ethyl 1-{[(trifluoromethyl)sulfonyl]imino}-3,4-dihydro-1H-isochromene-3-carboxylate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: ethyl 1-{[(trifluoromethyl)sulfonyl]imino}-3,4-dihydro-1H-isochromene-3-carboxylate
• 英文别名: ethyl (1Z)-1-(trifluoromethylsulfonylimino)-3,4-dihydroisochromene-3-carboxylate
• 化学式: C₁₃H₁₂F₃NO₅S
• 分子量: 351.303
• InChiKey: IIBDZRXCDYNTCS-BOPFTXTBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  90.4
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  乙基1-氧亚基-2,3-二氢-1H-茚-2-甲酸基酯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 ethyl 1-{[(trifluoromethyl)sulfonyl]imino}-3,4-dihydro-1H-isochromene-3-carboxylate
  参考文献：
  名称：

  Reactions of Benzocyclic β-Keto Esters with Sulfonyl Azides. 2.¹ Further Insight into the Influence of Azide Structure and Solvent on the Reaction Course

  摘要：

  The reactions of 2-ethoxycarbonyl-1-benzosuberone, with 4-methoxybenzenesulfonyl, 2,4,6-triiso-propylbenzenesulfonyl, methanesulfonyl, and trifluoromethanesulfonyl azide, in the presence of triethylamine, have been investigated in N,N-dimethylformamide, acetonitrile, or tetrahydrofuran with the intent of clarifying the influence of both the azide electrophile and solvent on the reaction course. The present findings, in addition to those previously obtained with tosyl and 4-nitrobenzenesulfonyl azide, indicate that both the electronic features of the sulfonyl azide and the solvent polarity greatly affect the possible occurrence of azidation and/or Favorskii-type ring contraction at the expense of deacylating diazo transfer. Azidation is promoted by the less electrophilic azides, while it is virtually avoided by the more electrophilic ones. Ring contraction occurs to a limited extent with the less electrophilic azides, but it becomes the main process with those more electrophilic. Moreover, azidation is virtually unaffected by the solvent polarity, while ring contraction can markedly be enhanced by a highly polar solvent. Firm evidence has additionally been obtained that, in contrast to a previous claim, trifluoromethanesulfonyl azide can normally perform diazotization of acyclic beta-keto esters in preference to azidation.

  DOI：

  10.1021/jo9901541

文献信息

• Reactions of Benzocyclic β-Keto Esters with Sulfonyl Azides. 2.¹ Further Insight into the Influence of Azide Structure and Solvent on the Reaction Course
  作者：Luisa Benati、Daniele Nanni、Piero Spagnolo

  DOI：10.1021/jo9901541

  日期：1999.7.1

  The reactions of 2-ethoxycarbonyl-1-benzosuberone, with 4-methoxybenzenesulfonyl, 2,4,6-triiso-propylbenzenesulfonyl, methanesulfonyl, and trifluoromethanesulfonyl azide, in the presence of triethylamine, have been investigated in N,N-dimethylformamide, acetonitrile, or tetrahydrofuran with the intent of clarifying the influence of both the azide electrophile and solvent on the reaction course. The present findings, in addition to those previously obtained with tosyl and 4-nitrobenzenesulfonyl azide, indicate that both the electronic features of the sulfonyl azide and the solvent polarity greatly affect the possible occurrence of azidation and/or Favorskii-type ring contraction at the expense of deacylating diazo transfer. Azidation is promoted by the less electrophilic azides, while it is virtually avoided by the more electrophilic ones. Ring contraction occurs to a limited extent with the less electrophilic azides, but it becomes the main process with those more electrophilic. Moreover, azidation is virtually unaffected by the solvent polarity, while ring contraction can markedly be enhanced by a highly polar solvent. Firm evidence has additionally been obtained that, in contrast to a previous claim, trifluoromethanesulfonyl azide can normally perform diazotization of acyclic beta-keto esters in preference to azidation.