Submitted by J. A. Scarrow and C. F. H. Allen.
Checked by Reynold C. Fuson and Charles F. Woodward.
1. Procedure
This preparation must be carried out in a hood having good suction. Methyl sulfate has a high vapor pressure in spite of its high boiling point and is very poisonous. Ammonia is a specific antidote and should be kept on hand to destroy any of the ester accidentally spilled. It is advisable to wash the hands in dilute ammonium hydroxide frequently.
In a
1-l. three-necked, round-bottomed flask, fitted with a
stirrer, a thermometer for reading low temperatures (Note
1), and a
dropping funnel, are placed
98 g. (2 moles) of pulverized sodium cyanide (Note
2) and 200 cc. of water. The stirrer is started, and
60 g. of paraformaldehyde (2 moles) (Note
3) is added in small quantities until the temperature rises to 20–25° and the
sodium cyanide has dissolved. The flask is then surrounded by a freezing mixture, and the temperature is kept below 25° during the introduction of the remaining
paraformaldehyde.
Two hundred cubic centimeters (270 g., 2.1 moles) of technical methyl sulfate is placed in the dropping funnel, and, when the temperature inside the flask has dropped to 13°, a
20- to 30-cc. portion of the sulfate is added. An exothermic reaction should set in; the
ice bath is removed, if necessary, to get the reaction to start (Note
4). When the temperature begins to fall, the remainder of the
methyl sulfate is admitted at such a rate as to keep the temperature at 12–15°; this takes at least twenty minutes. When the addition is complete the mixture is stirred an additional forty minutes; during this time the temperature will drop to about 5°. The stirrer is stopped, and the oily, upper layer is separated at once (Note
5). The lower, aqueous layer is returned to the flask and methylated as before with a second
200-cc. portion of methyl sulfate (Note
6).
The oily, upper layer is dried with
10 g. of anhydrous sodium sulfate (Note
7) and is distilled under diminished pressure. For this purpose an
efficient fractionating column (Note
8) is used. The portion boiling below
70° at 15 mm. is mainly
methoxyacetonitrile and weighs
60–70 g. The upper layer from the second methylation is treated in a similar manner; the distillate weighs
55–60 g. The residue in the distilling flask is
methyl sulfate and is used in a subsequent run (Note
9).
The crude fractions are combined and distilled at atmospheric pressure through a
good column; about
95 per cent distils at
118–122° as a colorless liquid. The
methoxyacetonitrile so prepared weighs
100–110 g. (
70–77 per cent of the theoretical amount).
2. Notes
1. A
30- to 35-cm. thermometer reading from −50 to +50° is most convenient since the graduations used are then outside the flask.
3. An equivalent amount of commercial
formalin solution can be used with equally good results, provided that allowance is made for the volume of water—the total volume must not exceed 200 cc.
4. The reaction usually starts immediately; occasionally it does not start until the mixture becomes warm.
5. If the mixture is allowed to stand, the temperature rises to 40–50°, a red color develops, and the yield drops to almost nothing.
7. No drying agent is completely satisfactory;
sodium sulfate does the least harm.
8. The authors found a
Glinsky column most satisfactory. A
capillary tube reaching to the bottom of the flask for the admission of air is essential to prevent bumping. In the redistillation a
piece of porous plate is sufficient for this purpose.
9. The density of the residual liquid in two runs was found to be 1.31, 1.32. The pure ester has a density of 1.35.
3. Discussion
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