The Chemistry of Ethylene Oxide: V. The Reaction of Ethylene Oxide With Halide Ions in Neutral and Acid Solution

Eastham, A. M.; Latrèmouille, G. A.

doi:10.1139/v52-025

Cited by 14 publications

(7 citation statements)

References 1 publication

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“…The synthetic usefulness of such a relationship is readily apparent. A similar effect has been observed previously for much simpler epoxides (16,23). Table 5 compares the relative rates of attack upon the six epoxides studied by methanol and by water.…”

Section: Reactionssupporting

confidence: 78%

The competitive scissions of cycloalkane oxiranes by charged and neutral nucleophiles in acidic aqueous methanol

Bovenkamp¹,

Moir²,

Bannard³

1977

Can. J. Chem.

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. Can. J. Chem. 55,4144 (1977).Six related oxiranes (the cis and trans isomers derived from 3-methoxycyclopentene and from 3-methoxvcvclohexene. as well as the oxiranes from the corresuonding unsubstituted olefins) were each treated under the same conditions with an acidic soiution containing charged and uncharged nucleophiles (chloride ion, water, and methanol). The corresponding perchloric acid catalyzed scissions were also carried out. Accurate and reproducible methods of product analysis for the reaction mixtures were developed. In this way, nucleophilic attacks upon different oxiranes were compared directly. Attacks by different nucleophiles upon the same oxirane, or by a single nucleophile upon different positions of the same oxirane, were compared in the very same solution. The results are considered to provide the most extensive demonstration of the effects of charge orientation yet available. The synthesis of some new isomeric 1,2,3-trisubstituted diols and dimethoxyalcohols are reported. Chem. 55,4144 (1977).Six oxirannes de m&me type (les isomeres cis et trans du mCthoxy-3 cyclopentene et du methoxy-3 cyclohextne, aussi bien que les oxirannes provenant des olefines non-substitukes) sont traitks individuellement dans les mCmes conditions par une solution acide contenant des nucltophiles charges et non-charges (ion chlorure, eau et methanol). On rkalise aussi les scissions correspondantes catalysees par I'acide perchlorique. On met au point des mtthodes d'analyse prkcises et reproductibles des produits provenant du mklange rtactionnel. De cette f a~o n , les attaques nuclkophiles sur les differents oxirannes sont comparees directement. Les attaques de differents nuclkophiles sur le m&me oxiranne, ou par un seul nuclkophile ti diffkrentes positions du mdme oxiranne, sont comparees dans la m&me solution. Les resultats semblent apporter la demonstration la plus marquee connue jusqu'ti maintenant sur les effets d'orientation de charge. On rapporte la synthtse de quelques nouveaux diols trisubstituks-1,2,3 isomtres et de dimethoxyalcools.[Traduit par le journal]The mechanism of oxirane2 opening and the stereo-and regioselectivity of the nucleophilic addition have been topics of great interest (1-8).In these laboratories, we have expended a good deal of effort in this area due to our interest in conformational factors and the interaction of substituents in the cyclopentane and cyclohexane ring systems (see refs. 7-10 and references cited therein). In fact, it was the availability of compounds synthesized during these studies (for 'Present address: Defence Research Establishment Ottawa, Ottawa, Ont., Canada KIA 024.'For the remainder of this paper oxiranes will be designated as epoxides or cycloalkene oxides. These designations have been in use for many decades.example most of 1-19) (see Figs. la and 1b)which allowed us to proceed with the experiments described in this paper.Although several papers deal with the scission of 3-substituted cyclohexene or cyclopentene oxides (see, for example, refs. 7, 8, and 1...

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Section: Reactionssupporting

confidence: 78%

The competitive scissions of cycloalkane oxiranes by charged and neutral nucleophiles in acidic aqueous methanol

Bovenkamp¹,

Moir²,

Bannard³

1977

Can. J. Chem.

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“…As far as reactions in basic or neutral solution are concerned, kinetic studies covering a range of epoxides (more than three) have been carried out for the reactions with ammonia and various amines (6, 7), thiocyanate ion (192), nitrate ion (206), thiosulfate ion in aqueous acetone (224), and thiosulfate ion in aqueous ethanol (81). Less extensive studies, covering not more than three epoxides, have been made for the reactions with water (28, 67, 142, 214, 241), ammonia (16, 75, 100, 211, 240), various amines (11, 65, 100, 101, 102, 240, 241), a series of phenols (25), chloride ion (10,28,67,206,209,210), bromide ion (10, 28, 67, 206), iodide ion (10, 28, 67, 259), thiocyanate ion (28), various carboxylate ions (28), hydroxide ion (67,142,215), and sulfite ion (232). The acid-catalyzed reaction with water has been studied for a series of epoxides (212), and less extensive studies (not more than three epoxides) have been carried out for the acid-catalyzed reactions with water (28,67,206,243,289), chloride ion (28, 67), bromide ion (28, 67), iodide ion (67, 259), nitrate ion (206), and pyridine (also used as solvent) (64,66).…”

Section: Kinetics Of Ring Openingmentioning

confidence: 99%

“…Less extensive studies, covering not more than three epoxides, have been made for the reactions with water (28, 67, 142, 214, 241), ammonia (16, 75, 100, 211, 240), various amines (11, 65, 100, 101, 102, 240, 241), a series of phenols (25), chloride ion (10,28,67,206,209,210), bromide ion (10, 28, 67, 206), iodide ion (10, 28, 67, 259), thiocyanate ion (28), various carboxylate ions (28), hydroxide ion (67,142,215), and sulfite ion (232). The acid-catalyzed reaction with water has been studied for a series of epoxides (212), and less extensive studies (not more than three epoxides) have been carried out for the acid-catalyzed reactions with water (28,67,206,243,289), chloride ion (28, 67), bromide ion (28, 67), iodide ion (67, 259), nitrate ion (206), and pyridine (also used as solvent) (64,66). Unless otherwise stated all the reactions were studied in aqueous solution.…”

Section: Kinetics Of Ring Openingmentioning

confidence: 99%

Mechanisms Of Epoxide Reactions

Parker¹,

Isaacs²

1959

Chem. Rev.

1,202

512

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“…The configurations of these compounds were established by studying their nmr spectra. Both allylic (1,3) and homoallylic (1,4) coupling are recognized in the acetal spectrum. The former is evidenced by the octet observed for the olefmic proton, the latter by the quartet observed for the methyl group attached to the double bond; furthermore, the allylic proton gives rise to a quintet.…”

mentioning

confidence: 99%

Chemistry of gem-Dihalocyclopropanes. IV. Ring Opening of gem-Dichlorocyclopropyl Ethers

Skattebøl¹

1966

J. Org. Chem.

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The Chemistry of Ethylene Oxide: V. The Reaction of Ethylene Oxide With Halide Ions in Neutral and Acid Solution

Cited by 14 publications

References 1 publication

The competitive scissions of cycloalkane oxiranes by charged and neutral nucleophiles in acidic aqueous methanol

The competitive scissions of cycloalkane oxiranes by charged and neutral nucleophiles in acidic aqueous methanol

Mechanisms Of Epoxide Reactions

Chemistry of gem-Dihalocyclopropanes. IV. Ring Opening of gem-Dichlorocyclopropyl Ethers

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