Mechanism of C N bond breaking in hydrodenitrogenation

C N bond rupture is the final step in the hydrodenitrogenation of nitrogen-containing molecules and occurs by substitution of the alkylamine by H 2S to form an alkanethiol and NH 3. To study the mechanism of the C N bond breaking, we investigated the reactions of the chiral 2-( S)-butylamine and of...

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Bibliographic Details
Published in:Journal of catalysis 2005-09, Vol.234 (2), p.509-512
Main Authors: Prins, R., Zhao, Y., Sivasankar, N., Kukula, P.
Format: Article
Language:English
Subjects:
2-butylamine
Catalysis
Chemistry
chiral amine
Exact sciences and technology
General and physical chemistry
Hydrodenitrogenation
Imine intermediate
Iminium cation
Mechanism
N,N-dihexylmethylamine
Substitution
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
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Summary:C N bond rupture is the final step in the hydrodenitrogenation of nitrogen-containing molecules and occurs by substitution of the alkylamine by H 2S to form an alkanethiol and NH 3. To study the mechanism of the C N bond breaking, we investigated the reactions of the chiral 2-( S)-butylamine and of N, N-dihexylmethylamine. The amine-to-thiol substitution occurred not through a classic organic substitution reaction, but rather through (de)hydrogenation steps via an imine or through redox and (de)protonation steps, in which an alkyliminium cation acts as an intermediate. For alkylamines and dialkylamines, the reaction may well occur via imine intermediates, but for trialkylamines, the intermediate can only be an iminium ion.
ISSN:0021-9517
1090-2694
DOI:10.1016/j.jcat.2005.06.034