1-(5,6-dihydro-2-methyl-6-(phenylthio)-1,4-oxathiin-3-yl)ethanone | 170469-82-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 1-(5,6-dihydro-2-methyl-6-(phenylthio)-1,4-oxathiin-3-yl)ethanone
• 英文别名: 1-(6-Methyl-2-phenylsulfanyl-2,3-dihydro-1,4-oxathiin-5-yl)ethanone
• CAS: 170469-82-6
• 化学式: C₁₃H₁₄O₂S₂
• 分子量: 266.385
• InChiKey: SGZHPXXGCFSOGY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  76.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(5,6-dihydro-2-methyl-6-(phenylthio)-1,4-oxathiin-3-yl)ethanone 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以85%的产率得到1-((4R,6R)-2-Methyl-4-oxo-6-phenylsulfanyl-5,6-dihydro-4H-4λ⁴-[1,4]oxathiin-3-yl)-ethanone
  参考文献：
  名称：

  α-氧代亚砜第1部分：从1,4-氧杂环氧化物-S-氧化物的逆Diels-Alder反应获得的α-氧代亚砜的反应性

  摘要：

  1,4-氧杂ath啶衍生物10–16的氧化可提供高产率和良好的立体选择性的相应亚砜17–26。所述oxathiin-小号-oxides经历逆狄尔斯-阿尔德（RDA）反应以形成α-oxosulfines非常温和的条件下。这些反应性中间体可以成功地捕获为亲电子体或逆电子需量狄尔斯-阿尔德反应（IEDDA）中的贫电子二烯。起始亚砜的结构，中间亚砜的几何形状和最终环加合物的立体化学之间的关系已被初步关联。

  DOI：

  10.1016/0040-4020(96)00710-7
• 作为产物：
  描述：

  4-(三甲基硅氧基)-3-戊烯-2-酮 在 吡啶 作用下， 以 氯仿 、 溶剂黄146 为溶剂， 反应 63.0h， 生成 1-(5,6-dihydro-2-methyl-6-(phenylthio)-1,4-oxathiin-3-yl)ethanone
  参考文献：
  名称：

  Phthalimidesulfenyl Chloride. 9. A Simple Access to .alpha.,.alpha.'-Dioxothiones, a New Class of Bis-heterodienes. Synthesis of 1,4-Oxathiin Systems

  摘要：

  alpha,alpha'-Dioxothiophthalimides 4a and 4b react with pyridine to generate the alpha,alpha'-dioxothiones 5a and 5b which undergo chemo- and regiospecific inverse electron demand Diels-Alder reactions With electron-rich alkenes to give 1,4-oxathiin heterocyclic systems. Enol ethers, silyl enol ethers, vinyl sulfides, vinyl amides, substituted styrenes, and electron rich alkynes and allenes can be fruitfully employed as dienophiles. Among the vinyl ethers tested tri-O-benzylglucal was successfully used as a dienophile. Ab initio molecular orbital calculations performed on thiones 5a and 5b as well as on a selected enol ether are consistent with the experimental results. When thione 5a was generated in the presence of 2,3-dimethyl-2-butene (31) and -(beta)-pinene (33) a selective ''thiophlic ene reaction'' was observed leading to the formation of sulfides 32 and 34. Thione 5b reacted similarly with 33 to generate the sulfide 35. Additionally a competition between the dienic versus dienophilic behavior of alpha,alpha'-dioxothiones 5a and 5b was observed in reactions with 2,3-dimethoxy-1,3-butadiene (45) and 2-methoxyfuran (50). A preliminary screening of the reactivity of 1,4-oxathiins 7c and 8b, used as model substrates, is also outlined.

  DOI：

  10.1021/jo00125a030

文献信息

• Phthalimidesulfenyl Chloride. 9. A Simple Access to .alpha.,.alpha.'-Dioxothiones, a New Class of Bis-heterodienes. Synthesis of 1,4-Oxathiin Systems
  作者：G. Capozzi、R. W. Franck、M. Mattioli、S. Menichetti、C. Nativi、G. Valle

  DOI：10.1021/jo00125a030

  日期：1995.10

  alpha,alpha'-Dioxothiophthalimides 4a and 4b react with pyridine to generate the alpha,alpha'-dioxothiones 5a and 5b which undergo chemo- and regiospecific inverse electron demand Diels-Alder reactions With electron-rich alkenes to give 1,4-oxathiin heterocyclic systems. Enol ethers, silyl enol ethers, vinyl sulfides, vinyl amides, substituted styrenes, and electron rich alkynes and allenes can be fruitfully employed as dienophiles. Among the vinyl ethers tested tri-O-benzylglucal was successfully used as a dienophile. Ab initio molecular orbital calculations performed on thiones 5a and 5b as well as on a selected enol ether are consistent with the experimental results. When thione 5a was generated in the presence of 2,3-dimethyl-2-butene (31) and -(beta)-pinene (33) a selective ''thiophlic ene reaction'' was observed leading to the formation of sulfides 32 and 34. Thione 5b reacted similarly with 33 to generate the sulfide 35. Additionally a competition between the dienic versus dienophilic behavior of alpha,alpha'-dioxothiones 5a and 5b was observed in reactions with 2,3-dimethoxy-1,3-butadiene (45) and 2-methoxyfuran (50). A preliminary screening of the reactivity of 1,4-oxathiins 7c and 8b, used as model substrates, is also outlined.
• α-Oxosulfines part 1: Reactivity of α-oxosulfines obtained from Retro Diels-Alder reaction of 1,4-oxathiin-S-oxides
  作者：Giuseppe Capozzi、Paola Fratini、Stefano Menichetti、Cristina Nativi

  DOI：10.1016/0040-4020(96)00710-7

  日期：1996.9

  Retro Diels-Alder (RDA) reaction to form α-oxosulfines under very mild conditions. These reactive intermediates can be successfully trapped as dienophiles or as electron poor dienes in Inverse Electron Demand Diels-Alder reaction (IEDDA). The relationship between the structure of the starting sulfoxide, the geometry of the intermediate sulfine and the stereochemistry of the final cycloadduct have been

  1,4-氧杂ath啶衍生物10–16的氧化可提供高产率和良好的立体选择性的相应亚砜17–26。所述oxathiin-小号-oxides经历逆狄尔斯-阿尔德（RDA）反应以形成α-oxosulfines非常温和的条件下。这些反应性中间体可以成功地捕获为亲电子体或逆电子需量狄尔斯-阿尔德反应（IEDDA）中的贫电子二烯。起始亚砜的结构，中间亚砜的几何形状和最终环加合物的立体化学之间的关系已被初步关联。