tert-butyl 1,1,3,3-tetramethyl-2-oxo-5-thiaspiro<3.4>octane-7-carboxylate | 137145-02-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tert-butyl 1,1,3,3-tetramethyl-2-oxo-5-thiaspiro<3.4>octane-7-carboxylate
• CAS: 137145-02-9
• 化学式: C₁₆H₂₆O₃S
• 分子量: 298.447
• InChiKey: UNFVLBJQDMNAIN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.46
• 重原子数：
  20.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  2,2,4,4-tetramethyl-3-thioxocyclobutanone 以 乙醚 为溶剂， 反应 8.0h， 生成 tert-butyl 1,1,3,3-tetramethyl-2-oxo-5-thiaspiro<3.4>octane-7-carboxylate
  参考文献：
  名称：

  Can polymerization trap intermediates in 1,3-dipolar cycloadditions?

  摘要：

  2,2,4,4-Tetramethyl-3-thioxocyclobutanone S-methylide (TTCM) is a nucleophilic 1,3-dipole which is known to undergo two-step cycloadditions to very electron poor olefins. When this 1,3-dipole is generated from its precursor, the 1,3,4-thiadiazoline 7, in acrylonitrile or acrylic esters at 45-degrees-C, only cycloaddition and no polymerization is observed, suggesting a concerted cycloaddition. Small amounts of polymers were observed alongside the cycloadducts with nitroethylene, methacrylonitrile, and methacrylates. Most cycloadducts were produced as regioisomeric mixtures. The reaction of TTCM with benzylidenemalononitrile, a nonpolymerizable olefin, is nonconcerted and furnished in THF and 1 vol % methanol or 3 vol % water a 7-membered lactim methyl ether or lactam formed by interception of a ketene imine. The observed polymerizations are radical in nature and are proposed to be initiated by a minor contribution of a diradical intermediate to the cycloaddition reaction.

  DOI：

  10.1021/ja00027a035