Tetrahydrofurfuryl chloride

The acetylenic alcohol 4 pentyn-l-ol is conveniently prepared by treatment of tetrahydrofurfuryl chloride with sodamide iu liquid ammonia ... 

Tetrahydrofurfuryl chloride. Place 204 g. (194 ml.) of freshly distilled tetrahydrofurfuryl alcohol (b.p. 177°) and 174 g. (178 ml.) of dry pyridine in a 1-litre three-necked flask, fitted with a dropping funnel, mechanical stirrer and thermometer. Cool in an ice bath, stir vigorously and add 250 g. (153 ml.) of freshly distilled thionyl chloride at the rate of 3-5 drops per second. A pasty crystalline mass begins to separate and the temperar ture commences to rise rapidly when one-third to one-half of the thionyl chloride has been added subsequently the mass largely redissolves and a dark brown liquid forms. Remove the ice bath when the addition is complete and stir the mixture for 3-4 hours. Pour the reaction product into a large separatory funnel and extract with seven 250 ml. portions of ether break up any lumps that may form with a glass rod. Remove the ether from the combined extracts by distillation, wash the residue with three 50 ml. portions of water, dry with anhydrous magnesium sulphate and distil under reduced pressure. The yield of tetrahydrofurfuryl chloride, b.p. 47-48°/15 mm., is 180 g. 

This procedure illustrates a general method for the stereoselective synthesis of ( P)-disubstitnted alkenyl alcohols. The reductive elimination of cyclic /3-halo-ethers with metals was first introduced by Paul3 and one example, the conversion of tetrahydrofurfuryl chloride [2-(chloromethyl)tetrahydrofuran] to 4-penten-l-ol, is described in an earlier volume of this series.4 In 1947 Paul and Riobe5 prepared 4-nonen-l-ol by this method, and the general method has subsequently been applied to obtain alkenyl alcohols with other substitution patterns.2,6-8 (I )-4-Hexen-l-ol has been prepared by this method9 and in lower yield by an analogous reaction with 3-bromo-2-methyltetra-hydropyran.10... 

Freshly distilled tetrahydrofurfuryl alcohol should be used in the preparation of tetrahydrofurfuryl chloride according to the procedure of Organic Syntheses.3... 

A related elimination is the formation of 4-pentyn-l-ol from tetrahydrofurfuryl chloride and sodamide [139] ... 

A suspension of 3.5 mol of sodantide in about 2 1 of liquid ammonia is prepared [1,3,4]. Tetrahydrofurfuryl chloride (1.0 mol, see exp. 33), dissolved in 200 ml of Et20 is added dropwise over 40 min. After an additional 30 min, 120 g of powdered ammonium chloride is added in 1 to 2-g portions over 15 min, after which the ammonia is allowed to evaporate (fig. 

Tetrachloroethane, purification of, 176 Tetradecanoic acid, 938, 940, 941 n-Tetradecyl bromide, 283 1 2 3 4-Tetrahydrocarbazole, 852 Tetrahydrofuran, 271 Tetrahydrofurfuryl chloride, 896, 901 Tetrahydropyran, 271 Tetralin, dehydrogenation of, 948, 949 purification of, 949 a-Tetralone, 728, 737 Tetramethyl base, 987 pp -Tetramethyldiaminodiphenyl-methane, 987... 

Tetrahydrofurfuryl chloride has been prepared from the alcohol and thionyl chloride 3 or phosphorus trichloride. 4-Penten-l-ol has been prepared from tetrahydrofurfuryl bromide or chloride and magnesium or sodium.4 6... 

A similar rearrangement occurs with a-(l-chloroethyl)-furan 5-ethylfuryl cyanide is formed. Also, 3-furylmethyl chloride and aqueous potassium cyanide furnish an isomeric mixture of nitriles, a 9 1 ratio of 3-furylaceto-nitrile and 3-methyl-2-furonitrile. Tetrahydrofurfuryl chloride behaves normally although its halogen is mote firmly held. As expected, the halides of pyridine, quinoline, and isoquinoline react satisfactorily without a solvent-promoter. 

Dehydrohalogenation and ether cleavage of tetrahydrofurfuryl chloride by sodium sand produces 4-penten-l-ol in 82% yield. Likewise, 4-octen-l-ol is obtained from 3-chloro-2- -propyltetrahydropyran. This synthesis is general for 4-alken-l-ols from the commercially available di-hydropyran (cf. method 21). ... 

The chlorine atom in furftiryl chloride, like that in benzyl chloride, is very reactive and is readily replaced by the alkoxyl group (80%). On. the other hand, the chlorine atom in tetrahydrofurfuryl chloride is unreactive, so that the corresponding ethers are prepared from the alkali alcoholate and alkyl halides (80%). ... 

Ckavage of P-chhro cyclic ethers. Tetrahydrofurfuryl chloride (I) is cleaved to 4-pentene-l-ol (2) by powdered sodium in ether. ... 

C5H9Br 1 -bromo-2-methyl-cis-2-butene 57253-29-9 397.15 34.930 1,2 5074 C5H9CIO tetrahydrofurfuryl chloride 3003-84-7 423.60 36.595 Li... 

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