N¹-(p-Methoxyphenyl)-N²-(p-nitrophenyl)acetimidine | 128915-19-5

• 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: N¹-(p-Methoxyphenyl)-N²-(p-nitrophenyl)acetimidine
• 英文别名: N-(4-methoxyphenyl)-N'-(4-nitrophenyl)ethanimidamide
• CAS: 128915-19-5
• 化学式: C₁₅H₁₅N₃O₃
• 分子量: 285.302
• InChiKey: CBSWPYKGQILXBO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  79.4
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N¹-(p-Methoxyphenyl)-N²-(p-nitrophenyl)acetimidine 在 盐酸 作用下， 以 1,4-二氧六环 、 水 为溶剂， 生成 对硝基乙酰苯胺 、 甲氧苯胺
  参考文献：
  名称：

  Amidines. III. A kinetic study of acid hydrolysis of unsymmetrical N1,N2-disubstituted amidines.

  摘要：

  在水合二氧六环溶液中，动力学研究了不对称N1, N2-二取代乙酰胺和甲酰胺的酸性水解反应。该反应生成了更碱性的胺和较不碱性胺的N-酰衍生物。增加溶剂中二氧六环的含量提高了反应速率。该反应可以通过特定酸-一般碱催化的理论进行解释。

  DOI：

  10.1248/cpb.38.1158
• 作为产物：
  描述：

  N¹-Tosyl-N¹,N²-di(p-methoxyphenyl)acetamidine 、 4-硝基苯胺 在 12-冠醚-4 、 potassium tert-butylate 作用下， 生成 N-(4-甲氧基苯基)-4-甲基苯磺酰胺 、 N¹-(p-Methoxyphenyl)-N²-(p-nitrophenyl)acetimidine
  参考文献：
  名称：

  Amidines. II. Preparation of unsymmetrical N1,N2-disubstituted amidines.

  摘要：

  不对称的N1、N2-二取代氨基脲通过传统方法和新开发的方法制备而成。N1-对苯磺酰基-N1、N2-二芳基乙酰氨基脲与芳胺反应，在碱性催化剂的存在下生成不对称乙酰氨基脲，而N1-酰基-N1、N2-二(对硝基苯基)甲酰氨基脲与芳胺在中性条件下生成不对称甲酰氨基脲。不对称氨基脲因两个氮原子之间的质子转移而在溶液中以 tautomeric 混合物的形式存在，并且基于质子核磁共振 (1H-NMR) 的证据证明，氢原子与更基本的氮原子结合的 tautomer 是占主导地位的。

  DOI：

  10.1248/cpb.38.866

文献信息

• Amidines. VIII. A kinetic study of alcoholysis of N1-arenesulfonyl-N1,N2-diarylacetamidines.
  作者：Machiko ONO、Reiko TODORIKI、Shinzo TAMURA

  DOI：10.1248/cpb.39.558

  日期：——

  Alcoholysis of N1-Arenesulfonyl-N1, N2-diarylacetamidines (1-30) was studied kinetically. The rate of the reaction between the substrates and ethoxide ion depended on the electron-withdrawing resonance effect of the substituents on both the N1-aryl and N2-aryl groups to a similar extent. The rate of the neutral alcoholysis depended on the resonance effect of the N1-aryl substituent to a larger extent than in the former reaction, and depended hardly at all on the electron-releasing resonance effect of the N2-aryl substituent, showing that the reaction does not proceed by the solvolysis mechanism.A reaction mechanism is proposed in which the rate-determining attack of the nucleophile is accompanied by the concerted departure of the N-arylarenesulfonamide group.

  对 N1-壬磺酰基-N1，N2-二芳基乙酰胺（1-30）的醇解进行了动力学研究。底物与乙氧离子的反应速率在类似程度上取决于 N1 芳基和 N2 芳基上取代基的吸电子共振效应。与前一种反应相比，中性醇解反应的速率在更大程度上取决于 N1-芳基取代基的共振效应，而几乎不取决于 N2-芳基取代基的电子释放共振效应，这表明该反应不是通过溶解机理进行的。
• Amidines. VI. 1,3-N,N-acylotropic amidine rearrangement of N1-acyl derivatives of N1,N2-disubstituted amidine.
  作者：Machiko ONO、Kazumi AOKI、Shinzo TAMURA

  DOI：10.1248/cpb.38.1379

  日期：——

  N1-Tosyl-N1, N2-diarylacetamidines (1) undergo uncleophilic attack of N-tosylamide anion at the amidine central carbon, and the less basic N-tosylamido group is expelled from the intermediate, resulting in an amide exchange reaction. Reaction of 1 and N-arylcarboxamide afforded N1-acyl-N1, N2-diarylacetamidine (2). N1-(p-Chlorobenzoyl)-N1-(p-methoxyphenyl)-N2-(p-chlorophenyl)acetamidine (2a) could not be obtained as such, but was obtained as an equilibrium mixture of 2a and N1-(p-chlorobenzoyl)-N1-(p-chlorophenyl)-N2-(p-methoxyphenyl)acetamidine (2a') owing to rapid 1, 3-N, N-acylotropic rearrangement.N1-Acyl derivatives of unsymmetrical N1, N2-disubstituted formamidines could be isolated as such, showing that 1, 3-N, N-acyl migration takes place more slowly in the acylated formamidine system. An acyl derivative of formamidine in which the acyl group is attached at the less basic nitrogen of amidine underwent 1, 3-N.N-acyl migration to give another acyl derivative at elevated temperature.Reaction of N1-tosyl-N1-(p-nitrophenyl)-N2-(m-nitrophenyl)acetamidine (1h) and N-acylarylamines gave N1-acyl-N1-aryl-N2-(m-nitrophenyl)acetamidines (2) which underwent alcoholysis to give carboxylic acid ester and N1-aryl-N2-(m-nitrophenyl)acetamidines (3) at room temperature, and the latter was hydrolyzed to give arylamines and N-acetyl-m-nitroaniline on heating in aqueous tetrahydrofuran solution in the presence of acetic acid. Thus, the alcoholysis of N-acylarylamines was achieved under mild conditions.

  N1-托斯基基-N1, N2-二芳基乙醇胺（1）在N-托斯基酰胺阴离子对胺基中间碳的亲核攻击下发生反应，较弱基础性的N-托斯基酰胺基团从中间体中排出，导致酰胺交换反应。1与N-芳基羧酰胺的反应生成N1-酰基-N1, N2-二芳基乙醇胺（2）。N1-(对氯苯甲酰基)-N1-(对甲氧基苯基)-N2-(对氯苯基)乙醇胺（2a）无法单独获得，而是作为2a和N1-(对氯苯甲酰基)-N1-(对氯苯基)-N2-(对甲氧基苯基)乙醇胺（2a'）的平衡混合物获得，这归因于快速的1, 3-N, N-酰基转位。非对称N1, N2-二取代福尔马胺的N1-酰基衍生物能够作为独立物质分离出来，显示在酰基福尔马胺系统中，1, 3-N, N-酰基迁移的速度较慢。一种在胺基的较弱基本氮原子上连接酰基的福尔马胺酰基衍生物在升高温度下经历1, 3-N, N-酰基迁移，形成另一种酰基衍生物。N1-托斯基基-N1-(对硝基苯基)-N2-(间硝基苯基)乙醇胺（1h）与N-酰基芳胺反应生成N1-酰基-N1-芳基-N2-(间硝基苯基)乙醇胺（2），该化合物在室温下发生醇解，生成羧酸酯和N1-芳基-N2-(间硝基苯基)乙醇胺（3），后者在水合四氢呋喃溶液中与醋酸共同加热时水解生成芳胺和N-乙酰-间硝基苯胺。因此，N-酰基芳胺的醇解是在温和条件下实现的。
• Amidines. II. Preparation of unsymmetrical N1,N2-disubstituted amidines.
  作者：Machiko ONO、Reiko TODORIKI、Shinzo TAMURA

  DOI：10.1248/cpb.38.866

  日期：——

  Unsymmetrical N1, N2-disubstituted amidines were prepared by conventional and newly developed methods. Reaction of N1-tosyl-N1, N2-diarylacetamidines and arylamines gave unsymmetrical acetamidines in the presence of basic catalysts, and N1-acyl-N1, N2-di(p-nitrophenyl)formamidines and arylamines gave unsymmetrical formamidines under neutral conditions. Unsymmetrical amidines exist as tautomeric mixtures in solution owing to proton transfer between the two nitrogen atoms, and it was proved on the basis of proton nuclear magnetic resonance (1H-NMR) evidence that the tautomer in which the hydrogen is attached to the more basic nitrogen atom is predominant.

  不对称的N1、N2-二取代氨基脲通过传统方法和新开发的方法制备而成。N1-对苯磺酰基-N1、N2-二芳基乙酰氨基脲与芳胺反应，在碱性催化剂的存在下生成不对称乙酰氨基脲，而N1-酰基-N1、N2-二(对硝基苯基)甲酰氨基脲与芳胺在中性条件下生成不对称甲酰氨基脲。不对称氨基脲因两个氮原子之间的质子转移而在溶液中以 tautomeric 混合物的形式存在，并且基于质子核磁共振 (1H-NMR) 的证据证明，氢原子与更基本的氮原子结合的 tautomer 是占主导地位的。
• Amidines. III. A kinetic study of acid hydrolysis of unsymmetrical N1,N2-disubstituted amidines.
  作者：Machiko ONO、Reiko TODORIKI、Ichiro ARAYA、Shinzo TAMURA

  DOI：10.1248/cpb.38.1158

  日期：——

  Acid hydrolysis of unsymmetrical N1, N2-disubstituted acetamidine and formamidine was examined kinetically in aqueous dioxane solution. The reaction afforded the more basic amine and the N-acyl derivative of the less basic amine. Increasing the dioxane content in the solvent increased the reaction rate. The reaction can be rationalized in terms of specific acid-general base catalysis.

  在水合二氧六环溶液中，动力学研究了不对称N1, N2-二取代乙酰胺和甲酰胺的酸性水解反应。该反应生成了更碱性的胺和较不碱性胺的N-酰衍生物。增加溶剂中二氧六环的含量提高了反应速率。该反应可以通过特定酸-一般碱催化的理论进行解释。