A Dichlorination-Reductive-Dechlorination Route to N-Acetyl-2-Oxazolone

Abstract

We have shown that sulfuryl chloride is an efficient ­reagent for the conversion of 2-oxazolidinone into the dichloro ­derivative, N-acetyl-4,5-dichloro-2-oxazolidinone. Subsequent Zn/AcOH reductive dehalogenation of this trans-dichloride gives N-acetyl-2-oxazolone. The dichloride was previously reported as an undesired side product in the preparation of N-acetyl-2-oxazolone from the monochloro oxazolidinone. In our hands, the dichloride is a key intermediate in a new synthesis of 2-oxazolone, that avoids the use of chlorine gas.

Key words

2-oxazolone - synthesis - sulfuryl chloride - chlorination - zinc - dehalogenation - chlorination

References and Notes

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14

Careful examination by HMQC proved that the dichloride was vicinal based on the fact that the singlet at δ = 6.21 ppm coupled to two different carbon atoms.

15

Sulfuryl chloride was purchased from Aldrich, and used in many reactions with complete reproducibility. Recently, two batches from Aldrich were used in an identical manner, but required a larger excess of reagent, longer reaction times, and gave poorer yields. Aldrich simply stated that they had a different supplier, but did not elaborate. We could detect no difference in the batches by GC-MS or IR analysis.