& ALLAMA IQBAL OPEN UNIVERs] : TY BS/M.So. Chemistry Tif geolt Se 1 Stereochemlstry of Organic Compounds (2 eetan Par wed: 03 Hours #586) Memunatas #2016 ‘Time Allowed: Pass Marks: i a EMPT FIVE TIONS. Note: ATT! QUESTIONS. ALL CARRY EQUAL M [ano | (ae : : Questions Q#i! |4) Define and explain the differences between enantiomers and diastereomers by citing Marks suitable examples. ay b) Draw all possible isomers of C4H6, for each par of structures identify whether they are | (9g constitutional or stereoisomers. Q#2 | What are geometrical isomers? Discuss the nomenclature of geometrical isomers in detail. | (29) _ Q#3 | a) Make a comparison between conformations and configurations. (uy b) Explain with suitable example/s (09) i) Homotopic ii) Bnantiotopie _ iti) Diastereotopic Qua a) Discuss methods used for distinguishing cis-trans isomers. (ui) b) Explain with suitable example/s i)Ring strain ii) Angle strain iii) Optical acitvity (09) “Qi#5 | What is asymmetric synthesis? Elaborate your answer ‘by citirig example of sharpless 20) epoxidation, Discuss historical development and importeince of it, Q4H6 | a) Differentiate between stereoselective and stereospecific reactions by discussing two a4 reactions of each type. b) Explain the following terms with suitable examples. (06) i) Chirality ii) Alternating axis of symmetry _ifi) Meso compounds #7 | 5) Give reasons for the following reactions. a0) | ‘tBu, H NaOH t-Bu, H wo Oke | ———_——+ Ww ee Feat ce tBu, OAc NaOH tBu, y {OH wt Hee aH Slow b) Discuss the optical isomerism in substituted allenes and biphenyls. #8 Q a) Assign the absolute configuration to each stereocentre in the following i) wphcou ii) Ju iti) rh HeN’ 'CO.H ") Be wy Hscoac. 02H ' oa if Bec HgcoH,c® "“CH2OH b) Discuss conformational isomerism by citing example of cyclohexane. Explain conformational energy profile. (20)ALLAMA IQBAL OPEN UNIVERS Iry BS/M.Sc. Chemistry ; f : Sa Spectroscopic Methods in Organic Chemistry (2589) ester: : Maximum Make; Spring 2016 100 M6 towed: 03 H pint Allowed: fours Pas Wate 50/40 Note: ATTEMPT FIVE QUESTIONS. ALL CARRY EQUAL MARK. S. Q-1. a) Write down the NMR equation and explain the variables in the equation. (5) b) What is Boltzman Population Excess? State and explain Boltzmann Population Distribution equation. (5) ¢) Calculate the energy difference between the two spin states of: (5) i)*H in a magnetic field strength of 7.05T. 1 y= 267.512x10° rad Ts? ii) °C in a magnetic field strength of 7.05T. Y o= 67.264x10° rad T's d) A proton has a chemical shift (relative to TMS) of5.56 ppm. i) What is its chemical shift, expressed in Hz, in a 300 MHz instrument? il) What is its resonance frequency, expressed in Hz, in a 300 MHz instrument? On a 200 MHz instrument?(Assume that in the instrument, the TMS protons resonate at exactly 300 MHz) Q2 a) Identify the protons shown in each molecules as Homotopic, diastereotopic ae f Enantiotopic ot Clo) \ H Me. 0. 7 Ch hs a0) O a o‘" 0 nt 00. 0. oO. OW - ~— ee my 5 ~— x, nga 5 fe} (10) b) Solv ructur Formula is CsH: ) Solve the Structure. Moleculal la is CsHe pro— 6508 683 —— S939 ——— 63 — 6582 = — 6553 Lo i f Q-3a) In Benzaldehyde two of the ring protons have resonances at 7.87ppm while the other three protons in the range of 7.5to 7.6ppm.Explain. (05) b) Assign Spin System to the following molecules, and provide approximate chemical shift and splitting pattern(multiplicity) for each proton. tos) chy Hy cH TO cats CH CH— CH chy Re cH cH, () {b) {ec} (a) (e) c) There are three isomeric pentanes with a molecular formula of CsH12 Draw structural formula for each of these compounds, name them and draw their 33 C- NMR spectra ( No. of signals and approximate chemical shifts). (10) Q-4 Assign Spin system to the following molecule, Assign chemical shift to each multiplet and calculate coupling constants for all couplings. (20Q5a) How can you differentiate between the three molecules from their H- Ay cl Hy == _ Hy Hy a Hp ot ca cl ci >< He Cy (by © NNR spectra. (05) b) Justify the mass spectrum of Butylbenzene by writing the fragment ions for m/z:105, 91, 79, 65, 53,39. Moreover, identify base peak. (10)Relative Abmniene ss with suitable examples. (05) ) Define Average Mass and Monisotopic Ma: entiated Q-6a) How could the following pairs of isomeric compounds be differ aa 1 by mass spectrometry. ® (CHy~CH,~CHy Or oho i ie ot eta, wt af Scag her CH wy b) An unknown Hydrocarbon has a molecular ion peak at m/z 84, with a relative intensity of 31.3.The M+1 peak has a relative intensity of 2.06 and M+2 peak of relative intensity 0.08.Calculate the molecular formula for the hydrocarbon. ; Cie) Q-7a) What do you understand by.the term ‘Broad Band Decoupled 3C-NMR . What are the advantages and disadvantages of Broad Band Decoupled °c NMR spectra. How is DEPT useful in structure elucidation? (10) b) Write Short notes on the following: (10) i) Mactafferty Rearrangement _ii) Retro Diels Alder Fragmentation Q-8a) Predict the structure of the unknown organic compound on the basis of following data: (10) Molecular Formula: CicHia *H-NMR: 6 (ppm): 7.61(5H, m), 2.89(2H, d, J=7Hz), 2.29(1H, nonet, J=7Hz), 1.34(6H, d, J=7Hz). 3C.NMR: 6 (ppm): 141.8, 129.4, 128.4, 126.0, 45.8, 30.5, 22.7. b) Explain why the signals of acid labile protons are generally broad. (05) c) Explain Why quaternary carbons give weak signals in *C-NMR. (05)ALLAMA IQBAL OPEN UNIVERSITY Level: I Paper: ee Chemistry Somoster: Autumn 2018 Time All Ctenoeyclic Chemistry (2585) Maximum Marks: 100 «Allowed: 03 Hours Pass Marks: 50/40 Note: ATTEMPT FIVE QUESTIONS. ALL CARRY EQUAL MARKS. Q.No.1 4) Write down names of following heterocycles according to IUPAC nomenclature? Oy H S\/ 0. S N Ph G ‘si, [ \ NH 3

) Suggest a reasonable mechanism for the following Vilsmeier-Hlaak formylation reaction, © CY POCIs, HCONMe, oS ©) Propose the major products for the following reactions of indole, @ 4) Postulate a reasonable mechanism for the’gischer indole synthesis. (8) QNo.6 a) Explain that both pyridine and nitrogen containing heterocycles but pyridine behaves as a base while pyrrole has ly acidic properties. 4 +b) Suggest a reasonable mechanism for the ‘Hantzsch Synthesis of pyridine. (10) oO Bt0Oe. /COOFt wt i N ) Predict the major products of the followiakedction of pyridine, Q) Ke, a B CO eg 4) Explain the mechanism of Chichibabiu@Action of pyridine to produce 2-aminopyridine derivatives, 3 co Q.No.7 4) Suggest a reasonable mechanism for the following synthesis of imidazoles, @) Ph me oe wh Soon Page 3 of 4Allama Iqbal Open University Level: BS/M.Se. Chemistry Semestfis Spring 2017 Paper: Spectroscopic Methods in Organic Chemistry (2589) Maxim ‘Marks: 100 Time Allowed: 03 Hours Pass irks: 50/40 Note: ATTEMPT FIVE QUESTIONS (Ingluding 0.10 which is compulipr ALL CARRY EQUAL MARKS, ey Qa) Derive the fundamental equation of Lh io) mac” ein AN ca wi et rei NMR (05) Senin rene at ty ten (05) ‘Q2a) How does the phenomenon of res : 0) b) Define diamagnetic anisotropy. “S i © © Gene and ce of che cop ead fen NMR © Q3a) Define the flowing terms: Ringing an{iperation, _ 6 b) Predict the structure of the compound tonf oie mass spectrum ©{ , ALLAMA IQBAL OPEN UNIVERSITY Level: Paper, ‘Time Allowed: 03 Hours BS/MSc. Chemistry ‘Semester: ‘Spring 2017 Stereochemistry of Organic Compounds (2586) Maximum Marks: 100 Pass Marks: 50/40 Note: ATTEMPT FIVE QUESTIONS, ALL CARRY EQUAL MARKS. [ Q.No Juestions Qa 8) Assign stereochemistry to the (Mowing compounds according to E/Z system. HO » 2 CH, Hse cl 3) YT 3 =, B>Apa' Hooc™ “ 2 5) ll bY Asa ‘on 2. A ‘ ) Assign absolute configuration to(eagh stereocentre in the following structures, 33 bs Hom “ydey 2 dc ‘Coon = x 2 2 e £ toALLAMA IQBAL OPEN UNIVERSITY BS / MSc Chemistry Semester: Spring 2017 Paper: Heterocyclic Chemistry (2585) Maximum Marks: 100 Time Allowed: 03 Hours Pass Marks: 50 Note: ATTEMPT FIVE QUESTIONS. ALL QUESTIONS CARRY EQUAL MARKS. Q.No.1 a) Write down the criteria to establish base component of a polycyclic heterocyclic compound according to Hantzsch nomenclature, Explain by giving names to following heterocycles. (6) Courmee) NON 'N x7 @ = ) b) Propose a reasonable mechanism for the folfywing Corey Synthesis of oxirane. (4) ee cxyfpriso wo J HyC” CH; HC oO ©) Deoxygenation of 2,3-disubstituted oxirang§Jo olefins using triphenyl phosphine is a stereo selective reaction, Explaid by giving suitabl es. © 4) Briefly explain the structure, synthesis andigpplications of epoxy resins? 4 Q.No.2 a a) Explain by giving suitable examples that im{@Gzoles behave amphoterically? @ b) Propose a reasonable mechanism for followfag Radiszewski synthesis of imidazoles. © Pay PhO O° t + 2 I M RCH Ph’ R Pao W ©) Suggest a reasonable mechanism for the following reaction of oxazoles, © R, R, ‘N N ‘NH; Th, eT R 0" R N’ R H 4) Discuss the importance of f-lactum ring for biological activity of penicillin’s? (4) Page 1 of 3