CS (MAIN) Exam ‘STH-D-CHM wars faa / / CHEMISTRY ‘wea-ua IL / Paper II Frafta are : ata ae ST HH : 250 Time Allowed : Three Hours Maximum Marks : 250 Wea-aa are fasts aye pre weal a sere Bt oF et Preheat arte agaer wt eae Te: a weet # Her oma WEF fee Te & ait Meet OF STAR cat F FE 1 tice oh ret aber weal & a 34 & 1 rer wer 1 site 5 oaPtard & aor a Fa yee avg a anda v ¥ a oer wee ere zifere eles wer /um % frre Rrra sie sere art Re re BF * aremy # fre z, FR 37 aan hi 8 oft 3a aren ar Bre Be WET (PAV) WI % ya-7S W PNT I uv ra nea silat sr arrear fered re sere ae BIE tas TAT Freeh | igh staves Bh, Pidares oneal ah wer aor sor at a fore fete me cera a aa BI wa wee ashe 7 Bt, aera regret walera arte srert A wee BI We rrr Bi, a ae art ear rar are on sre Pec wae | . * a BATTER BO aeH | siifres 7B Re Te & aa # ot ane 7 ab / erase GPT FAT BIS Te BIE es evar yes HT wh gel: 1 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. Questions no. 1 and 5 are compulsory and out of the remaining, any 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 ina 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 struch 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. STH-D-CHM rwas A SECTION A Ql. (a) frfefer sqewit a Wifes, swe-tifes wi aatiafes A ariipa fifa | are st sit sax ot shea sf fag Fire | aoe ia Gai) (iv) w) Classify the following examples into aromatic, anti-aromatic and non-aromatic. Justify your answer. 10 H N. A Gi) Gi) (iv) wo (b) sere A sit BST deed fea car gt waa [G) AK Gd] & wes qearin send a age sik shface-sfoarer Fife | Me Me hfe Br @_~NaOEt Gi) ‘Buk A+B Write the structure of products A and B and mention the major/minor products in each of these conversions [(i) and (ii)] with justification. 10 Me ean Br (i): NaOEt Gi) ‘BuoK A+B STH-D-CHM 2(©) @ () (STH-D-CHM frafafac aftiiea & song at faftag sit gah oat & Geanfattes art at fafra fifi | Foo SK Me | BtNH —— Write the product of the following reaction and depict the mechanistic pathway for its formation. 10 Foo SK Me Bt,NH Cwm DA dernat wl sarge sik St aA sr seca ifr | 3 Atk Cos Li 78°C Mel a -— e cD re THE (=) Give the structures of C and D and account for their formation. 10 a Agi wh. CoH; | Li , — 78°C Mel 5 > 6 SD major) THF frafefas afieensit Aa yee & sere A deen et svaw ffea-errt freanf & gro fefae sit at sett a) we.us. ait. firgra ft gerrat a Sha fag aif | a Me—\_-—Me S Write the structure of the product with proper stereochemical outcome, in each of the following reactions and justify your answers with the help of FMO theory. 10 by As == Me -—Me = 2Q2. (a) sete 4 aif are [] of feafa aula ge, AO Woe A deena a ega ita | o™, Me or & [fl irl Give the structures of E to H showing the position of the labelled carbon [+] in each. 10 o™y Me Me © S3 [E]—(F]—G ° C> oO (HW) A+@ + &) 35-3Rtie-aRria sit 26-seie-sagthaia Ha shea w sift ornate @ otk wat 2 Out of 3,5-dimethyl-4-nitrophenol and 2,6-dimethyl-4-nitrophenol, which one is more acidic and why ? 10 STH-D-CHM 4© Laka A deme w fafa | Ae sigfee waa & ue ao HK gafieare @ tar 8 | seer a ferftay ait sacs dina Geenfatty saree | 0 va eee H,0* ara H,SO, —————- 1 —— K Write the structures of I to K. The conversions mentioned below involve a rearrangement at one step. Name it and depict the corresponding mechanism. 15 oO Mg, Et,O [er ‘42 y H,0* yp SE HBO x cold @) Frafefad attire Fa ste & sere aw wales Fie ait wets eater At Grenfate faftag | suftrert Na, EtOH, 1L EtO OEt — @_Na, sget, 11 (i) HO Predict the product in each of the following reactions and write the mechanism for each conversion. 15 excess Na, EtOH, 1. ° ° BAAK EtO OEt Gi) H,O STH-D-CHM 5Q3. (a) PN Mal 2 Ta 2,4-terergaia At siftieat MeMgl & UH geais a act 2 ? amy sight Siesta at 2,4-Reavergaiia H ha waichta He wed B 7 What happens when 2,4-pentadione is treated with one equivalent of MeMgl ? How can you convert the mentioned dione to 2,4-hexadione? 10 (b) & Geen Yer aa A we ad qias tesla a aM A Fahy fafax | ae dt serfs, fidtes atk qdiee teateiet a fatter ee arf em fare fafa | Write a method of preparation of a tertiary alcohol containing two identical alkyl groups. Write one method for distinguishing primary, secondary and tertiary alcohols. 10 © Lana # Bian der fafar an nS faire epia a feoh ifsc | anf tepiete a fefire gol + x2 1 Me »Py KOAc, a DMF, A OH L M—>N Write the stereo structures of L to N and comment on the specific rotation of N. Specific rotation of the starting alcohol is + x. 10 Me »Py KOAe, ° DMF, A OH L M—+N STH-D-CHM 6(a) Praftftaa watawil 3 a yet & senesendi Ft aca ferfian sik wets caftifgpan
Ck OH Oo cis — diol 4 @ szeTeserd aw yatqar Ae sik aftieensit Ht Bfea-carrt stags Ft faa Bet ge sy Se aT sitferce fire iT | NaOEt ® af “= NaOEt NaOEt , (ii) "Ge cl Predict the product(s) und justify your answer discussing on the stereochemical requirement of the reactions. 10 NaOEt ® atlaZ ae NaOEt NaOEt , «i cl STH-D-CHM 9(e) STH-D-CHM Frfatad eae HB vate faq craw fife oftentat & am fear | ‘fifaa-fafine’ (ifeifation) cor Aifea-acncrsn’ (eifeaatiea) 4a shea we sete afte & fee sqm er? @ Me Me Me \/ Il Me ii) Me a ‘Me Write specific reagents necessary for each of the following transformations. Out of ‘stereospecific’ and ‘stereoselective’, which one suits for each reaction ? 10 é Me Me Me Xf Il Me Gi) ae , ‘Me 10Q5. (a) (b) (© @) STH-D-CHM aEB SECTION B fea oro a aegis At anfed 13-feergite fee aot dk a afta 2, aren Aig cat Rragite safiana afitarsit % fae gqead-etoar ae fran sega Fifa | Explain why concerted 1,3-sigmatropic shift of hydrogen is thermally forbidden and give Woodward-Hoffmann selection rules for sigmatropic rearrangement reactions. 10 amg frafataa afters at da a-aei area seq gm sere Ho wciahe eet 2 are frrenfate A rare | ° CHO hint How will you convert the following reactant into product by a two-step process ? Also give the mechanism. 10 ° CHO O Prafefaa afitea & fae song feftae wd gah oat At fieenfater aaree fas fee ware ar ar DO= 06 onde ac ST | CH, CHyly, Zn - Cu OH C,H, -O-C,H, Write the product for the following reaction and give the mechanism along with type of addition at the }C = 0 bond. CH, CHyl,, Zn - Cu ae OH C,H, -O-C,H, um teh faire QR etfeften) atria At ofan ifse | sia fea vere 2 ticle mM pci sete F ahaa Het? Define a regio specific reaction. How will you convert aniline into p-phenylene diamine ? 10 if 10(ec) feifefad aftet & anet at mR etait sei arg ha fader ax wade? @ « Afefeits ora wi pagia tise aa Gi) Whsitrtfesags wi tear How can you distinguish between the following pairs of compounds by using IR spectroscopy ? 10 (i) Salieylie acid and p-Hydroxy benzoic acid Gi) Propionaldehyde and Acetone Q6. (a) fefefas afiieasit & send a gaa Fifer 1 NY LON a6 ert né CN Predict the products of the following reactions. 10 ) @ teresa For, cen Gi) Fereeshea saree & anita wabtewr sr fafen-erert art een ett 2 What will be the stereochemical course of thermal cyclization of (i) Pentadieny] anion, and (ii) Pentadienyl cation ? 10 STH-D-CHM 12() Prafefad afifteansit % ser at fefar | Sy poy @ Az Ty Loi, ifr yar I ° @ JOY ™, ifr yer IT Write the products for the following reactions. 10 S, ss hy o AA ao las Norrish type I ° @ ACA bY Norrish type II @) afte A cn BS verfercdiem (atdlfeerditcea) & vied Tea 1 (Aa) FR TM IV (BA) waa S | STH Beat Ht aT | Oo oy ©, conten A o ™.co+m+v (STH-D-CHM 13Compounds A and B undergo photodecarbonylation resulting in the formation of I and I (From A) and III and IV (From B), Give their structures. 10 oO ky >}. co+nsn A o ©. cosmrar B (@) =eriagst wi =e A dean die ak wea H Saw. sik SRG, At srearfirer (aifers) aeeansit At fae ifr | Give the structures of nucleosides and nucleotides and discuss the primary structures of DNA and RNA. 10 Q. @ @ fefafad verte afin & fae qeradf an cine sand at ferfiax | Basen * Mog EE Ee "Or, O-R Gi) Late cer asia & fer arg feet lea. cara. ferrti Ft stan wrt 2 sah fares wired ar faa die 1 Gi) IR Baer a seit ee fafeafad aifrst F sma da Ae aw 2 Ha a SM cm) Ff afte ar dem (aa FR) aT Hasler HoT, sie wat 2 ° oO H cl cl H @ ap () Write the intermediates and possible products in the following photochemical reaction. 5 9 + U hy H,07 Son, \ O-R STH-D-CHM 14(i) How many 1H NMR signals do you expect for 1-bromopropane and 2-bromopropane ? Give their splitting pattern. Gii) How will you distinguish the following compounds by IR spectroscopy ? Which will absorb more wave number in cm=!, and why ? ° i at i cl cl H o a (>) eafafad afiiensit F aaa areal yer sere (Z) Ht VERT | () os0,, @ 8,-08,-0 IO ® > gly Eyes 0 HOW A~ OH y® um Bene ee ae (2) LiAlH, @) H,0® (iii) Na, NH3 @ C,H,0H H H 0 STH-D-CHM 15Identify the major product (Z) formed in the following reactions. “15 Gi ii) H Na, NH, amo (~H GH,OH oH © aa. Gast aera a weit ach feed & Se wi gar anaaat (agate) & ate arg Ha Aq HE 2 caren Fife | How can you distinguish between cis and trans isomers of stilbenes from UV spectral study ? Explain. 10 (a) orpfis wn, vifeeagte afk toca St gaat sora At deere faftac | Steia cen data. (PVC) at arg a sae 2 Write structures of repeating units of natural rubber, polystyrene and teflon, How will you prepare terylene and PVC ? 10 STH-D-CHM 16Q8. (a) Praftiaa farsi aft & deaeor } fe sag ones aia atk Sensi wt gaa ae | HCO ‘N~ “CH. 3 ww) Suggest suitable starting compounds and structures for the synthesis of the following heterocyclic compounds. 10 HCO ‘N’ CH. Oo 3 STH-D-CHM iFoO. oO @v) 7 cOCH, cH-co0c,H; W) 0 (bo) Frafafiad atfret & few M+ & fratt an gern Be Gert or yal aifsre, | i CH, - CH, - C - CH, CH, - CHg OCH, Predict the M+ peaks and mass spectral fragmentation for the following compounds. 10 i CH, - CH, - C-CH, CH, ~CHy and OCH, () Frafefad aftitear 9 sorg veaie sit serge & ato oft frenfafe a aia afifare | (i) Na, NHg, 2% ° Gi) NH,Cl STH-D-CHM 18Identify the product in the following reaction and provide the mechanism for the formation of the product. 10 zy ()_Na, NH, ether 0 Gi) NHC @ && agra aries afte fea onftes a CoH, 02 2, fraferiad Bagi sites cae @ : UV: 270 nm; IR: 1680 cm 1H NMR : 87-6 (2H, d, J = 8 Hz), 6-9 (2H, d, J = 8 Hz), 3-9 (3H, s), 2-0 (3H, s). A acon Ht Fafa fire | An unknown organic compound having molecular formula CgH902 exhibited the following spectral data : UV: 270 nm; IR: 1680 cm 1H NMR : 87-6 (2H, d, J = 8 Hz), 6-9 (2H, d, J = 8 Hz), 3-9 (3H, s), 2:0 (3H, s). Deduce the structure of the compound. 10 (e) Frafeftan atfitet at ang ha sari 2 @ | Gi) ° H = Gi) as ° pou (iv) “ OH ) COOMe COOMe STH-D-CHM 19How do you prepare the following compounds ? @ ] (i) ° H. ZA | oO (ii) ~~ “a ° pu (iv) ™ OH ) COOMe COOMe STH-D-CHM 20 10°