22. 23. 24. 25. a) Describe the diastereoselective synthesis, (or) b) Explain the saponification of ester. a) Explain the effect of aromaticity on induced ring current and resonance energies. : (or) b) What are annulenes? Explain its aromaticity with examples. a) Explain the synthesis and reactions of oxazoles. (or) b) Elucidate the structure of zingiberene. a) Discuss the mechanism of Knoevenagal reaction. (or) b) Explain the mechanism of Demjanoy rearrangement. SECTION-C (3*10=30) Answer any THREE questions. 26. 27. 28. 29, 30. (i) Predict the preferred conformation of 1,2 and 1,3 di substituted cyclohexane. (6) (ii) Explain the stereochemistry of allenes. (4) (i) Discuss the conformation and reactivity of di substituted cyclohexanone. (6) (5) (ii) Write a note on sharpless asymmetric epoxidation. (i) State and explain Huckel’s rule of aromaticity. (ii) Discuss the aromaticity of azulene. Establish the structure of morphine. Explain the mechanism of the following rearrangements (i) Claisen rearrangement. (ii) Sommelet-Hauser rearrangement. eeeapimidazere” b) thiazole > ona cj oxazole > imide d) imidazole? oxaz ‘ane double bond must be Present bet, zole > imidazole fovele > thiazole fole > thiazole 14, In morphine Ca Ce BNC )Ce-Cw dd Conca eae ample for antimalarial drug is. * aeorphine bquinine ©) Papaverine rq 16, Oxidation of a-pinene in presence of sunlight gives SerDing a) sorbrerol+verbenoltverbenione a by sorbrerolrcamphor+borneo! <¢) sorbrerol+borneal+isoborneo! d)sorbreroltcamphortisoborneot 17. The best reagent for Knoevenagel reaction is. a) pyridine/piperidine b) sodium ethoxideyetha, In ©) KOH/EtOH d) EtsN/EtOH by 18, Which of the following mechanism proceeds via lactone formation? a) Stobbe condensation b) Vilsmeier - Haack c) Knoevenagel d) Houben - Hoesch 19, In Neber rearrangement, the intermediate is, a) oxime b) oxime c) azirine 20. Demjanov rearrangement reaction involve: a) reduction d) oxine b) diazotizay) 6) diazotization+ring expansion/ring contraction d) only ringad SECTION-B (5*5=25) Answer ALL the questions. >I. a) Explai 21. a) Explain the Newman and Fisher projection formulae. | (or) b) Discuss the stereochemistry of decalin. 24. a) Write a note on Vibrational Raman spectra. (or) b) Explain in detail about Laser Raman spectroscopy. 25, a) Discuss about Spin - Spin Coupling Mechanism in NMR spectra. Give an example. (or) b) Write Bloch equations and explain it in detail. SECTION-C (310-30) Answer any THREE questions. 26. Prove that Cav point group is Non-Abelian point group 27. Discuss about the vibrational modes of H:O and NHb in IR and Raman spectroscopy using group theory. 28. (i) Compare crustal symmetry and molecular symmetry. (5) (ii) Determine the hybridization scheme of methane molecule using group theory. 6) 29. (i) Give an account on PQR branches with energy level diagram. 6) (ii) Narrate the effect of isotopic substitution on vibrational frequencies. 8) 30. (i) Explain the theory and advantages of 2D-NMR spectroscopy. 6) (ii) Describe the effect of quadrupole nuclei on relaxation mechanism. ©) ee16. The molecule wiuch is” vO is a) HCl b) SO : ax 17, An example of spinning nuclear magnet is ‘ot by BCs 0" ays, 18, Anisotropic chemical shift values are possible for a) Solids byLiquids —_«) Gases @) Ema 19. The spin-lattice relaxa tion time gap may be measureg ty ay COSY b) NOESY ¢) Inversion recovery method gy 20. Which one of the following is example of NQR active a) a)*Hi b) Ce ©) "Fu 4)"p,, ‘| SECTION-B (5*5=25) Answer ALL the questions. 21. a) Define abelian group. Explain an abelian group witha (or) b) Using great orthogonalitytheorem derive the charactyi) for Cav point group. 22, a) What is meant by direct product? Explain in detail. (or) b) Discuss about electronic transitions in formaldehydess group theory. 23. a) Explain in detail on Hermann Mauguin symbols in pe group. (or) b) Describe about Symmetry Adapted Linear Combinatitt (SALC) procedure in detail. 22, 23. 24, | 1) Show that 18 electron rule is followed in CoxCO)s (or) by Explain the properties of ferrocene. a) What is meant by metathesis ? Explain with an example (on) by Discuss the structure and function of urease. a) Discuss L-S coupling and j-j coupling, (9 b) Discuss the Orgel diagram of high spin d' complexes. a) Discuss the structural elucidation of NOr with Raman and IR spectral data. (or) b) Explain the synthesis of transuranic elements. SECTION-C (310-30) Answer any THREE questions. 26. 27. 28. 29. Discuss any one theory of Trans effect. Explain i) The properties and structure of Vaska’s complex ii) The structure and properties of Fe(CO)s i) Disc the structure and functions of cytochrome oxidase. Explain mechanism of Olefin Oxidation by Wacker process. Discuss i) L + M Charge transfer spectra. ii) Compare Orgel and Tanabe - Sugano diagram. . i) Discuss the effect of isotopic substitution on vibra ional frequencies of metal carbonyls. ® ii) Explain the applications of MB spectra to iron complexes. (6) waetee18. Which of the following methods used for terpenoids? a. steam distillation b, solvent extractions c. enfleurange proc d. all of these 19. A bicyclic monoterpenoid used in Rast method for determination of molecular wt is jation of a.menthol b.a-pinene ¢. camphor d. borneol 20. Which is not a terpenoid? a.zingiberene b, squalene c. cholesterol. d. lanosterol SECTION-B (5x5=25) Answer ALL the questions. 21. a) Explain Newman projection formula with example. (or) b) Explain asymmetric synthesis with example. 22. a) Derive Weinstein - Elie! equation. (or) b) What is saponification of ester? 23. a) Explain the Cope rearrangement with mechanism. (or) b) Discuss the Demjanov rearrangement with mechanism. 4. a) Explain the photosensitization with suitable example. (or) b) Discuss the Woodward Haffmann rules for electrocyclic and cycloaddition reactions. 25. a) Elucidate the structure of camphor. » (or) a b) Describe the structural elucidation of flavone, SECTION-C (3*10=30) Answer any THREE questions. 26. Explain the conformational analysis of “aisub tt cyclohexane. \ 27. State and explain Huckel’s rule for aromaticity wig example. 28. iscuss the Schmidt and Neber rearrangements vg mechanism. 29, Explain the Frontier molecular orbital approach ir addition reaction. 30. Explain the structural elucidation and medicinal we zingiberene, eee |guish between crystal symmetry. : TY With mol, cular Di vn) ymmee ae the effect of isotopic substin i: write the ‘ PIC substitution ©n Vibratio frequeney n (or) in the theory and ady, explain ery Antages of Raman scattering, BSS of surface enhanced p) Write Bloch equation and highlight its importan ‘ance. SECTION-c (3*10=30) answer any THREE questions, 26. 29. 30. Give a detailed account ona Systematic procedure for symmetry classification of molecules, . How will you determine the symmetry of vibrational modes and their Raman activities in NH, molecule? . Explain briefly about SALC. How it can be used by Projection Operator. a) Write a short note on properties and types of lasers [6 marks}. b) Write the advantages of laser Raman spectroscopy [4 marks] jour of bar magnet in a magnetic Jain the behav! 2 fe a NMR spectroscopy [5 marks] b) How will you measure T: by FTS in FT-NMR {5 marks] spectroscopy? setective Bul Kaman active 5, 10 Ni yee is studied in by Radiofrequency A) Visible region ye nuclear magn 16. The molecule which is TR in a. HCl b.SO: © 17. The proton magnetic resonan a) Microwave region ©) Infrared region 18, Nitrogen has nuclear spin of 1. Ths “log resonance of nitrogen has a) On . J Three lines d) Five the tscale ald b.6 25 dig 20. Which is used as lard reference in 'H-NMR spectroscopy? a.DPPH — b.KBr TMS 4.CDch SECTION-B (5*5=25) Answer ALL the questions. 21. a) Examine the symmetry operation performed in tetraheg,, and octahedron symmetry element. (or) b) Construct a character table for C2. point group. 22. a) Explain briefly the electronic transition in HCHO and applying group theory. (or) b) Write the selection rules for vibrational and rotational spectra in IR spectroscopy. 23, a) Explain briefly about the Hermann-Manguin symbol in symmetry of crystals. (or) ain yitann” How is its goin the following reaction wi 17. ExPIipy reduction Mpipmensen reduction in -C? a exempts: mechanisms of Benzo th OF Benzoin and Dargo jensation reactions. atzen's Rlycai c ynthesized by glucose? (5)8. What is stereospecific re : 9. What are Morphine 10. Complete the following reaction and predict the product Zingiberene —>—> ? SECTION-B (5*4=20) Answer ALL the questions. 11. a) Write any two synthesis and uses of thiazole. (or) b) Give an account on non-classical carbocations. 12. a) Derive Hammet equation and write the significance of pando. (or) b) What is Isotopic effect? Explain its types. 13. a) Discuss the conformational Analysis of Decalin. (or) b) Illustrate Cram’s rule with example. 14. a) Write the esterification reaction of an alcohol. (or) b) Explain sharpless asymmetric epoxidation with example. 15, a) State Huckel’s rule and say whether the follo compounds are aromatic (07) not () SZ ay (or 4 b) What are sydnones? Explain how it behaves as, aromatic compound. SECTION-C (310-30) Answer any THREE questions. 16. 17. 18, 19. 20. What are nitrenes? How they are generated? Discus, structure. Illustrate how the following experiments are usedin determining the reaction mechanism? 1. Product analysis. 2. Cross over experiments, How will you determine the configuration of g¢ isomers by physical methods? State curtine - Hammet principle show that the prod ratio depends on the difference in energies of two Transition states with suitable example. Write the structural elucidation of zingiberene., Reserpine isa diester, These two ester groups are attached to a. The same ring, ¢, The indole nucleus b. different rings d. none of these TON-B (55°25) Answer ALL the questions. 21. a) Show how decalin exist in two diastereoisomeric forms and represent in Newmann projection formula. (or) b) Write the various methods of determination of configuration of geometrical isomers. 22. a) Derive Winstein-Eliel equation. Write its significance. (or) b) Whatis stereo specific and stereo selective reaction? Explain with examples. 23. a) What is Darzen’s glycidic ester condensation reaction? Explain with mechanism. (or) b) Explain Claisen rearrangement with mechanism. 24, a) Explain photoreduction of ketones by Norrish type I reaction. (or) b) Show (442) cycloaddition is thermally allowed.as Give the hydrolysis and oxiq 6, nae ation re, 17 and show that itis diester ‘ ‘Action of and has oy reve, A Tpine Ne indole te Nucleus, p) Elucidate the structure of squalene SECTION-C (3% 10-30) answer any THREE questions, 36. a) Write any two methods of asymmetric synthesis. b) Discuss the various conformations of disubstituted cyclohexane and mention its stability, (5) (5) 77. a) Classify which of the annulenes are aromatic (or) non aromatic. Explain with structure. i) [14] annulene ii) [16Jannulene iii) [18] annulene iv) [10] annulene (6) b) What is saponification? Explain the various steps involved in the mechanism of saponification of ester. (4) 28. Explain th mehanisms: (i) Neber (ii) Dienone - phenol owing rearrangement reactions with 29. What is sigmatropic reaction? Explain (i) [1,3] (ii) [1,5] and (iii) [3,3] sigmatropic ) rearrangements. | Give the oxidative degradation of a-pinene and establish its structure. yapSECTION-B (5*5=25) Answer ALL the questions. 21. a) List the rules to form a group. (or) b) Define symmetry element and symmetry operations. Also write the symmetry elements and its corresponding, symmetry operation. 22, a) How mutual exclusion rule can be derived from group theory? Explain with reference to COr, NH and FLO. (or) b) Give the symmetry selection rule for IR, Raman and electronic spectroscopy. 23. a) Compare molecular and crystallographic symmetry. (or) b) Write a note on SALC procedure in group theory. tional - vibrational spectra of a 24. a) Discuss the theory of rotal armonic oscillator. diatomic molecule assuming as a h (or) b) Explain the properties and types of laser. 25. a) Explain the effect of quadrupolar nuclei on relaxation mechanism. (or) b) Write the theory and advantages of 2D NMR.SECTION. o +C (3x Answer any THREE questio (310-30) stions, 26. a. Construct ¢. 2y characte; , orthogonality theorem, . Assign the point Bre 5 Assign the Broup of the following, molecules: (ii) carbondioxide (iii) allene ‘able on the basis of great 27. Determine the symmetries of vj ? f vibrati molecule and show which is IR ce modes of water Obtain the possible hybridizati y ion sch ii using group theory. eme in CH: molecule a) Explain P,Q, R branches in vibration — rotation spectroscopy. b) Explain the following: (i) hot band (ii) overtones (iii) combination bands. Outline the principle and discuss the applications of nuclear magnetic resonance imaging (NMRI). seeSECTION-B (5*4=20) ‘Answer ALL the questions. 11. a) Give the IUPAC names for the following compounds. ce r () CH,C=CCH, (ii) CH,-CH,-CH =CH-CH,-CH, Br (iii) CH,\CH, ~CH~CH,CH, (iv) CH, =CH-CH = CH, (or) b) Discuss the generation and structure of nitrenes. 12a) Derive Hammet equation and write the significance of pand (or) b) Whatis Isotopic effect? Explain its types, 13a) Discuss the conformational analysis of Decalin. (or) b) Ilustrate Cram’s rule with example. 14. a) Explain the reaction of chromic acid oxidation of cyclohexanol and substituted cyclohexanols, . (0) b) Write a note on stereospecific and stereoselective syntheses. 15, a) Discuss the aromaticity of annulenes, (or) b) Write the medicinal values of quinine, SECTION-C (310-30) Answer any THREE questions. 16. Give the preparation and reactions of Imidazoj Thiazole, 17, Illustrate how the following experiments are ug, A determining the reaction mechanism? 1. Product analysis. 2. Cross over experimen 18. How will you determine the configuration of geome isomers by physical Methods? 19. a) Compare the products obtained in the dear reaction of Cis - and trans - 2 — b) State minaig aminocyclohexay, and explain Curtin ~ Hammett principle y 0. Write the structural elucidation of zingiberene. Porennya) ‘ - —=_, « ~ aoe 1 G& Of the three Sten inactive whkh Ss re stenso specific reactions? I Sroup participation? © What is meant by cing current effect? 10. State Huckel's rule of Aromaticity. SECTION-B (5x4=20) Answer ALL the questions. 11a) Write any two synthesis and uses of thiazole. (or) b) Give an account on non-classical carbocations. 12. a) How isotopic labeling studies help in determining reaction mechanism? (or) b) Write the application of Hammett equation and the significance of sigma and rho. 0 isomers of tartaric acid, one is optically 13. a) Draw the various conformations of cis- and decaline and mention its stereochemistry, (or) : b) Explain the optical isomerism exhibited by by 14. a) Write the esterification reaction of an alcohol _ (or) , b) Explain sharpless asymmetric ——s—s " 7. What is soapanification reaction? 8. What are stereo selective reactions? 9. Draw the structure o| 10. Identify whether the following compound is aromatic or non-aromatic. Answer ALL the questions. 11. a) Write the synthesis and reactions of imidazole. (or) b) List out the nomenclature rules of alicyclic and bicyelic compounds. 12. a) Explain the Primary kinetic isotopic effect with an example. (or) b) How does the cross over experiments support in determining reaction mechanism? 13.) Discuss the conformation analysis of cyclobutang , (or) b) Explain the concept asymume!ric synthesis, 14.) Explain Neighbouring GP with suitable exampye (or) b) Explain conformation and stability of disubsttuey cyclohexane. 15. a) What are alternant and non-alternant hydrocarber.s Explain with example. (or) b) Describe the aromaticity of sydnones and fullerene: SECTION-C (3*10=30) Answer any THREE questions. 16, What are benzynes? How they are prepared? Desa: their structure and stability. 17. Derive Hammett equation and give its significance, 18. Differentiate enantiomers and diastereoiosmers with examples, Assign E/Z notations for following compre 19. Derive Weistein - Eliel equation. 20. Write the structural elucidation of quinine.10. Draw the structure of NS. SECTION-B (S«4=20) Answer ALL the questions. 11. a) Explain the Template effect. cr) b) Explain about the factors which affect the stability of coordination compounds. 12. a) Give short note on insertion reactions, (or) 'b) What are the functions of urease and hydrogenase. Give one example in each case? 13. a) Account the following : (or) b) How will you explain the Tanabe-Sugano diagram for [Cr(NHb})* complex? ‘oupling ii) L-S coupling 14. a) Explain the spectral characteristics of coordination compounds of actinides. (or) ») List out the applications of IR and Raman spectroscopy in the structural elucidation of compounds. 15. a) Give the preparation and structure Of borazines, (or) b) Write about the effects of isotopic substitution on vibrational spectra of metal carbonyls, SECTION-C (3*10=30) Answer any THREE questions. 16, Enumerate the electron transfer reactions of complementary and non-complementary reactions 18. a) Derive the term symbol for P* system. b) Bring out the characteristics of Orgal diagram, 19, Illustrate Mossbauer transition, isomer shift and quardrapole effect. 20. Give an account on the structure of phosphazene uisg Craigg, Paddock and Dewar models.