Kinetic study of competitive catalytic transfer hydrogenation on a multi-functional molecule: 4-benzyloxy-4′-chlorochalcone

Kinetic study of competitive catalytic transfer hydrogenation on a multi-functional molecule: 4-benzyloxy-4′-chlorochalcone

A combined chemical and mathematical approach was used to study the reduction process of 4-benzyloxy-4′-chlorochalcone involving catalytic transfer hydrogenation with ammonium formate and palladium on carbon. Several solvents were investigated to evaluate the effect of solvent-type on competitive re...

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Bibliographic Details
Published in:Reaction kinetics, mechanisms and catalysis Vol. 111; no. 1; pp. 1 - 14
Main Authors: Nguyen, Tyler, Arciero, Julia, Piltz, Joshua, Hartley, K. Danielle, Rickard, Timothy, Denton, Ryan
Format: Journal Article
Language:English
Published: Dordrecht Springer Netherlands 01-02-2014
Subjects:
Catalysis
Catalysts
Chemistry
Chemistry and Materials Science
Chlorides
Formates
Industrial Chemistry/Chemical Engineering
Mathematical models
Palladium
Physical Chemistry
Reaction kinetics
Reduction
Reduction
Palladium
Mathematical modeling
Catalytic transfer hydrogenation
Multi-functional
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Summary:A combined chemical and mathematical approach was used to study the reduction process of 4-benzyloxy-4′-chlorochalcone involving catalytic transfer hydrogenation with ammonium formate and palladium on carbon. Several solvents were investigated to evaluate the effect of solvent-type on competitive reduction rates. A mathematical model based on Michaelis–Menten reaction kinetics was developed using a least squares approximation method to estimate several model parameters according to time-dependent reduction data. The conjugated alkene was found to reduce fastest in all solvents except alcohols, which is likely related to the solvent’s ability to support partially-charged intermediate species in the RDS of aryl chloride hydrogenolysis. Substrate concentration and pH dependence of the reduction were also investigated to confirm prior mechanistic findings. Hydrogen transfer from the formate to palladium appears to be rate determining in multiple reactions. Also, catalyst poisoning by HCl may affect aryl chloride reduction more significantly than reduction of other functionalities.
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content type line 23
ISSN:1878-5190
1878-5204
DOI:10.1007/s11144-013-0627-5