71057-22-2Relevant academic research and scientific papers
Alkyl radical generation in water under ambient conditions - A new look at the Guareschi reaction of 1897
Nguyen, Bao,Chernous, Katya,Endlar, Daniel,Odell, Barbara,Piacenti, Michela,Brown, John M.,Dorofeev, Alexander S.,Burasov, Alexander V.
, p. 7655 - 7658 (2008/09/18)
(Chemical Equation Presented) Chemical and biochemical significance of a long-forgotten 19th century observation: The hydrocarbon production from quaternary glutarimides on neutralization in water is the consequence of formation of alkyl radicals, which means that it is possible to generate alkyl radicals under very mild conditions. Oxygen trapping competes with hydrogen abstraction (see scheme).
Orientation in the Addition of HD Molecules to Buta-1,3-diene over ZnO Catalyst. A Method of Judging Heterolytic and Homolytic Dissociation of Hydrogen in Catalysis
Tanaka, Ken-ichi,Aomura, Kazuo,Okuhara, Toshio,Miyahara, Koshiro
, p. 1697 - 1706 (2007/10/02)
Selective 1,2-addition of HD molecules to butadiene on ZnO catalyst yielded 75percent of but-1-ene and 25percent of but-1-ene.Although the adsorption of HD on ZnO prefers conformation at room temperature and the reverse conformation at -40 deg C, reaction of HD at these two temperatures gave an identical ratio of / = 3.The dissociation of HD is in general expressed by In the case of homolytic dissociation H(I) and H(II) or D(I) and D(II) should be identical, i.e. β = 1, but in heterolytic dissociation it may not be unity.Provided that the hydrogen molecular identity is maintained in the hydrogenated products, the following equations were derived for n- and sec-butenyl intermediates: / = (1+ΑΒ)/(Α+Β) for sec-butenyl and / = (Α+Β)/(1+ΑΒ) for n-butenyl, where Α is a relative rate constant of the reaction of H(I) and H(II) or D(I) and D(II) with butadiene.Accordingly, in homolytic dissociation the simple relations / = / or / should be established for homolytic dissociation, because α = 1 and Β = 1, whereas / will be equal to neither / nor / in heterolytic dissociation.It was confirmed that the hydrogenation on MoS2 is brought about by homolytic dissociation but that on ZnO it is caused by heterolytic dissociation.A plausible mechanism assuming ?-allyl anionic intermediates. was proposed and it is explainable in terms of first-order kinetics in hydrogen pressure and the temperature-independent orientation in the 1,2-addition of HD.
