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TITLE
DEDICATON
CERTIFICATE
DECLARATION
ACKNOWLEDGEMENT
CONTENTS
I. INTRODUCTION.
I.1. Polymer-supported Peracids
I.2. Polymer-supported Periodate
I.3. Polymer-supported Sulphur Reagents
I.4. Polymer-supported Chromium (VI) Compounds
I.5. Polymer-supported Halogen Compounds
I.6. Supported Permanganate Reagents
I.7. Miscellaneous Polymeric Oxidising Agents
II. OBJECTIVES OF THE PRESENT WORK.
III. PREPARATION AND ANALYSIS OF THE POLYMER-SUPPORTED OXIDISING AND BROMINATING REAGENTS
III. 1. Poly[4-vinyl (pyridinium permanganate) ] as a new Recyclable Solid-phase Oxidising Agent
III. 1. i. Preparation of Crosslinked Poly (4-vinyl-pyridine) Supports
III. 1. ii. Functionalization of Poly (4-vinylpyridine) with Permanganate
III. 2. Incorporation of Permanganate Function into Poly[4-vinyl (pyridine-co-styrene) ] Matrix (Styrene content 10%)
III.3.i Oxidising and Brominating Functions on Polymer-supported 8-HydroxyQuinoline and 2-Hydroxypyridine
III. 3.ii.Functionalization of Polystyrene-supported Quinoline Resin (2) and Pyridine resin (3) with Permanganate, Chlorochromate and Bromine Functions
III. 3.iii. Analysis and Characterisation of the Permanganate-functionalized Resins
III. 3.iv. Analysis and Characterisation of the Chlorochromate Function
III. 3.v. Analysis and Characterisation of the Bromoresin
III. 4.i. Polymer-supported Arsonium Permanganate
III. 4.ii. Preparation of the Crosslinked Polymer supported Arsonium Chloride (10)
III.4.iii. Analysis and Characterisation of Polymer-supported Arsoniun Permanganate Resins
III.4.iv. Functionalization of Polymer-supported Arsonium chloride resin (10) with Dichromate, Chromate, Triiodide and Chlorochromate Functions
III. 4. v. Analysis and Characterisation of the Dichromate, Chromate, Triiodide and Chlorochromate Functions.
III.5. Introduction of Oxidising and Brominating Functions in Differently Crosslinked Polyacrylamides: Correlation of Reactivity with Structure
III. 5.i. Synthesis of Crosslinked Polyacrylamide Resins
III.5.ii. Trans-amidation of Polyacrylamides Preparation: of Poly[N- (2-aminoethyl) - acrylamide]s
III.5 iii. Functionalization of the Polyacrylamide Resin with Permanganate Function
III.5.iv. Analysis and Characterisation of the Permanganate-functionalized Resins (16) and (18)
IV. REACTIONS WITH THE POLYMER-SUPPORTED REAGENTS
IV.1.Oxidation Reactions
IV. 1.i. Oxidation Reactions using Poly[4- vinyl (pyridinium permanganate) ] Resin
IV. 1.ii.Comparisons with other Polymer-supported Oxidising Agents
IV. 1.iii. Effect of Solvent
IV. 1.iv. Monitoring the Course of the Reaction
IV. 2.i. Oxidation Reactions of Polymer-supported B-Hydroxyquinoline Resin
IV. 2.ii.Oxidation Reactions of Polymer-supported Permanganate Derived from 2-Hydroxy- pyridine Resin (5)
IV. 2.iii. Oxidation Reactions of Polymer-supported Chlorochromate Resins (7) and (9)
IV. 3. i. Oxidation Reactions of Polymer-supported Arsonium Permanganate
IV. 3.ii. Oxidation Reactions of Polystyrene- supported Arsonium Dichromate
IV.3.iii. Oxidation Reactions of Permanganate Functions Attached to the Polyacry-- lamide Resins
IV. 3.iv. Effect of Solvents on the Oxidation Reaction
IV. 4. Halogenation Reactions
IV. 5.Regeneration and Recycling of the Spent Resin
V. EFFECT OF POLYMER STRUCTURE AND REACTION CONDITIONS ONREACTIVITY
V. 1. i.Effect of Crosslink Density
V. 1.ii.Functionalization of the resin
V.1. iii. Effect of Crosslink Density on Oxidation Reactions
V. 1.iv.Effect of Polymer-matrix on Oxidation Reactions
V. 1. v.Effect of Solvent on the Oxidation Reactions
VI. EXPERIMENTAL.
VI.1.General
VI.1. ii. Preparation of theCrosslinked. Poly (4- vinylpyridine) Resin (PVP)
VI.1.iii. Preparation of Poly[4-vinyl (pyridine -co- styrene] (styrene content 10%) (PVPS)
VI.1. v. Incorporation of Permanganate Function into Poly[4-vinyl (pyridine-co-styrene)
VI.1.vi. Estimation of Permanganate in the Functionalized Resins: General Procedure
VI.1.vii. Preparation of Polystyrene-supported 8-Hydroxyquinoline Resin
VI.1. viii. Estimation of Residual Chlorine in Polystyrene-supported 8-hydroxyquinoline Resin (2)
VI.1. ix. Functionalization of the Polystyrene- supported 8-Hydroxyquinoline Resin with Permanganate
VI. 1. X.Estimation of Permanganate in the Functionalized Resin (4)
VI. 2. i. Preparation of Polystyrene-supported 2-Hydroxypyridine Resin (3)
VI. 2. ii. Estimation of Residual Chlorine in Polystyrene-supported 2-Hydroxypyridine Resin (3)
VI. 2. iii. Functionalization of the Polystyrene- supported 2-Hydroxypyridine Resin with Permanganate
VI. 2. iv. Estimation of the Permanganate in the Functionalized Resin (5)
VI. 2. v.Functionalization of the Polystyrene- supported 8-Hydpxyquinoline Resin (2) and 2-Hydroxypyridine Resin (3) with Bromine
VI.2.vi. Estimation of Bromine Capacity of the Polymer-supported 8-Hydroxyquinoline Bromoresin (6) and 2-Hydroxypyridine Bromoresin (8)
VI. 2. vii. Functionalization of the Polystyrene supported 8-Hydoxyquinoline Resin (2) and 2-Hydroxypyridine Resin (3) with Cr03/HCl
VI.2. viii. Estimation of Chlorochromate Capacity of the Functionalized Resins
VI. 3. i. Preparation of Polymer-supported Arsonium Chloride
VI. 3. ii. Estimation of the Chloride ion Capacity of the Polymer-supported Arsonium Chloride Resin
VI. 3. iii. Preparation of the Polymer-supported Arsonium Permanganate
VI. 3. iv. Estimation of Permanganate Function- in the Polymer-supported Arsonium Permanganate Resin
VI. 4. Preparation of Crosslinked Polyacrylamides
VI. 4.i. Preparation of Poly (acrylamide-co-N, N- methylene-bis-acrylamide)
Vi. 4.ii. Preparation of Poly (acrylamide-co- divinylbenzene)
VI. 4.iii. Trans-amidation of Polyacrylamides to Poly[N- (2-aminoethyl) acrylamide]s
VI. 4.iv. Determination of the Capacity of the Amino Resins: General Procedure
VI. 4. v. Quaternisation of the Aminated Polyacrylamide Resins with HCI
VI. 4. vi. Quaternisation of the Ammoniated Polyacrylamide Resin with Methyl Iodide
VI. 4. vii. Estimation of the Halide ion in Quaternised Polyacrylamide Resin
VI. 4.viii. Functionalization of the Halide Resin
VI. 4.ix. Estimation of Permanganate in the Functionalized Resin
VI. 5. Oxidation of Alcohols General Procedures
VI. 5.i. Oxidation of Alcohols with Permanganate Containing Resins
VI. 5.ii. Measurement of the Reaction Course
VI. 5.iii. Oxidation of Alcohols with Polymer supported Arsonium Permanganate
VI. 5.iv. Oxidation Reactions of Alcohols Using Resins Functionalized with Chlorochromate, Chromate and Dichromate Function
VI.5.v. Bromination Reaction
VI.5.vi. Recycling and Reuse of the Spent Resins
VII. SUMMARY AND OUTLOOK
VIII. REFERENCES