ethyl 13-desmethylretinoate | 60347-68-4

• 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: ethyl 13-desmethylretinoate
• 英文别名: ethyl all-E-13-demethylretinoate；7-Methyl-9-(2,6,6-trimethyl-cyclohex-1-enyl)-nona-2,4,6,8-tetraen-1-carbonsaeure-ethylester；all-trans-13-Desmethyl-vitamin-A-saeureethylester；ethyl (2E,4E,6E,8E)-7-methyl-9-(2,6,6-trimethylcyclohexen-1-yl)nona-2,4,6,8-tetraenoate
• CAS: 60347-68-4
• 化学式: C₂₁H₃₀O₂
• 分子量: 314.468
• InChiKey: BNCXNZKXIXUNMU-MWGMEIKSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl 13-desmethylretinoate 在 氢氧化钾 作用下， 以 乙醇 为溶剂， 反应 3.0h， 以77%的产率得到13-demethyl all-trans-retinoic acid
  参考文献：
  名称：

  Preparation and biological activity of 13-substituted retinoic acids

  摘要：

  13-Demethyl or 13-substituted all-E- and 9Z-retinoic acids were synthesized using a palladium-catalyzed coupling reaction of enol triflates and tributylstannylolefins. Their biological activities were then measured. The 13-ethyl analogs exhibited approximately one-half of the antiproliferative and differentiation-inducing activity of ATRA in HL-60 cells. In contrast, in the 9Z-derivatives, all analogs, except for the 13-butyl derivatives, showed apoptosis-inducing activity. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2004.04.047
• 作为产物：
  描述：

  4-(1,4-二甲基-1-乙基)戊基酚 在 N,N-二甲基丙烯基脲 、 manganese(IV) oxide 、 正丁基锂 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 6.5h， 生成 ethyl 13-desmethylretinoate
  参考文献：
  名称：

  Preparation and biological activity of 13-substituted retinoic acids

  摘要：

  13-Demethyl or 13-substituted all-E- and 9Z-retinoic acids were synthesized using a palladium-catalyzed coupling reaction of enol triflates and tributylstannylolefins. Their biological activities were then measured. The 13-ethyl analogs exhibited approximately one-half of the antiproliferative and differentiation-inducing activity of ATRA in HL-60 cells. In contrast, in the 9Z-derivatives, all analogs, except for the 13-butyl derivatives, showed apoptosis-inducing activity. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2004.04.047

文献信息

• A comprehensive survey of stille-type Csp2-Csp2 single bond forming processes in the synthesis of retinoic acid and analogs
  作者：Beatriz Domínguez、Beatriz Iglesias、Angel R. de Lera

  DOI：10.1016/s0040-4020(99)00962-x

  日期：1999.12

  coupling for the formation of the side-chain single bonds. On employing the experimental catalytic conditions developed by Farina [Pd2(dba)3, AsPh3, NMP] we have modified the electronic and steric requirement of the coupling parters, alkenyl stannanes and electrophiles (alkenyl iodides and triflates). The comprehensive survey afforded appropriately matched components for every bond formation considered.

  已经使用Stille偶联详尽地研究了类维生素A骨架的合成以形成侧链单键。使用Farina [Pd 2（dba）3，AsPh 3，NMP]，我们已经修改了偶联伙伴，烯基锡烷和亲电子试剂（烯基碘化物和三氟甲磺酸酯）的电子和空间要求。全面的调查为所考虑的每种债券形成提供了适当匹配的组成部分。此外，通过比较具有不同空间位阻程度的不同偶联配偶体的反应性，证实了斯蒂勒偶联对空间效应的敏感性。除了为类维生素A合成提供了多种构建基块之外，该研究还强调了一些趋势，这些趋势对于将Stille反应应用于未取代共轭多烯的合成可能有用。
• Cross metathesis of β-carotene with electron-deficient dienes. A direct route to retinoids
  作者：Agnieszka Wojtkielewicz、Jadwiga Maj、Jacek W. Morzycki

  DOI：10.1016/j.tetlet.2009.06.032

  日期：2009.8

  Cross metathesis (CM) reactions of beta-carotene and alkenes occur regioselectively in the presence of the Hoveyda second generation catalyst. Scission of the C15-C15' and C11-C12 bonds of P-carotene in all CM reactions predominates. The reaction with ethyl (2E,4E/Z)-3-methylhexa-2,4-dienoate is both regio and diastereoselective, and affords ethyl all-trans-retinoate as the major product, if suitable CM conditions are applied. (C) 2009 Elsevier Ltd. All rights reserved.
• Preparation and biological activity of 13-substituted retinoic acids
  作者：Akimori Wada、Kouki Fukunaga、Masayoshi Ito、Yukari Mizuguchi、Kimie Nakagawa、Toshio Okano

  DOI：10.1016/j.bmc.2004.04.047

  日期：2004.7

  13-Demethyl or 13-substituted all-E- and 9Z-retinoic acids were synthesized using a palladium-catalyzed coupling reaction of enol triflates and tributylstannylolefins. Their biological activities were then measured. The 13-ethyl analogs exhibited approximately one-half of the antiproliferative and differentiation-inducing activity of ATRA in HL-60 cells. In contrast, in the 9Z-derivatives, all analogs, except for the 13-butyl derivatives, showed apoptosis-inducing activity. (C) 2004 Elsevier Ltd. All rights reserved.