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CHEMISTRY paper II

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CHEMISTRY

PAPER-II

1. Delocalised covalent bonding:

Aromaticity, anti-aromaticity; annulenes, azulenes, tropolones, fulvenes, sydnones.

2. (i) Reaction mechanisms: General methods (both kinetic and non-kinetic) of study of mechanisms or organic reactions: isotopies, mathod cross-over experiment, intermediate trapping, stereochemistry; energy of activation; thermodynamic control and kinetic control of reactions.

(ii) Reactive intermediates: Generation, geometry, stability and reactions of carboniumions and carbanions, free radicals, carbenes, benzynes and nitrenes.

(iii) Substitution reactions: SN 1, SN 2, and SN i, mechanisms; neighbouring group participation; electrophilic and nucleophilic reactions of aromatic compounds including heterocyclic compounds—pyrrole, furan, thiophene and indole.

(iv) Elimination reactions: E1, E2 and E1cb mechanisms; orientation in E2 reactions— Saytzeff and Hoffmann; pyrolytic syn elimination—acetate pyrolysis, Chugaev and Cope eliminations.

(v) Addition reactions: Electrophilic addition to C=C and CC; nucleophilic addition to C=O, C N, conjugated  olefins  and carbonyls.

(vi) Reactions and Rearrangements: (a) Pinacol-pinacolone, Hoffmann, Beckmann, Baeyer- Villiger, Favorskii, Fries, Claisen, Cope, Stevens and Wagner—Meerwein rearrangements.

(b) Aldol condensation, Claisen condensation, Dieckmann, Perkin, Knoevenagel, Witting, Clemmensen, Wolff-Kishner, Cannizzaro and von Richter reactions; Stobbe, benzoin and acyloin condensations; Fischer indole synthesis, Skraup synthesis, Bischler-Napieralski, Sandmeyer, Reimer-Tiemann and Reformatsky reactions.

3. Pericyclic reactions: Classification and examples; Woodward-Hoffmann rules—electrocyclic reactions, cycloaddition reactions [2+2 and 4+2] and sigmatropic shifts [1, 3; 3, 3 and 1, 5], FMO approach.

4. (i) Preparation and Properties of Polymers: Organic polymerspolyethylene, polystyrene, polyvinyl chloride, teflon, nylon, terylene, synthetic and natural rubber.

(ii) Biopolymers: Structure of proteins, DNA and RNA.

5. Synthetic Uses of Reagents:

OsO4, HlO4, CrO3, Pb (OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3, LiAIH4, NaBH4, n-BuLi, MCPBA.

6. Photochemistry: Photochemical reactions of simple organic compounds, excited and ground states, singlet and triplet states, Norrish-Type I and Type II reactions.

7. Spectroscopy:

Principle and applications in structure elucidation:

(i) Rotational—Diatomic molecules; isotopic substitution and rotational constants.

(ii) Vibrational—Diatomic molecules, linear triatomic molecules, specific frequencies of functional groups in polyatomic molecules.

(iii) Electronic—Singlet and   triplet   states.   n   and      transitions;  application   to

conjugated double bonds and conjugated carbonyls Woodward-Fieser rules; Charge transfer spectra.

(iv) Nuclear Magnetic Resonance (1HNMR): Basic principle; chemical shift and spin-spin interaction and coupling constants.

(v) Mass Spectrometry :—Parent peak, base peak, metastable peak, McLafferty rearrangement

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