2-(2-benzylthioethyl)-3-methyl-2-cyclohexenol | 148043-43-0

• 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-(2-benzylthioethyl)-3-methyl-2-cyclohexenol
• 英文别名: 2-(2-benzylsulfanylethyl)-3-methylcyclohex-2-en-1-ol
• CAS: 148043-43-0
• 化学式: C₁₆H₂₂OS
• 分子量: 262.416
• InChiKey: HZSAXBWWTHHYGP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.17
• 重原子数：
  18.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-(氯甲基)-4-硝基苯 、 2-(2-benzylthioethyl)-3-methyl-2-cyclohexenol 在 吡啶 作用下， 以90%的产率得到2-(2-benzylthioethyl)-3-methyl-2-cyclohexenyl p-nitrobenzoate
  参考文献：
  名称：

  A search for maximal neighboring group participation in Solvolyses of allylic substrates. Ethanolysis of 2-(ω-alkylthioalkyl)-3-methyl-2-cyclohexenyl p-nitrobenzoates

  摘要：

  The solvolysis of 2-(omega-methylthioalkyl)- and 2-(omega-benzylthioalkyl)-3-methyl-2-cyclohexenyl p-nitrobenzoates 5 and 6 in 80 vol % ethanol includes several competitive reactions. Path k1 is a stepwise process (k(H)/k(D) = 1.18-1.20) which includes allylic cation 9 as a reaction intermediate, while path k2 involves a neighboring sulfur participation (k(H)/k(D) = 1.01 - 1.03) and formation of an intermediate cyclic sulfonium cation 10. Esters 5 and 6 solvolyze in 80% EtOH with a greater neighboring group participation than in 97% TFE. IL has been concluded that in solvolytic reactions of allylic substrates a pronounced neighboring group participation (k2/k1= 900) may occur only with very strong internal nucleophiles, and in solvents which can not form strong hydrogen bonds with these nucleophiles.

  DOI：

  10.1016/s0040-4020(01)86349-3
• 作为产物：
  描述：

  3-(2-Benzylsulfanyl-ethyl)-2-methyl-4-oxo-cyclohex-2-enecarboxylic acid ethyl ester 在 氢氧化钾 、 lithium aluminium tetrahydride 作用下， 以 乙醚 、 乙醇 为溶剂， 生成 2-(2-benzylthioethyl)-3-methyl-2-cyclohexenol
  参考文献：
  名称：

  A search for maximal neighboring group participation in Solvolyses of allylic substrates. Ethanolysis of 2-(ω-alkylthioalkyl)-3-methyl-2-cyclohexenyl p-nitrobenzoates

  摘要：

  The solvolysis of 2-(omega-methylthioalkyl)- and 2-(omega-benzylthioalkyl)-3-methyl-2-cyclohexenyl p-nitrobenzoates 5 and 6 in 80 vol % ethanol includes several competitive reactions. Path k1 is a stepwise process (k(H)/k(D) = 1.18-1.20) which includes allylic cation 9 as a reaction intermediate, while path k2 involves a neighboring sulfur participation (k(H)/k(D) = 1.01 - 1.03) and formation of an intermediate cyclic sulfonium cation 10. Esters 5 and 6 solvolyze in 80% EtOH with a greater neighboring group participation than in 97% TFE. IL has been concluded that in solvolytic reactions of allylic substrates a pronounced neighboring group participation (k2/k1= 900) may occur only with very strong internal nucleophiles, and in solvents which can not form strong hydrogen bonds with these nucleophiles.

  DOI：

  10.1016/s0040-4020(01)86349-3

文献信息

• Neighboring sulfur participation in the solvolysis of 2-(ω-alkylthioalkyl)-3-methyl-2-cyclohexenyl p-nitrobenzoates
  作者：Mladen Ladika、Branko Juršić、Zlatko Mihalić、Dionis E. Sunko

  DOI：10.1016/s0040-4039(00)84352-x

  日期：1986.1

  As shown by kinetic and product analysis, the solvolysis of and in 97% TFE includes several competitive reactions, one of them being neighboring sulfur participation and formation of intermediate cyclic sulfonium cation.

  如动力学和产物分析所示，在97％的TFE中，溶剂化反应包括几个竞争反应，其中之一是邻近的硫参与和中间环sulf阳离子的形成。