Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.
Procedure: 3-Fluoro-4-methoxyaniline (1, R=H, R2=CH3, R3=F) (95 g, 0.67 mol) was added to concentrated hydrochloric acid (250 mL), the suspension was stirred at ambient temperature for 18 hours, then it was cooled to 0° C. and a solution of sodium nitrite (53.7 g, 0.78 mol) in water (200 mL) was added dropwise at 0-5° C. When the addition was complete, the resulting solution was stirred at 0° C. for 1 hour then it was added dropwise at 0-5° C. to a stirred solution of tin (11) chloride dihydrate (638.9 g, 2.83 mol) in concentrated hydrochloric acid (500 mL). The mixture was allowed to warm to ambient temperature then it was stored at 4° C. for 18 hours. The resulting precipitate was collected by filtration, washed with water (400 ml), and ether (1000 mL) and dried in vacuo. The solid hydrochloride salt was basified by addition to 10% aqueous sodium hydroxide solution (800 mL), the free base was extracted into ether (2×400 mL), and the combined extracts were dried (MgSO4) and the solvent removed in vacuo to give (3-fluoro-4methoxyphenyl)hydrazine (2, R1=H, R3=CH2, R3=F) (51.9 g, 50%) as a yellow solid, mp 46-50° C.; 1HNMR (CDCl3/250 MHz): 1.5 (s, 1H, NH—NH2), 3.85 (s, 3H, OCH3), 5.0 (s, 2H, NH—NH2), 6.44 (m, 1H, phenyl 6-H), 6.60 (dd, 1H, phenyl 5-H), 6.79 (t, 1H, phenyl 2-H).
it was cooled to 0° C.
When the addition
the resulting solution was stirred at 0° C. for 1 hour
to warm to ambient temperature
it was stored at 4° C. for 18 hours
The resulting precipitate was collected by filtration
washed with water (400 ml), and ether (1000 mL)
dried in vacuo
The solid hydrochloride salt was basified by addition to 10% aqueous sodium hydroxide solution (800 mL)
the free base was extracted into ether (2×400 mL)
the combined extracts were dried (MgSO4)
the solvent removed in vacuo
Source ID: ord-6379048805fc4c489e5fb4198f5b4311