4-Chloro-N1-(p-tolyl)benzene-1,2-diaMine synthesis

Yield:-

Reaction Conditions:

with iron;ammonium chloride in ethanol;water at 90; for 3 h;

Steps:

4.2.2. General procedure for the synthesis of target compounds 9a, 9b and 9c

General procedure: The main procedure is shown in Scheme 2. The raw products of compound 7 were synthesized via one-pot method in a flask containing compounds 5 (30 mmol), 6 (30 mmol), K₂CO₃ (15 mmol) and PEG1000 (0.45 mmol). The reactions were carried out under stirring at 185 °C and were monitored by TLC. After reactions completion, the desired diphenylamine derivatives 7 were obtained via column chromatographic purification. Next, compounds 7 (20 mmol), reductive iron powder (60 mmol), solid NH₄Cl (60 mmol) and ethanol aqueous solution (75%, 50 mL) were added. The reactions proceeded with refluxing for 3 h at 90 °C and compounds 8 were obtained. Then, compound 3 (30 mmol) and SOCl₂ (thionylchloride, 30 mL) were added. The mixture was heated to reflux at 90 °C for 3 h. Residual SOCl₂ was removed by vacuum distillation in order to obtain compound 4. Finally, the primary amines 8 (10 mmol) dissolved in dichloromethane (CH₂Cl₂, 5 mL) and triethylamine(Et₃N, 10 mL) were added. The mixture was cooled to 0 °C and compound 4 (20 mmol) dissolved in dichloromethane (CH₂Cl₂, 10 mL) was added dropwise under stirring at a temperature not exceeding 5 °C. The final mixture was stirred at room temperature for 10 h and the target compounds 9a, 9b and 9c were purified via column chromatography and recrystallization.

References:

Zhang, Xiao-Xiao;Jin, Hong;Deng, Yuan-Jie;Gao, Xu-Heng;Li, Yong;Zhao, Yong-Tian;Tao, Ke;Hou, Tai-Ping [Chinese Chemical Letters,2017,vol. 28,# 8,p. 1731 - 1736]