Kinetic deuterium isotope criterion applied to the thermolysis of alkyl allyl ethers.  II

Kwart, Harold; Slutsky, Joel; Sarner, Stanley F.

doi:10.1021/ja00797a024

Cited by 16 publications

(8 citation statements)

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“…Here, the kinetic temperature was extracted from temperature dependent product yields assuming a simple first-order decomposition kinetics. Both methods were found to agree well within ∆T ≈ ±25 K. Based on the known Arrhe-nius parameters of the allylethylether decomposition [37,38], the same measurements were used to estimate an effective reaction time t eff of the reaction mixture in the SiC tube. A reasonable value of t eff ≈ 65µs was obtained, which is somewhat longer than the minimum conceivable passage time calculated from the sonic speed of Ar, t min ≈ 39 µs.…”

Section: Methodsmentioning

confidence: 97%

The Products of the Reactions of o-Benzyne with Ethene, Propene, and Acetylene: A Combined Mass Spectrometric and Quantum Chemical Study

Friedrichs¹,

Goos²,

Gripp³

et al. 2009

Zeitschrift Für Physikalische Chemie

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The primary products of the bimolecular reactions of ortho-benzyne, o-C6H4 (1,2-dehydrobenzene), with ethene, propene, and acetylene have been detected by molecular beam mass spectrometry at a combustion relevant temperature of T = 1475 K. o-Benzyne was produced by flash pyrolysis of phthalic anhydride in the absence and presence of the respective reactant. Potential reaction pathways of the addition reactions were investigated by quantum chemical calculations. Channels with biradical intermediates were found to be energetically more favorable than alternative quasi-concerted [2+1] cycloaddition and concerted H-transfer pathways. Bicyclic benzocyclobutene and benzocyclobutadiene were identified as the main products of the reactions with C2H4 and C2H2, respectively. At combustion temperatures, however, these cyclic products are likely to undergo sequential ring opening. In the case of propene, the presence of an allylic H atom initiates a favorable ene-type reaction sequence yielding the open-chain product allylbenzene. Overall, hydrocarbon reactivity was found to increase in the order C2H2, C2H4 to 3H8. The range of the estimated bimolecular rate constants is comparable to the rate constants of the corresponding phenyl radical reactions and hence point out a potentially important role of o-C6H4 reactions in flame and soot formation chemistry.

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Section: Methodsmentioning

confidence: 97%

The Products of the Reactions of o-Benzyne with Ethene, Propene, and Acetylene: A Combined Mass Spectrometric and Quantum Chemical Study

Friedrichs¹,

Goos²,

Gripp³

et al. 2009

Zeitschrift Für Physikalische Chemie

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“…If this is the case, the observed magnitude of the kinetic deuterium isotope effect should be maximum for the said nonlinear three-center hydrogen transfer. A linear configuration [7] for the 1-5 hydrogen rearrangement has been proposed for the pyrolysis of allyl ethers [8] based on the absence of substituent effects on rates and the temperature dependence of the kinetic deuterium isotope effect. The greater bulk of the sulfur atom probably accounts for this difference in the geometry of the transition states for the oxygen and sulfur systems.…”

Section: Discussionmentioning

confidence: 99%

Gas‐phase thermolysis of sulfur compounds. Part IV. n‐propyl allyl sulfide

Martín

Ropero

1982

Int J of Chemical Kinetics

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The pyrolysis of n-propyl allyl sulfide has been studied in static and stirred-flow systems at temperatures between 270 and 400°C. Propene and 2,4,6-triethyl-1,3,5-trithiane were the only reaction products. The order of the reaction was 0.99 f 0.05 a t 377OC. The firstorder rate coefficients followed the Arrhenius equationThe rate coefficients and the product distribution remained unchanged when cyclohexene was used as carrier gas. A molecular mechanism involving a six-centered cyclic transition state is proposed to explain the present results. This mechanism is further supported by the pyrolysis of 4-thia-5-dideutero-1-heptene at 377OC, where only 3-deuteropropene is formed. The kinetic deuterium isotope effect had a value of 2.6 f 0.3 a t this temperature. The results are compared with those obtained in the pyrolysis of n-butyl allyl sulfide previously reported.

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“…generation of some carbon-heteroatom double bonds; among these can be cited C‫ס‬O [4][5][6], C‫ס‬S [7,8], C‫ס‬N [9][10][11][12], C‫ס‬Si [13,14], and recently, C‫ס‬P [15,16].…”

Section: Introductionmentioning

confidence: 99%

“…These studies have permitted also to make suggestions about the nature and the likely geometry of the transition state. The temperature dependence of the kinetic deuterium isotope effect and a lack of substituent effects on the reaction rate for allyl ethers [4][5][6] were used as evidence to propose a nonplanar transition state and a highly concerted mechanism. The allyl sulfides [7,8], on the other hand, showed a temperature-independent kinetic isotope effect [8] and an important substituent effect [7] on the rate of the pyrolysis, suggesting a polar transition state in which the higher reactivity was due to an enhanced acidic character of the ␣-H atom to be transferred in a nonlinear 1-5 shift path.…”

Section: Introductionmentioning

confidence: 99%

Transition structure for the retroene-type elimination reaction of propene from allylamines

et al. 1997

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Kinetic deuterium isotope criterion applied to the thermolysis of alkyl allyl ethers. II

Cited by 16 publications

References 1 publication

The Products of the Reactions of o-Benzyne with Ethene, Propene, and Acetylene: A Combined Mass Spectrometric and Quantum Chemical Study

The Products of the Reactions of o-Benzyne with Ethene, Propene, and Acetylene: A Combined Mass Spectrometric and Quantum Chemical Study

Gas‐phase thermolysis of sulfur compounds. Part IV. n‐propyl allyl sulfide

Transition structure for the retroene-type elimination reaction of propene from allylamines

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