Chemistry Paper –II UPSC Mains Syllabus
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 mechanism of organic reactions: isotopic method, 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 carbonium ions and carbanions, free radicals, carbenes, benzynes and nitrenes.
(iii) Substitution Reactions: SN1, SN2 and SNi 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 – Chugaev and Cope eliminations.
(v) Addition Reactions: Electrophilic addition to C=C and C=C; nucleophilic addition to C=0, 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 polymers–polyethy-lene, polystyrene, polyvinyl chloride, teflon, nylon, terylene, synthetic and natural rubber.
(ii) Biopolymers: Structure of proteins, DNA and RNA.
5. Synthetic Uses of Reagents: OsO4, HIO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3, LiAlH4, NaBH4, n-BuLi and 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 Ý p* and p p*Ý transitions; application to conjugated double bonds and conjugated carbonyls–Woodward-Fieser rules; Charge transfer spectra.
(iv) Nuclear Magnetic Resonance (1H NMR): Basic principle; chemical shift and spin-spin interaction and coupling constants.
(v) Mass Spectrometry: Parent peak, base peak, metastable peak, McLafferty rearrangement.