CS (Main) ExAM.2021 pater peracHaBLe Tara - fae (aer-wa 1) CHEMISTRY (Paper 11) Pratt wore : cia 0 HPT 36 : 250 Time Allowed : Three Hours Maximum Marks : 250 wera wear fate saeet wee 38 oe freafateea Reeth st ger araeriictes Uy | wat ore wer Et I ast F fans & aan feed we ath ae HI ee wahan @t ga are wet & ae BIE we tari at 5 aftard € aan art weit a wets ave & anda UH WT ATE dita weit & oar Sfire | wets wet /arr & fer Prat ss gee aret feu me E | weit & gar vet onftiga area H fora ora aie, raat seta are waet-aa F farar war 2, otk Se rena ar re seta wer-we- (FLAILY,) yerar H TUTE we sie Pike eK iran arr arfee, | safer rere & arfetten are fet arena 3 fa ay aeRO aE sis aT fire | ae oraere et, Pigare oitat at wet ar gar Bt & fare ee ae eat HA aa 2 | wa ae sfefaa 4 Gt, ata cer aeractt wafer are sat A wa e | aft sare @, dt saa atest an aaa Fife gar saat fase Fife | weit & set A aor waTaaR Ft oTeh | airs | a fee ae We sae aA A ara at ameeft af sa aren a aren St | wer -ae-seR Yea H are BE we aA ye sear Ye aM a pita: are difire | QUESTION PAPER SPECIFIC INSTRUCTIONS Please read each of the following instructions carefully before attempting questions. There are EIGHT questions divided in TWO SECTIONS and printed both in HINDI and in ENGLISH. Candidate has to attempt FIVE questions in all. Question Nos. 1 and 5 are compulsory and out of the remaining, THREE are to be attempted choosing at least ONE question from each Section. The number of marks carried by a question/part is indicated against it. Answers must be written in the medium authorized in the Admission Certificate which must be stated clearly on the cover of this Question-cum-Answer (QCA) Booklet in the space provided. No marks will be given for answers written in a medium other than the authorized one. Coordinate diagrams, wherever required, shall be drawn in the space provided for answering the question itself. Unless otherwise mentioned, symbols and notations have their usual standard meanings. Assume suitable data, if considered necessary, and indicate the same clearly. Attempts of questions shall be counted in sequential order. Unless struck off, attempt of a question shall be counted even if attempted partly. Any page or portion of the page left blank in the Question-cum-Answer Booklet must be clearly struck off. 1 HXS-B-CHML@) 1.() 1.) 1.@) aS ‘A’ SECTION ‘A’ a aftfrar # R—COO™ +Br—CN—>R—CN+Br” +CO, T IIRTES (CN) BAG Ge H wel sew ea & 7 rE Safer wAaAY Bs wear WR Ge a | In the reaction R—COO” +Br—CN—>R—CN+Br- +CO, T What is the origin of —CN group in the product ? Explain by using isotopic labelling technique. 10 afar agen ania sam a oa afar dares & are Fer ora ak St aA & after axa € dt senat & aa an fear S 1 (CH,);N—CH) —CeHs X Discuss the product(s) formation when above quaternary ammonium salt is treated with sodium amide at low temperature and at high temperature. 10 Rrafafaa afiGen & sere A ak B ARE | Ta aay A Gena tS 1 ga a ae ar ye veng @ ak wt? Write the products A and B in the above reaction, Also give the mechanism of their formation. Which one of these is the major product and why ? 10 Peatitiea aifrat A anfrastd F uP BF, : OF, saeate H aiftbemer A faa ifaa : (@) taper afeseres (i) Aa) zigtfrseres Discuss the reactivity of following compounds towards nucleophile in the presence of BF; : OEt, : (i) p-trifluoromethyl benzaldehyde (ii) p-tolualdehyde 10 HXS-B-CHM 21.(e) 2.(a) 2.(b) frafatiar eaiaait at pt at: (@) Me 7 oo Ho. oH NY te a i Me Me ‘Me H H eth — H H Complete the above transformations. 10 Pte Taate dec at atfad ae ee a At safe H atfie A dk BH SR aaeR A gaa se | after & seas at oh fas | Or, OG CH, ‘CH, A B Involving the stereochemical concept, compare the elimination behaviour of compounds A and B in the presence of base. Also give the product(s) of the reactions. 20 @) Feira after A der sik entra x feo at | Comment upon the structure and stability of cyclopropylmethy! carbocation. (i) Prafafad atfret ata ar sarer anetia @ sik Hil 2 Which one of the above compound is more acidic and why ? (ii) Prafafad after % sere /sene at fre : oO ll A + Me,C — 0 — C— CHN, —~—> Write the product(s) in the above reaction. 15 3 HXS-B-CHM2(0) () sere A Pier carer Ft aad ee Prafefas after a fenfatr Ba em pT mR: Ph, we — OH 2002, 2 fatcert CH, Pyridine Indicating the stereochemistry of the product, complete the above reaction with mechanism. lo (i) rafters aifttiensit % seret at fer : On ad [pP] —+> (CH,),SiCl R Write down the products in the above reactions. 5 3.(a) Frente aft at sae Beats aut QR oe a: OH of ah ) Ph AIRH,SO,, 10 Cone. H,SO, cH, “ EO, (ii) —_——_* 10 cHoc™ Complete the above reactions with mechanisms. 3.0) 3-adereininta atk SbCl, A WER afta & sere A ert fs | za vere @ HNMR ag HF ast fedeat are 7 Write the structure of the reaction product between 3-chlorocyclopropene and SbCls. What is the unique feature of this product in 'H NMR spectrum ? HXS-B-CHM 4(ii) Poafeafian aAfrat Hatt ar sarer ancien 2 sik it? A B Which one of the above compounds is more acidic and why ? (iii) dre she Reta A RAReeT aT se aE | Predict the aromaticity of tropolones and sydnones. 15 3.0.) Frafefac afitiensit a sah frenfay & ara pt at: () Fai-2,3-rSsteea A ° | OEt B cH, 7 | AgNO, —c—cui— cn, “8%, 2 (i) cH, cH aoa CH, Complete the following reactions along with mechanisms : ° (i) meso-2,3-dibromobutane —! 5 4 5 2 | gt B cu, ; AgNO, ‘CH, —C— CHI— CH, ———*»» _? (ii) cH, ¢ cHI— cH, Soe 10 cH, 4.) (i) Sapteda a mf eet we qatar a enfin gear 81 Gene Bee WaaTT | Heating of 3-deuteroindene causes scrambling of the deuterium, Explain with mechanism. 5 HXS-B-CHM4.(b) 4.(0) (i) Wes Creeges A areata & ara seta after Far serch ht Gera ford | frenfaftt & area weree | Write the structure of product(s) formed during the thermal reaction of maleic anhydride with cyclopentadiene. Explain with mechanism. 20 frafafad aftirersit & vere /seret a fer : () (CH); C—CH=CH, —#C_, 2 5 ue 10 (i) CH,=CH—CH,—Br —* ? npr | Sorergs—|\ weivaTes benzoyl benzoyl peroxide Br peroxide 2 2 Write the product(s) of the above reactions. () frafatea carafe eciteit a gene fad afk afta afta at Tear we am fafac: CHP (2) RLi oC oO . tat Saifewars, I. PhCH,Cl TL PhNHNH, + I acetic acid Predict the product in the above chemical conversions and also identify the name reaction involved. 10 Gi) frafefas 4 3 ae a are am A sae F, a,p-siga areiferer atfres ea R727 TR A fg RK: I HCHO si PhCHO I. PhCHO aft Ph—CH—CHO ch, Il. PhCHO a CH,CH,CHO IV. HCHO a& PhCOPh HXS-B-CHM 6Which of the following pair(s) gives a,8-unsaturated carbonyl compound in presence of base ? Justify the answer. 5 I. HCHO and PhCHO I. PhCHO and = Ph—CH—CHO | CH, TI. PhCHO and CH,CH,CHO IV. HCHO and PhCOPh GTS ‘B’ SECTION ‘B’ 5.(a) HNMR @age 4 2,4Arcreesite vis flere cater @ | sa dem ar Sar gts spate ware Pea (free fire) ot frd 2,4-Pentadione exhibits five signal in 'HNMR spectrum. Account for the observation. Also write the approximate chemical shift. 10 5.(b) @) frafafad vaaat 4 aor ager Ft vedi @ atiaa ar aA ATE | (CH=CH, CH=CH, CH=CH, cH, NO; cock, I tr ti Arrange the above monomers in order of decreasing ability to undergo anionic polymerization. 5 (i) FR wag sik wrpfes wag At dear ford stk Gam faenat At faa ae | Draw the structures of synthetic rubber and natural rubber and discuss their configurations. 3 5.(c) raferfaa cerafte Scie F sere /serat a STA aT, st were St frarfetty aw gam % 1 oO L or SO, ; COOH Na, NH. t. =arer © C,H,OH Predict the product(s) and suggest mechanism in each of the above chemical transformations. 10 7 HXS-B-CHM5.(a) 5.(0) 6.(a)(i) (i) frrafafaa aagt H aftat at sae aie ces-11 erg ara Ft aera & Het Si waren fafae a suger areT ifsc, | (i) Ph—CO—CH,CH,CH, Ph—CO— CH,CH,CH,CH, Ph—CO—CH,CH,— CH(CH,), 1 i 1 5 ° acy CH,CH,CH, (ii) Ph— CO—CH,CH,CH, coPh 5 1 0 m ‘Arrange the compounds in the above groups for ease of Norrish type-II H-abstraction in decreasing order giving the plausible explanations. 2aaaa att 33a dears aaa E | a a Fae UH THAT Aare affara cuter 21 ge aaraadt St Aad Get at fafer ae stk cate | GA aararh, st dated der adi cular @ sae arene irae Ft ETAT FH | 2-Pentanone and 3-Pentanone are structural isomers. Only one of the isomers exhibits McLafferty rearrangement. Identify and show the McLafferty fragmentation for this isomer, Also propose base peak for the other isomer, which does not exhibit the McLafferty rearrangement. 10 tetas atk aq atten ceers A after Fart star oy frafetas ag arise cutter & 1 gat aiey AY aca fe IR : 1620 cm“ and 1695 cm 1H NMR: 6 1-9(s, 3H), 2-1(s, 6H), 6-15(s, 1H) The molecule obtained on treatment of acetone with dilute sodium hydroxide exhibits the above spectral data. Propose the structure of this molecule. 15 frafafaa ware art aa atres A ear a GT sera org an arelifter ara ferrrat fearet @: oO IL. \ Il CH, —C—O—CH, C,H,— C—O — CH, ak and Identify the compound in each of the above pairs, that can be expected to exhibit carbonyl stretching signal at higher frequency. 5 HXS-B-CHM 86.(b) | SagRh CAT onet ar aad aka EU wa ag, esi onea, aaa aed ok sirens ag ga aida] eardian a aut | Show salt bridge, hydrogen bond, van der Waals’ interaction and disulfide bridge for stabilization of protein by choosing appropriate amino acid residues in the protein chain, 15 6.(c) frafeftrr afhfiersit at sah frenfity % arr oot at: oO pA 5 5 Complete the above reactions by giving the suitable mechanisms. 7a) frafefad afifrarsit & age HA, B sk C A dean faa wi a: n-BuLi 13-3 Lcw-cu=cr, SE ep (excess) #0 c ° _wnion 55% H,SO, A IL CY ee Sp ee Complete the above reaction sequence by writing the structures of A, B and C. 20 9 HXS-B-CHM7.() LiAIH, 3% NaBH, afreidt A fare & wit sagen ok sah sate afiansttcan 3 sacar arott At Paar Ae | Prafettad eciaentt & fer, eee a at aftrasies carer armor 2 ae At aad: CONH, CONH, 2 — COcH, ° — CH, OH OH — CH. cae" a ™~ W i Discuss the solvent compatibility for LiAIH, and NaBH, reagents and the factors responsible for differential reactivity. Also suggest preferred reagent between the two for the above transformations. 15 7.(c) Wa am Farrar sts GA Cplt,,0 BAe IR BARA ue faega ae 3464 Se! oR caer 21 eee are Bae FH m/z 135% aT Aira sik TH NMR @aga 4 Preafetiad fer woffa axa & 513 (4, 6H); 2-4 (s, 3H), 3-4 (m, 1H), 4-6 (s, D,0 fafa (exchangeable)), 6:6 (s, 1H), 68 (d, 1H) 38% 7-1 (d, 1H). 4 3 A aT FE | ‘A molecule with molecular formula Cj H,,O exhibits a broad band at 3464 em" in IR spectrum. Its mass spectrum exhibits base peak at m/z 135 and the 'H NMR spectrum exhibits the following signals : 5 13 (4, 6H); 2-4 (s, 3H), 3-4 (m, 1H), 46 (s, D,O exchangeable), 6-6 (s, 1H), 68 (d, 1H) and 7-1 (d, 1H). Deduce the structure. 15 8.(a) () Prafatea ceratin erect H senfer afte xs At der ferfar : L MCPBA, x fh 8 L 050, x Nal. y HXS-B-CHM 108.(b) 8.(c) Gi) Gi) Gi) OH Il. Wee COOH BH, / THF x cro, -fifeer WV. Oo Cr0s-Pyridine CHCl, Write the products X/¥Y in the above chemical transformations. 15 2Afra- Lag oft erate Ht afi & gene a agar aac | ga afer H ot dfenaatefad tat af saat Aart 31 Predict the product in the reaction of 2-methyl-I-butene with diborane. Account for the regioselectivity observed in the reaction. 5 wm ay frre sift: Yt CyH,,0 @ Fe HNMR @RgH H Fae we ferret 51-2 ppm % Gar S| Fe IR Vag Ft cH war savy 1710 Aa! ax Rar 21 se ay A dear afta aR A molecule with molecular formula CoH,,O exhibits only one signal at 5 1-2 ppm in 'H NMR spectrum. This also exhibits a strong absorption at 1710 cm” in IR spectrum. Propose structure for this molecule. 10 ida at UV Gace fafa diaasit & a fea = UF Ang, 280 nm BR AT Apge 190nm HK sea ea ferret & ara saat aw a sifea we 1 The UV spectrum of acetone exhibits two signals of different intensities, one at Angx 280 nm and the other at Aq. 190 nm. Assign corresponding electronic transitions to the observed signals. 5 After sidtaee & |W NMR Baga H feeratt A dem, ferret ar eer (s/d/t/m) aft afte cera frensar ar ser ae | Predict the number of signals, nature of the signals (s/d/t/m) and approximate chemical shifts in 'H NMR spectrum of methyl propenoate. 10 IR Sage & teats Sara ww anal aaa arafer safes aeietetteta 1725 aati oe 1745 Aa cals Bota wi, are | Acetone exhibits only one carbonyl stretching frequency in IR spectrum whereas chloroacetone exhibits two at 1725 and 1745 cm-!. Explain why. 5 IL HXS-B-CHM