methyl 8-cyano-1,1,3,3-tetramethyl-2-oxo-7-phenyl-5-thiaspiro<3.4>octane-8-carboxylate | 137145-18-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 8-cyano-1,1,3,3-tetramethyl-2-oxo-7-phenyl-5-thiaspiro<3.4>octane-8-carboxylate
• 英文别名: methyl (7R,8R)-8-cyano-1,1,3,3-tetramethyl-2-oxo-7-phenyl-5-thiaspiro[3.4]octane-8-carboxylate
• CAS: 137145-18-7
• 化学式: C₂₀H₂₃NO₃S
• 分子量: 357.474
• InChiKey: VFYCBRLNPPMFQQ-KUHUBIRLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  92.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  2,2,4,4-tetramethyl-3-thioxocyclobutanone 以 乙醚 、 乙腈 为溶剂， 反应 3.0h， 生成 methyl 8-cyano-1,1,3,3-tetramethyl-2-oxo-7-phenyl-5-thiaspiro<3.4>octane-8-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

文献信息

• Can polymerization trap intermediates in 1,3-dipolar cycloadditions?
  作者：Rolf Huisgen、Jacques Penelle、Grzegorz Mloston、Anne Buyle Padias、H. K. Hall

  DOI：10.1021/ja00027a035

  日期：1992.1

  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.