M.Sc. Chemistry Syllabus Revised Implemented ... - Shivaji University

Types of reactions, strength of acids and bases. Generation, structure, stability and
reactivity of carbocations and carbanions, free radicals, carbenes, arynes, nitrenes
and ylids. Efect of structure on reactivity, resonance and field , steric effects.
b) Aliphatic Nucleophilic substitutions: (7)
The SN 2 , SN 1 and SN i reactions with respects to mechanism and stereochemistry.
Nucleophilic substitutions at an allylic, aliphatic trigonal, benzylic, aryl and
vinylic carbons. Reactivity effect of substrate structure, effect of attacking
nucleophiles, leaving groups and reaction medium. SN reactions at bridge head
carbon, competition between SN 1 and SN 2 ,Ambident nucleophiles, Neighbouring
Group Participation.
UNIT-II
a) Aromatic Electrophilic Substitutions:- (8)
Introduction, the arenium ion mechanism, orientation and reactivity in Nitration,
Sulphonation, Friedel-Crafts and Halogenation in aromatic systems, energy profile
diagrams. The ortho/para ratio, ipso attack, concept of aromaticity, orientation in
their ring systems. Diazo-coupling, Vilsmeie reaction, Von Richter rearrangement
. Nucleophilic aromatic substitution reactions SN 1 , SN 2 .
b)Addition to Carbon–Carbon Multiple Bonds: (7)
Mechanism and stereochemical aspects of the addition reactions involving
electrophiles and free radicals, region- and chemo-selectivity, orientation and
reactivity. Hydrogenation of double and triple bonds, hydrogenation of aromatic
rings. Michael addition reaction.
UNIT-III
a) Elimination Reactions: (8)
The E1, E2 and E1cB mechanisms. Orientation in Elimination reactions. Hofman
versus Saytzeff elimination, Pyrolytic syn-elimination, competition between
substitution and elimination reactions, Reactivity: effects of substrate structures,
attacking base, the leaving group, the nature of medium on elimination reactions.
Pyrolytic elimination reactions.
b) Study of following reactions: (7)
Beckman, Fries, Benzilic acid, Hoffman, Schmidt, Curtius, Lossen, Witting,
Neberland Prins, Ortaon, Hofmann-Martius and Demjanov reaction..
UNIT-IV (15)
Stereochemistry: Concept of chirality and molecular dissymmetry, Recognition of
symmetry elements and chiral centers, Prochiral relationship, homotopic,
enantiotopic and disteriotopic groups and faces. Recemic modifications and their
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