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A Systematic Approach to Understanding Organic Reactivity

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A Systematic Approach to Understanding Organic Reactivity A Systematic Approach to Understanding Organic Reactivity in Ionic Liquids: Changes in Cybotacticity-Induced Solvent Heterogeneity as an Important Determinant In Reaction Outcomes of Substitution Processes This thesis is presented for the partial fulfilment of the requirements for the degree of Doctor of Philosophy in the School of Chemistry by Hon Man Yau October, 2011 PLEASE TYPE THE UNIVERSITY OF NEW SOUTH WALES Thesis/Dissertation Sheet Surname or Family name: Yau First name: Hon Man Other name/s: Abbreviation for degree as given in the University calendar: Ph.D. School: School of Chemistry Faculty: Science Title: A Systematic Approach to Understanding Organic Reactivity in Ionic Liquids: Changes in Cybotacticity-Induced Solvent Heterogeneity as an Important Determinant In Reaction Outcomes of Substitution Processes Abstract 350 words maximum: (PLEASE TYPE) Described herein is the initial development towards a general framework for predicting changes in organic reactivity in ionic liquids through the mechanistic studies of several representative substitution processes with well-defined mechanisms. The temperature-dependent kinetic behaviour of the ethanolysis of 1-fluoro-2,4-dinitrobenzene as a model nucleophilic aromatic substitution reaction was examined in molecular and ionic solvents. Activation parameters obtained and relevant molecular dynamics simulations performed highlight the importance of cybotactic regions characterised by anion-π interaction. Activation parameters and free energy relationships for the Menschutkin reactions between pyridine and a series of substituted benzyl bromides and unsubstituted benzyl halides in both molecular and ionic liquid solvents were investigated. The Menschutkin reaction was found to be entropically favoured in ionic liquid regardless of the leaving group involved. By systematically replacing the aromatic starting materials with non-aromatic ones, the effect of delocalised electron density in either the electrophile or the nucleophile of the aforementioned Menschtkin reaction was evaluated. Cybotacticity associated with nitrogen centre in the nucleophiles and related changes were found to be responsible for changes in reactivity observed on changing solvent to the ionic liquid and are consistent with related molecular dynamics simulations of the starting materials. Kinetic analyses were also carried out for the reaction between 1-(1-chloroethyl)-4-methoxybenzene and pyridine, which proceeds through both unimolecular and bimolecular pathways simultaneously. The results are discussed in relation to the bimolecular Menschutkin reactions presented in the early chapters of this thesis as well as previous work on a unimolecular substitution process and the potential for solvent-controlled reactivity is discussed. The Menschutkin reaction between benzyl bromide and pyridine was investigated in ionic liquids composed of either a 1,3- dialkylimidazolium cation or a 1,2,3-trialkylimidazolium cation. The generality of electrostatic interactions and the impact of charge density were examined based on the activation parameters obtained from temperature-dependent kinetics analysis. A general “one-pot” method for obtaining relative rates of reaction in complex mixtures has been established through the construction of free energy relationships for various reactions under competitive conditions. The advantages of the technique, compared to existing methods in the literature, are discussed in terms of accuracy, efficiency and applicability. Declaration relating to disposition of project thesis/dissertation I hereby grant to the University of New South Wales or its agents the right to archive and to make available my thesis or dissertation in whole or in part in the University libraries in all forms of media, now or here after known, subject to the provisions of the Copyright Act 1968. I retain all property rights, such as patent rights. I also retain the right to use in future works (such as articles or books) all or part of this thesis or dissertation. I also authorise University Microfilms to use the 350 word abstract of my thesis in Dissertation Abstracts International (this is applicable to doctoral theses only). 21st February, 2012. .. ..... Signature Witness Date The University recognises that there may be exceptional circumstances requiring restrictions on copying or conditions on use. Requests for restriction for a period of up to 2 years must be made in writing. Requests for a longer period of restriction may be considered in exceptional circumstances and require the approval of the Dean of Graduate Research. FOR OFFICE USE ONLY Date of completion of requirements for Award: THIS SHEET IS TO BE GLUED TO THE INSIDE FRONT COVER OF THE THESIS COPYRIGHT STATEMENT ‘I hereby grant the University of New South Wales or its agents the right to archive and to make available my thesis or dissertation in whole or part in the University libraries in all forms of media, now or here after known, subject to the provisions of the Copyright Act 1968. I retain all proprietary rights, such as patent rights. I also retain the right to use in future works (such as articles or books) all or part of this thesis or dissertation. I also authorise University Microfilms to use the 350 word abstract of my thesis in Dissertation Abstract International (this is applicable to doctoral theses only). I have either used no substantial portions of copyright material in my thesis or I have obtained permission to use copyright material; where permission has not been granted I have applied/will apply for a partial restriction of the digital copy of my thesis or dissertation.' Signed .............................................................................. Date .................................................................................. AUTHENTICITY STATEMENT ‘I certify that the Library deposit digital copy is a direct equivalent of the final officially approved version of my thesis. No emendation of content has occurred and if there are any minor variations in formatting, they are the result of the conversion to digital format.’ Signed .............................................................................. Date .................................................................................. ORIGINALITY STATEMENT ‘I hereby declare that this submission is my own work and to the best of my knowledge it contains no materials previously published or written by another person, or substantial proportions of material which have been accepted for the award of any other degree or diploma at UNSW or any other educational institution, except where due acknowledgement is made in the thesis. Any contribution made to the research by others, with whom I have worked at UNSW or elsewhere, is explicitly acknowledged in the thesis. I also declare that the intellectual content of this thesis is the product of my own work, except to the extent that assistance from others in the project's design and conception or in style, presentation and linguistic expression is acknowledged.’ Signed ................................................................. Date ..................................................................... Author’s Statement I solemnly declare that the work presented in this thesis has not previously been submitted at the University of New South Wales or any other institution for the consideration of a degree or diploma. To the best of my knowledge, none of the work reported herein has previously been published or presented by another person except where due reference is made. It should be noted that the publication of a closely related study completed during my honours year is included in Appendix 6 for reference and completeness due to the extensive discussion related to the publication in the text. Shon Glyn Jones, who is affiliated with the University of Wales, Bangor, carried out the molecular dynamics simulations presented in Chapter 1 as a result of collaboration with Dr Anna Croft. Associated analysis of the molecular dynamics simulation data and all other material presented in this thesis is the outcome of my own work, except to the extent where the conception and design of the project as well as stylistic and linguistic presentation are acknowledged. Yau, Hon Man 28th October, 2011. Dedicated to my grandmother CVIVSVIS HOMINIS EST ERRARE NVLLIVS NISI INSIPIENTIS IN ERRORE PERSEVERARE The Twelfth Philippic, M. Tullius Cicero A Systematic Approach to Understanding Organic Reactivity in Ionic Liquids: Changes in Cybotacticity-Induced Solvent Heterogeneity as an Important Determinant In Reaction Outcomes of Substitution Processes Contents Acknowledgements i Publications and Colloquia v Abstract vii Abbreviations 1 List of Compounds 3 Introduction 7 Results and Discussion, Chapter 1 24 A Nucleophilic Aromatic Substitution Process in an Ionic Liquid Results and Discussion, Chapter 2 34 Menschutkin Reactions as Model Bimolecular Nucleophilic Substitution Reactions in an Ionic Liquid Results and Discussion, Chapter 3 46 Menschutkin Reactions Revisited: Cybotacticity about Nitrogen Nucleophiles as an Important Determinant in Reaction Outcomes Results and Discussion, Chapter 4 61 Towards Solvent-Controlled Reactivity in Ionic Liquids Results and Discussion, Chapter 5 67 The Importance of Electrostatic Interactions in Determining Reaction Outcomes in Ionic Liquids Results and Discussion, Chapter 6 76 A General “One-Pot” Method for Relative Rates Analysis Conclusions 94 Experimental 97 References 167
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