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EP1311469A1 - Procede de preparation de beta-cetoenol esters - Google Patents

Procede de preparation de beta-cetoenol 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
Authority
EP
European Patent Office
Prior art keywords
alkyl
alkoxy
iii
haloalkyl
general formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP01967292A
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German (de)
English (en)
Inventor
Steffen Kudis
Ulf Misslitz
Ernst Baumann
Wolfgang Von Deyn
Klaus Langemann
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BASF SE
Original Assignee
BASF SE
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Publication of EP1311469A1 publication Critical patent/EP1311469A1/fr
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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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

Procédé de préparation de β-cétoénolesters de formule générale Ia ou Ib dans lesquelles Ar, Ra et Rb possèdent les significations figurant dans la revendication 1. Ledit procédé consiste à mettre en réaction un halogénure d'aryle de formule générale (II) avec une 1,3-dicétone de formule générale (III) ou ses tautomères dans une atmosphère de monoxyde de carbone en présence d'une base et d'un catalyseur qui contient au moins un métal de transition du groupe VIII du tableau périodique.
EP01967292A 2000-08-22 2001-08-21 Procede de preparation de beta-cetoenol esters Withdrawn EP1311469A1 (fr)

Applications Claiming Priority (3)

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DE10041044 2000-08-22
DE10041044 2000-08-22
PCT/EP2001/009672 WO2002016305A1 (fr) 2000-08-22 2001-08-21 PROCÉDÉ DE PRÉPARATION DE β-CÉTOÉNOLESTERS

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EP (1) EP1311469A1 (fr)
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KR (1) KR100766637B1 (fr)
CN (1) CN1261404C (fr)
AR (1) AR030574A1 (fr)
AU (1) AU2001287700A1 (fr)
BR (1) BR0113359A (fr)
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ATE449081T1 (de) 2002-12-30 2009-12-15 Celgene Corp Fluoralkoxy-substituierte 1, 3-dihydro-isoindolyl-verbindungen und ihre pharmazeutischen verwendungen
CN111763181A (zh) * 2019-04-02 2020-10-13 重庆大学 一种制备含共轭二烯酮片段的苯并磺内酰胺类季碳氨基酸衍生物的合成方法

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HUP0300820A3 (en) 2009-01-28
IL154332A0 (en) 2003-09-17
JP2004506709A (ja) 2004-03-04
KR100766637B1 (ko) 2007-10-15
IL154332A (en) 2008-11-26
HUP0300820A2 (hu) 2003-09-29
US6903221B2 (en) 2005-06-07
CN1461294A (zh) 2003-12-10
CN1261404C (zh) 2006-06-28
AR030574A1 (es) 2003-08-27
US20030191318A1 (en) 2003-10-09
BR0113359A (pt) 2003-07-15
KR20030043936A (ko) 2003-06-02
AU2001287700A1 (en) 2002-03-04
WO2002016305A1 (fr) 2002-02-28

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