119. Effect of replacement of methyl by alkyl and aryl on the stability of the xanthate molecule

McAlpine, Irene Mary

doi:10.1039/jr9320000906

Cited by 6 publications

(2 citation statements)

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“…The whole problem of the ease of xanthate pyrolysis, and indeed of the mechanism of the reaction, has been somewhat confused by the recent discovery by Nace, Manly, and Fusco (140) that the so-called "stable xanthates" of Me Alpine (136,137) are in reality normal xanthates from which the last traces of peroxides have been removed. Thus menthyl xanthate, which ordinarily decomposes to a mixture of menthenes on attempted distillation, becomes distillable after washing with ferrous salt solutions and higher temperatures are required for its decomposition.…”

Section: Thiol Sulfurmentioning

confidence: 99%

Pyrolytic Cis Eliminations.

DePuy¹,

King²

1960

Chem. Rev.

423

161

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Section: Thiol Sulfurmentioning

confidence: 99%

Pyrolytic Cis Eliminations.

DePuy¹,

King²

1960

Chem. Rev.

423

161

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“…Kinetic thermal stability of xanthates and this results in a studies of the pyrolysis of these xanthates showed lower initial pyrolysis temperature (3). The order that a n increase in the electronegativity of the Sof stability of S-substituted xanthates of menthyl alkyl group decreased the stability of the xanthate alcohol was found to be as follows:…”

Section: S -C H~+ N O mentioning

confidence: 93%

The Effect of S-Substituent Variation on the Pyrolysis of Xanthates of Primary Alcohols

Gilman¹,

Bogdanowicz²

1971

Can. J. Chem.

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A study of the pyrolysis of a series of S-substituted xanthates of cyclohexanemethanol was undertaken to determine the effect of variations in the nature of the S-substituent on the course of the pyrolysis of xanthates. Xanthates with the following S-substituents were prepared by standard reactions and pyrolyzed at 240": n-hexyl, 2-phenylethyl, benzyl, phenacyl, and diphenylmethyl. Evidence is presented that supports the view that a competitive homolytic pathway becomes more significant as the stability of the free radical derived from the S-substituent increases. At the two extremes, the S-hexyl xanthate yields 90% methylenecyclohexane and no cyclohexanemethanol whereas the S-diphenylmethyl xanthate yields only 25% alkenes (methylenecyclohexane and 1-methylcyclohexene) along with 65% cyclohexanemethanol.Une Ctude a Ct C effectute sur une strie de xanthates de la cyclohexanemethanol S-substitues afin de determiner l'influence du S-substituant sur le cours de la pyrolyse des xanthates. Les xanthates avec les S-substituants suivants ont tte prepares par des mCthodes classiques et pyrolyses a 240": n-hexyle, 2-phenylethyle, benzyle, phknacyle, et diphenylmethyle. Des preuves sont presentees pour confirmer le fait qu'un processus homolytique cornpititif peut devenir plus important si la stabilite du radical libre issu du S-substituant augmente. Aux deux extrCmes, le xanthate S-hexyle conduit a 90% de mtthylenecyclohexane sans trace de cyclohexanemethanol, alors que le xanthate S-diphCnylniethyle conduit a seulement 25% d'alcene (methylenecyclohexane et methyl-1 cyclohex$ne) et a 65% de cyclohexanemCthanol.

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The Preparation of Olefins by the Pyrolysis of Xanthates. TheChugaev Reaction

Nace

2011

Organic Reactions

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In this chapter the Chugaev reaction is defined as the thermal decomposition of the xanthate ester of an alcohol that contains at least one beta‐hydrogen atom to produce one or more olefins, carbon oxysulfide and a mercaptan. The formation of olefins by the pyrolysis of xanthates was discovered in 1899 by Chugaev in connection with his studies on the optical properties of xanthates and other compounds. He subsequently employed the reaction in his investigation of terpenes and demonstrated both its utility as an olefin‐forming reaction and its usefulness in structural determination. The reaction, which is particularly valuable for the conversion of sensitive alcohols to the corresponding olefins without the rearrangement of the carbon skeleton is analogous to the thermal decomposition of carboxylic esters of alcohols and other derivatives such as carbamates and carbonates, to yield olefins.

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119. Effect of replacement of methyl by alkyl and aryl on the stability of the xanthate molecule

Cited by 6 publications

References 0 publications

Pyrolytic Cis Eliminations.

Pyrolytic Cis Eliminations.

The Effect of S-Substituent Variation on the Pyrolysis of Xanthates of Primary Alcohols

The Preparation of Olefins by the Pyrolysis of Xanthates. TheChugaev Reaction

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