2-Chloroethyl Dichloromethyl Ether

[13930-34-7]  · C3H5Cl3O  · 2-Chloroethyl Dichloromethyl Ether  · (MW 163.44)

(reagent for forming cyclopropanols from alkenes1)

Alternate Name: dichloromethyl 2-chloroethyl ether.

Physical Data: bp 106-110.5 °C/10 mmHg.

Solubility: sol most organic solvents.

Preparative Method: not commercially available. It can be prepared by the action of Phosphorus(V) Chloride on b-chloroethyl formate (eqs 1 and 2).2,3

This is the reagent of choice for the preparation of cyclopropanols from alkenes. The method is very versatile and general in scope. It involves carbene insertion into an alkene to form the b-chloroethyl cyclopropyl ether (eq 3) which is then converted to the cyclopropanol (eq 4).1

The alkenes employed ranged from monosubstituted to tetrasubstituted to give the cyclopropyl ethers in 23-86% yield (eqs 5-9).1

A more recent example yields an interesting spiro compound (eq 10).4

Cyclopropyl ethers have been prepared by a similar carbene insertion using 2-chloroethyl dichloromethyl ether as shown in eq 11.5

1. Schöllkopf, U.; Paust, J.; Al-Azrak, A.; Schumacher, H. CB 1966, 99, 3391.
2. Baganz, H.; Domaschke, L. CB 1958, 91, 653.
3. Gross, H.; Rieche, A.; Höft, E. CB 1961, 94, 544.
4. Applequist, D. E.; Nickel, G. W. JOC 1979, 44, 321.
5. Danheiser, R. L.; Martinez-Davila, C.; Morin, Jr., J. M. JOC 1980, 45, 1340.

Regina Zibuck

Wayne State University, Detroit, MI, USA

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