A mixture of
200 g. (1.9 moles) of anhydrous sodium carbonate (Note
1) and
300 g. (1.25 moles) of ethyl bromomalonate (Org. Syn. Coll. Vol. I, 1941, 245) is heated for three hours in a
1-l. flask (Note
2) immersed in an
oil bath at 150–160° (Note
3). After the heating period,
300 cc. of xylene (Note
4) is added while the contents of the flask are still hot (Note
5). The solid is broken up carefully with a rod, and the mixture is transferred to a
2-l. beaker. The reaction flask is then rinsed with a mixture of
100 cc. of xylene and 100 cc. of water. This washing is poured into the 2-l. beaker, and an additional 600 cc. of water is added. The solid readily dissolves upon stirring. The liquid mixture is transferred to a
separatory funnel, shaken well, and allowed to settle (Note
6). The lower aqueous layer is discarded (Note
7). The
xylene layer is transferred to a 1-l. distilling flask and distilled until the temperature of the liquid itself is 170°. The liquid residue is then transferred to a
500-cc. Claisen flask and distilled under reduced pressure. The fore-run up to 170°/15 mm. is discarded. The product, which is collected at
170–230°/15 mm. (Note
8) and (Note
9), solidifies within about fifteen minutes. The yield is
150–160 g. (
75–80 per cent of the theoretical amount).
The crude product is dissolved in
75 cc. of 95 per cent alcohol at a temperature of 40°, which is sufficient to ensure complete solution. The alcoholic solution is cooled to 12° (Note
10) and (Note
11) and filtered. The yield of air-dried, colorless product melting at
52.5–53.5° is
95–110 g. (
47–55 per cent of the theoretical amount). By evaporation of the alcohol, distillation of the residue under reduced pressure, and recrystallization of the solidified distillate, the yield may be increased to
110–115 g. (
55–57 per cent of the theoretical amount).