Department of Chemistry

Organic Chemistry-I

Course Title: Organic Chemistry-I

L	T	P	Cr
4	0	0	4

Paper Code: CHM.510

Total Contact Hours: 60

 

Learning Outcome: After the completion of the course students will be able to

 

• Identify various methods and intermediate species involved while determining the mechanism of organic reactions.
• Examine the mechanistic and synthetic aspects of nucleophilic and electrophilic substitution reactions. 
• Explore the implication of enolate chemistry for the synthesis of various molecules.

 

Unit 1                                                                                15Hours

Reaction mechanism, structure and reactivity: Classification and determination of reaction mechanisms, kinetic and thermodynamic control, Hammond's postulate, Curtin-Hammett principle, methods of determining mechanisms, isotope effects, effect of structure on reactivity: Hammett equation, Taft equation.

Reactive intermediates: Generation, structure and reactions of carbocations, carbanions, free radicals, carbenes, nitrenes and benzynes. Neighbouring group participation, classical and non-classical carbocations, phenonium ions and norbornyl system.

Aromaticity: Aromaticity in benzenoid and non-benzenoid compounds, antiaromaticity, homoaromatic compounds.

 

Unit 2                                                                                         15Hours

Aliphatic nucleophilic substitution reaction: The S_N², S_N¹, mixed S_N² and S_N¹, the S_Nⁱ mechanism. Energy profile diagram, nucleophilic substitution at an allylic, aliphatic and vinylic carbon.reactivity effects of substrate structure, attacking nucleophile, leaving group and reaction medium, ambident nucleophile, regioselectivity, effect of solvent in substitution reaction, competition betweenS_N² and S_N¹ mechanisms.

Aromatic nucleophilic substitution: The S_N^Ar, bimolecular displacement mechanism and benzyne mechanism, reactivity effect of substrate structure, leaving group and attacking nucleophile.

Aromatic electrophilic substitution: The arenium ion mechanism, orientation and reactivity, energy profile diagrams, ortho/para ratio, ipso attack, orientation in other ring systems, quantitative treatment of reactivity in substrates and electrophiles.

 

Unit 3                                                                                         15Hours

Elimination reactions: E2, E1 and E1cB mechanisms and their spectrum, orientation of the double bond, effects of substrate structures, attacking base, the leaving group and the medium, mechanism and orientation in pyrolytic elimination.

Addition to carbon-carbon multiple bonds: Mechanistic and stereochemical aspects of addition reactions involving electrophiles, nucleophiles and free radicals, addition of halogen polar reagents to alkenes, Regio- and chemoselectivity, orientation and reactivity, hydroboration, epoxidation and hydroxylation.

 

Unit 4                                                                                         15Hours

Addition to carbon-hetero multiple bonds: Structure and reactivity of carbonyl group towards nucleophilic addition: addition of CN, ROH, RSH, H₂O, hydride ion, ammonia derivatives, LiAlH₄, NaBH₄, organozinc and organolithium reagents to carbonyl and conjugated carbonyl compounds, Arndt-Eistert synthesis. Mechanism of condensation reactions involving enolates: Aldol, Knoevenagel, Claisen, Dieckmann, Mannich, Benzoin, Perkin and Stobbereactions. Carboxylic acids and derivatives, hydrolysis of esters and amides, ammonolysis of esters.

Mode of Transactions: Lecture, Demonstration, Presentation, Group Discussion, Lecture cum demonstration, Problem solving, Brain storming

Suggested Readings

1.        Clayden, J., Greeves, N., Warren, S. and Wothers, P. (2012) Organic Chemistry,Oxford  University Press.

2.        Finar, I. L. (1996). Textbook OfOrganic Chemistry. ELBS, Pearson Education UK.

3.        McMurry, J. (1996). Organic Chemistry, Brooks. Cole, New York, 657.

4.        Smith, M. B., and March, J. (2013). March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure. John Wiley and Sons.

5.        Ahluwalia, V. K., andParashar, R. K. (2011). Organic Reaction Mechanisms. Narosa Publishing House (P) Ltd.

6.        Bansal, R. K. (2012). A Textbook of Organic Chemistry. New Age International.

7.        Bansal R.K. (2010) Organic Reaction Mechanism. New Age International (P) Ltd.

8.        Kalsi, P.S. (2010) Organic Reactions and Their Mechanisms. New Age International, New Delhi.

9.        Lowry, T. H. and Richardson K. S. (1998) Mechanism and Theory in Organic Chemistry, Addison-Wesley Longman Inc., New York.

10.    Morrison, R.T. and Boyd, R.N. (2011) Organic Chemistry, Prentice- Hall of India.

11.    Mukherjee, S.M. and Singh, S.P. (2009) Reaction Mechanism in Organic Chemistry. Macmillan India Ltd., New Delhi.

12.    Solomon, T.W.G, Fryhle, C.B. and Snyder, S. A. (2013) Organic Chemistry. John Wiley and Sons, Inc.

13.    Sykes, P. A. (1997) Guide Book to Mechanism in Organic Chemistry, Prentice Hall.

Department of Chemistry

Green Chemistry

Course Title: Green Chemistry		L	T	P	Cr
Paper Code: CHM.520		4	0	0	4

 

Learning outcome: Students will be able to

• Differentiate various aspects of green chemistry for sustainable development
• Utilize ionic liquids and soild supported reaction conditions to reduce or eliminate use of volatile organic solvents
• Use water as solvent in chemical transformations
• Utilize energy efficient MW and sonicator in organic synthesis

 

Unit 1                                                                                         15 Hours

Introduction to green chemistry:History, need and goals. Green chemistry and sustainability, dimensions of sustainability, limitations/obstacles in pursuit of the goals of green chemistry.Opportunities for the next generation of materials designers to create a safer future. Basic principles of green chemistry: Atom economy and scope, Prevention/Minimization of hazardous/toxic products, Designing safer chemicals, Selection of appropriate auxiliary substances (solvents, separation agents etc), use of renewable starting materials, Avoidance of unnecessary derivatization-careful use of blocking/protection groups.  Use of catalytic reagents (wherever possible) in preference to stoichiometric reagents, Designing biodegradable products, Prevention of chemical accidents, Strengthening/development of analytical techniques to prevent and minimize the generation of hazardous substances in chemical processes. Development of accurate and reliable sensors and monitors for real time in process monitoring.

Unit 2                                                                                         15 Hours

Green Solvents: Role of solvents in chemical synthesis, Environmental and health concerns of organic solvents, Need for Alternative/Cleaner solvents, Criteria for selection and design of green solvents Water: the natural solvent on earth, organic reactions: hydrophobic effects enhancing the reaction selectivities, low solubility of O2 in water, water soluble catalysts, challenges in using water as solvent,

Ionic liquids: physicochemical properties, Synthesis of Ionic Liquids, Directed Inorganic and Organometallic Synthesis, formation of oxides, electrochemical synthesis in ionic liquids,

Glycerol: solvent properties, volatility, polarity, availability, glycerol as a solvent combining the advantages of water and ionic liquids, enhancement of reaction selectivity, glycerol as a solvent for catalyst design and recycling, separation processes and material synthesis in glycerol, examples of synthesis of transition metal and metal oxide crystals

Supercritical fluids: supercritical CO₂ and its properties, advantages of using CO2 as solvent, Synthesis of metal nanoparticles, CO₂ as solvent for coatings and lithography, biomaterial processing, other supercritical fluids.

Unit 3                                                                                         15 Hours

Microwave induced and ultrasound assisted green synthesis: Introduction to synthetic organic transformation under microwave (i) Microwave assisted reactions in water (ii) Microwave assisted reactions in organic solvents. (iii) Microwave solvent free reactions Ultrasound assisted reactions: Introduction, substitution reactions, addition, oxidation, reduction reactions. Biocatalysts in organic synthesis: Introduction, Biochemical oxidation and reductions.

Unit 4                                                                                           15 Hours

Approaches to green synthesis: Use of green reagents: polymer supported reagents: peptide coupling reagents. Green catalysts, Phase-transfer catalysts in green synthesis.Advantages of PTC, Application of PTCs in C-alkylation, N-alkylalion, S-alkylation.Darzens reaction, Williamsons synthesis, Wittig reaction, Click Chemistry. Use of Crown ethers in esterification, saponification, anhydride formation, aromatic substitution and elimination reactions.

Mode of Transactions: Lecture, Demonstration, Presentation, Group Discussion, Lecture cum demonstration, Problem solving, Brain storming

Suggested Readings:

1.    Ahulwalia, V.K.; Kidwai M. (2004). New Trends in Green Chemistry, Springer

2.    Anastas, P.T.; Warner J. C. (2000). Green chemistry, Theory and Practical. Oxford University Press.

3.    Grieco, P.A. (1997). Organic Synthesis in Water. Publisher: Kluwer Academic.

4.    Peter Wasserscheid and Tom Welton (2008), Ionic Liquids in Synthesis, WILEY-VCH Verlag GmbH & Co. KGaA, 2008.

5.    Sheldon, R.A., Arends, I. and Hanefeld U. (2007), Green Chemistry and Catalysis, WILEY-VCH Verlag GmbH & Co. KGaA.

6.    William M. N.; (2003) Green Solvents for Chemistry: Perspectives and Practice, Oxford University Press.

 

Course creator: Virender Singh

Biocinorganic and Bio physical chemistry

Course creator: Rakesh Kumar

Organic Chemistry-III

Course Title: Organic Chemistry-III

Paper Code: CHM.552

Total Contact Hours: 45

 

Course Outcome: The students will acquire knowledge of:

1.   Designing a retrosynthetic approach for the synthesis of a target molecule.

2.   Oxidation and reduction reagents and their application for functional group conversion in organic synthesis.

3.   Nomenclature, synthesis and reactivity of smaller, five and six membered heterocyclic compounds.

Unit 1                                                                                                 11 Hours

Retrosynthesis: Synthon, synthetic equivalent, functional group interconversion (FGI), functional group addition, functional group elimination, criteria for selection of target, linear and convergent synthesis, retrosynthetic analysis involving chemoselectivity, reversal of polarity (umpolung), importance of the order of events in organic synthesis. One group and two group C-X disconnections, two group C-C disconnections; Diels-Alder reaction, control in carbonyl condensation.

Unit 2                                                                                                12 Hours

Metal and non-metal mediated oxidation: Mechanism, selectivity, stereochemistry and applications of oxidation reactions, Baeyer-Villiger, Oppenauer oxidation, oxidation reactions using DDQ, NBS, Pb(OAc)₄, Selenium dioxide, PCC, PDC, Cr and Mnreagents, phase transfer catalysis, Periodic acid, Ceric ammonium nitrate, OsO₄, Swern oxidation, hydroboration, Sharpless asymmetric epoxidation, epoxidations using peracids. Recent approaches for oxidation using green oxidants.

Unit 3                                                                                                  11 Hours

Metal and non-metal mediated reduction: Mechanism, selectivity, stereochemistry and applications of catalytic hydrogenations using Pd, Pt and Ni catalysts (Lindlar, Rosenmund, Adam’s catalysts)Clemmensen reduction, Wolff-Kishner reduction, Meerwein-Pondorff-Verley reduction, dissolving metal reductions, metal hydride reductions using NaBH₄, NaBH₃CN, NaBH(OAc)₃, LiAlH₄, DIBAL. Wilkinson’s catalysis, Birch reduction.

Unit 4                                                                                               11 Hours

Heterocyclic Chemistry: Systematic nomenclature (Hantzsch-Widman system) for monocyclic, fused and bridged heterocycles, aromatic heterocycle, non-aromatic heterocycle: bond angle and torsional strains and their consequences in small ring heterocycles, conformation of six-membered heterocycles and their synthesis.

Three-membered and four-membered heterocycles: aziridines, oxiranes, thiranes, azetidines, oxetanes.Five membered heterocycles containing two heteroatoms (S,N,O): Diazoles (imidazole, pyrazole), triazoles, oxazoles and thiazoles.

Benzo-fused five-membered and six membered heterocycles:Indoles, benzofurans and benzimidazoles.

Six-membered heterocycles: Synthesis and reactions of coumarins, chromones, pyridine.

 

Suggested Readings

1.     Ahluwalia, V. K., andParasar R. K., (2011).Organic Reaction Mechanism.Narosa Publishing House (P) Ltd., New Delhi.

2.     Bansal, R. K. (2012). A Textbook of Organic Chemistry. New Age International.

3.     Bansal, R.K. Hetrocyclic Chemistry, 5^thEdition, 2010, New Age International (P) Ltd., New Delhi. 

4.     Carey, F. A., andSundberg, R. J. (2007). Advanced organic chemistry: part B. Springer Science and Business Media.

5.     Finar, I. L. (1996). Textbook of Organic Chemistry. ELBS, Pearson Education UK.

6.     Gilchrist, T.L.,(1997). Heterocyclic Chemistry. Addison Wesley Longman Publishers, US.

7.     Gupta R.R., Kumar M., and Gupta V., (2010).Heterocyclic Chemistry-II  Five Membered Heterocycles. Vol. 1-3, Springer Verlag, India.

8.       Joule, J.A.,and Mills, K.,(2010). Heterocyc1ic Chemistry.Blackwell Publishers, New York.

9.     Smith, M. B.,(2013). March's Advanced Organic Chemistry: Reactions, Mechanisms and Structure.John Wiley and Sons.

10.  Warren, S., (2010). Organic synthesis: The Synthon Approach. John Wileyand Sons.

11.  Warren, S.,andWyatt, P., (2010).Designing Organic synthesis: A Disconnection Approach. John Wiley and Sons.

12.  Corey, E.J.,and Cheng X.-M., (1989).The Logic of Chemical Synthesis. John Wiley and Sons.

 

Department of Chemistry

Pharmaceutical Products

Course Outcome: The students be able to rationalize the importance of pharmaceutical products.

 

Unit 1                                                                                                          8 Hrs

Herbal Products:

General Properties, Chemistry, Phytoconstituentsand bioactive constituents and medicinal importance

Alkaloids Containing Herbal Drugs: Papaversomniferium (morphine), Rauvolfiaserpentina (reserprine), Atropabelladona (atropine), Ephedra gerardiana (ephedrine), biosynthesis of alkaloids.

Terpenes Containing Herbal Drugs: Lemon grass oil (citral and geraneol), Artemesiaannua (artemisinin) and Taxusbaccata, biosynthesis of terpenoids

Phenolics containing Herbal Drugs: Vitisvinifera (reservertrol), Pterocarpusmarsupium(Pterostilbene)

Various Berry fruits (strawberry, cherry, raspberry etc.).

 

Unit 2                                                                                                         8 Hrs

Edible Oils and Fats: General study of the quality assessment, hydrogenation of oils, rancidity, iodine value, acid value, saponification value, Reichert-Meissel value, Polenski value and Kirschner value, adulteration of oils and fats, modifications to produce specialty fats (structured fats, nutraceuticals). Essential fatty acids: ω-3 and ω-6 fatty acids.

 

Unit 3                                                                                                         7 Hrs

Soap: Introduction, manufacturing process different types of soap and their composition, Recovery of glycerin from soap spent lye. Metathesis and co metathesis reactions of fats and oils and their application in oleo chemical industry. hydroformylation reaction, cracking of fatty acids and fatty acid esters.

 

Unit 4                                                                                                          7 Hrs

Chemistry of Cosmetics and Perfumes: Cosmetic necessities: Acids, bases, buffers, topical agents. protective and antimicrobials, Astringents; Chemistry of emulsions in cosmetic formulation; safety issues of cosmetics. Storage and preparation of herbal drugs for commercial market. Essential oils and their importance in cosmetic industries.

Antiperspirants, artificial and natural flavors, colors and preservatives, artificial sweeteners. 

 

Suggested Readings:

7.   Foye, W. O. (2008). Foye'sPrinciples of Medicinal Chemistry. Lippincott Williams and Wilkins.

8.   Poucher, W. A. (2012). Poucher’s Perfumes, Cosmetics and Soaps: Volume 3: Cosmetics. Springer Science and Business Media.

9.   Edwards, S. E., da Costa Rocha, I., Heinrich, M., and Williamson, E. M. (2015). Phytopharmacy: An Evidence-Based Guide to Herbal Medicinal Products. John Wiley and Sons.