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  • Title
  • CERTIFICATE
  • DECLARATION
  • ACKNOWLEDGEMENT
  • DEDICATIONs
  • CONTENTS
  • ABBREVIATIONS
  • 1 Introduction and Objetives
  • Objectives of the Work
  • Organisation of the Thesis
  • 2 Polymer Bound Reagents - A Review
  • 2.1 Introduction
  • 2.2 Nature of Polymer Support
  • 2.2.1 Physical form of the polymer
  • 2.2.1a Linear polymers
  • 2.2.1b Crosslinked polymer
  • i) Microporous or gel type resins
  • ii) Macroporous and Macroreticular resins
  • iii) Popcorn polymers
  • iv) Macrunet polymers
  • 2.3 Methods of Functionalisation of Polymer
  • 2.3.1 Copolymerisation of functional monomer
  • 2.3.2 Chemical modification of preformed polymer
  • 2.4 Effect of Solvent
  • 2.5 Molecular Character and Extent of Cross linking
  • 2.6 Diffusional and Molecular Sieving Effects
  • 2.7 Steric Effects and Spacer Effects
  • 2.8 Microenvironmental Effects
  • 2.9 Site-Site Interactions and Site Isolation
  • 2.10 Neighbouring Group Effect
  • 2.11 Characterisation of Functionalised Polymers
  • 2.12 Polymer Supported Reducing Agents
  • 2.12.1 Polyvinylpyridine-borane reagent
  • 2.12.2 Polymer bound borohydride
  • 2.12.3 Polymer supported tin hydrides
  • 2.12.4 Polypropylene sulfide-borane and haloborane reagents
  • 2.12.5 Polymer supported amino alcohol-borane
  • 2.13 Conclusion
  • 3 Preparation of Ethylenediamene-borane Reagent on Cross linked Polystyrene Resins
  • 3.1 Preparation of Cross linked Polystyrene Resins
  • 3.2 Characterisation of HDODA-PS and BDDMA-PS resins
  • 3.3 Chloromethylation of Cross linked Polystyrene Resins
  • 3.4 Preparation of Ethylenediaminomethyl Resins (lc, 2c1, -2c6and 3c)
  • 3.5 Conversion of Aminated Resins to Amine Hydrochloride Resins
  • 3.6 Preparation of Polymer Bound EDA-borane
  • 3.7 Characterisation of Polymer Bound EDA-borane
  • 3.8 Swelling Studies
  • 4 Reduction Stud Using the Polymer Bound EDA-borane Reagent
  • 4.1 Reduction Studies
  • 4.1.a Reduction of aldehydes
  • 4.1.b Reduction of ketones
  • 4.2 Mechanism of Reduction Using polymer Bound EDA-borane
  • 4.3 Chemoselectivity of the Polymer Bound EDA-borane Reagent
  • 4.4 Effect of Nature of Cross linking Agent on the Reduction Reaction
  • 4.5 Extent of Conversion with Time
  • 4.6 Effect of Degree of Cross linking on the Reactivity of the Polymer Bound EDA-borane Reagent
  • 4.7 Effect of Solvent on the Reactivity of Polymer Bound EDA-Borane
  • 4.8 Effect of Temperature
  • 4.9 Effect of Catalyst
  • 4.10 Effect of Concentration of Polymeric Reagent
  • 4.11 Regeneration and Recyclability of the Polymer Supported EDA-borane Reagent
  • 4.12 Effect of Mononofunctional Amines on the Reactivity of the Polymer Bound Amine-boran
  • 4.12.1 Preparation of aminomethyl polystyrene (2c)
  • 4.12.2 Preparation of ethylaminomethyl polystyrene
  • 4.12.3 Preparation of diethylaminomethyl polystyrene
  • 4.12.4 Preparation of Polymer bound 10: 20 and 30 amine-boranes from 2c, 2c and 2c
  • 4.12.5 Reduction of aldehydes using 2e, 2en and Ze
  • 5 Preparation of Polyacrylamide Supported Amine-borane Reagent and Investigation of its Reducing Properties
  • 5.1 Introduction
  • 5.2 Preparation of 5-mole Percentage NNMBA Cross linked Polyacrylamide.
  • 5.3 Preparation of 5% HDODA. Cross linked Polyacrylamide
  • 5.4 Amino Functionalisation of Polyacrylamide Resins
  • 5.5 Preparation of Polyacrylamids Bound Amine-borane Reagent
  • 5.6 Swelling Studies
  • 5.7 Reduction of Aldehyde with the Polyacrylamide Supported Amine-Borane Reagent
  • 6 Experimental
  • 6.1 Materials
  • 6.2 Instrumental
  • 6.3 Preparation of Cross linked Polystyrene Resins
  • 6.3.1 Preparation of 2% DVB crosslinked polystyrene (la)
  • 6.3.2 Preparation of HDODA crosslinked polystyrene resins
  • 6.3.3 Preparation of 2% BDDMA crosslinked polystyrene (3a)
  • 6.4 Funtionalisation of the Cross linked Polymers (DVB-PS, BDDMA-PS, HDODA-PS)
  • 6.4.3 Chloromethylation of crosslinked polystyrene resins: Preparation ofresins (lb, 2bl-2b6 and 3b)
  • 6.5 Estimation of Chlorine Capacity
  • 6.6 Conversion of Chloromethyl Resins to Ethylenediaminomethyl Resins (1c, 2c1-2c6 and 3c)
  • 6.7 Estimation of Amino Group Capacity: Gisins Method
  • 6.8 Conversion of Ethylenediaminomethyl Resins to the Corresponding Amine Hydrochloride Resins (lad, 2d, -2d6 and 3d)
  • 6.9 Preparation of Polymer Supported EDA-borane Reagents (1 e, 2e, -2e6 and 3e)
  • 6.10 Determination of the Borane Reagent Function Available for Reduction
  • 6.11 Reduction of Aldehydes with the Polymer Supported EDA-Borane Reagent
  • 6.12 Selective Reduction of Benzaldehyde in the Presence of Acetophenone
  • 6.13 Quantitative Study of Reduction
  • 6.14 Extent of Reduction of 2-nitrobenzaldehyde with Polymer Bound EDA-borane Reagents (l e and 2e1)
  • 6.15 Effect of Various Parameters en the Reactivity of the Polymer Bound EDA-borane
  • 6.15.1 Effect of degree of crosslinking
  • 6.15.2 Effect of solvent
  • 6.15.3 Effect of temperature
  • 6.15.4 Effect of acid catalyst on the reactivity of polymer bound EDA- borane
  • 6.15.5 Effect of concentration of polymeric reagent
  • 6.16 Regeneration and Recycling of the Resin
  • 6.17 Preparation of Polymer Bound Monofunctional Amines
  • 6.17.1 Preparation of aminomethyl polystyrene
  • 6.17.2 Preparation of polymer-bound ethylamine
  • 6.17.3 Preparation of diethylaminomethyl polystyrene resin
  • 6.18 Preparation of Polymer Bound Amine-borane Reagents Using Monofunctional Amines
  • 6.18.1 Preparation of Polymer bound methylamine-borane (lo amine-boranereagent (2e) from aminomethyl polystyrene)
  • 6.18.2 Preparation of polymer bound secondary amine-borane (2e) fromethylaminomethyl resin
  • 6.18.3 Preparation of polymer bound diethylamine-borane (2e)
  • 6.19 Reduction of Aldehydes Using. Polymer Bound Amine-borane Reagents (2e, 2e, 2e)
  • 6.20 Swelling Studies
  • 6.21 Preparation of Amine-borane Reagents on Cross linked Polyacrylamide Resins
  • 6.21.1 Preparation of 5% NNMBA crosslinked polyacrylamide
  • 6.21.2 Preparation of 5% HDODA crosslinked polyacrylamide
  • 6.21.3 Incorporation of amino groups on crosslinked polyacrylamide resinby transamidation
  • 6.21.4 Estimation of amino capacity
  • 6.21.5 Conversion of the amino functionalised resins to the correspondingamine-hydrochloride
  • 6.21.6 Preparation of amine-borane reagent on polyacrylamide resins
  • 6.22 Reduction of Aldehydes
  • 6.22.1 Reduction of aldehyde at high temperature
  • 6.22.2 Reduction in the presence of acid catalyst
  • 7 Summary and Outlook
  • References