ethyl (2E,4E)-5-chloropenta-2,4-diene-1-carboxylate | 24338-73-6

• 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: ethyl (2E,4E)-5-chloropenta-2,4-diene-1-carboxylate
• 英文别名: (2E,4E)-5-chloropenta-2,4-dienoate；ethyl-(2E,4E)-5-chloropenta-2,4-dienoate；5-Chlor-penta-trans-2-trans-4-diensaeureethylester；Ethyl (2e,4e)-5-chloro-penta-2,4-dienoate；ethyl (2E,4E)-5-chloropenta-2,4-dienoate
• CAS: 24338-73-6
• 化学式: C₇H₉ClO₂
• 分子量: 160.6
• InChiKey: WSVRCQBEWAVNQQ-GGWOSOGESA-N

物化性质

• 沸点：
  209.3±23.0 °C(Predicted)
• 密度：
  1.098±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.29
• 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 (2E,4E)-5-chloropenta-2,4-diene-1-carboxylate 、 正戊基溴化镁 在 iron(III)-acetylacetonate 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以78%的产率得到ethyl 2E,4E-decadienoate
  参考文献：
  名称：

  Iron-Catalyzed Synthesis of Sarmentine

  摘要：

  DOI：

  10.1134/s1070428021060178
• 作为产物：
  描述：

  (2E)-5-chloro-5-ethoxypenta-2,4-dienal 以 氘代氯仿 为溶剂， 反应 480.0h， 以50%的产率得到ethyl (2E,4E)-5-chloropenta-2,4-diene-1-carboxylate
  参考文献：
  名称：

  摘要：

  Contrary to the rearrangement of 3-amino-3-X-prop-2-enals 2 (R = H),which easily give 3-X-prop-2-enamides 3 at low temperature, the postulated rearrangement (Scheme 1) of the vinylogous 5-amino-5-X-penta-2,4-dienals 6(R = H)normally stops at the level of 2-aminopyrylium salts 7. The main reason is that the charge in salts of type 7 is highly delocalized, leading to low-energy species, which make addition of weak nucleophiles difficult. In this paper, two concepts for increasing the chances of the 'aminopentadienal rearrangement' 6 --> -->, 8 are presented and substantiated by typical experiments. On one side, the easily available 2-aminopyrylium chlorides 7 (X = Cl) are reacted with a twofold excess of secondary amines (Scheme 2) to give 5-(dialkylamino)penta-2,4-dienamides of type 9 and 10. On the other hand, after replacing the amino groups of 6 by PhO and EtO groups the corresponding 5-chloro-5-phenoxy-(13b) and 5-chloro-5-ethoxypenta-2,4-dienals (13a) easily rearrange at low temperature to give 5-chlorapenta-2,4-diene-1-carboxylates 18a and 18b, respectively, which are now obviously lower in energy than the corresponding pyrylium-salt intermediates 16 (Scheme 4).

  DOI：

  10.1002/1522-2675(20000607)83:6<1182::aid-hlca1182>3.0.co;2-t

文献信息

• Oxygenated dienes and the synthesis of methylenedioxybiphenyl derivatives
  作者：E.J.J. Grabowski、R.L. Autrey

  DOI：10.1016/s0040-4020(01)82970-7

  日期：1969.1

  function in a tetrahydrophthalic acid derivative was achieved, allowing esterification of the other and removal of the first in an oxidative decarboxylation. The oxidative decarboxylation was brought about by 2,3-dichloro-5,6-dicyanobenzoquinone, a novel reaction for quinones. The combination of these reactions allowed selective syntheses of 2- and 3-piperonylbenzoic acids (17 and 19) and their ethyl esters

  新二烯酸酯和三烯酸酯5，8，9和10中描述。由Wittig反应的两个标准变体制备它们导致效用的罕见逆转，因为磷烷方法证明比膦酸根阴离子方法好得多。新的二烯酸酯酯8和10以及相关的二烯醛衍生物3和4的反应性探索了几种亲双烯体。通过卤代内酯化反应，实现了对四氢邻苯二甲酸衍生物中一个羧基官能团的选择性保护，从而允许另一个酯化并在氧化脱羧中去除了第一个羧基。氧化脱羧是由2,3-二氯-5,6-二氰基苯并醌引起的，这是一种新颖的醌反应。这些反应的结合使得可以选择性合成2-和3-哌啶基苯甲酸（17和19）及其乙酯（18和20）以及母体3,4-亚甲基二氧基联苯（16），讨论了许多这类化合物的NMR光谱，因为它们阐明了桥连卤代内酯所期望的刚性构象。
• Synthesis of ethyl (2E,4E)- and (2E,4Z)-5-chloropenta-2,4-dienoates
  作者：R. N. Shakhmaev、A. Sh. Sunagatullina、D. A. Akimova、V. V. Zorin

  DOI：10.1134/s1070428017040194

  日期：2017.4

  An efficient synthetic approach to 2E,4E and 2E,4Z isomers of ethyl 5-chloropenta-2,4-dienoate has been developed on the basis of one-pot oxidation–olefination of readily accessible (E)- and (Z)-3-chloroprop-2-en-1-ols by the action of barium manganate and ethyl (triphenyl-λ5-phosphanylidene)acetate.

  一种有效的合成方法是在易于获得的（E）和（E）的一锅氧化-烯烃化的基础上，开发出5-氯戊2,4-二烯酸乙酯的2 E，4 E和2 E，4 Z异构体。ž）-3-氯丙-2-烯-1-醇由锰酸钡和乙基（三苯基-λ的动作5 -phosphanylidene）乙酸乙酯。
• Iron-Catalyzed Synthesis of Sarmentine
  作者：R. N. Shakhmaev、M. G. Ignatishina、V. V. Zorin

  DOI：10.1134/s1070428021060178

  日期：2021.6
• ——
  作者：Christian Bacilieri、Stefanie Reic、Markus Neuenschwander

  DOI：10.1002/1522-2675(20000607)83:6<1182::aid-hlca1182>3.0.co;2-t

  日期：2000.6.7

  Contrary to the rearrangement of 3-amino-3-X-prop-2-enals 2 (R = H),which easily give 3-X-prop-2-enamides 3 at low temperature, the postulated rearrangement (Scheme 1) of the vinylogous 5-amino-5-X-penta-2,4-dienals 6(R = H)normally stops at the level of 2-aminopyrylium salts 7. The main reason is that the charge in salts of type 7 is highly delocalized, leading to low-energy species, which make addition of weak nucleophiles difficult. In this paper, two concepts for increasing the chances of the 'aminopentadienal rearrangement' 6 --> -->, 8 are presented and substantiated by typical experiments. On one side, the easily available 2-aminopyrylium chlorides 7 (X = Cl) are reacted with a twofold excess of secondary amines (Scheme 2) to give 5-(dialkylamino)penta-2,4-dienamides of type 9 and 10. On the other hand, after replacing the amino groups of 6 by PhO and EtO groups the corresponding 5-chloro-5-phenoxy-(13b) and 5-chloro-5-ethoxypenta-2,4-dienals (13a) easily rearrange at low temperature to give 5-chlorapenta-2,4-diene-1-carboxylates 18a and 18b, respectively, which are now obviously lower in energy than the corresponding pyrylium-salt intermediates 16 (Scheme 4).