Synthesis
The general procedure for the synthesis of 4-hydrazinylbenzonitrile from 4-aminobenzonitrile was as follows: aqueous hydrochloric acid solution was slowly added to a conical flask solution of 4-cyanobenzenamine (6.0 g, 0.050 mol) under cooling conditions. Subsequently, sodium nitrite solution (3.85 g, 0.055 mmol) was added dropwise at -15 °C. The reaction mixture was stirred at 0-10 °C for 15 min and then filtered to remove insoluble matter. The filtrate was slowly added to a pre-cooled hydrochloric acid solution of stannous chloride (24.0 g, 0.166 mmol). The reaction temperature was maintained at -15°C and stirring was continued for 30 minutes. Upon completion of the reaction, the solid product was collected by filtration to afford 5.2 g of the target compound 4-hydrazinylbenzonitrile. The structure of the product was confirmed by 1H NMR (300 MHz, DMSO-d6) with the following characteristic peaks: δ 7.04 (d, 2H), 7.70 (d, 2H), 9.17 (br s, 1H), 10.66 (br s, 2H).
References
[1] Organic Letters, 2015, vol. 17, # 24, p. 6258 - 6261
[2] Journal of the American Chemical Society, 1944, vol. 66, p. 1849
[3] Journal of Organic Chemistry, 2012, vol. 77, # 23, p. 10699 - 10706
[4] Patent: WO2013/186692, 2013, A1. Location in patent: Page/Page column 73
[5] Molecules, 2016, vol. 21, # 11,
