NOTES

2-Furanmethanethiol was prepared by H. Kofod's method, i.e.,

by reaction between furfuryl alcohol and thiourea in presence of
hydrochloric acid.

OTHER METHODS OF PREPARATION

5-(Furfurylthiomethyl)-2-furoic acid has been prepared only

by the method described above 2 •

LITERATURE CITED

1 H.
Kofod, Acta Chern. Scand. 7, 1320 (1953).
2 A.
L. Mndzhoian, G. T. Tatevosian, S. G. Agbalian, and N. M.
Divanian, Doklady Akad. Nauk Arm. SSR (Proc. Acad. Sci. Armenian
SSR) 25, 207 (1957).

FURFURYL ALCOHOL

OcHo + CH20 + NaOH -

OcH,OH + HCOONa

Checked by 0. L. Mndzhoian and A. N. Grigorian

PREPARATION

A mixture of 96 g (1 mole) of freshly distilled 2-furaldehyde

(Note 1), 250 ml of water, and 250 ml (3.46 moles) of 40% form-
aldehyde solution (Note 2) was prepared in a one-liter four-necked
round-bottomed flask fitted with mercury-sealed stirrer, dropping
funnel, thermometer, and reflux condenser.

70
A. L. Mndzhoian (ed.), Syntheses of Heterocyclic Compounds
© Springer Science+Business Media New York 1959
 The mixture was cooled to 5°, and gradually, over a period
of 25-30 minutes with continuous stirring, 230 g of 50% aqueous
sodium hydroxide (2.87 moles) was added from the dropping
funnel with maintenance of the temperature of the reaction mixture
in the range 15-20° (Note 3), which was attained by external
cooling of the flask with ice water and control of the rate of
addition of alkali.

When the whole of the sodium hydroxide solution had been

added, stirring was continued for five hours while the mixture
was maintained at 40-45° (Note 3); it was then left at room tem-
perature for 15-18 hours (Note 4), after which it was extracted
with five 150-ml portions of ether. The combined ether extract
was dried over anhydrous sodium sulfate, solvent was distilled
off, and the residue was vacuum-distilled. About 10 ml of head
fraction, mainly unchanged 2-furaldehyde, came over up to 75°/
/15 mm, and this was followed by furfuryl alcohol at 75-76°/15
mm. The yield was 80.0--82.0 g (81.6-83.6%).

Furfuryl alcohol (C 5 Hs~; mol. wt. 98.05) is a colorless liquid

of characteristic odor, readily soluble in water, alcohol, and
ether; d 22 • 74 1.1282; n22 • 7D 1.4851. On standing in the air it assumes
a light-yellow color.

NOTES

1. Technical 2-furaldehyde may be used without appreciable

effect on the yield of furfuryl alcohol.
2. The use of equimolecular amounts of reactants lowers
the yield of furfuryl alcohol to 53-55%. If the amounts of form-
aldehyde and sodium hydroxide are reduced to 1.5 and 1.8 moles,
respectively, per mole of 2-furaldehyde, furfuryl alcohol is
obtained in 71-73% yield. A certain reduction in the yield is
compensated, however, by the fact that with stoichiometric pro-
portions of components the total duration of reaction may be
only 3-3.5 hours (optimum temperature 15-25°); in this case,
leaving the mixture for 15-18 hours has no effect on the yield
of furfuryl alcohol.

71