Kinetic study of competitive catalytic transfer hydrogenation on a multi-functional molecule: 4-benzyloxy-4-chlorochalcone
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- 作者：Tyler Nguyen (1) (2)
Julia Arciero (2)
Joshua Piltz (1)
K. Danielle Hartley (1)
Timothy Rickard (1)
Ryan Denton (1) - 关键词：Palladium ; Catalytic transfer hydrogenation ; Reduction ; Multi ; functional ; Mathematical modeling
- 刊名：Reaction Kinetics, Mechanisms and Catalysis
- 出版年：2014
- 出版时间：February 2014
- 年：2014
- 卷：111
- 期：1
- 页码：1-14
- 全文大小：490 KB
- 作者单位：Tyler Nguyen (1) (2)
Julia Arciero (2)
Joshua Piltz (1)
K. Danielle Hartley (1)
Timothy Rickard (1)
Ryan Denton (1)
1. Department of Chemistry and Chemical Biology, Indiana University-Purdue University Indianapolis, 402?N Blackford Street, Indianapolis, IN, 46202, USA
2. Department of Mathematical Sciences, Indiana University-Purdue University Indianapolis, 402?N Blackford Street, Indianapolis, IN, 46202, USA - ISSN：1878-5204
文摘
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.