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Full Screen- TITLE
- DEDICATION
- CERTIFICATE
- DECLARATION
- ACKNOWLEDGEMENT
- ABBREVIATIONS
- COTNENTS
- 1. INTRODUCTION AND OBJECTIVES
- 1.1 Introduction
- 1.2 Objectives of the Work
- 1.3 Organisation of the Thesis
- 2. POLAR SUPPORTED REACTIONS - AN OVERVIEW
- 2.1 Introduction
- 2.2 Characteristics of Functionalised Polymers
- 2.2.1 Physical Properties
- 2.2.1A Linear Polymers
- 2.2.1 B Cross linked Polymers
- a) Microporous or gel type resins
- b) Macroporous resins and macroreticular resins
- c) Popcorn polymers
- d) Macronet polymers
- e) Composite resins
- 2.2.2 Reactivity of Functionalised Polymers
- a) Molecular character and extent of crosslinking of the polymer matrix
- b) Microenvironmental effects
- c) Solvation and swelling
- d) Spacer effect
- 2.3 Characterisation of Functionalised Polymers
- 2.4 Applications of Functionalised Polymers
- 2.4.1 Organic Synthesis
- 2.4.2 Enzyme Immobilization
- 2.4.3 Mechanistic Studies Using Solid Supports
- a) The Three Phase Test
- b) Cyclobutadiene intermediates
- c) Benzyne intermediate trapping
- d) Fries rearrangement
- e) Hoffmann rearrangement
- f) Benzil-benzilic acid rearrangement
- 2.4.4 Polymer Supported Halogen Containing Reagents
- a) Polymeric halogen compounds as oxidising agents
- b) As halogenating agents
- 3. PREPARATION AND BECKMANN REARRANGEMENT REACTION OF POLYMER SUPPORTED KETOXIMES
- 3.1 Syntnesis of DVB and HDODA Cross linked Polystyrene Supports
- 3.1 1 Divinylbenzene (DVB) - Crosslinked Polystyrene
- 3.1.2 Hexanediol Diacrylate (HDODA) -Cross linked Polystyrene
- 3.2 Characterisation of the HDODA Crosslinked Polystyrene
- 3.3 Preparation of DVB Crosslinked and HDODA Crosslinked Polystyrene bound Ketoximes
- 3.4 Beckmann Rearrangement of the Polystyrene Bound Oximes
- 3.5 Swelling Studies
- 3.6 Influence of Different Structural Parameters on the Beckmann Rearrangement Rate
- 3 6 1 Effect of the Nature of Cross linking
- 3.6.2 Effect of the Degree of Cross linking
- 3.6.3 Effect of Solvent
- 3.6.4 Effect of Temperature
- 3.6.5 Effect of Methylene Spacers
- 3.66 Effect of Nonmigrating Group
- 4. POLYMER-BOUND N-BROMOANILIDE- A POLYMERIC RECYCLABLE OXIDISING AND BROMINATING REAGENT
- 4.1 Introduction
- 4.2 Preparation of Polymer Bound N-bromoamides
- 4.3 Characterisation of Polymer Bound N-bromoamides
- 4.4 Swelling Studies
- 4.5 Oxidation and Bromination Reactions Using the Polymeric N-bromoamide Reagents
- 4 5 1 Oxidation of Alcohols
- 4.5.2 Effect of Reaction Conditions on the Course of Oxidation Reactions Using Polymeric N-bromoamide
- 4.5.2a Effect of Temperature
- 4 5 2b Presence of Catalyst
- 4.5.2c Effect of Solvent
- 4.4.2d Effect of Concentration of Polymeric Reagents
- 4.5.2e Effect of the Spacer Group
- 4.5.3 Bromination Reactions Using Polymeric N-bromoamide
- 4.5.4 Bromination of Toluene Under Radical Conditions
- 4.5. 5 α-Bromination of Ketones
- 4.6 Regeneration and Recyclability of the Polymer Supported N-bromoamides
- 5. EXPERIMENTAL
- 5.1 Source of Chemicals
- 5.2 Physical Measurements
- 5.3 Synthesis of Styrene-divinylbenzene Copolymer General Procedure
- 5.4 Synthesis of Styrene-Hexanediol Diacrylate Copolymer
- 5.5 Preparation of Polymer Supported Ketones: Friedel-Crafts Reaction of Polystyrene with Acid Chlorides or Acid Anhydrides
- 5.5A Preparation of DVB Crosslinked and HDODA Crosslinked Polystyrene Supported Acetophenone and Benzophenones
- 5.5B Preparation of Polymeric Ketones with Methylene Spacers between the Polymer Backbone and the Keto Functional Group
- 5.6 Conversion of the Polymeric Ketones to Polymeric Oximes General Procedure
- 5.7 Estimation of the N-hydroxyl Capacity of Polymeric Oximes; General Procedure
- 5.8 Beckmann Rearrangement of the Polymeric Ketoximes
- 5.9 Analysis of Rearranged Amide Products
- 5.10 Determination of Amino Group Capacity of the Amino Polystyrene Resin-General Procedure
- 5.11 Swelling Studies
- 5 12 Effect of Various Parameters on the Beckmann Rearrangement of Polymer Bound Ketoximes
- 5.12.1 Effect of Nature of Cross linking
- 5.12.2 Effect of Degree of Cross linking
- 5.12.3 Effect of Solvent
- 5.12.4 Effect of Temperature
- 5 12.5 Effect of Methylene Spacers
- 5.12.6 Effect of Nonmigrating Group
- 5.13 Preparation of Polymeric N-bromoamide Reagent
- 5.14 Determination of the Bromine Capacities of the Polymer-bound N-bromoamides by lodometric Titration
- 5.15 Oxidation of Alcohols-General Procedure
- 5.16 Investigation of the Effect of the Reaction Conditions on Oxidation Reactions
- 5.16.1 Effect of Temperature
- 5.16.2 Effect of Acid Catalyst
- 5.16.3 Effect of Solvent
- 5.16.4 Effect of Concentration of the Polymeric Reagent
- 5.16.5 Effect of Methylene Spacers
- 5.17 Bromination Reactions Using Polymer-bound N-bromoanilide General Procedure
- 5.18 α-Bromination of Ketones
- 5.19 Recycling of the Spent Polymeric Reagent
- 6. SUMMARY AND OUTLOOK
- REFERENCES