29887-60-3Relevant articles and documents
Conformational analysis of cyclohexane-1,2-diol derivatives and MM3 parameter improvement
Rockwell, Glen D.,Grindley, T. Bruce
, p. 379 - 390 (1996)
The positions of the equilibria between the diequatorial and diaxial conformers of trans-1,2-dimethoxycyclohexane (2) and trans-2-methoxycyclohexanol (3) have been measured accurately by13C n.m.r. spectroscopy at -80°C in a series of solvents r
The role of hydrogen migration in the mechanism of alcohol elimination from MH+ ions of ethers upon chemical ionization
Morlender-Vais,Mandelbaum
, p. 1124 - 1132 (2007/10/03)
An enhanced elimination of alcohol under isobutane CI conditions, resulting in highly abundant [MH - ROH]+ ions, has been observed in several primary and secondary ethers having a tertiary β-position (methine), as compared with those with β-methylene. This elimination exhibits a significant degree of stereospecificity in stereoisomeric 2-methyl-1-methoxycyclohexanes 4 and 1-methoxy-trans-decalins 7, affording more abundant [MH - ROH]+ ions in the cis isomers 4c and 7tc than in their trans counterparts 4t and 7tt. These findings suggest involvement of a 1,2-hydride migration from the β- to α-position in the course of the alcohol elimination from the MH+ ions of the above cis-ethers, resulting in tertiary carbocation structures. The proposed mechanism of alcohol elimination is supported by a considerable deuterium isotope effect detected in β-deuterium-labeled cis-2-methyl-1-methoxycyclohexane and by a CID study of the structures of [MH - ROH]+ ions obtained from cis- and trans-1,2-dialkoxycyclohexanes. Ring contraction by a Meerwein-type rearrangement has also been observed in the latter system.
Oxidatively Assisted Nucleophilic Substitution/Elimination of Alkyl Iodides in Alcoholic Media. A Further Study
Davidson, Robert I.,Kropp, Paul J.
, p. 1904 - 1909 (2007/10/02)
Oxidation of a series of alkyl halides with alcoholic 3-chloroperoxybenzoic acid afforded the results outlined in Charts I-III and Tables I-III.The reaction was found to be a powerful and convenient method for effecting nucleophilic substitution in a variety of systems, including the highly inert 1- and 7-bicycloheptyl systems.Qualitatively, the number of molar equivalents of oxidant required varied inversely with the expected ease of substitution for a given system.A mechanism is suggested whereby the iodide is oxidized stepwise to a species RIOn in which n is an integer sufficiently large that the system in question will undergo nucleophilic substitution or elimination.Reaction in the presence of added chloride or bromide ion usually resulted in a facilitation of reaction rate and a decrease in the number of molar equivalents of oxidant required; the principal product under these conditions was usually the corresponding chloride or bromide.