SEMESTER 3
AP3C09 ADVANCED SYNTHETIC ORGANIC CHEMISTRY
Credit : 4 Contact Lecture Hours: 72
Unit 1: Organic Synthesis via Oxidation and Reduction (9 Hrs)
Survey of organic reagents and reactions in organic chemistry with special reference to oxidation and reduction. Metal based and non-metal based oxidations of (a) alcohols to carbonyls (Chromium, Manganese, aluminium and DMSO based reagents). (b) alkenes to epoxides (peroxides/per acids based), Sharpless asymmetric epoxidation, Jacobsen epoxidation, Shi epoxidation.(c) alkenes to diols (Manganese and Osmium based), Prevost reaction and Woodward modification, (d) alkenes to carbonyls with bond cleavage (Manganese and lead based, ozonolysis) (e) alkenes to alcohols/carbonyls without bond cleavage (hydroboration-oxidation, Wacker oxidation, selenium/chromium based allylic oxidation) (f) ketones to esters/lactones (Baeyer-Villiger).
Unit 2: Modern Synthetic Methods and Reagents (9 Hrs)
Baylis-Hillman reaction, Henry reaction, Nef reaction, Kulinkovich reaction, Ritter reaction, Sakurai reaction, Tishchenko reaction, Ugi reaction, Noyori reaction. Brook rearrangement, Tebbe olefination. Metal mediated C-C and C-X coupling reactions: Heck, Stille, Suzuki, Suzuki-Miyaura, Negishi and Sonogashira, Nozaki-Hiyama, Buchwald-Hartwig, Ullmann and Glaser coupling reactions, Wohl-Ziegler reaction. Reagents such as: NBS, DDQ, DCC, Gilmann reagent.
Introduction to multicomponent reactions, Click reactions.
Unit 3: Stereoselective Transformations (9 Hrs)
Assymmetric induction, chiral auxiliaries and chiral pool.
Enatioselective catalytic hydrogenation developed by Noyori and Knowels.
Assymetric aldol condensation pioneered by Evans.
Assymmetric Diels Alder reactions.
Assymmetric epoxidation using Jacobsen’s catalyst.
Unit 4: Construction of Carbocyclic and Heterocyclic Ring Systems (9 Hrs)
Different approaches towards the synthesis of three, four, five and six-membered rings. Photochemical approaches for the synthesis of four membered rings, oxetanes and cyclobutanes. ketene cycloaddition (inter and intra molecular), Pauson-Khand reaction, Volhardt reaction, Bergman cyclization, Nazarov cyclization, Mitsunobu reaction, cation-olefin cyclization and radical-olefin cyclization.
Inter-conversion of ring systems (contraction and expansion), Demjenov reaction, Reformatsky reaction. Construction of macrocyclic rings, ring closing metathesis.
Formation of heterocyclic rings: 5-membered ring heterocyclic compounds with one or more hetero atom like N, S or O: pyrrole, furan, thiophene, imidazole, thiazole and oxazole.
Unit 5: Molecular Recognition and Supramolecular Chemistry (9 Hrs)
Concept of molecular recognition, host-guest complex formation, forces involved in molecular recognition.
Molecular receptors: Cyclodextrins, Crown ethers, Cryptands, Spherands, Tweezers, Carcerands, Cyclophanes, Calixarenes, Carbon nanocapsules.
Importance of molecular recognition in biological systems like DNA and protein, Controlled release phenomena.
Applications of supramolecular complexes in medicine and perfumery industries.
Unit 6: Chemistry of Natural products and Biomolecules (9 Hrs)
Basic aspects of structure and classification of carbohydrates, alkaloids, steroids, plant pigments, vitamins, amino acids, proteins and nucleic acids.
Methods for primary structure determination of peptides, proteins and nucleic acids. Replication of DNA. Flow of genetic information. Protein biosynthesis. Transcription and translation. Genetic code. Regulation of gene expression. DNA sequencing. The Human Genome Project. DNA profiling and the Polymerase Chain Reaction (PCR).
Unit 7: Reterosynthetic Analysis (9 Hrs)
Basic principles and terminology of reterosynthesis, synthesis of aromatic compounds, one group and two group C-X disconnections, one group C-C and two group C-C disconnections.
Amine and alkene synthesis, important strategies of retrosynthesis, functional group transposition, important functional group interconversions. Enantioselective synthesis of Corey lactone, Longifolene and luciferin. Umpolung equivalence, Peterson olefination, enolate formation, Ireland method.
Unit 8: Green Alternatives of Organic Synthesis (9 Hrs)
Principles of Green Chemistry, Basic concepts, Atom Economy, Principles of Green Organic Synthesis.
Green alternatives of Organic Synthesis: Coenzyme catalysed reactions, thyamine catalyzed benzoin condensation. Green alternatives of Molecular rearrangements: Pinacol-pinacolone and Benzidine rearrangement. Electrophilic aromatic substitution reactions. Oxidation-reduction reactions. Clay catalysed synthesis. Condensation reactions. Green photochemical reactions.
Green Solvents: ionic liquids, supercritical CO2, fluorous chemistry.
General principles of Microwave and Ultrasound assisted Organic Synthesis
References
M.B. Smith, Organic Synthesis, 3rd Edition, Wavefunctions Inc., 2011.
F.A. Carey, R.I. Sundberg, Advanced Organic Chemistry, Part A and B, 5th Edn., Springer, 2009.
S. Warren, Organic Synthesis: The Disconnection Approach, John Wiley & Sons, 2004.
V.K. Ahluwalia, Oxidation in Organic Synthesis, Ane Books, 2012.
J. Tsuji, Palladium Reagents and Catalysts: New Perspectives for the 21st Century, John Wiley & Sons, 2003.
I. Ojima, Catalytic Asymmetric Synthesis, 2nd Edn., Wiley−VCH, 2000.
W. Carruthers, I. Coldham, Modern Methods of Organic Synthesis, Cambridge University Press, 2005.
J. Clayden, N. Greeves, S. Warren, P. Wothers, Organic Chemistry, Oxford University Press, 2001.
R. Noyori, Asymmetric Catalysis in Organic Synthesis, John Wiley & Sons, 1994.
L. Kuerti, B. Czako, Strategic Applications of Named Reactions in Organic Synthesis, Elsevier Academic Press, 2005.
R.O.C. Norman, J.M.Coxon, Principles of Organic Synthesis, ELBS and Chapmann and Hall, 1995.
V.K. Ahluwalia, L.S. Kumar, S. Kumar, Chemistry of Natural Products, Anne Books, 2009.
J.M. Lehn, Supramolecular Chemistry: Concepts and Perspectives, VCH, 1995.
F. Vogtle, Supramolecular Chemistry: An Introduction, John Wiley & Sons, 1993.
W. Carruthers, Modern Methods of Organic Synthesis, Cambridge University Press, 1996.
V. K.Ahluwalia, Green Chemistry: Environmently Benign Reactions, Anne Books, 2009.
AP3C10 CHEMISTRY AND BIOCHEMISTRY OF FATTY ACIDS
Credit : 4 Contact Lecture Hours: 72
Unit 1:Lipids (9 Hrs)
Classification of lipids-sources and classification of oils and fats, nomenclature of triglycerides, stereospecific numbering
Nutritional functions of fats and oils, Caloric and non caloric functions, Non nutritional functions of edible fats.
Unit 2: Isolation and Characterization of Fatty Acids (9 Hrs)
Crystallisation methods, Chromatographic techniques: TLC, paper chromatography, GLC, HPLC. Use of IR, UV, NMR and mass spectrometry.
Nomenclature of fatty acids- IUPAC and omega reference systems, uses of fatty acids in textiles, leather, pharmaceuticals and petroleum processing.
Unit 3: Fatty Acids Occurring in Nature (18 Hrs)
Saturated fatty acids: important sources, structure and synthesis of naturally occurring straight chain and branched chain saturated fatty acids.
Unsaturated fatty acids: monoethenoid fatty acids-their occurrence and general methods of synthesis. Oleic acid and petroselenic acid-properties and constitution, other monoethenoid acids occurring in animal and vegetable oils and fats.
Polyunsaturated fatty acids, cyclopropenoid acids, conjugated acids, epoxy acids, keto acids, cyclopentenoid acids, hydroxy acids, acetylenic acids, furanoid acids, artificially produced fatty acids, synthetic fatty acids.
Unit 4: Physical properties of Fatty Acids (9 Hrs)
Crystal properties, thermal properties, spectral properties, solubility and solution properties of fatty acids in the liquid state.
Unit 5: Chemical properties of Fatty Acids (18 Hrs)
Salt formation, esterification, halogenation, oxidation uses of various oxidizing agents like chromic acid, ozone, peroxides, potassium permanganate, periodic acid and lead tetra acetate. Hydrogenation, dehydration, pyrolysis, polymerization, addition reactions to double bond.
Unit 6: Biochemistry and Metabolism of Fats (9 Hrs)
Biochemical transformation of fats in the body-biosynthesis of fats in plants and animal organisms.
Prostaglandins: synthesis, biosynthesis, applications of prostaglandins as drugs.
References
M.G. Wohl, R.S. Goodhart, M.E. Shils, Modern Nutrition in Health and Disease, 6th Edn., Lea & Febiger, 1980.
K.S. Markley, Fatty acids: Their Chemistry, Properties, Production and Uses, Parts I- V, Interscience, 1960.
D. Swern, Bailey’s Industrial oil and Fat Products, Vol. I-II, 4th Edn., John Wiley & Sons, 1982.
T.H. Aplewhite, Bailey’s Industrial Oil and Fat Products, Vol.III, 4th Edn., John Wiley-Interscience,1985
T.P. Hilditch, P.N. Williams, The Chemical Constitution of Natural Fats, 4th Edn., John Wiley & Sons, 1964
F.D. Gunstone, An introduction to Chemistry and Biochemistry of Fatty acids and their Glycerides, Chapman and Hall, 1968.
H.B. Bull, The Biochemistry of Lipids, John Wiley, 1937.
T. Galliard, E.I. Mercer, Recent Advances in the Chemistry and Biochemistry of Plant Lipids, Academic Press, 1975.
F.D. Gunstone, Topics in Lipid Chemistry, Vol.I-II, Logos Press, 1970.
H.M. Sinclair, Essential Fatty Acids, Butterworths, 1958.
E.E. Conn, P.K. Stumpf, G. Bruening, R.H. Doi, Outlines of Biochemistry, 5th Edn., John Wiley, 1987.
AP3C11 ESSENTIAL OILS AND AROMATICS
Credit: 4 Contact Lecture Hours:72
Unit 1: Production and isolation of Essential Oils (9 Hrs)
Production of essential oils, Methods of isolation-Hydrodistillation, Solvent extraction, Enfleurage, Maceration, Expression, Supercritical fluid extraction.
Unit 2: Sources, Nature and Uses of Essential Oils (18 Hrs)
Study of the sources, production, general nature and use of the following essential oils: Lemongrass oil, Lemon oil, Citronella oils, Bergamot oil, Neroli oil, Palmarosa oil, Rosemary oil, Campher oil, Eucalyptus oil, Turpentine oil, Jasmine oil, Lavender oil, Rose oil, Geranium oil, Sandal wood oil, Clove oil, Cinnamon oil, Vetiver oil, Peppermint oil.
Unit 3: The Origin and Function of Essential Oils in Plants (9 Hrs)
Classification of Terpenoids, Isoprene rule, Physical and Chemical methods used for the investigation of essential oils and determination of the structure of terpenoids.
Biosynthesis of terpenoids, Formation of Mevalonic acid as intermediate, Biosynthesis of Monoterpenoids and Sesquiterpenoids.
Unit 4: Study of Essential Oil Constituents (36 Hrs)
Production, chemistry, classification, properties, reaction and synthesis of essential oil constituents with reference to the following:
Hydrocarbons:Ocimene,p-Cymene,Limonene,Carene,Pinene,Camphene,
Fenchene, Bisabolene, Zingiberiene, Caryophyllene.
Alcohols: Linalool, Geraniol, Citronellol, Terpineol, Menthol, Borneol,
IsoBorneol, Fernesol, Fenchyl Alcohol, Sandalols, Leaf alcohol.
Aldehydes: Citral, Citronellal, hydroxycitronellal.
Ketones: Methyl Heptenol, Menthone, Piperitone, Pulgone, Carvone,
Fenchone, Campher, Ionones, Irones.
Spectral studies of the following compounds using UV-Visible, IR and Mass Spectrometry: Ocimene, Citral, Geraniol, Campher, Zingiberiene, Alpha Pinene, Pulgone, Piperitone, Ionone and Carvone.
References
1. E. Guenther, The Essential Oils, Vol I-VI, D.Van Nostrand, 1948.
A.A. Newman, The Chemistry of Terpenes and Terpenoids, Academic Press, 1972.
V. K. Ahluwalia, Terpenoids,Ane Books, 2009.
Y. Masada, Analysis of Essential Oils by Gas Chromatography and Mass Spectrometry, Wiley, 1976.
J.L. Simonson, The Terpenes, Vol.5, University Press, 1957.
A.R. Pinder, The Chemistry of Terpenes, Chapman and Hall, 1960.
J. Varghese, Terpene Chemistry, Tata McGraw Hill, 1982.
P. De Mayo, Mono and Sequiterpenoids, Interscience, 1969.
P.Z. Bedoukian, Perfumery Synthetics and Isolates, LCC, 2012.
AP3C12 SPECTROSCOPIC METHODS IN CHEMISTRY
Credit : 3 Contact Lecture Hours: 54
Unit 1: Ultraviolet-Visible and Chirooptical Spectroscopy (9 Hrs)
Energy levels and selection rules, Woodward-Fieser and Fieser-Kuhn rules.
Influence of substituent, ring size and strain on spectral characteristics. Solvent effect, Stereochemical effect, non-conjugated interactions. Chirooptical properties-ORD, CD, octant rule, axial haloketone rule, Cotton effect.
Problems based on the above topics.
Unit 2: Infrared Spectroscopy (9 Hrs)
Fundamental vibrations, characteristic regions of the spectrum (fingerprint and functional group regions), influence of substituent, ring size, hydrogen bonding, vibrational coupling and field effect on frequency, determination of stereochemistry by IR technique.
IR spectra of C=C bonds (olefins and arenes) and C=O bonds.
Problems on spectral interpretation with examples.
Unit 3: Nuclear Magnetic Resonance Spectroscopy (18 Hrs)
Magnetic nuclei with special reference to 1H and 13C nuclei. Chemical shift and shielding/deshielding, factors affecting chemical shift, relaxation processes, chemical and magnetic non-equivalence, local diamagnetic shielding and magnetic anisotropy. 1H and 13C NMR scales.
Spin-spin splitting: AX, AX2, AX3, A2X3, AB, ABC, AMX type coupling, first order and non-first order spectra, Pascal’s triangle, coupling constant, mechanism of coupling, Karplus curve, quadrupole broadening and decoupling, diastereomeric protons, virtual coupling, long range coupling-epi, peri and bay effects. NOE. NOE and cross polarization.
Simplification non-first order spectra to first order spectra: shift reagents, spin decoupling and double resonance, off resonance decoupling. Chemical shifts and homonuclear/heteronuclear couplings. Basis of heteronuclear decoupling.
2D NMR and COSY, HOMOCOSY and HETEROCOSY
Polarization transfer. Selective Population Inversion. DEPT, INEPT and RINEPT. Sensitivity enhancement and spectral editing, MRI.
Problems on spectral interpretation with examples.
Unit 4: Mass Spectrometry (9 Hrs)
Molecular ion: ion production methods (EI). Soft ionization methods: SIMS, FAB, CA, MALDI, PD, Field Desorption Electrospray Ionization. Fragmentation
patterns-nitrogen and ring rules. McLafferty rearrangement and its applications. HRMS, MS-MS, LC-MS, GC-MS.
Problems on spectral interpretation with examples.
Unit 5: Structural Elucidation Using Spectroscopic Techniques (9 Hrs)
Identification of structures of unknown organic compounds based on the data from UV-Vis, IR, 1H NMR and 13C NMR spectroscopy (HRMS data or Molar mass or molecular formula may be given).
Interpretation of the given UV-Vis, IR and NMR spectra.
References
D.L. Pavia, G.M. Lampman, G.S. Kriz, Introduction to Spectroscopy, 3rd Edn., Brooks Cole, 2000.
A.U. Rahman, M.I. Choudhary, Solving Problems with NMR Specroscopy, Academic Press, 1996.
L.D. Field, S. Sternhell, J.R. Kalman, Organic Structures from Spectra, 4th Edn., John Wiley & sons, 2007.
C.N. Banwell, E.M. McCash, Fundamentals of Molecular Spectroscopy, 4th Edn., Tata McGraw Hill, 1994.
D.F. Taber, Organic Spectroscopic Structure Determination: A Problem Based Learning Approach, Oxford University Press, 2007.
H. Gunther, NMR Spectroscopy, 2nd Edn., Wiley, 1995.
R.M. Silverstein, G.C. Bassler, T.C. Morril, Spectroscopic Identification of Organic Compounds, 5th Edn., Wiley, 1991.
D.H. Williams, I. Fleming, Spectroscopic Methods in Organic Chemistry, 6th Edn., McGraw-Hill, 2008.
W. Kemp, Organic Spectroscopy, 2nd Edn., Macmillan, 1987.
F. Bernath, Spectra of Atoms and Molecules, 2nd Edn., Oxford University Press, 2005.
E.B. Wilson Jr., J.C. Decius, P.C. Cross, Molecular Vibrations: The Theory of Infrared and Raman Vibrational Spectra, Dover Pub., 1980.
Online spectral databases including RIO-DB.
