ENGINEERING CHEMISTRY DEPARTMENT

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ENGINEERING CHEMISTRY DEPARTMENT

School of Engineering & Technology

Suresh Gyan Vihar University, Jaipur

TEACING SCHEME & DETAILED SYLLABUS

FOR

MSc Green Chemistry Degree Course Ist year

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School of Engineering & Technology

Suresh Gyan Vihar University

ENGINEERING CHEMISTRY DEPARTMENT

MSc Green Chemistry Degree Course Ist years

MSc Green Chemistry Degree Course Ist year Semester I

S.No Course

Code Course Name Credits

Contact Hrs/ wk Exam Hrs Weightage (in %) L T/S P CE ESE

1 CY-501 Advanced Inorganic

chemistry I 04 3 1 - 3 30

70

2 CY-503 Advanced Organic

Chemistry I 04 3 1 - 3 30 70

3 CY-505 Advanced Physical

Chemistry I 04 3 1 - 3 30 70

4 CY-507 Advanced Instrumental &

Analytical Techniques I 04 3 1 - 3 30 70

5 CY-509 Principles of Green

Chemistry 03 3 - - 3 30 70

6 CY-551 Advanced Chemistry

Practicals I 06 - - 12 9 (2days:6+3) 60 40

Total ₂₅ ₁₅ ₀₄ ₁₂ ₂₄

Total Teaching Load 31

MSc Green Chemistry Degree Course Ist year Semester II

S.No Course

1 CY-502 Advnced Inorganic

chemistry I I 04 3 1 - 3 30

70

2 CY-504 Advanced Organic

Chemistry II 04 3 1 - 3 30 70

3 CY-506 Advanced Physical

Chemistry II 04 3 1 - 3 30 70

4 CY-508 Advanced Instrumental &

Analytical Techniques II 04 3 1 - 3 30 70

5 CY-510 Chemical Engineering for

Green Chemicals 03 3 - - 3 30 70

6 CY-552 Advanced Chemistry

Practicals II 06 - - 12 9 (2days:6+3) 60 40

Total ₂₅ ₁₅ ₀₄ ₁₂ ₂₄

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Department of Engineering Chemistry

School of Engineering & Technology

Suresh Gyan Vihar University

MSc Green Chemistry Degree Course Ist years

LIST OF COURSE OFFERED

Course

CY-501 Advanced Inorganic chemistry I ₀₄ ₃ ₁ _- ₃ ₃₀ 70

CY-502 Advanced Inorganic chemistry I I ₀₄ ₃ ₁ _- ₃ ₃₀ 70

CY-503 _Advanced

_{Organic Chemistry I}

04 3 1 - 3 30 70

_{Organic Chemistry I}

04 3 1 - 3 30 70

_{Physical Chemistry I}

04 3 1 - 3 30 70

_{Physical Chemistry II}

04 3 1 - 3 30 70

_{Instrumental & Analytical}

Techniques I

04 3 1 - 3 30 70

_{Instrumental & Analytical}

Techniques II

04 3 1 - 3 30 70

CY-509 Principles of Green

Chemistry 03 3 - - 3 30 70

CY-510 Chemical Engineering for Green

Chemicals 03 3 - - 3 30 70

CY-551 Advanced Chemistry Practicals I

06 - - 12

9 (2days:6

+3)

60 40

CY-552 Advanced Chemistry Practicals II

06 - - 12

9 (2days:6

+3)

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CY-501

ADVANCED INORGANIC CHEMISTRY I

C (L, T, P,) = 4

(3, 1, 0)

Objectives:

To understand the mechanism of a chemical react ion. Understand the techniques involved in the subst itut ion, addit ion and el iminat ion react ions. o appreciate the concept of subst itut ion, addi t ion and el iminat ion react ions and their react ion mechanism.

UNIT-1 : AROMATIC AND ALIPHATIC ELECTROPHILIC SUBSTITUTION - Aromat icity of non-benzenoid

and heterocycl ic compounds - Aromat ic electrophi l ic subst i tut ion: Mechanism, orientat ion and react ivity - Quant itat ive treatment of react ivity in the substrates and react ivity of the electrophi les. Select ivity relat ionship Hammet t and Taf t equat ions, the ef fect of the leaving group. Linear Free energy relat ionship. Reactions involving: a) Nitrogen electrophiles: nitration, nitrosation and diazonium coupling b) Sulphur electrophiles: sulphonation c) Halogen electrophiles: chlorination and bromination d) Carbon electrophiles: Friedel-Crafts alkylation, acylation and arylation reactions. echanisms: SE2 and SEi , SE1 ; Subst itut ion by double bond shif ts; other mechanism: addit ion-el iminat ion and cycl ic mechanism. ) Hydrogen as electrophile: Hydrogen exchange; hydro-dehydrogenation; keto-enol tautomerism. b) Halogen electrophiles: Halogenation of aldehydes and ketones; carboxylic acids c) Nitrogen electrophiles: aliphatic diazonium coupling; direct formation of diazo compounds; direct amination; insertion by nitrenes. d) sulphur electrophiles: sulphonation, sulphenylation. e) carbon electrophilesacylation; alkoxy carbonyl alkylation; alkylation; Stork-enamine reaction; insertion by carbene.

UNIT-- 2 : AROMATIC AND ALIPHATIC NUCLEOPHILIC SUBSTITUTION - Mechanisms: SNAr , SN1 and

Benzyne mechanisms. - React ivity, Ef fect of structureleaving group and at tacking nucleophi le. Typical react ions: O and S-nucleophi les, Bucherer and Rosenmund react ions, von Richter, Sommelet-Hauser and Smi les rearrangements. SN1, ion pair , SN2 and neighbour ing group mechanisms. Nucleophi l ic subst i tut ions atan al lyl ic carbon, al iphat ic tr igonal carbon and vinyl carbon. React ivi ty: Ef fect of substrate, at tacking nucleophi le, leaving group and the medium - Swain-Scot t , Grunwald-Winstein relat ionship - Ambient nucleophi les f study: Hydrolysis of alkyl hal ides, acyl hal ides, anhydrides, carboxyl ic esters and amides. Goldberg and Rosenmund-von Braun react ions, Stephens-Castro coupling.

UNIT-- 3 : ELIMINATION REACTIONS - E2, E1, E1cB and E2C mechanisms. - Syn El iminat ions - E1-E2-E1cB

spectrum Orientat ion of the double bond: Hof fmann and Saytzef f rules React ivi ty: Ef fect of substrate, at tacking bases, leaving group and medium. - Mechanisms and or ientat ion in pyrol it ic el iminat ions.

UNIT-4 : FREE RADICAL REACTIONS - Long Lived and short lived radicals - Detection of radicals and

characteristics of free radical reactions. - N-group participation and free radical rearrangements, Mechanisms in aromatic substrates. React ivi ty: React ivity on al iphat ic, aromat ic substrates, react ivity in the at tacking radical , ef fect of solvent

NIT - 5 : ADDITION TO CARBON-CARBON MULTIPLE BONDS - Mechanism: Electrophi l ic, nucleophi l ic, f ree

radical addit ion. Orientat ion and React ivity: Stereochemical or ientat ion, addi t ion to cyclopropane rings. React ions: Addit ion of hydrohydro; halo; hydroxy; alkoxy; acyloxy; alkyl thio; amino; amido; alkyl ; acyl ; carboxy; -carbonyl ; -al lyl groups to double bonds. Addit ion of dihydro-oxo; dialkyl groups to tr iple bonds. Addi t ion of boranes. Addit ion of halogen-oxygen; dihydroxy addit ion; oxyaminat ion; diaminat ion.

TEXT BOOKS

1. J. March and M Smith, Advanced Organic Chemistry, 5th edn, John-Wiley and sons, 2001. 2. I. L. Finar, Organic Chemistry Vol-2, 5th edn, Pearson Education Asia, 1975.

3. I. L. Finar, Organic Chemistry Vol-1, 6th edn, Pearson Education Asia, 2004.

4. F. A. Carey and R. J. Sundberg, Advanced Organic Chemistry, Part A and B, 4th edn, Kluwer Academic/Plenum Publishers,

2000.

REFERENCE BOOKS

5E.S. Gould, Mechanism and structure in organic chemistry, Holt, Rinehart and Winston Inc., 1959 6. S. H. Pine, Organic Chemistry, 5th edn, McGraw Hill International Edn, 1987.

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CY-502

ADVANCED INORGANIC CHEMISTRY II

C (L, T, P,) = 4

(3, 1, 0)

Objectives:

To know the synthetic ic techniques in inorganic chemistry and identify speci fic reagents to synthesize important classes of compounds with reference to Green Chemistry

UNIT - 1: NATURE OF BONDING OF MAIN GROUP ELEMENTS: Types of compounds and E-H, E-X, E-O, and E-N bond types for B, C, N, Si, P, and S. Element-element and multiple bonding. Catenation and heterocatenation: polysilanes and polyphosphazenes. Alkali and alkaline earth metal complexes: l igands-alkylamines, lakesides, β dike tones, crown ethers, crypt ands, and cal ixeranes Electron def icient , electron precise, and electron rich compounds of main group elements. Al lotropes of carbon: graphic te, diamond, full lerenes-types and sat ructures, carbon nanotubes. Biological significance: chlorophyl, Na+/K+ ion pump, biological roles of alkali and alkaline earth metal ions and ionospheres.

UNIT - 2: INORGANIC CHAINS, RINGS, AND CAGES: Chemistry of simple boranes, silanes, phosphanes and sulphanes. Boranes: synthesis of neutral boron hydrides, polyhedral borane anions and dianions, structure of polyhedral boranes-nido- , arachno and closo-frameworks, PSEPT (Wade’s rules) and polyhedral geometries. Carboranes: synthesis and polyhedral geometries, metalloboranes, and metailocarboranes.Boron-nitrogen compounds: azaboranes, pyrazaboles, borazines, and B-N clustersuble bonds. Silicates: classification ion-orthosilicates, noncyclic silicate anions, cyclic silicate anions, infinite chain anions, infinite sheet anions, framework minerals, and zeolites-typical examples and structure, cyclic silxanes and cyclopolysilanes. Isopoly and heteropoly acids and salts: isopolymolybdates and isopolytungstates; heteropolyanions-structure and react ivity; heteropoly blues. P-N and P-S compounds: polyphosphazene, cyclophosphazenes, and cyclic aminophosphanes, phosphorus-oxide and phosphorus-sulfide cages. Cyclic sulfur-nitrogen compounds: tetrasulfur-tetranitride, polythiazyl, and Sx

UNIT - 3: Bioinorganic Chemistry (8h) - Heme proteins: hemoglobin and myoglobin-structure, mechanism oxygen

transport. Copper proteins: type-I, type-I I, and type- III copper. Photosynthesis: chlorophyl l, photosystem I and photosystem I I, photosynthetic reaction center. Enzymes: superoxide dismutase, carboxypeptidase A-structure and functions.

UNIT - 4: Theories of Coordination Compounds - Crystal Field Theory: crystal f ield splitting in Td and Oh f ields,

HS vs LS complexes, spin crossover. Jahn Teller Theorem: Jahn Teller effect and stat ic-dynamic Jahn Teller effect .Tetragonal distort ions f room Oh symmetry and crystal f ield splitting in tetragonally distorted octahedral and square planar geometries. Molecular Orbital Theory: Evidences of metal- ligand covalency, TASO-MO concepts of Oh and Td complexes, MO energy level diagrams of σ- and π-bonding in Oh complexes, nature of metal- l ligand π-bonds, evidences for π-back bonding, spectochemical series, and π-acceptor series. Angular Over lap Model: Principles, quantification of metal-l igand orbital interact ions (eσ- and eπ-parameters), angular over lap and geometry, angular scal ing factors for eσ- and eπ-parameters, computation of ∆ο and ∆τ and their relationship.

UNIT - 5: SYNTHESIS AND TECHNIQUES IN MAIN GROUP CHEMISTRY - Specific reagents of main group elements: fluorinating agents-ClF, ClF3, and BrF3 (harsh); SF4, SbF3, and SbF5 (moderate) and organometallic reagents-Grignard reagents, organolithium, diorganomercury, and diorganomagnesium. Solvolysis of nonmetal halides, synthesis of chains, rings, and polyhedra of B, N, and P. Synthesis of important classes of nonmetal compounds: catenation by coupling (cyclic silicon and phosphorus compounds); hydrometalation-hydroborat ion and hydroalumination; substitution by hydrogen and organics (hydrogenation and alkylation/areolation). React ivity of boranes: hydroboration react ion as precursor for metalloboraneand heteroborane clusters.

TEXT REFERENCE BOOKS

1. F. A. Cotton, G. Wilkinson, C. A. Murillo and M. Bochmann, Advanced Inorganic Chemistry; 6th ed.; Wiley Interscience: New

York, 1988.

2. J. E. Huheey, E. A. Keiter, and R. L. Keiter, Inorganic Chemistry; 4th ed.; Harper and Row: New York, 1983. 3. K. F. Purcell, and J. C. Kotz, Inorganic Chemistry; Saunders: Philadelphia, 1976.

4. D. F. Shriver, P. W. Atkins, and C. H. Langford, Inorganic Chemistry; 3rd ed.; Oxford University Press: London, 2001. 5. T. Moeller, Inorganic Chemistry, A Modern Introduction; John Wiley: New York, 1982.

6. W. L. Jolly, Modern Inorganic Chemistry, 2nd Edn, McGraw-Hill International Edition, 1991.

7. W. L. Jolly, The Synthesis and Characterisation of Inorganic Compounds, Prentice Hall, New Jercy, 1970.

8. Cotton, F. A.; Wilkinson. G.; Murillo, C. A.; Bochmann, M. Advanced Inorganic Chemistry, 6th ed.; Wiley Inter-scie York, 1988

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CY-503

ADVANCED ORGANIC CHEMISTRY I

C (L,T,P,) = 4

(3,1,0)

Objectives:

To understand the mechanism of a chemical react ion, the path and the feasibility of a react ion. Synthetic route, to understand the techniques involved in the determination of mechanism of reactions and to propose methods to determine the mechanism of react ion

Unit - 1: MECHANISMS AND METHODS - Types of mechanism; Thermodynamic and kinetic requirements of react ions; Baldwin rules for ring closure; Hammond postulate; microscopic reversibility and Marcos theory Methods of determining mechanism: Non-kinetic methods: identification of products and intermediates; isotopic labeling; stereo chemical evidences; isotopic effects; cross-over experiments, trapping of intermediates. Kinetic methods- determination of rate law and rate constants; relation of rate with the mechanism of react ion. Self study: Acids and bases; Bronsted theory; proton transfer react ions; measurement of solvent acidity; hard and soft acids and bases; effect of structure and medium on the strength of acids and bases.

Unit - 2: REARRANGEMENT REACTIONS - Types of rearrangements: Nucleophilic; free radical and electrophilic react ions. Mechanisms: Nature of migration; migratory aptitude and memory effects, ring enlargement and ring contract ion rearrangements React ions: Wagner-Meerwin and related react ions, Benzil-benzilic acid , Favorskii, Hofmann and related rearrangements, Beckmann, Neber, Baeyer-Williger, Stevens, Claisen rearrangements, boron-carbon migration, Non-1,2-rearrangements, Fischer indole synthesis, Arndt-Eistert synthesis,

Unit - 3: OXIDATION AND REDUCTION REACTIONS. - Mechanisms: direct electron transfer, hydride transfer, displacement_ addition-elimination and format ion of ester intermediates3.2 Oxidation React ions: Aromatization of six member rings; dihydro elimination; oxidation of alcohols and dehydrogenation of amines; React ions involving cleavage of C-C bonds; ozonolysis; cleavage of double bonds; oxidative decarboxylation. Reduction Reactions involving replacement of oxygen by hydrogen: - Wolff Kishner and Clemmenson reductions; Removal of Oxygen from substrate; Reduction with cleavage; Reductive coupling.

Unit - 4: STEREOCHEMISTRY-I - Optical isomerism due to asymmetric carbon atoms Racemic modifications; racemisation; thermal , anion, cat ion, reversible format ion Epimerisation; mutarotation; I and II order asymmetric transformations Resolution of Racemic modifications; asymmetric transformations; asymmetric synthesis destruct ion; Cram’s and Prelog’s rules; absolute asymmetric synthesis Criteria for opt cal purity; D, L, R, S-notations; Cahn- In gold-Prelog rules, absolute and relative configuration; configurations of al lens, spiranes, and biphenyls

Unit - 5: STEREOCHEMISTRY-I I - Conformation and reactivity of acyclic systems; intramolecular rearrangement; neighbouring group participation; Curtin-Hammet principle Stability of six and seven-membered rings; mono and disubstituted cyclohexanes; conformation and react ivity in cyclohexane systems. Fused and bridged rings; bicyclic and poly cyclic systems; decal ins and Bret t ’s rule.Oxidation React ions: Aromatization of six membered rings; dihydro elimination; oxidation of alcohols and dehydrogenation of amines; React ions involving cleavage of C-C bonds; ozonolysis; cleavage of double bonds; oxidative decarboxylation. Reduction Reactions involving replacement of oxygen by hydrogen,Wolff Kishner and Clemmenson reductions; Removal of Oxygen from substrate; Reduction with cleavage; Reductive coupling.

REFERENCES

1. J. March and M. Smith, Advanced Organic Chemistry, 5th edn, John-Wiley and Sons. 2001. 2. E.S. Gould, Mechanism and Structure in Organic Chemistry Holt, Rinehart and Winston Inc., 1959. 3. E.L. Eliel, Stereochemistry of Carbon Compounds, Tata-McGraw Hill, (2000)

4. P.S. Kalsi, Stereochemistry, 3rd Edn, New Age International Publishers, 1995. 5. I.L. Finar, Organic chemistry. Vol-2, 5th Edition, Pearson Education Asia. 1975 6. I.L. Finar, Organic chemistry, Vol-1, 6th edition, Pearson Education Asia. 2004

7. F.A. Carey and R.J. Sundberg, Advanced Organic Chemistry Part-A and B, 4th Edn, Kluwer Academic/Plenum Publishers2000.

8. S.H. Pine, Organic Chemistry, 5th Edn, McGraw Hill International Edition. 1987. 9. L.F. Fieser and M. Fieser, Organic Chemistry, Asia Publishing House, Bombay, 2000. 10. Nasipuri, Stereochemistry, Alhed Publishers, 2003.

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CY-504

ADVANCED INORGANIC CHEMISTRY II

C (L, T, P,) = 4

(3, 1, 0)

Objectives:

To understand the mechanism of a chemical react ion. understand the techniques involved in the subst itut ion, addit ion and el iminat ion react ions. o appreciate the concept of subst itut ion, addi t ion and el iminat ion react ions and their react ion mechanism.