4-Iodoaniline → 4-Iodophenylhydrazine

Participants

Reaction Steps

The title compound was synthesized in accordance with Reaction Scheme 2. The product obtained had the formula of compound (13), in which X and X1 represent C(CH3)2, R/R1 represent C22H14 /C45H29 and A represents Cl. 4-iodophenylhydrazine was prepared by the procedure of Blaikie et al., J. Chem. Soc., 313:296 (1924). Sodium nitrate (16.56 g, 0.24 mol, Aldrich) dissolved in water (100 ml) was added dropwise within 45 mins. to a solution of 4-iodoaniline (43.9 g, 0.20 mol, Aldrich) in ice-water (600 ml) and concentrated hydrochloric acid (200 ml) which was cooled to 0°-2° C. The reaction mixture was stirred for a further 30 minutess at 0°-2° C. then tin(II) chloride (151.68 g, 0.8 mol, Aldrich) in c.HCl (150 ml) was added dropwise over 90 mins. while maintaining the temp. of the reaction mixture between 0°-2° C. Following the addition, the resulting solution was warmed to room temperature and stirred for 3 hours. The yellow solid which had separated from the solution was then collected by filtration, placed in ice water (800 ml) and the pH adjusted to 10 with 25% aqueous potassium hydroxide solution. The resulting solid was collected by filtration, washed with a small amount of water and dried under vacuum. The product was then placed in toluene (400 ml) and filtered to remove insoluble impurities. Hexane (1200 ml) was added and upon cooling in the refrigerator yellow needles separated which were collected by filtration, washed with hexane (100 ml) and dried under high vacuum to give pure 4-Iodophenylhydrazine (23.36 g, 50%), m.p.=94° C.

Provenance & Evidence