CS (MAIN) EXAM, 2010 oN 962 CHEMISTRY - Paper II Time Allowed : Three Hours} |Maximum Marks : 300) INSTRUCTIONS Each question is printed both in Hindi and in English. Answers must be written in the medium specified in the Admission Certificate issued to you, which must be stated clearly on the cover of the ‘answer-book in the space provided for the purpose. No marks will be given, for the answers written in a mediun other than that specified in the Admission Certificate. Candidates should attempt Question Nos. 1 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 usuai meaning, unless otherwise indicated. vara & : sryeeit ar feat SURAT BH TRA oa & fit oe we oa é/Section ‘A’ 1. Answer the following : 10x6=60 th . (a) Whether the following compound is aromatic, non-aromatic or antiaromatic, Justify. CO (b) In the reaction sequence * 'NHNH3 BF3 + CH3(C2Hs)CO ——» (P) —* (Q) identify (P) and (Q) and-clearly show isotopi- cally labelled *N. (c) Write the major product (X) of the reaction CH3ONa/C,H;OH CERNE Te aSO8 CH; (CH>)3 CHCH3 (o-0) on F (a) Write the major product formed on treatment of urea with NaOBr. Also write the name of the reaction involved. (e) Identify intermediate (P) and product (Q) in the reaction 2% (p} > 1 C-DTN-K-DIB 2 (Contd.ave ‘a . 1. freafefae & soe Hr : 10x6=60 (a) freafafear afer Wee, waar sear of Raafee F 1 eee sifser sere CO " NHNH>2 (a) afi oer : BF; cor + CH3(C3H)CO—> (PF) —+ (Q) # wy war (Q) At Tea Ag cat aaEMTeT araifna *N at feareat 1 : (a) Freaferftra afirfanar % ferg qea geqre (Xx) FT _ fafa CH;(CH2)3 CHCH3 F . (=) afer at NaOBr & Soa I Sat ae eT sere at fafag cer des aftfirar ar art ait Fare | (Ga) Femes (P) TAT (Q) Ferra Ht A St TE arta 4 cea Aifirg hy . > (Pp) —> 12) C-DTN-K-DIB 3 (Contd.) CH3ONa/C,Hs50H ae eS SS (XDcf) 2, (a) (b) ©) A mixture of formaldehyde and p-methoxy- benzaldehyde is treated with conc. KOH. ‘Write the products of reaction. Identify (P) to (S) in the reaction sequence 20 CoH; — CH— CH; KOH (ale.) ———_— i H2/ Ni 2-3 atm 293K H,0. ® ——=— @ HCOOH H2/ Ni 10 atm 400 K (s) 2-Methy1-3-pheny1-2,3-butanediol on treatment with H,SO, gives a major product (X). Identify (X) and write a mechanism to explain its ‘formation. Also write the name of reaction involved. 20 Draw resonating structures for the attack of SO,H® at different positions of Indole, using curved arrows. At which position attack occurs preferentially? Draw an energy profile diagram for the position of preferential attack. 20 C-DTN-K-DIB 4 (Contd.)(a) ordafmerss am pathadtinentiens fray ar dix KOH @ ovata frat war 31 orfiifirar & searet at ferfer | 2. (31) Foafefae afiirar ager HG) BF (S) AT ceart fife : 20 _CgHs— CH— CH; KGH (alc.) . > ' a . Hy / Ni 2-3aim 293K HAO; ® ~ HCOOH H2/Ni 10 atm 400K «) (a) 2 fare g-vitnen-2,2-apgiReter H,SO, 2 serarfce RT IX SETS (X) ATE. aT BCX) AT gear Aire aa saa aaret aAt fearfafer ar - fra ax ore Are | doa afta ar are at fefere 1 20 (a) afsre ci fret ar gaint acct ge SO3H* & Serer & fairer earl ox sraeror & fare seat eT araraet | fart carat oe afer Sa & step Star _ 32 afer aa & emt a fee or af | Shares site Frc) . 20 C-DTN-K-DIB 5 (Contd.)3. (a) (b) (c) Answer the following : oo 15 (i) A student carried out reaction of aniline with concentrated HNO /H,SO,. Write the structure of product/s he is likely to obtain. - (ii) Write a mechanism to explain the forma- ‘tion of major product in (i). iii). If the reaction in (i) is carried out only in -nitric acid, write an equation for the formation of NO}. Identify (P) to (R) in the following :- 15 (i) “OCH, (P) —————> ©,.H,(CH,),COOCH; Gi) H,0/H* OH anh. AICI; a (Q) HyC7 - COCH, "OH HyCOOC (CH2),COOCH; ~————» (R) Write the resonance structures of the following : . 15 cH=C—oO- HsCe nO “Nn —o Explain its aromaticity in nitration reaction. " C-DTN-K-DIB 6 (Contd.)3 (at) frerfarferr & gee dfn : “1s : @) wr ora A Orehia H giz HNO,/H,SO, & ' afiiser dea ft 1 ga gene /gendl Ft aoa ferfag sy ae are ae cect 8 1 Gi) Be fren-fafer @ PSifere SY (i) HF ore VT aed eT SATS BT SAT B | * Gi) aR @ & afi Fae age a a aaa AT TE Bt Tat NOS AAA are ATH fafa (a) freafafar F @) FR) aH TET: 15 : @ “OCH, . (Pe) ——————_ GH (CH2)xXCOOCH; @) H,0/Ht on anh. AICI; x @Q) H3C COCH; ~OH H3COOC (CH2)«COOCH; —————> (R) (@) frafirftrer & argare saat at fRe: 15 4 CH= C—O HsCo Ney) sragart aifear & QerAfeena at ease PtAirg | C-DTN-K-DIB 7 (Contd.)(d) Write the products of the reaction | 1s ai) Cis HCI cH, —cH=C > (PD cu, peroxide Gi) cel, CH, — CH= CH, —-———*—_+ (q) peroxide (Ss) Git) , trans-2-butene ba [R] ay 4. (a) Sketch the mechanism of following reactions : 15x3=45 @) cH; . CH2Br A CHy;=CH-COCH; Zn/Ag “ ® ‘CH>Br CH; Gi) OCH)CH = CH, 1c CH, A Gii) Ph Ph a Joe Ph-C= C- Ph ———> Ph Ph (b) Draw the structures of [6], [10}, {12] and [14] annulenes and discuss their aromaticity. 1s (Contd.) C-DTN-K-DIB 8(2) faetfafea after a sendt at fafa 15 @ Hi - _-CHs HCI cH,—cHu=c ——— cn, peroxide G@ CCl. CH; — CH == CH, ——————— (Q) . peroxide Gii) 3 s) trans-2-butene —2-» [R] Ph Ph (#) (6), (10), (12) eat (14) typha A east wT sere’ rer Sah UeeeneT HY orreaT HrfSee | . . 15 C-DTN-K-DIB 9 ~ (Contd.)Section ‘B’ 5. Answer the following : 10x6=60 (a) -Draw the structure of purine nucleotides present in DNA. . , (b) Benzoic acid on reduction with Na in liq NH; gives 1,2-dihydroproduct, whereas, anisole gives 2,5-dihydroproduct. Explain. (c) Predict the products and explain their forma- tion CsHsCOC,Hs CH;COCH,; A —__—— hv Av (d) What changes do you expect in the electronic spectrum of acetoacetic ester in hexane and ether. (e) ‘HNMR spectrum recorded for CH,-CH= CH, at 90 MHz gave coupling constant (J) of 5 Hz for vinyl protons. If spectrum is recorded at 500 MHz, write the expected value of coupling constant. ° . (f) What is the range of fingerprint region in infra- . red spectrum. Write the range in which carbonyl group normally absorbs. C-DTN-K-DIB 10 (Contd.)uve ‘w’ 5. frafafaa & gar ffir : / 10x6=60 (a) & ut ea fees afte —ftetiereel Ht ea aaa | (a) antes sea at et NH, 8 Na afer seer aey & 1,2-Rerest verre ore drat 3a fe ieitater 2,5-feeegh gene aar z, ease Aifera | (@) send an oqars cers car Sat TET a ETE ft farg i CoHsCOCsHs CH3;COCH3 B< —_—_——A Av Av (8) tae oe fax F Ofasttferes Rx & etagifrs aan F art fa oftadda ft aren axa S ? (&) CH,-CH = CH, #T 90 MHz % '@a UT UF ae @age afree fared gat & faq 5 He aT gam facie () tat 2 | af ae ar area 500 MHz a fat wer da gat feria ar agar art saree | (@) sacs Stage F sigh ore aa ar goa feat Bat 2 ae see fafa frat arti af arararad: aanitror axa 2 1 C-DTN-K-DIB WW (Contd.)6. (a) (i) Define thermoplast and thermosets. Which are thermoplast among the following ? : PVC Teflon Alkyd resin Phenolics Nylan Polyethylene Aminoresins Polyster Polypropylene Polystyrene Gi) Differentiate between LDPE and HDPE. 10+5=15 (b) Give the synthetic route of epoxy resin based on bisphenol-A. Mention the principal fields of applications of epoxy resins. 15 (c) Write the product formed in the oxidation of . quinoline by CrO3. 10 -(d) Identify A and B and discuss the selectivity of the reagents 2x10=20 oO ise A ws So ee coocH, at B C-DTN-K-DIB 12. (Contd.)6. (3%), G) ee foafefad 4 & amr quer ate & € ? Gi) AR Ean Ah FH sexe H Ee rire 1 . 10+5=15 (a) frefate-a ox aranfce gataet Ber ar dealt wet sare | ea Ver 3 er saat ait aor sera Are | 15 (a) featfert ar, CrO, ERT arene SR ae aT are sere a fafa 10 (@) Foafefaa ¥ A vat Bat tear aar afr sprceat Bt at sara at Saver =BtFSTe | 2x10=20 o priser A Se ee ALG B COOCH,; \ C-DTN-K-DIB “43: . Contd.)7. (a) (b) (ce) Write the structures of possible products of following photochemical teactions and mention the type of Norrish process (I or I) in each. . is ®@ 9 . a cr Ave. —_—_— i h CH,CH, — C— CH.CHEHCH, YY CHy Photochemical (2 + 2) addition of benzophe- none with cis- and tans-2-butene yield a mixture of same products. Explain their formation with the mechanism. 15 Gi) Which among the following.(A or B) is formed when Pent-2-ene is oxidised by OsO, and NaHSO,? Explain its formation with, the mechanism. : 10 CH,CH; ‘ CH2CH; H—C—onH. H—C— OH H— C — OH HO—C—H . bs big (A) . ®) C-DTN-K-DIB 14 (Contd.)7.. (3) frafafes genre afiieif ( wafia searat Sy deena ferfae om ae at . were fife fe sate F ata ar atfer gat a waat Oo) &1 15 @ 6 CH; diy ° CH;CH, — b_ cH,cH,cucH, 2% : CH; (a4) anifedt at arse ca froe2ag a we (242) fret ae set geal ar frat grea star B11 waht aavae at finer Rr afea erse Aifara | 15 (a) wat F2-2-44 at OsO, UH NaHSO, ait atria Fara re & a esa Sete A Beet By ada 2? gah frrsrfor wa far fafer at ore Arr | 10 CH,CH, CH2CHy u—e— oH H— Cc — OH H—c—on HO—C-—-H | | CH; oO CH; fA) . ® ,C-DTN-K-DIB 1S. (Contd.)(d) Identify the compound susceptible for HIO, oxidation and justify 10. Gi) cH CHNH CH,0H GD Ce, CH, CH20H (e€) Write the reagents required for the following conversions. 10 w ° ° . ( ) > are oO _ 0 9 Gi) cn, CHO e—® CH; CHO C-DTN-K-DIB 16 (Contd.)(@) 3a aifice at are’ sit HIO, atadtercr & ferr ate & aor gear wr aftfrer 2 ? “10 — @ cH , | otis CH.OH ‘ - GD CHA cH, bon (&) freafafaa wotacit & fer aaa aRrerat ar eared | ‘10 - _ i) ° aa.) - Lp — re / : ° , ° oO GD" oy, CHO Q—s cH; CHO C-DTN-K-DIB 17 (Contd.)8. (a) An organic compound with molecular formula CH gives following spectral characteristics. (b) (c) (@d) Electronic : A,,.4, at 235 nm spectrum . Infrared —:_ 3035, 3000, 2925, 1640, 990, spectrum 915, 740 and 615 cm™! NMR : 6 at 3-1@H), 4-8(1H), 5-1(1H), spectrum. = 5-8( 1H), 7-1(5H) Mass : me at 117 spectrum Suggest a possible structure with probabie justification for each spectral feature. 30 What characteristic bands. will be observed in the ir spectrum of 1-phenylethanone ?_ 10 Room temperature NMR spectrum of acetylacetone exhibits’ two close by peaks at 6 = 1-97 and 2:14 ppm. Explain the reason for their origin.- What other peaks will be observed, 10° How would you determine molecular wt of acetone on the basis of its mass spectrum ? Suggest possible fragmentation pattern. 10 C-DTN-K-DIB 1°8. (2) wee areca aii Poeramt antares Ea CylHyg & we afoafeters, fragt attra Far Ss “im 5 Zien 285 0 ai : b HATH : 3035, 3000, 2925, 1640, 990, eat 915, 740 U4 615 cm! waa : § €3-10H), 480), 510K), eat 5-8(1H), 7:1(5H), zat rome @N7 ~ * . wrfia dearer Gara war gets Saay crater F © ofits sift at vit rare” 30 (a) siergaeictr ir ag Fath at orf arerfras ofgat fears Sit ? . 10 (a) Bftrereetetetr ar wer arg et GH oe Blaze a - ufc firax 5 = 1-97 U4 2-14 ppm 3% fearat S| Saw Ae or arn ere fee | ae aa & frac ore StF | 10° (3) Ufeeta ar anfeeren onx, sera See BH sree Ww, sTT HA soa aU ? confaa fides afar ar qard | - 7 10 C-DTN-K-DIB 19C-DTN-K-DIB carat fart aea-9a Tl . aa: ar we ayaa eter rer fed ate atid atat F war F 1 gat ga set aneare F fort ort afer Rreest goorer airaae Taer-T4 A ferar war 2, HR FG AA BT ETE THT THR-JeH qa-ge i ofa fafée ext me fear ara aifed | 9aer-79 9 oferta area & afahr area feat aren A feet me sat 1 aS sae - et fret 1 et wea 1 sik Sattar & 1 areét seat FT uate aus & aa-a-am war ser qantas ater seat & sax aera! ate sree Bt at sracH atleast apr aware afore arear saree? fale Btfere | acter sea & fere Fae sien sea & ara F fae re} relist / ara tara? ar ararer aref 2, Wet Te STAT TET WAT BP | Note : English version of the Instructions is printed on the front cover of this question paper.