UNIVERSITY OF MADRAS
B.Sc. DEGREE COURSE IN CHEMISTRY
SEMESTER SYSTEM WITH CREDITS
(Effective from the Academic Year 2003-2004)

Semester V - Paper VI - Organic Chemistry-I

Duration: 3 hrs
Maximum Marks: 100
Credits: 4

(60 hrs)

Unit - I

(20 hrs)

1.1 Carbonyl polarization: Reactivity of carbonyl group - acidity of alpha hydrogen.

1.2 Mechanisms of Aldol, Perkin, Knoevenagal reactions and benzoin condensation - Claisen, Wiffig, Cannizaro, Reformatsky reactions.

1.3 Mechanisms of reduction with (sodium boro hydride, LiAlH₄, Woiff-Kishner and MPV) - mechanisms of haloform reaction and Michael addition.

1.4 Photochemistry of carbonyl compounds Norrish type I and II reactions.

1.5 lonisation of carboxylic acids - acidity constants - comparison of acid strengths of substituted halo acids - acid strengths of substituted henzoic acids. Conversion of acids to their derivatives.

1.6 Dicarboxylic acids - Preparation and properties of oxalic, malonic. succinic, glutaric and adipic acids.

1.7 Malonic and acetoacetic esters characterstic reactions of active methylene group - synthetic uses of malonic ester, acetoacetic ester and cyanoacetic ester.

1.8 Tautornerism - definition - keto-enol tautomerism (identification, acid and bae catalysed inter - conversion mechanism, preparation and characterstics) - amidoimidol and nitroacinitro tautomerisms.

Unit - II

(25 hrs)

2.1 Stereoisomerism - definition - classification into optical and geometric isomerism

2.2 Optical isomerism - optical activity - optical and specific rotations - conditions for optical activity - asymmetric centre -- chairality - achiral molecules - meaning of (+) and (-) and D and L notations - Elements of symmetry -. Racemisation - methods of racemisation (by substitution and tautomerism) - Resolution - methods of resolution (mechanical, seeding, biochemical and conversion to diastereoisomers) - Asymmetric synthesis (partial and absolute synthesis) - Walden inversion.

2.3 Projection formulae - Fischer, flying wedge, sawhorse and Newmann projection formulae - notation of optical isomers - Cahn-Ingold-Prelog rules - R - S notations for optical isomers with one and two asymmetric carbon atoms - erythro and threo representations.

2.4 Optical activity in compounds not containing asymmetric carbon atoms - Biphenyls, allenes and spiranes.

2.5 Geometrical isomerism - cis-trans, syn-anti and E-Z notations - geometrical isomerism in maleic and fumaric acids and unsymmetrical ketoximes - methods of distinguishing geometrical isomers using melting point, dipole moment, dehydration, cyclisation and heat of hydrogenisation.

2.6 Conformational analysis - introduction of terms - conformers, configuration, dihedral angle, torsional strain - Conformational analysis of ethane and n-butane including energy diagrams - conformers of cyclo hexane (chair, boat and skew boat forms) - axial and equatorial. Bonds-ring flipping showing axial equatorial inter conversions - conformers of mono and id substituted cyclohexanes - 1:2 and 1:3 interactions.

Unit - III

(15 hrs)

3.1 Aromaticity of heterocyclic compounds.

3.2 Preparation, properties and uses of furan, pyrrole and thiophene.

3.3 Synthesis and reactions of pyridine and piperidine - comparative study of basicity of pyrrole, pyridine and piperidine with amines.

3.4 Synthesis and reactions of quinoline, isoquinoline and indole with special reference to Skraup. Bischler and Napieralskii and Fisher indole synthesis.

3.5 Nitro compounds and amines -- Conversion of nitro benzene to ortho. para and meta dinitrobenzens, TNT. Aromatic nitro compounds reduction in neutral, acidic and alkaline media. Relative basic strengths of aliphatic and aromatic amines. Ring substitution in aromatic amines. diazotisation and its mechanism. Synthetic applications of diazonium salts.

Reference Books:

Organic Chemistry:

1. Textbook of Organic Chemistry - P.L.Soni - Sultan Chand
2. Advanced organic Chemistry - B.S.Bahl - S. Chand
3. Principles of Organic Chemistry - A.K.Bansal - New Age
4. A Textbook of Organic Chemistry - A.K.Bansal - New Age
5. Organic Chemistry - I.L.Finar - Volume I & II - Addision Welsey
6. Organic Chemistry - R.T.Morrison and Boyd - Prentice Hall
7. Stereochemistry of Organic Compounds - D.Nasipuri - New Age
8. Stereochemistry, Conformation and Mechanisms - Kalsi New Age
9. Organic Chemistry - P.H. Pine - Mcgrew Hill
10. Organic Chemistry - Solomons - John Wiley
11. Chemistry of Natural Products - O.P. Agarwal - Goel Publications
12. Organic Chemistry - John McMurny Vth Edition -Thompson Asia Pvt Ltd
13.Advanced General Organic Chemistry - Sachin K.Ghosh - Books and Allied (P) Ltd
14. Textbook of Organic Chemistry - P.S.Kalsi - Macmillan
15. Reaction Mechanism Inorganic Chemistry - S.M.Mukhergi and S.P. Singh - Macmillan