(E)-2-ethylidene-5-methyl-hex-4-enoic acid

• 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: (E)-2-ethylidene-5-methyl-hex-4-enoic acid
• 英文别名: (E)-2-ethylidene-5-methylhex-4-enoic acid；(2E)-2-ethylidene-5-methylhex-4-enoic acid
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: AMWATUIAWSMFDT-XBXARRHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-甲基-3-丁烯-2-醇 、 2-丁烯酰氯 在 三乙胺 、 三甲基氯硅烷 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 6.0h， 生成 (E)-2-ethylidene-5-methyl-hex-4-enoic acid
  参考文献：
  名称：

  DBU-mediated Ireland–Claisen rearrangement of allyl alk-3-enoates: an efficient synthesis of 2-ethylidene-γ,δ-unsaturated carboxylic acids

  摘要：

  Ireland-Claisen rearrangement, triggered by silyl enolization of allylic but-3-enoates 2, has been developed using DBU as the base in the presence of an excess amount of TMSC1 under reflux in acetonitrile for a couple of hours. The procedure allows the synthesis of a range of 2-ethylidene-gamma,delta-unsaturated carboxylic acids 5 in moderate to high yields. It is further revealed that the rearrangement proceeds equally well with allylic (E)-hexa-3,5-dienoates 10 derived from sorbic acid under similar conditions to provide 2-allyl substituted hexa-2,4-dienoic acids 13. (c) 2007 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2007.07.031

文献信息

• Experimental and theoretical investigations for the tandem alkylation–isomerization reactions between unsaturated carboxylic acids and allyl halides
  作者：Luis R Domingo、Salvador Gil、Margarita Parra、José A Sáez、Mercedes Torres

  DOI：10.1016/s0040-4020(03)01028-7

  日期：2003.8

  Abstract—Alkylation of dienediolates from unsaturated carboxylic acids with allylic halides when followed by solventless thermaltreatment at 150 to 2008C afford rearranged products on a trend highly dependent on the acarbon substitution. Thus, 2,2-bisallylated acidswith H atoms at C-2 lead to its 1,3-shift, whereas 2-methyl-2,2-bisallylated acids lead to the corresponding Cope rearrangement product

  摘要：在 150 至 2008C 下进行无溶剂热处理时，由不饱和羧酸与烯丙基卤化物对二烯二醇进行烷基化反应，得到重排产物，其趋势高度依赖于碳取代。因此，在 C-2 上具有 H 原子的 2,2-双烯丙基酸会导致其 1,3-移位，而 2-甲基-2,2-双烯丙基酸会导致相应的 Cope 重排产物。在后一种情况下，这种串联烯丙基化-Cope 反应以高度区域和非对映选择性的方式导致直接烷基化无法获得的产物。参与这些异构化的化合物的 B3LYP/6-31G p 能量与实验有合理的一致性，可以解释在热力学平衡下形成更稳定的产物。q 2003 Elsevier Ltd. 保留所有权利。1. 引言在过去几年 1-3 报道了关于二烯二醇锂与几种亲电试剂反应的区域和立体选择性研究表明，在与初级卤化物反应时，相应烷基化产物的区域选择性很大程度上取决于亲电试剂的反应性。无论空间效应如何，饱和烷基卤化物都显示出高选择
• DBU-mediated Ireland–Claisen rearrangement of allyl alk-3-enoates: an efficient synthesis of 2-ethylidene-γ,δ-unsaturated carboxylic acids
  作者：Yunxia Li、Andreas Goeke、Ruiyao Wang、Quanrui Wang、Georg Fráter

  DOI：10.1016/j.tet.2007.07.031

  日期：2007.9

  Ireland-Claisen rearrangement, triggered by silyl enolization of allylic but-3-enoates 2, has been developed using DBU as the base in the presence of an excess amount of TMSC1 under reflux in acetonitrile for a couple of hours. The procedure allows the synthesis of a range of 2-ethylidene-gamma,delta-unsaturated carboxylic acids 5 in moderate to high yields. It is further revealed that the rearrangement proceeds equally well with allylic (E)-hexa-3,5-dienoates 10 derived from sorbic acid under similar conditions to provide 2-allyl substituted hexa-2,4-dienoic acids 13. (c) 2007 Published by Elsevier Ltd.