CY7310 : Advanced Physical Organic Chemistry

Kinetics and thermodynamics – chemical equilibrium – activation – transition state model – potential energy surface for substitution and elimination reactions – the rate limiting step – Hammond postulate – the principle of microscopic reversibility – the principle of least motion – isokinetic relationship – kinetic and thermodynamic control of products – isotope effects – primary, secondary and solvent isotope effects.

Correlation of structure with reactivity – linear free energy relationships Hammett equation – interpretation of substitutent and reaction constants – ?, ?+, ? -, polar and steric substitutent constants – the Taft model – deviation from Hammett equation – acidity functions – determination of solvent polarity and solvent polarity scales.

Determination of reaction mechanism, reactions and mechanistic classifications – kinetics as an aid – detection and trapping of reactive intermediates – stereochemical probe – isotope effects – solvent effect – salt effect – ion pairs in solvolysis raction – intra- and intermolecular reactions – anchimeric assistance – stereoelectronic effects on rates and course.

Catalysis – homogeneous – acids and bases and their strengths – specific and general acid base catalysis – Bronsted catalysis law – intepretation of Bronsted coefficient – nucleophilic and electrophilic catalysis – mechanisms of some acid- base catalysed reactions in carbonyl and olefin chemistry.

Reactive intermediats – carbenes – nitrenes – arynes – free radicals – carbonium ions and carbanions – their generation, detection, characterization, structure and reactivity.

Recent topics in mechanistic organic chemistry – electron transfer reactions – electron transfer catalysed reactions – substitution via free radicals – free radical cyclization – Baldwin;s rules – Lewis acid catalysis of some common organic reactions.

References:

1. T.H. Lorry and K.S. Richardson, Mechanism and Theory in Organic Chemistry 2nd Edition, Harper & Row, New York, 1981.
2. N.S. Isaacs, Physical Organic Chemistry, ELBS / Longman, 1990.
3. P. Sykes, A Guidebook to Mechanism in Organic Chemistry, 5th edition, Longman, London, 1981.
4. L.P. Hammett, Physical Organic Chemistry, 2nd edition, McGraw Hill, New York, 1970
5. P. Deslongchamps, Stereoelectronic Effects in Organic Chemistry, Pergamon, London, 1983.
6. T.L. Gilchrist and R.W. Rees, Carbenes, Nitrenes and Arynes, Nelson, 1969.