2-(6-methylthiohexyl)-3-methyl-2-cyclohexenone | 148043-33-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(6-methylthiohexyl)-3-methyl-2-cyclohexenone
• 英文别名: 3-methyl-2-(6-methylsulfanylhexyl)cyclohex-2-en-1-one
• CAS: 148043-33-8
• 化学式: C₁₄H₂₄OS
• 分子量: 240.41
• InChiKey: CRMOEGHYXMXXMX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.37
• 重原子数：
  16.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2-(6-methylthiohexyl)-3-methyl-2-cyclohexenone 在 吡啶 、 lithium aluminium deuteride 作用下， 以 乙醚 为溶剂， 生成 1-deuterio-2-(6-methylthiohexyl)-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：

  2-甲基-4-羰基-2-环己烯-1-羧酸乙酯 在 氢氧化钾 、 sodium hydride 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 生成 2-(6-methylthiohexyl)-3-methyl-2-cyclohexenone
  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