4-phenyl-hexa-2,3-dienoic acid ethyl ester | 65359-61-7

• 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: 4-phenyl-hexa-2,3-dienoic acid ethyl ester
• 英文别名: racem.-4-Phenyl-2.3-hexadiensaeure-ethylester；Ethyl-4-phenyl-hexa-2,3-dienat；3-Ethyl-3-phenyl-1-carbethoxy-allen
• CAS: 65359-61-7
• 化学式: C₁₄H₁₆O₂
• 分子量: 216.28
• InChiKey: ZXVXMIVKVIPCKB-UHFFFAOYSA-N

物化性质

• 沸点：
  89-90 °C(Press: 0.1 Torr)
• 密度：
  0.990±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• 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：

  4-phenyl-hexa-2,3-dienoic acid ethyl ester 以 甲醇 、 乙醚 、 水 为溶剂， 生成 methyl 4-phenylhexa-2,3-dienoate
  参考文献：
  名称：

  Runge,W. et al., Justus Liebigs Annalen der Chemie, 1975, p. 1361 - 1378

  摘要：

  DOI：
• 作为产物：
  描述：

  重氮乙酸乙酯 、 2-苯基-1-丁烯-1-酮 在 5,10,15,20-tetrakis(p-chlorophenyl)porphyrin iron(III) chloride 三苯基膦 作用下， 以 甲苯 为溶剂， 以99%的产率得到4-phenyl-hexa-2,3-dienoic acid ethyl ester
  参考文献：
  名称：

  Iron Porphyrin-Catalyzed Olefination of Ketenes with Diazoacetate for the Enantioselective Synthesis of Allenes

  摘要：

  In the presence of Ph3P and catalytic Fe(TCP) Cl, ketenes could react with EDA to give allenes in high yields under neutral conditions for the first time. By employing chiral phosphine instead of PPh3, allenes could be synthesized with high enantioselectivity (93-98% ee) in good yields.

  DOI：

  10.1021/ja068642v

文献信息

• Regio- and Stereoselective Alkenylation of Allenoates with <i>gem</i>-Difluoroalkenes: Facile Access to Fluorinated 1,4-Enynes Bearing an All-Carbon Quaternary Center
  作者：Qi-Qi Zhang、Shi-Yong Chen、E Lin、Honggen Wang、Qingjiang Li

  DOI：10.1021/acs.orglett.9b00775

  日期：2019.5.3

  A regio- and stereoselective synthesis of fluorinated 1,4-enynes bearing an all-carbon quaternary center at the propargylic position is developed. The synthesis starts from readily available allenoates and gem-difluoroalkenes and proceeds via a key alkynylenolate intermediate following a nucleophilic addition/β-F elimination. This reaction occurs under mild reaction conditions with good tolerance to

  开发了在炔丙基位置带有全碳四元中心的氟化1,4-烯炔的区域和立体选择性合成。从容易获得的联烯酸酯和合成启动宝石-difluoroalkenes并且进行经由键alkynylenolate中间以下的亲核加成/β-F的消除。该反应在对各种官能团具有良好耐受性的温和反应条件下发生。产品的进一步转化证明了合成的效用。此外，该反应还可以通过使用3，3-二取代的脲基酸酯而应用于α-烯基脲基酸酯的合成。
• Study on the selectivity in the electrophilic monofluorination of 2,3-allenoates with Selectfluor™: an efficient synthesis of 4-fluoro-2(5H)-furanones and 3-fluoro-4-oxo-2(E)-alkenoates
  作者：Bo Lü、Chunling Fu、Shengming Ma

  DOI：10.1039/b917793k

  日期：——

  Different from the reaction of 2,3-allenoic acids with Selectfluor™, 4-fluoro-2(5H)-furanones and (E)-3-fluoro-4-oxo-2-alkenoates were highly selectively generated from 2,4-disubstituted 2,3-allenoates with Selectfluor™ under different conditions in moderate yields. The reaction of 2,4,4-trisubstituted 2,3-allenoates afforded the corresponding 4-fluoro-2(5H)-furanones highly selectively with up to 95% yield under different conditions. The scope of the substrates has been carefully explored. Due to the more readily availability of 2,3-allenoates as compared to 2,3-allenoic acids, new 4-fluoro-2(5H)-furanones were prepared. Based on the isolation and characterization of the minor fluorohydroxylation product E-5m, a mechanism has been proposed.

  与2,3-烯酸与Selectfluor™反应不同，在不同条件下，2,4-取代的2,3-烯酸酯与Selectfluor™反应，能够高选择性地生成4-氟-2(5H)-呋喃酮和(E)-3-氟-4-氧代-2-烯酸酯，产率适中。2,4,4-三取代的2,3-烯酸酯的反应在不同条件下高选择性地生成相应的4-氟-2(5H)-呋喃酮，产率高达95%。对底物的范围进行了仔细探讨。由于与2,3-烯酸相比，2,3-烯酸酯更易获得，因此合成了新的4-氟-2(5H)-呋喃酮。基于小量氟羟基化产物E-5m的分离和表征，提出了一种机制。
• Thermodynamically Favored Aldol Reaction of Propargyl or Allenyl Esters: Regioselective Synthesis of Carbinol Allenoates
  作者：Bo Xu、Gerald B. Hammond

  DOI：10.1002/anie.200704221

  日期：2008.1.11
• Kresze,G. et al., Justus Liebigs Annalen der Chemie, 1972, vol. 756, p. 112 - 127
  作者：Kresze,G. et al.

  DOI：——

  日期：——
• Iron Porphyrin-Catalyzed Olefination of Ketenes with Diazoacetate for the Enantioselective Synthesis of Allenes
  作者：Chuan-Ying Li、Xiao-Bing Wang、Xiu-Li Sun、Yong Tang、Jun-Cheng Zheng、Zheng-Hu Xu、Yong-Gui Zhou、Li-Xin Dai

  DOI：10.1021/ja068642v

  日期：2007.2.1

  In the presence of Ph3P and catalytic Fe(TCP) Cl, ketenes could react with EDA to give allenes in high yields under neutral conditions for the first time. By employing chiral phosphine instead of PPh3, allenes could be synthesized with high enantioselectivity (93-98% ee) in good yields.