2-methyl-3-(phenylthio)-2-sulfolene | 175438-48-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 2-methyl-3-(phenylthio)-2-sulfolene
• 英文别名: 5-Methyl-4-phenylsulfanyl-2,3-dihydrothiophene 1,1-dioxide；5-methyl-4-phenylsulfanyl-2,3-dihydrothiophene 1,1-dioxide
• CAS: 175438-48-9
• 化学式: C₁₁H₁₂O₂S₂
• 分子量: 240.347
• InChiKey: IZKBPMUFADYNEX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  67.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-methyl-3-(phenylthio)-2-sulfolene 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 对苯二酚 作用下， 以 甲苯 为溶剂， 以88%的产率得到3-(phenylthio)-1,3-pentadiene
  参考文献：
  名称：

  硫代1,3-二烯与芳基磺酰基异氰酸酯的氮杂-狄尔斯-阿尔德反应合成四氢-2-吡啶酮及其应用

  摘要：

  芳基磺酰基异氰酸与硫取代的1,3-二烯通过3-砜基烯前体1进行的首批aza-Diels-Alder反应，完全控制了化学选择性和区域选择性地得到了环化产物3。环化产物3a和5与亲核试剂和碱进一步反应，生成了有用的杂环化合物。环状产物的N-对甲苯磺酰基可以被选择性地替换为氢或其他取代基。

  DOI：

  10.1055/s-2001-18710
• 作为产物：
  描述：

  3-(phenylthio)-2-sulfolene 、 碘甲烷 在 正丁基锂 作用下， 生成 2-methyl-3-(phenylthio)-2-sulfolene
  参考文献：
  名称：

  Synthesis and Applications of 3-Phenylthio-2-Sulfolenes

  摘要：

  AbstractTreatment of 3‐phenylthio‐2‐sulfolene (1) with an equimolar proportion of butyllithium at −78 °C in THF followed by addition of an electrophile gave the 2‐substituted 3‐phenylthio‐2‐sulfolenes (2). The deprotonation was found to proceed only at the vinylic C‐2 position. Some of the 2‐sulfolenes 2 underwent desulfonylation upon heating with base. Of particular interest was the conversion of 3‐phenylthio‐2‐trimethylsilyl‐2‐sulfolene (2h) to its 3‐sulfolene isomer 6 by sequential addition of butyllithium and salicylic acid at low temperatures. The 3‐sulfolene 6 was desulfonylated by Kugelrohr distillation at 150° C under vacuum to give (Z)‐2‐phenylthio‐l‐trimethylsilyl‐1,3‐butadiene (8). The regiochemistry of the Diels Alder reaction of this highly reactive diene 8 was found to be controlled by the phenylthio group, and the stereochemistry is endo addition. Diene 8 was oxidized to its sulfone derivative 12 which also underwent a stereospecific Diels‐Alder reaction.

  DOI：

  10.1002/jccs.199600009

文献信息

• Synthesis and Applications of Tetrahydro-2-pyridinones via aza-Diels-Alder Reactions of Thio-substituted 1,3-Dienes with Arylsulfonyl Isocyanates
  作者：Shang-Shing Chou、Chia-Cheng Hung

  DOI：10.1055/s-2001-18710

  日期：——

  The first aza-Diels-Alder reactions of arylsulfonyl isocyanates with thio-substituted 1,3-dienes via the 3-sulfolene precursors 1 gave the cyclized products 3 with complete control of chemo- and regioselectivity. The cyclized products 3a and 5 underwent further reactions with nucleophiles and bases to give useful heterocyclic compounds. The N-tosyl group of the cyclic products could be selectively replaced by hydrogen or another substituent.

  芳基磺酰基异氰酸与硫取代的1,3-二烯通过3-砜基烯前体1进行的首批aza-Diels-Alder反应，完全控制了化学选择性和区域选择性地得到了环化产物3。环化产物3a和5与亲核试剂和碱进一步反应，生成了有用的杂环化合物。环状产物的N-对甲苯磺酰基可以被选择性地替换为氢或其他取代基。
• Synthesis and Applications of 3-Phenylthio-2-Sulfolenes
  作者：Shang-Shing P. Chou、Mao-Hsun Chao

  DOI：10.1002/jccs.199600009

  日期：1996.2

  AbstractTreatment of 3‐phenylthio‐2‐sulfolene (1) with an equimolar proportion of butyllithium at −78 °C in THF followed by addition of an electrophile gave the 2‐substituted 3‐phenylthio‐2‐sulfolenes (2). The deprotonation was found to proceed only at the vinylic C‐2 position. Some of the 2‐sulfolenes 2 underwent desulfonylation upon heating with base. Of particular interest was the conversion of 3‐phenylthio‐2‐trimethylsilyl‐2‐sulfolene (2h) to its 3‐sulfolene isomer 6 by sequential addition of butyllithium and salicylic acid at low temperatures. The 3‐sulfolene 6 was desulfonylated by Kugelrohr distillation at 150° C under vacuum to give (Z)‐2‐phenylthio‐l‐trimethylsilyl‐1,3‐butadiene (8). The regiochemistry of the Diels Alder reaction of this highly reactive diene 8 was found to be controlled by the phenylthio group, and the stereochemistry is endo addition. Diene 8 was oxidized to its sulfone derivative 12 which also underwent a stereospecific Diels‐Alder reaction.