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COMMUNICATIONS TO THE EDITOR
40 mc. and was made possible by grants from the National Research Council of Canada and the National Cancer Institute of Canada.
way..' Water-soluble products were isolated by continuous ether extraction. Mixtures of solid products (entries 10-13) were analyzed by chromatographic separation. Liquid mixtures (entries DEPARTMENT OF CHEMISTRY UNIVERSITY OF BRITISHCOLUMBIA C. REID 1, 2, 5-9) were analyzed by mass spectrometry; VANCOUVER, CANADA in most cases the analyses were checked by infraRECEIVED MAY1, 1956 red comparison with synthetic mixtures. The reduction mixture for experiments 2 , 6, 7, 9, 11 and ANOMALOUS REDUCTION OF EPOXIDES WITH 13 was obtained by adding standardized ethereal LITHIUM ALUMINUM HYDRIDE lithium aluminum hydride to cold ethereal alumiSir: num chloride, or by adding allyl bromide in ether Lithium aluminum hydride attacks unsymmetri- to the standardized hydride solution prior to addically substituted epoxides predominantly a t the least tion of the epoxide. \Ye are presently studying the mechanism of the substituted carbon atom to give the more highly abnormal ring opening as well as extensions of the substituted alcohol. 1-3 Thus primary-secondary TABLE I REDUCTION OF EPOXIDES VITH LITHIUXALUMISPM HYDRIDE Entry compound
1 Propylene oxide 2 Propylene oxide 3 1,2-Epoxydecane 4 Styrene oxide 5 Styrene oxide 6 Styrene oxide 7 Styrene oxide 8 Isobutylene oxide 9 Isobutylene oxide 10 1,l-Diphenylethylene oxide 11 1,l-Diphenylethylene oxide 12 1,1,2-Triphenylethylene oxide oxide 13 1,1.2-Triphenylethylene . . a This work. Aluminum chloride. material.
Ri
Ri
Me H H Me H H Oct H H Ph H H Ph H H Ph H H Ph H H Me Me H Me Me H Ph Ph H Ph Ph H Ph Ph Ph Ph Ph Ph Generated in situ from
epoxides (I, R1 = alkyl, R2 = R3 = H) give secondary alcohols (11, same), and primary-tertiary or secondary-tertiary epoxides (I, R 1 , R? = alkyl, Ra = H or alkyl) give tertiary alcohols (11,
Moles AlXa
Products
yo I11 Ref. Yo I1 100 0 a 0.3 0 60 ca. 20 a ca. 80 .25 I' ca. 42 0 2 100 .25 0 90 0 3 100 .25+ 0 94 90-95 a 5-10 .3 0 82 90-98 u 2-10 .25 lb 87 28 a 71 1.5 c 80 2-5 a 95-98 0.3 0 26 93-95 a 5-7 .25 lb 55 100 0 a .4 0 97 86 a 14 2.4 c 85 0 a 100 2,2 0 1l.jd 100 U 0 2.4 c 91 Also recovered 81% starting 1 mole of allyl bromide. LAH
Ra
Yield, %
method to other epoxides, including alicyclic and steroid cases. This work is supported in part under Atomic Energy Commission contract AT(11-1)-38. (4) Shell Research Fellow, 1955-1956.
RIRzCHCHOHR~ +R'>C--C
