroxyalkylthio, Cχ-C 6 -alkoxy-Cχ-Cg-alkylthio,
Phenyl, Phenyl-Cχ-Cg-alkyl, Phenylcarbonyl, Phenylcarbo- nyloxy, Phenoxycarbonyl, 5-, 6- oder 7-gliedriges Heterocyclyl, Phenoxy, Phenylamino, Diphenylamino, Heterocy- clyl-Cχ-Cg-alkyl, Heterocyclyloxy, Heterocyclylcarbonyl, Heterocyclyloxycarbonyl, Heterocyclylcarbon loxy, wobei die Phenyl- und Heterocyclylgruppen der 14 letztgenannten Reste ihrerseits partiell oder vollständig halogeniert und/oder einen, zwei oder drei Substituenten, ausgewählt unter Nitro, Cyano, Hydroxy, Cχ-C4-Alkyl, Cχ-C-Halogenal- kyl, C-C4-Alkoxy und Cχ-C4-Halogenalkoxy, tragen können, Cχ-Cg-Alkylamino, Di-Cχ-C6-alkylamino, C3-C6-Cycloalkylamino, wobei die Alkyl- und Cycloalkylgruppen der drei letztgenannten Reste teilweise oder vollständig halogeniert und/oder ein bis drei Substituenten, ausgewählt un- ter Cχ-C -Alkoxy oder Hydroxy tragen können,Phenyl, phenyl-Cχ-Cg-alkyl, phenylcarbonyl, phenylcarbonyloxy, phenoxycarbonyl, 5-, 6- or 7-membered heterocyclyl, phenoxy, phenylamino, diphenylamino, heterocyclic-Cχ-Cg-alkyl, heterocyclyloxy, heterocyclylcarbonyloxycarbonyl, heterocyclyloxy , Heterocyclylcarbon loxy, the phenyl and heterocyclyl groups of the 14 last-mentioned radicals in turn partially or completely halogenated and / or one, two or three substituents selected from nitro, cyano, hydroxy, Cχ-C 4 -alkyl, Cχ-C-halogenal- kyl, CC 4 -alkoxy and Cχ-C 4 -haloalkoxy, can carry, C C-Cg-alkylamino, di-Cχ-C 6 -alkylamino, C 3 -C 6 -cycloalkylamino, the alkyl and cycloalkyl groups of the latter three radicals partially or completely halogenated and / or can carry one to three substituents selected from C C-C alkoxy or hydroxy,
Kohlenstoffringlieder auch als Carbonylfunktion, Thiocar- bonylfunktion, Oxim- oder Oximetherfunktion vorliegen können; oderCarbon ring members can also be present as a carbonyl function, thiocarbonyl function, oxime or oxime ether function; or
Rla und R2a oder R3a und R4a einen 5- oder 6-gliedrigen, gesättigten oder ungesättigten Heterocyclus bilden, der 1, 2 oder 3 Heteroatome, ausgewählt unter N, S und 0 aufweisen kann, wobei die Ringatome des Heterocyclus in der oben beschriebenen Weise substituiert sein können; undR la and R 2a or R 3a and R 4a form a 5- or 6-membered, saturated or unsaturated heterocycle which can have 1, 2 or 3 heteroatoms selected from N, S and 0, the ring atoms of the heterocycle in the may be substituted as described above; and
die verbleibenden Reste Rla, R2a, R3a und R4a unabhängig voneinander die für Rla genannten Bedeutungen aufweisen, oder R2a für Wasserstoff oder 5-, 6- oder 7-gliedriges Heterocyclyl steht, das 1, 2 oder 3 Heteroatome, ausgewählt unter N, S und O aufweist, wobei die Ringatome des Heterocyclus in der oben beschriebenen Weise substituiert sein können; 5 undthe remaining radicals R la , R 2a , R 3a and R 4a independently of one another have the meanings given for R la , or R2a represents hydrogen or 5-, 6- or 7-membered heterocyclyl which has 1, 2 or 3 heteroatoms selected from N, S and O, it being possible for the ring atoms of the heterocycle to be substituted in the manner described above; 5 and
Rla, R3a und R4a unabhängig voneinander die zuvor für Rla genannten Bedeutungen aufweisen.R la , R 3a and R 4a independently of one another have the meanings given above for R la .
10 9. Verfahren nach Anpsruch 8, dadurch gekennzeichnet, dass das Arylhalogenid II durch die allgemeine Formel Ilb repräsentiert wird:9. The method according to claim 8, characterized in that the aryl halide II is represented by the general formula IIb:
2020
worin Hai die zuvor genannten Bedeutungen und Rlb die zuvor für Rla und R4b die zuvor für R4a genannten Bedeutungen aufweisen,in which shark has the meanings mentioned above and R lb has the meanings previously mentioned for R la and R 4b the meanings previously mentioned for R 4a ,
2525
R5b fü Wasserstoff, Cχ-C6-Alkyl, C-C6-Halogenalkyl, Cχ-Cg-Alkylcarbonyl, Cχ-C6-Alkoxy-Cχ-Cg-alkyl, C2-Cg-Alkenyl, C2-Cg-Alkinyl, Cχ-C6-Hydroxyalkoxy, Cχ-Cg-Alkoxy-Cχ-Cg-alkoxy, C3-C8-Cycloalkyl, Phenyl, R 5b for hydrogen, Cχ-C 6 -alkyl, CC 6 -haloalkyl, Cχ-Cg-alkylcarbonyl, Cχ-C 6 -alkoxy-Cχ-Cg-alkyl, C 2 -Cg-alkenyl, C 2 -Cg-alkynyl, Cχ-C 6 -hydroxyalkoxy, Cχ-Cg-alkoxy-Cχ-Cg-alkoxy, C 3 -C 8 cycloalkyl, phenyl,
30 Pheny1-Cχ-Cg-alkyl steht, wobei Phenyl in den zwei letztgenannten Gruppen einen, zwei oder drei Substituenten, ausgewählt unter Halogen, Nitro, Cyano, Hydroxy, Cχ-C4-Alkyl, Cχ-C4-Halogenalkyl, Cχ-C4-Alkoxy und Cχ-C4-Halogenalkoxy, tragen kann,30 Pheny1-Cχ-Cg-alkyl, where phenyl in the latter two groups has one, two or three substituents selected from halogen, nitro, cyano, hydroxy, Cχ-C 4 alkyl, Cχ-C 4 haloalkyl, Cχ- C 4 alkoxy and Cχ-C 4 haloalkoxy, can carry
35 n für 0, 1 oder 2 steht und35 n stands for 0, 1 or 2 and
X Sauerstoff oder Schwefel bedeutet.X means oxygen or sulfur.
40 10. Verfahren nach Anpsruch 8, dadurch gekennzeichnet, dass das Arylhalogenid II durch die allgemeine Formel IIc repräsentiert wird:10. The method according to claim 8, characterized in that the aryl halide II is represented by the general formula IIc:
45 45
worin Hai die zuvor genannten Bedeutungen aufweist und Rlc die 10 für Rla genannten Bedeutungen hat,in which shark has the meanings mentioned above and R lc has the 10 meanings mentioned for R la ,
R3c für Halogen, Cχ-C6-Alkyl, C-C6-Halogenalkyl,R 3c for halogen, Cχ-C 6 alkyl, CC 6 haloalkyl,
Cχ-C6-Alk lthio, Cχ-C6-Alkylsulfinyl, C-C6-Alkylsulfonyl, Cχ-Cg-Alkoxy oder Cχ-C6-Halogenalkoxy steht,Cχ-C 6 -alkthio, Cχ-C 6 -alkylsulfinyl, CC 6 -alkylsulfonyl, Cχ-Cg-alkoxy or Cχ-C 6 -haloalkoxy,
15 eine Doppelbindung oder eine Einfachbindung bedeutet und15 denotes a double bond or a single bond and
R6C für Wasserstoff oder Cχ-C4-Alkyl steht.R6C represents hydrogen or Cχ-C 4 alkyl.
20 11. Verfahren nach Anpsruch 8, dadurch gekennzeichnet, dass das Arylhalogenid II durch die allgemeine Formel Ild repräsentiert wird:11. The method according to claim 8, characterized in that the aryl halide II is represented by the general formula Ild:
30 worin Hai die zuvor genannten Bedeutungen und Rld die für Rla genannten Bedeutungen hat und30 wherein shark has the meanings mentioned above and R ld has the meanings mentioned for R la and
R3d für Halogen, Cχ-C6-Alkyl, Cχ-C6-Halogenalkyl, C-C6-Al- 35' kylthio, Cχ-C6-Alkylsulfinyl, Cχ-C6-Alkylsulfonyl, cι_Cg-Alkoxy oder Cχ-Cg-Halogenalkoxy steht. R 3d for halogen, Cχ-C 6 -alkyl, Cχ-C 6 -haloalkyl, CC 6 -Al- 35 'kylthio, Cχ-C 6 -alkylsulfinyl, Cχ-C 6 -alkylsulfonyl, c ι _ Cg-alkoxy or Cχ -Cg-haloalkoxy.
12. Verfahren zur Herstellung von 2-Aroyl-substituierten 1,3-Di- ketonen der Formel X oder ihren Tautomeren Xa, Xb oder Xc 4012. A process for the preparation of 2-aroyl-substituted 1,3-di-ketones of the formula X or their tautomers Xa, Xb or Xc 40
45 45
worin Ra, Rb, und Ar die in Anspruch 1 angegebene Bedeutung haben, umfassend die folgendenden Reaktionsschritte:wherein R a , R b , and Ar have the meaning given in claim 1, comprising the following reaction steps:
1. Umsetzung eines 1,3-Diketons der in Anspruch 1 definier- ten allgemeinen Formel III oder seiner Tautomere III' oder III" mit einem Arylhalogenid Ar-Hal, worin Hai für Chlor, Brom oder Iod steht, in einer Kohlenmonoxid-Atmosphäre in Gegenwart einer Base und eines Übergangsmetallkatalysators, der wenigstens ein Übergangsmetall der Gruppe VIII des Periodensystems enthält, zu einem ß-Ketoenolester der in Anspruch 1 definierten allgemeinen Formel Ia oder Ib, und1. Reaction of a 1,3-diketone of the general formula III defined in claim 1 or its tautomers III 'or III "with an aryl halide Ar-Hal, in which shark represents chlorine, bromine or iodine, in a carbon monoxide atmosphere in Presence of a base and a transition metal catalyst, which contains at least one transition metal of group VIII of the periodic table, to a β-ketoenol ester of the general formula Ia or Ib defined in claim 1, and
2. Umlagerung der Verbindung Ia oder Ib zu einer Verbindung X oder Xa, Xb und/oder Xc, durch Behandlung von Ia und/ oder Ib mit einer Base und einer katalytisch aktiven Menge wenigstens einer Cyanid-Verbindung. 2. Rearrangement of the compound Ia or Ib to a compound X or Xa, Xb and / or Xc, by treating Ia and / or Ib with a base and a catalytically active amount of at least one cyanide compound.
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HUP0300820A2 (en) 2003-09-29
WO2002016305A1 (en) 2002-02-28
CN1461294A (en) 2003-12-10
CN1261404C (en) 2006-06-28
AU2001287700A1 (en) 2002-03-04
US6903221B2 (en) 2005-06-07
IL154332A0 (en) 2003-09-17
KR100766637B1 (en) 2007-10-15
BR0113359A (en) 2003-07-15

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