3,3-Dimethyl-6-(phenylthio)-4-hexenenitrile | 143706-96-1

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 3,3-Dimethyl-6-(phenylthio)-4-hexenenitrile
• 英文别名: (E)-3,3-dimethyl-6-phenylsulfanylhex-4-enenitrile
• CAS: 143706-96-1
• 化学式: C₁₄H₁₇NS
• 分子量: 231.362
• InChiKey: RRIUZBOONLJZCT-RMKNXTFCSA-N

物化性质

• 沸点：
  368.9±35.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  49.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,3-Dimethyl-6-(phenylthio)-4-hexenenitrile 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 15.0h， 以95%的产率得到(E)-6-(benzenesulfinyl)-3,3-dimethylhex-4-enenitrile
  参考文献：
  名称：

  Enantiospecific synthesis of a chrysanthemic acid precursor

  摘要：

  1,4 Addition of the lithium anion of allyl phenyl sulfide to 3,3-dimethylacrylonitrile and to methyl 3,3-dimethyl acrylate occurred at the alpha position of the carbanion. The resulting adducts 5 and 6 were converted to the allylic alcohols 1 and 9 by [2,3] sigmatropic shift of the sulfoxides, obtained by oxidation. Besides sulfoxide 7, sulfenate 13 arising from [2,3] sigmatropic shift and sulfinate 10 were detected. Alcohol 1 was epoxidized according to the Katsuki-Sharpless procedure to the (4S,5R) epoxy alcohol 17 with an ee > 94%. Its silyl ether 19 was converted to a mixture of cis and trans cyclopropylnitriles by the Stork cyclization. After removal of the silyl group and periodate cleavage, trans and cis aldehydes 24 and 25 were separated. The trans aldehyde 24 was converted to (1R,3R)-trans-chrysanthemic nitrile 26 (ee 92%).

  DOI：

  10.1021/jo00049a043
• 作为产物：
  描述：

  3,3-Dimethyl-4-(phenylthio)-5-hexenenitrile 在 甲基锂 、 二乙胺 、 对甲苯磺酰氯 、 间氯过氧苯甲酸 作用下， 反应 38.5h， 生成 3,3-Dimethyl-6-(phenylthio)-4-hexenenitrile
  参考文献：
  名称：

  Enantiospecific synthesis of a chrysanthemic acid precursor

  摘要：

  1,4 Addition of the lithium anion of allyl phenyl sulfide to 3,3-dimethylacrylonitrile and to methyl 3,3-dimethyl acrylate occurred at the alpha position of the carbanion. The resulting adducts 5 and 6 were converted to the allylic alcohols 1 and 9 by [2,3] sigmatropic shift of the sulfoxides, obtained by oxidation. Besides sulfoxide 7, sulfenate 13 arising from [2,3] sigmatropic shift and sulfinate 10 were detected. Alcohol 1 was epoxidized according to the Katsuki-Sharpless procedure to the (4S,5R) epoxy alcohol 17 with an ee > 94%. Its silyl ether 19 was converted to a mixture of cis and trans cyclopropylnitriles by the Stork cyclization. After removal of the silyl group and periodate cleavage, trans and cis aldehydes 24 and 25 were separated. The trans aldehyde 24 was converted to (1R,3R)-trans-chrysanthemic nitrile 26 (ee 92%).

  DOI：

  10.1021/jo00049a043

文献信息

• Enantiospecific synthesis of a chrysanthemic acid precursor
  作者：Laurent Lambs、Narrinder P. Singh、Jean Francois Biellmann

  DOI：10.1021/jo00049a043

  日期：1992.11

  1,4 Addition of the lithium anion of allyl phenyl sulfide to 3,3-dimethylacrylonitrile and to methyl 3,3-dimethyl acrylate occurred at the alpha position of the carbanion. The resulting adducts 5 and 6 were converted to the allylic alcohols 1 and 9 by [2,3] sigmatropic shift of the sulfoxides, obtained by oxidation. Besides sulfoxide 7, sulfenate 13 arising from [2,3] sigmatropic shift and sulfinate 10 were detected. Alcohol 1 was epoxidized according to the Katsuki-Sharpless procedure to the (4S,5R) epoxy alcohol 17 with an ee > 94%. Its silyl ether 19 was converted to a mixture of cis and trans cyclopropylnitriles by the Stork cyclization. After removal of the silyl group and periodate cleavage, trans and cis aldehydes 24 and 25 were separated. The trans aldehyde 24 was converted to (1R,3R)-trans-chrysanthemic nitrile 26 (ee 92%).