Syllabus (CHEMISTRY)

Course Type: MAJ-11

Semester: 7

Course Code: BCEMMAJ11C

Course Title: Organic Chemistry – V

(L-P-Tu): 4-2-0

Credit: 6

Practical/Theory: Combined

Course Objective: COURSE OBJECTIVE OF MAJOR - 11: The syllabus of Major -11 has been designed to provide the students with in-depth knowledge of carbocycles and heterocycles, cyclic stereochemistry, pericyclic reactions, carbohydrates and biomolecules.Discussion of biomole

Learning Outcome: COURSE OUTCOMES OF MAJOR – 11: CO- 11.1 Thorough understanding ofcarbocycle and heterocycle systems and corresponding reactions. CO- 11.2 Detailed study of stereochemistry of alicyclic compound s and corresponding reactions viz, elimination, substituti

CARBOCYCLES AND HETEROCYCLES: (15 L)

1. Polynuclear hydrocarbons and their derivatives: synthetic methods include Haworth, Bardhan-Sengupta, Bogert-Cook and other useful syntheses (withmechanistic details); fixation of double bonds and Fries rule; reactions (withmechanism) of naphthalene, anthracene, phenanthrene and their derivatives.

2. Heterocyclic compounds: 5- and 6-membered rings with one heteroatom; reactivity, orientation and important reactions (with mechanism) of furan, pyrrole, thiophene and pyridine; synthesis (including retrosynthetic approach and mechanistic details): pyrrole: Knorr synthesis, Paal-Knorr synthesis, Hantzsch; furan: Paal-Knorr synthesis, Feist- Benary synthesis and its variation; thiophenes: Paal-Knorr synthesis, Hinsberg synthesis; pyridine: Hantzsch synthesis; benzo-fused 5- and 6-membered rings with one heteroatom: reactivity, orientation and important reactions (with mechanistic details) of indole, quinoline and isoquinoline;synthesis (including retrosynthetic approach and mechanistic details): indole: Fischer, Madelung and Reissert; quinoline: Skraup, Doebner- Miller, Friedlander;isoquinoline: Bischler-Napieralski synthesis.

CYCLIC STEREOCHEMISTRY: (10 L)

Alicyclic compounds: concept of I-strain; conformational analysis: cyclohexane, mono and disubstituted cyclohexane; symmetry properties and optical activity; topomerisation; ring-size and ease of cyclisation; conformation & reactivity in cyclohexane system: consideration of steric and stereoelectronic requirements; elimination (E2, E1), nucleophilicsubstitution (SN1, SN2, SNi, NGP), merged substitution-elimination; rearrangements; oxidation of cyclohexanol, esterification, saponification, lactonisation,epoxidation, pyrolytic syn elimination and fragmentation reactions.

PERICYCLIC REACTIONS: (10 L)

Mechanism, stereochemistry, regioselectivity in case of

1. Electrocyclic reactions: FMO approach involving 4π- and 6π-electrons (thermal and photochemical) and corresponding cycloreversion reactions.

2. Cycloaddition reactions: FMO approach, Diels-Alder reaction,photochemical [2+2] cycloadditions.

3. Sigmatropic reactions: FMO approach, sigmatropic shifts and their order; [1,3]-and [1,5]- H shifts and [3,3]-shifts with reference to Claisen and Coperearrangements.

CARBOHYDRATES: (10 L)

1. Monosaccharides: Aldoses up to 6 carbons; structure of D-glucose & D-fructose(configuration & conformation); ring structure of monosaccharides (furanoseand pyranose forms): Haworth representations and non-planar conformations;anomeric effect (including stereoelectronic explanation); mutarotation; epimerization;reactions (mechanisms in relevant cases): Fischer glycosidation, osazone formation,bromine-water oxidation, HNO3 oxidation, selective oxidation of terminal –CH₂OHof aldoses, reduction to alditols, Lobryde Bruyn-van Ekenstein rearrangement;stepping–up (Kiliani-Fischer method) and stepping–down (Ruff’s & Wohl’smethods) of aldoses; end-group-interchange of aldoses; acetonide (isopropylidene)and benzylidene protections; ring-size determination; Fischer’s proof ofconfiguration of (+)-glucose.

2. Disaccharides: Glycosidic linkages, concept of glycosidic bond formation byglycosyl donor-acceptor; structure of sucrose, inversion of cane sugar.

3. Polysaccharides: starch (structureand its use as an indicator in titrimetricanalysis).

BIOMOLECULES: (15 L)

1. Amino acids: synthesis with mechanistic details: Strecker, Gabriel, acetamidomalonic ester, azlactone, Bücherer hydantoin synthesis, synthesis involvingdiketopiperazine; isoelectric point, zwitterions; electrophoresis, reaction (withmechanism): ninhydrin reaction, Dakin-West reaction; resolution of racemic aminoacids.

2. Peptides: peptide linkage and its geometry; syntheses (with mechanisticdetails) of peptides using N-protection & C-protection, solid-phase (Merrifield)synthesis; peptide sequence: C-terminal and N-terminal unit determination (Edman,Sanger & ‘dansyl’ methods); partial hydrolysis; specific cleavage of peptides: use ofCNBr.

3. Nucleic acids: pyrimidine and purine bases (only structure & nomenclature);nucleosides and nucleotides corresponding to DNA and RNA; mechanism for acidcatalysed hydrolysis of nucleosides (both pyrimidine and purine types); comparisonof alkaline hydrolysis of DNA and RNA; elementary idea of double helical structureof DNA (Watson-Crick model); complimentary base–pairing in DNA.

READING REFERENCES:

1. Clayden, J., Greeves, N., Warren, S. Organic Chemistry, Second edition, Oxford University Press, 2012.
2. Eliel, E. L. & Wilen, S. H. Stereochemistry of Organic Compounds, Wiley: London.
3. Nasipuri, D. Stereochemistry of Organic Compounds, Wiley Eastern Limited.
4. Sen Gupta, Subrata. Basic Stereochemistry of Organic molecules.
5. Kalsi, P. S. Stereochemistry Conformation and Mechanism, Eighth edition, New Age International, 2014.
6. Fleming, I. Molecular Orbitals and Organic Chemical reactions, Reference/Student Edition, Wiley, 2009.
7. Fleming, I. Pericyclic Reactions, Oxford Chemistry Primer, Oxford University Press.
8. Gilchrist, T. L. & Storr, R. C. Organic Reactions and Orbital symmetry, Cambridge University Press.
9. Finar, I. L. Organic Chemistry (Volume 1), Dorling Kindersley (India) Pvt. Ltd.(Pearson Education).
10. Finar, I. L. Organic Chemistry (Volume 2: Stereochemistry and the Chemistry of Natural Products), Dorling Kindersley (India) Pvt. Ltd. (Pearson Education).
11. Morrison, R. T. & Boyd, R. N. Organic Chemistry, Dorling Kindersley (India) Pvt. Ltd. (Pearson Education).
12. Loudon, G. M. Organic Chemistry, Fourth edition, Oxford University Press.
13. James, J., Peach, J. M. Stereochemistry at a Glance, Blackwell Publishing, 2003.
14. Robinson, M. J. T., Stereochemistry, Oxford Chemistry Primer, Oxford University Press, 2005.
15. Davis, B. G., Fairbanks, A. J., Carbohydrate Chemistry, Oxford Chemistry Primer, Oxford, University Press.
16. Joule, J. A. Mills, K. Heterocyclic Chemistry, Blackwell Science.
17. Acheson, R.M. Introduction to the Chemistry.

PRACTICALS:

Chromatographic Separations

1. TLC separation of a mixture containing 2/3 amino acids.

2. TLC separation of a mixture of dyes (fluorescein and methylene blue).

3. Column chromatographic separation of leaf pigments fromspinach leaves.

4. Paper chromatographic separation of a mixture containing 2/3 amino acids.

Spectroscopic Analysis of Organic Compounds

1. Assignment of labelled peaks in the 1H NMR spectra of the known organiccompounds explaining the relative δ-values and splitting pattern.

2. Assignment of labelled peaks in the IR spectrum of the same compoundexplaining the relative frequencies of the absorptions (C-H, O-H, N-H, C-O, C-N, CX,C=C, C=O, N=O, C≡C, C≡N stretching frequencies; characteristic bendingvibrations are included).

3. The students must analyze full spectra of at least 10 (ten) compoundsfrom the following list:

a. 4-Bromoacetanilide

b. 2-Bromo-4'-methylacetophenone c. Vanillin

d. 2-Methoxyacetophenone e. 4-Aminobenzoic acid

f. Salicylamide

g. 2-Hydroxyacetophenone h. 1,3-Dinitrobenzene

i. Benzylacetate

j. trans-4-Nitrocinnamaldehyde k. Diethyl fumarate

l. 4-Nitrobenzaldehyde

m. 4-Methylacetanilide

n. Mesityl oxide

o. 2-Hydroxybenzaldehyde

p. 4-Nitroaniline

q. 2-Hydroxy-3-nitrobenzaldehyde r. 2,3-Dimethylbenzonitrile

REFERENCES FOR PRACTICALS:

1. S. Perry, Practical Liquid Chromatography, 2012
2. C.F. Poole, ‎S.A. Schuette, Contemporary Practice of Chromatography, · 2012
3. Ivor Smith, ‎J. W. T. Seakins, Paper and Thin Layer Chromatography, · 2013
4. B. Ravindranath · Principles and Practice of Chromatography,1989.

5. Rosaleen J. Anderson, ‎David J. Bendell, ‎Paul W. Groundwater, Organic Spectroscopic Analysis,2004.