Pyridine → Ethyl 4-(methoxycarbonylmethoxy)acetoacetate
Reaction equation
Cl[C:2]([CH2:4][O:5][CH2:6][C:7]([O:9][CH3:10])=[O:8])=[O:3].[CH3:11][C:12]1(C)[O:17]C(=O)[CH2:15][C:14](=O)[O:13]1.N1C=CC=CC=1>ClCCl>[CH3:10][O:9][C:7]([CH2:6][O:5][CH2:4][C:2](=[O:3])[CH2:11][C:12]([O:13][CH2:14][CH3:15])=[O:17])=[O:8]Participants
Conditions
- Temperature
- 5 °C
Procedure
Methyl 2-(chloroformylmethoxy)acetate (216.6 g) was added over 45 minutes to a stirred solution of 2,2-dimethyl-1,3-dioxane-4,6-dione (173.9 g) and pyridine (189.6 g) in dichloromethane (1000 ml) keeping the temperature below 5° C. The mixture was stirred at 5° C. for 30 minutes, allowing to warm up to room temperature over one hour, washed with 2.4M hydrochloric acid and water, dried over magnesium sulphate and evaporated. The resulting browm oil was dissolved in ethanol (300 ml) and the solution heated under reflux for 2.5 hours and evaporated. The residual oil was distilled to give the title compound (32.5 g), b.p. 138°-140°/l torr which was characterised by its N.m.r. spectrum in CDCl3, δ values: 4.27 (2H,s); 4.20 (2H, q, J 7 Hz); 4.16 (2H,s); 3.75 (3H, s); 3.54 (2H, s); 1.29 (3H, t, J 7 Hz).
Workup
- customthe temperature below 5° C
- temperatureto warm up to room temperature over one hour
- washwashed with 2.4M hydrochloric acid and water
- dry with materialdried over magnesium sulphate
- customevaporated
- dissolutionThe resulting browm oil was dissolved in ethanol (300 ml)
- temperaturethe solution heated
- temperatureunder reflux for 2.5 hours
- customevaporated
- distillationThe residual oil was distilled
Sources & evidence
- ORD record
- ord-9a830c34682e4d26bc6c765c40153146
- Source dataset
- uspto-grants-1986_10
- Patent number
- US04616024
Reaction notes
Loading…