Methanolysis of Stereoisomeric Oxides of 3-Methoxycyclohexene

McRae, J. A.; Moir, R. Y.; Haynes, Jack W.; Ripley, L. G.

doi:10.1021/jo50012a008

Cited by 14 publications

(8 citation statements)

References 9 publications

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“…The acetate (8b) was obtained in 92% yield as colorless, feathery needles, mp 86.5-88°C. One recrystallization from light petroleum gave the analytical sample, whose mp (88.5-89.5"C) was similar to that of its isomer (76) (23 I ,3-Di-0-methyl-r-I ,t-2,c-3-cyclohexanetl (9a) and its Acetate (96) The alcohol (9a) (22,23,27), available in the pure state (glc) from previous work, was recognizable in the nmr chiefly by its very sharp single methoxyl peak, appearing in spectra of the pure compound at 3.39 (T-60) or 3.40 (cal. A-60), but in spectra of synthetic mixtures with its isomer (10a) overlapping the downfield methoxyl of the latter.…”

Section: 23-cyclohexanetriol (16c)mentioning

confidence: 98%

“…1, which also serves to unite the chemistry of our previous (22,23,27,28) and following (e.g. 29) papers on the mechanisms of epoxide scission and formation.…”

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confidence: 99%

“…The results obtained were unaffected either by the use of a weaker base or by subjecting the isolated product of an interrupted solvolysis to further reaction. Further formation of 9a and 10a during isolation was in any case impossible, since the half-life of 5 under more severe conditions of base catalysis is known to be about 30 h (27).…”

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confidence: 99%

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Migration of hydroxyl in secondary systems during solvolysis in acid solution

Cathcart¹,

Bovenkamp²,

Moir³

et al. 1977

Can. J. Chem.

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Can. J. Chem. 55,3774 (1977). A system of compounds has been prepared which is well adapted for displaying the role of trans vicinal, secondary hydroxyl in solvolysis. On methanolysis in acid solution, compounds 5, 7a, and 8a all gave the same products, 9a and 10a, and in practically the same proportions, suggesting that at least one intermediate was common to all three reactions. These intermediates were such that 7a and 8u were not interconverted during the solvolysis, a fact in support of 6 as a common intermediate. Several alternative explanations were shown to be untenable, largely by taking advantage of the remarkable differences between hydroxyl and methoxyl. The work provides the most decisive evidence available for the covalent participation of hydroxyl as a neighbor group in the solvolysis of secondary systems, and contributes also to the study of the reverse reaction, the acid-catalyzed scission of epoxides. On prepare un systeme de composes lequel est bien adapte pour mettre en evidence le r61e du groupe hydroxyle trans vicinal dans des reactions de solvolyse. La mkthanolyse en solution acide des composks 5, 7a et 8a conduit aux mCmes produits 9a et 10a et essentiellement aux m&mes proportions suggerant qu'au moins un intermediaire est commun aux trois reactions. Ces intermediaires sont de telle sorte que 7a et 8a ne sont pas convertis I'un dans I'autre pendant la solvolyse, ce qui est en accord avec l'hypothese que 6 soit un intermediaire commun. Plusieurs interprktations ne peuvent Ctre soutenues, essentiellement parce qu'elles ne tiennent pas compte des grandes differences entre un groupe hydroxyle et methoxyle. Ce travail apporte l'evidence tres nette de la participation covalente du groupe hydroxyle comme groupe voisin dans la solvolyse de systemes secondaires et contribut aussi a l'etude de la reaction inverse, la scission catalyske par un acide des Cpoxydes.[Traduit par le journal]

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Section: 23-cyclohexanetriol (16c)mentioning

confidence: 98%

“…1, which also serves to unite the chemistry of our previous (22,23,27,28) and following (e.g. 29) papers on the mechanisms of epoxide scission and formation.…”

mentioning

confidence: 99%

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Migration of hydroxyl in secondary systems during solvolysis in acid solution

Cathcart¹,

Bovenkamp²,

Moir³

et al. 1977

Can. J. Chem.

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show abstract

“…McRae et al (10)). On the basis of refractive index and infrared spectra of the various fractions (see Table V) it was estimated that the yield of trans-, or lower-boiling, oxide is 63% and that of the cis-, or higher-boiling, oxide is 19y0.…”

mentioning

confidence: 99%

“…The presence of dichlorides in the 1-alkoxycyclohexene-2 chlorohydrins detracts from their usefulness for preparation of the corresponding oxides, since both the trans-, or lower-boiling, oxide (VII) and the cis-, or higher-boiling, oxide (VIII) were contaminated with chlorinated substances (10). Furthermore, the fact that the isomeric chlorohydrins are not readily separable malces them impractical as intermediates for preparation of Can.…”

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confidence: 99%