3,5,6-trimethyl-2-phytylhydroquinone | 74515-24-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 3,5,6-trimethyl-2-phytylhydroquinone
• 英文别名: 2,3,5-trimethyl-6-[(E)-3,7,11,15-tetramethylhexadec-2-enyl]benzene-1,4-diol
• CAS: 74515-24-5；85353-80-6
• 化学式: C₂₉H₅₀O₂
• 分子量: 430.715
• InChiKey: OFEQNCKDGRVQKM-PTGBLXJZSA-N

物化性质

• 沸点：
  544.2±45.0 °C(Predicted)
• 密度：
  0.937±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11.4
• 重原子数：
  31
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,5,6-trimethyl-2-phytylhydroquinone 在 吡啶 、 三氯氧磷 作用下， 以1.08 g的产率得到3,5,6-trimethyl-2-phytylhydroquinone 1,4-diphosphate
  参考文献：
  名称：

  Byzova, V. N.; Zakharova, E. I.; Zhukova, E. E., Journal of Organic Chemistry USSR (English Translation), 1988, vol. 24, # 11, p. 2135 - 2140

  摘要：

  DOI：
• 作为产物：
  描述：

  4-羟基-2,3,6-三甲基乙酸苯酯 在 Lindlar's catalyst 、 aluminosilicate ASHNTS-3 氢氧化钾 、 air 、 氢气 作用下， 以 吡啶 为溶剂， 反应 2.0h， 生成 3,5,6-trimethyl-2-phytylhydroquinone
  参考文献：
  名称：

  Byzova, V. N.; Zakharova, E. I.; Zhukova, E. E., Journal of Organic Chemistry USSR (English Translation), 1988, vol. 24, # 11, p. 2135 - 2140

  摘要：

  DOI：

文献信息

• Tocopherols, tocotrienols, other chroman and side chain derivatives and uses thereof
  申请人：——

  公开号：US20020107207A1

  公开（公告）日：2002-08-08

  The present invention provides an antiproliferative compound having a structural formula 1 where X and Y independently are oxygen, nitrogen or sulfur; R 1 is alkyl, alkenyl, alkynyl, aryl, heteroaryl, carboxylic acid, carboxylate, carboxamide, ester, thioamide, thiolacid, thiolester, saccharide, alkoxy-linked saccharide, amine, sulfonate, sulfate, phosphate, alcohol, ethers or nitrites; R 2 and R 3 are hydrogen or R 4 ; R 4 is methyl, benzyl carboxylic acid, benzyl carboxylate, benzyl carboxamide, benzylester, saccharide or amine; and R 5 is alkenyl; where when Y is nitrogen, said nitrogen is substituted with R 6 , wherein R 6 is hydrogen or methyl. Also provided are methods for treating a cell proliferative disease and for inducing apoptosis in a cell comprising administering this compound is also provided.

  本发明提供了一种具有结构式1的抗增殖化合物，其中X和Y独立地是氧、氮或硫；R1是烷基、烯基、炔基、芳基、杂环芳基、羧酸、羧酸盐、羧酰胺、酯、硫代酰胺、硫酸、硫酸酯、糖苷、烷氧基连接的糖苷、胺、磺酸盐、硫酸盐、磷酸盐、醇、醚或亚硝酸盐；R2和R3是氢或R4；R4是甲基、苄基羧酸、苄基羧酸盐、苄基羧酰胺、苄基酯、糖苷或胺；R5是烯基；其中当Y为氮时，所述氮被R6取代，其中R6是氢或甲基。还提供了治疗细胞增殖性疾病和诱导细胞凋亡的方法，包括给予该化合物。
• [EN] MANUFACTURE OF TOCOPHERYL ACETATE<br/>[FR] FABRICATION D'ACETATE DE TOCOPHERYLE
  申请人：DSM IP ASSETS BV

  公开号：WO2004046126A1

  公开（公告）日：2004-06-03

  A process for the manufacture of 3-phytyl-2,5,6-trimethylhydroquinone-l-acetate, and optionally therefrom tocopheryl acetate, comprises either C-alkylating 2,3,6-trimethylhydroquinone-l-acetate with isophytol or phytol in the presence of a sulphur(VI) containing catalyst of the formulaR1SO2OH, wherein Rl signifies hydroxy, halogen, lower alkyl, halogenated lower alkyl or aryl, in an aprotic organic solvent, or O-alkylating 2,3,6-trimethylhydroquinone-l-acetate with a phytyl halide in a polar aprotic organic solvent in the presence of a base, and subjecting the so-obtained 4-O-phytyl-2,3,6-trimethylhydroquinone-l-acetate to a rearrangement reaction, and in each case optionally submitting the so-obtained 3-phytyl-2,5,6-trimethylhydroquinone-l-acetate to a ring closure reaction to produce tocopheryl acetate. The invention also includes the novel compound 3-phytyl-2,5,6-trimethylhydroquinone-l-acetate and certain stereoisomers thereof, and also the further novel compound 4-hydroxy-2,3,6-trimethyl-5-[3-(4,8,12-trimethyltridecyl)-but-3enyl]phenyl acetate which itself is one of several isomers of 3-phytyl-2,5,6- trimethylhydroquinone-l-acetate formed by isomerization under the influence of heating, e.g. during its distillation as part of the isolation and purification procedure following its manufacture as indicated above. (All-rac)-α -tocopherol, which may be derived from its acetate, is known to be the most active industrially important member of the vitamin E group.

  一种制备3-辅酰基-2,5,6-三甲基对羟基苯甲酸-1-乙酸酯的工艺，以及可选择性地由此制备生育酚乙酸酯，包括将2,3,6-三甲基对羟基苯甲酸-1-乙酸酯在含有符合R1SO2OH式的硫(VI)催化剂的无极性有机溶剂中与异生育醇或生育醇进行C-烷基化，其中R1表示羟基、卤素、低烷基、卤代低烷基或芳基，或者在极性无极性有机溶剂中，在碱的存在下，将2,3,6-三甲基对羟基苯甲酸-1-乙酸酯与生育醇卤化物进行O-烷基化，并将所得的4-O-生育醇-2,3,6-三甲基对羟基苯甲酸-1-乙酸酯进行重排反应，然后可选择性地将所得的3-辅酰基-2,5,6-三甲基对羟基苯甲酸-1-乙酸酯进行环闭合反应以产生生育酚乙酸酯。该发明还包括新型化合物3-辅酰基-2,5,6-三甲基对羟基苯甲酸-1-乙酸酯及其某些立体异构体，以及进一步的新型化合物4-羟基-2,3,6-三甲基-5-[3-(4,8,12-三甲基十三烷基)-丁-3-烯基]苯乙酸酯，它本身是在受热影响下异构化形成的3-辅酰基-2,5,6-三甲基对羟基苯甲酸-1-乙酸酯的若干异构体之一，例如在其作为随后其制备过程中的分离和纯化过程的一部分的蒸馏过程中。从其乙酸酯中提取的(全反)-α-生育醇被认为是维生素E类中最活跃的工业重要成员。
• [EN] PROCESS FOR THE MANUFACTURE OF alpha-TOCOPHERYL ACETATE<br/>[FR] PROCESSUS DE FABRICATION D'ACETATE TOCOPHERYLE
  申请人：DSM IP ASSETS BV

  公开号：WO2004063182A1

  公开（公告）日：2004-07-29

  The present invention is concerned with a novel process for the manufacture of α-tocopheryl acetate which comprises reacting 2,3,6-trimethylhydroquinone-1-acetate with a compound selected from the group consisting of phytol (formula IV with R = OH), iso-phytol (formula III with R = OH), and (iso) phytol derivatives represented by the following formulae III and IV with R = C2-to C5-alkonoyloxy, benzoyloxy, mesyloxy, benzenesul-fonyloxy or tosyloxy, (IV) in the presence of a catalyst of the formula Mn+(R1SO3-)n, wherein Mn+ is a silver, copper, gallium, hafnium or rare earth metal cation, n is the valence of the cation Mn+, and R1 is fluorine, C1-8-perfluoroalkyl or perfluoroaryl, and, if required, cyclizing any 3-phytyl-2,5,6-trimethylhydroquinone-1-acetate or a double bond isomer thereof obtained as an intermediate reaction product, to produce α-tocopheryl acetate. In the catalyst Mn+ is preferably Ag+, Cu+, Ga3+, Sc3+, Lu3+, Ho3+, Tm3+, Yb3+ or Hf4+.

  本发明涉及一种用于制备α-生育酚醋酸酯的新型工艺，包括将2,3,6-三甲基对羟基苯甲酸醋酯与从植物醇（式IV，其中R = OH）、异植物醇（式III，其中R = OH）或以下式III和IV（其中R = C2至C5-烷酰氧基，苯甲酰氧基，甲磺氧基，苯基磺酰氧基或对甲苯基磺酰氧基）所表示的（异）植物醇衍生物中选择的一种化合物反应，催化剂为式Mn+（R1SO3-）n，其中Mn+是银、铜、镓、铪或稀土金属阳离子，n是阳离子Mn+的化合价，R1是氟、C1-8全氟烷基或全氟芳基，如有必要，将作为中间反应产物获得的任何3-植醇-2,5,6-三甲基对羟基苯甲酸醋酯或其双键异构体环化，以制备α-生育酚醋酸酯。在催化剂Mn+中，优选Ag+，Cu+，Ga3+，Sc3+，Lu3+，Ho3+，Tm3+，Yb3+或Hf4+。
• Isolation and identification of intermediate compounds in the synthesis of dl-α-tocopherol
  作者：M. B. Tarabrin、V. S. Konyaeva、É. Yu. Bulychev、I. K. Sarycheva、R. P. Evstigneeva

  DOI：10.1007/bf00762063

  日期：1982.5

  requirement for vitamin E and the scarceness of its reserves in natural resources has initiated investigations into the area of making dl-~-tocopherol (I) and its homologs possessing similar properties. Compound (I) was synthesized for the first time by Karrer and coworkers [I] from trimethyl-p-hydroquinone (II) and phytyl bromide in the presence of various acidic catalysts and in various solvents [2]. Up

  对维生素 E 日益增长的需求及其在自然资源中的稀缺性已开始对制造 dl-~-生育酚 (I) 及其具有类似特性的同系物进行研究。Karrer 及其同事 [I] 首次在各种酸性催化剂存在下和各种溶剂中，由三甲基对氢醌 (II) 和植基溴合成化合物 (I) [2]。到目前为止，缩合机制的问题一直存在争议。根据缩合条件，该过程可以通过 C-烷基化 [3] 或通过形成 O 烷基醚 [4] 进行。然而，上述研究的作者没有提出中间产物的形成（分离的复合物除外）以及反应机理的证据。
• Process for the manufacture of chroman derivatives, especially alpha-tocopherol and alkanoates thereof
  申请人：Bonrath Werner

  公开号：US20050277777A1

  公开（公告）日：2005-12-15

  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-1-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.

  本发明涉及一种制备类似α-生育酚（TCP）和其烷酸酯，特别是α-生育酚醋酸酯（TCPA）的新型过程，其中所述过程的至少一步在Lewis酸或Lewis酸与Bronsted酸的混合物存在下，在压力下进行，优选在至少1.1巴的绝对压力下进行。用于制备TCP及其烷酸酯的起始材料可以是2,3,5-三甲基对苯二酚（TMHQ）或2,3,6-三甲基对苯二酚-1-烷酸酯（TMHQA）的混合物和从菲醇（pH）、异菲醇（IP）和（异）菲醇衍生物或2-菲基-3,5,6-三甲基-对苯二酚（PTMHQ）/3-菲基-2,5,6-三甲基对苯二酚-1-烷酸酯（PTMHQA）和/或其异构体中选择的化合物。适用的Lewis酸包括铟（III）盐和钪（III）盐。适用的酸混合物包括铁/二氯化亚铁/氯化氢和锌（II）氯化物/氯化氢。