N,N'-bis(4-methylphenyl)-N-(4-methylphenyl)sulfonylethanimidamide | 89523-40-0

• 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,N'-bis(4-methylphenyl)-N-(4-methylphenyl)sulfonylethanimidamide
• 英文别名: N¹-Tosyl-N¹,N²-di(p-methylphenyl)-acetamidine；N¹-tosyl-N¹,N²-bis(p-methylphenyl)acetamidine；N¹-tosyl-N¹,N²-di(p-methylphenyl)acetamidine
• CAS: 89523-40-0
• 化学式: C₂₃H₂₄N₂O₂S
• 分子量: 392.522
• InChiKey: XISVYRKTBGOCPF-HIXSDJFHSA-N

物化性质

• 熔点：
  107 °C(Solv: ethanol (64-17-5))
• 沸点：
  554.4±60.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.56
• 重原子数：
  28.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  49.74
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  N,N'-bis(4-methylphenyl)-N-(4-methylphenyl)sulfonylethanimidamide 在 正丁基锂 作用下， 以 四氢呋喃 、 吡啶 、 正己烷 为溶剂， 反应 48.5h， 生成 N¹-(p-Nitrobenzenesulfonyl)-N²-(p-methylphenyl)-N¹-(p-chlorophenyl)-acetamidine
  参考文献：
  名称：

  Amidines. V. Smiles rearrangement of N1-(p-nitrobenzenesulfonyl)-N1,N2-diarylacetamidines.

  摘要：

  N1-甲苯磺酰基-N1,N2-二芳基乙脒(1)在脒中心碳上受到N-甲苯磺胺和N-酰胺的亲核攻击，得到N-1,N2-二取代乙脒的N1-甲苯磺酰基和N1-酰基衍生物尝试制备N1-(对硝基苯磺酰基)-N1,N2-二芳基乙脒(8)以获得用于上述酰胺交换反应的更好的起始原料。然而，这些化合物被证明不适合该目的，因为它们很容易进行 Smiles 重排，得到 N1-(对硝基苯基-N1, N2-二芳基乙脒 (9))，同时失去二氧化硫。 N1-(对硝基苯基)-N1当 N1-(对硝基苯磺酰基)-N1-(对氯苯基)-N2-(对甲基苯基)乙脒的乙醇溶液(9d)形成-(对甲基苯基)-N2-(对氯苯基)乙脒(9d)。 8d)在没有任何催化剂的情况下回流2.5小时。

  DOI：

  10.1248/cpb.38.1373
• 作为产物：
  描述：

  N,N'-di(p-tolyl)acetamidine 、 对甲苯磺酰氯 在 三乙胺 作用下， 以 苯 为溶剂， 反应 48.0h， 以77%的产率得到N,N'-bis(4-methylphenyl)-N-(4-methylphenyl)sulfonylethanimidamide
  参考文献：
  名称：

  Ono, Machiko; Tanaka, Hinako; Hayakawa, Kazuhide, Chemical and pharmaceutical bulletin, 1983, vol. 31, # 10, p. 3534 - 3543

  摘要：

  DOI：

文献信息

• Amidines. IV. Hydrolysis of N1-acyl derivatives of N1,N2-diarylamidine in carboxylate buffer solution.
  作者：Machiko ONO、Kazuhide HAYAKAWA、Shinzo TAMURA

  DOI：10.1248/cpb.38.1176

  日期：——

  In the hydrolysis of N1-benzoyl-N1, N2-diphenylacetamidine (1) in carboxylate buffer solutions, nucleophilic attack of the catalytic acid was proved to take place at the amide carbonyl carbon (pathway d) and presumably also at the amidine central carbon (pathway e) in parallel to the normal hydrolysis processes. Mixed acid anhydride and N1, N2-diphenylacetamidine were formed by pathway d, and the former reacted with aniline formed by further hydrolysis of the latter to give two N-acylanilines. In parallel with this process, the mixed anhydride reacts with water to give two carboxylic acids. In this case, carboxylic acid acts as a nucleophilic catalyst.The reaction of 1 and p-methoxybenzoic acid under anhydrous conditions gave products derived from the attack of p-methoxybenzoate ion at both amide carbonyl and amidine central carbons.Hydrolysis of N1-benzoyl-N-1, N2-diphenylformamidine (7) in acetate buffer solution proceeded mainly through the ordinary hydrolysis pathway. Formation of a small amount of acetanilide implies that the reaction proceeds through pathway d or e to a small extent.In hydrolysis of N1-tosyl-N1, N2-di(p-methylphenyl)acetamidine (6b) in glycolate buffer solution, a small amount of N-(acetoxyacetyl)-p-toluidine was formed together with the ordinary hydrolysis products. This implies that the reaction proceeds through pathway e to a small extent.

  在N1-苯甲酰-N1, N2-二苯基乙酰胺（1）在羧酸盐缓冲溶液中的水解过程中，催化酸的亲核攻击被证明发生在酰胺羰基碳（路径d），并且推测同时也在氨基中央碳上发生（路径e），与常规水解过程并行。通过路径d形成了混合酸酐和N1, N2-二苯基乙酰胺，而前者与通过对后者的进一步水解生成的苯胺反应，生成两个N-酰氨基苯。他们同时，混合酸酐与水反应，生成两个羧酸。在这种情况下，羧酸作为亲核催化剂。N1-苯甲酰-N-1, N2-二苯基甲酰胺（7）在醋酸盐缓冲液中的水解主要通过普通水解路径进行。少量乙酰苯胺的形成意味着反应在一定程度上通过路径d或e进行。在N1-对甲苯磺酰-N1, N2-二（对甲基苯基）乙酰胺（6b）在乙二醇酸盐缓冲液中的水解过程中，除了普通水解产物外，还形成了少量N-(乙酰氧乙酰)-对甲基苯胺。这意味着反应在一定程度上通过路径e进行。
• ONO, MACHIKO;TAMURA, SHINZO, CHEM. AND PHARM. BULL., 38,(1990) N, C. 590-596
  作者：ONO, MACHIKO、TAMURA, SHINZO

  DOI：——

  日期：——
• ONO, MACHIKO;TANAKA, HINAKO;HAYAKAWA, KAZUHIDE;TAMURA, SHINZO, CHEM. AND PHARM. BULL., 1983, 31, N 10, 3534-3543
  作者：ONO, MACHIKO、TANAKA, HINAKO、HAYAKAWA, KAZUHIDE、TAMURA, SHINZO

  DOI：——

  日期：——
• Ono, Machiko; Tanaka, Hinako; Hayakawa, Kazuhide, Chemical and pharmaceutical bulletin, 1983, vol. 31, # 10, p. 3534 - 3543
  作者：Ono, Machiko、Tanaka, Hinako、Hayakawa, Kazuhide、Tamura, Shinzo

  DOI：——

  日期：——
• Amidines. V. Smiles rearrangement of N1-(p-nitrobenzenesulfonyl)-N1,N2-diarylacetamidines.
  作者：Machiko ONO、Ichiro ARAYA、Shinzo TAMURA

  DOI：10.1248/cpb.38.1373

  日期：——

  N1-Tosyl-N1, N2-diarylacetamidine (1) suffered nucleophilic attack of N-tosylamines and N-acylamines at the amidine central carbon to give N1-tosyl and N1-acyl derivatives of N-1, N2-disubstituted acetamidine in the presence of a basic catalyst.Preparation of N1-(p-nitrobenzenesulfonyl)-N1, N2-diarylacetamidines (8) was attempted to obtain better starting materials for the above amide exchange reaction. These compounds, however, proved to be unsuitable for the purpose because they readily underwent Smiles rearrangement to give N1-(p-nitrophenyl-N1, N2-diarylacetamidines (9) with loss of sulfur dioxide.N1-(p-Nitrophenyl)-N1-(p-methylphenyl)-N2-(p-chlorophenyl)acetamidine (9d) was formed when an ethanol solution of N1-(p-nitrobenzenesulfonyl)-N1-(p-chlorophenyl)-N2-(p-methylphenyl)acetamidine (8d) was refluxed for 2.5h in the absence of any catalyst.

  N1-甲苯磺酰基-N1,N2-二芳基乙脒(1)在脒中心碳上受到N-甲苯磺胺和N-酰胺的亲核攻击，得到N-1,N2-二取代乙脒的N1-甲苯磺酰基和N1-酰基衍生物尝试制备N1-(对硝基苯磺酰基)-N1,N2-二芳基乙脒(8)以获得用于上述酰胺交换反应的更好的起始原料。然而，这些化合物被证明不适合该目的，因为它们很容易进行 Smiles 重排，得到 N1-(对硝基苯基-N1, N2-二芳基乙脒 (9))，同时失去二氧化硫。 N1-(对硝基苯基)-N1当 N1-(对硝基苯磺酰基)-N1-(对氯苯基)-N2-(对甲基苯基)乙脒的乙醇溶液(9d)形成-(对甲基苯基)-N2-(对氯苯基)乙脒(9d)。 8d)在没有任何催化剂的情况下回流2.5小时。