| FIRST SEMESTER
C101: INORGANIC CHEMISTRY-I
(Chemical Bonding and chemistry of the main Group Elements)
I Chemical Bonding 55 hrs
A. Periodic properties of elements, oxidation numbers, octet rule, concepts of resonance and
hybridization. VSEPR model, shapes of molecules; Electro negativity and partial ionic character;
Bonds: covalent, coordinate multicentre and quadruple: Hydrogen bond-types and detection,
agnostic bond, intermolecular forces, metallic bond. 10 hrs
B. Lattice energy, Born-Lande equation, Fajans rules, Slaters rules, radius-ratio rules, structures of
simple solids, MO Theory: and molecular orbitals, MOs of diatomic molecular orbitals, MOsof diatomic molecules, electron angular momentum, classification of states, MO calculations, SCF
Theory, Huckel method, MO diagram of AH2 and AX2 systems, Walsh diagrams. 12 hrs
II Chemistry of the Main Group Elements
Periodicity and general trends in properties, polymorphism of carbon, phosphorous and sulphur; properties, structure and bonding in boranes, carboranes, borazines, phosphazenes, phosponitrilic compounds, sulphur-nitrogen compounds, oxyacids of nitrogen, phosphorous, sulphur and halogens; noble gas compounds. [
11 hrs ]
Silicates-classification and structures, isomorphous replacement, pyroxenes, layered and vitreous silicates, silicate glasses, borosilicate glasses, glass ceramics, silica gel, zeolites and molecular sieves, condensed phosphates, polyhalides.[
12 hrs ]
Solvent system: Bronsted and Lawis acids and bases, pH and pKa, HSAB concept, acid-base concept in
non-aqueous media, leveling effect, super acids, reactions in BF3, N2O4.[
6 hrs ]
III Isopoly and heteropoly acids and their salts. [
4hrs ]
C102: ORGANIC CHEMISTRY-I
[55 hrs]
I Nature of Bonding in Organic Molecules
Delocalized chemical bonding: conjugation, cross conjugation, resonance, hyper conjugation, bonding in fullerenes, Tautomerism. Aromaticity in benzenoid and non-benzenoid compounds, alternant and non-alternant hydrocarbons, Huckel's rule, energy level of - -molecular orbitals, annulenes, antiaromaticity, homo-aromaticity. Bonds weaker than covalent bonds: addition compounds, crown ether complexes and cryptands, inclusion compounds, cyclodextrins, catenanes and rotaxanes.
10 hrs
II Reaction Mechanisms: Structure and Reactivity
Types of mechanism,types of reactions, thermodynamic and kinetic requirements, kinetics and thermodynamic control, Hammond's postulates, Curtin-Hammett principle. Potential energy diagrams, transition states and intermediates, methods of determining mechanisms, isotope effects, hard and soft acids and bases. Generation, structure, stability and reactive of carbocations, carbonions, free radicals, carbenes and nitrenes. Effect of structure on reactivity-resonance and fields effects, steric effects. The Hammett equation and linear free energy relationship, substituent and reaction constants. Taft equation.
Nucleophilic substitution reaction at a saturated carbon: Limiting cases of SN1, SN2 and SNi mechanism. Nucleophilicity, leaving group effects, ambident nucleophiles and substrates. [
13 hrs ]
III Stereochemistry
Conformational analysis of acyclic (ethane, propane, n-butane and 1, 2, disubstituted ethanes) and cyclic alkanes(mono-methyl, isopropyl, tert-butyl and di-substituted cyclohexanes e.g., dialkyl, dihalo, diols). Optical isomerism. Fischer, Newman and sawhose projection and their interconversions. Elements of symmetry and chirality D-L and R-S convertion. Method of resolution of optical isomers. Prochirality:Enantiotopic and diadtereotopic groups and faces. Geometrical isomerism in acyclic, cyclic, condensed and bridged ring systems. Cis-trans and E-Z conventions. Methods of interconversion of E and Z isomers. [
10 hrs ]
IV Heterocyclic compounds
Structure, reactivity, synthesis and reactions of pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole and pyrimine. [
7 hrs ]
V Natural Colouring Compounds
Anthocyanins: Methods of isolation, basic structural features of coumarins, chromones, flavones and isoflavones. Structural elicidation and synthesis of quercetin and wedelolactone Carotenoids: Mothods of isolation. Structure elucidation and synthesis of β-carotene. Structural relationship of isolation. Structure elucidation and synthesis of β-carotene. Structural relationship of β and γ – carotenes. 8 hrs
VI Carbohydrates
Determination of configuration of the monosaccharides. Conformational analysis of glucose and galactose. Structure elucidation of maltose and sucrose. Structure of starch and cellulose.
7 hrs
C 103:PHYSICAL CHEMISTRY-I 55 hrs
I Quantum Chemistry
Introduction to Exact Quantum Mechanical Results
The Schrodinger equation and the postulates of quantum mechanics. Discussion of solution of the Schroding equation to some system viz., particle in a box, the harmonic oscillator, the rigid, the hydrogen atom. [
10 hrs ]
Approximate methods
The variation theorem, linear variation principle, perturbation theory( first order and non degenerate). Applications of variation method and perturbation theory to the helium atom [
4 hrs ]
Angular momentum
Ordinary angular momentum, generalized angular momentum, eigen function for angular
momentum, addition of angular momenta, spin anti symmetry and pauli exclusion principle [5 hrs]
Electronic structure of atoms
Electronic configurations, Russel- Saunders terms and coupling schemes, term separation
energies of the Pn configurations term separation energies for the dn configurations., magnetic
effects : spin – orbit coupling and zeeman splitting , introduction to methods of self- consistent field. [6 hrs]
Molecular orbital theory
Huckel theory of conjugated systems, bond orders and charge density calculations.
Applications to ethylene, butadiene, cyclopropenyl radiacal radical cyclobutadiene etc.
introduction to extended Huckel theory. [5 hrs]
II Thermodynamics
A. Classical themodynamics
Brief resume of concept of laws of thermodynamics, free energy, chemical potential and entropies. Partial molar properties: partial molar free energies: Partial molar volume and Partial molar heat content and their significance. Determination of these quantities, concepts of fugacity and determination of fugacity. Non – ideal systems: excess functions of non- ideal solutions. Activity, activity coefficients, determination of activity coeffiecients : ionic strength. Application of phase rule two three component systems
B. Statistical Theromodynamics
Concepts of distribution, thermodynamic probability and most probabile distribution, Ensemble averaging, postulates of ensemble of ensemble averageing. Canonical, grand canonical and micro canonical ensembles. Corresponding distribution laws(using Language s method of undetermined multipliers). Partition functions-translational, rotational, vibrational and electronic partition functions, calculation of the thermodynamic properties in terms of partition functions. Applications of partition functions. Heat capacity behaviour of solids-chemical equilibrium and equilibrium constant in term of partition functions, Fermi-Dirac statistics, distribution law and applications to metal. BoseEinstein statistics – distribution law and application to helium. 10 hrs
C. Non Equilibrium Thermodynamics
Thermodynamic criteria for non-equilibrium states, entropy production and entropy flow, entropy balance equation for different irreversible process (e.g., heat flow, chemical reaction etc.) transformations of the generalized fluxes and forces, non equilibrium stationary states, phenomenological equations, microscopic reversibility and Onsager's reciprocity relations. 5 hrs
C 104: MATHEMATICS FOR CHEMISTS AND COMPUTER
APPLICATION IN CHEMISTRY
PART-A Mathematics for Chemists 55 hrs
I Vectors and Matrix Algebra
A. Vectors
Vectors, dot, cross and triple products etc. The gradient, divergence and cult. Vector calculus, Gruss' theorem, divergence theorem etc. Matrix Algebra Addition and multiplications; inverse, adjoint and transpose of matrices, special matrices (Symmertric, skew-symmetric, Hermitian, skew-Hermitian, unit, diagonal, unitary etc.) And their properties. Martrix equations: Homogeneous, non-homogeneous linear equations and
conditions for the solution, linear dependence and independence introduction to vector spaces,
matrix eigen values and eigen vectors, diagonalization, determinants( examples from Huckel
theory). Introduction to tensors: polarizability and magnetic succeptibility as exmples 10 hrs
II Differential calculus
Functions continuity and differentiability, rules for differentiation, application differential calculus including maxima and minima ( examples related to maximally populated rotational energy levels, Bohr's radius and most probable velocity from Maxwells distribution etc), exact and inexact differentials with their application to thermodynamic properties, integral calculus, basic rules for integration, integration by parts, partial fraction and substitution. Reduction formula, application of integral calculus. Function of several variables, partial differentiation, co ordinate transformation ( eg. cartesian to spherical polar), curve sketching. 10 hrs
III Elementary differential equation
Variables- separable and exact first order differential equation, homogeneous, exact and linear equations. Applications to chemical kinetics. Secular equillibria, quantum chemistry etc. solution of different equations by the power series method, Fourier series, solutions of harmonic oscillator and Legendre equation etc, spherical harmonics , second order differential equations and their solutions 7 hrs
IV Permutations and probability
Permutation and combinations, probability and probability theorems , probability curves average , root mean square and most probable errors, examples form the kinetic theory etc. curve fitting (including least square fit etc.) with a general polynomial fit. 3 hrs
C105 AND C 106: PRACTICALS (4.5 hrs per day; 4 days per week)
Inorganic Chemistry Practical-I
I. Semi-micro qualitative analysis mixtures containg two each of common cations and anions and one of the following less familiar elements: W, Mo, Ce. Th, Zr, V, U and Li.
II. Preparation and quantitative analysis of inorganic complexes:
1. Ferrous oxalate.
2. Potassium trioxalatoferrate(lll)trihydrate.
3. Haxammine cobalt (lll) chloride.
4. Cis and trans-potassium dioxalatodiaquochromium(lll).
Inorganic Chemistry Practical-II
Gravimetric determination of Fe an iron ore as Fe2O3.
Volumetric/redox and gravimetric determination of the following mixtures:
A) Copper and nickel.
B) Copper and iron.
C) Copper and Zinc.
Analysis of alloys:
A) German silver.
B) Steel.
C) Solder.
Colorimetric determination of nickel and bismuth.
Organic Chemistry Practical - I
I Preparation (One stage)
Cannizarro reaction: Benzaldehyde.
Fries rearrangement: Phenyl acetate.
Friedel-Crafts reaction: Benzene and Acetyl chloride.
Claisen-Schmidt reaction: Acetophenone and Benzaldehyde.
Sandmeyer reaction: p-Chlorotoluene and Benzaldehyde.
Pechmann reaction: Resorcinol and ethlacetoacetate.
Oxidation of Cyclohexanol.
Preparation of S-benzylisothiuronium chloride.
II Qualitative analysis
Systematic analysis and identification of organic compounds.
Organic Chemistry Practical – II
I Preparation (Two and three stages)
Preparation of the following compounds:
P-Nitroaniline from aniline.
p-Bromoaniline from acetanilide.
m-Nitrobenzoic acid from methylbenzoate.
Anthranilic acide from phthalic acid.
2,4-Dinitrophenylhydrazine from chloronitrobenzene.
Anthrone from anthracene.
Benzanilide from benzophenone.
Benzilic acid from benzoin.
II Quantitative analysis
Determination of equivalent weight of carboxylic acids.
Saponification value of an oil.
Estimation of keto group.
Estimation of glucose.
Estimation of amines\ phenols by acylation method.
Iodine value of an oil.
Physical Chemistry Practical-I
I Chemical Kinetics:
Determination of the velocity constant, catalytic coefficient, temperature coefficient and energy of activation and Arrhenius parameters for the acid hydrolysis of methyl acetate.
Evaluation of Arrhenius parameters for the reaction between potassium persulphate and potassium iodide(lorder).
Velocity constant for the saponification of ethlacetate.
Determination of the order of reaction between hydrogen peroxide and potassium iodide-(clock reaction).
Kinetics of reaction between K2S2O8-Kl. (salt effect).
II Colorimetry:
Test for the validity of Beer – Lambert law and determination of the unknown concentration of solution. Calculation of molar extinction coefficient. Titration of ferrous ammonium sulfate with potassium permanganate colorimetrically. Simultaneous estimation of Mn and Cr in a solution of KMnO4 and K2Cr2O7.
Kinetics of reaction between K2S2O8 – Kl colorimetrically.
III Cryoscopy
Determination of molecular weight of a solute by cryoscopy.
Determination of degree of dissociation of an electrolyte and association of benzoic acid in benzene.
IV Partial Model Volume
Determination of partial modal volume of ethanol by reciprocal density method. Determination of PMV by apparent molar volume method, NaCl –H2o system. Molecular weight of a polymer using Schrodinger equation (Poly vinyl alcohol) by Viscosity method.
Physical Chemistry Practical –II I Conductivity
Determination of the solubility of sparing soluble salt.
Titration of mixture of strong and weak acid against strong base.
Titration of weak acid against weak base.
Titration of mixture of strong acid, weak acid and salt (copper sulfate) against strong base.
Precipitation titration : Llithium sulfate against barium chloride.
Potentiomentry
Determination of single electrode potential of Cu2+/Cu and Zn2+/Zn and testing the validity of Nernst equation.
Determination of pH of buffers by using quinhydrone electrode and comparison of the pH values obtained with glass electrode.
Titration of ferrous ammonium sulfate against potassium dichromate calculation of formal redox potential of Fe3+/Fe2+.
Titration of potassium iodide against potassium permanganate.
Titration of silver nitrate against potassium chloride, calculation of solubility product of siliver chloride.
Titration of weak acid against a strong base using quinhydrone electrode and calculation of pKa value of the weak acid.
Titration of a mixture of HCI and CH3COOH potentiometrically and determination of the composition of the mixture.
Dissociation constant of weak electrolyte(weak base – NH4OH; weak acid CH3COOH).Onsager's equation, determination of λ0 of an electrolyte.
SECOND SEMESTER
C201: INORGANIC CHEMISTRY-II (CO-ORDINATION CHEMISTRY)
55 hrs
I Metal –Ligand Equilibrian in solution
Step-wise and overall formation constants and their relationship, trends in step-wise constants, kinetic and thermodynamic stability of metal complexes, factors affecting the stability of metal complexes with reference to the nature of the metal ion and ligand, chelate and macro cyclic effects and their thermodynamic orgin, determination of ligand, chelate and macrocyclic effect and their thermodynamic origin, determination of binary formation constant by pH-metry and spectrophotometry.
10 hrs
II Metal –Ligand Banding
Crystal field theory-limitations, stereochemistry, coordination Nos, 3 to 8 , Evidences for metal –ligand orbital overlap, MOtheory (including II-bonding), Jahn-Teller distortion in metal complexes and metal chelates, spectrochemical series, nephelauxetic series, angular overlap model. 10 hrs
III Structure and Bonding –Hydride, dihydrogen, isocyanide, simple metal carbonyl, Nitrosyl, dinitrogen, dixygen and tertiary phosphine complexes, metal complexes as liquid crystals, stereochemical non-rigidity, self assembly in supramolecular chemistry; Stereoisomerism-chirality, optical activity, CD,ORD Cotton effect and magnetic circular dichroism, absolute configurations. 15 hrs
IV Electronic Spectra of Transition Metal Complexes Spectroscopic ground states, selection rules, term symbols for dn ions, Racah parameters, Orgel, correlation and Tanabe-Sugano diagrams, spectra of 3d metal aqua complexes of trivalent V, Cr, divalent Mn, Co and Ni, [CoCI4]2-, calculation of Dq, B and β parameters, charge transfer spectra. 12 hrs
V Magnetic Properties of Metal Complexes
Magnetic susceptibility, types of magnetic behaviour, diamagnetic corrections, orbital contribution, spin-orbit coupling, ferro and antiferromagnetic coupling, ferro and antiferromagnetic, coupling, spin crossover.
8 hrs
C202 ORGANIC CHEMISTRY II 55 hrs
I Aromatic Substitution Reactions
Electrophilic Substitution Reactions: The arenium ion mechanism, orientation and reactivity, energy profile diagrams. The ortho/para ratio, ipso attack, aorientation in other ring systems. Quantitative treatment of reactivity in substrates and electrophiles. Diazonium coupling, Vilsmeir reaction, Gattermann-Koch reaction.
6 hrs
II Addition Reactions
Additions to carbon –crabon multiple bonds: mechanistic and stereochemical aspectsOf addition reactions involving electrophiles, nucleophiles and free radicals.
Regiostereo- and chemoselectivity, orientation and reactivity. Addition to cyclopropane
Ring. Hydrogenation of double and triple bonds, hydrogenation of aromatic rings.
Hydrogenation. Michale reaction. Sharpless asymmetric epoxidation.
7 hrs
Addition to carbon- heteroatom multiple bonds: mechanism of metal hydride reduction
Of saturated and unsaturated carbonl compounds, acids, esters and nitriles. Addition
Of Grignard reagents, organozinc and organolithium regents to carbonyl compounds and unsaturated compounds. Addition of water and formation of acetals, ketals, oximes and hydrazones from carbonyl compounds. Witting reaction. Mechanism of condensation reactions involving enolates, Aldol, Knoevenagel, Claisen, Mannich, Benzoin, Perkin and Stobbe reactions. Hydrolysis of easter and amides, ammonolysis of esters.
7hrs
III Elimination Reactions
The E2, E1 and E1cB mechanism and their spectrum. Orientation of the double bond. Reactivity-effect of substrate structure, attacking base, the leaving group and the medium. Mechanism and orientation in pyrolytic elimination.
5hrs
IV Rearrangements
Pinacol-pinacolone, Wagner-Meerwein, Fries, Wolff, Hofmann, Curtius, Lossen, Schmidt and Backmann rearrangements.
5 hrs
V Lipids
Introduction, isolation and properties of lipids. Oils and fats: Hydrogenation, iodine value, saponification value and auto-oxidation of oil and fats. Phospholipids: Synthesis of lecithins, cephalins and phosphatidyl serine. Sphingolipids: Synthesis of sphingosine, sphingomyelin and cerebrocides.
7 hrs
VI Amino acids and Peptides
Classification, general methods of preparation, properties and reaction of amino acids. General idea of the peptide linkage and primary structure of proteins.
7 hrs
VII Nucleic acids
Purine and pyrimidine bases: Structure and synthesis of nucleosides and nucleotides. Structure of nucleic acids and biosynthesis of proteins.
6 hrs
C203: Physical Chemistry-II 55 hrs
I Chemical Dynamics
Methods of determining rate laws, collision theory of reaction rates, steric factor, activated complex theory, Arrhenius equation and the activated complex theory; ionic reactions, kinetic salt effects, steady state kinetics and thermodynamic control of reactions, treatment of unimolecular reactions.Dynamic chain (hydrogen-bromine reaction, pyrolysis of acetaldehyde, decomposition of ethane), photochemical (hydrogen-bromine and hydrogen-chlorine reactions) and oscillary reactions (Belousov-Zhabotinsky reaction), homogeneous catalysis, knitics of enzyme reaction, general features of fast reaction, study of fast reaction by flow method, relaxation method, flash photosis and the nuclear magnetic resonance method, dynamic of molecular motions, probing the transition state, dynamics of barrierless chemical reactions in solutions, synamics of unimolecular reactions(Lindemann-Hinhshelwood and Rice-Ramsperger-Kassel-Marcus{RRKM} theories of unimolecular reactions).
II Surface Chemistry
A) Adsorption
Surface tension, capillary action, pressure difference across curved surface (Laplace equation), vapour pressure of droplets (Kelvin equation), Gibbs adsorption isotherm, estimation of surface area (BET equation), surface film on liquids(Electro-Kinetic phenomenon), catalytic activity at surfaces. Statistical of Chemisorption, Surface acidity and basicity determination.
B) Micelles
Surface active agents, classification of surfaceactive, Micelization, hydrophobic intraction, critical; micellar concentration (CMC), factors affecting the CMC of surfactants, counter ino binding to micelles, thermodynamics of micellization –Phase separation and mass action models solubillzation, micro emulsion, reverse micelles. 15 hrs
III Electrochemistry
Electrochemistry of solution. Debye-Huckel-onsager treatment and its extension to ion solvent interactions. Debye –Huckel-Bjerrum mode. Thermodynamics of electrified interface equations. Derivation of electro – capillary, Lippmann equations (surface excess), methods of determination. Structure of electrified interfaces, Guoy – Chapmann, stern, Graham – Devanthan – Mottwatts, Tobin, Bockris, Devanthan models. Tafel Plot, Quantum aspects current density, derivation of butler – Vol mer equation. Tafel Plot. Quantum aspects of charge transfer at electrodes – solution interfaces, structure of double layer interfaces. Effect of light at semiconductor solution interface. Electrocatalysis – with respect to hydrogen evolution reaction, influence of various parameters. Hydrogen electode.
C204: SPECTROSCOPY-I
55 hrs
I Symmetry and Group Theory in Chemistry
Definition of groups, subgroups, cyclic groups, conjugate relationships, classes, simple theorems in group theory. Symmetry elements and symmetry operations, point groups, Shoenflies notations, representations of groups by matrices, reducible and irreducible representations, character of representations, Great Orthogonality Theorem (without proof) and its applications, character tables of Cn, Cnv, Cnh, Dnh etc., group (to be worked out explicity). Muliken symbols fo irreducible representations. Direct products, Applications of group theory to quantum mechanics identifying non-zero matrix elements, derivation of the orthonormalization conditions.
14 hrs
II Unifying Principles
Interaction of electromagnetic radiation with matter: time – dependent perturbation theory, transition moment integral, and selection rules – symmetry and spin forbidden transitions. 3 hrs
III Microwave Spectroscopy
Rotations of molecules, rigid diatomic moloecule-rotatinal energy expression, energy level diagram, rotational wave functions and their symmetry, selection rules, expression for the energies of spectral lines, computation of intensities, effect of isotopic substitution, centrifugal distortion and the spectrum of a non-rigid rotor. Rotational spectra of polyatomic molecules – linear, symmetric top and asymmetric top molecules. Stark effect, technique and instrumentation. 6 hrs
IV Infrared Spectroscopy
Vibration of molecules harmonic and harmonic oscillators vibrational energy expression energy level diagram, vibrational wave functions and their symmetry, selection rule, expression for the energies of spectral lines, computation of intensities, hot bands, effect of isotopic substitution. Diatomic vibrating rotor, Born – Oppenheimer approximation, Vibrational-rational spectra of diatomic molecules, P,Q and R branches, breakdown of the Born-Oppenheimer approximation. Vibration of polyatomic molecules: Normal Coorinates, translations, vibrations and rotations, vibrational energy levels and wave functions, fundamentals, overtones and combinational. Vibration-rotation spectra of polyatomic molecules-parallel and perpendicular vibrations of linear and symmetric top molecules, Techniques and instrumentation, FTIR. 12 hrs
V Raman Spectroscopy
Classical theory of the Raman effect, polarizability as a tensor, polarizability ellipsoids,quantum theory of the Raman effect, Pure rotational Raman spectra of linear and asymmetric top molecules, vibrational Raman spectra, Raman activity of vibration rule of mutual exclusion, rotational fine structure –O and S branches, polarization of Raman scattered photons. Structure determination from Raman and IR spectroscopy – AB2 and AB3 molecules, Techniques and instruments. 7 hrs
.
VI Electronic Spectroscopy
Born – Oppenheimer approximation, vibrational coarse structure intensities by Frank condom principle, Dissociation energy rotational fine structure, Fortat diagram , pre dissociation. Electronic structure of diatomic molecules – basic results of Mo theory classification of states by electronic angular momentum, selection rules spectrum of singlet and triplet molecular hydrogen. Electronic spectra of polyatomic molecule- localized Mos spectrum of HCHO, change of shape on excitation. Decay of excited states –n radiative ( fluorescence and phosphorescence) and non-radiative decay internal conversion. 13 hrs
C 205 AND 206
PRACTICALS
(4.5 hrs per day; 4 days per week)
Inorganic chemistry Practical –I and II . Organic Chemistry Practical-I and II
Physical Chemistry Practical –I and II Experiments are in First Semester. Every students will carry out experiments in each of the branches of Chemistry on a rotation basis from First to Third semesters.
C 301 OC – ORGANIC REACTION MECHANISMS 55 hrs
I. Aliphatic nucleophilic and electrophilic substitution reaction
Nucleophilic substitution reactions: Substitution at allylic and trional carbon atoms. Hydrolysis of easters, use of DCC in the formation of anhydrides. Neighbouring group participation.
Electrophilic substitution reactions: SE2,SE1 and SEi mechanism. Hydrogen, exchange, migration of double bonds, halogenation of aldehydes, ketones, acids. Aliphatic diazonium coupling nitrosation at carbon and nitrogen, diazo transfer reaction, carbine and nitrene insertion, decarboxylation of aliphatic acids, haloform reaction, Hauller-Bauer reaction.
11 hrs
II Free – radical chemistry Types of free radical reaction, free radical substitution mechanism, at an aromatic substrate, neighbouring group assistance. Reactivity in the attacking radicals. The effect of solvents on reactivity.
Allylic halogenation (NBS) oxidation of aldehydes to acids, auto-oxidation, coupling of alkynes. Sandmeyer reaction, Free radiacal rearrangement. Hunsdiecker reaction. 14 hrs
III Photochemistry
General consideration: activation in thermal and photo chemial reactions. Light absorption and excitation, singlet and triplet states. Morse curve Franck condom principle
Deexcitation: physical process, Jablonski diagram. Photo sensitization ( donor
Acceptor concept, resonance and collision transfer) chemical process, quantum efficiency, quantum and chemical yields.
Photochemistry of functional groups:
(i)Olefins Cis – trans isomerism, [2+2] cycloaddition, rearrangements. Reaction of conjugated olefins: di-π-methane rearrangement (ii)Ketones : excitesd of C=O. Norrish type –I and Type –II clevages. Paterno Buchi reaction .α, β-unsaturated ketones. , [2+2] addition, cis-trans isomerisation. Rearrangements of cyclohexadienones.
(iii)Aromatic compounds: Photorearrangement of benzene and its derivatives cycloadditon of benzene.
(iv)Photochemical oxidations and reductions: cycloaddition of singlet molecular oxygen. Oxidative coupling of aromatic compounds, photoreduction by hydrogen absorptions. 13 hrs
IV. Pericyclic reactions
Molecular orbital symmetry, frontier orbitals of ethylene , 1,3 –buutadiene , 1,3,5-hexatriene and allyl system. Classificatiobn of pericyclic reactions. Woodward – Hoffmann correlation diagrams. FMO and PMO approach. Electrocyclic reactions –conrotatory and disrotatory motions: 4n, 4n+2 and allyl systems. Cyclo addition – antarafacial and suprafacial additions, [2+2] addition of ketenes, 1,3 –dipolar cycloadditions and cheleotropic reactions.
Sigma tropic rearrangements – antarafacial and suprafacial shifts of H sigma tropic shifts involving carbon moieties, [3,3] and [5,5]- sigmatropic rearrangements, Claisen, Cope and aza –copre rearrangemets. 10 hrs
V. Biochemical mechanisms
Introductionthe mechanism role of the following in livin systems .
i) thiamine pyrophosphate (TPP) in non oxidative and oxidative decarboxylation of α- ketoacid and in the formation of α-ketols.ii) Pyroxidal phosphate (PLP) ion transamination, decarboxylation, dealdolisation and elimination reactions of amino acids.
iii) Lipoic acid in the transfer of acyl group and redox reactions.
iv) Coenzyme A in the transfer of acyl group.
v) Biotin in the carboxylation reactions
vi) Tetra hydrofolic acid (H4F) in one carbon transfer reactions.
vii) Vitamin B12 coenzyme in molecular rearrangement reactions, in the synthesis of methionine and methane.
viii) Nicotinamide and flavin coenzymes in biological redox reactions.
[7hrs]
C302 OC ORGANIC SYNTHESIS [ 55 hrs ]
I. C-C and C-N bond forming reactions [
14 hrs ]
Friedel Crafts reaction, Diels-Alder reaction, Chichibabin reaction, Darzens's reaction. Use of acetylides in C-C bond formation reactions. Acid-catalyzed self condensation of olefins, Skraup synthesis, Prins reaction, Shaipro reaction, Dieckmann cyclisation. Reformatsky reaction, Robinson annulation, Hofmann-Loeffler-Freytag reaction.
Stoke enamine synthsis. Meyer synthesis. Use of nucleophilic nitrogen and electrophilic carbon, electrophilic nitrogen and nucleophilic carbon (NH3, amines and nitrite as nucleophiles in substitution, NH3 and amines in addition in addition to ketones and aldehydes) and electrophilic nitrogen and nucleophilic carbon (nitration, nitrosation, diazonium couping) for the bond formation reaction.
II. Reagents in oraganic synthesis 12 hrs
Use of the following in organic synthesis and functional group transformations. LDA, DCC, DDQ, TMS- iodide, TMS- cyanide , TBDMS- chloride . 1,3- Dithiane ( reactivity and umpolung) Merrified resin, Baker's yeast, phase –transfer catalysis Woodward and provost hydroxylation, Peterson reaction.
III Oxidations
CrO3, K2Cr2O7, KMnO4, OsO4, SeO2, Pb(OAc)4, HIO4, OXYGEN (singlet & triplet), ozone, peroxides and peracids as oxidizing agents. Oppenauer oxidation.
IV Reduction 8 hrs
Complex metal hydrides, dissolving metal reductions, diimide reduction, catalytic hydrogenation( homogeneous and heterogeneous), use of tri-n-butyltin hydride organoboranes as reducing agents. Meerwein-Ponndorf-Vereley, Wolff_ kishner and Clemmensen reductions.
V Molecular rearrangements 13 hrs
Benzyl-benzillic acid, Favorskii, Fries , Woiff rearrangements& Arndt – Eistert reaction, Sommelet- Hauser, Smiles rearrangements. Baeyer- Villiger oxidation, Tiffeneau Demjanov reaction, rearrangement of amino ketones, Firtsch-Buttenberg_Wiechell,Neber, Stevens and Wittig rearrangements. Mechanism of Fischer indole synthesis and benzidine rearrangements.
C303 OC –Chemistry of natural productsI. Terpenoids 13 hrs
Classification, nomenclature occurrence, isolation, isoprene rule. Structure elucidation, synthesis and biosynthesis of the following terpenoids. Monoterpenoids: geraniol, menthol, α –pinene, camphor and camphene. Sesquiterpenoids: farnesol, zingeberene, β-caryophyllene, α-santonin. Diterpenoids: abietic acid and gibberrillic acid (synthesis not required) Triterpenoids: squalene-cyclisation of squalene into α-lanosterol nd friedelene.
II. Steroids 13 hrs
Occurrence, nomwnclature, basic skelton, diels hydrocarbon and stereo chemistry, isolation, structure and structural elucidation of sterols and bile acids. Synthesis of chloestrol, estrone, progesterone androsterone ,testosterone and aldosterone. Marker degradation and brief discussion of homosteriods and norsteroids, oral contraceptive, Synthesis of (dl)-norgestrel and ethinyl oestradiol.
III. Alkaloids 13 hrs
Definition, normenclature, occurrence, isolation, classification, general methods of structure elucidation.
Structure elucidation., synthesis and biosynthesis of the following alkaloids.
Ephedrine, hygrine, coniine, nicotine, cocaine, cinchonine, papaverine, morphine, ergotamine and colchicines.
Photochemical synthesis of corydaline, tylophorine and nuciferine.
IV. Porphyrins and vitamins B12 5 hrs
Structure and synthesis of haemin, chlorophyll-a and vitamin-B12.
V. Prostaglandins 6 hrs
Instruction , norenclature, classification and biological role of prostaglandins. Structure elucidation and stereochemistry of PGE1, PGE2 and PGE3. synthesis of PGE1, by Corey, Stork and Upjohn's approach.
VI. Insect Pheromones 5hrs
Introduction, Classification. Pheromones in pest control. Synthesis of
i) Grandisol (component of bollweevil pheromone)
ii) Farenal (trail pheromone of pharaoh's ants)iii) Brevicomin (pheromone from Dendroitis brevicomis)
iv) (+)-disparlure (gypsy moth sex pheromone).
v) 3,11-dimethy1-2-nonacosanone).
vi) Bombykol.
vii) Multistriatin.
C304 SPECTROSCOPY-II
(Common to inorganic, Organic and Physical Chemistry)
55 hrs
I. C304Spectroscopy-II
I Ultraviolet and visible spectroscopy 8 hrs
Varoius electronic transisitions (185-800nm), Beer- lambert law, effect of solvent on electronic transistions, ultra violet bands for carbonyl compounds, unsaturated carbonyl compounds, dienes, conjugated polyenes, Wood ward – Fischere rules for conjugated dienes and carbonyl compounds, ultraviolet spectra of aromatic compounds, Steric effecting biphenyls.
II Infra red spectroscopy 8 hrs
Characterstic vibrational frequencies of alkanes, alkenes, alkynes, aromatic compounds alcohols, ethers, phenols and amines. Detailed study of vibrational frequencies of carbonyl compounds ( ketones, aldehydes, esters, amides, acids, anhydrides, lactones, lactams and conjugated carbonyl compounds). Effect of hydrogen bonding and solvent effect on the vibrational frequencies, overtones combination bands and Fermi resonance.
III Nuclear Magnetic Resonance Spectroscopy 22 hrs
General introduction and definition, chemical shift, spin-spin interaction, shielding mechanism, mechanism of measurement, chemical shift values and correlation for the proton bonded to carbon ( aliphatic, olefinic, aldehyde, and aromatic) and other nucei( alcohols, phenols, enols, carboxylic acid, amines, amides and mercapto) chemical exchange, effect of deuteration, complex spin-spin interaction between two, three, four and five nuclei( first order spectra) , virtual coupling stereochemistry, hindered rotation, Karplus curve-variation of coupling constants with dihedral angle. Simplification of complex spectra- nuclear magnetic double resonance, contact shift reagents, solvent effects, Fourier transfrormer technique, nmuclear overhauser effect(NOE) 13C, 19F, 31P, NMR and PMR spectral analysis. Two dimensional NMR spectroscopy- COSY NOESY, INADEQUATE
IV Electron spin resonance spectroscopy 5 hrs
Introduction, ESR spectrometer, the positiom of ESR absorption; the g factor electron-nucleus coupling , electron-electron coupling, double resonanace in ESR, ENDOR, ECDOR. Interpretation of ESR spectra and structure elucidation of organic radicals using ESR spectroscopy.
Mass spectroscopy 9 hrs
Introduction, instrumentation, ion production- EI, CI, FD and FAB, factors affecting fragementation, ion analysis, ion abundance. Mass spectral fragmentation of organic Compounds, common functional groups, molecular ion peak, metastable perak McLafferty rearrangement. Nitrogen rule. High resolution mass spectrometry.
Examples of mass spectral fragmentation of organic compounds with respect to their structure determination.
Composite problems 3 hrs
Problems involving the application of the above spectroscopic techniques for structural elucidation of organic molecules.
IV SEMESTER
C401 ORGANOMETALLIC CHEMISTRY
I Organometallic complexes 6 hrs
Stability and decomposition pathways, classification of ligands, nomenmclature of organometallic complexes, 16- and 18-lectron rules, electron counting- covalent and ionic models.
II Organometallic compounds of main group elements 8 hrs
Group trends- synthesis, structure and bonding in Li, Be, Mg and Al alkyls.
III Synthesis, structure bonding and decomplexation reactions of organo transisition metal complexes having σ- and π-M-C bonds 15 hrs
σ- bonded systems involving carbonyls, carbenes and carbynes π- bonded systems involving dihapto to octohapto ligands like acetylene, olefins, allyl moieties, butadiene, cyclobutadiene, cyclopentadiene, arenes, cyclohexa and cycloheptadienyl moieties, cyclohepta and cyclooctatrienes, cyclooctatetrene moieties, Fluxional organometallid compounds, cyclometallation and ring slippage reactions. Activation of small molecules (H2 and CO)
IV Isoelectronic and isolobal concepts 6 hrs
Structure and bonding in carbonyl clusters, wade-MIngos-Lauher rules, cluster valence electron count.
V Organometallic compounds in organic synthesis
General introduction, Greens rule. Use of iron amd chromium carbonyls in the synthesis of aromatic compounds, Rhodium complexes in hydrogenation and other reactions, palladium complexes in the synthesis of carbonyl compounds. Heck reaxction, Wacker process and carbonylation reactions (specific application in the synthesis of some natural products)
Use of zinc dizlkykls, grignard reagents, lithium alkyls. Gilman reagents ( lithioum dialkyl cuprates), organoselenium, organoaluminium, organosilicon, organogermanium, organolin, and organomercurials in organic synthesis.
STEREOCHEMISTRY AND RETROSYNTHETIC ANALYSIS
Optical activity in the absence of chiral atoms
Chirality in allenes, alkyildenecycloalkanes, spiranes, biphenyls, adamentanes, ad compounds, para-cyclophanesd, trans-cyclooctene, catenanes, rotaxenes and helicenes. Assignment of R-S configuiration to these classes of compounds.
OPTICAL ACTIVITY DUE TO THE PRESENCE HETERO ATOMS
Chirality of organic compounds due to the presence of silicon, nitrogen, phosphorus, arsenic and sulphur atoms. Determination of R-S configuration of these compounds using CIP rules.
METHODS OF DETERMINING ABSOLUTE CONFIGURATION
i) chemical correlation: a) without affecting bonds attached to a stereo centre b) affecting bonds attached to a stereo centre in a predictable manner.
ii) Optical rotatory dispersion: α- axial haloketone rule and octant rule, application of these rule in the determination of absolute configuration of cyclohexane decalones and cholestanones.
iii) Study of quasi-racemates
iv) Anomalous X-ray scttering technique.
STEREOSELECTIVE REACTIONS
Enantio and diastereoselectives
Enanatioselective synthesis: reduction with chiral hydride donors, hydro borationcatalytic hydrogenation, alkylation, sharpless epoxidation, phase transfer catalysed intramolecular aldol condensation and Michael addition.
Diasteroselective synthesis: Cram's and Prelon's rules- application in synthesis of chiral molecules. Diastereoselectivity in OsO4 oxidation and in prevost Woodward oxidation. Epoxidation of cyclic allyl alcohols. Host- guest chemistry.CONFORMATIONAL ANALYSIS
Conformational analysis of cyclobutane, cyclopentane, cycloheptane, cyclooctane, cyclodecane, decalins and cholestane. Conformation of cyclohexene and cyclohexanone: steric aspects of bromination of cyclohexene and cyclohexanone, enolisation of cyclohexanones.
TRANSANNULAR REACTIONS
Trasannular reactions of medium rigns: hydrolysios of meium ring epoxides and bromination of C8-C10 cyclic dienes.
RESTROSYNTHETIC ANALYSIS
Disconnection approach
Introduction to disconnection approach. Basic principles and terminologies used in disconnection approach. Synthons and synthetic equivalents. Omne group C-X and tweo group C-x disconnections. Synthesis of aromatic compounds
PROTECTING GROUPS
Principle of protecting of alcohols. Amines, acids and carbonyl groups
C-C ONE GROUP AND C-C TWO GROUP DISCONNECTIONS
Use of C-C disconnections in the synthesis of 1,2-, 1,3-, 1,4-, 1,5- and 1,6- difunctionalised compounds.
RETOSYNTHETIS ANALYSIS
Retrosynthetic analysis of alcohols, carbonyl compounds, cyclic and acyclic alkenes, lactones. Retrosynthetic analysis of bisabolene, nuciferal, lycorane, multistraitin and iprindole.
C 403 OC- INDUSTRIAL ORGANIC CHEMISTRY
I. Polymers 15 hrs
Importance of polymers. Basic concepts: Mononers repeat units, degree of polymerization, linear branched and network polymers. Classification and nomenclature of polymers. Properties of polymers ( brief explanation of molecular weight, glass transisition temperature- Tg , solubility and visco-elasciticity).
Method of polymerization- addition and condensation polymerization, ionic and free-radical polymerization. Processes, polymerization with complex catalysts(Zieger-Natta catalysis), co-polymerization and their mechanisms. Technique of polymerization- bulk, emulsion etc.
Rubber: Natural and synthetic rubbers, structure elucidation of natural rubber. Polymer degradation reactions: thermal oxidative ad radiative processes.
Synthesis and properties of Buna-S-butyl rubbers and polyanilines.
II Petrochemicals 7 hrs
Petroleum refining, constituents of petroleum and their separation. Conversion processes ( cracking , reforming, alkylation etc.) for precursors of petrochemicals. A brief description of the chemistry of manufacture of methane, ethane, ethylene, propylene, butylenes, acetylenes, benzene and some its derivatives and their conversions to some usefule products. Fischer – Tropsch synthesis.
III Synthetic dyes 12 hrs
Synthesis and method of application of the following dyes( explanation of the principles involved): Dyes with ppolar groups ( congo red), disperse dyes ( 1-am,ino-4-hydroxyanthraquinone, 2-amino-5-nitrothiazole, 3-amino-benisothiazole) fibre reactive dyes (triazine dyes) developed dyes( indigo, tyrian purple, thiazole dyes) photographic sensitizers (cyanines). Florescent-brightening agents. Colour photography( additive and substractive processes). Chemistry of colour developers “ instant” colour processes.
IV Pesticides and insecticide 8 hrs
Introduction, classification. Naturally occurring insecticides: Rotenones, pyrethrins, precocenes, synthetic insecticides: properties & synthesis of DDT, BHC, chlorodane, aldrin , dieldrin, parathion, malathion.
Introduction to the use of the following in the control of pests and insects: fumigants, nematicides, acaricides, harmones( juvienile harmone), insect repellents, molluscicides, rodenticides.
V Synthesis of peptides 13 hrs
Introduction . Amino acid sequencing. End group analysis. Methods of peptide synthesis- solution and solid phase techniques. Use of DC, EEDQ, HOBt and Merrifield resin> reacemisation during peptide synthesis. Synthesis and bioklogical importance of glutathione, enkephalin, oxytocin and gramicidin. Brief discussion of MSH, SCTH and insulin.
C:404 OC MEDICINAL ORGANIC CHEMISTRY
Introduction 3 hrs
Chemotherapy, pharmocokinetics, pharmacodynamics, metabolites and antimetabolites, prodrugs and soft drugs agonists and antagonists. Concept of drug receptors. Elementary treatment of drug receptor interactions. Quantitative structure activity relationship (QSAR). Theories of drug activity. Occupancy theory, rate theory, induced fit theory.
Mechanism of drug action and the synthesis of the following classes of drugs (interconversions as applicaple):
1. Antipyretics and analgesics 2 hrs
Aspirin, paracetamol, phenacetin, novalgin
2. Antiinflammatory
Phenylbutazone, ibuprofen
3. Antihistamines
methapyrilene, chjlorpheniramine
4. Antibiotics
Pencillin-G, ampicillin, amoxycillin, chloramphenicol, cephalosporins, tetracyclinsaureomycin and terramycin, streptomycin.
5. Antineoplastic agents
Mechlorethamine, cyclophosphamide, melphalan, uracil mustards and 6-mercaptopurine. Brief discussion of the recent developments in cancer chemotherapy. Hormone and natural products
6. Cardiovascular drugs 5 hrs
Amyl nitrite, sorbitrate, quinidine, verapamil, methyldopa
7. Local antiinfective drugs 9 hrs
sulphonamides, furazolidone, nalidixic acid, ciprofloxacin, norfloxacin,dapsone, aminosalicyclic acid, isoniazid, ethionamide, ethambutal, griseofulvin, chloroquin and primaquin
8. Psychoactive drugs – the chemotherapy of the mind 9 hrsPhenobarbital, pethidine, methadone, chlordiazepoxide, diazepam, meprobamate, chloropromazine, alprazolam, phenytoin, ethosuximide, trimethadione, barbiturates, thiopental sodium, glutethimide.
9. Vitamins 11 hrs
Biological importance and synthesis of vitamins A, Vitamin B1 (thiamine), Vitamin B6 (pyridoxine), vitamin C, vitamins D , vitamin E( a -tocopherol) vitamin H(biotin), vitamin K1, K2, folic acid , pantothenic acid , riboflavin.
ORGANIC CHEMISTRY PRACTICALS
C405-practical-I
A- preparations
Preparation of NBS from succinic acid and its application in allylic bromination reactions.
Preparation of benzpinacolone fron benzophenone.
skraup synthesis: preparation of quiniline from aniline.
Preparation of 2-phenylindole from phenylhydrazine.
Reduction of ethyl acetate using Baker's yeast to yield enantiomeric excess of S(+) ethyl-3-hydroxybutanoate.Synthesis using phase transfer catalysts: alkylation of diethyl malonate or ethyl acetoacetate with an alkyl halide.
Preparation of tetraphenyldihydrophthalic anhydride from N-phenylglycine.
Preparation of 2,4,5-triphenyloxazole from benzoin.
Estimations:
Estimation of nitro group by reduction using SnCl2
Estimation of nitrogen by Kjeldahl's method. Estimation of an acid in presence of an amide.
Estimation of an ester in the presence of an acid.
C406 Practical –II
A- QUALITATIVE ANALYSIS
Separation of a binary mixture of an organic compounds and identification of the separated components by systematic qualitative analysis.
B- EXTRACTIONS AND SEPARATIONS
(Preliminary Chromatographic Techniques)
Extractions
Extraction of piperine from pepper.
Extraction of caffeine from tea leaves.
Extraction of (+)- limonene from citrus rinds.
Extraction of azelaic acid from caster oil.
Separations
Separation of p-rosaniline and methyl red by column chromatography.
Separation of amino acids by paper chromatography.
Separation of carbohydrates by thin layer chromatography. |
