N-propenyl-2-methylbenzamide | 139583-84-9

• 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: N-propenyl-2-methylbenzamide
• 英文别名: 2-methyl-N-prop-1-enylbenzamide
• CAS: 139583-84-9；139583-85-0
• 化学式: C₁₁H₁₃NO
• 分子量: 175.23
• InChiKey: CNPRHPQOVVZEJV-UHFFFAOYSA-N

物化性质

• 沸点：
  350.6±25.0 °C(Predicted)
• 密度：
  1.014±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-propenyl-2-methylbenzamide 在 盐酸 作用下， 以 1,4-二氧六环 为溶剂， 反应 6.0h， 生成 3-n-butyl-1(2H)-isoquinolinone
  参考文献：
  名称：

  Heteroatom-directed metalation. Lithiation of N-propenylbenzamides and N-propenyl-o-toluamides. Novel routes to ortho-substituted primary benzamide derivatives and N-unsubstituted isoquinolin-1(2H)-ones

  摘要：

  Reaction of N-propenylbenzamides 4 and 9, obtained by LDA-induced isomerization of the corresponding N-allylbenzamides 1, 8, and 14, with 2 equiv of sec-butyllithium or tert-butyllithium at low temperature regiospecifically generates the highly reactive N,ortho-dilithiated species (e.g., 5 and 17). These dilithio species react avidly with a wide spectrum of electrophilic reagents, including alkyl halides, giving adducts which on hydrolysis with warm 50% aqueous acetic acid are converted into ortho-substituted primary benzamides in excellent yields. Ortho-lithiation of N-propenylbenzamides is thus formally equivalent to ortho-lithiation of primary benzamides themselves. The utility of this important, previously unknown, synthetic operation is enhanced by the well-known facility with which the primary amide moiety can be transformed into other useful functional groups, as exemplified by the synthesis of 2-methoxy-6-methylbenzoic acid (12) and 2-methoxy-6-methylbenzonitrile (13) from N-propenyl-2-methoxybenzamide (9), N-Propenyl-o-toluamide (7) undergoes regiospecific dilithiation on nitrogen and on the methyl group under conditions analogous to those used for the N-propenylbenzamides. These dilithio species react with DMF or "Weinreb type" amides to give condensation products which cyclize to N-propenylisoquinolin-1(2H)-ones under midly acidic conditions. Removal of the N-propenyl moiety under more strongly acidic conditions provides N-unsubstituted isoquinolin-1(2H)-ones with high overall efficiency. This process is exemplified by the synthesis of isoquinolin-1(2H)-one (23) and its 3-n-butyl congener 26 from N-propenyl-2-methylbenzamide (7).

  DOI：

  10.1021/jo00035a030