CHM-624: ADVANCED ORGANIC REACTION MECHANISM PART- II Credit Hours (3+0)

ELECTROPHILC & NUCLEOPHILIC ADDITION TO CARBON-CARBON DOUBLE BONDS Addition of halogens: Mechanism (ANTI & SYN), Effect of substitutents on rate of addition, Orientation of addition, Addition of unsymmetrical reagents (Addition of halogen derivatives, Hydration, carbocations, Hydroxylation). Addition 0f symmetrical reagents (Hydrogenation, Ozonolysis), Addition to conjugated dienes (1,2 & 1,4-addition, Dicls-Aldcr reaction), Nuclcophilic addition (Cyanoethylation, Michael reaction). Oxymercuration and demercuration, hydroboration etc. Regioselectivity, regiospecificity and stereochemical aspects of addition products. NUCLEOPHILIC ADDITION TO CARBON-OXYGEN DOUBLE BONDS Electrophilic and nucleophilic reactivity of carbon-oxygen double bond. Simple addition reactions:(Addition of water-Hydration, Addition of alcohol, Addition of thiol, Addition of Hydrogen cyanide, Addition of Bisulphate, Addition of hydride ions: Metal hydride ions, Meerwein-Pondrof reaction, Cannizaro reaction; Addition-elimination reactions: Derivatives of ammonia; Carbon as Nucleophile. Grignard reagent, Acetylide anions, Aldol reactions, Nitroalkanes Perkin reaction, Knoevenagel & Stobbe reactions, Benzoin condensation, Leukart reaction, Streker syntllesis. Nucleophilic addition to carbonyl analogues. Stereo selectivity in carbonyl addition reaction: Cram's Rule. MOLECULAR ORBITAL & ORGANIC REACTIONS Pericyclic reactions, Frontier orbital theory. General description of the Diels Alder reactions Dienes, dievophiles the endo rule for the diels Alder reactions Intermolecular Dicls Alder reactions. The woodward- Hoffmann description of Diels Alderson ELIMINATION REACTIONS 1,2-or -elimination, E1 mechanism, E1 CB mechanism, D2 mechanism: Stereochemistry in E2 mechanism, Orientation in E2 elimination (Saytzev elimination, Hofmann elimination, Bredts elimination) Elimination vs Substitution, Effect of activating groups, 1,1- ( ) elimination, Pyrolytic elimination (Chugaev reaction, Cope reaction). CHEMISTRY OF ORGANOMETALLIC COMPOUNDS Structure and bonding in transition and non-transition metal compounds and complexes. Donar vs acceptor ligands and their effect on the central metal atom. 16 and 18 electrons complexes. Complexes or organic functionalities, olefins, acetylenes, arenas and their reactivities. Oxidative additions and reaductive eliminations. Applications of organometallic compounds usin Cu, Pd, Co, Fe, Ni, W, Zn in organic synthesis: hydrogenation, isomerisation, coupling, cyclisation, cycloaddition, carboxalation rearrangements. BOOKS RECOMMENDED 1. Lowry TH and Richardson K.S Mechanism and theory in Organic Chemistry (1976) Harper and Row 2. Sykes P A Guide Book to Mechanism in Organic Chemistry (1986) Longman 3. Gould ES Mechanism and Streucture of Oranic Chemistry (1959) Holt, Rinehart and Winston Inc 4. Streitwieser A and Heathocock CH Introduction to Organic Chemistry 3rd Ed (1989) Macmillan Publishing Company 5. March J Advanced Organic Chemistry Reactions, Mechanisms and Structures 4th Ed (1992) John Wiley and Sons Inc 6. Den G, Warren and Wothers Organic Chemistry (2001) Oxford University Press