(2-ethoxy-3-ethoxycarbonyl-2-propenylidene)triphenylphosphorane | 27271-28-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2-ethoxy-3-ethoxycarbonyl-2-propenylidene)triphenylphosphorane
• 英文别名: ethyl 3-ethoxy-4-(triphenylphosphoranylidene)but-2-enoate；ethyl 3-ethoxy-4-(triphenylphosphoranylidene)-2-butenoate；Ethyl 3-ethoxy-4-(triphenyl-lambda~5~-phosphanylidene)but-2-enoate；ethyl 3-ethoxy-4-(triphenyl-λ5-phosphanylidene)but-2-enoate
• CAS: 27271-28-9
• 化学式: C₂₆H₂₇O₃P
• 分子量: 418.472
• InChiKey: DYDASETXHJTSJR-UHFFFAOYSA-N

物化性质

• 熔点：
  166 °C
• 沸点：
  560.8±60.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.15
• 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：

  (2-ethoxy-3-ethoxycarbonyl-2-propenylidene)triphenylphosphorane 在 三乙烯二胺 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 4.0h， 生成 ethyl-(E)-3-((E)-9-acetyl-2-(2-(benzyloxy)-2-oxoethylidene)-2,3,4,9-tetrahydropyrano[2,3-b]indol-4-yl)-3-ethoxyacrylate
  参考文献：
  名称：

  Diverse synthesis of pyrano[2,3-b]indol and dihydropyrano[2,3-b]indol via tunable Lewis bases catalyzed domino reactions

  摘要：

  We first reported an example of diverse synthesis of pyrano[2,3-b]indol and dihydropyrano[2,3-b]indol from the same starting materials. In these domino reactions, we can control the reaction conditions to give three new products: pyrano[2,3-b]indol, dihydropyrano[2,3-b]indol with E or Z exocyclic double bond. Using DABCO as catalyst in THF, dihydropyrano[2,3-b]indol with E exocyclic double bond and pyrano[2,3-b]indol were obtained at room temperature and 65 degrees C, respectively. In contrast, when DMAP was selected as catalyst, dihydropyrano[2,3-b]indol with Z exocyclic double bond was formed in toluene at 80 degrees C. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.07.057
• 作为产物：
  描述：

  在 sodium amide 作用下， 生成 (2-ethoxy-3-ethoxycarbonyl-2-propenylidene)triphenylphosphorane
  参考文献：
  名称：

  Bestmann, Hans-Juergen; Roth, Kurt, Angewandte Chemie, 1981, vol. 93, # 6/7, p. 587 - 593

  摘要：

  DOI：

文献信息

• Condensations of Ethyl 3-Ethoxy-4-(triphenylphosphoranylidene)-2-butenoate with α,β-Unsaturated Carbonyl Compounds
  作者：Cornelis M. Moorhoff

  DOI：10.1007/s00706-002-0527-2

  日期：2002.12.1

    Wittig condensations of α,β-unsaturated carbonyl compounds with ethyl 3-ethoxy-4-(triphenylphosphoranylidene)-2-butenoate gave good to high yields of (2 E ,4 E ,6 E )-ethyl 3-ethoxy-2,4,6-alkatrienoates. Some of last mentioned compounds were almost quatitatively hydrolysed to (4 E ,6 E )-ethyl 3-oxo-4,6-alkadienoates. This method can therefore be used as an attractive alternative for the preparation

    α，β-不饱和羰基化合物与3-乙氧基-4-（三苯基正膦 亚基）-2-丁烯酸乙酯的Wittig 缩合得到良好的高产率的（2 E ，4 E ，6 E ）-乙基3-乙氧基-2,4 ，6-链烷酸。最后提到的一些化合物几乎被定量水解为（4 E ，6 E ）-3-氧代-4,6-链二烯酸乙酯。因此，该方法可以用作制备不饱和共轭β-酮酯的有吸引力的替代方法，该不饱和共轭β-酮酯以前是由α，β-不饱和羰基化合物和3-氧代-4-（三苯基正膦基）丁酸乙酯以极低的收率制备的。
• 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](ClO4)。这些铑络合物[Cp′Rh(bpy)Br](ClO4)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。
• Thermal intramolecular cycloaddition of 4-alkenylfulvene; highly regio- and diastereoselective formation of [4+2] adduct
  作者：Hiroyoshi Kitano、Shinya Fujita、Yutaka Takehara、Masakazu Hattori、Toshio Morita、Kazutsugu Matsumoto、Minoru Hatanaka

  DOI：10.1016/s0040-4020(03)00297-7

  日期：2003.4

  4-Alkenylfulvenes were prepared by the annulation of 1,4-ynediones and allylidenetriphenylphosphorane and subjected to a thermal reaction. Highly regio- and stereoselective [4+2] cycloaddition is accomplished with 4-((R)-3-benzyloxypent-4-en-1-yl)fulvene and the resulting adduct is transformed into bicyclo[3.3.0]octene derivative.

  通过将1，4-乙二酮和烯丙基二苯并苯基膦环化，制备4-烯基富烯烯，并进行热反应。高度区域和立体选择性的[4 + 2]环加成反应是通过4-（（R）-3-苄氧基戊-4-烯-1-基）富烯完成的，所得的加合物转化为双环[3.3.0]辛烯衍生物。
• A simple approach to the synthesis of ethyl 2-ethoxy-4-methoxy-6-perfluoroalkylbenzoates via acyclic precursors
  作者：Weiguo Cao、Weiyu Ding、Tian Yi、Zhongmei Zhu

  DOI：10.1016/s0022-1139(96)03508-7

  日期：1997.3

  The acyclic precursors, methyl 3-perfluoroalkyl-4-carboethoxy-5-ethoxy-6-(triphenylphosphoranylidene)hexa-2,4-dienoates 3a-c were obtained through the addition reaction of ethyl 3-ethoxy-4-(triphenylphosphoranylidene)but-2-enoate 1 with equally molar of methyl 2-perfluoroalkynoates 2a-c.Ethyl 2-ethoxy-4-methoxy-6-perfluoroalkylbenzoates 4a-c were synthesized with high yields via an intramolecular elimination

  通过乙基3-乙氧基-4-（三苯基膦基亚烷基）的加成反应获得了无环前体3-全氟烷基-4-羰基乙氧基-5-乙氧基-6-（三苯基磷亚烷基）六甲基2,4-二烯酸酯3a-c。通过与2-全氟炔酸甲酯2a-c摩尔等摩尔的-2-烯酸酯1。通过分子内消除3a-c的Ph 3 PO来高收率地合成2-乙氧基-4-甲氧基-6-全氟烷基苯甲酸酯4a -c。在密封管中在无水苯中加热。这些化合物的结构通过IR，MS，1 H，13 C和19确认F NMR光谱和元素分析。还提出了反应机理。
• Convenient Synthesis of Angular Triquinane from 4-Alkenylfulvene via Thermal Cycloaddition Followed by Skeletal Rearrangement of the Resulting [4 + 2] Adduct
  作者：Sho Inagaki、Keisuke Imura、Toshio Morita、Yasuharu Yoshimi、Minoru Hatanaka、Tomikazu Kawano

  DOI：10.1246/cl.2008.454

  日期：2008.4.5

  Alkenylfulvene prepared by the annulation of allylidenetriphenylphosphorane with 1,4-ynedione proceeded thermal cycloaddition in a highly regio- and stereoselective manner to give [4 + 2] adduct wh...

  通过烯丙基三苯基膦与 1,4-炔二酮的环化制备的烯基富烯以高度区域和立体选择性的方式进行热环加成，得到 [4 + 2] 加合物，其中...