C. S. (MAIN) EXAM, 2099 SNe. 258 CHEMISTRY Paper I 0886sSs=$=—0 Sl INSTRUCTIONS Each question is printed both in Hindi and in English. Answers must be written in the medium specified in the Admission Certificate issued fa you, which must be stated clearly on the cover of the answer-book in the space provided for the purpose. No marks will be Siven for the answers written in a medium other than that specified in the Admission Certificate. Candidates should attempt Question Nos. I .and 5 which are compulsory, and any three of the remaining questions selecting at least one question from each Section. Assume suitable data if considered necessary and indicate the same clearly. The number of marks carried by each question is indicated at the end of the question. Symbols and notations carry usual meaning, unless otherwise indicated. fart Saget ar feet STR Be RA-TF & ees ge We Bae} :Section ‘A’ 1. Answer any three of the following : (a) What are the products from ozonolysis of ortho-xylene after treatment with Zn ? 20 (b) () What kind of substitution on benzene ting stabilizes the phenyl carbanion and where is it most effective ? Explain mechanistically. (ii) Which has higher dipole moment between D= 3 and CHs 4 Cyes and why ? 15+5 CH; (c) Pyridine follows nucleophilic substitution easily but not electrophilic. Explain mecha- nistically. 20 C-DTN-J-DIB 2 » (Contd.)aus ‘a’ 1. freaferfaa & & fend cite & sax aif - (&) sthafsnscitt &, Zn & are afeefaa axa ava, ataie- fase at ox ala & Gee aaa e? 20 (@) @ ait aaa a fee gar af sffema fra arated ar cari ax Sar & ait ae fea sete 9¢ Fae SAAT THAT Stat @ ? aifenc: eat ara at ere Arc | Gi) O-Q« eds cre CH; & ata fea ar saax feua arf @ sik wat ? 15+5 (a) fae orarit & arfreetet offeroa ar aqecr adit @ afer etagmeret at ae aifrea: ere fre | 20 C-DTN-J-DIB 3 (Contd.)(d) What are the catalyst(s) for the following chemical reactions ? (i) Aldol condensation (ii) Claisen condensation (iii) Perkin reaction (iv) Fries rearrangement (vy) Pinacol-pinacolone rearrangement 20 CH3 2. (a) Fusion of Teh with NaNH, gives cl two derivatives (m & p). Explain mechanisti- cally. 15 CH; * _Br (b) Optically active aN on refluxing in H CoHs polar solvent like THF or DMF recemizes but it does not occur in cyclohexane. Explain. 15 (c) For conversion of CgH¢ to C6Dg using excess DCI, the used catalyst is one of the following. _ Identify it and justify with mechanism : (i) H,SO,4 (ii) Pd (iii) Pt (iv) Ni. 15 (d) The addition of Br, to CH, = CH, in presence of excess CI~ produces Br —-CH,-—CH,-Cl as one of the products. Explain mechanisti- cally. 15 C-DTN-J-DIB 4 (Contd.)(3) freafafaa cee afifeaorit & faa ata & vars? G) Uesta aaa Gi) Fete HaAT Git) Wa arar (iv) erest qafaearet (vy) frarata-fraraitcie gaffer 20 CH; 2. (#) 3 NaNH, % ara eer & at Or, at aera (m ait p) ae Stet & | aire: ease afrfore | 15 * (@) garitaa: afer ae ada fae, H CoHs 3@ THF at DMF, 4 dgeaa at % are Ueritsea et ora & aft ae area areacieaae # vet edt & | ease Afar | 15 ee eee CoD, # Sticke axa & fee freafafaa FF firett cap Sew apr gece fear sire @ | Sah gear Alfa atk aifracat & ara saat aer Seay: @ H,SO, (ii) Pd (iii) Pt Gv) Ni 15 (3) safe ci- ft safeafa 4 CH, = CH, # Br, art & sat arr genet 4 A GF Br—CH,- CH, — CL aaa @ | £8 Set Ht aie: TART | 15 C-DTN-J-DIB 5 < (Contd.)3. Identify the intermediates and products in the following reactions ; (a) an a) Mg H* CHa — C— Cells Sy per> A pentane” a) 1; + NaOH Be = b) acid c+D 4x3=12 (b) NaBH. GS +80: —> A ——>B Pd a 3x3=9 (7 ‘) CONH3 NaNO OBr_ +HCl oy CH; i -Cresol NayS20. Bee See +B 5x3=15 +alkalic (d) ‘So + CH) =CH— CH; WAS —S2> p EPS c+p 4x3=12 ©) 9- Co (CHy).- CHS Cl. Zn (Hi AIS 4 ees 236 heat HCI OH C-DTN-J-DIB 6 (Contd.)3. Prafafaa afifeenrsit % aeaaffat atc geri Ft wear aif : (*) i Ci, =O Gg, SS 4 : “* by HCI treat 5. HS Sap 4x3=12 b) stat : (=) Nab a S +80; —— > A Osi we fo a 3x3=9 T al CONH; NaNO, Br +HCI _— > AB cH; m- NazS204 +E = Paeeee ee Cc D+E 5x3=15 oo Icl Ce) +cH,=cH-cH, ACh, , O25 HPO op 4x3=12 : SAT () | 9 co- cH) CH; AICl, Zn (Hg) 2x3=6 iangine = OH C-DTN-J-DIB i; (Contd.)NaNO? HBr “nor 2“ cur 2? 2x3=6 Hcl CuBr CHs 4. (a) Explain the following transformation through mechanism . CH; CHs CH; > CHS + - 3 cl CH; Camphene Chloride - (b) Identify the products in following reactions : CHCHC-H + CH;0 mild alia ° we 2x4=8 Gi) OH _CHC1 / KOH, reflux. Acidify, steam distil (CH;CO),0 CH;COONa reflux 2x4=8 C-DTN-J-DIB 8 jibNG, Se 2x3=6 HCI CuBr ere CH; 4. (&) aifrecat & aren @ freafefea eciacr at aAaTRT : Nay CHy CHs _— CH: 3 CH, cl cl CHy ahha aaergs 20 (@) Feafefaa afifrareit ¥ genet ar cearfre : @ cuycnsc-1 + cH,0 —*25E ys 4 3" 2" 2" é treat aH5BOs 2x4=8 Gi) on CHCl; / KOH, tee arrettnen Afra, ary fire, araaa Athra (CH,CO),0 CH,COONa tera c D 2x4=8 C-DTN-J-DIB 9 (Contd.)(ii) ° oN SeO Cro. (ey CH; a ts 9 heat CN_ in alkaline” ° Catalyst” 4xA=16 medium GY) coort ea | + CH3CO>Et “Aeidify> 1 COOEt eighty BrCH,COOEt 2 J 2x4=8 Zn Section ‘B’ 5. Answer any three of the following : (a) (@ Nylon 6 can be produced from a monomer. What is that monomer and what is the mechanism of polymeriza- tion ? (ii) Phenol condenses with formaldehyde in acidic medium. What is the mechanism of condensation ? 20 (b) (i) The presence of P +1 peak (P =parent peak) in mass spectra of organic com- pounds may be attributable to natural abundance of some isotopes. What are those isotopes ? C-DTN-J-DIB 10 (Contd.)(ii) ° Cc > Cy Ct ees pale ee GO aE H 4x4=16 saa area mene - (iv) COOEt NORE: + CH3CO,Et ———> 1 ARTO BrCH,COOEt Brecon J 2x4=8 COOEt ae ‘a’ 5. freafafaa & & fare ate & sax diferc : (®) @ aR 6 ue Uses & scrfea feat oT aaa 2) sa cH HT Fa ATA @ aK agachian ci aT aiftencat & ? Gi) fra seeta areaa A Hefeseres & art wafer et sat @ | deat ar sar aire a? 20 (@) @ writer atret & cera tacat F P+ frat (P= saa firac) at soferfa ar art geo anecahiat ft orpfaer sacar aware oT aaa & 1 a aHEAAH Shr aS ? C-DTN-J-DIB ll (Contd.)Gi) ©) @ C-DTN-J-DIB Write numbers of major peaks in 'H NMR spectra of the following com- pounds : te CH; H Sened CH; H 2, CH _H ci “H 3. H H De=cl Br Bs H CH; H 10+10 Proton NMR of Cl —CH,—CH,Cl shows only one signal whereas Cl—CH,-CH,-Br shows more than one signal. Explain. 12 (Contd.)aaa firadt ft deard forferr : 1. cu H cat wie fo cS ae Ose Li We “H ae in H c=c Br H Ain CH; 4 10+10 (@) @ Cl-CH,-CH,Cl a at NMR Saat us ef daa eater & wales Cl-CH,-CH,—Br wm & afte da aufar 21 ere fifa | C-DTN-J-DIB 13 (Contd.)aid @ @ Gi) 6 (a) @ Gi) C-DTN-J-DIB p-hydroxy acetophenone is mixed with D,O (very excess): in mild alkaline condition. The mass spectra of. final product (parent peak) will differ from parent peak of p-hydroxy acetophenone. What is the difference in unit of mass ? 10+10=20 DNA precipitates with cationic polymer but not with anionic polymer. Explain. Acid hydrolysis of Nylon 6 is faster than acid hydrolysis of polyester. Explain with mechanism. 10+10=20 Write products for photochemical disso- ciation of 2-pentanone. Write the possi- ble intermediate. Identify A and B cl oe + H N H A NaOH B CO en . 3 Write products of photochemical oxida- tion of following : 2x10=20 14 (Contd.)Gi) () @ Gi) 6. (#) (i) Gi) C-DTN-J-DIB p-erghet tferhtitt st D,0 (afte aftreat).& ara argeit aia eer # freer aren @ | sift sere & sean etaeH (AT fRrax) p-eregtat Rrra & Aer firax & fra der | sera & areas B aa saz ze? 10+10=20 DNA saraat seen Fi are saerftea Stet @ Rel wat ages & art ael Sar ease Arr | alee 6 Hl rat ea-aTa NH Tifeteet wea wea-aTae At ater ctaax Stat 21 aire % arr aaaret | 10+10=20 Aerie & ger carafe fad & sere fran | aaa aerad? vit ferfer | AaB & wear ati cl mr ff N H BOA NaOH B ~*~ hy 2x10=20 H 2 15 (Contd.)(b) (©) 7. (a) (b) (c) (dd) () (i) Htion shifts n> z* transition of >C =O to higher energy. Explain. 12 (ii) Which reagent can be used to convert CH, - CH = CH - CH, ~- CO,Me to CH, — CH = CH — CH, — CH,OH. 6 (i) Polar solvent shifts 2, of 2— 2* transi- tion of >C =O to higher value. Explain. 12 (ii) Ethene and Ethyne unlike propene and propyne do not give C to C multiple bond stretching bonds: in their IR spectrum. Explain. 10 Write equation for the formation of glyptal resin ? How can it be made softer ? 20 Write monomer of Teflon. How is the monomer synthesized ? 10 In 'H NMR spectra C,H, and CF;COOH gives signals at different positions, why ? 10 Why does (Ph),C—C(Ph), produce colour when dissolved in any polar solvent ? 10 Write suitable reagents for converting cyclo- hexene to OHC(CH,),CHO. 10 C-DTN-J-DIB 16 (Contd.)(@) @ Ht amet >C=0 ® na" awa at Sankt gulf oem fae Far @ | eres Are | 12 Gi) CH, - CH= CH-CH,-CO,Me 4 CH, - CH =CH~CH,-CH,0OH ¥ eatata at & fare ate & aftrearin ar eeaaret frat ot aera & ? : 6 @) @ >C=08% 237° Sas 2,, Bt gale fae Seaat ATT aes eararafca aX Bat 21 ce Hf 12 Gi) Stee att Sieve & fata ita sik fares art IR Sag FCA C ag-aEt aha Se met 8a & 1 ere Are | 10 7. (&) fees thr & faces & fae ater fafa) Saat Saar af het SAAT ST AHS ? 20 (@) Qacitea at capers ferfar | ge Caer ar aeereer fer were ferar aire & ? 10 . (7) THNMR agai # C,H, a CF,COOH aerm- wen feafeat F dea ta F| eae? 10 (4) st (Ph),C-C(Ph), at feet gata faeraa # ale Stat @, da ae Gt eat Far aarz@? 10 (=) areaetteritt FY OHC(CH,),CHO # eaiaftt at & faa sagen afiresion ferferc | 10 C-DTN-J-DIB 17 (Contd.)8. (a) (b) (c) (d) ©) When does p-cresol not produce thermo- setting polymer with aes C=O? Explain. 15 What is the name of the reaction CH; == CH2 . C : « 2.35 cD, CHD, What are the structural differences between Nylon 6-6 and Nylon 6 ? 10 How are the following compounds distin- guished by mass spectrometry ? (A) DCH,CH,COCH, (B) CH,CH,COCH,D (C) CH,CHDCOCH, 15 Write the reactions which produce vinyl chloride from ethanol (in three steps). 15 C-DTN-J-DIB 188. (%) p-frita f>c=0 ara a-ge ages Het wet aarat & | ers Ht | 15, (a) freafafaa afitfear ar aa art & ? G~Cs — CH; €. = « 5 cD, CHD, (7) aR 6.6 SK ae 6 & ate dears firaare aa = ? 10 (3) freafafaa atfreat ar cera etacafiia ae fier genx fatten fesat ara @ ? (A) DCH,CH,COCH, (B) CH,CH,COCH,D (C) CH,CHDCOCH, 15 (a) wF aftifiearet ar fefag ot erie & areateet FARIS HI Jad Hea & (cia ait A) | 15 C-DTN-J-DIB 19C-DTN-J-DIB varaa fanart wea-cat I wre aw area water sen Bedi site sido dat F oar 21 geal & sat seat areaa F fed art afer Brean sete arte aer-T4 FH fear war 2, SR FT ATT FT RTE eT TAR- TT qa-78 7 sifera fale ear oe feat araT aifeg | Ta1-74 1 steele aneaH & sifahr area feet areaa F frat ae sat OR aS sie aet fret | gee Hea 1 sik 5 afraré & | arét eat FA aie aos & aH-a-aa Uer TeT TAaR feeret ater seat & sae afsre | afe snare et at sq aiest ar Fat aifsre war grat fafice bitferg | Oe eee mel Tete / creat aeat ar arares arf @, Tat TH HPA TF HET WAT BT | Note : English version of the Instructions is printed on the front cover of this question paper.