CS (MAIN) EXAM:2018 EGT-D-CHM Tara—fagrt (394-0a-I1) wag: ela ee | sitar a: 250 -ua aera fasta saat Gra rei Fan 8 aoe fefotem wae agin Sort we) A ard) A ge ome oer fe my Eat Eat oa sidOH ai A wt Fy sehen a) ga wie wea & am B By wa Bem 1 af § siitard & our ard ue} 2 wee ewe a an-2 a ea oe gaat af vel ee if) sreder ura ir 3 fem fea oh sath wa fe ne Hy peat see seh sftp ream 8 feed re wre, Fen es ayes walang 3 ean en & fe eam ETE ga WH-ae-am (Fe Ae yo) yee 1 afea Affe eo ve fen aon anita, srfiga ean S alti sa fret wean A fers me ee a mI Siem aE] FRE ret sarees eh, Fteren anita at ore a ae 2 fem fee oe ear A eh aT BI a we sigan a A, wa cer ecach wafs wor sel Homey 1 af oraere a aye sles ar ser Efe ae seat fee fe sei & sare Aon gar A are) oes ey 8 fee geal ow) A wean a act ae 3a wea Ten a) wera glare Harel Ors ame sae yw are ge aM aT a: He aif CHEMISTRY (PAPER-II) Time Allowed | Three Hours QUESTION PAPER SPECIFIC INSTRUCTIONS (Please read cach 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 8 are compulsory and out of the remaining, THREE are to be attempted choosing at least ONE question from each Section. ‘The mumber of marks carried by a question/part is indicated agains 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. EG?-D- emmy] 2 1 [P.T0.7wE—A / SECTION—A 1. fa) Prafeftrd & fare n-anfites safia sefen ante ae: fy aire (i) rreTreyETERA fi) saaereefe wor Draw the m-molecular orbital energy level diagram for the following : fi) Benzene (i) Cyclobutadiene fii) Cyclopentadienyl anion 10 fb) NBS afaarge BAR mow Phe oar 87 geet ahha ater avon AY oR A ferftray sarhh Gera farm How is NBS obtained from succinimide? Write its reaction with propene in presence of sunlight. Outline the mechanism. 10 fo) (Q Se tea aa are aerge fis chs a wesaew are BIT aera wet 8 1H =e A (i) Wa Zia-2-2 CH COC! * Wa faa ACL, WM saRaie A afte acm et, 7 aT Ben? f) Account for the fact that compound A is almost as strong an acid as HySO, OH | ‘OH A (i) What happens when trans-2-butene is reacted with CH,COCI in presence of anhydrous AICI? 10 Eg7-0-game|2 %(@) Frefafan aa forgive gatiene sftiensit #8 sae sfefaen Wa nf 8 a ahaa ve nf & gh? aa’ sa} A een Fife # fi cHy-cH=cp, —> cis=cn—eo, : “O- Which of the following known sigmatropic rearrangements would proceed readily and which slowly? Explain your answers : fi) CHy—CH=cn, —> ciy=cH H oO ta) } —> 10 fey Preaferfere safer @ fore ard forfiam, @ safe aay 4 afte aol 1 ager afm athe sa Fe nae afin sania & ° he 2 Explain the conditions for the following reaction, very briefly describe the steps involved and comment if the reaction is reversible = Avia 10 2. fa) i-inr at ee engidtie-steies afiien = caer) fre AB, fue Bias (Hides) @ aedia-aeomes GPa) atti 8) By taking 1-methylcyclopentene as an example, explain hydroboration- oxidation reaction, Justify that it is stereoselective and regioselective. 10 (b) Seat 6 feces siren & om am TR BP Se oA o-Rtas a paefie whe deel wh en Sim What do you mean by secondary structure of proteins? Explain a-helix and Ppleated sheet structures of proteins. 10 E97-D-eam|2 2 [P-T.O.‘“HeRAARAP’ A NaBH, fA wR A LIAIH, & yaad fiw 87 Gutline the mechanism for the following reaction ; 4) Liat, Aualtie a. iyo ROH In what way is NaBH, different from LiAlH, in ‘chemoselectivity? 1s fd) frafafan =geei & amt ures @ faces % feu, afifen asi a) mfia aca gy, fee Genfated fh fren fae f) Ares 66 (ip 2a (iy Reefer Give the synthetic schemes including reaction conditions for the preparation of the following polymers from their monomers : f) Nylon 66 Gi) Teflon (ii) Terylene 15 N- “OH HW ih "OL . Carry out the following transformations = : eCLI- Co. EGT-D- gamit] 2 4(6) Prefers aor sata Hi zen dif; wy suite, wed) A A Seay asia BR wR B-Brorstie & fain A Spetata sentra ifs (i) an sree 2 ay few aA fe AT Pena afiiee deen Pw denier ora ree er 8 wor Sifee Answer the following briefly : () How can you prepare 8-methyiquinoline starting with o-toluidine as one of the starting materials? (i! With suitable example, comment whether Fries rearrangement proceeds intermolecularly or intramolecularly. Give evidence in favour of your answer, 10 to) Prsfefers 2 fararfatts ferfere ; CHPR oO pam Hes Ob 4 WScHO ci : eR SO4-MeoH 1) Hy804-4 iy AiWisoroeeon: és 2) H30 Write the mechanism of the following : guPh ope _Phaghr tila “mote ; CHy=cl—cH= | ZSEESI TORE og NcHo * A CHy oH; OAs ; 1) MySO4-MeOH (iit) > 2) 10" EG7-D- gam D 5 [P.T.0.(a) PrerRafere & Req Reena fee eae seal a gal wee + Ph angpiiata Qn osoe: SEE "ge - OTs ‘i LD 1) Lipa, Nig 2) 4,0" i al. = ast Ss Predict the product(s) with mechanism for the following Ph 1,4-dioxane (@ yv}—Osoer ae aed Ha ors 1) Liflig. fa) LD Tei” 2) H,0* (ii —s_., Ar 4. (a) Prefotan daa Sedat a8 Aa Gea-seet afin A amtee & ag fief et won? Th TE FL oa sew fee Ae, iy a cr i) AN cH, a “OO Cy e ean Which of the following conjugated dienes would not react with a dienophile in Diels-Alder reaction? Justify your answer : Hy fo cr i) chs ce EGT-D-eam 2 6fb) 2 fara ergectttetnl % soma Bg m/z = 98 we anit sre fire ent #) cw ea m/z = 69 7 gem freee (4 fe) anit 8 a gen m/z = 83 yer frac oni t) al erential fH wear Fife) The mass spectra of two different cycloalkanes both show a molecular ion peak at m/z=98. One spectrum shows a base peak at m/z= 69 and the other shows a base peak at m/z= 83, Identify the two cycloalkanes. 10 fo) een taeregrs 1,3-sqgrerhe @ fam 8 often aan 2, wai es ere ari cemsit Fege ofkiran afi sam 8) ee srg Maleic anhydride reacts rapidly with 1,3-butadiene, but does not react at all with ethene under thermal conditions, Explain. 1s (@) cH aria che (MP CH, )0) Pefefisa Aagt safe zetia UV (max } 280 nm) IR Ving | 1715em~? ‘HNMR (8, ppm) ; 0:90 GH, t), 160 (2H, m), 2:20 GH, s), 2-40 (2H, 1) FER (m/z): 86, 71, 58, 43 (100%) ie A deen #8 finite Afi te gem Bag A Ofer gee ae woe eAtfiray An organic compound (MF CsH,90) exhibits the following spectral characteristics UV Pgiax 2 280. nm) IR Vmax } 1715em7! “HNMR (5, ppmj : 090 GH, 1), 160 @H, m), 2:20 GH, s), 2-40 (2H, ty Mass (m/z) ; 86, 71, 58, 43 (100%) Deduce the structure of the compound and explain the principal ions observed in the mass spectrum. 15 ave—B / SECTION—B 5. (a} NaOMe/McOH % #4 PhCH,COCH,Cl 4 PhCHCICOCH, 3fifran 4 tm # sere cart @) at cee ora feaiahe wah gar ord fee on wad 87 Each of PhCH,COCH,Cl and PhCHCICOCH, in reaction with NaOMe/McOH furnishes the same product, What mechanistic implication can be drawn from the above fact? EG?-D-CAMIZ 7 [P.T.0.(b) 3-zeith-3-hftet-1 eye & afew WH (CH,COO™ Nat) A ee see a Sy) TET 3 soften 8 a wfeear are aa’ 8) seo A yea APS) sft gene ae Te war a fatea Ffae) Two substitution products result from the reaction of 3-chtoro-3- methyl-I-butene with sodium acetate (CHjCOQO"Na*) in acetic acid under Sy1 conditions. Identify the products. Indicate the thermodynamic product and kinetic product. 10 fo) HDPE @ LDPE % as a9& aera fen a wifes qoen & sen ae tea ftfeey get 3 fem feat 2 sed at ga Am) Distinguish between HDPE and LDPE with reference to their mode of production and physical properties. Mentian any two applications for each. 10 (@) NMR @eaghict 4, Pep gare angit 60 MHz 8, TMS @ 120 Hz eerfiee Hom aa anit an 81 (i) ye Sfterey fee en 87 fi) 100 MHz Saver araft & a ore geen fae free fae eon? (ii) LOO MHz eeghite 4 ae da TMs 8 fea’ ede erates ee? A signal has been reported to occur at 120 Hz downfield from TMS in an NMR spectrometer with = 60 MHz operating frequency, (} What is its chemical shift? (i) What would its chemical shift be in an instrument operating at 100 MHz? ii) Hew many hertz downfield from TMS would the signal be in a 100 MHz spectrometer? 40 fe) DNA ot RNA & ata seh afresiags derqsl, stfenai af vafeel a ward A sie a fair ARM) Distinguish between DNA and RNA with regard to their nucleotide structures, location in the cells and functions, 10 EG7-D- CRD 86. fa} (b) fo (a wa zia-4-2ffat-epR-2-FIa_ mCPBA FR V (acac), /ziat-weRceTeS- Fhaess 3 ara ater after een &, wa gat arfiefien beet wm ene aaa 8, wale gee amma Fa eee Sere ar ew fern re Tren 81 shat eftrmenst A wy sere A eieen sft fafam-tanm a ert & ara fafa When trans-4-tert-butyleyclohex-2-enol is reacted separately with mCPBA and ‘V (acac} 2 /tert butylhydroperoxide, in the second reaction only one product is formed, whereas in the first case a mixture of two isomeric products is obtained. Wite the structure of the product in each case with proper sterco- chemical outcome and justification. afta faftn-rane anit ge Riel a otal-ota-2-saemedtenete & teehee a = Se (sere) 3 arn fee ote are A aah otha ae A are Ae) Write the product(s) with proper stereochemical outcome of acetolysis of each of threo- and erythro-3-phenyl-2-butyltosylate giving the reaction pathway in each case, ee fifa FH ae A oth BH a wae Mia F KOH & ore aii wea 8 ak AS fey B a pre afin ce aga fia aA a dey Pear one %, wa za Dan} afte wer ote fafsarn & ait 9 a-8 ford fet on aad t a oa 1 1 oy t peel t A B Explain what inferences about the type of reaction and stereochemistry can be gained from the observation that when each of A and B undergoes reaction with KOH in methanol the rate of reaction is very slow for A compared with that of Bs ‘Pies chil a, ia Ske em aiesAteie ibe Risa wed afin = SS agar sents Pg tie ore em See age SERIE + Oe" ad a cis Arrange the following compounds in order of their decreasing reaction rate of substitution with aqueous formic acid and justify your answer : hy i pote Béucnzcrase ty 15 15 10 10 Sg7-D-eamI2 9 [PT.0.7. fa} ib) (c) (a) 8. (a) frafatar sami a) ties, RAR my otis Bowie Atm ze aca of fetta: (arenes fa) Taher eRe ees (it) Rage fiyy Saree Classify the following examples as aromatic, anti-aromatic or non-aromatic. Write their structures also : fj) Tetrahydrofuran (i) Cyclooctatrienyl dianion (iii) Azuiene (ix) Tropotone Fees ae a wis Hea % O50, /Py a0 eestettder aafiriear 8 aaa wa wenfta sera) A deer fafay ot a faite of) ani) se fii # fice Al wn fem 8? Write the structures of the products expected from hydroxylation of maleic acid and fumaric acid using Os0, /Py, with the stereochemistry, What is the role of pyridine in the above reaction? ad sree war 27 ee shan sere 22 ge aA feat aero) en ae 8 a oe oe 8 Sts genta sheet on fe ae 8 fr oe seats -safer ga cr ah, ah safer rth a Aer serena 8? What is Birch reduction? Suggest its mechanism by taking a suitable example, Why does Birch reduction on benzene derivatives with an electron-donating group happen an ortho and meta positions? ange etroys #, arise ote we denis haere oA ue, ye eR olen age 8 eae ae aA Explain the mechanism of free radical chain polymerization of vinyl chloride using benzoyl peroxide as an initiator. iat saa sit opeife gen 7% afta, shea saree aien, faite SM Distinguish between fluorescence emission and phosphorescence emission giving suitable examples £G7-D- Gam 10 10 10 1s 15 10(o} i) (a) @) fee 9) gia-eieia % 313. nm waa Pon a 93% fia a 7% geste fem om ein 8, fe feo & aren aS ese Pe a wen 2) eae fee oe afr ard aga | ‘The direct irradiation of cither cis- or trans-stilbene at 313 nm results in the formation of a mixture of 93% cis- and 7% trans-olefin, ne matter how long, within reason, the irradiation is continued. Give a suitable explanation for that, 10 Frafefera afiien a1 afieen fife she ea fae en avg fanfare: coch Sy RR eae am em - CO i UV Pte FE Apna 296i, Emgx 1O7OO FM Agpax 281M, € mex 20800 fH wee Xa YA aeaaot a Fos ae aera act #7 How do the UV spectral data Aga, 296MM, tmec 10700 and Armax 281m, Emax 20800 help in deciding between structures X and ¥? ohn area arg sissies a sere 24 gu aTa-ginee legal oA} ore Ff Explain charge-transfer spectra by taking a suitable donor-acceptor type complex, 10 10 10 ee EG?-D- CAM] uw BS9—348