3,4-dimethylspiro[2,5-dihydrothiopyran-6,2'-adamantane] 1,1-dioxide | 136175-85-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫吡喃类
• 英文名称: 3,4-dimethylspiro[2,5-dihydrothiopyran-6,2'-adamantane] 1,1-dioxide
• CAS: 136175-85-4
• 化学式: C₁₆H₂₄O₂S
• 分子量: 280.431
• InChiKey: WWPCWRVZFXWLSP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  4',5'-dimethylspiro 在 Oxone 作用下， 以 甲醇 、 水 、 丙酮 为溶剂， 反应 5.0h， 以20%的产率得到1,6-dimethylspiro[7-oxa-3λ6-thiabicyclo[4.1.0]heptane-4,2'-adamantane] 3,3-dioxide
  参考文献：
  名称：

  Face selection in thermal cycloaddition and -reversion

  摘要：

  The isomer distribution has been determined in several cycloaddition reactions involving 5-fluoro- and 5-phenyladamantane derivatives in which C2 serves as one of the trigonal termini. The reactions include a [2 + 2] cycloaddition with dichloroketene, a nucleophilic addition followed by cyclization, a [2 + 2] cycloreversion of a beta-lactone, and two Diels-Alder reactions; in the latter case, the adamantane moiety was incorporated in the diene in one instance and in the dienophile in the other. In all these reactions, the reagent attacking the adamantane substrate was found to do so preferentially at the zu face, by modest but clear margins. This observation is in accord with the concept of transition-state hyperconjugation. This explanation is extended to several literature examples involving substrates with faces that are not isosteric because the polarizing group is placed closer to the site of attack; the ratios are substantial and in favor of the more hindered product in many of these examples.

  DOI：

  10.1021/jo00020a041

文献信息

• Face selection in thermal cycloaddition and -reversion
  作者：Haifang Li、Jack E. Silver、William H. Watson、Ram P. Kashyap、William J. Le Noble

  DOI：10.1021/jo00020a041

  日期：1991.9

  The isomer distribution has been determined in several cycloaddition reactions involving 5-fluoro- and 5-phenyladamantane derivatives in which C2 serves as one of the trigonal termini. The reactions include a [2 + 2] cycloaddition with dichloroketene, a nucleophilic addition followed by cyclization, a [2 + 2] cycloreversion of a beta-lactone, and two Diels-Alder reactions; in the latter case, the adamantane moiety was incorporated in the diene in one instance and in the dienophile in the other. In all these reactions, the reagent attacking the adamantane substrate was found to do so preferentially at the zu face, by modest but clear margins. This observation is in accord with the concept of transition-state hyperconjugation. This explanation is extended to several literature examples involving substrates with faces that are not isosteric because the polarizing group is placed closer to the site of attack; the ratios are substantial and in favor of the more hindered product in many of these examples.