2-Methyl-5-(2-nitro-phenylamino)-thiazole-4-carbonitrile → 2-methyl-4H-3-thia-1,4,9-triazabenzo[f]azulene-10-ylamine hydrochloride

Participants

Reaction Conditions

Reaction Steps

Combine a suspension of 2-methyl-5-(2-nitroanilino)thiazole-4-nitrile (36 g, 138.5 mmol) in isopropanol (400 ml) in a 2.0 liter 3-necked RB flask equipped with a reflux condenser, thermometer, magnetic stirrer bar and heat with stirring to 65° C. (orange solution). Add tin (II) chloride hydrate (78.7 g, 415.4 mmol) in hydrochloric acid (400 ml; 5M) and heat the resulting solution at reflux. After 2.5 h., cool the reaction to 15° C., filter the suspension, wash with isopropanol/water (2:1) and dry at 50° C. under reduced pressure to leave a yellow solid (36.7 g). Evaporate the filtrate to around 200 mL to form a yellow slurry. Filter the slurry again and dry at 50° C. under reduced pressure to leave a yellow solid (10 g). Combine the solid and suspend in 1 N HCl (700 mL) and heat to reflux for 20 min, cool to 15° C. Filter the resulting yellow slurry and dry at 50° C. under reduced pressure to leave a yellow solid (32.4 g, 88%): mass spectrum (m/e): 231 (M+1); 1HNMR(300 MHz, DMSO-d6, ppm): δ 2.5(s, 3H), 6.78(dd, 1H), 6.85(dd, 1H), 6.98(t, 1H), 7.02(t, 1H), 8.80(s, 1H), 9.10(s, 1H), 9.98(s, 1H), 10.78(s, 1H). 13CNMR(75 MHz, DMSO, ppm): δ 19.6, 120.1, 120.8, 123.6, 125.8, 127.8, 129.2, 137.6, 154.4, 159.3, 160.4. Formula C11H11N4S.

Provenance & Evidence