Chemistry Syllabus

Semester wise to be effective from 2010-2011

Note:

  1. In all 72 credits are to be completed in M.Sc. out of which18 credits shall be taken by the student in one semester.
  2. In semester III and IV the student will opt one branch out of three branches i.e. Inorganic, Organic and Physical according to the availability of faculty in the department. The student will also take 18 credits in III and IV semesters out of which 9 credits i.e. two core courses will be compulsory and rest of 9 credits will be from elective courses.

M.S.c. I

Semester ICourse MMCredits

  1. Inorganic Chemistry I C0011003
  2. Organic Chemistry I C0021003
  3. Physical Chemistry I C0031003
  4. Group Theory & Spectroscopy C0041003
  5. Laboratory Course IA C0051003

6. Laboratory Course IB C006 100 3

Semester IICourse MMCredits

  1. Inorganic Chemistry II C0071003
  2. Organic Chemistry II C0081003
  3. Physical Chemistry II C0091003
  4. Spectroscopy & Separation C0101003

Methods

  1. Laboratory Course IIAC0111003

6. Laboratory Course IIB C0121003

M.S.c. II

Semester IIICourse MMCredits

[A] Inorganic Chemistry

1. Laboratory Course Inorganic IIIA C0131003

2. Laboratory Course Inorganic IIIB C0141003

3. Organometallic Chemistry C0151003

4. Spectroscopy, X-ray & Solid E0011003

State

5. Bioinorganic, Bioorganic, E0021003

Biophysical I

6. Bioinorganic & Supramolecular E0031003

Chemistry I

7. Analytical Chemistry E0041003

[B] Organic Chemistry

1. Laboratory course- Organic IIIA C0161003

2. Laboratory course- Organic IIIB C0171003

3. Organic Synthesis & Photochem. C0181003

4. Bioorganic, Bioorganic & Bio. E002 100 3

Physical Chemistry I

5. Spectroscopy & Solid State E0051003

6. Organometallic reagents and E0061003

Organic Synthesis

7. Medicinal E0071003

Chemistry

[C] Physical Chemistry

  1. Laboratory Course C0191003

Physical IIIA

  1. Laboratory Course C0201003

Physical IIIB

3. Chemistry of Materials C0211003

4. Spectroscopy, X-ray & E0011003

SolidState

5. Bioinorganic, Bioorganic E002 1003

and Biophysical Chemistry I

  1. Analytical ChemistryE0041003
  2. Liquid State E0081003

M.Sc. II

Semester IV Course MMCredits

[A] Inorganic Chemistry

  1. Laboratory Course Inorganic IVA C0221003
  2. Laboratory Course Inorganic IVA C0231003

3. Inorganic PolymersC0241003

4. SpectroscopyE0091003

5. Bioinorganic, Bioorganic E0101003

and Biophysical Chemistry II

  1. Photoinorganic ChemistryE0111003
  2. Environmental ChemistryE0121003

[B]Organic Chemistry]

  1. Laboratory Course Organic IVAC0251003
  2. Laboratory Course Organic IVBC0261003
  3. Natural ProductsC0271003
  4. Spectroscopy E0091003
  5. Bioinorganic, Bioorganic and E0101003

Biophysical Chemistry II

  1. Environmental Chemistry E0121003
  2. Heterocyclic ChemistryE0131003

[C]Physical Chemistry]

  1. Laboratory Course Physical IVAC0281003
  2. Laboratory Course Physical IVBC0291003
  3. Advanced Quantum ChemistryC0301003
  4. Spectroscopy E0091003
  5. Bioinorganic, Bioorganicand E0101003

Biophysical Chemistry II

6. Environmental ChemistryE0121003

7. PolymersE0141003

Self Study Courses

1. Computer for Chemists S001100 3

2. Mathematics for ChemistsS0021003

3. Nanoscience and Nanotechnology S003100 3

S.No. / Paper / Category / Paper Code / L / T / P / C
1 / Inorganic Chemistry - I / Core / SOS/C001 / 3 / 0 / 0 / 3
2 / Organic Chemistry - I / Core / SOS/C002 / 3 / 0 / 0 / 3
3 / Physical Chemistry - I / Core / SOS/C003 / 3 / 0 / 0 / 3
4 / Group Theory & Spectroscopy / Core / SOS/C004 / 3 / 0 / 0 / 3
5 / Laboratory Course-IA / Core / SOS/C005 / 0 / 0 / 9 / 3
6 / Laboratory Course-IB / Core / SOS/C006 / 0 / 0 / 9 / 3
7 / Inorganic Chemistry - II / Core / SOS/C007 / 3 / 0 / 0 / 3
8 / Organic Chemistry - II / Core / SOS/C008 / 3 / 0 / 0 / 3
9 / Physical Chemistry II / Core / SOS/C009 / 3 / 0 / 0 / 3
10 / Spectroscopy and Separation Methods / Core / SOS/C010 / 3 / 0 / 0 / 3
11 / Laboratory Course-IIA / Core / SOS/C011 / 0 / 0 / 9 / 3
12 / Laboratory Course-IIB / Core / SOS/C012 / 0 / 0 / 9 / 3
13 / Laboratory Course- Inorganic IIIA / Core / SOS/C013 / 0 / 0 / 9 / 3
14 / Laboratory Course- Inorganic IIIB / Core / SOS/C014 / 0 / 0 / 9 / 3
15 / Organometallic Chemistry / Core / SOS/C015 / 3 / 0 / 0 / 3
16 / Spectroscopy, X-ray and SolidState / Elective / SOS/E001 / 3 / 0 / 0 / 3
17 / Bioinorganic, Bioorganic
Biophysical Chemistry-I / Elective / SOS/E002 / 3 / 0 / 0 / 3
18 / Bioinorganic and Supramolecular Chemistry / Elective / SOS/E003 / 3 / 0 / 0 / 3
19 / Analytical Chemistry / Elective / SOS/E004 / 3 / 0 / 0 / 3
20 / Laboratory Course-Org IIIA / Core / SOS/C016 / 0 / 0 / 9 / 3
21 / Laboratory Course-Org IIIB / Core / SOS/C017 / 0 / 0 / 9 / 3
22 / Organic Synthesis and Photochemistry / Core / SOS/C018 / 3 / 0 / 0 / 3
23 / Spectroscopy and SolidState / Elective / SOS/E005 / 3 / 0 / 0 / 3
24 / Organometallic Reagents and Organic Synthesis / Elective / SOS/E006 / 3 / 0 / 0 / 3
25 / Medicinal Chemistry / Elective / SOS/E007 / 3 / 0 / 0 / 3
26 / Laboratory Course Phy.-IIIA / Core / SOS/C019 / 0 / 0 / 9 / 3
27 / Laboratory Course Phy.-IIIB / Core / SOS/C020 / 0 / 0 / 9 / 3
28 / Chemistry of Materials / Core / SOS/C021 / 3 / 0 / 0 / 3
29 / LiquidState / Elective / SOS/E008 / 3 / 0 / 0 / 3
30 / Laboratory Course-Inorg. IVA / Core / SOS/C022 / 0 / 0 / 9 / 3
31 / Laboratory Course-Inorg. IVB / Core / SOS/C023 / 0 / 0 / 9 / 3
32 / Inorganic Polymers / Core / SOS/C024 / 3 / 0 / 0 / 3
33 / Spectroscopy / Elective / SOS/E009 / 3 / 0 / 0 / 3
34 / Bioinorganic, Bioorganic, Biophysical Chemistry-II / Elective / SOS/E010 / 3 / 0 / 0 / 3
35 / Photoinorganic Chemistry / Elective / SOS/E011 / 3 / 0 / 0 / 3
36 / Environmental Chemistry / Elective / SOS/E012 / 3 / 0 / 0 / 3
37 / Laboratory Course Org.-IVA / Core / SOS/C025 / 0 / 0 / 9 / 3
38 / Laboratory Course Org.-IVB / Core / SOS/C026 / 0 / 0 / 9 / 3
39 / Natural Products / Core / SOS/C027 / 3 / 0 / 0 / 3
40 / Heterocyclic Chemistry / Elective / SOS/E013 / 3 / 0 / 0 / 3
41 / Laboratory Course Phy.-IVA / Core / SOS/C028 / 0 / 0 / 9 / 3
42 / Laboratory Course Phy.-IVB / Core / SOS/C029 / 0 / 0 / 9 / 3
43 / Advanced Quantum Chemistry / Core / SOS/C030 / 0 / 0 / 0 / 3
44 / Polymers / Elective / SOS/E014 / 3 / 0 / 0 / 3

Semester- I

SOS/C001 / Inorganic Chemistry - I / L / T / P / C / MM
3 / 0 / 0 / 3 / 100

Unit I

Stereochemistry and Bonding in Main Group Compounds

VSEPR, Walsh diagrams (tri-atomic molecules), dπ-pπ bonds, Bent rule and energetics of hybridization, some simple reactions of covalently bonded molecules.

Unit II

Metal- Ligand Equilibria in Solution

Stepwise and overall formation constants and their interaction, trends in stepwise constants, factors affecting the stability of metal complexes with reference to the nature of metal ion and ligand, chelate effect and its thermodynamic origin, determination of binary formation constants by pH-metry and spectroscopy.

Unit III

Reaction Mechanism of Transition Metal Complexes

Energy profile of a reaction, reactivity of metal complexes, inert and labile complexes, kinetic application of valence bond and crystal field theories, kinetics of octahedral substitution, acid hydrolysis, factors affecting acid hydrolysis, base hydrolysis, conjugate base mechanism, direct and indirect evidences in favour of conjugate mechanism, anation reactions without metal ligand bond cleavage. Substitution reactions in square planar complexes, the trans effect, mechanism of the substitution reaction. Redox reactions, electron transfer reactions, mechanism of one electron transfer reactions, outer and inner sphere type reactions.

Unit IV

Metal- Ligand Bonding

Limitations of crystal field theory. Jahn-Teller distortion. Evidence of covalent character in Metal-Ligand bonding. Molecular orbital theory as applied to octahedral, tetrahedral and square planar complexes.

Books suggested

  1. Advanced Inorganic Chemistry 6th Ed., F.A. Cotton and Wilkinson, John Wiley, (1999).
  2. Inorganic Chemistry, 4th Ed., J.E. Huheey, Harper & Row (2000).
  3. Chemistry of the Elements, 2nd Ed., N.N. Greenwood and A. Earnshow, Butterworth. Heinenann (1997).
  4. Inorganic Electronic Spectroscopy, 2nd Ed., A.B.P. Lever, Elsevier (1986).
  5. Magnetochemistry, R.L. Carlin, Springer Verlag, (1986).
  6. Comprehensive Coordination Chemistry Eds., G. Wilkinson, J.A.. Gillar and J.A. McCleverty, Oxford (1987).
  7. Concise Inorganic Chemistry, J.D. Lee, 5th Ed., Chapman & Hall (1996).
  8. Inorganic Chemistry, 3rd Ed., Shriver & Atkins. Oxford (1999).
  9. Inorganic Chemistry, 3rd Ed., Alan G. Sharpe, Addison-Wesley (1992).

SOS/C002 / Organic Chemistry - I / L / T / P / C / MM
3 / 0 / 0 / 3 / 100

Unit I

Nature of Bonding in Organic Molecules

Hyperconjugation, bonding in fullerenes, tautomerism.

Aromaticity in benzenoid and non benzenoid compounds, alternant and non alternant hydrocarbons. Huckel’s rule, energy level of π-molecular orbitals, annulenes, antiaromaticity, homo-aromaticity, PMO approach.

Bonds weaker than covalent, crown ether complexes and cryptands, inclusion compounds, cyclodextrin, catenanes and rotaxanes.

Unit II

Stereochemistry

Conformational analysis of cycloalkane, decalins, effect of conformation on reactivity, conformation of sugars, steric strain due to unavoidable crowding, optical purity, enantiotopic and diastereotopic atoms, groups and faces, stereospecific and stereoselective synthesis. Asymmetric synthesis, chirality due to helical shape.Stereochemistry of the compounds containing nitrogen, sulphur and phosphorus.

Unit III

Reaction Mechanism : Structure and Reactivity

Types of mechanisms, types of reactions, thermodynamic and kinetic requirements, kinetic and thermodynamic control, Hammond’s postulate, Curtin-Hammett principle. Potential energy diagrams, transition states and intermediates, methods of determining mechanisms, isotope effects.

Effect of structure on reactivity – resonance and field effects, steric effect, quantitative treatments. Hammett equation and linear free energy relationship, substituent and reaction constants. Taft equation.

Unit IV

Aliphatic Nucleophilic Substitution

SN1, SN2 and mixed SN1 and SN2 mechanism. The neighbouring group mechanism, neighbouring group participation (by π- and σ bonds). Anchimeric assistance. SN1 mechanism- Nucleophilic substitution at an allylic, aliphatic trigonal and vinylic carbon. Reactivity effects of substrate structure, attacking nucleophilic group, leaving group and reaction medium, ambident nucleophile.

Unit V

Aliphatic Electrophilic Substitution

Bimolecular mechanism- SE2 and SEi. The SE1 mechanism, electrophilic substitution accompanied by double bond shift. Effect of substrates, leaving group and the solvent polarity on the reactivity.

Books suggested

  1. Advanced Organic Chemistry, Reaction, Mechanism and Structure, Jerry March, 6th Ed., John Wiley.
  2. Advanced Organic Chemistry, Carey and Sundberg, Springer Verlag, Germany.
  3. AGuide Book to Mechanism in Organic Chemistry, Peter Sykes.
  4. Structure and Mechanism in Organic Chemistry, C.K. Ingold, CornellUniversity Press.
  5. Organic Chemistry, Boyd and Morrison, Prentice Hall of India.
  6. Modern Organic Reactions, H.O. House, Benjamin.
  7. Principles of Organic Synthesis, Norman and Coxon, Blackwell.
  8. Reaction Mechanism in Organic Chemistry, Mukherji and Singh, Macmillan.
  9. Stereochemistry of Organic Compounds, D. Nasipuri, New Age International.
  10. Stereochemistry of Organic Compounds, P.S. Kalsi, New Age International.

SOS/C003 / Physical Chemistry - I / L / T / P / C / MM
3 / 0 / 0 / 3 / 100

Unit I

Quantum Chemistry

  1. Introduction to Exact Quantum Mechanical Results

The Schrodinger equation and the postulates of quantum mechanics. Discussion of solutions of the Schrodinger equation to some model systems viz. particle in a box, the harmonic oscillator, the rigid rotor, the hydrogen atom.

  1. Approximate Methods

The variation theorem, linear variation principle,perturbation theory (first order and nondegenerate). Applications of variation method and perturbation theory to the Helium atom.

  1. Angular Momentum

Ordinary angular momentum, generalized angular momentum, eigenfunctions for angular momentum, eigenvalues of angular momentum, operator using ladder operators, addition of angular momenta, spin, antisymmetry and Pauli exclusion principle.

  1. Electronic Structure of Atoms

Electronic configuration, Russell-Saunders terms and coupling schemes, Slater-Condon parameters, term separation energies of the pπ configuration, term separation energies for the dπconfigurations, magnetic effects: spin-orbit coupling and Zeeman splitting, introduction to the methods of self-consistent field, the viral theorem.

Thermodynamics

  1. Classical Thermodynamics

Brief resume of concepts of laws thermodynamics, free energy, chemical potential and entropies. Partial molar properties: partial molar free energy, partial molar volume and partial molar heat content and their significance. Determination of these quantities.

Concept of fugacity and determination of fugacity.

Non-ideal systems: Excess functions for non-ideal solutions. Activity, activity coefficient.

Debye-Huckel theory for activity coefficient of electrolytic solutions, determination of activity and activity coefficients, ionic strength. Application of phase rule to three component systems, second order phase transitions.

Unit II

Surface Chemistry

  1. Adsorption

Surface tension, capillary actions, pressure difference across curved surface (Laplace equation), vapour pressure of droplets (Kelvin equation), Gibbs adsorption isotherm, estimation of surface area (BET equation), surface films on liquids (Electro-kinetic phenomenon), catalytic activity at surfaces.

  1. Micelles

Surface active agents, classification of surface active agents, micellization, hydrophobic interaction, critical micellar concentration (CMC), factors affecting the CMC of surfactants, counter ion binding to micelles, thermodynamics of micellization-phase separation and mass action models, solubilization, micro emulsion, reverse micelles.

  1. Macromolecules

Polymer-definition, types of polymers, electrically conducting, fire resistant, liquid crystal polymers, kinetics of polymerization, mechanism of polymerization. Molecular mass, number and mass average molecular mass, molecular mass determination (osmometry, viscometry, diffusion and, light scattering methods sedimentation), chain configuration of macromolecules, calculation of average dimensions of various chain structures.

Books suggested

  1. Physical Chemistry, P.W. Atkins, ELBS.
  2. Introduction to Quantum Chemistry, A.K. Chandra, Tata McGraw Hill.
  3. Quantum Chemistry, Ira N. Levine, Prentice Hall.
  4. Coulson’s Valence, R. McWeeny, ELBS.

5. Micelles: Theoretical and Applied Aspects, V. Moroi, Plenum.

6. Introduction to Polymer Science, V.R. Gowarikar, N.V. Vishwanathan and J, Sridhar, Wiley Eastern.

7. Chemical Kinetics, K.J. Laidler, McGraw Hill.

8. Kinetics and Mechanisms of Chemical Transformations, J. Rajaraman and J.Kuriacose, MacMillan.

SOS/C004 / Group Theory & Spectroscopy / L / T / P / C / MM
3 / 0 / 0 / 3 / 100

Unit I

Symmetry and Group Theory in Chemistry

Symmetry elements and symmetry operation, definitions of group, subgroup, relation between orders of a finite group and its subgroups, conjugacy relation and classes. Point symmetry group, Schonflies symbols, representations of groups by matrices (representation for the Cn, Cnv, Cnh, Dnh etc. group to be worked out explicitly). Character of a representation. The great orthogonalilty theorem (without proof) and its importance. Character tables and their use in spectroscopy.

Unit II

Unifying Principles

Electromagnetic radiation, interacton of electromagnetic radiation with matter. Absorption, emission, transmission, reflection, refraction, dispersion, polarization and scattering. Uncertainty relation and natural line width and natural line broadening, transition probability, result of the time dependent perturbation theory, transition moment, selection rules, intensity of special lines, Born-oppenheimer approximation, rotational, and electronic energy levels.

Unit III

Atomic Electronic Spectroscopy

Energies of atomic orbitals, vector representation of momenta and vector coupling, spectra of hydrogen atom and alkali metal atoms.

Unit IV

Microwave Spectroscopy

Classification of molecules, rigid rotor model, effect of isotopic substitution on the transition frequencies, intensities, non-rigid rotor, Stark effect, nuclear and electron spin interaction and effect of external field. Applications.

Unit V

Infrared Spectroscopy

Review of linear harmonic oscillator, vibrational energies of diatomic molecules, Zero point energy, force constant and bond strengths; anharmonicity, Morse potential energy diagram, virbration-rotation spectroscopy; P,Q,R branches. Selection rules, normal modes of vibration, group frequencies, overtones, hot bands, factors affecting the band positions and intensities, far IR region., metal-ligand vibrations.

Books Suggested

  1. Modern Spectroscopy, J.M. Hollas, John Wiley.
  2. Physical Methods for Chemistry, R.S. Drago, Saunders Company.
  3. Chemical Applications of Group Theory, F.A. Cotton.
  4. Introduction of Molecular Spectroscopy, G.M. Barrow, McGraw Hill.
  5. Basic Principles of Spectroscopy, R. Chang, McGraw Hill.
  6. Symmetry and Spectroscopy of Molecules, K. Veera Reddy, New Age International.

SOS/C005 / Laboratory Course-IA / L / T / P / C / MM
0 / 0 / 9 / 3 / 100

Note: The duration of examination will be of eight hours. Students are required to do one practical of 20

marks each from Inorganic, Organic and Physical sections. Each exercise will be 20 marks.

Viva 15 marks

Seminar/Attendance/Assessment/Record 25 marks.

Inorganic Chemistry

Qualitative Analysis

Qualitative analysis of mixture by semi-micro method containing not more than six cations and anions including:

(i). Rare-earth elements

(ii). Anions, which have not been done in under graduate practical.

(iii). Insolubles.

Organic Chemistry

Qualitative Analysis

Separation, purification and identification of compounds of binary mixture (solid-solid or liquid and solid) using TLC and Paper Chromatography, chemical tests and spectroscopic analysis.

Physical Chemistry

Chemical Kinetics

  1. Determination of the effect of (a) Change of temperature (b) Change of concentration of reactants and catalyst and (c) ionic strength of the media on the velocity constant of hydrolysis of an ester/ionic reactions.
  2. Determination of the velocity constant of hydrolysis of an ester.
  3. Determination of the rate constant for the oxidation of iodide ions by hydrogen peroxide studying the kinetics of the reaction.
  4. Flowing clock reactions (Ref: Experiments in Physical Chemistry by Showmaker).
  5. Determination of the primary salt effect on the kinetics of ionic reactions and testing of the Bronsted relationship (iodide ion is oxidized by persulphate ion).

SOS/C006 / Laboratory Course-IB / L / T / P / C / MM
0 / 0 / 9 / 3 / 100

Note: The duration of examination will be of eight hours. Students are required to do one practical each

from Inorganic, Organic and Physical sections. Each exercise will be 20 marks.

Viva 15 marks

Seminar/Attendance/Assessment/Record 25 marks.

Inorganic Chemistry

Chromatography

Separation of cations and anions by-

Paper Chromatography

Thin Layer Chromatography

Ion Exchange Chromatography

Organic Chemistry

Organic Synthesis

Acetylation: Acetylation

Oxidation: Adipic acid by chromic acid oxidation of cyclohexanol.

Grignard reaction: Synthesis of triphenylmethanol from benzoic acid.

Sandmeyer reaction: p-Chlorotoluene from p-toluene

Physical Chemistry

Electrochemistry

Conductometry

  1. Determination of the velocity constant, order of the reaction and energy of activation for saponification of ethyl acetate by sodium hydroxide conductometrically.
  2. Determination of solubility and solubility product of sparingly soluble salts (e.g., PbSO4, BaSO4) conductometrically.
  3. Determination of the strength of strong and weak acids in a given mixture conductometrically.
  4. To study the effect of solvent on the conductance of AgNO3/CH3COOH and to determine the degree of dissociation and equilibrium constant in different solvents and in their mixtures (DMSO, DMF, dioxane, acetone, water) and to test the validity of Debye-Huckel-Onsager theory.
  5. Determination of the activity coefficient of zinc ions in the solution of 0.002 M zinc sulphate using Debye Huckel’s limiting law.

Semester- II

SOS/C007 / Inorganic Chemistry - II / L / T / P / C / MM
3 / 0 / 0 / 3 / 100

Unit I

Electronic Spectra Magnetic Properties of Transaction Metal Complexes

Energy levels in an atom. Determination of ground state terms. Hund’s rules. Hole formulation. Laporte Orbital selection rule, splitting of electronic energy levels and spectroscopic states (d1-d9 states), Orgel and Tanabe-Sugano diagrams. Calculations of Dq, B and Beta parameters. Charge transfer spectra.

Magnetic moments, magnetic exchange coupling and spin crossover.

Unit II

Metal-π-Complexes

Important reactions, preparation, bonding and structure of metal carbonyls, metal nitrosyls and dinitrogen complexes. Vibrational spectra of metal carbonyls and nitrosyls for bonding and structure elucidation.

Tertiary phosphine as ligand.

Unit III

Metal Clusters

Higher boranes, structure and bonding in boranes. Wade’s rules. Reations of boranes. Polyhedral borane anions and carboranes. Metal complexes of carboranes and boranes. Metal carbonyl and halide clusters. Metal carbonyl hydrides.

Unit IV

Silicates

Classification and structure. Asbestos and zeolites. Silicates in technology.

Books suggested

1Advanced Inorganic Chemistry 6th Ed., F.A. Cotton and Wilkinson, John Wiley, (1999).

2Inorganic Chemistry, 4th Ed., J.E. Huheey, Harper & Row (2000).

3Chemistry of the Elements, 2nd Ed., N.N. Greenwood and A. Earnshaw, Butterworth. Heinemann (1997).

4Inorganic Electronic Spectroscopy, 2nd Ed., A.B.P. Lever, Elsevier (1986).

5Magnetochemistry, R.L. Carlin, Springer Verlag (1986).

6Comprehensive Coordination Chemistry Eds., G. Wilkinson, R.D. Gillars and J.A. McCleverty, Pergamon (1987).

7Concise Inorganic Chemistry, J.D. Lee, 5th Ed., Chapman & Hall (1996).

8Inorganic Chemistry, 3rd Ed., Shriver & Atkins,Oxford (1999).

9Inorganic Chemistry, 3rd Ed., Alan G. Sharpe, Addison-Wesley (1992).

SOS/C008 / Organic Chemistry - II / L / T / P / C / MM
3 / 0 / 0 / 3 / 100

Unit I

Aromatic Electrophilic Substitution

Orientation and reactivity, energy profile diagrams. The ortho/para ratio, ipso attack, orientation in other ring systems. Quantitative treatment of reactivity in substrate and electrophiles. Diazonium coupling, Vilsmeir Haak reaction, Gattermann-Koch reaction.

Unit II

Aromatic Nuecleophilic Substitution

The SNAr, SN1, benzyne and SRN1 mechanisms. Reactivity- effect of substrate structure, leaving group and attacking nucleopile. The von Rictor, Sommelet-Hauser, and Smiles rearrangements.

Unit III

Free Radical Reactions

Types of free radical reactions, free radical substitution mechanism, mechanism of an aromatic substrate, neighboring group assistance. Reactivity for aliphatic and aromatic substrates at a bridgehead. Reactivity in the attacking radicals. The effect of solvents on reactivity.

Allylic halogenation (NBS), oxidation of aldehydes to carboxylic acids, auto-oxidation, coupling of alkynes and arylation of aromatic compounds by diazonium salts. Sandmeyer reaction. Free radical rearrangement. Hunsdiecker reaction.