DFT calculations on the retro-ene reactions, part II: allyl n-propyl sulfide pyrolysis in the gas phase

Izadyar, Mohammad; Gholami, Mohammad Reza; Haghgu, Mohammad

doi:10.1016/j.theochem.2004.07.033

Cited by 10 publications

(2 citation statements)

References 32 publications

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“…All the electronic structure calculations reported in this work were performed using the Spartan '14 v1.1.0 program packages. The geometries included in the reaction of hydrazine / hydrazinium ion with iodine were fully optimized using density functional theory (DFT) method [35,36,37]. To check the influence of basis set, PM3 of semi empirical method and 6-311+G** basis set of DFT at the B3LYP levels of computation were employed to optimize the geometries of the reactants, intermediates, transition states and products.…”

Section: Geometry Optimization Of Reactants Intermediates Transitiomentioning

confidence: 99%

Computational Study of the Mechanism of the Oxidation of Hydrazine / Hydrazinium Ion by Iodine in the Gas Phase

Shallangwa¹

2015

IJCTC

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The reaction mechanisms of the oxidation of hydrazine / hydrazinium ion by iodine have been studied using 6311+G** basis set of the density functional theory (DFT) method at the B3LYP level of computation. The study shows that the oxidation reactions can proceed via four independent routes or pathways that can be separately monitored. Two of the proposed pathways involved a two-step reaction mechanism each, in which two transition states were produced while each of the other two routes involved three-step reaction mechanism in which three activated complexes were produced. The results obtained were based on the analyses of the computational energetics of the optimized reactants, intermediates, transition states and products of the reaction of iodine with hydrazine / hydrazinium ion. The study showed that all the four proposed routes were possible by comparing the enthalpies of reactions of the four proposed pathways as well as the activation barriers of the respective rate determining steps which were found to be reasonably acceptable. Rate laws, which were consistent with the written mechanisms, were also derived for each of the proposed mechanisms.

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Section: Geometry Optimization Of Reactants Intermediates Transitiomentioning

confidence: 99%

Computational Study of the Mechanism of the Oxidation of Hydrazine / Hydrazinium Ion by Iodine in the Gas Phase

Shallangwa¹

2015

IJCTC

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“…The most popular concerted mechanism for the retro-ene reaction includes a six-membered transition structure (TS). [1][2][3][4][5][6][7][8] Two convenient methods for direct conversion of sulfoxides to olens are base-catalyzed b-elimination and simple pyrolysis. A yield of 90% of propene was reported by heating of diisopropyl sulfoxide and potassium-tbutoxide in dimethyl sulfoxide as solvent for 17 hours at 358 K. 9 In comparison, thermal elimination requires a higher temperature but is potentially a cleaner reaction.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and mechanism of diallyl sulfoxide pyrolysis; a combined theoretical and experimental study in the gas phase

Izadyar

Gholami

2014

RSC Adv.

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Retro‐Ene Reaction

2010

Comprehensive Organic Name Reactions and Reagents

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The intramolecular thermolysis of organic compounds with an unsaturated functional group involving the transfer of a γ‐hydrogen to the unsaturated center via a six‐membered transition state to yield both ene and enophil is generally known as the retro ‐ene reaction or retro ‐ene fragmentation. The study finds that in most cases, this reaction involves a concerted mechanism, and gives a product with the stereochemical integrity preserved. This reaction does not take place among cyclic alkenes smaller than a seven‐membered ring or fused rings except for a cyclopropyl ring. This reaction has broad applications in organic synthesis.

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DFT calculations on the retro-ene reactions, part II: allyl n-propyl sulfide pyrolysis in the gas phase

Cited by 10 publications

References 32 publications

Computational Study of the Mechanism of the Oxidation of Hydrazine / Hydrazinium Ion by Iodine in the Gas Phase

Computational Study of the Mechanism of the Oxidation of Hydrazine / Hydrazinium Ion by Iodine in the Gas Phase

Kinetics and mechanism of diallyl sulfoxide pyrolysis; a combined theoretical and experimental study in the gas phase

Retro‐Ene Reaction

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