A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1964, 44, 7
DOI: 10.15227/orgsyn.044.0007
[Allylamine, 2-bromo-N-ethyl-]
Submitted by Albert T. Bottini and Robert E. Olsen1.
Checked by Thomas H. Lowry and E. J. Corey.
1. Procedure
Caution! This preparation should be carried out in a hood to avoid exposure to ethylamine, 2,3-Dibromopropene, and the product. 2,3-Dibromopropene is a strong lachrymator. The operator should wear rubber gloves and protective goggles because some 2-haloallylamines have caused severe skin and eye irritation.
A 1-l. three-necked flask is fitted with a sealed mechanical stirrer, a dropping funnel, and a dry ice condenser charged with an ice-salt mixture (Note 1). Three hundred milliliters (240 g., 3.7 moles) of aqueous 70% ethylamine solution (Note 2) is placed in the flask, the stirrer is started, and 200 g. (1.00 mole) of 2,3-dibromopropene (Note 3) is added dropwise over a period of 1 hour. After the addition is complete, the reaction mixture is stirred for 3 hours. Ether (300 ml.) is added, and the mixture is cooled in an ice bath. Sodium hydroxide (100 g.) is added with stirring and cooling. The cold mixture is transferred to a separatory funnel, and the phases are separated. The organic layer is dried in two stages over 25-g. portions of sodium hydroxide. The organic layer and the small amount of water that separates during the second stage of drying are decanted into a separatory funnel, and the phases are separated. Most of the ether and unreacted ethylamine are removed from the organic layer by distillation through a 250-mm. × 13-mm. column packed with glass helices, and the residue is distilled through the same column at reduced pressure under nitrogen to give 115–128 g. (70–78%) of N-(2-bromoallyl)ethylamine; b.p. 53–55° (27 mm.), 79–81° (75 mm.) (Note 4); n25D 1.4765–1.4770.
2. Notes
1. The checkers used an inner-spiral water condenser. The cooling water was chilled to about 0° by prior passage through a short copper coil immersed in ice.
2. The aqueous 70% ethylamine solution used was the practical grade obtained from Eastman Organic Chemicals.
3. The 2,3-dibromopropene used was obtained from Columbia Organic Chemicals Co., Columbia, South Carolina, and was redistilled before use. The preparation of 2,3-dibromopropene is described in an earlier volume of this series.2
4. The reported boiling point of N-(2-bromoallyl)ethylamine is 148–153°.3 It is strongly recommended that the product and other 2-haloallylamines be distilled at reduced pressure under nitrogen, for the submitters have noted two instances when a 2-haloallylamine polymerized with considerable evolution of heat during slow distillation at atmospheric pressure.
3. Discussion
This method is essentially that described by Pollard and Parcell.3 No other procedure appears to have been used to prepare N-(2-bromoallyl)ethylamine. A number of N-(2-haloallyl)alkylamines have been prepared by treatment of a 2,3-dihalopropene with a primary alkylamine in water,3,4 ether,3,4 or benzene.5
4. Merits of the Preparation
The method described here has been used for the preparation of a number of N-(2-haloallyl)alkylamines from a water-soluble amine and the corresponding 2,3-dihalopropene.3,4
Treatment of an N-(2-bromoallyl)alkylamine with sodium amide in liquid ammonia yields the N-alkylallenimine together with a small amount of the N-alkylpropargylamine.3,4,5,6,7 Similar treatment of an N-(2-chloroallyl)alkylamine yields only the N-alkylpropargylamine.4,6
This preparation is referenced from:

References and Notes
  1. Department of Chemistry, University of California, Davis, California.
  2. R. Lespieau and M. Bourguel, Org. Syntheses, Coll. Vol. 1, 209 (1941).
  3. C. B. Pollard and R. F. Parcell, J. Am. Chem. Soc., 73, 2925 (1951).
  4. A. T. Bottini, B. J. King, and R. E. Olsen, J. Org. Chem., 28, 3241 (1963).
  5. J. V. Braun, M. Kuhn, and J. Weismantel, Ann., 449, 254 (1926).
  6. A. T. Bottini and J. D. Roberts, J. Am. Chem. Soc., 79, 1462 (1957).
  7. A. T. Bottini and R. E. Olsen, this volume, p. 541.

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

ammonia (7664-41-7)

Benzene (71-43-2)

ether (60-29-7)

sodium hydroxide (1310-73-2)

nitrogen (7727-37-9)

copper (7440-50-8)

2,3-Dibromopropene (513-31-5)

sodium amide (7782-92-5)

ethylamine (75-04-7)

Allylamine, 2-bromo-N-ethyl- (871-23-8)