Org. Synth. 1953, 33, 41
DOI: 10.15227/orgsyn.033.0041
ITACONYL CHLORIDE
Submitted by Henry Feuer and Stanley M. Pier
1.
Checked by William S. Johnson and Ernest F. Silversmith.
1. Procedure
In a
500-ml. round-bottomed flask fitted with a
reflux condenser and a drying tube leading to a gas-absorption
trap2 are placed
234 g. (1.1 mole) of phosphorus pentachloride (Note 1) and
65 g. (0.5 mole) of itaconic acid (Note 2). The reagents are mixed by shaking the flask; after a few minutes a vigorous reaction commences, resulting in partial liquefaction of the mixture and copious evolution of
hydrogen chloride. When the initial reaction subsides, the mixture is gently heated to cause reflux of
phosphorus oxychloride until all the solid dissolves; then heating is continued for an additional 15 minutes
(Note 3). The
reflux condenser is replaced by a
12-in. Vigreux column, and the
phosphorus oxychloride is removed by distillation at reduced pressure provided by a
water aspirator (Note 4), the major portion coming over at about 45°/85 mm. When all the
phosphorus oxychloride has been removed, the pressure is reduced (
vacuum pump) and the material boiling at
70–75°/2 mm. is collected. Liquid boiling in this range weighs
50–55 g., representing a yield of
60–66%. This material,
nD20 1.4915,
nD25 1.4900, is pure enough for most purposes, but it may be further refined by distillation through a packed column, yielding
47–53 g. of a water-white liquid,
nD20 1.4919, boiling at
71–72°/2 mm.
2. Notes
1.
The slight molar excess of
phosphorus pentachloride has been found to increase the yield of product. It is best to use apparatus with ground-glass joints.
2.
Chas. Pfizer and Company technical grade itaconic acid was employed without purification.
33.
Heating for a longer period results in a rather sudden change in color from pale yellow to deep orange or red, and a decrease in yield.
4.
Considerable dissolved
hydrogen chloride is liberated at this point and passes into the
water aspirator. A mechanical vacuum pump should not be used at this stage because it would be damaged by corrosion.
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3. Discussion
Itaconyl chloride has been prepared previously only by the reaction of
itaconic anhydride with
phosphorus pentachloride.
4
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
hydrogen chloride (7647-01-0)
phosphorus pentachloride (10026-13-8)
Phosphorus Oxychloride (21295-50-1)
Itaconic anhydride (2170-03-8)
Itaconic acid (97-65-4)
Itaconyl chloride (1931-60-8)
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