1-(6-ethoxy-5,6-dihydro-2-methyl-1,4-oxathiin-3-yl)ethanone | 152420-84-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧硫杂环己烯
• 英文名称: 1-(6-ethoxy-5,6-dihydro-2-methyl-1,4-oxathiin-3-yl)ethanone
• 英文别名: Ethanone, 1-(6-ethoxy-5,6-dihydro-2-methyl-1,4-oxathiin-3-yl)-(9CI)；1-(2-ethoxy-6-methyl-2,3-dihydro-1,4-oxathiin-5-yl)ethanone
• CAS: 152420-84-3
• 化学式: C₉H₁₄O₃S
• 分子量: 202.274
• InChiKey: JDHUXOUAPDTLRL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  60.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(6-ethoxy-5,6-dihydro-2-methyl-1,4-oxathiin-3-yl)ethanone 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 生成 3-Sulfinylpentane-2,4-dione
  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 2.5h， 生成 1-(6-ethoxy-5,6-dihydro-2-methyl-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 part 6. The First Example of an α-oxothione acting as heterodiene: Synthesis of 2,3-dihydro-1,4-oxathiines.
  作者：Giuseppe Capozzi、Stefano Menichetti、Cristina Nativi、Alessandro Rosi、Richard W. Franck

  DOI：10.1016/s0040-4039(00)60541-5

  日期：1993.6

  α-α'-Dioxothione 3a acts as heterodiene undergoing 4+2 cycloaddition reactions with enol ethers with the regiospecific formation of 2,3-dihydro-1,4-oxathiines 5 in good yields. The reaction is very simple and quite general. Using this reaction the thiosugar derivative 5e has been also prepared.

  α-α'-二氧杂环丁烷3a用作异二烯，与烯醇醚进行4 + 2环加成反应，并以良好的产率形成2,3-二氢-1,4-氧杂亚砜5的区域特异性形成。该反应非常简单并且非常笼统。使用该反应，还制备了硫糖衍生物5e。
• Generation and trapping of α,α′-dioxosulfines from 1,4-oxathiine-S-oxides
  作者：Giuseppe Capozzi、Paola Fratini、Stefano Menichetti、Cristina Nativi

  DOI：10.1016/0040-4039(95)00947-b

  日期：1995.7

  The 1,4-oxathiine-S-oxides 6 when heated at 60 °C in CHCl3 undergo a retro Diels-Alder reaction with generation of α,α′-dioxosulfine 8. This reactive intermediate can be trapped by electron rich dienophiles as well as by dienes. In both cases the cycloaddition reactions show interesting stereoselective features.

  当在60℃下于CHCl 3中加热时，1,4-氧代嘧啶-S-氧化物6发生逆狄尔斯-阿尔德反应，生成α，α'-二氧嘧啶8。该反应性中间体可以被富电子的亲二烯体和二烯捕获。在这两种情况下，环加成反应均显示出有趣的立体选择性特征。