4-Iodoaniline → 4-Iodophenylhydrazine

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.

1. customThe product obtained
2. custom4-iodophenylhydrazine was prepared by the procedure of Blaikie et al., J
3. additionwas added dropwise within 45 mins
4. temperaturewhile maintaining the temp
5. custombetween 0°-2° C
6. additionthe addition
7. stirringstirred for 3 hours
8. customThe yellow solid which had separated from the solution
9. filtrationwas then collected by filtration
10. filtrationThe resulting solid was collected by filtration
11. washwashed with a small amount of water
12. customdried under vacuum
13. filtrationfiltered
14. customto remove insoluble impurities
15. additionHexane (1200 ml) was added
16. temperatureupon cooling in the refrigerator yellow needles
17. customseparated which
18. filtrationwere collected by filtration
19. washwashed with hexane (100 ml)
20. customdried under high vacuum

ORD record

ord-fc3f702a52074c60ba3626660e0e91b2

Source dataset

uspto-grants-1997_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05667764