β-(m-Toluidino)acrolein | 51217-95-9

• 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: β-(m-Toluidino)acrolein
• CAS: 51217-95-9
• 化学式: C₁₀H₁₁NO
• 分子量: 161.203
• InChiKey: GPDFBNDQHCULNL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.12
• 重原子数：
  12.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  29.1
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  β-(m-Toluidino)acrolein 在 sodium hydroxide 作用下， 以 乙醇 、 水 为溶剂， 生成
  参考文献：
  名称：

  A kinetic study of alkaline hydrolysis of .BETA.-arylaminoacrolein.

  摘要：

  这项研究探讨了β-芳胺基丙烯醛(1)（一种酰胺的乙烯基类似物）的碱性水解动力学。研究发现动力学涉及羟离子的一级和二级项。 反应的第一步(速率常数k1)是羟离子对1的β位置的进攻，形成的四面体中间体有两种分解途径： 1. 不需要羟离子辅助的途径(k2(k1/k-1)) 2. 需要羟离子辅助的途径(k3(k1/k-1)) 研究对12种底物测定了速率常数k1、k2(k1/k-1)和k3(k1/k-1)，并对其中5种底物评估了每个步骤的活化参数ΔH≠和ΔS≠。随着芳基取代基吸电子效应的增强，k2/k-1值降低。 通过分子轨道(MO)计算评估了中间体与起始物质之间的ΔHf差异。结果表明，随着取代基吸电子效应的增强，k2降低。 二级反应的第二步k2(k1/k-1)是水作为普通酸催化阴离子中间体的分解。对于"典型"底物，三级反应的第二步k3(k1/k-1)是在羟离子和水的共同催化下芳胺基团从阴离子中间体上离去，而对于β-(对硝基苯胺基)丙烯醛(1j)，则是对硝基苯胺负离子直接从双负电荷中间体上消除。

  DOI：

  10.1248/cpb.37.2902
• 作为产物：
  描述：

  Benzenamine, 3-methyl-N-(3-((3-methylphenyl)amino)-2-propenylidene)- 在 水 、 sodium acetate 、 溶剂黄146 作用下， 以 乙醇 为溶剂， 反应 25.0h， 以49%的产率得到3-甲基苯胺
  参考文献：
  名称：

  Hydrolysis of malonaldehyde dianil and .BETA.-arylaminoacrolein derivatives.

  摘要：

  β-芳基氨基丙烯醛的可逆水解生成芳胺和丙二醛的动力学研究。评估了氢离子催化系数 (kH+) 和 β-芳基氨基丙烯醛的共轭酸的离解常数 (KBH+)。kH+ 和 KBH+ 的 Hammett 图呈线性。log kH+ 和 pKBH+ 的值分别通过方程 log kH+=1.38σ-2.81 和 pKBH+=-1.20σ+0.90 表示。丙二醛二苯胺的可逆水解生成 β-芳基氨基丙烯醛和芳胺的过程也被考察，以其与 β-芳基氨基丙烯醛的水解进行比较。在弱酸性条件下，通过丙二醛二苯胺的水解成功制备了 β-芳基氨基丙烯醛。

  DOI：

  10.1248/cpb.28.2356

文献信息

• β-Arylaminoacrolein Derivatives. I. The Investigation of Combes Reaction and the Syntheses of β-Arylaminoacrolein Derivatives as the Possible Reactant
  作者：SHINZO TAMURA、EMIKO YABE

  DOI：10.1248/cpb.21.2105

  日期：——

  The limitations of Combes reaction were reinvestigated. 4-(p-Chloroanilino)-3-penten-2-one (III), hitherto believed to be insusceptible to cyclodehydration in sulfuric acid, reacted at a higher temperature to give 2, 4-dimethyl-6-chloroquinoline (IV). 4-Anilino-3-buten-2-one (V), however, was sulfonated in concentrated sulfuric acid and no quinolines were detected in the reaction mixture. 4-(p-Chloroanilino)-3-buten-2-one (VI) was cyclodehydrated to give 6-chloroquinaldine (VIII) in dioxane containing sulfuric acid in low yield. β-Anilinoacrolein (X), a pussible reactant of Combes reaction, and its derivatives were synthesised for further studies, and their structure was confirmed by chemical evidences and by their infrared and nuclear magnetic resonance (NMR) spectra. The conformational analysis of β-arylaminoacroleins in three solvents was carried out using their NMR spectra.

  Combes反应的局限性被重新研究。迄今为止认为在硫酸中不易发生环化脱水的4-(4-氯苯胺基)-3-戊烯-2-酮(III)，在较高温度下反应生成了2,4-二甲基-6-氯喹啉(IV)。然而，4-苯胺基-3-丁烯-2-酮(V)在浓硫酸中被磺化，反应混合物中未检测到喹啉类化合物。4-(4-氯苯胺基)-3-丁烯-2-酮(VI)在含有硫酸的二氧六环中环化脱水，低产率地生成了6-氯喹哪啶(VIII)。β-苯胺基丙烯醛(X)，Combes反应的可能反应物及其衍生物被合成以供进一步研究，并通过化学证据和红外光谱、核磁共振(NMR)光谱确认了它们的结构。利用NMR光谱对β-芳胺基丙烯醛在三种溶剂中的构象进行了分析。
• Hydrolysis of malonaldehyde dianil and .BETA.-arylaminoacrolein derivatives.
  作者：SHINZO TAMURA、MACHIKO ONO、KAZUMI FURUYAMA

  DOI：10.1248/cpb.28.2356

  日期：——

  The reversible hydrolysis of β-arylaminoacrolein to form arylamine and malonaldehyde was studied kinetically. The catalytic coefficient of hydronium ions (kH+) and dissociation constant of the conjugate acid of β-arylaminoacrolein (KBH+) were evaluated. Hammett plots for kH+ and for KBH+ were linear. The values of log kH+ and pKBH+ were expressed by the equations log kH+=1.38σ-2.81 and pKBH+=-1.20σ+0.90, respectively. The reversible hydrolysis of malonaldehyde dianil to form β-arylaminoacrolein and arylamine was examined in relation to that of β-arylaminoacrolein. The preparation of β-arylaminoacrolein by hydrolysis of malonaldehyde dianil was achieved under weakly acidic conditions.

  β-芳基氨基丙烯醛的可逆水解生成芳胺和丙二醛的动力学研究。评估了氢离子催化系数 (kH+) 和 β-芳基氨基丙烯醛的共轭酸的离解常数 (KBH+)。kH+ 和 KBH+ 的 Hammett 图呈线性。log kH+ 和 pKBH+ 的值分别通过方程 log kH+=1.38σ-2.81 和 pKBH+=-1.20σ+0.90 表示。丙二醛二苯胺的可逆水解生成 β-芳基氨基丙烯醛和芳胺的过程也被考察，以其与 β-芳基氨基丙烯醛的水解进行比较。在弱酸性条件下，通过丙二醛二苯胺的水解成功制备了 β-芳基氨基丙烯醛。
• A kinetic study of alkaline hydrolysis of .BETA.-arylaminoacrolein.
  作者：Machiko ONO、Reiko TODORIKI、Akihisa MITAKE、Miho YUKAWA、Yoshinobu GOTO、Shinzo TAMURA

  DOI：10.1248/cpb.37.2902

  日期：——

  Alkaline hydrolysis of β-arylaminoacrolein (1), a vinylog of amides, was studied kinetically. The kinetics involved terms both first and second order in hydroxide ion. The first step of the reaction (rate constant k1) is an attack of hydroxide ion on the β-position of 1, and the tetrahedral intermediate formed was partitioned in two ways : one without the aid of hydroxide ion (k2(k1/k-1)), and the other with the aid of hydroxide ion (k3(k1/k-1)). The rate constants, k1, k2(k1/k-1) and k3(k1/k-1) were obtained for 12 substrates, and the activation parameters, ΔH≠ and ΔS≠, of each step were evaluated for 5 substrates. The k2/k-1 values decreased with increasing electron-withdrawing effect of aryl substituents. The differences of ΔHf between the intermediates and the starting materials were evaluated by molecular orbital (MO) calculatins. The results showed that k2 decreases with increasing electron-withdrawing effect of the substitutents. The second step of the second-order reaction, k2(k1/k-1), is partitioning of anionic intermediates catalyzed by water as a general acid. While the second step of the third-order reaction, k3(k1/k-1), for "typical" substrates is departure of the arylamino group from the anionic intermediates catalyzed by both hydroxide ion and water, that for β-(p-nitrophenylamino)acrolein (1j) is direct expulsion of p-nitroanilide ion from the dinegatively charged intermediate.

  这项研究探讨了β-芳胺基丙烯醛(1)（一种酰胺的乙烯基类似物）的碱性水解动力学。研究发现动力学涉及羟离子的一级和二级项。 反应的第一步(速率常数k1)是羟离子对1的β位置的进攻，形成的四面体中间体有两种分解途径： 1. 不需要羟离子辅助的途径(k2(k1/k-1)) 2. 需要羟离子辅助的途径(k3(k1/k-1)) 研究对12种底物测定了速率常数k1、k2(k1/k-1)和k3(k1/k-1)，并对其中5种底物评估了每个步骤的活化参数ΔH≠和ΔS≠。随着芳基取代基吸电子效应的增强，k2/k-1值降低。 通过分子轨道(MO)计算评估了中间体与起始物质之间的ΔHf差异。结果表明，随着取代基吸电子效应的增强，k2降低。 二级反应的第二步k2(k1/k-1)是水作为普通酸催化阴离子中间体的分解。对于"典型"底物，三级反应的第二步k3(k1/k-1)是在羟离子和水的共同催化下芳胺基团从阴离子中间体上离去，而对于β-(对硝基苯胺基)丙烯醛(1j)，则是对硝基苯胺负离子直接从双负电荷中间体上消除。