Accession Number : AD0622727

Title :   CYCLOHEXANE COMPOUNDS. V. THE REACTION OF 1-METHOXYCYCLOHEXENE-2 WITH AQUEOUS N-BROMOSUCCINIMIDE. THE 1-METHOXY-2-BROMO3-HYDROXYCYCLOHEXANES,

Corporate Author : DEFENCE CHEMICAL BIOLOGICAL AND RADIATION LABS OTTAWA (ONTARIO)

Personal Author(s) : Bannard,R. A. B. ; Casselman,A. A. ; Hawkins,L. R.

Report Date : 06 APR 1965

Pagination or Media Count : 13

Abstract : Interaction of 1-methoxycyclohexene-2 and aqueous Nbromosuccinimide gave a mixture of stereoisomeric bromohydrins, which, on treatment with aqueous sodium hydroxide, furnished 1-beta-methoxy-2-alpha, 3-alphaepoxycyclohexane (I) and 1-alpha-methoxy-2-alpha, 3alpha-epoxycyclohexane (II) in the ratio 3:1. The mixture from the N-haloimide-olefin reaction was separated by preparative vapor phase chromatography into three isomeric bromohydrins, 1-alpha-methoxy-2-alphahydroxy-3-beta-bromocyclohexane (IV), 1-alpha-methoxy2-alpha-bromo-3-beta-hydroxycyclohexane (V), and 1-alpha-methoxy-2-beta-bromo-3-alpha-hydroxycyclohexane (VI) in the relative proportions 1:10:4. The 3bromo isomer IV was identified by comparison with an authentic specimen prepared by the action of hydrobromic acid on the oxide II. Compounds V and VI were shown to have the indicated structures by deetherification to the corresponding bromodiols VII and VIII in high yield, followed by debromination of the latter to trans- and cis1,3-cyclohexanediol respectively. The product distribution is considered in relation to the intervention of electronic and steric factors in a possible mechanism suggested for the reaction between aqueous N-bromosuccinimide and 1-methoxycyclohexene-2. (Author)

Descriptors :   (*CYCLOHEXANES, CHEMICAL REACTIONS), (*CYCLOHEXANOLS, SYNTHESIS(CHEMISTRY)), (*CYCLOHEXANES, SYNTHESIS(CHEMISTRY)), (*STEREOCHEMISTRY, CYCLOHEXANES), ETHERS, BROMINE COMPOUNDS, SUCCINATES, HALOHYDRINS, MOLECULAR ISOMERISM, CHROMATOGRAPHIC ANALYSIS

Distribution Statement : APPROVED FOR PUBLIC RELEASE