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TITLE
DEDICATION
CERTIFICATE
DECLARATION
ACKNOWLEDGEMENT
ABBREVIATIONS
CONTENTS
1. INTRODUCTION
Organisation of the thesis
2. POLYMER-SPPORTED REAGENTS: AN OVERVIEW
2.1. Introduction
2.2. Advantages and limitations of reactive polymers
2.3. Design of polymer-supporled reagents
2.4. Characterisation of functional polymers
2.4.1 Chemical analysis
2.4.2 Instrumental analysis
2.5. Factors affecting the reactivity of polymer-supported reagents
2.5.1 Nature and type of the polymer support
Fig.2.1. Schematic representation of linear and crosslinked polymers
Table 2.1. Effed of plymer matrix on the oxidation reaction
2.5.2 Swelling nature of functional polymers
Table 2.2. Effect of crosslinking density on the oxidation of cyclohexanol catalysed by crosslinked PVP-iodine complex
2.5.3 Effect of spacer handles
2.5.4 Nature and degree of crosslinking
Fig.2.2. Schematic representation of polymer-matrix with: (a) rigid and (b) flexible crosslinking agents
Table 2.3. Nature of crosslinking on bromination reactions catalysed by bromine complexes of crosslinked PVP
2.5.5 Microenvironmental effects
2.5.6 Diffusional and molecular sieving effects
2.6. Polymer bound oxidising reagents
2.6.1 Redox polymers
Fig. 2.3. Structure of polymer-supported flavin reagent
2.6.2 Polymer-supported peracids
2.6.3 polymer-supported periodate
2.6.4 Polymer-supported sulphur reagents
2.6.5 Halogen containing reagents
Table 2.4. Elecbolytic side-chain oxidation of alkylbenzenes using polymeric electron carrier
2.6.6 Polymer-supported chromium (VI) compounds
2.6.7 Supported permanganate reagents
Fig.2.4. KMnO, complexed dicyclohexyl 18-crown-6
Table 2.5. Oxidation reactions using KMnO4 complexed crownether
2.6.8 Miscellaneous oxidising reagents
3. RESULTS AND DISCUSSION
3.1 Preparation of crosslinkecl polystyrenes
3.2 Chloromethylation of DVB-, EGDMA-, BDDMA- and HDODA crosslinked polystyrenes
Fig.3.1. Chlorine capacities of crosslinked chloromethylpolystyrenes
3.3 Synthesis of various crosslinked polystyrene-supported polyoxyethylene
Fig.3.2. Schematic representation of polymeric pseudocrown ether
Fig.3.3. Polyoxyethylene capacities of various crosslinked chloromethyl polystyrenes
3.4 Incorporation of potassium permanganate into various crosslinked polystyrene-supported polyoxyethylene (PSPOE)
Table 3.1. Details of the UV Spectra of KMnO4 complexed PSPOE
Fig.3.4. Effect of nature of crosslinking on the binding of potassium permanganate into 2 mol% crosslinked polystyrene-supported polyoxyethylene
3.5 Swelling studies
Table 3.2a. Swelling studies of crosslinked chloromethylated polystyrene
Table 3.2b. Swelling studies of crosslinked PSPOE
Table 3.2c. Swelling studies of crosslinked PSPOE-KMnO4
3.6 Oxidation reactions using various crosslinked PSPOE-KMn04 resins
3.6.1 Oxidation reactions using D VB (macro) crosslinked PSPOE-KMn04 resin
Table 3.3 Oxidation of primary and secondary alcohols using 2 mol% DVB (macro) PSPOE-KMnO4 resin
Table 3.4. Oxidation of aldehydes using 2 mol% DVB (macro) PSPOE-KMnO4 resin
3.6.2 Oxidation reactions using DVB (MACRO) -crosslinked PSPOE-KMn04 resin
3.6.3 Oxidation reactions using EGDMA-crosslinked PSPOE-KMn04 resin
Table 3.5. Oxidation of primary and secondaly alcohols using 2 mol% DVB (macro) PSPOE-KMnO4 resin
Table 3.6.Oxidation of aldehydes using 2 mol% DVB (micro) -PSPOE-KMnO4 resin
Table 3.7. Oxidation of primay and secondary alcohols using 2 mol% EGDMA-PSPOE-KMnO4 resin
Table 3.8. Oxidation of aldehydes using 2 mol% EGDMA-PSPOE-KMnO4 resin
3.6.4 Oxidation reactions using BLDMA-crosslinked PSPOE-KMn04 resin
3.6.5 Oxidation reactions using HDODA-crosslinked PSPOE-KMn04 resin
Table 3.9. Oxidation of primary and secondary alcohols using 2% 1, 4-BDDMA-PSPOE-KMn04 resin
Table 3.10. Oxidation of aldehydes using 2% 1, 4-BDDMA-PSPOE-KMnO4 resin
Table 3.11. Oxidation of primary and secondary alcohols using 1, 6-HDODA-PSPOE-KMnO4 resin
Table 3.12. Oxidation of aldehydes using 2%1, 6-HDODA-PSPOE-KMnO4 resin
3.7 Characterisation of the products
3.8 Effect of reaction conditions on the course of oxidation reactions
3.8.1 Solvent effect
Fig.3.5. Effect of solvent on the extent of reaction of 2 mol% DVB (macro) crosslinked PSPOE KMnO4 resin
Fig.3.6. Effect of solvent on the extent of reaction of 2 mol% DVB (macro) crosslinked PSPOE KMnO4 resin
Fig.3.7. Effect of solvent on the (extent of reaction of 2 mol% EGDMA-crosslinked PSPOE KMnO, resin
Fig.3.8. Effect of solvent on the extent of reaction of 2 mol% BDDMA-crosslinked PSPOE KMnO4 resin
Fig.3.9. Effect of solvent on the extent of reaction of 2 mol% HDODA-crosslinked PSPOE KMnO4 resin
3.8.2 Temperature effect
Fig.3.10. Effect of temperature on the extent of reaction of 2 mol% DVB (macro) crosslinked PSPOE -KMnO4 resin
Fig.3.11. Effect of temperature on the extent of reaction of 2 mol% DVB (macro) crosslinked PSPOE-KMnO4 resin
Fig.3.12. Effect of temperature on the extent of reaction of 2 mol% EGDMA-crosslinked PSPOE-KMnO4 resin
Fig.3.13. Effect of temperature on the extent of reaction of 2 mol% BDDMA-crosslinked PSPOE-KMnO4 resin
Fig.3.14. Effect of temperature on the extent of reaction of 2 mol% HDODA-crosslinked PSPOE-KMnO4 resin
3.8.3 Effect of molar excess of the reagent
Fig.3.15 Effect of molar excess on the extent of reaction of 2 mol% DVB (macro) crosslinked PSPOE-KMnO4 resin
Fig.3.16. Effect of molar excess on the extent of reaction of 2 mol% DVB (macro) crosslinked PSPOE-KMnO4 resin
Fig.3.17. Effed of molar excess on the extent of reaction of 2 mol% EGDMA-crosslinked PSPOE-KMnO4 resin
Fig.3.18. Effect of molar excess on the extent of reaction of 2 mol% BDDMA-crosslinked PSPOE-KMnO4 resin
Fig.3.19. Effect of molar excess on the extent of reaction of 2 mol% HDODA-crosslinked PSPOE-KMnO4 resin
3.9 Stability and shelf life of the reagents
Table 3.13. Stability of various PSPOE-KMnO4 resins
3.10 Recycling and reuse of the reagents
Table 3.14. Recyclability of KMnO4 complexed resin
4. EXPERIMENTAL
4.1 General
4.2 Preparation of 2% DVB-, EGDMA-, BDDMA- and HDODAcrosslinked polystyrenes: General procedure
4.3 Chloromethylation of crosslinked polystyrene: General procedure
4.4 Preparation of polystyrene-supported polyoxyethylene (PSPOE)
4.5 Synthesis of polystyrene-supported permanganates
4.6 Swelling studies
4.7 Oxidation studies using the potassium permanganate complexes of crosslinked polystyrene-supported polyoxyethylene
4.8 Monitoring the course of the oxidation reaction
4.9 Recycling and reuse of the spent polymeric permanganate resins
5. SUMMARY AND OUTLOOK
REFERENCES