3,3,5-trimethyl-4-(methoxyamino)cyclopentene | 140705-84-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,3,5-trimethyl-4-(methoxyamino)cyclopentene
• 英文别名: N-methoxy-2,2,5-trimethylcyclopent-3-en-1-amine
• CAS: 140705-84-6
• 化学式: C₉H₁₇NO
• 分子量: 155.24
• InChiKey: PZLCNSVZXMAXQS-UHFFFAOYSA-N

物化性质

• 沸点：
  174.6±43.0 °C(Predicted)
• 密度：
  0.92±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  21.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  O-Methyl-N-(2,2,5-trimethyl-4-tributylstannanyl-cyclopent-3-enyl)-hydroxylamine 在 盐酸 作用下， 以 乙醚 为溶剂， 以77%的产率得到3,3,5-trimethyl-4-(methoxyamino)cyclopentene
  参考文献：
  名称：

  Tributyltin Hydride-Mediated Free-Radical Cyclization of Allene-Tethered Oxime Ethers and Hydrazones

  摘要：

  In this work, we have shown that the tributyltin hydride-mediated cycloisomerization of allene-tethered oxime ethers or hydrazones is a convenient method for the preparation of (vinylstannyl)cyclopentylamine derivatives in terms of simplicity and chemical yields. As a result, the first and detailed analysis of the tributyltin hydride-mediated free-radical cyclization of alkyl-substituted allene-tethered oxime ethers and hydrazones is reported. The site-directed intermolecular attack of the tributyltin radical at the allene moiety and the final size of the ring after cyclization depends on the type of substitution in the substrate. Some general trends can be observed: (1) In crowded substrates having full substitution at C beta or at the terminal-trigonal carbon, the steric hindrance favors attack at the digonal carbon. (2) When different positions in the allene are free for attack, the kinetically more favored irreversible mode of cyclizations (5-exo > 6-exo > 6-endo) determines the ratio of isomers or the final size of the ring. Finally, after acid hydrolysis of the vinyltin products,the resulting O-methyl- or O-benzyl(hydroxylamino)cycloalkanes have been obtained in good yield.

  DOI：

  10.1021/jo962225r

文献信息

• Radical cyclization of β-allenic oxime ethers
  作者：J. Hatem、C. Henriet-Bernard、J. Grimaldi、R. Maurin

  DOI：10.1016/s0040-4039(00)91859-8

  日期：1992.2

  β-allenic O-methyl oximes undergo a free radical hydrostannylation reaction to afford cyclopentenes bearing a protected amine group and a vinyl stannyl fonction. These compounds were destannylated to yield the corresponding cyclopentenes.

  β-烯烃O-甲基肟经过自由基加氢甲氧基化反应，得到带有受保护的胺基和乙烯基锡烷基官能团的环戊烯。将这些化合物脱锡，得到相应的环戊烯。