Mechanistic Insights Into the Hydrocyanation Reaction

Mechanistic insights into the hydrocyanation reaction Citation for published version (APA): Bini, L. (2009). Mechanistic insights into the hydrocyanation reaction. Technische Universiteit Eindhoven. https://doi.org/10.6100/IR644067 DOI: 10.6100/IR644067 Document status and date: Published: 01/01/2009 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal. If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license above, please follow below link for the End User Agreement: www.tue.nl/taverne Take down policy If you believe that this document breaches copyright please contact us at: [email protected] providing details and we will investigate your claim. Download date: 04. Oct. 2021 Mechanistic Insights into the Hydrocyanation Reaction Laura Bini A catalogue record is available from the Eindhoven University of Technology Library ISBN: 978-90-386-1936-1 © 2009, Laura Bini This research was financially support by Bayer MS and Evonik Oxeno HPP Cover Design: Renée Mans: “ De Kleuren zijn de kleuren van de door Laura gebruikte ingrediënten. HCN kobalt, AlCl3 wit, nitriles geel, Ni oranje. De kleuren zijn de kleuren van de regenboog. De cirkel is rond. Alles in het heelal is te hergebruiken.” Printed at Wöhrmann Print Service, Zutphen, The Netherlands Mechanistic Insights into the Hydrocyanation Reaction PROEFSCHRIFT ter verkrijging van de graad van doctor aan de Technische Universiteit Eindhoven, op gezag van de rector magnificus, prof.dr.ir. C.J. van Duijn, voor een commissie aangewezen door het College voor Promoties in het openbaar te verdedigen op donderdag 10 september 2009 om 16.00 uur door Laura Bini geboren te Lucca, Italië Dit proefschrift is goedgekeurd door de promotor: prof.dr. D. Vogt Copromotor: dr. C. Müller Dit proefschrift is goedgekeurd door de manuscriptcommissie: Prof. Dr. Dieter Vogt (Technische Universiteit Eindhoven) Dr. Christian Müller (Technische Universiteit Eindhoven) Prof. Dr. William Jones (University of Rochester) Prof. Dr. Hans de Vries (Rijksuniversiteit Groningen) Prof. Dr. Cor Koning (Technische Universiteit Eindhoven) Contents Chapter 1. Mechanistic studies on hydrocyanation reaction: a general introduction 11 1.1. Introduction 12 1.2. The DuPont process: first study on the reaction mechanism and the hydrocyanation of butadiene 14 1.3. The DuPont process: isomerization of 2-methyl-3-butenenitrile and C-CN bond activation 19 1.4. The DuPont process: hydrocyanation of 3-pentenenitrile, formation of alkyl intermediates and application of Lewis acids 27 1.5. Asymmetric hydrocyanation: use of chiral ligands and prochiral substrates 31 1.6. The hydrocyanation of unactivated monoalkenes: the role of the Lewis acid 39 1.7. The hydrocyanation reaction applying different metals 42 1.7.1. Cobalt-catalyzed hydrocyanation 42 1.7.2. Copper-catalyzed hydrocyanation 43 1.7.3. Palladium-catalyzed hydrocyanation 44 1.7.4. Platinum-catalyzed hydrocyanation 47 1.8. Conclusions and outlook 48 1.9. Scope of the thesis 49 1.10. References and notes 50 Chapter 2. Highly selective hydrocyanation of butadiene towards 3- 55 pentenenitrile 2.1. Introduction 56 2.2. Synthesis of the ligand 57 2.3. Synthesis of Pt(II) and Ni(0) complexes 58 2.3.1. The coordination towards platinum 59 2.3.2. The coordination towards nickel 60 2.4. Hydrocyanation of butadiene 61 2.5. Mechanistic explanation 63 2.6. Isomerization of 2M3BN towards 3PN 64 2.7. Comparison with other ligands 65 2.8. Conclusions 67 2.9. Experimental section 69 Contents 2.10. References and notes 73 Chapter 3. Nickel catalyzed isomerization of 2-methyl-3-butenenitrile to 3-pentenenitrile. A kinetic study using in situ FTIR-ATR spectroscopy 75 3.1. Introduction 76 3.2. In situ FTIR-ATR spectroscopy applied to the analysis of the 2M3BN isomerization reaction 77 3.3. IR spectra: interpretation and kinetic profiles 79 3.3.1. In situ or operando technique 79 3.3.2. The nitrile region 80 3.3.3. The C-H deformation band region 83 3.3.4. The (C=)C-H stretching band region 85 3.4. DFT calculation and peak assignment 86 3.5. ”Quasi-multivariate” analysis 89 3.6. Multivariate analysis 91 3.7. Limitation of the IR analysis technique and outlooks 93 3.8. Conclusions 94 3.9. Experimental section 96 3.10. References and notes 99 Chapter 4. Hydrocyanation 3-pentenenitrile with tetraphenol-based diphosphite ligands: formation of π-allyl and σ-alkyl intermediates 101 4.1. Introduction 102 4.2. Hydrocyanation of 3-pentenenitrile 103 4.3. Comparison with the diphosphite ligand BIPPP 106 4.4. NMR studies 107 4.5. IR studies 109 4.6. Coordination of ZnCl 2 to the [Ni(2M3BN)(TP2)] complex 112 4.7. Conclusions 114 4.8. Experimental section 115 4.9. References and notes 119 Chapter 5. Lewis acid-controlled regioselectivity in styrene hydrocyanation 121 5.1. Introduction 122 8 Contents 5.2. Hydrocyanation of styrene 123 5.3. Deuterium labeling experiments 126 5.4. Lewis acid effect on the reaction rate: hydrocyanation versus polymerization 130 5.5. DFT calculations and NMR spectroscopy 132 5.5.1. DFT calculations and NMR experiments on AlCl3 coordination 132 5.5.2. DFT calculations based on the hydrocyanation catalytic cycle 136 5.5.3. Addition of mechanistic details in the catalyic cycle 140 5.6. Screening of reaction conditions and Lewis acids in styrene hydrocyanation 145 5.6.1. Styrene hydrocyanation at different temperature and reaction time 145 5.6.2. Comparison with other Lewis acids 146 5.6.3. DFT calculations on styrene hydrocyanation in the presence of CuCN as Lewis acid 147 5.7. Conclusions 148 5.8. Experimental section 150 5.9. References and notes 153 Chapter 6. Hydrocyanation of 1-octene: an open challenge 155 6.1. Introduction 156 6.2. Hydrocyanation of 1-octene 157 6.2.1. The hydrocyanation of 1-octene applying the monodentate phosphite ligand P(OPh) 3 157 6.2.2. The hydrocyanation of 1-octene applying the bidentate phosphite ligand BIPPP 159 6.3. Application of different monoalkene substrates: the polarity of the reaction medium 160 6.4. Deuterium labeling experiments 162 6.5. DFT calculations 166 6.6. Conclusions 168 6.7. Experimental section 169 6.8. References and notes 171 Summary 173 Samenvatting 177 Sommario 181 9 Contents List of Publications 185 Curriculum Vitae 187 Acknowledgements 189 10 Chapter 1 Mechanistic Studies on Hydrocyanation Reactions: a General Introduction. In this chapter, an overview will be given on the literature dealing with mechanistic studies on the hydrocyanation reaction. Pertinent data on this topic are not easily available, due to the instability of the reactive intermediates and the lack of isolable catalyst species. However, mechanistic considerations are imperative for a detailed understanding of the reaction. Especially a profound knowledge of the delicate structure-performance relation of the catalyst and intermediate species and on the product formation is missing. The major focus of this thesis is to elucidate some of these aspects. Chapter 1 1.1. Introduction Hydrocyanation is the process in which HCN is added across a double bond of an alkene to form a nitrile (Scheme 1.1).1 Nitriles are very versatile building blocks that can be used as precursors for amines, isocyanates, amides, carboxylic acids and esters (Scheme 1.2). 2 Scheme 1.1. Hydrocyanation of alkenes. Scheme 1.2. Synthetic versatility of nitriles. Despite the apparent simplicity of addition reactions to alkenes, it is still an important challenge to control the regioselectivity of such processes.3 For example, the achiral (linear) anti-Markovnikov products are important intermediates for the chemical industry. Every year linear aliphatic alcohols and amines are produced on a multimillion ton scale as bulk-chemical intermediates. Due to the relatively low price of these products, the corresponding production processes must be highly efficient (product yields > 95%, low catalyst costs, etc.). 12 Mechanistic Studies on Hydrocyanation Reaction: a General Introduction. On the other hand, the chiral branched products are often intermediates in organic synthesis on a smaller scale and for natural product synthesis. They are also valuable for the fine chemical industry as intermediates for pharmaceuticals and agrochemicals. Apart from the aspect of regioselectivity, the control of stereochemistry is an important issue for these reactions. In the last decades, more studies have therefore focused on the synthesis of nitriles, based on HCN addition to alkenes or to related systems in the presence of a transition metal catalyst, most commonly based on nickel.4 This reaction can be considered as an important tool in synthetic chemistry.

Load more