Org. Synth. 1927, 7, 16
DOI: 10.15227/orgsyn.007.0016
[Acetamide, α-chloro-]
Submitted by W. A. Jacobs and M. Heidelberger.
Checked by C. S. Marvel and D. D. Coffman.
1. Procedure
In a 2-l. round-bottomed flask fitted with a mechanical stirrer and surrounded by an ice-salt bath is placed 215 g. (1.75 moles) of ethyl chloroacetate (Note 1). Vigorous stirring is started, and to the cold ester (Note 2) 200 cc. of chilled aqueous ammonia (sp. gr. 0.9) is added. The solution is stirred in the cold for about fifteen minutes; then another 200-cc. portion of aqueous ammonia is added, and the stirring is continued for about fifteen minutes. The mixture is then allowed to stand for thirty minutes, filtered with suction, and washed with two 25-cc. portions of cold water to remove ammonium chloride. The yield of air-dried material melting at 118–119° (Note 3) is 128–138 g. (78–84 per cent of the theoretical amount).
This product contains traces of ammonium chloride which may be removed by crystallization from water. When 100 g. of crude product is recrystallized from 400 cc. of water, about 80 g. of product is obtained. The recrystallized product melts at 119–120°.
2. Notes
1. The ethyl chloroacetate used may be a commercial grade which boils at 141–146°. The ethyl chloroacetate and the chloroacetamide have the usual irritating effect of chloroacetyl compounds.
2. The temperature is best maintained at 0–5°. At higher temperatures there is more replacement of the chlorine and the yields are considerably lower.
3. Traces of moisture lower the melting point considerably.
3. Discussion
Chloroacetamide can be prepared from chloroacetyl chloride and dry ammonia gas,1 and by the treatment of ethyl chloroacetate2 or methyl chloroacetate3 with cold aqueous ammonia solutions. The procedure described was developed from the methods of Scholl2 and Tröger and Hille.2
This preparation is referenced from:

References and Notes
  1. Willm, Ann. 102, 110 (1857).
  2. Willm, Ann. 102, 110 (1857); Menschutkin and Jermolajev, Z. Chem. 5 (1871); Bauer, Ann. 229, 165 (1885); Scholl, Ber. 29, 2417 (1896); Tröger and Hille, J. prakt. Chem. (2) 71, 204 (1905).
  3. Henry, Rec. trav. chim. 24, 165 (footnote 3) (1905).

Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

chloroacetyl compounds

ammonia (7664-41-7)

ammonium chloride (12125-02-9)

chlorine (7782-50-5)

Acetamide, α-chloro- (79-07-2)

Ethyl chloroacetate (105-39-5)

chloroacetyl chloride (79-04-9)

methyl chloroacetate (96-34-4)