2-methyl-2-[2-(1-hydroxycyclohexyl)ethynyl]-1,3-dithiolane | 253436-93-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-methyl-2-[2-(1-hydroxycyclohexyl)ethynyl]-1,3-dithiolane
• 英文别名: 1-[2-(2-Methyl-1,3-dithiolan-2-yl)ethynyl]cyclohexan-1-ol
• CAS: 253436-93-0
• 化学式: C₁₂H₁₈OS₂
• 分子量: 242.406
• InChiKey: GBFJZGUAYYATDF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  70.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-methyl-2-[2-(1-hydroxycyclohexyl)ethynyl]-1,3-dithiolane 在 甲基锂 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 6.75h， 生成 4-methyl-1,1-pentamethylene-5,8-dithia-1,2,3-dodecatriene
  参考文献：
  名称：

  Umpolung of Carbon−Sulfur Bonds. Novel Synthesis of Substituted Allenes from Propargylic Dithioacetals

  摘要：

  Umpolung of the carbon-sulfur bonds can be achieved by treatment of propargylic dithioacetals 1 with organocuprates. The organocopper intermediates 3 gave the corresponding allenyl thioethers 4 upon protonolysis. When alkyl halides were used, propargylic thioethers 5 were obtained exclusively. Transmetalation of organocopper intermediates 3 with ZnBr2 followed by Pd(PPh3)(4)- catalyzed coupling with vinylic or aryl halides afforded the corresponding allenyl thioethers 4. Either 4 or 5 reacted with Grignard reagents in the presence of NiCl2(dppf) to yield the corresponding allenes 9 or 10, respectively. The overall reaction can be considered to use 1 as allene-1,3-zwitterion synthons. The relative reactivities of a propargylic ether versus a propargylic dithioacetal toward an organocopper reagent were compared. The sulfur moiety apparently has higher reactivity toward the copper reagent.

  DOI：

  10.1021/jo991032b
• 作为产物：
  描述：

  环己酮 、 2-ethynyl-2-methyldithiolane 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以83%的产率得到2-methyl-2-[2-(1-hydroxycyclohexyl)ethynyl]-1,3-dithiolane
  参考文献：
  名称：

  Umpolung of Carbon−Sulfur Bonds. Novel Synthesis of Substituted Allenes from Propargylic Dithioacetals

  摘要：

  Umpolung of the carbon-sulfur bonds can be achieved by treatment of propargylic dithioacetals 1 with organocuprates. The organocopper intermediates 3 gave the corresponding allenyl thioethers 4 upon protonolysis. When alkyl halides were used, propargylic thioethers 5 were obtained exclusively. Transmetalation of organocopper intermediates 3 with ZnBr2 followed by Pd(PPh3)(4)- catalyzed coupling with vinylic or aryl halides afforded the corresponding allenyl thioethers 4. Either 4 or 5 reacted with Grignard reagents in the presence of NiCl2(dppf) to yield the corresponding allenes 9 or 10, respectively. The overall reaction can be considered to use 1 as allene-1,3-zwitterion synthons. The relative reactivities of a propargylic ether versus a propargylic dithioacetal toward an organocopper reagent were compared. The sulfur moiety apparently has higher reactivity toward the copper reagent.

  DOI：

  10.1021/jo991032b