Org. Synth. 1939, 19, 27
DOI: 10.15227/orgsyn.019.0027
n-BUTYL SULFATE
Submitted by C. M. Suter and H. L. Gerhart.
Checked by C. R. Noller and M. Synerholm.
1. Procedure
In a
2-l. three-necked flask, fitted with a
dropping funnel,
mercury-sealed stirrer, and
condenser, is placed
625 g. (3.2 moles) of n-butyl sulfite (p. 112). The condenser is connected to a
gas absorption trap, and
217 g. (131 cc., 1.6 moles) of sulfuryl chloride (Note 1) is added over a period of thirty minutes, with rapid stirring and cooling with tap water. The dropping funnel is then replaced by a
thermometer dipping into the liquid, and the flask is heated slowly, with stirring, until the refluxing of the
butyl chloride becomes vigorous (about 100–110°).
Sulfur dioxide is evolved copiously during this time. The condenser is replaced with a
40-cm. Vigreux column and downward condenser; the temperature is gradually raised to 130–135° and kept there until no more
sulfur dioxide or
butyl chloride distils. The heating and distillation require about two hours. The residue of crude
n-butyl sulfate is cooled to room temperature, and
100 cc. of saturated sodium carbonate solution is added. The mixture is stirred for about ten minutes, poured into a
separatory funnel, and let stand for thirty minutes to allow the layers to separate. The upper layer is dried with
calcium chloride, at least overnight, and then allowed to stand over
15 g. of anhydrous sodium or
potassium carbonate for a day, with occasional shaking. The product is filtered into a
500-cc. modified Claisen flask with a 25-cm. fractionating side arm, and distilled from an
oil bath. The first distillation gives
250–280 g. (
74–83 per cent of the calculated amount) of
n-butyl sulfate, b.p.
110–114°/4 mm., which has a sharp odor. Redistillation gives a pure material with a slight ester odor, boiling at
109–111° at 4 mm., with only a small mechanical loss
(Note 2).
2. Notes
1.
Commercial
sulfuryl chloride was redistilled and the fraction boiling at
69–70° was used.
2.
The submitters report that
n-propyl sulfate may be prepared in similar fashion, the yield being about
66–70 per cent. The second distillation in this case should be done through a
short column to remove higher-boiling material;
n-propyl sulfate distils at
88–91° at 4 mm.
3. Discussion
n-Butyl sulfate has been prepared by the action of
n-butyl chlorosulfonate upon
n-butyl orthoformate or
n-butyl sulfite.
1 It has been obtained also by oxidation of
n-butyl sulfite with
potassium permanganate in glacial
acetic acid solution.
2 The method described above appears to be the most satisfactory for laboratory-scale preparations.
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
calcium chloride (10043-52-4)
potassium carbonate (584-08-7)
acetic acid (64-19-7)
potassium permanganate (7722-64-7)
sodium carbonate (497-19-8)
sulfur dioxide (7446-09-5)
sulfuryl chloride (7791-25-5)
sodium (13966-32-0)
Butyl chloride (109-69-3)
n-butyl sulfite (626-85-7)
n-BUTYL SULFATE (15507-13-8)
n-propyl sulfate
n-butyl chlorosulfonate
n-butyl orthoformate
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