UPSC Exam-Indian Civil Services Exam 2013 -Main Exam-Optional Syllabus-Chemistry-Paper 2

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 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 _π* and π π*_ 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.