Paper II
1. Delocalised covalent bonding :
Aromaticity, anti-aromaticity; annulenes, azulenes, tropolones, kekulene,
fulvenes, sydnones.
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A D V E R T I S E M E N T
2(a) Reaction mechanisms : General
methods (both kinetic and non-kinetic) of study of mechanism or organic
reactions illustrated by examples�use of isotopes, cross-over experiment,
intermediate trapping, stereochemistry; energy diagrams of simple organic
reactions�transition states and intermediates; energy of activation;
thermodynamic control and kinetic control of reactions.
(b) Reactive intermediates :
Generation, geometry, stability and reactions of carbonium and carbanium ions,
carbanions, free radicals, carbenes, benzynes and niternes.
(c) Substitution reactions : SN1,
SN2, SNi, SN1�, SN2�, SNi� and SRN1 mechanisms; neighbouring group
participation; electrophilic and nucleophilic reactions of aromatic compound
including simple heterocyclic compounds�pyrrole, thiophene, indole.
(d) Elimination reactions : E1, E2
and E1cb mechanisms; orientation in E2 reactions�Saytzeff and Hoffmann;
pyrolytic syn elimination�acetate pyrolysis, Chugaev and Cope
eliminations.
(e) Addition reactions :
Electrophilic addition to C=C and C=C; nucleophilic addition to C=O, C=N,
conjugated olefins and carbonyls.
(f) Rearrangements :
Pinacol-pinacolune, Hoffmann, Beckmann, Baeyer�Villiger, Favorskii, Fries,
Claisen, Cope, Stevens and Wagner-Meerwein rearrangements.
3. Pericyclic reactions :
Classification and examples; Woodward-Hoffmann rules�clectrocyclic reactions,
cycloaddition reactions [2+2 and 4+2] and sigmatropic shifts [1, 3; 3, 3 and 1,
5] FMO approach.
4. Chemistry and mechanism of
reactions : Aldol condensation (including directed 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.
5. Polymeric Systems
(a) Physical chemistry of polymers :
Polymer solutions and their thermodynamic properties; number and weight average
molecular weights of polymers. Determination of molecular weights by
sedimentation, light scattering, osmotic pressure, viscosity, end group analysis
methods.
(b) Preparation and properties of
polymers : Organic polymers�polyethylene, polystyrene, polyvinyl chloride,
Teflon, nylon, terylene, synthetic and natural rubber. Inorganic polymers�phosphonitrilic
halides, borazines, silicones and silicates.
(c) Biopolymers : Basic bonding in
proteins, DNA and RNA.
6. Synthetic uses of reagents :
OsO4, HIO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3, LiAlH4, NaBH4 n-BuLi,
MCPBA.
7. Photochemistry : Photochemical
reactions of simple organic compounds, excited and ground states, singlet and
triplet states, Norrish-Type I and Type II reactions.
8. Principles of spectroscopy and
applications in structure elucidation
(a) Rotational spectra�diatomic
molecules; isotopic substitution and rotational constants.
(b) Vibrational spectra�diatomic
molecules, linear triatomic molecules, specific frequencies of functional groups
in polyatomic molecules.
(c) Electronic spectra : Singlet
and triplet states. N�>* and �>* transitions; application to conjugated double
bonds and conjugated carbonyls�Woodward-Fieser rules.
(d) Nuclear magnetic resonance :
Isochronous and anisochronous protons; chemical shift and coupling constants;
Application of 1H NMR to simple organic molecules.
(e) Mass spectra : Parent peak,
base peak, daugther peak, metastable peak, fragmentation of simple organic
molecules;� cleavage, McLafferty rearrangement.
(f) Electron spin resonance :
Inorganic complexes and free radicals.
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AKHAND PRATAP SINGH
