(E)-Methyl 3-bromo-2-(formylamino)-3-(3,4-(methylenedioxy)phenyl)acrylate

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-Methyl 3-bromo-2-(formylamino)-3-(3,4-(methylenedioxy)phenyl)acrylate
• 英文别名: methyl (E)-3-(1,3-benzodioxol-5-yl)-3-bromo-2-formamidoprop-2-enoate
• 化学式: C₁₂H₁₀BrNO₅
• 分子量: 328.119
• InChiKey: QFJVVAAPYXOGEB-ZHACJKMWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  73.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (E)-Methyl 3-bromo-2-(formylamino)-3-(3,4-(methylenedioxy)phenyl)acrylate 在 三乙胺 、 三氯氧磷 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以73%的产率得到(E)-Methyl 3-bromo-2-isocyano-3-(3,4-(methylenedioxy)phenyl)acrylate
  参考文献：
  名称：

  A Novel Synthesis of Methyl 1,5-Disubstituted Imidazole-4-carboxylates Using 3-Bromo-2-isocyanoacrylates (BICA)

  摘要：

  Methyl 1,5-disubstituted imidazole-4-carboxylates 1 were synthesised using methyl 3-substituted 3-bromo-2-isocyanoacrylates 3 (BICA), and the reaction mechanism was elucidated. Reactions of 3, which were prepared by bromination of 3-substituted 2-(formylamino)acrylates 6 followed by dehydration of the formylamino group, with a variety of primary amines gave imidazoles 1 in good overall yields. A mechanistic study suggested a Michael reaction of an amine with 3 followed by p-elimination of hydrogen bromide exclusively afforded (E)-N,3-disubstituted 3-amino-2-isocyanoacrylates 2. Geometric isomerization to (Z)-2 with a base and subsequent cyclization gave imidazoles 1.

  DOI：

  10.1021/jo00104a018
• 作为产物：
  描述：

  (Z)-3-Benzo[1,3]dioxol-5-yl-2-formylamino-acrylic acid methyl ester 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氯化碳 为溶剂， 反应 3.0h， 生成 (Z)-Methyl 3-bromo-2-(formylamino)-3-(3,4-(methylenedioxy)phenyl)acrylate 、 (E)-Methyl 3-bromo-2-(formylamino)-3-(3,4-(methylenedioxy)phenyl)acrylate
  参考文献：
  名称：

  A Novel Synthesis of Methyl 1,5-Disubstituted Imidazole-4-carboxylates Using 3-Bromo-2-isocyanoacrylates (BICA)

  摘要：

  Methyl 1,5-disubstituted imidazole-4-carboxylates 1 were synthesised using methyl 3-substituted 3-bromo-2-isocyanoacrylates 3 (BICA), and the reaction mechanism was elucidated. Reactions of 3, which were prepared by bromination of 3-substituted 2-(formylamino)acrylates 6 followed by dehydration of the formylamino group, with a variety of primary amines gave imidazoles 1 in good overall yields. A mechanistic study suggested a Michael reaction of an amine with 3 followed by p-elimination of hydrogen bromide exclusively afforded (E)-N,3-disubstituted 3-amino-2-isocyanoacrylates 2. Geometric isomerization to (Z)-2 with a base and subsequent cyclization gave imidazoles 1.

  DOI：

  10.1021/jo00104a018

文献信息

• A Novel Synthesis of Methyl 1,5-Disubstituted Imidazole-4-carboxylates Using 3-Bromo-2-isocyanoacrylates (BICA)
  作者：Ken-ichi Nunami、Masaki Yamada、Toshio Fukui、Kazuo Matsumoto

  DOI：10.1021/jo00104a018

  日期：1994.12

  Methyl 1,5-disubstituted imidazole-4-carboxylates 1 were synthesised using methyl 3-substituted 3-bromo-2-isocyanoacrylates 3 (BICA), and the reaction mechanism was elucidated. Reactions of 3, which were prepared by bromination of 3-substituted 2-(formylamino)acrylates 6 followed by dehydration of the formylamino group, with a variety of primary amines gave imidazoles 1 in good overall yields. A mechanistic study suggested a Michael reaction of an amine with 3 followed by p-elimination of hydrogen bromide exclusively afforded (E)-N,3-disubstituted 3-amino-2-isocyanoacrylates 2. Geometric isomerization to (Z)-2 with a base and subsequent cyclization gave imidazoles 1.