Furylmethyl Acetate

Submitted by The Miner Laboratories. Checked by Roger Adams and C. G. Gaulrke. 

A mixture of i 1. of benzene, 600 g. (6.1 moles) of 2-furyl-carbinol (Org. Syn. 6, 44) (Note 1), 225 g. of fused and powdered sodium acetate, and 650 g. (6.4 moles) of a good grade of acetic anhydride are placed in a 5-I. round-bottom flask (Note 2) fitted with a mechanical stirrer (Org. Syn. 1, 4, Fig. 1 b) and a reflux condenser provided with a calcium chloride Lube. The flask is heated on a steam bath (Note 1) for four hours with stirring to prevent caking of the sodium acetate. 

The reaction mixture is allowed to cool and is poured into 4 1. of cold water (Note 3). The upper layer is separated and allowed to stand for two hours over about 500 cc. of 5 per cent sodium carbonate solution with frequent shaking or mechanical stirring. This decomposes any excess of acetic anhydride. It 

If the water-insoluble form of the alcohol (Org. Syn. 6, 46) is used, the mixture should be allowed to stand under a reflux condenser for about two hours before it is heated. During this period a certain amount of heat is evolved, and sometimes it is sufficient to cause the benzene to boil vigorously, thus making cooling necessary. After it has stood the required time, the mixture is refluxed as described above. 

If a two- or three-necked flask is available it can be used to advantage. 

---

Furylmethyl acetate has been prepared by heating 2-furyl-carbinol with acetic anhydride alone, or with acetic anhydride and sodium acetate.1... 

A condensation occurs between 5-hydroxymethylfurfural and malonic ester20 and in a similar way, two molecules of malonic ester react with furan 2,5-dialdehyde.88 A condensation product, XXXV, has also been obtained with hydantoin.89 5-Hydroxymethylfurfural and its acetyl derivative undergo the Perkin reaction with sodium acetate and acetic anhydride giving 5-acetoxymethylfuran 2-acrylic acid (XXXVI).70 Similar products of the same reaction are obtained from 5-methyl-furfural71 and 5,5 -diformyl-l,l -furylmethyl ether (XXVII).61,72... 

High values of the epoxidation rate of 2-furylmethyl 3-cyclohexenecarboxy-late (XII) cannot be explained by the induction effect of the substituent. Apart from this effect, which is transmitted through the 8-hnkages and through the space inside and around the rings (the electrostatic field effect), there are steric effects and the specific solvatation of the XII molecule with acetic acid. 

---