Benzoic Acid → 3,5-Diiodobenzoic acid

Participants

Reaction Conditions

Reaction Steps

The titled compound was prepared according to previously reported synthetic procedures under modified conditions (see e.g., Mak et al., J. Org. Chem. 2001, 66, 4476-4486). 4-amino-3,5-diiodobenzoic acid (2.0 g, 5.4 mmol) was added portion-wise to a stirred solution of t-butyl nitrite (1.07 g, 10.4 mmol) in DMF (10 mL) heated at 50° C. in a 3-neck round bottom flask equipped with a reflux condenser. Additional DMF (10 mL) was added halfway through the addition. Gas evolution was observed after each addition of the benzoic acid. Upon completion of the addition the reaction mixture was heated at 60° C. for 30 minutes and then allowed to cool to room temperature. The brown solution was diluted with diethyl ether (60 mL) and poured over dilute HCl (100 mL, 3N). The ethereal layer was removed and washed with 3N HCl (2×20 mL), water (3×20 mL) and brine (1×20 mL) then dried over anhydrous MgSO4. Removal of diethyl ether in vacuo and subsequent recrystallization in methanol afforded the desired compound in 77% yield (1.5 g, 4.0 mmol); mp 234-236° C. 1H-NMR (300 MHz, DMSO-d6) δ (ppm): 13.49 (s, 1H), 8.31 (s, 1H), 8.17 (s, 2H)13C-NMR (75 MHz, DMSO-d6) δ (ppm): 165.1, 148.6, 137.5, 134.7, 96.6 HRMS (m/z): [M−H]− calc. for C7H3I2O2, 372.8222. found 372.8231.

Provenance & Evidence