Ethanol → 4-(aminomethyl)-2-iodoaniline

To a solution of (2.44 g, 10 mmol) 4-amino-3-iodobenzonitrile (Helv. Chim. Acta. 54: 1486-1488, 1971, Toth: "Die jodierung von desaktivierten aromatischen aminen in wasseriger phase.") in dry THF (5 ml) was added 30 ml of borane-tetrahydrofuran complex solution (30 mmole) with stirring. The solution was heated at reflux temperature for 1 hr. under argon. Upon cooling, ethanol (2 ml) was added to quench excess borane. After the vigorous reaction subsided, water (30 ml) and ether (40 ml) were added and the mixture was separated. The aqueous layer was again extracted with ether (2×40 ml) and the combined ether extracts were dried. HCl gas was bubbled through the ether solution for 10 min. and the granular white precipitate which resulted was collected and recrystallized from methanol (3.0 g, 94%): mp 185°-195° C. (dec); IR (cm-1) Nujol 3500, 1545, 1595 (amine salt); PMR (DMSO-d6) γ8.5 (br, S, 2H), 7.8 (m, 3H), 7.2 (br, S, 2H), 3.7 (S, 2H). Anal. Calcd. for C7H9NI.2HCl: C, 26.17; H, 3.43; N, 8.72. Found: C, 26.21; H, 3.42; N, 8.75.

1. temperatureThe solution was heated
2. temperatureat reflux temperature for 1 hr
3. temperatureUpon cooling
4. customto quench excess borane
5. customAfter the vigorous reaction
6. customthe mixture was separated
7. extractionThe aqueous layer was again extracted with ether (2×40 ml)
8. dry with materialthe combined ether extracts were dried
9. customHCl gas was bubbled through the ether solution for 10 min.
10. customthe granular white precipitate which resulted
11. customwas collected
12. customrecrystallized from methanol (3.0 g, 94%)

ORD record

ord-79422372cf1f4405ba11efed839126a0

Source dataset

uspto-grants-1986_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04622217