A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1955, 35, 20
DOI: 10.15227/orgsyn.035.0020
Submitted by P. J. Ashworth, G. H. Mansfield, and M. C. Whiting1.
Checked by John C. Sheehan, George Buchi, and Walfred S. Saari.
1. Procedure
Caution! The experimental procedure involving liquid ammonia should be conducted in a hood.
In a 3-l. three-necked round-bottomed flask fitted with a reflux condenser and a mercury-sealed stirrer, 250 g. (2 moles) of 1,3-dichloro-2-butene (Note 1) and 1.25 l. of 10% sodium carbonate are heated at reflux temperature for 3 hours. The 3-chloro-2-buten-1-ol is extracted with three 300-ml. portions of ether, which are then dried over anhydrous magnesium sulfate. The ether is removed by distillation through a 20-cm. Fenske column, and the residue is distilled from a 250-ml. Claisen flask, yielding 134 g. (63%) of 3-chloro-2-buten-1-ol, b.p. 58–60°/8 mm., n20D 1.4670.
A solution of sodium amide in liquid ammonia is prepared according to the procedure described on p. 763 using a 4-l. Dewar flask equipped with a plastic cover (Note 2) and a mechanical stirrer. Anhydrous liquid ammonia (3 l.) is introduced through a small hole in the plastic cover, and 1.5 g. of hydrated ferric nitrate is added followed by 65 g. (2.8 g. atoms) of clean, freshly cut sodium. The mixture is stirred until all the sodium is converted into sodium amide, after which 134 g. (1.26 moles) of 3-chloro-2-buten-1-ol is added over a period of 30 minutes. The mixture is stirred overnight, then 148 g. (2.8 moles) of solid ammonium chloride is added in portions at a rate that permits control of the exothermic reaction. The mixture is transferred to a metal bucket (5-l., preferably of stainless steel) and allowed to stand overnight in the hood while the ammonia evaporates. The residue is extracted thoroughly with five 250-ml. portions of ether, which is removed by distillation through a 20-cm. Fenske column. Distillation of the residue yields 66–75 g. (75–85%) of 2-butyn-1-ol, b.p. 55°/8 mm., n20D 1.4550 (Note 3).
2. Notes
1. 1,3-Dichloro-2-butene was obtained from Eastman Kodak Company. Redistillation of the crude material did not appreciably alter the yield in the first stage of the reaction.
2. The checkers used an ordinary flask, well insulated, for this reaction.
3. Others have reported b.p. 91–93°/50 mm., n25D 1.4630;2 b.p. 160.5°, n25D 1.4635;3 b.p. 160–161°, n25D 1.4635, for 3-chloro-2-buten-1-ol, and b.p. 87–88° /100 mm., n25D 1.4520;2 b.p. 140–141°, n25D 1.45174 for 2-butyn-1-ol.
3. Discussion
2-Butyn-1-ol has been prepared as above for the first stage2,3,4 but using aqueous sodium hydroxide2 and alcoholic potassium hydroxide4 for the second stage. The reaction between propynylmagnesium bromide and formaldehyde also has been employed.5,6,7

References and Notes
  1. Victoria University of Manchester, Manchester, England.
  2. Hatch and Nesbitt, J. Am. Chem. Soc., 72, 729 (1950).
  3. Hatch and Hudson, J. Am. Chem. Soc., 72, 2505 (1950).
  4. Hatch and Chiola, J. Am. Chem. Soc., 73, 360 (1951).
  5. Yvon, Compt. rend., 180, 748 (1925).
  6. Hurd and Cohen, J. Am. Chem. Soc., 53, 1074 (1931).
  7. Schulte and Reiss, Chem. Ber., 87, (1954).

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

ammonia (7664-41-7)

ether (60-29-7)

ammonium chloride (12125-02-9)

sodium hydroxide (1310-73-2)

formaldehyde (630-08-0)

sodium carbonate (497-19-8)

potassium hydroxide (1310-58-3)

sodium (13966-32-0)

magnesium sulfate (7487-88-9)

sodium amide (7782-92-5)

ferric nitrate

2-Butyn-1-ol (764-01-2)


3-Chloro-2-buten-1-ol (40605-42-3)

propynylmagnesium bromide