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    • 6. 发明授权
    • MANUFACTURE OF RETINOIDS
    • 维甲酸的生产
    • EP1442014B1
    • 2007-03-21
    • EP02779506.1
    • 2002-10-24
    • DSM IP Assets B.V.
    • RADSPIELER, AlexanderRUETTIMANN, August
    • C07C403/08C07C403/10C07C403/14
    • C07C403/14C07B2200/09C07C403/04C07C403/08C07C403/10C07C403/12C07C403/22C07C2601/16
    • A process for the manufacture of retinal (I) comprises reacting a 5-(2,6,6-trimethyl-cyclohex-1-enyl)-1,4-pentadiene derivative (IIa) or a 5-(2,6,6-trimethyl-cyclohex-2-enyl)-1,4-pentadiene derivative (IIb) or a 5-(2,6,6-trimethyl-2-cyclohexen-1-ylidene)-1-pentene derivative (IIc) or a 5-(2,6,6-trimethyl-cyclohex-1-enyl)-penta-1-en-4-yne derivative (IId) or a 5-(2,6,6-trimethyl-cyclohex-2-enyl)-penta-1-en-4-yne derivative (IIe) with a 1,3-butadiene derivative H2C=C(CH3)CCH=CHOR4 (III) in the presence of a Lewis or Brönsted acid and subjecting the compound obtained in each case [(IVa), (IVb), (IVc), (IVd) or (IVe), respectively] to basic or acidic conditions to eliminate therefrom the moiety R2H and thus produce, according to the immediate precursor, retinal itself or a particular derivative thereof [(I'), (I''), (Va) or (Vb), respectively] and, where in two cases such derivative is produced featuring a triple bond [derivative (Va) or (Vb)], hydrogenating this to produce retinal (I) or the derivative (I'), respectively, and each case where a derivative (I') or (I'') has been produced, isomerizing this under basic or acidic conditions or in the presence of a metal catalyst to the desired retinal (I). The so-produced retinal is usually in the form of an isomeric mixture, normally as (9 E/Z, 13 E/Z)-retinal, and this can be isomerized according to a further inventive aspect to (all-E)-retinal by the acid-catalysed formation of an adduct of (all-E)-retinal with hydroquinone in crystalline form. The so obtained (all-E)-retinal-hydroquinone adduct can then if desired be converted to vitamin A alcohol in the predominantly (all-E)-isomeric form by a method known per se. The novel starting materials (IIa), (IIb), (IIc), (IVI) and (IIe) represent a still further inventive aspect. Retinal is a valuable intermediate in the synthesis of further vitamin A compounds (retinoids). The retinoids, particularly vitamin A alcohol (retinol), are known to be valuable substances which promote the well-being of humans, inter alia in respect of vision, the immune system and growth, and for this reason are often used as components of multivitamin preparations and as additives for certain food- and feedstuffs.
    • 7. 发明公开
    • Novel use
    • Neuartige Verwendung
    • EP2965785A1
    • 2016-01-13
    • EP14176720.2
    • 2014-07-11
    • DSM IP Assets B.V.
    • KLOCK, JochenSCHUELER, GoedeROSENBERGER, VolkerRADSPIELER, Alexander
    • A61Q19/00A61Q19/10A61K8/81
    • A61Q19/00A61K8/8152A61Q19/10
    • The present invention relates to skin cleansing composition comprising an anionic surfactant and an acrylic emulsion polymer obtainable by emulsion polymerization of a monomer composition consisting of a mixture of methacrylic acid, ethyl acrylate and n-butyl methacrylate, characterized in that the acrylic emulsion polymer is incorporated into the skin cleansing composition in a concentration ranging from 0.1 to 2 wt.-% based on the total weight of the composition. Furthermore the invention relates to the use of an acrylic emulsion polymer obtainable by emulsion polymerization of a monomer composition consisting of a mixture of methacrylic acid, ethyl acrylate and n-butyl methacrylate as skin conditioning agent.
    • 本发明涉及包含阴离子表面活性剂和通过由甲基丙烯酸,丙烯酸乙酯和甲基丙烯酸正丁酯的混合物组成的单体组合物的乳液聚合而获得的丙烯酸乳液聚合物的皮肤清洁组合物,其特征在于将丙烯酸乳液聚合物掺入 以组合物总重量的0.1至2重量%的浓度进入皮肤清洁组合物。 此外,本发明涉及通过由甲基丙烯酸,丙烯酸乙酯和甲基丙烯酸正丁酯的混合物组成的单体组合物通过乳液聚合获得的丙烯酸乳液聚合物作为皮肤调理剂的用途。
    • 8. 发明公开
    • MANUFACTURE OF RETINOIDS
    • HERSTELLUNG VON RETINOIDEN
    • EP1442014A1
    • 2004-08-04
    • EP02779506.1
    • 2002-10-24
    • DSM IP Assets B.V.
    • RADSPIELER, AlexanderRUETTIMANN, August
    • C07C403/08C07C403/10C07C403/14
    • C07C403/14C07B2200/09C07C403/04C07C403/08C07C403/10C07C403/12C07C403/22C07C2601/16
    • A process for the manufacture of retinal (I) comprises reacting a 5-(2,6,6-trimethyl-cyclohex-1-enyl)-1,4-pentadiene derivative (IIa) or a 5-(2,6,6-trimethyl-cyclohex-2-enyl)-1,4-pentadiene derivative (IIb) or a 5-(2,6,6-trimethyl-2-cyclohexen-1-ylidene)-1-pentene derivative (IIc) or a 5-(2,6,6-trimethyl-cyclohex-1-enyl)-penta-1-en-4-yne derivative (IId) or a 5-(2,6,6-trimethyl-cyclohex-2-enyl)-penta-1-en-4-yne derivative (IIe) with a 1,3-butadiene derivative H2C=C(CH3)CCH=CHOR4 (III) in the presence of a Lewis or Brönsted acid and subjecting the compound obtained in each case [(IVa), (IVb), (IVc), (IVd) or (IVe), respectively] to basic or acidic conditions to eliminate therefrom the moiety R2H and thus produce, according to the immediate precursor, retinal itself or a particular derivative thereof [(I'), (I''), (Va) or (Vb), respectively] and, where in two cases such derivative is produced featuring a triple bond [derivative (Va) or (Vb)], hydrogenating this to produce retinal (I) or the derivative (I'), respectively, and each case where a derivative (I') or (I'') has been produced, isomerizing this under basic or acidic conditions or in the presence of a metal catalyst to the desired retinal (I). The so-produced retinal is usually in the form of an isomeric mixture, normally as (9 E/Z, 13 E/Z)-retinal, and this can be isomerized according to a further inventive aspect to (all-E)-retinal by the acid-catalysed formation of an adduct of (all-E)-retinal with hydroquinone in crystalline form. The so obtained (all-E)-retinal-hydroquinone adduct can then if desired be converted to vitamin A alcohol in the predominantly (all-E)-isomeric form by a method known per se. The novel starting materials (IIa), (IIb), (IIc), (IVI) and (IIe) represent a still further inventive aspect. Retinal is a valuable intermediate in the synthesis of further vitamin A compounds (retinoids). The retinoids, particularly vitamin A alcohol (retinol), are known to be valuable substances which promote the well-being of humans, inter alia in respect of vision, the immune system and growth, and for this reason are often used as components of multivitamin preparations and as additives for certain food- and feedstuffs.
    • 制备视网膜(I)的方法包括使5-(2,6,6-三甲基 - 环己-1-烯基)-1,4-戊二烯衍生物(IIa)或5-(2,6,6 - 三甲基 - 环己-2-烯基)-1,4-戊二烯衍生物(IIb)或5-(2,6,6-三甲基-2-环己烯-1-亚基)-1-戊烯衍生物(IIc)或 5-(2,6,6-三甲基 - 环己-1-烯基) - 戊-1-烯-4-炔衍生物(IId)或5-(2,6,6-三甲基 - 环己-2-烯基) - 戊-1-烯-4-炔衍生物(IIe)与1,3-丁二烯衍生物H 2 C-C(CH 3)CCH-CHOR 4(III)在路易斯或布朗斯台德酸存在下反应, 情况[(IVa),(IVb),(IVc),(IVd)或(IVe)]分解为碱性或酸性条件以从其中除去部分R 2 H,从而根据直接前体产生视网膜本身或特定 衍生物[(I'),(I“),(Va)或(Vb)],并且在两种情况下,以三键[衍生物(Va)或(Vb)]为特征的衍生物, 这产生视网膜(I)或 衍生物(I'),以及衍生物(I')或(I“)的每种情况,在碱性或酸性条件下或在金属催化剂存在下使其异构化为所需的视网膜(I )。 如此产生的视网膜通常为异构体混合物的形式,通常为(9E / Z,13E / Z) - 视网膜,并且其可以根据另外的发明方面异构化为(全E) - 视神经 通过酸性催化形成(全E) - 视黄酸与氢醌的结晶形式的加合物。 如果需要,可以通过本身已知的方法将如此获得的(全E) - 视黄醛 - 氢醌加合物转化为主要(全E)异构体形式的维生素A醇。 新型起始原料(IIa),(IIb),(IIc),(IVI)和(IIe)代表又一发明方面。 视网膜是合成其他维生素A化合物(类视黄醇)的有价值的中间体。 维生素A,特别是维生素A酒精(视黄醇)已知是促进人类福祉的有价值物质,特别是在视力,免疫系统和生长方面,因此通常用作多种维生素的组分 制剂和某些食品和饲料的添加剂。