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Conversion of Alcohols Into Amines by Borrowing Hydrogen

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Conversion of Alcohols Into Amines by Borrowing Hydrogen University of Bath PHD Conversion of Alcohols into Amines by Borrowing Hydrogen Hamid, Malai Award date: 2008 Awarding institution: University of Bath Link to publication Alternative formats If you require this document in an alternative format, please contact: [email protected] 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 ? Take down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Download date: 03. Oct. 2021 Conversion of Alcohols into Amines by Borrowing Hydrogen Malai Haniti Sheikh Abdul Hamid A thesis submitted for the degree of Doctor of Philosophy Department of Chemistry University of Bath November 2008 COPYRIGHT Attention is drawn to the fact that copyright of this thesis rests with its author. This copy of the thesis has been supplied on condition that anyone who consults it is understood to recognise that its copyright rests with its author and that no quotation from the thesis and no information derived from it may be published without the prior written consent of the author. This thesis may be made available for consultation within the University Library and may be photocopied or lent to other libraries for the purposes of consultation. Signed ............................................. Date ............................................. CONTENTS CHAPTER 1.......................................................................................................................1 1. INTRODUCTION......................................................................................................1 1.1 AMINES ..............................................................................................................1 1.2 SYNTHESIS OF AMINES ............................................................................................3 1.2.1 Synthesis of Secondary Amines .......................................................................6 1.2.2 Synthesis of Tertiary Amines...........................................................................8 1.3 TRANSITION METAL-CATALYSED TRANSFER HYDROGENATION ...........................12 1.4 N-ALKYLATION OF AMINES WITH ALCOHOLS .......................................................22 1.5 REFERENCES..........................................................................................................36 CHAPTER 2.....................................................................................................................42 2. RESULTS AND DISCUSSION I............................................................................42 2.1 BACKGROUND..................................................................................................42 2.2 RESEARCH GOALS............................................................................................46 2.3 IRIDIUM-CATALYSED N-ALKYLATION OF AMINES WITH PHENETHYL ALCOHOL BY BORROWING HYDROGEN .....................................................................................47 2.4 RUTHENIUM-CATALYSED N-ALKYLATION OF PRIMARY AMINES WITH PRIMARY ALCOHOLS BY BORROWING HYDROGEN ..............................................................50 2.4.1 N-Alkylation of Primary Alkyl and Aromatic Amines with Benzyl Alcohol and Phenethyl Alcohol ................................................................................61 2.4.2 N-Alkylation of Aniline with Primary Alcohols ..........................................64 2.5 CHAPTER SUMMARY ........................................................................................70 2.6 REFERENCES ....................................................................................................71 CHAPTER 3.....................................................................................................................73 3. RESULTS AND DISCUSSION II ..........................................................................73 3.1 AIM ..................................................................................................................73 3.2 BACKGROUND..................................................................................................73 3.3 INITIAL STUDIES...............................................................................................75 3.4 RUTHENIUM-CATALYSED N-ALKYLATION OF PRIMARY ALCOHOLS WITH SECONDARY AMINES BY BORROWING HYDROGEN ..............................................84 3.5 RUTHENIUM-CATALYSED SYNTHESIS OF DIMETHYLAMINES BY BORROWING HYDROGEN ..............................................................................................................87 3.5.1 Initial Studies ..............................................................................................87 3.5.2 Ruthenium-Catalysed Synthesis of N,N-Dimethylamines from Alcohols by Borrowing Hydrogen ..................................................................................95 3.6 CHAPTER SUMMARY ......................................................................................100 3.7 REFERENCES ..................................................................................................101 CHAPTER 4...................................................................................................................103 4. APPLICATION...................................................................................................103 4.1 INTRODUCTION...............................................................................................103 4.2 THE ROLE OF THE RECEPTOR .........................................................................104 4.3 AGONISTS ......................................................................................................105 4.3.1 Synthesis of Piribedil ................................................................................107 4.3.2 Ruthenium-Catalysed Synthesis of Piribedil by Borrowing Hydrogen.....109 4.4 ANTIHISTAMINES OF H1 RECEPTOR ANTAGONISTS ........................................111 4.4.1 Synthesis of Antergan and Tripelennamine ..............................................114 4.4.2 Synthesis of Corresponding Alcohols of Antergan and Tripelennamine by Conventional Methods and Borrowing Hydrogen Methodology..............115 4.4.3 Ruthenium-Catalysed Synthesis of Antergan and Tripelennamine by Borrowing Hydrogen ................................................................................117 4.5 CHAPTER SUMMARY ......................................................................................120 4.6 CONCLUSION AND FUTURE DIRECTIONS ........................................................120 4.8 REFERENCES ..................................................................................................123 CHAPTER 5...................................................................................................................126 5. EXPERIMENTAL .................................................................................................126 5.1 GENERAL EXPERIMENTAL METHODS.............................................................126 5.2 EXPERIMENTAL PROCEDURES FOR CHAPTER 2...............................................127 5.3 EXPERIMENTAL PROCEDURES FOR CHAPTER 3...............................................147 5.4 EXPERIMENTAL PROCEDURES FOR CHAPTER 4...............................................169 5.5 REFERENCES ..................................................................................................175 APPENDICES ........................................................................................................... 176 Acknowledgements ACKNOWLEDGMENTS My heartiest thank you goes out to Professor Jonathan Williams for his constant support and excellent supervision over the last three years. Thank you for the excitement we shared when things went well and comforting me when things didn’t. You’ve been such an inspiration to me! I would also like to thank all the members of the Williams group as well as the Bull group especially Slatto, Sonia, Gareth A., Nathan, Simon, Tracy, Hannah, Nik, Gareth L., Iwan, Mike, Andy, Paul, Liana, Ory and James for the fun times we’ve had in the lab. I shall miss working in the Williams lab so much. Thank you Anneke, Sheila, Mary, Hilary and all staff at the University of Bath for making my time in Bath run smoothly. A special thank you to John Lowe for answering all my NMR questions. I am very grateful to His Majesty’s Government of Brunei Darussalam and Universiti Brunei Darussalam for giving me this opportunity to pursue my research at the University of Bath. A big thank you to my family especially my parents and two daughters Hana and Zahra for their love, support and understanding in everything that I do. Thank you to my sister Zeiti for spoiling me all the time and finally to my husband, Sufri I love you and thank you for everything. And I dedicate this to my late father-in-law, Pg Ali Pg Hj Osman. i Synopsis SYNOPSIS This thesis describes
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