In a
3-l. three-necked round-bottomed flask fitted with a stirrer and a low-temperature thermometer is placed
500 ml. of concentrated hydrochloric acid (6.0 moles), and the solution is cooled to 0°. To the cooled solution,
142 g. (1.5 moles) of 2-aminopyrimidine (Note
1) is added portionwise with stirring until a homogeneous solution is obtained. The solution is cooled to −15° (Note
2), and a
500-ml. dropping funnel is fitted to the flask. A cold solution of
207 g. (3.0 moles) of sodium nitrite in 375 ml. of water is then added dropwise with stirring over a period of 55 minutes, the reaction temperature being maintained at −15° to −10° (Note
3). The solution is stirred an additional hour, and the temperature is allowed to rise to −5°. The mixture is then carefully neutralized to about pH 7 with a
30% solution of sodium hydroxide (about 3.0 moles), care being taken not to allow the temperature to rise above 0° (Note
4). The solid which forms, consisting of
2-chloropyrimidine and
sodium chloride, is collected by filtration and washed thoroughly with
ether to dissolve all the
2-chloropyrimidine. The cold solution is extracted with four
75-ml. portions of ether (Note
5). The combined extracts are dried over
anhydrous sodium sulfate, the solvent is removed, and the residue is recrystallized from
isopentane to give white crystals of
2-chloropyrimidine. The yield is
44–46 g. (
26–27%), m.p.
64.5–65.5°.