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PAPER-II

1. Delocalisedcovalentbonding:

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

2. (i) Reactionmechanisms:Generalmethods(bothkineticandnon-kinetic)ofstudyofmechanisms or organic reactions : isotopies, mathod cross-over experiment, intermediate trapping,stereochemistry;energyofactivation;thermodynamiccontrolandkineticcontrolofreactions.
   • Reactive intermediates : Generation, geometry, stability and reactions of carboniumionsandcarbanions,freeradicals,carbenes,benzynesandnitrenes.
   • Substitutionreactions :—SN 1, SN 2, and SN i, mechanisms ; neighbouring group

participation;electrophilic and nucleophilic reactions of aromatic compounds including heterocycliccompounds—pyrrole,furan,thiopheneandindole.

• Eliminationreactions:—E1,E2andE1cbmechanisms; orientation  in  E2  reactions—SaytzeffandHoffmann; pyrolytic syn elimination—acetate pyrolysis, Chugaev and Copeeliminations.
• Addition reactions :—Electrophilic addition to C=C and CC; nucleophilic addition to C=O,CN,conjugatedolefinsandcarbonyls.
• Reactions and Rearrangements :—(a) Pinacol-pinacolone, Hoffmann, Beckmann, Baeyer-Villiger,Favorskii,Fries,Claisen,Cope,StevensandWagner—Meerweinrearrangements.

(b)         Aldolcondensation,Claisencondensation,Dieckmann,Perkin,Knoevenagel,Witting,Clemmensen, Wolff-Kishner, Cannizzaro and von Richter reactions; Stobbe, benzoin and acyloincondensations;Fischerindolesynthesis,Skraupsynthesis,Bischler-Napieralski,Sandmeyer,Reimer-TiemannandReformatskyreactions.

3. Pericyclicreactions:—Classificationandexamples;Woodward-Hoffmannrules—electrocyclicreactions,cycloaddition reactions [2+2 and 4+2] and sigmatropicshifts [1,3; 3,3 and 1, 5], FMOapproach.
4. (i) PreparationandPropertiesofPolymers:Organicpolymerspolyethylene,polystyrene,polyvinylchloride,teflon,nylon,terylene,syntheticandnaturalrubber.

(ii)         Biopolymers:Structureofproteins,DNAandRNA.

5.                 SyntheticUsesofReagents:

OsO4,HlO4,CrO3,Pb(OAc)4,SeO2,NBS,B2H6,Na-LiquidNH3,LiAIH4,NaBH4,n-BuLi,MCPBA.

6. Photochemistry:—Photochemicalreactionsofsimpleorganic compounds,  excited  and  groundstates,singletandtripletstates,Norrish-TypeIandTypeIIreactions.

7.                 Spectroscopy:

Principleandapplicationsinstructureelucidation:

• Rotational—Diatomicmolecules;isotopic substitutionandrotationalconstants.
• Vibrational—Diatomicmolecules,lineartriatomicmolecules,specificfrequenciesoffunctionalgroupsinpolyatomicmolecules.
• Electronic—n* and * transitions;applicationtoconjugateddoublebondsandconjugatedcarbonylsWoodward-Fieserrules;Chargetransferspectra.
• NuclearMagneticResonance(1HNMR):Basicprinciple;chemicalshiftandspin-spininteractionandcouplingconstants.
• MassSpectrometry:—Parentpeak,basepeak,metastablepeak,McLaffertyrearrangement.
  
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