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TITLE
CERTIFICATE
DECLARATION
ACKNOWLEDGEMENT
CONTENTS
ABBREVIATIONS AND ACRONYMS
1. INTRODUCTION
1.1 α-OXOKETENEDITHIOACETALS
1.2 SOLVOLYTIC STUDIES ON FUNCTIONALIZED KETENEDITHIOACETALS
1 3 LEWIS ACID CATALYZED HYDROLYSIS OF α-OXOKETENEDITHIOACETALS
1.4 POLY (N-VINYLPYRROLIDONE) -BROMINE COMPLEX: A MILD REAGENT FOR THE PARTIAL. HYDROLYSIS OF α-OXOKETENEDITHIOACETALS
1.5 α -OXOKETENEDITHIOACETALS ON POLYMER SUPPORT.
1.6 LEWIS ACID CATALYZED SULFHYDROLYSIS OF α-OXOKETENE-DITHIOACETALS
1.7 REACTION OF α-OXOKETENEDITHIOACETALS WITH DIMSYI. ANION
1.8 REACTION OF LAWESSONS REAGENT WITH α-HYDROXY KETENEDITHIOACETALS
1.9 CONCLUSIONS
1.10 REFERENCES
2. α-OXOKETENEDITHIOACETALS IN ORGANIC SYNTHESIS
2.1 INTRODUCTION
2.2 α-OXOKETENEDITHIOACETALS: SYNTHESIS
2.3 α-OXOKETENEDITHIOACETAIS: REACTIVITY
2.3. 1 Reaction with Binucleophiles
2.3.2 1, 2-Addition Reactions of Carbon Nucleophiles
2.3.3 1, 4-Addition Re actions of Carbon Nucleophiles.
2.3.4 Miscellaneous Reactions Leading to Heterocycles
2.3.5 Solyolysis and Hydrolysis of α-Oxo and α-Hydroxyketenedithioacetals
2.4 REFERENCES
3. PARTIAL HYDROLYSIS OF α -OXOKETENEDITHIOACETALS
3.1 INTRODUCTION
3.2 β-OXTHIOLCARBOXYLATES: SYNTHESIS
3.2.1 β- Oxothiolcarboxylates:.Synthesis
3.2.2 β-Oxothiolcarhoxylates: Reactions I.
3.3 RESULTS AND DISCUSSION
3.3.1 Boron Trifluoride Assisted Partial Hydrolysis of α-Oxoketenedithioacetals
3.3.2 Poly (. N-vinylpyrrolidone) -Bromine Complex.A polymer Supported Reagent for Effective Partial Hydrolysis of Functionalized Ketenedithioacetals
3.3.3 α-Oxoketenedithioacetals on Polymer Support
3.3.3.1 Reaction of β -Oxodithioesters with Merrified Resin.
3.4 EXPERIMENTAL
3.4.1 Preparation of Starting Materials
3.4.2 Boron Trifluoride Assisted Partial Hydrolysis of α-Oxoketene-dithioacetals
3.4.3 Reaction of α-Oxoketenedithioacetals with Poly- (N-Vinylpyrrolidone) -Bromine Complex
3.4.4 Preparation of Ketenedithioacetal functionalized Resins 97α-f
3.5 REFERENCES
4. PREPARATION OF β-OXODITHIOESTERS FROM α -OXOKETENEDITHIOACETALS
4.1 INTRODUCTION
4.2 β- -OXODITHIOESTERS: SYNTHESIS AND SYNTHETIC POTENTIAL
4.2.1 β-Oxodithioesters: Synthesis
4.2.2 β-Oxodithioesters: Reactions
4.3 RESULTS AND DISCUSSION
4.3.1 Sulfhydrolysis of α-Oxoketenedithioacetals
4.3.2 Reacton of α-Oxoketenedithioacetals with Sodium Methylsulfenylmethylide
4.3.2.1 Sodium Methylsulfenylimethylide: A Versatile Reagent in Organic Synthesis
4.3.2.2 Reaction of Dimsyl Anion with Diethyl α-oxoketenedithioacetals
4.3.2.3 Reaction of Dimsylanion with 2-Substituted Methylene-1, 3-dithiolanes: Formation of Vinyl β-oxodithioesters
4.4 EXPERIMENTAL
4.4.1 Preparation of 2-Substituted Methylene-l, 3-dithiolanes Lewis Acid Catalyzed Sulfhydrolysis of Dimethyl α-oxoketenedithioacetals
4.4.2 Lewis Acid Catalyzed Sulfhydrolysis of Dimethyl a-oxoketenedithioacetals
4.4.3 Reaction of α-Oxoketenedithioacetals with Sodium Methylsulfenyl-methylide
4.4.3.1 Preparation of Methyl b oxodithioesters
4.4.3.2 Preparation of Vinyl β-oxodithioesters
4.5 REFERENCES
5. REACTION OF LAWESSONS REAGENT WITH α -HYDROXYKETENEDITHIOACETALS
5.1. INTRODUCTION
5.2 α, β-UNSATURATED DITHIOCARBOXYLATES
5.3 RESULTS AND DISCUSSION
5.3.1 Preparation of α, β-Unsaturated Dithioesters
5 3.2 Preparation of- 14substituted α, β-Unsaturated Dithioesters
5.4 EXPERIMENTAL
5.4.1 Reactions of α-Oxoketenedithioacerals with Sodium borohydride Followed by Treatment with Lawessons Reagent: Preparation of α, β-Unsaturated Dithioesters.
5.4.2 Reaction of α-Oxoketenedithioacetals with Methylmagnesium Iodide Followed by Treatment with Lawessons Reagent: Preparation of β-Disubstituted α, β-Unsaturated Dithioesters
5.5 REFERENCES AND NOTES