反应详情

A solution of triphosgene (19.5 g, 0.065 mol) in CH2Cl2 (200 mL) was added stepwise to a CH2Cl2 solution (150 mL) of ethyl 2,2-bis(methylol)propionate (MPAEt) (21.1 g, 0.131 mol) and pyridine (64 mL, 0.786 mol) over 30 min at −75° C. with dry ice/acetone. The reaction mixture was kept stirring for another 2 hours under chilled condition and then allowed to heat to room temperature. Saturated NH4Cl aqueous solution (200 mL) was added to the reaction mixture to decompose excess triphosgene. The organic phase was then treated with 1 N HCl aq (200 mL), followed by saturated NaHCO3 (200 mL), brine (200 mL), and water (200 mL). After the CH2Cl2 solution was dried over MgSO4 and evaporated, the residue was recrystallized from ethylacetate to give white crystals (13.8 g, 56%). 1H NMR: delta 4.68 (d, 2H, CH2OCOO), 4.25 (q, 1H, OCH2CH3), 4.19 (d, 2H, CH2OCOO), 1.32 (s, 3H, CH3), 1.29 (t, 3H, CH3CH2O). 13C NMR: delta 171.0, 147.5, 72.9, 62.1, 39.9, 17.3, 13.8. HR-ESI-MS: m/z calcd for C8H12O5.Na, 211.0582; found, 221.0578.

1. temperatureunder chilled condition
2. dry with materialAfter the CH2Cl2 solution was dried over MgSO4
3. customevaporated
4. customthe residue was recrystallized from ethylacetate