6-bromo-2-oxochromene-3-carboxylic acid N-benzylamide | 38472-68-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 香豆素及其衍生物
• 英文名称: 6-bromo-2-oxochromene-3-carboxylic acid N-benzylamide
• 英文别名: N-benzyl-6-bromo-2-oxochromene-3-carboxamide
• CAS: 38472-68-3
• 化学式: C₁₇H₁₂BrNO₃
• 分子量: 358.191
• InChiKey: PJVCBGDEHNTACQ-UHFFFAOYSA-N

物化性质

• 沸点：
  609.2±55.0 °C(Predicted)
• 密度：
  1.543±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-溴代异丁酸甲酯 、 6-bromo-2-oxochromene-3-carboxylic acid N-benzylamide 在 锌 作用下， 以 六甲基磷酰三胺 、 乙醚 、 苯 为溶剂， 以85%的产率得到N-benzyl-6-bromo-4-(1-methoxycarbonyl-1-methylethyl)-2-oxochroman-3-carboxamide
  参考文献：
  名称：

  Reformatsky Reaction with N-Substituted 6-Bromo-2-oxochromene-3-carboxamides

  摘要：

  Reformatsky reactions of ethyl a-bromopropionate, methyl a-bromobutyrate, and methyl alpha-bromoisobutyrate with N-substituted 6-bromo-2-oxochromene-3-carboxamides in the system diethyl ether-benzene-HMPA give N-benzyl-6-bromo-4-(1-alkoxycarbonylalkyl)-2-oxochroman-3-carboxamides, while in the system diethyl ether-benzene-HMPA-THF, 3-R-1-1-R-2-1-R-3-9-bromo-2,3,4,4a,5,10b-hexahydro-1H-chromeno[3,4-c]pyridine-2,4,5-triones are obtained.

  DOI：

  10.1023/b:rujo.0000044556.65215.ea

文献信息

• Cyclopropanation of N-Substituted 2-Oxochromene- and 6-Bromo-2-oxochromene-3-carboxamides with Zinc Enolates Derived from 1-Aryl-2,2-dibromoalkanones
  作者：V. V. Shchepin、P. S. Silaichev、R. V. Shchepin、M. A. Ezhikova、M. I. Kodess

  DOI：10.1007/s11178-005-0199-6

  日期：2005.4

  Zinc enolates derived from 1-aryl-2,2-dibromoalkanones react with N-cyclohexyl-2-oxochromene-3-carboxamides to give N-cyclohexyl-1-alkyl-1-aroyl-2-oxo-1a,7b-dihydrocyclopropa[c]chromene-1a-carboxamides mainly as cis isomers with respect to the substituents in positions 1 and 1a. Reactions of the same zinc enolates with N-benzyl-2-oxochromene-3-carboxamide and N-benzyl-6-bromo-2-oxochromene-3-carboxamide lead to formation of 1-aryl-2-benzyl- and 1-aryl-2-benzyl-6-bromo-1-hydroxy-9c-alkyl-1,2,9b,9c-tetrahydro-5-oxa-2-azacyclopenta[2,3]cyclopropa[1,2-a]naphthalene-3,4-diones. The reaction of zinc enolates with N-aryl-2-oxochromene-3-carboxamides in a weakly polar solvent (diethyl ether or ethyl acetate) affords mixtures of cis-N-aryl-1-aroyl-1-alkyl-2-oxo-1a,7b-dihydrocyclopropa[c]chromene-1a-carboxamides and their cyclic isomers, 9c-alkyl-1,2-diaryl-1-hydroxy-1,2,9b,9c-tetrahydro-5-oxa-2-azacyclopenta[2,3]cyclopropa[1,2-a]naphthalene-3,4-diones, the latter prevailing. N-Substituted 1-alkyl-1-aroyl-2-oxo-1a,7b-dihydrocyclopropa[c]chromene-1a-carboxamides in which the aroyl group on C1 and the carboxamide group on C1a are arranged trans are formed by reactions of zinc enolates with the corresponding 2-oxochromene-3-carboxamides in the presence of hexamethylphosphoric triamide.

  源自1-芳基-2,2-二溴代烷基酮的锌烯醇盐与N-环己基-2-氧代色烯-3-羧酰胺反应，主要生成顺式异构体，相对于位置1和1a的取代基，形式为N-环己基-1-烷基-1-芳酰基-2-氧代-1a,7b-二氢环丙[c]色烯-1a-羧酰胺。同样的锌烯醇盐与N-苄基-2-氧代色烯-3-羧酰胺和N-苄基-6-溴-2-氧代色烯-3-羧酰胺反应，生成1-芳基-2-苄基和1-芳基-2-苄基-6-溴-1-羟基-9c-烷基-1,2,9b,9c-四氢-5-氧-2-氮杂环戊[2,3]环丙[1,2-a]萘-3,4-二酮。锌烯醇盐与N-芳基-2-氧代色烯-3-羧酰胺在弱极性溶剂（乙醚或乙酸乙酯）中反应，得到顺式N-芳基-1-芳酰基-1-烷基-2-氧代-1a,7b-二氢环丙[c]色烯-1a-羧酰胺及其环状异构体，即9c-烷基-1,2-二芳基-1-羟基-1,2,9b,9c-四氢-5-氧-2-氮杂环戊[2,3]环丙[1,2-a]萘-3,4-二酮，后者占优势。在六甲基磷酸三胺存在下，锌烯醇盐与相应的2-氧代色烯-3-羧酰胺反应，生成N-取代的1-烷基-1-芳酰基-2-氧代-1a,7b-二氢环丙[c]色烯-1a-羧酰胺，其中C1上的芳酰基和C1a上的羧酰胺基团以反式排列。
• Synthesis of 8-R-9c-alkyl-1-aryl-2-benzyl-1-hydroxy-1,2,9b,9c-tetrahydro-5-oxa-2-aza-cyclopenta[2,3]cyclopropa[1,2-a]naphthalene-3,4-diones and reaction thereof with acetic anhydride
  作者：Vasiliy V. Shchepin、Pavel S. Silaychev、Anton R. Rakitin、Mikhayl I. Kodess

  DOI：10.1016/j.tetlet.2005.11.036

  日期：2006.1

  The reaction of zinc enolates synthesized from 1-aryl-2,2-dibromoalkationes and zinc with 6-R-2-oxochromene-3-carboxylic acid N-benzylamide affords 8-R-9c-alkyl-1-aryl-2-benzyl-1-hydroxy-1,2, 9b,9c-tetrahydro-5-oxa-2-aza-cyclopenta[2,3]cyclopropa[1,2-a]naphthalene-3,4-diones. Acylation of these compounds is accompanied by an unexpected rearrangement producing a sole geometrical isomer of 4'-alkyl-5'-aryl-1'-benzyl-3,4,2',3'-tetrahydro-2,2'-dioxospiro[chroman-3,3'-pyrrol]-4-yl acetates. (c) 2005 Elsevier Ltd. All rights reserved.
• Reformatsky Reaction with N-Substituted 6-Bromo-2-oxochromene-3-carboxamides
  作者：V. V. Shchepin、D. V. Fotin、V. V. Fotin、M. I. Vakhrin

  DOI：10.1023/b:rujo.0000044556.65215.ea

  日期：2004.6

  Reformatsky reactions of ethyl a-bromopropionate, methyl a-bromobutyrate, and methyl alpha-bromoisobutyrate with N-substituted 6-bromo-2-oxochromene-3-carboxamides in the system diethyl ether-benzene-HMPA give N-benzyl-6-bromo-4-(1-alkoxycarbonylalkyl)-2-oxochroman-3-carboxamides, while in the system diethyl ether-benzene-HMPA-THF, 3-R-1-1-R-2-1-R-3-9-bromo-2,3,4,4a,5,10b-hexahydro-1H-chromeno[3,4-c]pyridine-2,4,5-triones are obtained.