(1E,3E)- and (1Z,3E)-4-methoxy-2-methyl-1-(phenylthio)buta-1,3-diene | 151018-34-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (1E,3E)- and (1Z,3E)-4-methoxy-2-methyl-1-(phenylthio)buta-1,3-diene
• 英文别名: (3E)-4-methoxy-2-methyl-1-(phenylthio)buta-1,3-diene
• CAS: 151018-34-7
• 化学式: C₁₂H₁₄OS
• 分子量: 206.309
• InChiKey: SPLOZZNNVMFDNC-XWQZHWJLSA-N

物化性质

• 沸点：
  306.7±34.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.84
• 重原子数：
  14.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (1E,3E)- and (1Z,3E)-4-methoxy-2-methyl-1-(phenylthio)buta-1,3-diene 在 对苯二酚 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 72.0h， 生成
  参考文献：
  名称：

  Synthesis and Cycloaddition Reactions of 1-(Arylthio)-1,3-dienes. A Combined Experimental and Theoretical Study of Bicyclic Adducts Structures

  摘要：

  A method giving simple access to various 1-(phenylthio)-4-substituted-1,3-dienes (5-10) is described. The influence of the different functionalizations introduced on the dienic systems has been tested in a set of classical [4 + 2] cycloaddition reactions. Both the endo/exo and regio selectivities have been investigated. While the endo compound is, as expected, the only or major isomer in all cases, the regio competition between sulfur and oxygen is in favor of the oxygen substituent in the case studied here, in contrast to related works. For one type of adduct, X-ray crystallographic analysis and NMR spectroscopy have been used in conjunction with ab initio and semiempirical AM1 calculations to determine the structure and conformations of products as well as the energetic pathway from the primary concave endo cycloadduct (28) to a rearranged bicyclic structure (39), The theoretical results fully support the occurrence of a photochemical [1,3] sigmatropic shift of the thiophenyl group.

  DOI：

  10.1021/jo9519120
• 作为产物：
  描述：

  (E/Z)-1,1-dimethoxy-3-methyl-4-(phenylthio)but-2-ene 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以90%的产率得到(1E,3E)- and (1Z,3E)-4-methoxy-2-methyl-1-(phenylthio)buta-1,3-diene
  参考文献：
  名称：

  在不饱和缩醛上的共轭消除：一步一步的方法来官能化1,3-二烯。

  摘要：

  γ-官能化的α，β-不饱和二甲基硬脂酸酯经过碱性处理后会被甲醇δ消除，从而以良好的收率得到1,4-二取代的1,3-二烯，在某些情况下，对新形成的双键具有高度的立体控制。

  DOI：

  10.1016/0040-4039(95)01832-3

文献信息

• The OSM (oxidation state modification) concept: Application to a new and rapid synthesis of retinoids
  作者：Lucette Duhamel、Pierre Duhamel、Jean-Erick Ancel

  DOI：10.1016/0040-4039(94)88025-5

  日期：1994.2

  The OSM (oxidation state modification) concept for the elaboration of new synthetic pathways is demonstrated for the synthesis of β-ionylidene acetaldehyde 11 and retinal 13. According to this new scheme, electrophilic addition to ω-heterosubstituted enol ethers 5 of the cationic species 9, generated from β-ionol led to aldehydic intermediates 10 which undergo easy elimination to β-ionylidene acetaldehyde

  OSM（氧化态修饰）概念用于阐述新的合成途径，已被证明可用于合成β-亚砜基乙醛11和视网膜13。根据该新方案，由β-紫罗兰醇向阳离子物种9的ω-杂取代的烯醇醚5中的亲电子加成导致醛中间体10，其易于被消除为β-紫罗兰乙醛11。类似地，经由醛16从乙烯基-β-紫罗兰醇14和二烯醇醚12获得视网膜13。
• Unexpected behavior of dienol thio ethers gives versatile access to a large set of functionalized dienes
  作者：Odile Gaonac'h、Jacques Maddaluno、Joe Chauvin、Lucette Duhamel

  DOI：10.1021/jo00012a045

  日期：1991.6
• A mild and direct oxidation of dienol thioethers into ketene dithioacetals.
  作者：Frank Freidanck、Jacques F. Maddaluno、Odile Gaonac'h、Lucette Duhamel

  DOI：10.1016/s0040-4039(00)79250-1

  日期：1993.6

  Functionalized dienol thioethers reacts with 3 eq. of thiophenol at room temperature in presence of dioxygen to give directly corresponding ketene dithioacetals in high yields.