A. Takeda, S. Tsuboi, T. Moriwake
Dec 1, 1972
Citations
0
Influential Citations
10
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
Reactions of 5,5,5-trichloro-3-penten-2-one (1) with a number of nucleophiles have been carried out. It was found that the Grignard reagents (5) primarily attacked the carbonyl carbon of 1 yielding the corresponding tertiary alcohols (7). The reaction sequence of ethylmagnesium bromide (5a) is given as an example. The reaction of 5a with 1 gave 6,6,6-trichloro-3-methyl-4-hexen-3-ol (7a) as the major constituent of the primary product. The hexenol 7a readily underwent the allylic rearrangement by heating at distilling temperature (88–90°C/6 mmHg) to afford 4,6,6-trichloro-3-methyl-5-hexen-3-ol (8a), which was in turn converted into 6,6-dichloro-3-methyl-3,4-epoxy-5-hexene (9a) by treatment with sodium methoxide. The stereoselective synthesis of dl-erythro-4,6,6-trichloro-3-methyl-5-hexen-3-ol (8a-I) was achieved by using 3,5,5-trichloro-4-penten-2-one (3) as the starting material in place of 1. dl-trans-6,6-Dichloro-3-methyl-3,4-epoxy-5-hexene (9a-I) was derived by the cyclization of 8a-I with a base. The ...