A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1945, 25, 84
DOI: 10.15227/orgsyn.025.0084
Submitted by L. A. Brooks and H. R. Snyder.
Checked by Nathan L. Drake and W. Mayo Smith.
1. Procedure
A. Tetrahydrofurfuryl chloride. In a 2-l. three-necked flask, fitted with a mechanical stirrer, a dropping funnel, and a thermometer, are placed 408 g. (4 moles) of freshly distilled tetrahydrofurfuryl alcohol (Note 1) and 348 g. (4.4 moles) of pyridine. To the rapidly stirred mixture, which is cooled in an ice bath, 500 g. (4.2 moles) of freshly distilled thionyl chloride (Note 1) is added from the dropping funnel at the rate of 3–5 drops per second. When one-third to one-half of the thionyl chloride has been added, a pasty crystalline mass begins to separate and the temperature begins to rise rapidly. The temperature should not be allowed to go above 60°. As more thionyl chloride is added the mass redissolves and a dark brown liquid forms. When the addition is complete, the bath is removed and the mixture is stirred for 3–4 hours. The liquid (or the slurry, if some crystallization has occurred) is poured into a beaker (Note 2) and extracted seven times with 500-ml. portions of ether (Note 3); the ether extracts are decanted and combined. The ether is removed by distillation, and the residue is washed three times with 100-ml. portions of water, dried over anhydrous magnesium sulfate, and distilled under reduced pressure. The yield of tetrahydrofurfuryl chloride boiling at 41–42° /11 mm. (47–48° /15 mm.) is 354–360 g. (73–75%).
B. 4-Penten-1-ol. A 2-l. three-necked flask containing 112 g. (4.87 moles) of powdered sodium (Note 4) under 700 ml. of anhydrous ether is fitted with a mechanical stirrer, a separatory funnel, and a reflux condenser with a drying tube. A few milliliters (2–3) of a mixture of 300 g. (2.5 moles) of tetrahydrofurfuryl chloride and 300 ml. of anhydrous ether is added to the rapidly stirred suspension. A vigorous reaction occurs, and the solution turns blue. The remainder of the solution of the chloride is then added dropwise over a period of 5 hours, during which time the flask is cooled in an ice bath (Note 5). When the addition is complete, stirring is continued for 2 hours. The suspension is decanted from any sodium that remains (Note 6) into a dry beaker and decomposed with sufficient ice water to give two liquid layers. The ether layer is separated and dried over magnesium sulfate. After the removal of the ether by distillation on a steam cone, the residue is distilled. The yield of 4-penten-1-ol boiling at 134–137° is 161–178 g. (76–83%).
2. Notes
1. Undistilled commercial thionyl chloride and Eastman practical tetrahydrofurfuryl alcohol may be used, but the yields are slightly lower (65–70%).
2. The checkers found it easier to separate the ethereal extract from the residue when the mixture was in a large separatory funnel.
3. The yield will be low if extraction is incomplete. It is advisable to stir with a heavy glass rod and break up any lumps that have formed.
4. The powdered sodium is prepared under hot xylene with the aid of a Hershberg stirrer; the xylene is decanted and replaced with ether.
5. The ice bath is not used until the reaction has definitely started.
6. Occasionally a little sodium is left on the bottom of the flask. This is destroyed with ethanol and the flask is washed with ice water.
3. Discussion
Tetrahydrofurfuryl chloride has been prepared from the alcohol and thionyl chloride1 or phosphorus trichloride. 4-Penten-1-ol has been prepared from tetrahydrofurfuryl bromide or chloride and magnesium,2,3 sodium,4,5,6 sodium-potassium,6 or lithium;6 and by the reaction of allylmagnesium chloride with ethylene oxide, followed by hydrolysis.7
This preparation is referenced from:

References and Notes
  1. Kirner, J. Am. Chem. Soc., 52, 3251 (1930).
  2. Paul, Bull. soc. chim. France, (4) 53, 424 (1933).
  3. Robinson and Smith, J. Chem. Soc., 1936, 195.
  4. Paul, Bull. soc. chim. France, (5) 2, 745 (1935).
  5. Gaubert, Linstead, and Rydon, J. Chem. Soc., 1937, 1971.
  6. Paul and Normant, Bull. soc. chim. France, (5) 10, 484 (1943).
  7. Kharasch and Fuchs, J. Org. Chem., 9, 359 (1944).

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

tetrahydrofurfuryl bromide or chloride

ethanol (64-17-5)

ether (60-29-7)

thionyl chloride (7719-09-7)

magnesium (7439-95-4)

pyridine (110-86-1)

sodium (13966-32-0)

phosphorus trichloride (7719-12-2)

Ethylene oxide (75-21-8)

xylene (106-42-3)

tetrahydrofurfuryl alcohol (97-99-4)

lithium (7439-93-2)

magnesium sulfate (7487-88-9)

4-Penten-1-ol (821-09-0)

Tetrahydrofurfuryl chloride (3003-84-7)


Allylmagnesium chloride (2622-05-1)