反応 #84347

反応方程式

HCl

4-amino-3,5-diiodobenzoic acid

t-butyl nitrite

benzoic acid

→

desired compound

3,5-diiodobenzoic acid

溶媒

DMF

diethyl ether

DMF

反応条件

後処理

1. 1
   その他The titled compound was prepared
2. 2
   その他equipped with a reflux condenser
3. 3
   workup.ADDITIONthrough the addition
4. 4
   workup.ADDITIONUpon completion of the addition the reaction mixture
5. 5
   温度was heated at 60° C. for 30 minutes
6. 6
   温度to cool to room temperature
7. 7
   その他The ethereal layer was removed
8. 8
   洗浄washed with 3N HCl (2×20 mL), water (3×20 mL) and brine (1×20 mL)
9. 9
   乾燥then dried over anhydrous MgSO4
10. 10
    その他Removal of diethyl ether
11. 11
    その他in vacuo and subsequent recrystallization in methanol

実験手順

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.

出典