The Reactivity of the Cyclic Polyenes Towards Free Radicals: Ii. Metathesis With the Ethyl Radical

Brown, A. C. R.; James, D. G. L.

doi:10.1139/v65-084

Cited by 7 publications

(4 citation statements)

References 16 publications

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“…creased monotonically from 6.6% to 10.6y0. Twelve experiments were performed on the cyclohexadiene-l,4 system, encompassing a much wider variation in [H]/ [01]. The same six products were formed in each experiment: cyclohexene, benzene, cyclohexane, cyclohexadietle-1,3, n-hexane, and hexene-2.…”

Section: Resultsmentioning

confidence: 99%

“…A complementary set of experiments was performed, using much higher values of [H]/[Ol] than any of the experiments ofTable I[18]. Five experiments were performed on the cyclohexene system, encompassing a threefold variation in [H]/[01]. The sole detectable products were cyclohexane and n-hexane.…”

mentioning

confidence: 99%

“…The sole detectable products were cyclohexane and n-hexane. When [H]/[01] was increased, the total yield increased monotonically from l.7yo to 4.oyO, and the molar percentage of n-hexane in the products in-Full details are given at the end of this section.…”

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confidence: 99%

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A kinetic study of the reactions of the hydrogen atom with the cyclohexadiene isomers in the gas phase

Furukawa

James

Papic

1974

Int J of Chemical Kinetics

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Absolute values of the rate constants for the reaction of hydrogen atoms with cyclic olefins in the gas phase have been measured in a discharge-flow system under 3.5, 16, and 22 torr Ar at 23OC. The attenuation of hydrogen atom concentration in the reaction tube in the presence of a large excess of olefin was measured with an ESR spectrometer, and the products were analyzed by gas chromatography. Cyclic Cg hydrocarbons were the only significant products obtained when the hydrogen atom concentration was 2.6 X mole/l., the olefin concentration was in the range of 9 to 22 X lo-* mole/l., and the pressure was 16 torr Ar. The values for the rate constants for reaction with cyclohexadiene-1,3,cyclohexadiene-l,4, and cyclohexene are, respectively, (9 i 2) X lo8, (12 + 1) X lo8, and (6 & I ) X lo8 I./mole-sec, and they are not changed significantly by a sixfold change in total pressure. The fraction of the total interaction that proceeds by addition is 8470 in the cyclohexadiene-I ,3 system, but only I8y0 in The cyclohexadiene-l,4 system, and the cyclohexadienyl radical is therefore the dominant radical species in the latter system. The pattern of interaction between the hydrogen atom and the cyclohexadienyl radical was determined, and comprises 65Y0 of disproportionation, and 13y0 and 23% of combination to yield cyclohexadiene-l,3 and cyclohexadiene-1,4, respectively. These results are consistent with the general patterns of reactivity emerging from studies of the reactions between free radicals and olefins in related systems.

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

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A kinetic study of the reactions of the hydrogen atom with the cyclohexadiene isomers in the gas phase

Furukawa

James

Papic

1974

Int J of Chemical Kinetics

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“…[7][8][9][10][11][12][13][14][15][16][17][18][19] is suggested for the ethyl sulfide photolysis. The primary process, reaction 6, will be followed by [7], etc.…”

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confidence: 99%

Reactions of Thiyl Radicals. X. Photolysis of Ethyl Sulfide Vapor

Smith¹,

Knight²

1973

Can. J. Chem.

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The photolysis of ethyl sulfide vapor at 2537 r\ has been investigated as a function of substrate and CF4 pressure, time, and temperature. Reaction products with quantum yields in parentheses are ethyl disulfide (0.178), ethane (0.138). butane (0.086), ethanethiol (0.096), 4-methyl-3-thiahexane (0.034) and 4-methyl-3.5-dithiaheptane.Ethyl and ethylthiyl radicals are formed in the primary process and the product yields indicate a net primary decomposition quantum yield of 0.48. A reaction mechanism involving subsequent reactions of the primary fragments is proposed and explains the observed products and the observed variation in rates. Excited radicals and hot radical combination products play a minor role in this system, in contrast to the behavior of lower molecular weight sulfides. Secondary photolysis of the disulfide produced and consumption of ethanethiol are important factors in determining the time dependence of reaction rates in this system. La photolyse de la vapeur de sulfure d'ethyle a 2537 r\ a ete etudiee en fonction de la nature du substrat et de la pression de CF4 ainsi que du temps et de la temperature. Les produits de la reaction, dont les rendements quantiques sont donnes entre parentheses. sont les suivants, disulfure d'ethyle (0.178) ethane (0.138). butane (0.086) ethanethiol (0.096), methyl-4 thia-3 hexane (0.034), et methyl-4 dithia-3,5 heptane.Les radicaux ethyle et ethylthiyle sont formes dans la premiere phase et les rendements de produits indiquent fort nettement un rendement quantique de la decomposition primaire egal a 0.48. Un mecanisme reactionnel impliquant des reactions subsequentes des fragments primaires est propose: celui-ci permet d'ailleurs d'expliquer la formation des produits observes ainsi que les fluctuations observees dans les vitesses deformation. Les radicaux excites et les produits de combinaison de radicaux chauds jouent, en realite. un r61e negligeable dans ce systeme. ce qui va a I'encontre du compoi-tement des sulfures ayant des poids moleculaires plus bas. La photolyse secondaire du compose disulfure obtenue ainsi que la consommation d'ethanethiol sont des facteurs importants pour determiner dans ce systtme la dependance existagt entre le temps et les vitesses de la reaction.[Traduit par le journal]

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Strahlungschemie von Kohlenwasserstoffen. 14. Mitteilung. Mögliche Radikalreaktionen in Benzol

Zimmerli¹,

Gäumann²

1969

Helvetica Chimica Acta

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The behaviour of benzene and its mixtures with naphthalene, anthracene, cyclohexene and cyclohexadienes under the influence of γ‐irradiation is examined. A mechanism of the product formation in pure benzene is proposed and discussed, that is mainly based on radical reactions between cyclohexadienyl and phenylcyclohexadienyl radicals. The existence of phenyl radicals is shown by the formation of phenylnaphthalenes with naphthalene as additive. The inhibiting effect of cyclohexene and cyclohexadiene on the biphenyl and phenylcyclohexadiene formation can be explained by hydrogen abstraction by the phenyl radicals.

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The Reactivity of the Cyclic Polyenes Towards Free Radicals: Ii. Metathesis With the Ethyl Radical

Cited by 7 publications

References 16 publications

A kinetic study of the reactions of the hydrogen atom with the cyclohexadiene isomers in the gas phase

A kinetic study of the reactions of the hydrogen atom with the cyclohexadiene isomers in the gas phase

Reactions of Thiyl Radicals. X. Photolysis of Ethyl Sulfide Vapor

Strahlungschemie von Kohlenwasserstoffen. 14. Mitteilung. Mögliche Radikalreaktionen in Benzol

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