乙基3-氧代-2,6-二氮杂双环[3.2.2]壬烷-6-羧酸酯 | 220828-11-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 中文名称: 乙基3-氧代-2,6-二氮杂双环[3.2.2]壬烷-6-羧酸酯
• 英文名称: 6-ethoxycarbonyl-2,6-diazabicyclo<3.2.2>nonan-3-one
• 英文别名: 3-Oxo-2,6-diaza-bicyclo[3.2.2]nonane-6-carboxylic acid ethyl ester；ethyl 3-oxo-2,6-diazabicyclo[3.2.2]nonane-6-carboxylate
• CAS: 220828-11-5
• 化学式: C₁₀H₁₆N₂O₃
• 分子量: 212.249
• InChiKey: VSPLNJPUUNMAAH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  58.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  乙基3-氧代-7-氮杂双环[2.2.2]辛烷-7-羧酸酯 在 hydroxylamine-O-sulfonic acid 作用下， 以 甲酸 为溶剂， 反应 3.0h， 以79%的产率得到乙基3-氧代-2,6-二氮杂双环[3.2.2]壬烷-6-羧酸酯
  参考文献：
  名称：

  Regioselective Functionalization. 7.¹ Unexpected Preferences for Bridgehead Migration in Schmidt Rearrangement Syntheses of Novel 2,6-Diazabicyclo[3.2.x]alkan-3-ones (x = 1−3)

  摘要：

  Regioselective syntheses of 2,6-diazabicyclo[3.2.x]alkan-3-ones (x = 1-3) 34 by insertion of nitrogen next to the bridgehead (BH) of 2-azabicyclo[2.2.x]alkanones 32 with hydroxylamine-O-sulfonic acid are described. The ketones 32 under Schmidt reaction conditions (HN3/H2SO4) afford major amounts of BK migrated lactams 34 but also, when x = 2 or 3, the methylene (IM) migrated lactams, 3,6-diazabicycl[3.2.x]alkan-2-ones 37. The present N-insertion reactions favoring BH migration with azabicyclic ketones contrast markedly with reactions of the related carbocycles la,b, which give only methylene migrated lactams 2a,b with HN3/H2SO4. Schmidt reactions of 3-anti/syn-methyl- and 3-anti-phenyl-2-azabicyclo[2.2.2]octan-5-ones 17, 20, and 23 (64:36 +/- 9, BH:M) follow the reaction pattern of the parent ketone 14, but the S-syn-phenyl ketone 26 gives major (65%) methylene migration. The results offer insights into the BH vs M migration dichotomy for the Beckmann and Schmidt reactions of bridged bicyclic ketones.

  DOI：

  10.1021/jo981977d

文献信息

• Regioselective Functionalization. 7.¹ Unexpected Preferences for Bridgehead Migration in Schmidt Rearrangement Syntheses of Novel 2,6-Diazabicyclo[3.2.<i>x</i>]alkan-3-ones (<i>x</i> = 1−3)
  作者：Grant R. Krow、Steven W. Szczepanski、Jee Y. Kim、Nian Liu、Askia Sheikh、Yushi Xiao、Jing Yuan

  DOI：10.1021/jo981977d

  日期：1999.2.1

  Regioselective syntheses of 2,6-diazabicyclo[3.2.x]alkan-3-ones (x = 1-3) 34 by insertion of nitrogen next to the bridgehead (BH) of 2-azabicyclo[2.2.x]alkanones 32 with hydroxylamine-O-sulfonic acid are described. The ketones 32 under Schmidt reaction conditions (HN3/H2SO4) afford major amounts of BK migrated lactams 34 but also, when x = 2 or 3, the methylene (IM) migrated lactams, 3,6-diazabicycl[3.2.x]alkan-2-ones 37. The present N-insertion reactions favoring BH migration with azabicyclic ketones contrast markedly with reactions of the related carbocycles la,b, which give only methylene migrated lactams 2a,b with HN3/H2SO4. Schmidt reactions of 3-anti/syn-methyl- and 3-anti-phenyl-2-azabicyclo[2.2.2]octan-5-ones 17, 20, and 23 (64:36 +/- 9, BH:M) follow the reaction pattern of the parent ketone 14, but the S-syn-phenyl ketone 26 gives major (65%) methylene migration. The results offer insights into the BH vs M migration dichotomy for the Beckmann and Schmidt reactions of bridged bicyclic ketones.