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Selective hydrogenation of nitriles to imines over a multifunctional heterogeneous Pt catalyst
Author(s) -
Long Jilan,
Yin Biaolin,
Li Yingwei,
Zhang Lianjie
Publication year - 2014
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.14545
Subject(s) - dabco , catalysis , benzonitrile , chemistry , selectivity , yield (engineering) , lewis acids and bases , nitrile , heterogeneous catalysis , organic chemistry , combinatorial chemistry , materials science , metallurgy
Imines and their derivatives are versatile synthetic intermediates for the industrial preparation of both bulk and fine chemicals and for pharmaceuticals, but preparing these compounds efficiently through direct hydrogenation of nitriles are hindered by overhydrogenation to secondary amines. Here we report a highly efficient multifunctional catalyst system for selective hydrogenation coupling of nitriles to secondary imines using a heterogeneous Pt catalyst that was deposited on a nickel‐based metal‐organic framework (MOF) containing DABCO. The catalyst showed excellent synergy in promoting the hydrogenation of a variety of nitriles, giving significantly improved activity and selectivity (up to >99% yield) even under atmospheric pressure of H 2 . It is suggested that the Lewis base (DABCO) sites on the Ni‐MOF inhibit further hydrogenation of the imines. The influence of H 2 pressure, reactant concentration, stirring speed, and reaction temperature was investigated. The kinetics and mechanism of hydrogenation of benzonitrile (BN) by the Pt/Ni‐MOF catalyst has been studied. The reaction showed a first‐order dependence on both BN concentration and H 2 pressure. A kinetic model was proposed based on the mechanism of nitriles hydrogenation and compared with experimental observations. © 2014 American Institute of Chemical Engineers AIChE J , 60: 3565–3576, 2014