1、Organic Syntheses, Vol. 38, p. 37 (1958); Coll. Vol. 4, p.534 (1963).3-HYDROXYTETRAHYDROFURANFuran, 3-hydroxy-1,2,3,4-tetrahydro-Submitted by Hans Wynberg and A. Bantjes1.Checked by John C. Sheehan and Gregory L. Boshart.1. ProcedureA 500-ml. flask is charged with 318 g. (3 moles) of 1,2,4-trihydrox
2、ybutane (Note 1) and 3 g. of p-toluenesulfonic acid monohydrate. A few Carborundum boiling chips are added, the flask is equipped with a 30.5-cm. Vigreux column, condenser, and receiver arranged for vacuum distillation, and the contents are heated, with swirling, to dissolve the acid (Note 2). The f
3、lask is then heated in a bath held at 180220 so that 300306 g. of distillate, b.p. 8587/22 mm., is collected over a period of 22.5 hours (Note 3). The colorless liquid obtained is refractionated, the same apparatus being used, and two fractions are collected: the first, 5060 g., b.p. 4244/24 mm., nD
4、25 1.3343, is mainly water. After a negligible intermediate fraction, 215231 g. (8188%) of pure 3-hydroxytetrahydrofuran, b.p. 9395/26 mm., nD25 1.4497, d420 = 1.095, is collected (Note 4).2. Notes1. Supplied by the General Aniline and Film Corporation.2. Considerable darkening occurs even when the
5、acid is well dispersed. The yield appears not to be affected.3. Other temperatures are: b.p. 7577/16 mm.; 9092/28 mm. This first distillate contains 14% (3%) of water as determined by interpolation of the refractive indices.4. Calcd. MD = 21.64. Found: 21.72. As obtained by this single fractionation
6、 the submitters found the alcohol to be analytically pure: Calcd. for C4H8O2: C, 54.53; H, 9.14. Found: C, 54.74; H, 9.32. Others have reported: b.p. 50/1 mm., nD18 1.4486, d420 = 1.090,2 and b.p. 81/13 mm., d18 = 1.07, nD18 1.4478.33. Discussion3-Hydroxytetrahydrofuran has been obtained during the
7、preparation of 1,2,4-trihydroxybutane,3 by hydrolysis of 4-chloromethyl-1,3-dioxane2 and by acid catalyzed dehydration of 1,2,4-trihydroxybutane.4 The present procedure is similar to that described by Reppe.4References and Notes1. Tulane University, New Orleans, Louisiana. 2. Price and Krishnamurti,
8、 J. Am. Chem. Soc., 72, 5335 (1950). 3. Pariselle, Ann. chim. (Paris), 824, 315 (1911). 4. Reppe, Ann., 596, 1 (1955), see p. 112; DBP 841 592 (1942), BASF (H. Krzikalla, E. Woldan). AppendixChemical Abstracts Nomenclature (Collective Index Number);(Registry Number)Carborundum3-Hydroxytetrahydrofuran, Furan, 3-hydroxy-1,2,3,4-tetrahydro- (453-20-3)1,2,4-trihydroxybutane (42890-76-6)4-chloromethyl-1,3-dioxanep-toluenesulfonic acid monohydrate (6192-52-5)Copyright 1921-2007, Organic Syntheses, Inc. All Rights Reserved
