1861-00-3Relevant articles and documents
Kinetics and mechanism of benzyl chloride reaction with zinc in dimethylacetamide
Egorov,Matyukhova,Dashkova
, p. 1686 - 1699 (2012)
Oxidative dissolution of zinc in the system of benzyl chloride- dimethylacetamide was investigated. The reaction stereochemistry as well as intermediates and reaction products formed were studied. The kinetic and thermodynamic parameters of the process were measured. The process was shown to follow the Langmuir-Hinshelwood mechanism with the formation of benzyl radicals and mono-solvated organozinc compound on the zinc surface. The components of mixture are adsorbed at various sites of the zinc surface, while recombination and the isomerization of the benzyl radicals occurs in solution. Pleiades Publishing, Ltd., 2012.
Deuterium isotope effects on the CH stretching overtone spectrum of toluene-α-d1
Kjaergaard, Henrik G.,Turnbull, David M.,Henry, Bryan R.
, p. 6095 - 6100 (1998)
The room-temperature vapor phase overtone spectrum of toluene-α-d1 has been recorded in the CH stretching regions corresponding to ΔυCH = 2-7. The vibrational overtone spectra are recorded by conventional near-infrared spectroscopy a
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Choppin,Smith
, p. 577 (1948)
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Preliminary investigations on the catalytic hydrogenation of polycyclic aromatic hydrocarbons via WGSR
Chen, Dabo,Gu, Jiale,Huang, Sheng,Li, Huan,Wu, Shiyong,Wu, Youqing
, (2021/10/04)
The water-gas shift reaction (WGSR) is a crucial reaction in the direct liquefaction of lignite in a syngas (CO + H2) system. In this study, anthracene was utilized as a polycyclic model compound of lignite, to which hydrogen is donated by the H2/D2 produced from CO and H2O/D2O via the WGSR. The results show that the model compound of the polycyclic aromatic hydrocarbon in coal (anthracene) undergoes partial cracking and polycondensation under non-hydrogen-donor conditions at 400 °C. In addition, WGSR catalyzed by NiO can generate hydrogen for the hydrogenation of anthracene. Comparing the mass spectra of deuterated products with those of conventional hydrogenation products by isotope labeling, the alkyl side chain positions of toluene, 1,4-xylene, methylnaphthalene, 1,1-diphenylethylene, methylanthracene and other compounds are prone to deuteration, enabling speculation of the main hydrogenation route of anthracene, which provides theoretical support for the catalytic hydrogenation in direct liquefaction of lignite in a syngas (CO + H2) system.
Methane Generation and Reductive Debromination of Benzylic Position by Reconstituted Myoglobin Containing Nickel Tetradehydrocorrin as a Model of Methyl-coenzyme M Reductase
Hayashi, Takashi,Miyazaki, Yuta,Oohora, Koji
supporting information, p. 11995 - 12004 (2020/09/15)
Methyl-coenzyme M reductase (MCR), which contains the nickel hydrocorphinoid cofactor F430, is responsible for biological methane generation under anaerobic conditions via a reaction mechanism which has not been completely elucidated. In this work, myoglobin reconstituted with an artificial cofactor, nickel(I) tetradehydrocorrin (NiI(TDHC)), is used as a protein-based functional model for MCR. The reconstituted protein, rMb(NiI(TDHC)), is found to react with methyl donors such as methyl p-toluenesulfonate and trimethylsulfonium iodide with methane evolution observed in aqueous media containing dithionite. Moreover, rMb(NiI(TDHC)) is found to convert benzyl bromide derivatives to reductively debrominated products without homocoupling products. The reactivity increases in the order of primary > secondary > tertiary benzylic carbons, indicating steric effects on the reaction of the nickel center with the benzylic carbon in the initial step. In addition, Hammett plots using a series of para-substituted benzyl bromides exhibit enhancement of the reactivity with introduction of electron-withdrawing substituents, as shown by the positive slope against polar substituent constants. These results suggest a nucleophilic SN2-type reaction of the Ni(I) species with the benzylic carbon to provide an organonickel species as an intermediate. The reaction in D2O buffer at pD 7.0 causes a complete isotope shift of the product by +1 mass unit, supporting our proposal that protonation of the organonickel intermediate occurs during product formation. Although the turnover numbers are limited due to inactivation of the cofactor by side reactions, the present findings will contribute to elucidating the reaction mechanism of MCR-catalyzed methane generation from activated methyl sources and dehalogenation.
Dramatic Synergy in CoPt Nanocatalysts Stabilized by "click" Dendrimers for Evolution of Hydrogen from Hydrolysis of Ammonia Borane
Wang, Qi,Fu, Fangyu,Yang, Sha,Martinez Moro, Marta,Ramirez, Maria De Los Angeles,Moya, Sergio,Salmon, Lionel,Ruiz, Jaime,Astruc, Didier
, p. 1110 - 1119 (2019/01/21)
Hydrolysis of ammonia borane (AB) is a very convenient source of H2, but this reaction needs catalytic activation to become practical under ambient conditions. Here this reaction is catalyzed by bimetallic late transition-metal nanoparticles (N
