Low Toxicity Imidazolium & Pyridinium Ionic Liquids ... Low Toxicity Imidazolium & Pyridinium Ionic

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  • Low Toxicity Imidazolium &

    Pyridinium Ionic Liquids:

    Synthesis, Antimicrobial Toxicity,

    Biodegradation Studies and

    Applications in Tsuji-Trost Reactions

    By Mukund Ghavre M.Sc.

    Under the supervision of Dr. Nick Gathergood

    School of Chemical Sciences

    Dublin City University

    For the award of PhD

    September 2012

  • i

    Dedicated to Mother…

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    Declaration

    I hereby certify that this material, which I now submit for assessment on the programme of

    study leading to the award of PhD is entirely my own work, and that I have exercised

    reasonable care to ensure that the work is original, and does not to the best of my knowledge

    breach any law of copyright, and has not been taken from the work of others save and to the

    extent that such work has been cited and acknowledged within the text of my work.

    Signed: ____________ (Candidate) ID No.: 58112723 Date: _______

    Name: Mr. Mukund D. Ghavre

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    Abstract

    A series of seventy achiral and chiral ionic liquids was designed, synthesized and

    characterized. Out of these seventy ILs, fifteen are achiral, twenty one lactic acid based and

    rest are mandelic acid based ILs. All compounds were characterized by a number of

    techniques including: 1 H,

    13 C,

    19 F NMR, IR, MS and specific rotation.

    Antimicrobial and antifungal toxicity studies were carried out using the representative

    examples chosen from these ILs. Lactic and mandelic acid based ILs and ester based achiral

    ILs were found to be non toxic towards eight strains of bacteria and twelve strains of fungi.

    Antifungal toxicity was performed on two monoester and two diester CILs. Twenty one ILs

    were screened for biodegradation studies out of which the ILs with diester functionality were

    found to be readily biodegradable.

    Six achiral ester and amide based ILs were chosen to employ in Tsuji-Trost reactions as

    reaction media. Reactions were performed using two methods consisting use of two different

    bases. Chiral catalysts (S,S)-iPr-phosferrox, mandyphos and R-BINAP were used for chiral

    induction. Excellent enantioselectivities with moderate yields were obtained in these

    reactions.

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    Acknowledgements

    First and foremost I would like to thank my supervisor Dr. Nick Gathergood for giving me the

    opportunity to work in his group and for his support and guidance throughout my PhD.

    I’d like to thank all the technical staff for their help, especially Damien, John, Ambrose,

    Vincent, Brendan, Catherine, Veronica and Julie (learned a lot from you guys).

    I would like to thank Dr. Marcel Spulak for antimicrobial screening (Charles University,

    Czech Republic), Dr. Teresa Garcia for biodegradation studies (CSIC, Spain), Sonia Ventura

    for antialgal screening (Aveiro, Portugal), Dr. Florence McCarthy for HRMS analysis (UCC,

    Cork) and Dr. Brid Quilty for her help in antibacterial screening (DCU).

    Also I would like to thank my friends I’ve made over the past four years, especially, Ian

    (thank you so much for organic synthesis problem sessions), Monika, Rohit, Jaywant,

    Harshad, Shelly, Thomas, Alan & Adam (thank you so much for the help during my thesis

    writing), Thu, Debbie, Dan, Andy and Will. I am also very thankful to Martin, Ewa, Wioleta,

    Mads and Pavel for their hard-work in LC-MS analysis and antibacterial screening. I’m

    grateful for the support from the other friends particularly Rahul, Jitu, Yogesh, Tushar and

    Sanjay.

    Lastly, I am very grateful to my brother Anand for looking after mother so I could pursue my

    PhD.

  • v

    Publications List

    � N. Gathergood, S. Morrissey, B. Pegot, I. Beadham, M. Gurbisz, M. Ghavre, ‘Ionic Liquid

    Solvents’, Eur. Pat. Appl. (2010), EP 2223915 A120100901.

    � N. Gathergood, B. Pegot, I. Beadham, M. Gurbisz, M. Ghavre, S. Morrissey, ‘Ionic Liquid

    Solvents’, PCT Int. Appl. (2010), WO 2010097412 A1 20100902.

    � Ed. A. Kokorin, ‘Ionic Liquids: Applications and Perspectives’, Intech, M. Ghavre, S.

    Morrissey, N. Gathergood, ‘Hydrogenation in Ionic Liquids’, 2011, chapter 15, 331-392.

    � Ed. H. Xie and N. Gathergood, ‘The Role of Green Chemistry in Biomass Processing and

    Conversion’, Wiley. Weilheim. J. Xu, W. Yu, H. Ma, F. Wang, F. Lu, M. Ghavre, N.

    Gathergood, ‘Catalytic Conversion of Glycerol’, 2012, Chapter 12, in press.

    � S. Ventura, M. Gurbisz, M. Ghavre, F. Ferreira, F. Gonçalves, I. Beadham, B. Quilty, J.

    Coutinho, N. Gathergood, ‘Imidazolium and Pyridinium Ionic Liquids from Mandelic Acid

    Derivatives: Synthesis and a Bacteria, Fungi and Algae Toxicity Evaluation’, 2012,

    submitted.

    � N. Ferlin, M. Courty, S. Gatard, M. Spulak, B. Quilty, I. Beadham, M. Ghavre, N.

    Gathergood, S. Bouquillon, ‘Biomass derived ionic liquids: synthesis, characterization,

    ecotoxicity and use as solvents for catalytic hydrogenation processes’, 2012, Submitted to

    ChemSusChem.

    � N. Ferlin, M. Courty, A. Hien, M. Spulak, B. Quilty, M. Ghavre, A. Haib, K. Kümmerer,

    N. Gathergood, S. Bouquillon, ‘Proline-based ionic liquids as chiral agents in Pd-

    catalyzed enantioselective hydrogenation of α,β-unsaturated ketones’, in preparation.

    � M. Ghavre, I. Beadham, N. Gathergood, ‘Enantioselective Tsuji-Trost reactions in low

    toxicity and readily biodegradable ionic liquids’, in preparation.

  • vi

    Contents

    Project Aim ........................................................................................................................... 1

    List of Abbreviations ............................................................................................................. 2

    Chapter 1 Introduction to Ionic Liquids ................................................................................. 6

    1.1 Need of Green Chemistry ............................................................................................ 7

    1.2 Development of Green solvents ................................................................................. 10

    1.3 What is an Ionic Liquid ? ........................................................................................... 13

    1.4 Brief History of Ionic Liquids .................................................................................... 14

    1.5 Synthesis of Ionic Liquids ......................................................................................... 16

    1.6 Purification of ILs ..................................................................................................... 19

    1.7 Physicochemical and Biological Properties of ILs...................................................... 20

    1.8 Applications of ionic liquids in organic synthesis ...................................................... 32

    1.9 Introduction to the work in thesis ............................................................................... 50

    1.10 References ............................................................................................................... 51

    Chapter 2 Synthesis and Characterisation of Ionic Liquids .................................................. 61

    2.1 Introduction ............................................................................................................... 62

    2.2 Synthesis of Achiral ester and amide based ionic liquids ............................................ 62

    2.3 Synthesis of Chiral Lactate and Mandelate based ionic liquids ................................... 71

    2.4 Miscellaneous ............................................................................................................ 91

    2.5 Summary ................................................................................................................... 95

    2.6 Conclusion ................................................................................................................ 96

    2.7 References ................................................................................................................. 97

    Chapter 3 Toxicity and Biodegradation ............................................................................... 99

    3.1 Introduction ............................................................................................................. 100

    3.2 Aqueous stability ..................................................................................................... 100

    3.3 Toxicity ................................................................................................................... 107

    3.4 Antibacterial toxicity of synthesized compounds ..................................................... 113

    3.5 Antifungal toxicity of synthesized compounds ......................................................... 118

  • vii

    3.6 Antibacterial toxicity studies at higher concentration ............................................... 122

    3.7 Antialgal Toxicity Studies ....................................

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