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Thesis Plan 23/06/2010 McMillan, Liam (2012) The palladium catalysed hydrogenation of multi- functional aromatic nitriles. PhD thesis. http://theses.gla.ac.uk/3175/ Copyright and moral rights for this thesis are retained by the author A copy can be downloaded for personal non-commercial research or study, without prior permission or charge This thesis cannot be reproduced or quoted extensively from without first obtaining permission in writing from the Author The content must not be changed in any way or sold commercially in any format or medium without the formal permission of the Author When referring to this work, full bibliographic details including the author, title, awarding institution and date of the thesis must be given Glasgow Theses Service http://theses.gla.ac.uk/ [email protected] The palladium catalysed hydrogenation of multi-functional aromatic nitriles Submitted for the Degree of Doctor of Philosophy The University of Glasgow School of Chemistry Liam McMillan October 2011 © Liam McMillan 2011 1 Abstract A series of model compounds and a commercial Pd/C catalyst were used to study the issues relevant to the hydrogenation of aromatic nitrile molecules that are associated with an industrial agrichemicals process, where a primary amine is the target product. Benzonitrile hydrogenation was found to be converted to high value benzylamine before an unexpected hydrogenolysis reaction led to the loss of ammonia to ultimately yield toluene as the final product. Indeed, gas phase infrared studies unambiguously showed the formation of ammonia for the first time. On closer investigation, the reaction was found to be a consecutive process where the order of reaction changed from first order for hydrogenation to zero order for hydrogenolysis. Co-adsorption studies proved that the two reactions occurred independently on two distinct Pd sites. The choice of catalyst and the use of an acid additive were shown to improve selectivity to benzylamine. A dramatic change was noted when the aliphatic chain was extended. For benzyl cyanide hydrogenation, conversion was observed but, by way of a “spillover” process, the amine product was retained by the catalyst. Extending the chain further resulted in a complete loss in reactivity showing that electronic and structural factors had a major effect on activity and product distribution. Mandelonitrile hydrogenation required an acid additive to facilitate conversion since a series of co-adsorption studies showed that under neutral conditions an intermediate hydroxyamine acted as a poison. Recycling of the catalyst showed that a cumulative poisoning effect was evident, but manipulation of Pd particle shape and size resulted in an extended lifetime and superior selectivity. Introducing additional functionality to the aromatic ring meant that stabilised imine species were observed in the liquid phase. The nature of the substituent also affected product distribution and catalyst lifetime. MeO-, Me- and Cl-substituents all showed signs of reduced catalyst performance, but an OH-substituent exhibited greater durability, albeit with reduced selectivity to the primary amine. These systems also indicated the presence of a high energy site on the catalyst, which was responsible for the formation of secondary and tertiary amines. 2 Acknowledgments I would like to thank everyone involved in this project and to those that have helped me throughout all my years at university and beyond. Special thanks of course go to the legend that is Dr. David Lennon. I thank him for all his goodwill, good spirit and all his support and guidance over the years. Thank you for having faith in me, for all the good advice and for the intriguing conversations on the road, in the lab and in the pub. Thanks to the following undergraduate project students: Justin Baker (University of Chicago), Ellen Keller (von Humboldt University), Stephen Howarth and Lauren Gilpin (University of Glasgow) who carried out work associated with this project throughout my time, adding insight and value to many of the results. Also thanks to Dr. David Lundie (Hiden Analytical) for his help in acquiring chemisorption and temperature programmes desorption data, Jim Gallacher for TEM analysis, Michael Beglan for carrying out atomic absorption measurements and Jim Tweedie for answering all my chromatography questions. Thank you to my industrial sponsors Syngenta for providing an interesting and successful project, and for trusting and supporting me throughout the three years. Particular thanks go to my industrial supervisor Dr. Colin Brennan, for the informative meetings and for letting out some of Dave’s secrets over dinner. I must also thank everyone at Jealott’s Hill who made my time there informative, productive and enjoyable, including Dr. Martin Bowden, Michelle O’Mahoney and Rachel Donkor. To Ian, Neil and June, thanks for making working in the Lennon group so enjoyable. Thanks to Andrew for the Mustang rides and drunken nights in California, for being a cracking mate and for never replying to text messages unless he’s after something. Thanks especially to Clément and Robbie for “dragging” me to the pub, introducing me to Jaegerbombs and for letting me kip on their couches on countless occasions. I might not be any healthier, any richer or any more sensible, but it was worth it! 3 Finally to my Mum, Dad and sister – thank you for all your love, patience and support through the good and the (more often than not!) bad times. To everyone else who helped in any way and in the words of the great David Lennon himself; “Cheers everybody, thank you, all the best!”. 4 For Mum 5 AUTHOR’S DECLARATION I declare that, except where explicit reference is made to the contribution of others, that this thesis is the result of my own work and has not been submitted for any other degree at the University of Glasgow or any other institution. Liam McMillan October 2011 6 Contents 1 Background and Introduction ................................................... 22 1.1 What is a catalyst? ................................................................................. 22 1.2 Heterogeneous catalysis ........................................................................ 24 1.3 Economic, Industrial and Environmental Considerations ........................ 25 1.4 Fine Chemicals ....................................................................................... 26 1.5 Hydrogenation Reactions ....................................................................... 27 1.6 Nitrile hydrogenation introduction ........................................................... 27 1.6.1 Assumed mechanism for the hydrogenation of nitriles .................... 30 1.7 The industrial process and application of model compounds ................. 33 1.8 Reaction kinetics and activation energy .................................................. 36 1.8.1 Calculation of rate coefficient, activation energy and order of reaction …………………………………………………………………………….37 2 Experimental .............................................................................. 39 2.1 Reactors ................................................................................................. 39 2.1.1 Buchi batch autoclave ..................................................................... 39 2.1.1.1 Buchi Pressure Flow Gas Controller ........................................ 40 2.1.1.2 The Autoclave Motor-Speed Controller .................................... 42 2.1.1.3 The Julabo Refrigerated and Heating Circulator ...................... 42 2.1.1.4 Experimental Procedure ........................................................... 42 2.1.2 Ambient pressure reactor ................................................................ 43 2.1.2.1 Experimental Procedure ........................................................... 45 2.1.3 Gas phase batch reactor ................................................................. 45 2.1.3.1 Experimental procedure ........................................................... 46 2.1.4 Syngenta Parr reactor ..................................................................... 48 2.1.4.1 Experimental procedure ........................................................... 49 2.2 Analytical techniques .............................................................................. 49 2.2.1 Gas-Liquid Chromatography ........................................................... 49 2.2.1.1 Flame Ionisation Detector ........................................................ 50 2.2.2 High performance liquid chromatography ........................................ 51 7 2.2.3 Nuclear magnetic resonance spectroscopy ..................................... 52 2.2.4 Infrared spectroscopy ...................................................................... 55 2.3 Catalyst preparation and characterisation .............................................. 55 2.3.1 Catalyst preparation for 1% Pd/Al2O3 .............................................. 55 2.3.2 Catalyst characterisation facility ...................................................... 56 2.3.2.1 Line Volume Calibration ........................................................... 57 2.3.3 Atomic Absorption Spectroscopy ..................................................... 59 2.3.4 Transmission Electron Microscopy .................................................. 59 2.3.5 CO chemisorption ............................................................................ 60 2.3.6 CO Temperature programmed desorption ...................................... 62 3 Results and discussion
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