Organic Syntheses, CV 1, 272
Submitted by H. T. Clarke and T. F. Murray.
Checked by C. S. Marvel and M. M. Brubaker.
1. Procedure
In a
5-l. flask, fitted with a
stirrer, a
reflux condenser, and a
dropping funnel, is placed
1 kg. (1266 cc.) of absolute ethyl alcohol (
p. 249 and
p. 259);
92 g. (4 atoms) of sodium, cut into strips, is then added through the condenser at such a rate that the alcohol does not boil too vigorously. When all the
sodium is in solution, the flask is cooled and
800 g. (754 cc., 5 moles) of diethyl malonate added through the condenser, with stirring. The mixture is warmed gently on the
steam bath and
700 g. (658 cc., 4.1 moles) of diethyl fumarate (Note
1) added from the dropping funnel. During this addition the solution is kept boiling gently, heat being applied if necessary (Note
2). The mixture is boiled for one hour after the
diethyl fumarate has been added. It is then cooled and
250 g. (238 cc., 4.2 moles) of glacial acetic acid is added.
Most of the alcohol is distilled off under slightly reduced pressure on the steam bath and the residue is poured into sufficient distilled water to dissolve all the solid. The water layer is separated and extracted four times with
carbon tetrachloride, which is added to the ester layer. The
ester-carbon tetrachloride mixture is washed twice with water and the water washings extracted once with
carbon tetrachloride. The
carbon tetrachloride is distilled off under atmospheric pressure through a
column, the moisture being carried over simultaneously.
The residue is then distilled under reduced pressure, when the
ethyl propane-1,1,2,3-tetracarboxylate comes over at
182–184°/8 mm. The yield is
1261–1273 g. (
93–94 per cent of the theoretical amount).
2. Notes
2. Heat is developed during the reaction, and the mixture may be kept boiling by adding the
ethyl fumarate at a suitable rate.
3. Discussion
This preparation is referenced from:
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