6-(dimethylamino)-3-nitrobenzoic acid methyl ester | 101905-71-9

• 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: 6-(dimethylamino)-3-nitrobenzoic acid methyl ester
• 英文别名: Methyl 2-(dimethylamino)-5-nitrobenzoate
• CAS: 101905-71-9
• 化学式: C₁₀H₁₂N₂O₄
• mdl: MFCD11706961
• 分子量: 224.216
• InChiKey: IRKCYPMJNYIJOB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  75.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (R)-4,6-Bis-dimethylamino-3-nitro-cyclohexa-1,3-dienecarboxylic acid methyl ester 生成 6-(dimethylamino)-3-nitrobenzoic acid methyl ester
  参考文献：
  名称：

  An Unexpected [1,5]-H Shift in the Synthesis of Nitroanilines

  摘要：

  DOI：

  10.1021/ol0265362

文献信息

• Demonstrating the Synergy of Synthetic, Mechanistic, and Computational Studies in a Regioselective Aniline Synthesis
  作者：Ian W. Davies、Jean-François Marcoux、Jeffery T. Kuethe、Michael D. Lankshear、Jeremy D. O. Taylor、Nancy Tsou、Peter G. Dormer、David L. Hughes、K. N. Houk、Vildan Guner

  DOI：10.1021/jo035677u

  日期：2004.2.1

  Tri- and tetrasubstituted anilines are formed in good to excellent yields by the addition of ketones to vinamidinium salts (up to 98%). The reaction proceeds via the formation of dienone intermediates, which react to form an enamine with the liberated amine. In the case of a nitro, or dimethylaminomethylene substituent, the enamines undergo a facile electrocyclic ring closure to form a cyclohexadiene, which goes on to form anilines with a high degree of selectivity (up to 50:1) with a minor competing pathway proceeding via the enol providing phenols. Competition experiments using isotopic substitution reveal that the rate determining step en route to dienone is enol/enolate addition to the vinamidinium salt, which is characterized by an inverse secondary isotope effect (k(H/D) 0.7-0.9). Computational studies have been used to provide a framework for understanding the reaction pathway. The original proposal for a [1,5]-H shift was ruled out on the basis of the calculations, which did not locate a thermally accessible transition state. The minimum energy conformation of the enamine is such that a facile electrocyclic ring closure is ensured, which is corroborated by the experimental studies. A framework for understanding the reaction pathway is presented.
• Unusual reactions of ?-nitro-?-dimethylaminoacrolein
  作者：Zh. A. Krasnaya、T. S. Stytsenko、V. S. Bogdanov、E. D. Daeva

  DOI：10.1007/bf00950150

  日期：1985.7
• KRASNAYA, ZH. A.;STYTSENKO, T. S.;BOGDANOV, V. S.;DAEVA, E. D., IZV. AN CCCP. CEP. XIM., 1985, N 7, 1604-1612
  作者：KRASNAYA, ZH. A.、STYTSENKO, T. S.、BOGDANOV, V. S.、DAEVA, E. D.

  DOI：——

  日期：——
• An Unexpected [1,5]-H Shift in the Synthesis of Nitroanilines
  作者：Ian W. Davies、Jean-François Marcoux、Jeremy D. O. Taylor、Peter G. Dormer、Robert J. Deeth、Félix-Antoine Marcotte、David L. Hughes、Paul J. Reider

  DOI：10.1021/ol0265362

  日期：2002.8.1