Ethyl 2-ethoxy-4-methyl-1,3-cyclopentadiene-1-carboxylate | 136848-46-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 乙烯酯类
• 英文名称: Ethyl 2-ethoxy-4-methyl-1,3-cyclopentadiene-1-carboxylate
• 英文别名: ethyl 2-ethoxy-4-methylcyclopenta-1,3-diene-1-carboxylate
• CAS: 136848-46-9
• 化学式: C₁₁H₁₆O₃
• 分子量: 196.246
• InChiKey: PEUBHOLTAFOUFV-UHFFFAOYSA-N

物化性质

• 沸点：
  296.7±40.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Ethyl 2-ethoxy-4-methyl-1,3-cyclopentadiene-1-carboxylate 在 盐酸 作用下， 以 氯仿 为溶剂， 以91%的产率得到Ethyl 4-methyl-2-oxo-3-cyclopentene-1-carboxylate
  参考文献：
  名称：

  亚丙基三苯基膦和α-卤代羰基化合物的环戊烯酮

  摘要：

  亚烷基三苯基磷烷3与α-卤代酮和α-卤代硫代酯反应，在碱的存在下，通过[3 + 2]环化过程得到2-乙氧基环戊二烯。2-乙氧基环戊二烯的弱酸处理为环戊烯酮提供了一条新途径。

  DOI：

  10.1016/0040-4039(91)80029-6
• 作为产物：
  描述：

  ethyl (E)-4-[bromo(triphenyl)-λ5-phosphanyl]-3-ethoxybut-2-enoate 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 生成 Ethyl 2-ethoxy-4-methyl-1,3-cyclopentadiene-1-carboxylate
  参考文献：
  名称：

  亚丙基三苯基膦和α-卤代羰基化合物的环戊烯酮

  摘要：

  亚烷基三苯基磷烷3与α-卤代酮和α-卤代硫代酯反应，在碱的存在下，通过[3 + 2]环化过程得到2-乙氧基环戊二烯。2-乙氧基环戊二烯的弱酸处理为环戊烯酮提供了一条新途径。

  DOI：

  10.1016/0040-4039(91)80029-6

文献信息

• Functionalized cyclopentadienyl rhodium(iii) bipyridine complexes: synthesis, characterization, and catalytic application in hydrogenation of ketones
  作者：Wan-Hui Wang、Yuki Suna、Yuichiro Himeda、James T. Muckerman、Etsuko Fujita

  DOI：10.1039/c3dt50445j

  日期：——

  A series of highly functionalized cyclopentadienyl rhodium(III) complexes, [Cp′Rh(bpy)Br](ClO4) (Cp′ = substituted cyclopentadienyl), was synthesized from various multi-substituted cyclopentadienes (Cp′H). [Rh(cod)Cl]2 and Cp′H were firstly converted to [Cp′Rh(cod)] complexes, which were then treated with Br2 to give the rhodium(III) dibromides [Cp′RhBr2]2. The novel complexes [Cp′Rh(bpy)Br](ClO4) were obtained readily by the reaction of 2,2′-bipyridine with [Cp′RhBr2]2. These rhodium complexes [Cp′Rh(bpy)Br](ClO4) were fully characterized and utilized in the hydrogenation of cyclohexanone and acetophenone with generally high yields, but they did not exhibit the same reactivity trends for the two substrate ketones. The different activity of these complexes for the different substrates may be due to the influence of the substituents on the Cp′ rings.

  以多种多取代环戊二烯（Cp′H）为原料，合成了一系列高功能化环戊二烯铑（III）络合物[Cp′Rh(mby)Br](ClO4)（Cp′=取代环戊二烯基）。首先将[Rh(cod)Cl]2 和 Cp′H 转化为[Cp′Rh(cod)]配合物，然后用 Br2 处理，得到铑（III）二溴化物[Cp′RhBr2]2。2,2′-联吡啶与[Cp′RhBr2]2反应，很容易得到新型络合物[Cp′Rh(bpy)Br]( )。这些铑络合物[Cp′Rh(bpy)Br]( )得到了充分表征，并被用于环己酮和苯乙酮的氢化反应，产量普遍较高，但它们对两种底物酮的反应趋势并不相同。这些配合物对不同底物的不同活性可能是由于 Cp′环上取代基的影响。
• Allylidenetriphenylphosphorane as a bifunctional reagent: synthesis of cyclopentenones and .alpha.,.beta.-unsaturated ketones with [3-(alkoxycarbonyl)-2-ethoxy-2-propenylidene]triphenylphosphorane
  作者：Minoru Hatanaka、Yuichiro Himeda、Ritsuo Imashiro、Yasuhiro Tanaka、Ikuo Ueda

  DOI：10.1021/jo00080a019

  日期：1994.1

  When (3-(ethoxycarbonyl)-2-ethoxy-2-propenylidene) triphenylphosphorane (6) was allowed to react with cu-bromo ketones 8a-d in dichloromethane in the presence of Cs2CO3 at room temperature, a [3 + 2] annulation occurred and led to the formation of the corresponding 2-ethoxycyclopentadienes 9a-d in excellent yields. Similarly, bromo thioester 8g underwent the annulation to give 4-(ethylthio)-cyclopentadiene 9g. Secondary bromides 2-bromo-3-pentanone and 2-bromocyclohexanone also afforded tetrasubstituted cyclopentadienes 9e and 9f in moderate yields when 2 equiv of 6 was used. The annulation is believed to proceed through a sequence involving a stepwise alkylation at the gamma position of 6 and an intramolecular Wittig reaction because of the fact that intermediate 11 was isolated. The resulting 2-ethoxycyclopentadienes 9a-g were converted quantitatively into the corresponding cyclopentenones 10a-g upon mild acid treatment. Furthermore, allylidenetriphenylphosphorane underwent a carbon elongation at both ends of the three-carbon unit via an alkylation-Wittig reaction sequence. (3-(tert-Butoxycarbonyl)-2-ethoxy-2-propenylidene)triphenylphosphorane (7) reacted first with alkyl halides and then with aldehydes in the presence of Cs2CO3 to give enol ethers 23a-f, which were converted into alpha,beta-unsaturated ketones 20, 21, and 25c-f by hydrolysis of the enol ether and then decarboxylation. In this way, shogaol (29), the pungent principle component of ginger, was conveniently synthesized starting from 2-methoxy-4-methylphenol.