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TITLE
CERTIFICATE
DECLARATION
ACKNOWLEDGEMENT
CONTENTS
1. INTRODUCTION
1.1 Organosulfur Compounds
1.2 α-Oxo Ketene Dithioacetals and β-Oxo Dithioesters
1.3 α-Oxo Ketene-N, S-Acetals and β-Oxo Thioamides
1.4 Vilsmeier Reactions of β-Oxo Dithioesters
1.5 Reactions of β-Oxo Thioamides with α-Haloketones: A Synthesis of Functionalized Thiophenes.
1.6 Reactions of Ketones with Aryl lsothiocyanates
1. 7 References
2. DITHIOCARBOXYLIC ESTERS AND THIOAMIDES: SYNTHESIS AND REACTIVITY
2.1 Introduction
2.2 Dithiocarboxylic Acids and Esters
2.2.1 Synthesis of dithiocarboxvlic acids and esters
2.2.1.1. Thioacylation
2.2.1.2 Reactions of Organometallic Reagents with Carbondisulfide
2.2.1.3 Sulfurization
2.2.1.4 Reactions of enolates with carbondisulfide
2.2.1.5 Reactions of Enolates with Dimethyl trithiocarbonate
2.2.1.6 Formation of α-Oxodithioesters
2.2.1.7 Friedel Crafts Type Reactions
2.2.1.8 Reactions Involving β-Thioxo-1, 2-dithiol
2.2.1.9 Reactions of Dithioenolates
2.2.2 Reactions of dithiocarboxylic acids and esters
2.2.2.1 Reactions of enethiolates
2.2.2. 2 Synthesis of 2H-thiopyran-2-thiones
2.2.2.3 Formation of Other Heterocycles
2.2.2.4 Oxidation Reactions
2.3 Thioamides
2.3.1 Synthesis of thioamides
2.3.2 Reactions of thioamides
2.4 References
3. REACTION OF β-OXODITHIOESTERS WITH CHLOROMETHYLENE IMINIUM SALTS
3. 1 Introduction
3. 1.1 Vilsmeier Haack Reagent
3.1.2 Reactions of Sulfur Compounds with Chloromethylene iminium Salts
3.2 Results and Discussion
Fig.1 IR Spectrum (neat) of compound 36
Fig.2 H NMR Spectrum (90 MHz) of compound 36
Fig. 3 13C NMR Spectrum (22.4 MHz) of compound 36
Fig.4 Mass Spectrum (GCM) of compound 36
3.2.1 A Synthesis of β-Methylthio α, β Unsaturated Ketones
Fig.5 IR Spectrum (KBr) of compound 43c
Fig. 6 H NMR Spectrum (90 MHz) of compound 43c
Fig. 7 Mass Spectrum (GCMS) of compound 43c
Fig.8 IR Spectrum (KBr) of compound 48
Fig.9 H NMR Spectrum (90 MHz) of compound 48
Fig.10 13C NMR Spectrum (22.4 MHz) of compound 48
Fig.11 Mass Spectrum (GCMS) of compound 48
3.2.2 Reaction of Methyl carbethoxy dithioacetate with Chloro methylene iminium Salt
Fig. 12 IR Spectrum (KBr) of compound 51
Fig. 13 H NMR Spectrum (90 MHz) of compound 51
Fig. 14 13C NMR Spectrum (22.4 MHz) of compound 51
Fig.15 Mass Spectrum (EIMS) of compound 51
3.3 Conclusion
3.4 Experimental
3.4.1 Reaction of Βoxodithioesters with Vilsmeier reagent: General procedure
3.4.2 Methyl carbethoxy dithioacetate (36)
3.4.3 Diethyl-6-methylthio-2-dithiopyrone-3, 5-dicarboxylate (57)
3.5 References
4. REACTIONS OF β-OXO THIOAMIDES AND β-OXO DITHIOESTERS WITH 1, 2-BIELECTROPHILES
4.1 Introduction
4.1.1 Reactions of carbanions with isothiocyanates followed by alkylation with functionalized electrophiles
4.1.2 Reactions of enamines
4.2 Results and Discussion
4.2.1 Reactions of Enolates with Phenyl isothiocyanate followed by alkylation with Phenacyl bromide
Fig. 1 IR Spectrum (KBr) of compound 65d
Fig. 2 H NMR Spectrum (90 MHz) of compound 65d
Fig. 3
Fig. 4 Mass Spectrum (EIMS) of compound 65d
Fig. 5 IR Spectrum (KBr) of compound 69
Fig. 6 H NMR Spectrum (90 MHz) of compound 69
Fig. 7
Fig. 8 Mass Spectrum (EIMS) of compound 69
Fig.9 IR Spectrum (KBr) of compound 71a
Fig. 10 H NMR Spectrum (90 MHz) of compound 71a
Fig. 11
Fig. 12 Mass Spectrum (EIMS) ofconlpound 71a
4.2.2 Reaction of β-oxo dithioesters with 1, 2-bielectrophiles
4.2.2.1 Reaction of benzoyl dithioacetate with 1, 2-dibromoethane
4.2.2.2 Reaction of benzoyl dithioacetate with Phenacyl bromide
Fig. 13 IR Spectrum (KBr) of compound 79
Fig. 14 H NMR Spectrum (300 MHz) of compound 79
Fig. 15 Mass Spectrum (EIMS) of compound 79
Fig. 16 LR Spectrum (KBr) of compound 83
Fig. 17 H NMR Spectrum (300 MHz) of compound 83
Fig. 18 Mass Spectrum (EIMS) of cornpound 83
4.3 Conclusions
4.4 Experimental
4.4.1 Reactions of enolates front substituted acetopohenones with phenyl isothiocyanate followed by alkylation with phenacyl bromide
4.4.2 Reactions of enolates from substituted acetopohenones with phenyl isothiocyanate followed by alkylation with αbromo-propiophenone
4.4.3 Reaction of the enolates from acetylthiophene with phenyl isothiocyanate followed by alkylation with phenacylbromide
4.4.4 Reaction of the enolates front acetylace tone with phenyl isothiocyanate followed by alkylation with phenacylbromide
4.4.5 Reaction of the enolates from ethylacetoacetate with phenyl isothiocyanate followed by alkylation with phenacylbromide
4.4.6 Reaction of the benzoyl dithioacetate with 1, 2-dibromoethane of the benzoyl dithioacetate with phenacyl bromide
4.4.7 Reaction of the benzoyl dithioacetate with phenacyl bromide
4.5 References
5. OXIDATIVE CYCLIZATIONS OF β-Oxo-N-ARYLTHIOAMIDES TO SUBSTITUTED BENZOTHIAZOLES
5.1 Introduction:
5.1.1 Benzothiazoles: Synthesis
5. 2 Results and Discussion
5.2.1 Reactions of Cyclohexanone with Aryl isothiocyanates
Fig. I 11 NMR Spectrum (90 MHz) of compound 19
Fig. 2 13C NMR Spectrum (22.4 MHz) of compound 19
Fig. 3 IR Spectrum (KBr) of cornpound 19
Fig. 4 Mass Spectrum (EIMS) of compound 1 9
5.2.2 Reactions of α-Tetralone with Aryl isothiocyanates
Fig. 5 11 NMR Spectrum (90 MHz) of compoundf 3 1
Fig.6 I3C NMR Spectrnni (22.4 MHz) of compound 31
Fig. 7 IR Spectrum (KBr) of compound 31
Fig.8 Mass Spectrum (EIMS) of compound 31
5.2.3 Reactions of Tetralone with Aryl isothiocyanates
Fig. 9 H WMR Spectrum (90 MHz) of compound 33a
Fig. 10 13C NMR Spectrum (22.4 MHz) of compound 33a
5.3 Conclusions
5.4 Experimental
5.4.1 Reactions of Cyclohexanone with Aryl isothiocyanates
5.4.2 Reactions of α-Tetralone with Aryl isothiocyanates
5.4.3 Reactions of Cyclohexanone with Aryl isothiocyanates
5.5 References