(3-CHLORO-2-METHYL-PHENYL)-HYDRAZINE synthesis

Yield:39943-64-1 98%

Reaction Conditions:

Stage #1: 3-chloro-2-methylbenzenaminewith hydrogenchloride;trifluoroacetic acid in water at 20; for 0.166667 h;
Stage #2: with sodium nitrite in water at 0; for 1 h;
Stage #3: with hydrogenchloride;tin(ll) chloride in water at 20;

Steps:

58a Example 58a (3-chloro-2-methylphenyl)hydrazine

3-chloro-2-methylaniline (30 g, 212 mmol) was treated with trifluoroacetic acid (65 mL) and concentrated hydrochloric acid (300 mL, 9874 mmol) in a 250 mL round-bottomed flask and then stirred at ambient temperature for 10 minutes. The suspension was cooled to about 0° C. in an ice bath. A solution of sodium nitrite (17.98 g, 261 mmol) in water (150 mL) was added dropwise via syringe. After the completion of addition, the mixture was stirred at 0° C. for 1 hour. A cold solution of tin(II) chloride (88 g, 466 mmol) in water (50 mL) and concentrated hydrochloric acid (100 mL, 3291 mmol) were added drop wise via dropping funnel to the reaction mixture. The mixture was stirred at ambient temperature, filtered through Buchner funnel to afford the title compound (40 g, 207 mmol, 98% yield). MS (ESI+): m/z 157 (M+H)⁺

References:

US2017/174688,2017,A1 Location in patent:Paragraph 0694