(1E,3E)-4--2-methyl-1-(phenylthio)buta-1,3-diene | 142351-24-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1E,3E)-4--2-methyl-1-(phenylthio)buta-1,3-diene
• 英文别名: [(1E,3E)-2-methyl-4-[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]oxybuta-1,3-dienyl]sulfanylbenzene
• CAS: 142351-24-4
• 化学式: C₂₁H₃₀OS
• 分子量: 330.535
• InChiKey: IDQNZBJZZJYBJV-XOBKOKFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  34.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  四氰基乙烯 、 (1E,3E)-4--2-methyl-1-(phenylthio)buta-1,3-diene 以 四氢呋喃 、 乙醚 为溶剂， 生成 、 (3S,6R)-4-methyl-6-[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]oxy-3-phenylsulfanylcyclohex-4-ene-1,1,2,2-tetracarbonitrile
  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)-4-bromo-1,1-dimethoxy-3-methylbut-2-ene 在 对甲苯磺酸 、 三乙胺 、 2,2-二甲氧基丙烷 作用下， 以 乙醚 为溶剂， 反应 2.0h， 生成 (1E,3E)-4--2-methyl-1-(phenylthio)buta-1,3-diene
  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

文献信息

• Synthesis and Cycloaddition Reactions of 1-(Arylthio)-1,3-dienes. A Combined Experimental and Theoretical Study of Bicyclic Adducts Structures
  作者：Jacques Maddaluno、Odile Gaonac'h、Albert Marcual、Loïc Toupet、Claude Giessner-Prettre

  DOI：10.1021/jo9519120

  日期：1996.1.1

  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.