反应详情

A suspension of MIBAHCl (220.00 g, 99.0% (GC), 1.56 mol) in methyl formate (767.32 g, 12.73 mol) was heated to reflux, and triethylamine (175.39 g, 1.73 mol) was added dropwise. The reaction mixture was heated to reflux. The reaction was monitored by TLC until disappearance of MIBAHCl. After 68 hours, the resulting white suspension was cooled to room temperature the solution was filtered and the residue rinsed with diethyl ether (2862 mL). The filtrate was concentrated by rotary evaporation under reduced pressure and the product, a yellow oil, was distilled under reduced pressure (1.5 mmHg). MIBF was yielded as a colorless liquid (201.34 g, 98% yield, 99.8% (GC), b.p.: 120.0-120.5° C./1.50 mmHg); TLC Rf 0.2 (4:1 ethyl acetate/hexanes, detection with p-anisaldehyde spray); FTIR(neat): ν 3300, 3061, 2977, 2938, 2831, 2751, 1671, 1534, 1469, 1385, 1368, 1287, 1238, 1183, 1164, 1079, 1034, 1004, 957, 858, 721, 666 cm−1; 1H-NMR (600 MHz, CDCl3): δ 1.13 (s, 6H, 2 CH3), 3.16 (s, 3H, OCH3), 3.28 (d, J=5.9 Hz, 2H, CH2), 6.12 (br s, 1H, NH), 8.19 (s, 1H, CHO); 13C-NMR (151 MHz, CDCl3): δ 22.5 (2 CH3), 46.0 (CH2), 49.4 (OCH3), 74.1 (C), 161.4 (CHO); MS (EI): m/z=132[M+H]+; MS (Cl): m/z=132[M+H]−.

1. temperaturewas heated
2. temperatureto reflux
3. temperatureThe reaction mixture was heated to reflux
4. filtrationwas filtered
5. washthe residue rinsed with diethyl ether (2862 mL)
6. concentrationThe filtrate was concentrated by rotary evaporation under reduced pressure
7. distillationthe product, a yellow oil, was distilled under reduced pressure (1.5 mmHg)
8. customMIBF was yielded as a colorless liquid (201.34 g, 98% yield, 99.8% (GC), b.p.: 120.0-120.5° C./1.50 mmHg)