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    • 33. 发明申请
    • PROCESS FOR THE MANUFACTURE OF CHROMAN DERIVATIVES, ESPECIALLY α-TOCOPHEROL AND ALKANOATES THEREOF
    • 制备色氨酸衍生物的方法,特别是α-氯代苯甲酸和其它烷基酯
    • WO2005121115A1
    • 2005-12-22
    • PCT/EP2004/013771
    • 2004-12-03
    • DSM IP ASSETS B.V.BONRATH, WernerFORICHER, YannNETSCHER, ThomasWILDERMANN, Angela
    • BONRATH, WernerFORICHER, YannNETSCHER, ThomasWILDERMANN, Angela
    • C07D311/00
    • C07D311/72
    • The present invention relates to novel processes for the manufacture of chroman deriva­tives such as α-tocopherol (TCP) and alkanoates thereof, especially α-tocopheryl acetate (TCPA), whereby at least one step of the processes is carried out in the presence of a Lewis acid or a mixture of a Lewis acid with a Bronsted acid as the catalyst under pressure, pref­erably at an absolute pressure of at least 1.1 bar. As starting materials for the manufacture of TCP and its alkanoates either a mixture of 2,3,5-trimethylhydroquinone (TMHQ) or 2,3,6-trimethylhydroquinone-l-alkanoate (TMHQA) and a compound selected from the group consisting of phytol (PH), isophytol (IP) and (iso)phytol derivatives or 2-phytyl-3,5,6-trimethyl-hydroquinone (PTMHQ)/3-­ phytyl-2,5,6-trimethylhydroquinone-1-alkanoate (PTMHQA) and/or an isomer thereof are used. Suitable Lewis acids are indium(III) salts and scandium(III) salts. Suitable acid mixtures are iron/iron(II) chloride/hydrogen chloride and zinc(II) chloride/hydrogen chloride.
    • 本发明涉及制造色氨酸衍生物如α-生育酚(TCP)及其链烷酸酯,特别是α-生育酚乙酸酯(TCPA)的新方法,其中至少一个步骤的方法是在 路易斯酸或路易斯酸与布朗斯台德酸的混合物作为催化剂,优选在至少1.1巴的绝对压力下进行。 作为制备TCP及其链烷酸酯的起始原料是2,3,5-三甲基氢醌(TMHQ)或2,3,6-三甲基氢醌-1-链烷酸酯(TMHQA)的混合物和选自植醇 (PH),异植醇(IP)和(异)植醇衍生物或2-植酰基-3,5,6-三甲基 - 氢醌(PTMHQ)/ 3-植酰基-2,5,6-三甲基氢醌-1-链烷酸酯(PTMHQA) 和/或其异构体。 合适的路易斯酸是铟(III)盐和钪(III)盐。 合适的酸混合物是氯化铁/氯化铁(II)/氯化氢和氯化锌(II)/氯化氢。
    • 35. 发明申请
    • PROCESS FOR THE MANUFACTURE OF ALKENYLATED HYDROXYLATED AROMATIC COMPOUNDS, OF CHROMAN COMPOUNDS AND OF THEIR ACYLATED DERIVATIVES
    • 烷基化羟基化合物,化合物及其衍生物的制备方法
    • WO2005054223A2
    • 2005-06-16
    • PCT/EP2004/013788
    • 2004-12-03
    • DSM IP ASSETS B.V.BONRATH, WernerFORICHER, YannNETSCHER, ThomasWILDERMANN, Angela
    • BONRATH, WernerFORICHER, YannNETSCHER, ThomasWILDERMANN, Angela
    • C07D311/00
    • C07D311/72Y02P20/582
    • The present invention relates to a novel process for the manufacture of alkenylated aro­matic compounds featuring at least one hydroxy group, their ring-closure reactions to chroman derivatives, as well as the acylation of the latter and the aromatic compounds featuring at least one hydroxy group themselves. The present invention relates especially to a process for the manufacture of tocol, tocopherols and their alkanoates such as α-tocopherol (TCP) and alkanoates (TCPA) thereof, preferably α-tocopheryl acetate (TCPAc). The processes of the present invention are characterized in that at least one step of the processes is carried out in the presence of an indium salt as the catalyst. Thus, an object of the present invention is the use of an indium salt as the catalyst in Friedel-Crafts alkylation reactions of aromatic compounds featuring at least one hydroxy group and ring-closure reactions of the latter to produce chroman-ring compounds in organic solvents. According to another aspect of the invention indium salts can be used as the catalyst in processes for the manufacture of tocyl alkanoates, tocopheryl alkanoates and alkanoates of aromatic compounds featuring at least one hydroxy group by reacting tocols, tocopherol and aromatic compounds featuring at least one hydroxy group, respectively, with an acylating agent. Suitable indium salts are indium(III) salts, especially indium trichloride, indium tribromide or indium triiodide, indium(III) triflate, indium(III) bis(trifluoromethanesulfonamide) and indium(III) acetate. In preferred embodiments of the invention the processes are carried out at a pressure of at least 0.96 bar, whereby the acylation can be carried out at an absolute pressure of at least 0.02 bar.
    • 本发明涉及一种制备具有至少一个羟基的烯基化芳族化合物的新方法,它们对苯并二氢吡喃衍生物的闭环反应以及后者的酰化反应和具有至少一个羟基的芳族化合物本身 。 本发明尤其涉及一种生产托生物,生育酚及其链烷酸酯如α-生育酚(TCP)和链烷酸酯(TCPA),优选醋酸α-生育酚酯(TCPAc)的方法。 本发明的方法的特征在于,在作为催化剂的铟盐存在下进行至少一个步骤。 因此,本发明的目的是在Friedel-Crafts烷基化反应中使用铟盐作为催化剂,其特征在于具有至少一个羟基和后者的闭环反应,在有机溶剂中产生苯并二氢吡喃酮化合物 。 根据本发明的另一方面,铟盐可以用作制备烷基链烷酸酯,生育酚基链烷酸酯和具有至少一个羟基的芳族化合物的链烷酸酯的方法,所述芳族化合物是通过使醇,生育酚和具有至少一个羟基 分别与酰化剂。 合适的铟盐是铟(III)盐,特别是三氯化铟,三溴化铟或三碘化铟,三氟甲磺酸铟(III),三氟甲磺酰胺铟(III)和乙酸铟(III))。 在本发明的优选实施方案中,该方法在至少0.96巴的压力下进行,由此酰化可以在至少0.02巴的绝对压力下进行。