methyl 3-benzylidene butyrate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl 3-benzylidene butyrate
• 英文别名: Methyl 3-methyl-4-phenylbut-3-enoate
• 化学式: C₁₂H₁₄O₂
• 分子量: 190.242
• InChiKey: IDMASOHBCKDHHK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  溴甲苯 在 盐酸 、 正丁基锂 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 methyl 3-benzylidene butyrate
  参考文献：
  名称：

  Lithium 3-Lithio-3-tosylalkanoates: .beta.-Acylvinyl Anion Equivalents of .beta.-Lithiated .alpha.,.beta.-Unsaturated Carboxylic Acids

  摘要：

  The dilithiation of beta-tosylated propanoic, 2-methylpropanoic, and butanoic acid 10 with n-butyllithium at -78 degrees C leads to the corresponding lithium 3-lithio-3-tosylalkanoates 11. They react with different electrophilic reagents (deuterium oxide, iodine, trimethylchlorosilane, alkyl halides, and acyl chlorides) to give the corresponding 3-substituted tosylated alkanoic acids 12. When carbonyl compounds are allowed to react with intermediates 11 followed by in situ lactonization with trifluoracetic anhydride and base-promoted elimination alpha,beta-butenolides are obtained. This methodology is applied to the direct synthesis of the rosefuran lactone precursor 14cg, the O-benzyl derivative of (+/-)-umbelactone (14ch), and (+/-)-andirolactone (14ci). The alkylation and acylation reactions of organolithium compounds 11 followed by esterification with hydrogen chloride in methanol and treatment with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) afford alpha,beta- and/or beta,gamma-unsaturated esters 17 and/or 18 and unsaturated 4-keto esters 19, respectively. The last methodology has been applied to the synthesis of the unsaturated 4-keto ester 19ae precursor of the seco acid of (+/-)-pyrenophorin (22).

  DOI：

  10.1021/jo00090a043

文献信息

• Cysteine derivatives
  申请人：Recherches Pharmaceutiques et Scientifiques

  公开号：US03950387A1

  公开（公告）日：1976-04-13

  S-substituted cysteines, alkyl esters of S-substituted cysteines and S-substituted glutathiones in which the substituent on the S atom is allyl, geranyl, cinnamyl, benzylidene-3-butyl, 1-(para-chlorophenyl)ethyl and (pyridyl-3)methyl but excluding S-allyl cysteine bring about a reduction in atheromatic deposits in the aorta of test animals as well as a reduction in hypercholesterolemia and are of low toxicity. They may be used by the conventional routes for the treatment of human atheromatic conditions and disorders of the lipid metabolism.

  S-取代半胱氨酸，S-取代半胱氨酸的烷基酯和S-取代谷胱甘肽中，S原子上的取代基为烯丙基，戊二烯基，桂皮基，苄基亚甲基-3-丁基，1-(对氯苯基)乙基和(吡啶-3)甲基，但不包括S-烯丙基半胱氨酸，在实验动物的主动脉中减少动脉粥样硬化沉积物，减少高胆固醇血症，并且毒性低。它们可以通过常规途径用于治疗人类动脉粥样硬化病症和脂质代谢紊乱。
• Lithium 3-Lithio-3-tosylalkanoates: .beta.-Acylvinyl Anion Equivalents of .beta.-Lithiated .alpha.,.beta.-Unsaturated Carboxylic Acids
  作者：Pedro Bonete、Carmen Najera

  DOI：10.1021/jo00090a043

  日期：1994.6

  The dilithiation of beta-tosylated propanoic, 2-methylpropanoic, and butanoic acid 10 with n-butyllithium at -78 degrees C leads to the corresponding lithium 3-lithio-3-tosylalkanoates 11. They react with different electrophilic reagents (deuterium oxide, iodine, trimethylchlorosilane, alkyl halides, and acyl chlorides) to give the corresponding 3-substituted tosylated alkanoic acids 12. When carbonyl compounds are allowed to react with intermediates 11 followed by in situ lactonization with trifluoracetic anhydride and base-promoted elimination alpha,beta-butenolides are obtained. This methodology is applied to the direct synthesis of the rosefuran lactone precursor 14cg, the O-benzyl derivative of (+/-)-umbelactone (14ch), and (+/-)-andirolactone (14ci). The alkylation and acylation reactions of organolithium compounds 11 followed by esterification with hydrogen chloride in methanol and treatment with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) afford alpha,beta- and/or beta,gamma-unsaturated esters 17 and/or 18 and unsaturated 4-keto esters 19, respectively. The last methodology has been applied to the synthesis of the unsaturated 4-keto ester 19ae precursor of the seco acid of (+/-)-pyrenophorin (22).