a Mee aed Org FleAbout the Author Mahendra Singh Chouhan (MSC Sir) is a renowned name in the realm of Organic Chemistry. Through a Chemical Engineer from Mumbai University, his great passion for the subject led him to impart guidance to IIT-JEE aspirants on a regular basis. His in depth knowledge and vast experience-has helped innumerable students to achieve their dream of excelling at IIT, JEE and other such tough challenges: He has launched a website to extend the benefits of his expertise beyond the geographical barriers to all those who dare to dream and seek - www.iitjeeorganic.com. The website provides expert guidance in all the areas of the subject ina most skillful manner. There are quizzes, challenging questions, notes, e- books and videos etc. This website is a complete guide in itself for ‘organic chemistry and has been designed for lIT-JEE aspirants, keeping | tomindthe various syllabi and CBSE. | Highly recommended forthe high flyers. ke callaati. BalaJi Advanced Problems in ORGANIC CHEMISTRY by: M.S. Chouhan Director Vibrant Academy, Kota SHRI BALAJI PUBLICATIONS (EDUCATIONAL PUBLISHERS & DISTRIBUTORS) [TANISO 9004-2008 CERTIFIED ORGANIZATION” ‘Muzatfamagar (U.P.) - 251001A few words to the JEE Aspirants Dear JEE aspirants, | | hope that this collection of problems will surely help you during your preparation for JEE. In this book, each chapter consists of two levels : Level 1 - includes the problems having only one option correct. These problems are based on different facts and their twists. Level 2 - includes unique approach which may be used to solve the problems altogether different from the prevailing trend followed by JEE. These approaches will undoubtedly help you in the quick revision of the key facts and their applications. | wish all of you a grand success in the ensuing Joint Entrance Examination. Your valuable suggestions and constructive criticism for the betterment of the book are welcome. M.S. ChouhanPreface It is a matter of great pleasure for me to present the eleventh edition of "Advanced Problems in Organic Chemistry for JEE" before JEE aspirants. During my teaching experience, | felt that the facts may be made more and more clear to the students through problematic approach. Although an ocean of material in Organic Chemistry is available with the students, yet the approach to design the problems has been changed in recent years and if one tries to swim in this ocean, it will be a very difficult task. To make the students more familiar with trends and tricks how to solve problems, the present problem book has been presented. In the current scenario of stiff competition especially for JEE, one must be clear that almost all the sincere applicants are well equipped with the facts of subject, yet the winner is one who knows how to use these equipments with accuracy and efficiency. As an experienced teacher, I would like to suggest students three golden rules to score high in Organic Chemistry: 1. Don'tgetbehind 2. Workoutanumber of problems of different types 3. Revise through short notes / learning chart. Thope that the present book will cater to the needs of JEE aspirants & as a matter of fact, they will enjoy the present venture and I would feel rewarded if this book is found helpful to the students and teachers in real terms. All attempts have been made to make the book error free however a few misprints may inadvertently creep. Iacknowledge the blessing and support of my mother Smt. Raj Kanwar, father Shri B.S. Chouhan, brother Dr. VS. Chouhan, my wife and daughter. They inspired me all the time during: the preparation of this book. The support and valuable suggestions from my colleagues especially Mr. N. Avasthi , Mr, VK. jaiswal, Mr. Nitin Jain, Mr. N.K. Sethia, Mr. Vikash Gupta, Mr. Pankaj Joshi, Dr. S. Kothari, Mr. Vineet Khatri, Mr. Ashish Mishra, Mr. Manish Arora, Mr. Govind Khandelwal, Mr. Rahul Pareek, Mr. Rahul Malay, Mr. Divyesh Tiwari, Mr. Omkar Kelapure, Mr. Kishore Kilani, Mr. Mayank Pareek, Mr. Gurpreet Singh, Mr. Yogesh Jain, Madam Anjana Kamal , Mr. Aneet Choudhary, Mr. Shaliwahan Singh Rathore, Mr. Akshay Chaudhary, Mr. Hanuman Sahay, Mrs. Neha Joshi, Mrs. Neetu Jha, Mr. Kamlesh Gupta and Mr. Kumud Ranjan are highly acknowledged. I also pay my sincere thanks to all the esteemed members of M/s Shri Balaji Publications in bringing out this book in such a nice form. In the last, constructive criticism and valuable suggestions from the readers are most welcome to make the book more useful. M.S. CHOUHANaa General Organic Chemistry [TZ Isomerism (structural & stereoisomerism) 1737) Grignard Reagent ak Hydrocarbons (Alkanes) (74877) Hydrocarbons (Atkenes) Ez | AC || Hydrocarbons (Alkynes) Ez | BA) Alkyl Halides (Substitution Reaction) ez Ezy =a =5) =z SBI) Alkyl Hatides (Elimination Reaction) Per ‘Alkyl Halides i | 6 | Alcohol, Ether and Epoxides [TJ Atdehydes and Ketones © 8) Aldol and Cannizaro Reaction ee Carboxylic Acid and their Derivatives i Ea Carbene and Nitrene Ceres [02M Aromatic compounds Byes) En Practical Organic Chemistry [RAM Biomotecutes [HN wrac Names [UES tearning chart f= Apr rots 342-388LEARNING CHART (AROMATIC COMPOUND) {gi = . 7 e he gay i 2 ‘S, ee Cs é S ay > fol. i cf Oy Oe oei (kO- [Or 2tlOn= | i o LEARNING CHART (ALIPHATIC) mth oll, tcp £[HipRocarsons (arkenes) 0) Reagents A HCL [B. Br, G. Hg(OAe), in H,0_[D. BaHg(BH,)inether E.H,0,° [F.KMn0, inH,0 |G. HoBr H. NaBH, In each reagent box write a letter designating the best reagent and condition selected from the above list of reagents, o (CH) ,CHCH(CDCH, “cli 3 methyl tatane i (cH) ,CHCHBrCH,Br 1, 2€ibomo-3-methyl butane |(CH,),CHCHOHCH,Br (CH ),CHCH = CH, 1, brome-3-ethyl 2-butanol ‘3.aethyld-butene |(ctig),CHCH(OH)CH, B-methy-2 butanol Gv) |(CH),CHCH(OH)CH,OH ‘S-methyll, 2batanedio w) Propene (CHg —CH = CH,) can be transformed to compounds (a to j) listed in the left-hand column. Write letter designating the reagent, you believe will achieve desired transformation. In the case of a multi step sequence write the reagent in the order they are to be used, TR aT Preis boos teg = Gut Pera ng Hg(OAd), in H,0 (CH,CHBICH Br BH, in THF (CH),CHOH242 ORGANIC Chemistry for ITT-JEE . | CH3CH,CH,OH : two C. | NaBH, in alcohol d. | cH,cocH, three D. | Br, in CHCl, } e. | cH3cH,cHO three E. | 1,0, in aqueous base f. | cHjcHCOH)CH,Br | one F. | HoBr (NBS in aqueous acetone) g- | (CHs)2CHBr one G.| HBrincH cl, Ih, Ik} CHCH(OH) CHZOH | two H. | 050, in ether i. | CHy -CHy -CHy -Cl | three 1. | Thionyl chloride (S0c1,) j. | CH, -C=CH two. J. | NaHSO, in aqueous acetone K | NaOH in alcohol and reflux L NaNH, (strong base)HYDROCARBONS((ALKENES) AC 243 3. In each reaction box write a single letter designating the best reagent and condition selected from the list at bottom of the page. (.S., ~ first step, 5.5 > second step, T.S. third step) Rey Reactant 5 Poetics A. NaBH,/alcohol |B. Ph -COjH/CH,Cl, | ¢. PCC D. CHjONa/CH30H E, ByHg in THF | F. H,02/aq.NaQH |G. HyPO, &heat | H, AICLs/CeHg 1.03 inCHCl, — |J. Brain CH,Cly K. 20% KOH &heat | L. Ph ~Li/ether244 ORGANIC Chemistry for 1T-JEE 4. Match the reagents a-j with produets AJ. There is one best product for each reaction, Ba ® ‘The molecule (x) is the starting material for all reactions in problem. Do the ones you know first and then tackle the rest by deductive reasor oar Op HO heat, pii7 tBuOK, polar aprotic solvent 2) 0a, ether HO, NaOH, H,0) Bry, CCl NBS, liv, CCl, ) #0) (2) NaOH, H,0 (1) BH, ether (2) 4,02 (1) 080, (2) NaOH, H,0 < Spr Cd _® | Ha/PayecexoryHYDROCARBONS (ALKENES) 245 5. Match the column: ee (@) | cH, —c =c—cH, (p) | cis-produet with Hy/Pd- BaSO', | coy [cxs, cry cmc (@) | Trans-prodiict with Na/liq, NH | (© | ct —c =cH () | white with amm. AgNO, | cw Jos, —cm (8) | Hy gas with Na | s sti pce oe Rl 246 ORGANIG Chemistry for IT-JEE 6. Match the column I with column II and with column II (Matrix). Number of chiral center | I present in product. | Reaction Nature of product formed | (Consider only one isomer | in case of racemic mixture or Diastereomer) ] J @] Fy, 2 (®) | Racemic mixture | (w) ° cH, | Fy @ | Meso 0 1 CH, | br, “cd, | «co (©) | Diastereomer w 2 | CH; rae | a) P= eae | (9) | vicinal dihatide @ 3 | H CHHYDROCARBONS'(ALKENES) 4 7. Match the column I and 13 247 Reaction Ene) Saat) Product |. OY | rs | | 2 ¥ | | | | , - | | ow CO jem @ Cr | ro, neon oe | A ou | © aa, © CL | | oH j = A cl @ O ayia © cL c CH, — OH HO on 8. (1) “Sw (2) i () on — on9. (1) C,FCIBr aa) (exclude stereoisomer) (aizomes) (2) CH alkene) —22s(B) (exclude stereoisomer) ‘al some) Total number of products A and B (i.e. A + B) is equal to : Reaction 1 Reaction 2 CAs CH Deal H——Br 1 on i. cH cle M (rans) —2->(Q) a fee te Hy CHy Reaction 3 Reaction 4 CHy a u—t— Br Reet Sera cH a Br, cH rea | cerans) 82,8) cu 7 Gh cas CH3 a Sum of products P, Q, R, S (i.e. P + Q+R +S) is equal to:Vladimir Markovnikov rule Alkenes undergo electrophilic addition reactions. It is triggered by the acid acting as a electrophile toward x-electrons of the double bond. Markovnikov’s rule states that when an unsymmetrically substituted alkene reacts with a hydrogen halide, the hydrogen atom adds to the carbon that has the greater number of hydrogen, e.g, CH [S-an+n-a 22, Xa anehyl cyclopentene 1 -hloro--methy eyopentane Mechanism : cH, + HCL CH; ge Step -1 ly = sal ra cH, 8, s supa oh er = LOX co Which of the following is most reactive toward Markovnikov addition ? 0. OO 9 «CX What is the energy profile for the given reaction ? Uy et @ Teacton coordinate Wesaton coordinate d) I Teacton coordinate Reaction coordinate In which of following reactions carbocation rearrangement is possible ? (a) (CH)2cH —CH = CH, Ho () (CH,),;C—CH =O Say (© Ph—CH, —CH =| HH, (@) All of theseORGANIC Chemistry for UTJEE D. Identify the major products r, , and ry in the given reactions. me Cy E>, O i [cH,on” "2 HBr —p,0> 3 OCH, CH dd Hy in all the reactions @ in all the reactions E. In which of the following reactions, product is racemic mixture ? CH (b) cact a One ctig 6c © og PS om (@) CH ~CH ~CH =CH, — oe i =c0" 7m, Allo © yas EE (4) All ofthese F._Inwhich of the following reactions, diastereomers will be formed ? Ce @ aS (b) chy (@) Allof these ©HYDROCARBONS '(ALKENES) Parner CH, —CH, —CH 12 +CH,OH —" cH, —CH, — ici, OcH, Consider the above reaction and answer A to E. ‘A. Whatis electrophile in first step ? @ (@ CH; @) He @ (© CH, —CH, —CH—CH, @ Ho® B.- What is nucleophile in first step ? (@) CH,OH (b) 1-butene © H,0 @ CH, -0-cH, G. What is electrophile in second step ? 3 (a) CH (b) H® ® ° (© CH, —CH, —CH—CH; @ CH, —CH, —CH, —CH, D. What is nucleophile in second step ? (@) CH, —CH, —CH =CH, (b) CH,OH (© H,0 (@ CH, —O—cH, E. Which step is rate determining step ? (a) attack of nucleophile CH,OH (b) attack of electrophile H® (©) attack of nucleophile H0 (4) attack of electrophile CHs252, 13. Match the column I and II: ORGANIC Chemistry for IT-JEE Reagent | =) ©) $0,Cl,/ hv (2 equivalent) (b) @ NBS (2 equivalent) | he NBS then S0,Cl,/hv I | | : | @ ©) ‘80, Cl / hy then NBSHYDROCARBONS (ALKENES) * 253 Paar) 1. @~A; (ii) -B (ill) - G; (iv) -C; ()-F 2. a-D;b-A,C;c—B,E;d-A,C,Fe-B, EF fF; g-G;h-1, KiB, E,1;j-D,L 3. Reaction 1: B, D; Reaction 2:5,F,C Reaction 3:1, A Reaction 4: L, G Reaction 5: B, L, C A. a-C;b-D;e-Asd-F eG f-J g-B N- Hy i-B;j-G 8. a-p,qsb-ns;c-15)d-p.q 6. a-1,s—z;b-p,s-¥iC-PS-Ysd-Gs—y 7. a-nb-pye-gd-s 8 A+B+C+D=312 9% A+B=5 10. P+Q+R+5=8 11. A-b;B—¢;C—d;D-bjE-G;F-d 12. A-b;B-b;C-c;D-b; E-b 13. ag; b4 5 08; dor HYDROCARBONS (ALKYNES) Pay ‘se : ee A), PES (B) 5 Product (B) is CH=CH, c= cH cH, @ Cr ©) CO © Cr @ cy 2 \AN\ 3S (As Product (A) is (a) H,C =CH—CH =CH, (b) CH; —C =C—cH, (© CH, —CH, —C =CH @ cH; —cH NaNH, 0 2. cxcicacr tt Le, Product (K) of the above reaction is JK) OH c=ac—kt C=C—ert @ )4 7: QH on = C—CH,—CcH, Cm C—CHy © @ CH, — CH, — CH, —C =CH + LiNH; —> (A) “8+ 5 (B) = Give the structural formula of compound (B) : (@) CH; — (CH), —C =C —S0,H (b) CHy — (CH), —C = C—CH, @ Oh— inh ene —o-f @ CH, —cH, —c =c—cH, _-CHly ~ CH, ~ CH 4S biceps Ss 5 This conversion can be acheived by : (@) NaNH2, CHjCHO () NaNH2, CHj—CH,—CH,—Br (© KOH, CHy — CH, — Br @ KOH, Gh. — Gi, BrooBr Which alkyne will give 3-ethylhexane on catalytic hydrogenation ? Ss i @ ” © @ Allof these Reactant P gives products Q or R. 7 S-Ni a obs “ The possible reagents are : (D 2Na/liq. NH (WD) Hy/Pd/CaCO, (quinoline) (uD) 2H, /Pd/c ‘The correct statement with respect to the above conversion is/are : (a) Qis obtained on treatment with reagent (1) (b) R and Q are obtained on treatment with reagent (11) (© Ris obtained on treatment with reagent (1)OL (d) Ris obtained on treatment with reagent (11) 8. Br—(CH3),2 —C = CH MMU (4) E(B) ; Product (B) fs + oko © (@ Br—(CH,)—CH = CH, 9. Ph—C=CH —¥2—, Major product of the reaction is : Ph. H Ph. OMe Ne Ne gw @ © exc wen Ky werk, (© Ph—C=c—oMe (@ Ph-g =chy e OMe 10. the —cH, “2, (A) 5 Product (4) i a ee (@) Ph—CH=CH, (b) Ph—C=CH (©) Ph—CH,—CH, (d) Ph—C=CNa 11. Which combination is best for preparation of the compound (A) shown below ? Hs Him c— cH,CH,CH,C = CH (CH3CH3 (A) 8 cH, nyc mi, cape eet, ne’, NaC wm CH @ MEM e—caicrgcHate “EA S4) (6) He — cucrycrbr ME~M4y HCH, HCH, 8 cH 2 Bct,GH cree CHCH, CHACH, 412. Which one of the following isthe intermediate in the preparation of ake fn alkyne in the presence of sulfuric aid and mercury Qt) sulphate > Vert OF 4 © Be faa (a) cay (a) Heyy ttt ’ 2. BCH CHG, cH14. 15. 16. 17. 18. ‘oun CH cu To carry out above conversion, (A) and (B) respectively, are : (a) NaNH,Cl—CH, —CH, —CH, — Br (b) NaNHz, F—CH, —CH, —CH, — Br (© NaNH;,1—CH, —CH, —CH, —Br (@) NaNH, I—CH, —CH, —CHy —I l : H—C=C—Ph ———+—-> Product; Product obtained in this reaction is : HON.) @ Ph—G—=cH—1 ) Ph—CH—CH, 1 (© Ph—c=c— (ovat, . ae

cH uate AH, (4) > (8); Product (B) =C—CH, mae neo °C) “ort aa en @ egy Which of the following alkyne on treatment with H(2 smole)/ B gives an optically inactive I (@1—C=c—H compound ? (a) 3-Methyl-1-pentyne (b) 4-Methyl-1-hexyne (©) 3-Methyl-I-heptyne (@) None of the above CoC, H(A) —ESEASUBY > (B), Product (B) of the reaction is : (catia tide (a) Toluene (b) Ethyl-benzene (©) Benzene @ Butyne What is the final product, C, of the following reaction sequence ? \ Naty A © CACHE Ai ASN) p 3 ang, °C Br Br Br Br Br or wo DK one one Br NH, Br19, 20. 21. 22. 24, s compound 002» {)— at — atl cH, — CH AO Preiiate ° 0 0 i tl ° a ll iL Wed H-C— CH, ~ CH, —C-C H+ H-C— @ CSc orcas ) (cH — cr — C= cH © € cic, cm ct @ Cec ccc Choose the sequence of steps that describes the best synthesis of 1-butene from ethanol : (@) () NaC = CH ; (2) Ha, Lindlar Pa (b) (1) NaC==CH ;, (2) Na, NH, (© @) HBr, heat ; (@2)NaC==CH ; () Hy, LindlarPd (@) (2) HBr, heat ; (2) KOC(CH)3 , DMSO ; (3) NaC-= CH ; (4) Hy, Lindlar catalyst Which alkyne yields butanoic acid (CH,CH,CH,CO,H) as the only organic product treatment with ozone followed by the hydrolysis? ae ae ° ° I I CHO. —0-H+H—C—O-H+] cHO ‘Compound (X) will be : (a) 1-Butyne (b) 4-Octyne (© 1L-Pentyne (@ 2Hexyne @) ya, CH — ont Carlina oxide Unit of unsaturation in compound (A) ? @7 os ©9 @10 ° LC» sot, (qy_MO_, gy Hebets, ey Prodtict (©) of above reaction is: @ HyC—=cH, ©) CH, ~c=mc—cu, (© HC=CcH @ CH; —CH=cH—cn, To convert 1-butyne to 1-D-butanal, one would carry out the following steps : (D_ Sodium amide, then D,O (I) Disiamy Iborane, then hydrogen peroxide/sodium hydroxide (QD The transformation can not be carried out with the indicated reagents. (@) |, followed by (b) Il, followed by1 (©) I @26. 27. 29. ‘An unknown compound (A)has a molecular formulaC,Hs. When (A) is treated with excess of Bry a new substance (B) with formula C,HgBrg is formed. (4) forms a white ppt. with ammonical silver nitrate solution. (A) may be : (@) But-1-yne (b) Bu-2-yne (© But-1ene @ But-2-ene One mole of 1,2-dibromopropane on treatment with X moles of NaNH, followed by treatment with ethyl bromide gave a pentyne. The value of X is : (@) One ®) Two (© Three @ Four i: CHy-CH-C=CH oust ‘The product of the above reaction is: Hy Br Br @ Br (@). CH ~ CH-CH- CH, (b) CH, ~ CH-C = CH, Is Br is ir (© cry -cH-F-cHhy @ cH - CH- CH, ~ CH Br r cata 0, CH, —C = C—CH, —*0804_4(4) Product (A) @ cue Le © on tL en HOH (© CHy—CH-CH—CH, @ 0=CH—cH, —cH,CcH=0 In which reaction last product is Ph —C = CH? Br I @ Cotte —6— CH entarar? Sued Br 2 Nani nage (b) ColHsCH = CHa ce ientonstear? — Il ‘nate (© Cette —C—cH, Fy, (@) All260 30. 31. 32. ORGANIC Chemistry for ITJEE Predict the product of the following reaction sequence. te (1) cess NaN Bog ICH, —a an (@) 6-iodo-1-hexyne (@) Thexyne (© S-decyne @ Liodo-1-hexene ‘The best sequence of reactions to prepare 2-heptanone is, (@) propyne Mais, x —#-Clste, y_ Hate” () ethyne PSH x State y ane” a0, (© 1hexyne Na, xB, yo @) 1—pentyne MH x —SHABE, y_tooi ‘The major product of the reaction of 2butene with cold alkaline KMnO,, is oS © A © A @ No HtBN ALKYL HALIDES Substitution Reactions (S,;,S,,,S,,) 1. Which of the following is not expected to be intermediate of the following reaction ? OH =, + Sit, One Oo CHy 2, Br an +Nal—aaaz Product; 8,2 product of the reaction is : H 3 CHa - CH6. 2 On cH, Ow CH, ~ CH Rate of S,,2 will be negligible in : Br Br of) wml y ‘What is the major product obtained in the following reaction ? ‘Br Hy-NHy, CHy-Br _ Ayn .CHy-NHy Og) oC] @ ‘Br NH NH cH, (Chita G ~ CHa ~CHy C+” — gg Product Major produc of this reaction i: cH, CH Hy (@) 1-CHHy ~G-CH CH, - AL ©) Cl-cHiy -G-cH ~cH, -1 CHy cH, on, oy i (© H,C=C- CH -CHy =C. @ Cl-cHy -C-cH, =cH, cH, Which of the following expressions is representative of the rate law for a2 reaction ? (@) Rate = k [electrophile] () Rate =k [electrophile} (nticleophile] (©) Rate =k [nucleophile]? (@) Rate =k{electrophile]? oe Nal (1 mole) —M8#*> (A): Major product of this reaction is:10. 11. 12. 13. Which of the following alky! halide undergo rearrangement in S,. reaction ? CH Cl | (a) CH, - C- CH-CH3(b) oO (d) All of these 1 chy cH, I Arrange the following three chlorides in decreasing order towards S,., reactivity. ava ary @ ei a @1>2>3 @) 2>3>1 © 2>1>3 @3>2>1 Which compound undergoes nucleophilic substitution with NaCN at the fastest rate ? @rAxX © mA Om xXCA, © oan Rank the following in order of decreasing rate of solvolysis with aqueous ethanol (Fastest —> slowest) nO ot I H,C =C—Br it. CHs -CHCH,CH(CH3)2 qa @) @) (a) 2>1>3 (b) 1>2>3 © 2>3>1 @1>3>2 ‘The reaction of 4-bromobenzyl chloride with sodium cyanide in ethanol leads to the formation of : (a) 4-bromobenzyl cyanide (b) 4-cyanobenzyl chloride © 4cyanobenzyl cyanide (@) 4-bromo-2-cyanobenzyl chloride ‘Which of the following reactant will not favour nucleophilic substitution reaction ? @ (b) Ph—-Br @ All the above oHConversion of t0 1: (@) takes pace by $,. (©) takes place both by. and Sys (b) takes place by S.,2 (@) does not take place 15. Which is the correct reaction coordinate diagram for the following solvolysis reaction ? Hs CHa pu ,, 10 f, 1 npp ty “OH + ” CHly : Pa + ag @ ® Reaction Coordinate Texan Cordis : LV _ ES Eee @ Reaction Coordinate ""Reacion Coordinate 14 labelled ¥ OTs at % _ —A622 product; Produet ofthis reaction is no label. @ (cor Be -0cor or oor (©) both (a) and (b) 1 Hy 17. MSs (4) TESA (B), Product (B) (@).None of theseHy-S-CHy Ia @ ® $-CH ‘HBr © (@) None of these 18. Which of the following represents the correct graph forS,,2 reaction ? Jog (rate) @ (lly ~Br CHly~CHiy~ Br CH, ~ H- Be CH, CH ~ log( rate) || __»__ &) CHy-Br 0 Bt-Bri-Pr-Br ¢~Bu-Br log (rate) © CHy-Br-Et-Br i-Pr-Br ¢-Bu-Br Gsopropyl)| JORGANIC Chemistry for UT-JEE log (rate) CHy-BrBt-Bri-Pr=Br t-Bu-Br 19. Which of the following graph represents correct graph forS,1 reaction : log (rate) CH ~ Br CH ~ Clg Br CHls~ CH-Br Cy Gilg F-Br log (rate) CHy-Br —Et-Br -Pr-Br ¢—Bu-Br log (rate) © CHy-Br Et-Br = i-Pr-Br ¢~Bu-Br20. 21, Jog (rate) ° ee CHy-Br | Be-Bri=-Pr-Br t-Bu-Br ‘Which of the following is most reactive toward S ,2 reaction ? Cl a cl cl @ O © 6 © © @ S CH; a NO, ‘Among the given pairs, in which pair first compound reacts faster than second compound in Sy reaction ? (8) CHy ~CH, ~CHz ~CH, ~Br oF CH ~CH, ~CH-CHy cH, ors (yc, -E-t, cry oF Gilg cH GH -cHy I be br Br Br -O-0 Os oy (a) CH -C-CH3, or CHy -¢ -CH; ( br I ‘What is the major product of the following reaction ? H,C =CH-CH, -OH 24> Product Br | (@ CH -CH-CH, ~Br (b) H,C =CH-CH, -Br Br OH 1 L (© CHy -CH-CH, -O# (@ GH, -CH-CH, -O#23, 24, 25. Sy and S,,2 products are same with (excluding stereoisomer) : cl oC oO @ (@) Ph- CH-CH-CH, cH, Cl a Consider the nucleophilic attacks given below. Select in each pair that shows the greater S,.2 reaction rate. eer + “en fa ae “CN a) an (®) H,C-Br+~sH or H,C -Br+CH,SH amp ™ © Cy sar ot Op» +1 in DMSO ™) ™) wore C8 inet (vi) wn ‘5 2 8 A B Cc p (@) @; dV); (VD; (VID &) GD ; (ID ; Cv) ; em © ©; aD;™); (vin @ © ; a;™; vm Which of the two stereoisomers of 4t-butyleyclohexyl iodide ("71-) will undergo $3 substitution with 181 faster, and why ? * 127 Hog poke ee @ ® (2) A will react faster because itis the more stable ofthe two isomers () A will react faster because it wil yeld a more stable product, and the ta both reactions is ofthe same energy aubitere stadt (© A will react faster because the approach of !2*1~ can depart unhindered, (@) B will react faster because it is less stable than A, and the tran: reactions is of the same energy sition state for both(Wik Hauipes (sussrrrvTION) 26. 27. 28. (Z}2-Burene reacts with Br,/H,O. The resulting bromohydrin when treated with methoxide in methanol undergoes an intramolecular $2 reaction. Taking into consideration the stereochemical consequences of the reaction mechanism involved, choose the final product(s) of these transformations. °O YO. oO tip’ Sat ) Hcy Sout ap How Sot Hy an CH HC "CH, (@) @ only () (iD only (© GUD only (€) Equal amounts of (1) and (1D) Rank the following species in order of decreasing nucleophilicity in a polar protic solvent (most — least nucleophilic): 9 IL CH,CH,CH,0- CH,CH,CH,S~ CH;CH,C-O- a @ o (@ 3>1>2 (b) 2>3>1 (© 1>3>2 (@) 2>1>3 Identify products of the given reactions : ,OTs Bee rs oh one a ~ cx4g003Na Reaction-2 are eae NMe, WON Hs oe aa : el + enantiomer NMe2 NMe x CHg 9 Hy . aaa samme: Mey NMe2 QO Hy © eas single product is obtained in both the reactions NMe 0. CH @ cL ~ single product obtained in both the reactions NMe229, 30. 31. 32, log(rate) > (CliyX Me-CHp-X MejCH-X —mesCH-x Which of the following is true about given graphs A and B? @ AS BISys (0) A>Sya, B>Syn © ARSE (ARBSE, In each of the following groups, which isthe strongest (best) nucleophile ? @a@)Hc-0- = @) 7 Sor (8) Hy C-S" in CH,OH ap ay on" @ 1,0 ( NH in DME ay a) a” @ ae (@) CH,O" in DMSO (@) 13:1,3 ;m2 © 12s ;m3 © 11; u25 LA (@ 135m sma i Nasty a ~ CHy — Cl (4) ; Product (A)is : o>} (CH)4~ CHa ~ Cl arenas? (A): Product (A)is fe} qt @ $-(CHa) -CH=CH, ~—) ©>- j O->>- Product Ha CH CH CH CH CH3 H Ny Nez H Ng H H N3 @H H (b) H On H @ H H ‘Cl cl: H H Cl cl 5G CH3 CH CHs CH, ‘What would be the effect of increasing solvent polarity on the rate of each of the following reactions ? (Nu =neutral nucleophile) ® (A) Nu+R-L—> Nu-R +E (@) increases () decreases (© constant (@ can notbe predicted (B)R-L9— R84: (a) increases (b) decreases (©) constant (@) cannot predict ‘Which of the following is most reactive toward S,,2 reaction ? (a) CH, =CH-CH, -Cl (b) Ph-CH —Cl (© Me-OCl @ Ph-G-CHy Cl ° 4-chloro-1-butanol + NaOH —+ (8) Product (B) of the above reaction is @ oO ) we) eb @ wo39. 40. 41. 42. 43. In the given pairs of alkyl-halide, in which pair the first compound is more reactive than second compound toward S,,2 reaction ? (@) (CHs)2CHBr or CHy~CH,-CH, -Br (b) CH -CH, CH, -Br or CH ~CH, -CH-I (© Ph-Br or CH, ~CH, ~CHy -Br (@) CH =CH-CH,-Cl or H,C-CH-cL 1n the given pair of reaction in which pair the second reaction is more reactive than first toward $2 reaction ? (@) CH ~CHy ~Cl+CHs -CHy-O- —+Bt-O-Bt (on) CH, ~CHy ~Cl+CHy ~CH, -OH—> Et-0-Et (b) Cy -CH, -Cl+ EO" Bt-O-Fr (on) (CH ~CH ~Cl+ tS” —s CH, -CH, -S-Bt © B-A+ckjo°— k-0-cHs (on) Gm) Ft —Cl+CH,0” —> Et-0-CHy ‘Gm “ay ° (@) Et-Br+Ph3P—>Et-PPhy (or) ° Et—Br +PhgN—>E+-NPhy Among the following pair of reactions in which pair the second reaction is more reactive than first in'S,; reaction ? (@) MegCCl+H,0O—+MesCOH (or) MegCBr + H,0—+ Me,COH (b) MegCCl+ CH30H—> MesC —OCH, (or) Me,C—Cl + H,0 ‘MejC—OH (© MegCCl+ Hy0 —> (or) MesCCl+ H,0 ak) aw (@) All of these Which is a true statement concerning the transition state of an S,.. reaction ? (a) Closely resembles a carbocation intermediate (b) The electrophile is responsible for the reaction (©) Lower is energy than the'starting materials (@ Involves both the nucleophile and electrop! Increasing the ee ofa nucleophile in a typical .2 reaction by a factor of 10 will (@) increase by a factor of 10 (b) increase by a factor of 102 (©) decrease by a factor of 10 @ remain about the same Decreasing the concentasion ofan elecrophile ina typical 2 reaction bya factor of 3 wil (a) increase by a factor of 3 (b) increase by a factor of 32 (©) decrease by a factor of 3 (@) remain about the same46. 47. Increasing the concentration of an electrophile in a typical $ 2 reaction by e factor of 3 and the concentration of the nucleophile by a factor of 3 will change the reaction rate to: (@) increase by a factor of 6 (b) increase by a factor of 9 (©) decrease by a factor of 3 (@) remain about the same Consider the following reaction and select the best choice that represents the reaction. Na® “SCHCH3 Product CHs CHy on ’ ‘SCH CHg CH, CH, @ "S$ —CH,CH3 I Me ‘H Ee 1p Ss Product; Identify the product. H SH H H SH Me H Me: H HS Me H: Me @ ef-p © et—pD © ey—D = MErt—p H SH H H ‘The reaction , OH H, gl ee +soc, —> 2X +80) + HCl ; proceeds by the. mechanism. @ Sy Sy2 OS. @8y Consider the following anions. t ies CO abo 1 oi oO a w aw om When attached to sp*-hybridized carbon, their leaving group ability in nucleophilic substitution reaction decreases in the order : (I> U>m>W @)1> M>V>il (© W>t>u>m @)V>ml>m>150. 51. 52. 53. | cu, ci—}— 1 —TRE*- Principal organic product ofthe reaction willbe: Ph a Ph H—-— Cty n—}—ary, © prs——x ® a—p—sh Ph bh a Ph Pa City n—t—cH On a @ y—} pn re Ph Reaction of R-2-butanol with p-oluenesulphonyl chloride in pyridine followed by reaction with LiBr gives: butyl bromide () 5-2-butyl tosylate ‘butyl tosylate (@) §-2-butyl bromide ‘The compound which undergoes $1 reaction most rapidly is : ‘Addition of KI accelerates the hydrolysis of primary alkyl halides because : (a) Klis soluble in organic solvents (B) the iodide ion is a weak base and a poor leaving group (© the iodide ion is a strong base (@) the iodide ion is a powerful nucleophile as well as a good leaving group Which of the following phrases are not correctly associated with Sy reaction ? (2) Rearrangement is possible (2) Rate is affected by polarity of solvent (3) The strength of the nucleophile is important in determining rate (4) The reactivity series is tertiary > secondary > primary (5) Proceeds with complete inversion of configuration (@) 3,5 () 5 only © 2.35 (@) 3 only“ALKYL HALIDES (SUBSTITUTION) a 275 : CH 54, 2 $382 (4) —MES_y (B) HSH (C) , Product (C) is : SH ‘SH Br ‘Br (@) 2 ®) 2 © 2, @ 55. Energy profile diagram for an exothermic reaction, A! +B—2¢ 25D, is given below. TWA = ¢ x > ogee —> ‘The rate determining step of the reaction is: (@ A—B ) B—c ©c—pD @ can not predict cH, 56. COs @ Major product is (A) is : Br ae “OLS ©) © @ Br Br 1 . ; 57. aay —ELLRUE 5 Major product 9) Senators ‘The product Xs :58. 59. 60. : Relative rate of reaction of the following amine with methyl iodide is: ~ Le (a)A>B>C (B)A>C>B ()B>C>A @B>A>C 4 ‘<0 prco. So. Ser "*\ ot ua \f00 kK er 2+ KD H a Cokes ‘Major product of the above reaction is HS HH :CH ae @ yor, CH, ‘Gis is 62. The decreasing order of reactivity of the compounds given below towards solvolysis under identical conditions i i CHy-E-cHy cy dcr, 4 CH;—¢-CH, ] Oo © co) ay @u>m>1 ) I> 020 © >>I @u>tem HH 63. on —PEOEEESOH (4); Product (4) i ooo) (a eectee (R}-2-ocryl tosylate is solvolyzed in water under ideal S,. conditions. The product(s) will be: (@) R-2-octanol and $-2-octanol in a1 : 1 ratio (b) R-2-octanol and $-2-octanol in a 1.5 : 1 ratio (© R-2--o © Meo“ @ Norns[uxt matipss Gunsterorion) 70. n. 72. 73. 74. HC = CNa+Cl- CH, ~ CH, ~CH, ~1 —+ (A); Major product (A) is : (@) H-C=C-CH, ~CH, ~CH, -1 (b) CH, Product. 0 aCe 2 OO @ H (b) HO’ (© Both (a) and (b) are correct (@) None is correct MeyG = CH ~ Cit, ~ CH, ~ Cl —Z2°—> (1); Major product of the reaction is on (0) Me~G- Gig ~ Cy =a (6) Me,C-=CH- CH, ~ CH - Me . on © eee @ ae, Bo), o 4) CH,OH OCH, Product (A) and (B) respectively are : O-O" GG" CH,Br CH,BrBr ‘O-O CHyBr CH,OH OCH, 78. Relative rate of reaction with H,0. gone —ONS = —0— j Gi) > Gi) &) Gi > @ > Gi) © Gi) > Gi)> @ @ Gi) > @ > GD 76. o 0 2 eq. KNH, N= GiHy—Br (py 5 ‘i A NHg(D then H30® End product (P) of the above reaction is : oO oO ° oO ok oo = Cc ° Oo tthe: i; a i. 77. Which of the following statements is correct regarding the i compounds (A) and (B) by Sy. reaction ? rate of hydrolysis of the Oe <> a 378. (a) A reacts faster than B (b) Breacts faster than A (© Both A and Breacts at the same rate (d) Neither A nor Breacts, ‘What are reactant X and product ¥ in the following sequence of reactions ? i we Via ? Tae ot Cy Reactant X 39> xe J pen Product ¥ H PyAaine Reactant X Product ¥ ‘Transition state of given Sy, iS: it“OX Br 3 80. CgHy3Br +OH” —> CgH,,OH + Bris an example of: (2) Nucleophilic addition (B) Nucleophilic substitution (©), Electrophilic addition (d) Electrophilic substitution © Free radical substitution a1. ‘Transition state 2 is structurally most likely as : 12 aga (@) intermediate 1 (b) transition state 3 (©) intermediate 2 (@ produc A He 82. Number of aromatic compound obtained when above xz Number of compound undergo complete @1 m2 @3 @4 83. Syland Sy 2reactions are (2) Both stereospecific ()) Both stereoselective (©) Stereoselective and stereospecific respectively (@) Stereospecific and stereoselective respectively(ALKYL HALIDES (SUBSTITUTION) 283) 84. Most reactive compound toward 5,1 is cyt CHI cyt tit of © a © @ cH tl & 1. NaN (209) ian 2CHCH—T 3.1 Hypa paso, Product (X) is OH CH,CH, > @ ) ‘CH,—O—CH, CH,CH, ‘OCH, CH, oO @ O—CH,CH, ‘CH, —OCH,CH; 1. {| 2 [om | 3. |] 4 | 9. [cy [40 | ca [41.[o 112.) @ 17.1 «a | a8. | ca) [49.| co [20.] a 25. | ca) | 26. | ca) | 27- | ca | 28. | ca 33.1 @) [34.| co) | 35: [acy | 35. lao) 40. | (a) | 43. | cay | 42 | a) 143.] co 48. |) | 49-| i) | 80. [a | 52. | 36. (a) |57. | | 58-| @ |59-| co) | 61. | (| 62. | ca) [63.1 ca) | 65. | a | 66. | a | 67. | (a) co | 69. @ [70.| @ [71.[ 1 | 73. | ca) | 74.| oy | 75. | cc | 76. | ca | 77. | oy | 78.1 oo) 179. Lod 81. | _[82-| | 83-1 84 | ca | 85-| {6 toy | 7 Lo | 8. bea COMET HITEC OMECANO! (b) | 22. | (ay [23. | cq [24 [ra (a) [30.| ca ['32.] @ | 32. a ca) |37. | [38.] a [39.1 oy ow) |45.] co [46 | cw [47 [ia ca | 53. | [54.] o [55.1 80. 3 eee1, Statement-1 : Nucleophilicity order in polar-protic solvent is I” < Br~ < Cl” < F~ Statement-2 : Due to bigger size of I” its less solvated in polar-protic solvent. (@) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1, (b) Statement: is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1. (© Statement-1 is true, statement-2 is false, (@) Statement-1 is false, statement-2 is true. 2, Statement - 1: Cli ~CH, ~Cl-+ NaI 4c, —CH, ~1+ Nac Statement- 2 : Acetone is polarprotic solvent and solubility order of sodium halides decreases dramatically in order Nal > NaBr > NaCl. The last being virtually insoluble in this. solvent and a 1° and 2° chloro alkane in acetone is completely driven to the side of Todoalkane by the precipitation reaction, (a) Statement-1 is true, Statement-2 is true and Statement-2 is correct explanation for statement-1. () Statement-1 is true, Statement-2 i true and Statement-2is Not the correct explanation for statement-1. (©) Statement-1 is true, Statement-2is false. (d) Statement-1 is false, Statement-2 is true. 3. Encircle whichever of the following : (a) is the stronger nucleophile (aprotic solvent) : F~ or I~ (b) is the stronger nucleophile (protic solvent) : F~ or I~ (c) is the stronger base : For 1” (@) is the stronger nucleophile (protic solvent) : NH, or NH NH (e) is the better leaving group :CHgCOO™ or CHyS03 4. Encircle whichever of the following : - r (@) undergoes an S,,,teaction more rapidly, CH ~Br or CH ~CH-cH, a (©) undergoes an 1 reaction more rapidly, CH ~Bror CH ~CH-CH, (©) undergoes an E, reaction to give (Z)-1,2-diphenylpropene : PS 7 ei " c Ph Ph Hs n—toor Bron Ht—cH, wry Ph Phut—sr Brn or Br——cH, Br—}—CHy Ph Ph (© undergoes an reaction more rapidly, Br Br 5. Encircle whichever of the following : Hy 3 (@ undergoes an S,.z reaction more rapidly Qe * or xX Br, (©) undergoes an $41 reaction more rapidly: wD at wD (@) undergoes an Sys teaction more rapidly: tb. oo cl ‘ Cl (e) undergoes an E, reaction more rapidly : os286. 6. Match the column, ORGANIC Chemistry for IIT-JEE in a Relative rate | Relative rate | ison Relative rat me Gy) v2 @ | cu, —er © 1 ww) 1200 (&) | ct, ~crt- Br @ 1.05 oo 40 @ |e © 16 ) by, © u o | CHy (a) | ct, -C-Br ©). 1,200000 @ 1 | city | Matrix : Cera) Career) Goanpoand| ‘Type of reaction | cr | j | | (ay CO (p)| 8,9 reaction can take place | cl ie) Coo (q) | Sy2 reaction can take place 1 © ad ) | 8,1 is not possible 1 a @®) (8) | 8,2 is not possible |8. Encircle whichever of the following : pe {05 mdecgowenndyx means, Dr. “A be (b) undergoes an $,,. reaction more rapidly, (CHy),C—Br or (CHy)3C-1 Br Br (© undergoes an yy reaction more rapidly, or 9. Reactivity : Circle the reaction that reacts FASTER by S,,2 in each pair : @) Sa 8288 @ SN) DK ton, Near mo NN to, NN mii, 10. Consider the potential energy diagram given below Bnerey. ‘Name the positions A-D Answer the following questions . (@ Both reaction pathways are 38 EXOTHERMIC or — ENDOTHERMIC Which step is the rate determi Boor =D Gii) Which product is most stable ? Eonar (iv) In accordance with Hammonds postulate, exothermic reactions tend to have (a) early transition states that are reactant - like (b) late transition states that are reactant-like (© early transition states that are product-like (@) late transition states that are product11, Select whether the following combinations of reactants will react by substitution (S,1 OrS 2 mechanism), elimination (E, or E, mechanism) _Natin set z 2c Os, Sy OB @E: ns (ie Naot nana = =e @sy 8,2 OB @ Ez OOO cn wm © Cy —— Sy ©) Sye OR @E, D. (cHyy,c-on | Be ‘ (Sys OS, © % (@) Ey B. (CH),CH-sr | —NeNinedana @ Sa OS y2 om er, Hon —_ = Br Neck in etal 3c @ Sys ) Sy OR On G. (CH ),CHCH,CH, -on —M“Stintn0 7 @ Sy ©) Sy2 Oh @E,ALKYL HALIDES (SUBSTITUTION) 289 12, Examine the ten structural formulas shown in fig. & select that satisfy each of the following conditions. Write one or more (a through j) in each answer box. CH; Br I a @ i: @] mo-e-a fe oe at cH CH; —Br ca @ CH -1 © Cr © Cy Gi WCQ" ch,—al aot | Hxc—¢—Gta—al | 4 a CHy CH, | x A. Which compounds give an $,.2 substitution reaction on treatment with alcoholic NaSH ? 1B. Which compounds give an E> elimination reaction on treatment with alcoholic KOH ? . Which compounds do not react under either of the previous reaction conditions ?290 13. ORGANIC Chemistry for HTJEE Select which reaction from the following reaction pairs will occur faster. Reaction A I OH CH Reaction B Reaction C OH Reaction D Reaction E Reaction F 1 Reaction G CK qe CX H | ™ |(Aik? HALIDES 291 CH, —1 Reaction I Br r | | Reaction J | | CHy = 14, Tick your answer in the given box. Sor roc aay Peet (at a reasonable rate) Br No Yes wo 1- Chlorobutane a No Br Yes © 2-Bromobutane pe No Qa ‘Yes @ 2-Chlorobutane aoe | No Y Yes {2 2.chioro-2-methyl propaneORGANIC Chemistry for LIT-JEE Br vs | | Bromocyciohexane O | - No | Br Yes oe O No CHy~ Br ves a) Benzyl bromide No | ¥Bromo-2,2-dimethyl mE SG propane No | Yes oO Bicyclo compound Br No a meee | QO ||" 6 -ALKYL HALIDES 293 15. Match the column: a (a) ® It will undergo Nucleophilic Substitution reaction CH,—Cl ic © —Cl () |e will undergo £; reaction Hy P @ Oo” (s) |e will undergo S,,; reaction | Giffen mangos, mane j 16. oo 0. O—Et OIL. How many (x) moles of HI consumed?294 17. 18. ORGANIC Chemistry for HT-JEE Ho @) | PhRoy-a—S ©) Sy i | Cl 32 Oo) AY th @ Sy2 ~E 1} [O —y © | carbocation is intermediate No @| -\=e> ()| carbanion is intermediate | I (Reaction sequence) (Reagent required) _| @ poo 7 Et-CI/Na ether fo) 5" fw 20° | w) a — > @ Etpr | y }@| >=— Se @ ELOH/H® © | _|ALKYL HALIDES — 19. Choose the one compound within each set that meets the in | (a) |The compound that reacts with alcoholic a KOH to liberate Halide ion through | substitution reaction. ) ON" CH | (b) |The compound that cannot be prepared by | a Williamson ether synthesis. @ Opec | (© | The compound that gives an acidic solution. | Mesattominanenscnns |p] C)-0-€) F B (@) |rhe ether that cleaves more rapidly in HI. } (S) —CHywd 2. © The reaction is Finkelstein reaction. 20D 0D: 0QD: OGD: 0G Br i 4. (@) CH, ~Br (b) CH ~CH-CH, oO Ge ASH Hs Br. 5. © br © oD al a @ © 6. wib-qxe-nyid-5z 2. DP. ge Br 8. (@ Dn ©) (CH,):C-1 © Br 9. a) ar a~™ @ Na 10. (X) A- reactants, B-ransition state, C-Inter mediate, D- transition state (1) (® exothermic (i) B (ii) F (iv) aA-b; B-b; C--d; D-a; E-b; F-b; G-b. Ax-c.def,ByB-b, 4 f1;C-a,8,) Part — a ae ovat Reaction A D E.G I Ye- @ b&b Go 4&4 & N- ¢ 8 & & kk PAHS EDP SHOP GEE 2 a-p b-qg c-s d-r 5 b-p; e-n d-a a-p b-5 a-q aeALKYL HALIDES Elimination Reactions (E,,E,,E,,.,E,) 2. Which of the following alkyl halide gives only one product (excluding stereoisomer) when undergo E, reaction ? (Ez =climination bi-molecular) Cl © @ ‘cl cl oy NR iofinana protued (Seyret produc (a)in the above reaction, maximum Saytzeft product will obtained when : (@ X=-1 (b) X=-Cl © X=-Br (@) X=-F (B) In the above reaction Hoffmann product is major when X is @-1 () -cl (© -Br an(AGKYE HALIDES (ELIMINATION) 299 3. {yn when (P) undergoes Hoffmann exhaustive methylation (twice) then the product obtained will be : of oY of of™ | 1 NMe, NMe, 8 + 4 (4), ioe —s(@), Ph 5 9a an aS om can 7 “Ph a Ph ® @ Product (A) & (B) of the above reaction is : (a) A=P,B=P — (W) A=QB=Q_ = A=P,B=Q_— @) A=Q.B=P polls . CO ES, uso rode ofthe ection i: "Mots oY oO ot “oY ‘Which of these dehydrates most easly ? CH, (@) CHy —CH, —CH, —OH © Ce OH ee © oH (@) CH; —¢—cH, —On CH CH NaOctly ” NS 5 Product; Product of the reaction is hy oy Br {ey reacton) Hg © cr ©) ee © ioe (@) No reaction OCH10. nu. 12. GANT Chemistry for NTTEE) NMe, HO" — a 4 antsjon Major product A is : @ a b) oO © O @ O OO A iajory Major product A is : "OO CO "OO *CO In which of the following reaction Saytzeff alkene is major product ? CH Le e (a) CH ~CHy-G -NMey > (b) CH -CH, -CH, ~GH-cHy BE CH, F is Br (© CH; CHa -CHly E> @ CH, ~-cH, ~CHy-G CH, cHOK Br CH - CHy ms ‘ake. KOH SHO Major ins a wae Erasing ® Major product of the reaction i CH Pho ACH Phy @ cae we Ph7 Hy ci, CHy \ Ph-CH~CH—Ph © oc Oral Ph CH, On ‘The conversion of 2, 3-dibromobutane to 2-butene with Zn is : (a) Redox reaction (b) a-Blimination (© -Elimination (@) Both a-elimination and redox reaction13. 14. 15. 1, 3-Dibromopropane is heated with zinc dust in ether. The product formed is, (a) propene (&) propane © cyclopropane (@) 3-bromopropane Reaction (1) or HE HOH, (A) (major) : Reaction (2) O. HE KOH, (B) (major) Reaction (3) tie KOH_, (¢) (major) Product obtained in above reactions (1), (2) & (3) is: (@) A= B but Cis different (b) A=, but Bis different (©) B=C, bur Ais different (@) A= B = Call product are identical el a <1 Reaction (1) roy Rms KOH (a) a a ‘nme ale KOH Reaction (2) Cl ® a mole ale KOH Reaction (3) ci Serer erasers Product obtained in above reactions (1), (2) & (3) is (@) A= B, Cis different (0) A= C,Bis different (© B=CAisdifferent @A=B=Cissame17. 18. 19. 20. 21. ale KOH Awe © is number of product obined Br Gincuding sterecsomers) Find @). @3 b) 4 @s @6 CHy I lyf pay, Ea) CH Br Major product (A) is @rAz. orX ort w> ®) + CHO Pyridine22. 23. 24. 25. bie Product (B) of given reaction i «Co © O @ oO ‘What product will be formed from Hoffmann exhaustive methylation of following compound? (@) Me—CH =cH, © cs —E matt, CHs CHy- OH n® 4) Product (A) is : @ oO ®) oO © Hy : Be 2; Products obtained are : OH (@) Racemic (b) Diastereomers CH, Naokt ‘ig om aN CH, CH, w Q ® Q ; Major product of the reacti chty-t (eee) MeCHCHNHCH,CH Me Product (Aei0 ta (b) HC =CH, @ cy —CH—GH =O Me © oO (@) oO © GI (@) Positional isomers CH; CHy © Q @aad 7c] 22> ; Major product of the reaction is: w gs CHy CHy cH @ QO © Q © Q @ Q 27. The E2 product of the following reaction will be ? CH; Naot mo, iH jr 2 cn, . | cry (a) (b) HH 4h OH © pele mn 28. An halide Cs¥,Br on treatment with alc, KOH give 2-pentene only. The halide will be : (@) CHy ~CHz CH, -CHy -CHy -Br (b) CH ~CH ~CH, “GG, cs Br (© CHy -CH, ~Geah CH, @ CHy eats Br . Br 29. End product (D) in the given sequence is: ait cHSNHCHS (oar ecvaent) > ABaC Hat Be Br apts ead Ae MB) Sc) BED) + (cHg)5N @ cH o oO © @ CO ° OH30. 31. 32, For each of the following pairs of £ reaction, select the one that occurs with the greater rate constant. CHy CH (1) CHsCH,CH,Cl+CH, - b-0- (2) CHyCH,CH,1+CHs ~ 6-0" ts ois (8) HjC-CH-CH, +CH,0- (4) HyC-CH-CH + CH3S™ be br Br “Or + "oH “or ~on @ 24,6 () 13,5 © 23,5 @) 24,5 Br Br sanity yal ee Cy—¢ —C—y —CHy we xandy mole consumed. Value of x+y = @5 ms 7 @s The following bimolecular elimination reaction (E,) is carried out with different halogen leaving groups. The per cent yield of the two products (2-hexene and L-hexene) for each leaving group is listed below. Aw vay eq ARS Leaving group Conj. Acid pK.y Séryield of 2-hexene %-yield of 1-hexene a1 =10 env 1% X=Br =¥ 72% 28% er -7 67% 33% X=F Berga 30% 70% Which of the following statement is (are) true concerning this series of E reactions ? (@) Based on the pX,'s of the conjugate acid, I” is the best leaving group and F~ is the poorest leaving group (b) When I”, Br~ and CI- are used as leaving groups, Zaitsev's rule is followed (© FF is the strongest base (and therefore the poorest leaving group) and the transition state for reaction with fluoride as the leaving group has the least double bond character (@) a,b, care true33. 34, 35. 36. 37. a A ~ ays N(CNg)2 a nee @> rs 1H Product (A) & (B) respectively are : oft & T " o ea . 4 D D cc H H of ] & ee LT, * | we, Ce ES a) SS @ EO Be Product in above reaction is : = uo Re Ft = Me~-N—~Me oo ‘Major product obtained in the reaction of 1-phenyl-2-bromobutane with NaOMe is : (@) ()-1-phenylbut-1-ene (©) ©-1-phenylbut-2-ene (©) L-phenyl-2-ethoxybutane @ @)-1-phenylbut-2-ene ‘Which of the following alkyl halides give most complex mixture of alkene in an Ey reaction? (a) CH, -CH, ~CH, ~CH) ~Br (b) CH, -CH, -CH, ~CH-« CH, . (© CHy seed ~CH3 (@) CH peat, -CHy 1 be ot OD H BREE (A), Product (A) is :38. 39. 41. 2 OH D (CH, D D o CS ), oO o CY OH on cr Ba; & : ‘Sum of number of a-hydrogen present is compound A + Bis: @ 18 19 © 20 @a e -@ excess 13003 (a) Oeste )_WI48.0 1,0 = CH-GH-CH =CH, (@)Asz0)/1820 Identify A: “OO QO N’ N’ IN’ N’ | | I | H H H H Br a I CH, —CH, —C —CH,— Er—20H., (4) (najon I CHa(n- Pr) n-Pr=n- propyl Product (A) is : Me Et Me Et Me Et Me Et Pr H w Ph OH eed Major product obtained by dehydration of given alcohol is :42. Ph “Oh OQ, *Q « Be NaOCH (2mole)_ ‘4 0* > Eagan (4) th? 4B) Br Product (B) of above reaction is : OH OH oH OH @ CL ) © @ OH LOCH ‘OH Ph—GH—CH, — Hs BSS Protas Br Br Product of the above reaction is : (@) Ph—CH =CH—CH, —Br (b) Ph. (© PH—CHBr—CH = CH, @ Ph—e OH ye “ow on Product (A) is : @ eo © Ox © @ H Ph, H moe, Me Pho * e- Major product of the above reaction is:Perens costae LDA = Lithium di-isopropyl amide a 2 OU. ON @ N : | 47. H Major product ofthe reaction, when the given compound undergoes Hoffmann exhaustive methylation is : 48. re product of the reaction is49. 50. SL. 52. Ph Ph | G=CH-C-on 06 68 em Stereochemistry of the product is : (@) Meso compound (b) Racemie mixture (© Diastereomer @ Optically pure enantiomers CH = S=o o Which of the following reactant is used to obtain above compound (A). (Assume that EtO™is used in all the reaction) OH 0 @ QO o Cr © O @ CL Rank the following in order of decreasing rate in an E reaction: CH CH 3 Camloamion © CH, @ ) (a) a>b>e @c>ard @crb>a @rsase54. 55. 56. 387. “ZF @ Ph Fy a Sw Be @ ne on Bt AY BSS caoigjor be O22, cnsioe NMeg Relation between (A) and (B) is : @ G1 () Positional isomer © Enantiomer (@ Chain isomer As iti rates te motu @ L (b) He ‘CHa @ H—C=c—CH,);04 C—(CH)0Na (©) NaC = C—(CH2)30Na Which best describes the product of the following reaction ? CH Keb" Ph "CD3 be product jr (a) Absolute configuration has been inverted (b) Absolute configuration has been retained (©) Racemization (loss of absolute configuration) has occurred (@) Loss of chirality has occurred (the product is achiral) What is the major product of the following reaction ? OH Hs I Chg CHF Product cH, CHSCH: HL C-cH, Bs © Je=c @ Amos, Hu” NowiscHy (CH3CHY ‘CH 58. What willbe the major product of each of the rwo reaction shown below ? ds connie ———_, Se eee 2 CCHF, + CH,CH,ONa—> Br @1-X,2-X WH 1-¥,2-X — @1-%2-¥ — @ 1-¥,2-¥ NHCH,CH, 59. + CH, (excess) —> product; The product is : (@) a primary amine (©) a tertiary amine (© asecondary amine @ aquatemary ammonium salt CH-OH 60. ‘on a) ase 4B) (A) on heating isomerizes to (B). What is the structure of (B) ? CH OH @ 0 © O @ oO Ph—C—Ph 1H-CH-OH w 61. AS (22, maior oduct) is:Ph—CH—Ph Ph—CH—OH ClCH CHy-CHy © On @ 62, Which ofthe following carbocation will undergo rearrangement ? a @ ® © a-gi-B=0 (0 oyna cH, CHy 63. In which of the following reaction resonance stabilized product will form ? CH-0H Ht @ Cy aad ) a, © OH _#_, (@ Allof these 64. In which of following reaction rearrangement take place with change in carbon skeleton ? Hg @ eae) &, (b) CH -CHCH,® oy @, (©) CHy at ~ CH, - CHa (@ CH, -CH® -cH, Is65. 66. 67. Consider the following reaction xX, “Ba + ‘Which response contains all the correct statement about this process ? (2) Dehydration (2) Ey mechanism (3) Carbon skeleton migration (4) Most stable alkene will form (5) Singléstep reaction @ 1,3 ) 1,23 © 1,25 @1,3,4 CH, ey te Nal : Ht on 2 00 SL 0) (Major); Product (1) is: CH G) cis-2-butene (b) trans-2-burene (© 1butene @ Iso-butene Br Br i I CH)—CH =CH—cH, —28-us)_,(4) Above reaction is an example of 1,4-elimination. Predict the product. (@) GH — cH CH () CH; —C =C—cH, (© CH, — =CcH @ HA =CH—cH = cH, «Oo — 121 2801, Major product of the reaction is: Ph: Ph Ph: Ph Ph:7. Ph O Ph O 1 tl Il (©) Ph—C—C—cH, @ ph—c—C—Ft 1 | CH, Et Ph O Ph O 1 it Io © ate © m@—e—C—B Et CH, ‘When (A) and (B) reacts with H,S0 , products obtained are : @ pans © pa © par @pas Which of the following compound gives even number of Hoffman's exhaustive methylation and elimination? we ®OD QQ ee h CH, bo T a SSG > x =Number of chiral products (including stereoisomer). @2 4 O68 @s O ES AD cays:(316 © O ‘ @ tut (taj) Cone 804 4 4 1,0 Which of the following is product “A” in the above reaction? rma (a) b) VAY me © @ S a ~[@ | 2 @)| 4 [oo] 5 |o (o) | 7- | @ | 8. | 9. | © co | 12| © | 13] © 14] @ @ |16.[ © 17.| @ [28.| a [39-| © |20.| @ | 21.| ow [22.[ @ [23.| @ fea. @ 25. | (by | 26. | (a) | 27-| @ | 28-| © | 29-| @ | 30.| ( | 31.] (a | 32.] @ 33.| (a) | 34. | @ | 35-| c@ | 36-| @ | 37-| © | 38.| @ | 39.| (@ | 40. 41.| ( | 42.| w | 43-| @ | 44 | @ | 45-| © | 46. | a | 47.| cw | 48.] o 49. | () | 50. | (a) | 51-| © | 52-| & | 53-| @&) | 54. | & [55.| © | 56. 57. | (a) | 58. | (b) | 59-| (a) | 60. | (by | 61-| (@ | 62. | @) | 63.| ca | 64. | c@ 65.| a) | 66.| cb | 67-| ce | 68.| cw | 69-| | 70. [cay] 72. | aw [72.1 a | 73.| (a) e JEz reaction > Elimination bimolecular In the general mechanism of the E reaction a strong base abstract a proton on a carbon atom adjacent to the one of the leaving group. As the base abstracts a proton, a double bond forms and the leaving group leaves. cy tft Ft a CH,ONa + CH3-CH-CH-cHy—> 2 ant-coplanar transition state (seaggered conformation “lower energy) | (erans-2-butene) ‘A. Identify the rate of reaction of given compounds in E reaction: 0990 © © @a>b>c>d. (b)a>c>b>d ()b>a>c>d (a) b>d>a>c B. In given pairs, which compound is more reactive toward E, reaction: Hs CH jr Bt ° oe @ (@ Ca GH cy Gil~ GH- Dy Bi Br an ™w wm (S) Ph—CH,—CH,—Br Ph—CH— CH, om Br vm) (@) P-1,Q-M, R-vI,s-vn (b) P-11, Q-IN,R-VI, S-VI (© P-1,Q-M,R-VI,S-va (@ P-1,Q-I, R-V,S- VI th Ph = cu-t—Hn lcKOH is sicKOH © oy 2 Sw. flo, @ Fh Ph Product (A) and (B) are : Ga) A= cis, B = cs (©) A= trans, B= cis (A= trans, B = trans @ A= cis, B= trans Select the products (4) and (B) from the compounds (P) and (Q) given below: Hs CH A 7 @ @A=P, B=P @A=O3=Q0 © A=Q8 @A=P,3=Q EE, Which of the fllowing compound is inert toward E, reaction, 7 r (3) Cy ~ GH~ CH, ~ CH, © Br Is Hy, (Q) CHy—G— CH, — Br (a) C3 — FH CH cts Gig BeALKYE HALIDES (ELIMINATION): 2. Match the column : 31 E, reaction (elimination bimolecular) No. of possible products. (including stereoisomerism) | @ ® ° @ | WN 22 © 2 | <* =e, de ; 3. Match the Column : HEM = Hoffmann exhaustive methylation followed by elimination. Reaction Product HEM HEM @| Seer eee @)| Hc =cH—cH,—cH= cH, 1 H 1 HEM ) @ HC =CH—CH, — CH, —CH = cHy OL mm, _ time © N’ @ (3) HC = CH— CH —cH=cH,320 4. Match the column : ORGANIC Chemistry for IT-JEE | @) as (p) | Product are Diastereomers ou * J a | YO esr, (a) | carbocation is intermediate | | () | 2nd order reaction ! 7 ae x08 @) pr * () | st order reaction Match the column : Column (1) Coren) @ CHy cl | ae, KOH, (@) eee (p) | Optically active product | cc | Cl KOH, | ®) ace (@) | optically inactive product | d a i a H | © ag. KOH, (@) | 2nd order reaction cl 3g. KOH, (5) | unimotecular reaction‘ALKYL HALIDES (ELIMINATION) 6. Match the column : 321 Eg reactions (elimination bimolecular) Number of products Gincluding stereoisomerism) oT) Ct) (@) | cHy~cHty cH, -crty —pr2 KOH, | py 1 | (CH ~CH~CH, ~crlg —ME-KOH ) \ @ 2 Ci, | ce | aE cr cry, HOH, © i © 3 Br | | PhCH ~CH-CH, ~Cily @ i ®) s Br Match the column : }@ i | a | | I i _Nai, | ) oat & (@ | £2 BONa © i (2) | Ei (elimination intramolecular) | br ] lo | Chae | Mes @ a (8) | Fico322 8. Match the column : ORGANIC Chemistry for IT-JEE Product }@ © GC ] ‘D ) @ Ceci | H () @®) , “| OCI Za = @ ae SO, 00 products Br ur ale. KOH, oo © aerate acKOH_, (zy Br CH oy @ cH +X alex, (py cH "PE a SumofX+¥+Z+P=10. ww 12, ALKYL HALIDES (ELIMINATION) o I Reaction-1 : Ph-C- CH, —PGs_, [INN __GHial_, ph_cac—cHy Br [yJNants, Reaction 2 Ay let te asl br Rescton PhCH, [pens 8-1 ph_cac-ue cia 2, Y, Zare moles used, Sum of [x+y +z ‘Sum of «hydrogen 1 major product of the reaction. 323 ~~ F-OH 3 Reaction-1 e HW (ay eo nesciona CO @ 7 Reaction-3 440 ox Reaction-4 So ‘Sum of a-hydrogen is A+B +C+D= ae ia Gis Cs — § —CH—CH, wt ou Reaction-1 Hc) Hy Reaction2 | CHy-CH-CH,-CH,-OH —#"_, (py rine Reaction-3 "© ‘Sum of a-hydrogenis(A+B+C= )324 ORGANIC Chemistry for IIT-JEE on 13. Reaction-1 » (A) ened Reaction-2 +, ‘OHS (malo Reaction3 ma © i «Gam fe : Sum of a-hydrogen (A + B + C) = ma toe O) Xo Gage ue & OH we ue © Hw ork AK by 3 ‘Total number of products obtained in above reactions including minor products is (including stereoisomer) 15. Match the column (1) and (ID. Reaction | Gj) Recintaam |g x0" Na | R-2ehtorobutane BEN, | Gay Sy: (© | 2- bromo- 2- methyl propane —' @ A | A want 854 aALKYL HALIDES (ELIMINATION) 325 16. Match the column (1) and (I). Column (1) Column (11) Reaction ‘Type of Reaction | cl @ ron, ) Swi al | ie stcxon, @ Sy cl | © _wo, @ x | ‘OH @ ca, @) Ey 17. Select whether the following reagent combination will result in elimination or substitution reactions leading to the major product. eet TSC ATCC326 ORGANIC Chemistry for 1T-JEE 18, ._Match the Column (1) and (II) (Matrix). | Reaction Comment on product | CH @ 0 a ©) Racemie mixture OH | CHs | Major product consist of even Ko) a @ number of a-hydrogen ! i on r OH | ¢e) a ae, ® Will nt undergo dehydration(ALKYL HALIDES (ELIMINATION) : 327) ‘Major product consist of odd (a) ‘number of a-hydrogen OH 19. For each of the following amines (A through D), exhaustive methylation (treatment with -xcess methy| iodide), followed by Hoffmann elimination (heating with AgOH), repeated as necessary, removes the nitrogen atom in the form of trimethylamine. Indicate the number of repetitive Hoffmann eliminations required to remove the nitrogen by a number (1 to 4) in the designated answer sheet. CD TAL E ie b. Fr pa c. da. f. 20 —————— eliminations) to remove nitrogen from given compound. ey IKON, y is total number of possible Ey product (including stereoisomer) Sum of x-ty=? 21. = (CHs—CH—CH—CH 1 10H, Br BOL, () (Sy +81) products. ( including stereoisomer) consider al products ‘Total number of products are328 ORGANIC Chemistry for IT-JEE 1. A-a;B-a;C-b;D-GE-c 2. a-s;b-r;c- -P -P 4. a-p.qsib-pie-asid 3. a-s;b-re-q 5. a-p,Gb-p.ne-pid-qr 6. a-pjb-rc-q;d- 7. a-pib-qic-s;d-r 8. a-p;b-qe-nd-s 9. X=3, ¥=3.Z2=2 P=0= 3+3+2+0=8 3 y=3 2-3 > 34+24+3=8 1. 32 12, 33 13. 28 14, x=3, y=1, 223 p=2 sum=9 15. (a—q), (b-s), (€-p), (d-) 16. (a-q), (b-s), (c-p), (d- 17. Substitution— d, f Elimination- a,b, e Pig; b-p,qye-qid-r a~3;b-2;e-3;d-1;e-2;f-3 20. 6 21. 6Ex ALKYL HALIDESORGANIC Chemistry for IT-JEE Eee 5 2. In the reactions given below, R= CORN OEY Product A ROSE OU, Product B the compounds A and B are : (2) chain isomers () position isomers (©) Functional isomers (4) metamers 8. Which is the major product expected from the following S,,2 teaction ? ag oS SL HOH, Product 4. Consider the following &; /S, reaction : ‘The missing product(s) is(are) : 1H in CH @ J HyetP ® aor i HyC7F (a) 1,2and3 (b) 3and 4 (©) 2and3 (@) 1,23and4| ADOT HALIDES 331 5. What is the product of the following S,.2 reaction ? (@ Hse —H CH Br—y—H H——Br Ph Ph 0, me 0. Me © BT As @ ioe Br ue Ph Ph 6. Select the reagent that will yield the greater amount of substitution on reaction with CH, ~CH, ~Br (a) CHyCH,0K in dimethyl sulfoxide (DMSO) (b) (CH, ),COK in dimethyl sulfoxide (DMSO) (©) Both (a) and (b) will give comparable amounts of substitution, (@) Neither (a) nor (b) will give any amount of substitution 7. Under the specified conditions, substrate X undergoes substitution and elimination reactions to give products A—D. A and B are stereoisomers, but not enantiomers. C and D are enantiomers. A is not an isomer of C. Which ofthe following could be the starting material X ? x2 asaece cH, Ta Buy® © ® ay C HC) HC EI @o oa © a @m city 8 cH, —G—cis, CHy— GACH, cH, Ga © Br Br @ ‘Compare rate of Ez reaction : @c>bra (b)a>b>e © b>a>c @c>a>b10. 11. 12. seeenennes ORGANIC Chemistry for TEE) Which reaction results in the formation of a pair of enantiomers ? 1,0 fa) Ac aaleetde (>) Ase? S HC. «, " oa on Rate limiting S,., follows the sequence 49 50 RBr = [RBP}]— [2B] ——R)— Br] @ o © ‘True statement about sequence on the basis of assumption that R contains 3 different groups is: (a) more stable carbocation, greater isin the proportion of racemization () the more nucleophilic the solvent greater in the proportion of inversion (© In above sequence (6) represent separately solvated, pair of ions (@) All of these ‘Compare the two methods shown for the preparation of carboxylic acids i 1.005 Method 1: RBI —aapraia PRMeBY > ROO aH Hz0, Het Method 2: RBr—X*+RCN. RCO 2H Which one of the following statements correctly describes this conversion ? o-& COnH (@) Both method 1 and method 2 are appropriate for carrying out this conversion (b) Neither method 1 nor method 2 is appropriate for carrying out this conversion (© Method 1 will work well, but method 2 is not appropriate (¢) Method 2 will work well, but method 1 is not appropriate Which of the following statements is true ? (@) CHyCH,S” is both a stronger base and more nucleophilic than CHijCH,O™ (&) CH,CH,S™ isa stronger base but i less nucleophilic than CH yCH0~ (© CH,CH,S™ is a weaker base bu is more nucleophilic than CHyCH,O- (@) CHiCH,S™ is both 2 weaker base and less nucleophilic than CHgCH,0~13. “In the given par of alcohols, in which pair second aleohol is more reactive than firs towards hydrogen bromide ? 3. on HOH ey OH w Oo and D-s - CH, OH © CHly ~GH-CHy ~CHy and CH ~CHy ~ GH ~CH, ~ on Gas (@ Cy ~CH-CH, ~GHty and (Clia),0-Cit,~CHa OH OH 14. Which product would be expected to predominate in the given reaction ? QSO,CF3 crrgoHt “sG0°) oO (@) None of these -802- CHa 15, Which is the major ee of the following reaction ? a NeH(ex8_, product H0 ‘CH2~ Br i a oh ‘CH,- OH ‘CH B16. 17. 18. 19. 20. N OH, ‘OH © . @ Tr CH,- OH aD 1 —AEKOH_, (4); Major product of this reaction is : OH D CH, D CHy CH. D @ Ch o oO iD @ ‘lea Rate of S.2 reaction is : Bs w @ oO (@) (B)> (4)> (©) @&) ©)>(A)>@) © (@)>@)>© @ (A)> ©) >@) 1-2-dichloro ethane + NaSCH,CH,SNa—» CHS» + (P) ‘Unknown product (P) of the above reaction is : oD af (© H-S~¢ =¢-cH=cH-S—H @ H-¢ =¢-cH=cH-s_H HOH Hd Br 4 MostA#29, (4) product Major product (A) is : "Qh oD ally MeO, cl fo - SY, Product of reactior (MOM chloride) (Methoxy methyl chloride)21. 22. 25. 26. (© Me-0-CH, ~CH, CN @ ox ‘CN In the given pair of compound, in which pairthe second compound is more reactive than frst, toward yx Teaction ? @ A\Naer NEE © (> —cH- cat © YS ie XA ~ @ a or ~~» 1 Which compound might be synthesized by the Sz displacement of an alkyl-halide ? ‘SCH2CH3 @ 1>W>ll OM aetna wh (© I>m>ven @I>msney30. 31. 32. 33. 35. 36. 37. 38. In solvolysis of 1,2-dimethyl propyl p-toluene sulfonate in acetic acid at 75" (alkene + substitution) products will be formed ? @2 3 o4 @s Benzotrichloride reacts with milk of lime to form : (@) Benzal (b) Benzoie acid _(€) Benzyl alcohol (d) Phenol Br CH ~ (CH) ~CH ~ Br + CHyNH, —» Product of the reaction is : @ o(J of @ N Y H HK ‘The configurations of the reactant and the product in the following reaction, respectively, C0,CH. 2CHly ae D @RR ORS SR @s,s 1-4-dichlorohexane (1 mole) + Nal (1 mole) —“°"*_+ Product of the reaction is : (0) CL Clty CH, FH CH CH) City ~CHtg CHCl CH i a (© Ho= CH GHG, Hy @ Gh, Gi, Cy ~ cc, ~ Cy cl a ‘Alkyl halides can be obtained by all methods except : (@) CH,CH,OH+ HCYZnCl,—> (©) Cl - CH, - CH, ~ cH, —2/0Viteme (© C,H;OH + NaCl — (@ CH,COOAg + Br, /CCl, In order to prepare -chloropropane, which of the following reactants can be employed ? @) Propene and HCI in the presence of peroxide (b) Propene and Cl, followed by treatment with aq. KOH (© Propanol-1 and SOCI2/pyridine (@) Any of the above can be used Which alkyl halide has maximum density ? (@) CgHy! () Colist (© Cat (@ cHyBe Which of the following molecules would have a carbon-halogen bond most susceptible to nucleophilic substitution ? (@) 2-fluorobutane (0) 2-chlorobutane (© 2-bromobutane (@) 2iodoburane338 39. 40. 41. 42. ORGANIC Chemistry for UT-IEE) When benzyl chloride is treated with ethanolic KCN, the major product formed is: (a) benzyl ethyl ether (b) benzyl alcohol (c) benzyl cyanide (4) benzyl isocyanide ‘Which of the following is most reactive towards nucleophilic substitution reaction ? (@) CH, =CH-Cl (b) CgHsCl (© CH CH =CHCI (@) CICH, -CH = CH» Which of the following reaction will not give ether as a major product ? (@) CHCH,CI+ Ag,0(éry) —> (b) (CH )gCCl+CH,CH;0"Nat—> Cis I (© CHyCH,CL+ Nato +O) (€) CHiCL+ Na*OT = G= Gila — CHs ° co) l so G-5-P ey ® Product (A) and (B) in above reaction is Oo oO 1 i t t ( o-—$-0—1,0°—$—0-cs 0" —$—0—H,0~ i @o~%—0, 0 — H‘ALKYL HALIDES 339 Lat nscale hee ld 1. The following organic halide derivatives (A to.) are reacted in ethanol solution with each of the nucleophiles : acetate, methylthiolate, cyanide and hydroxide anions. Six possible results from these combinations of reactants are designated (1) through (6) below Write the number corresponding to your best estimate ofthe outcome of each reaction in the appropriate answer box below. C1 cl cl ICO owe] oe fox ICL | | cn ae Perici, B @ D E | 7 CH - Br Br eer: GieN weld | H I [eae i Possible Outcome : (1) No reaction (2) Substitution (3) Elimination (4) Substitution and elimination (5) No reaction or slow substitution (6) No reaction or slow elimination Compound Bel paalecenn ere |r| io \arid 3. }os @ |cH,co.na | (i) |cHSNa (iii) |[NaCN:340 ORGANIC Chemistry for ITT-JEE 2. In each of the following sections three organic halogen compounds are listed. In the box given enter a'number (1 to 3) indicating the order of reactivity of the designated (1 is most reactive and 3 is least) (a) Sy: substitution by NaOCOCH, in methanol: 1CH,CH,CH,Br] (2. (CH,),CHBr 0 3. CH =CHCH,Br C1 (©) 8,2 substitution by Nal in acetone: 1'CgHCL QO 2cucHc O 3. CgHcHcIcH, CO (© S.y2 Substitution by NaCN in methanol: IcHcH,C| =O 2. CH CHF =O 3. CHyCH,I a (@) Sys substitution by NaSCH, in methanol: 1° (CH,).CHCH,CH;BrL] 2. CH,CH,CHBrCH,CH,U) 3. (CHy)CCH,Br 0 3. Isobutyl alcohol (2-methyl-1-propanol), (CH),CHCH,OH, can be transformed to each of the compounds (a through |) listed in the left-hand column, In each case the number of steps needed to accomplish the change is noted, and an answer box is provided for your reagent selections. Fourteen reagents (designated A through N) are listed in the right-hand column. Write letters designating the reagent or reagents you believe will achieve the desired transformation in the box to the right of the product formula. In the case of a multi-step sequence write the reagents in the order they are to be used. In some cases you may wish to use a previously prepared compound as a reactant. If so, write the number (a to 1) corresponding to the desired! compound a Pans pre nee R faa ee a. | (CH) ,CHCH.Br one A. | Hg(OAc), in H,0 b. | (cH), = CH one B. | pBr & heat ¢. | (CH,),CHCH=0 one C. | NaBH, in alcohol d. | (CH,),CHCO,H one D. | Liar, in THF (aqueous workup) |e. | ccs) CBr two E. | acn in alcohol £. | (CH,),CHCH,C. two F. | PCC in CHCl, | g. | (CH,),CHCH,OCOCHs one G. | Jones' reagent (CrO, in 1,0") | h. | (CH,),CHCO,C,Hs two H. | HBr in CH,Cl, | i. | (cHty),CHCH,OCH,(CH)_|_two 1, | 11,P0, and heat | 3. | (cH,),con three J._| (CH3C0),0 + pyridine k. | (CH,),CHCH,NH, three NaN in aqueous alcohol 1, | (Cl1,),CHCH,CH,NH, two CH CO5H in CHCl, (peracid) | NaH in ether and heat | 7 CjH,OH + acid catalyst & heat |SUBJECTIVE PROBLEMS Hy 1, cH0H Sho 4 Br X =Total number of subst tion and elimination product(s). Find the value of X. yVesers Wertaet cvatets! Petaey iseeee Aesece,-Puaten "getait J eae cea e eeeeaeete te Hate 6 aera Epa eee Hea 6 @y 2 #2 2 21 ae ate tte 3 Gorcear rere tenet ee ata 3 2 a-3>1>2; b-2>3>1; c-3>1>2; d-1>253 3. ¢-F;d—G;e-I, Hor 2H; f-B, Bor 1, B; g-J;h—G, Nor 4N '— B, K, D or 1KD; 1 ~B, E, D or 1ED or 6D. Subjective Problems 46 | ALCOHOL, ETHERS AND EPOXIDES 1. The following transformation involves a carbocation rearrangement. The carbocation is generated by protonation of the hydroxyl group, followed by the loss of water. Which bond has to migrate in the carbocation to yield the product indicated (after the deprotonation) ? Ht 14804 aa, Ry Z © CN @ @a > oc @d 2. Identify the major product. HO: 180, Product & FBCH, - OH Puree @ ® mt H I ¢-cH, i." é oO I Cig “CH 4 Et © @ I H H 4. Predict the product when given compound reaets with LiAIH , : ® 6 1 i H” OCH, «@ 0 i Qu C-0-CHy et C-0-CHy a 100 ® oO HH ° a 1 A HW 1H a @ o ©7 g ERS Predict the product when given compound (A, in the above question 4) reacts with NaBH ,. oH i C-O~CHg ° OH © 268. on 0-H + CHy- 08H ‘The labelled -O'* will be in : @ H,0 © Both (a) and () conH cH,- 6H [+d COjH | CH, -OH ° i 6-0-cHy @! | C-0-CH, IL oO Which is oxidized most easily ? @) CH, ~CHOH-CH, (© CH, ~ CH, -O-CH, ~CH, 9 OH Il oH I -0-CHy Taye +H,0 ‘Methyl benzoate (b) Methyl benzoate (@) Benzoic acid 1 > A); Product (A) is :% 10. nl. 12, 13. COsH ESO, ();Product (P) is: oy ay acy o of the following react with HBr at faster rate? ® ou ® — = x OH © oy fon @ aL fe) oO 1H tt ay-8 bon — ih co Above conversion can be done by : (@) NaBH, (b) LiAIH, © Pcc (a) KMn0, Coat 2008, (4) ; Product (A) is 1,504.8 COgH q ee 0,Ct, O,CHy C-cHy @ O..« ial Cont COnCHy ~ CH, s on Pen t 4A yO Ph 88, (P)_ Unknown (P) of the reaction is : 3 2 laa Ryn a @ On - ie ess 4 2 2 % 9 on Ph Ry len © 5 Pe @4 eoPn -—~OO OV, 15. Identify the major product, @ © © @ LA o Q 16. O&O (A); Product (A) is : 0 @ ©) © @° ‘0 z CH OGH; a7. AL (A) Major; product (A) is : CO,CH3 0 Hy OH 8H octt, @ io) © é o O @ CH,OH OH ‘OH CH,OHALCOHOL, ETHERS AND EPOXIDES 18. 19. 20. 21. 1H MOH Gn, 4A H (edtorm (Resorcinol) Le ° ° @ ‘ONa Il IL @ () H-O-C- (CH), - C- OH cO;Na 7004 CHE ° ° I (© CH ~ CH, ~ CH - CH, ~ C-OH (@ Cig ~ (CH) ~ C-ONa Cg Hs (4), Product (A) is : ett a : COjH a,c) 14_4(B) + CHIg4; Compound (B) is : ctieee)_4(4) 1 9(8) + CHly4; Compound (B) ai ONa CO;,Na CO,Na - i « “O) oH 128 Major product obtained in the reaction is :22. 23. ‘Consider the following alcohols, cH,0H a Son oor o) orn cron m Sr ,09 ™,. ‘The order of decreasing reactivities of these alcohols towards nucleophilic substitution with HBr is: @ U>i>W>T @)M>Iot>V © I>l>Vv>n @)I>M>t>Vv ony —~ SL (py 8 Soto, @ ‘Sum of number of 1° alcoholic groups in product (P) and (Q) is: @1 &) 2 o3 @5 In presence of dil. HCI, compound A is converted to a constitutional isomer (), compound B is: @Nh, 0- b=0 9 e i ° mo 9 $ OH Q (oN, o-¢--Ne, @ \/ 4 NH, Ar(AicoxoL, erHERs AND EPOXIDES” 349, Choe 4 5. His ton a encarbon stom = | oe dichloro methane ot y © © KD @ peo =O. 0H 8 26. est unt + prodiots of die reatsion tat (a) Racemic (®) Diastereomer (©) Meso (@ Optically pure OH 59 27, co,st OUULGSED, (a); Chemist added extra 0.5 mole of EtLi @u 10 A in above reaction to obtain product (A), which is? 9 9 oH g Ee :, SoCs o a ° HOH 9 28. LY Weg eee Tage Mrmr Ho CH, -0- bop og Jo o SY Ph’ “SS : of. Ph350 ORGANIC Chemistry for UT-JEE 4 ‘C label ye a OCOR _ ocx oe or" : 1 label @) Sy (b) Sy2 (¢) SN—NGP (d) SN—Ar Ho. nl 30. OL —*2__, (4); Product (A) of reaction is : NH Oo ° os oe ; O “O « eas 1H Gils -G- OH CH Ht cHo OH @ o © @ OH OH [OH 32. Which is the best reagent to convert isopropyl alcohol to isopropyl bromide ? Gta Ota Z CHy- CH-OH —>> cH,- CH- Br (a) HBr (b) SOBr, © Br, OH by Product of the reaction is : (@) CH yMgBr(ALCOHOL, ETHERS AND EPOXIDES 351, 33. 35. 36. Nit, Ph on ta AN W Cy Ph Major product obtained inthe above reaction is: 9 ° Git cr, Por (@ Ph—c @ ph—c—Y Ph Ph (© Racemie (@ Diastereomers Total number of stereoisomers of product (B) will be: (2 5 88 O4 are uas- lac, qq ERS + major product of the reaction is: “wo -G ~ CHy SH aad © Aa © c @ C “MOH fe 9 ee Hy liberated ® N22» no rapid reaction coy ‘cool CoHgO3, What is structure of (4)? : an oH CHis_OH 2 o @ (@ both (a) and (b) H Gy Lay Which are not cleaved by HIO,? 1: glycerol M1: glycol I: 1, 3-propenediol IV: methoxy-2-propanol (@ 1,1, ,1v © 1 © um @ mv Which of the following reactions require an oxidising agent ? (a) CH, —CH =CH,—> CH, —CH, —CH, (b) CH, —CH,OH—> CHCHO (©) CHy —CH,CI—+ CH —CH (@) CH, —CH,OH—+ CH, —CH,Cl What isthe major product of the following reaction ? Nant, . OL LS product CO;354 47. 48. 49. 50. 51. 52. Which of the esters shown, after reduction with LiAIH, and aqueous workup, will yield two molecules of only a single alcohol ? (@) CH,CH,CO,CH,CH, (b) CgHsCO,CH:CgHs, © CeHsCO,C,H (@) None of these For the following reaction, select the statement that best describes the change. RCH,OH + PCC [CgHsNH*CICrO5] ——> (a) The alcohol is oxidized to an acid, and the Cr(VI) is reduced (b) The alcohol is oxidized to an aldehyde, and the Cr(VD) is reduced (©) The alcohol is reduced to an aldehyde, and the Cr(III) is oxidized (@) The alcohol is oxidized to a ketone, and the Cr(VI) is reduced ‘What is the product of the following reaction ? CH, Hy CH, Als. oso,tcat (cr)scooon, HOH =. HOH HO. ‘H 2s0,feat), (CH),COOOH, Gi (a),coH” «HOH HO-—H = H—}—oH CH CH, CH, 1 2 3 (a) Only1 (b) 11 mixture of 2 and 3 (© Only2 (@) 1:1: 1 mixture of 1, 2, and 3 An organic compound B is formed by the reaction of ethylmagnesium iodide (CH,CH,Mg) ‘with a substance A, followed by treatment with dilute aqueous acid. Compound B dogs not react with PCC in dichloromethane. Identify A ? ° ° Il Il Z (a) CH; —C—H_ = (b) CH,CH, CCH, (¢) HC =O (d@) HxC- CH, ‘Which of the following reagents would carry out the following transformation ? (D = 7H) Onl. 44 O- (a) NaBD, in CH,OH (b) LiAIH,, then D,0 (© NaBD, inCHj0D (@) LAID, then D,0 Which sequence of steps describes the best synthesis of 2-methyl-3-pentanone ? ° a yw(aicotion ‘ernensianD prommes (a), (2) 1-Propanol + (CH;),CHMgBr, diethyl ether (2) H,0* (3) PCC, CH,Cl, () (2) 1-Propanol + Na,Cr,0,, H,S0,, H,0, heat (2) socl, (3) (CH,),CHCl, AICL, (© () 1-Propanol + PCC, CH,Cl> (2) (CH,),CHLi, diethyl ether (3) H,O* (4) Na,Cr,07,HSO,,H,0, heat (@) (1) 2-Propanol + NazCr,0,, H,SO,, H,0, heat (2) CH,CH,CH)Li, diethyl ether (3) HO" @ Pcc,cH,Cl, ; 53. _Diols (I-IV) which react with CrO, in aqueous H280, and yield products that readily under g0 dercarboxylation on heating, are : @ 107 a 1 You on ap ae mA ‘OH Hi (@) Tand It (®) Mand mt (© Mand @ Tandy 54. Which of following compounds are not oxidized by HIO,? CH, —CH—OH cH; —c =0 @ I @) I cH, —OH H—-C=0 cH, —C =0 cH, —c =0 @) | @ | cH, —C =O CH, —CH—NH, ° cH, —OCH, I 6) © | (@ c—oH cH, —OH | cH, —OH (a) 5,6,7 ©) 45,67 ©67 @ 3,4,5,6,7 (CH,OH 55. 7 ae (A) — > ©) 84%6; Final product (B) will be :356 ORGANIC Chemistry for IIT-JEE @ @) 3) 56. Unknown (A) in the reaction (given in Q. 55) is: Hz — OTs 7H,OH @ HL () at CH (Co) 1H @ oO 57. In the given table, identify the incorrect option. The digit in box indicate the moles of that substance. Reactant conmmescd formed tari OH (@) HO- cH, -u-cti, -O8 2 1 2 OH OH OH © rd Grorcr,-o1 2 7 OCH; © Ho ct -GH-cH,0H 2 0 9 OH OCH, @ Ho-cH,-bH- dy 1 1 T 58. Succinic acid —*-»(A) “+ 9(B) —72-+(C); Product (C) will be : -COjH CH, - CO2H CH, -CO3K* CH, -CO,H @| | ©| @| -CH,-NH, CH, -NH, CH, - NH, CH, -CH, - Br61. 62a, Ci, O# cH, - oH wo wo (@) 2,2 3,3 (©) 2,3 (d@) 3,2 Moles of formic acid formed in X and ¥ respectively are: @ 12 ) 2.1 © 23 @ 3,2 Moles of HCHO formed are: @ 11 ) 2,2 O12 @ 21 In which of the following group, each member gives positive iodoform test ? (a) methanol, ethanol, propanone (b) ethanol, isopropanal, methanal (© ethanol, ethanal, isopropyl alcohol___(@) propanal, propanol-2, propanone H,0" +Na —> (A) + (B) cs) 9 IL CH, ~ C- O-CH, ~CH3 +(A) —+ (C) + (D) alcohol Product (C) of the reactions is: ° o® I Il (@) CH, -C-9-H (®) CH; -C-0-H 9 ° ia i. (© CH; —C—O (@) CH; —C-0°N8 I © oe Noa (PhP BACT tore es © oneag (Contin rnogen Product (B) of the reaction is :358 ae z {GANIC Ghemistry for IT-JEE H G03 f@) 6 (b) No, NO, 9 Il -0-CHy O No, B. Product (C) of above reaction is HQ a HO. ‘OH @ o o @ oy 63. Two unknown compounds X and Y, both having molecular formula C,H,0, give following results with four chemical tests. Bromine Nametal__| Chromicacid_| Lucas reagent Compound X | decolourises bubbles | Orangeto Green| Norreaction _ | Compound ¥ | Noreaction | Noreaction | Noreaction | No reaction Compound X and ¥ respectively are : i @ Cy-G-C-o: NLR Aon, oo ia wha“ @ ot, -cH, cr, -b oy o ° i i aie or 6. Cot gee Ms cH,0n lnethony ethane Product (N) is : © Othe, eto aoe67. Assign the structure of major product (X) of the reaction given below. (oo > pi to aaa > a? a 3 @ - GHC on &) w+ sete acd (comais corn etiy.2.cloro ans ita acare mole ‘amok Product (A) and (B) respectively in the above reaction are : 9 9 I 1 @ Me—C-CMeg 0), Mes—CMey ML Me CMe, OH Br OH NH,76. 77. 78. ‘ORGANIC Ghemistry for HTJEE A OH ° a I} at © Meg CMe) —#Me-C-cMe, Gare : oH On r7 SR t ate 3 (B) and (C) both give +ve iodoform test. Compound (A) is : H I (@) CH, ~ CH =CH-0- cH, cH, ) Gi ~ G-0-CHy CH, cH, (© CH, - c 0-CH,-cH, (@) both (b) and (c) CH, 7 A solution of Ph3CCO,H in conc. H2SO, gives (X) when poured into methanol X is : ° oO I i (@) Phjc-C-0-CH, @) Ph,CH-C-0-cH, (©) PhjC- OCH, @ PhCH, oH Product (B) of the above reaction is : a CO "CO GO «Od In the given pair of alcohol, in which pair second alcohol is more reactive than first towards hydrogen bromide? 0 oo “oye De a (© CHy —GH— CH, —GH, nd CH, — CH, —CH—CH, — OH OH * CHy (@ City — GH Clty CH and (CH 46 = City — Cy on oHALCOHOL, ETHERS AND EPOXIDES 363, 80. 81. 82. 84. Rank the transition states that occur during the following reaction steps in order of increasing stability (least —> most stable) 1. HyC—OH, —> CH; +H1,0 2. (CHy)s6—OH, — (CHy),C* + 4,0 3. (CHg),CH —OH, —> CH,),CH" + H,0 @1<2<3 2<3<1 (1<3<2 (@2<1<3 no 8 82 (A), Product (A) is: CHO @o oe © 02 H Ge ° © oN © woot In which of the following reactions hydrogen gas will not be evolved ? (a) CH, —CH, —oH#—™* (b) CH, —CH, —OH—*> (© CH, —cH—oH—“.5 @ CH, —C—OH SRE» 1 CH cH, Poy Macher () 22s (9 ESS Grignard reagent Ho? ' |g cpy 25 (3, 4-cimethyl wee @ Sthexanol) When Grignard reagent reacts with (B) product (D) will obtained, Reactant (A) of the above reaction is : : (aS 0B); structure of (A) i (Chia aleba nt) i i I (@) CH eeeeece rt —CHy, (b) CH, metas —CH, Et Et Et Et 0 ye i aard Oo OH86. 87. 88. Above conversion can be acheived by : @ LAH, (©) NaBH, (© Hy/Ni @ cro, on cH- Con or + BOH —za> (86%) (tandcie Identify product of above Fischer esterification reaction : O-ke | 7 (@) Ph-CH-CO,H () Ph -GH-b=0 ° i © Ph-cH—cogte @ Ph-GH-C-Et OH OH i CHa, CH,CH,COH . 4 ott 4) 28 yc) Bc) ty Product (C) of the above reaction is : 7 ne oe = (@) CH ~€-CH,-CH, -C-CH, (0) CH, ~C-cH,-cH, -C-cH, | CHly CH ou Ib 1 q i g ! i (©) CH, ~C-CH, ~CH, -C-CH, (@ cH, ~C-cH, ~C-cH, What is the major product of the following reaction ? qu co, (CH ~CH-CH, CH, -OH $0,» Product eet Gk (a) CHs -CH-CH, -C-H (©) cH, -C-cH,-C-H I tl si (©) CH, ~C-CH, ~C-OH (@) CH, -CH~CH, toon‘ALCOHOL, ETHERS AND EPOXIDES 89. ‘The major reason that phenol is a better Bronsted acid than cyclohexanol is that : (a) itis a better proton donor. (b) the cyclohexyl group is an electron donating group by induction, which destabilizes the anion formed in the reaction by resonance. (©) phenol is able to stabilize the anion formed in the reaction. (@) the phenyl group is an electron withdrawing group by induction, which stabilizes the anion formed in the reaction. 90. Which of these reagents would accomplish the following reduction ? 1 u N=C—CH, -G-CH ~CH = CH, —> N =C-CHly ~G-CHy- CH = CH, (a) NaBH, (b) LiAIH, (© 1 mole H, poisoned catalyst, low pressure (4) H,0* CH-CO,Et GH-CH,-OH 1. a, =, CH-COgH GH -cHO (a) A=NaBH,,B (b) A=NaBH,, B= CH -CHO. CH -CO.H (© A=LiAIH,,B= 92. Ph -CH,-GH-CH, —K> SiH 4(A) OH : Product (4) in above reaction is: (@) Ph—CH, -CH ~CH,, (inversion) ©) PhCH -CH~CH,, (retention) oEt ort (©) PhCH -GH-~CHy, (racemic) @ Ph-CH=CH~cH, Et 1 . 93. Ph-C-O-H+CH, -0! -H 23 (x) +H,0; Identify Il (@) X= Ph-C-0" —cH (Trans esterification )95. 96. 97. ORGANIC Chemistry for mse ql (©) X= Ph-C-O! —cH, (Esteification reaction) I (© X= Ph-C-0" ~CH, (Saponification) 1 (@ X= Ph-C-0-CH, (Hydrolysis) ° i . I R-on+H-0-€- © >No, + n-0-L KO NO: Fastest rate of reaction will be when R is : ° cH, I (a) CH; ~ (b) CH; -CH, (© CH aie @ CH, cae CH, cH, Select the correct statement. (@) Solvolysis of (CH),C = CH—CH, ~Clin ethanol is over 6000 times greater than allyl chloride (25°C) (b) CH, —CH =CH—CH, ~OH when reacts with HBr give a mixture of 1-bromo-2-butene and 3-bromo 1-butene (© When solution of 3-buten-2-ol in aqueous sulphuric acid is allowed to stand for one week, it was found to contain both 3-buten-2-ol and 2-buten-1-ol (@) All of these oH -OH 2 — } Above transformation can be carried out by (a) H*/A, Zn(Hg), HCL (b) HIO,, LiAlH, (© HIO,,H*/A (@) H*/a, HIO, soa, ofan H,C =CH-CH, “oh Baty Ti OBES (8) a (cy 1H Compound (0) is on @) CH, CH-CH, -GH-cH a (b) HOCH, -CH, ~CH, ~CH ~CH, ~CH, -Cl a i (© HO-CH, ~CH, ~CH, -CH-CH, (@) HO ~CH, ~CH, -GH—CH, ~CH, a98. 99. 100. 101. 102. 103. 367 Jodoform can be obtained on warming NaOH and iodine with 9 1 (@) CH,CH,CH(OHDCH, (b) (CH),CHCCsHs © cH, —G—ocH, (@ (CH,),CHCH,OH Which of these is a reducing agent ? (@) C105 /#* (©) KMnO, (© LAH, @ 05 Crete a (Ps Product (P) in the reaction is: Hy @ C)-cxio1 a on Ce @ HH CH, oy 2&2, (P); Product (P) in the reaction is: on cH, os \ (@ CH, —C =CH, ( cH, —CH—cH, Gy Cis I (© CHy —¢—0—¢—CH, (@ No reaction CH, CH 1, 2, 3 butanetriol undergoes oxidative cleavage of HIO,.. During this process @) 1 equivalent of 110, consumed & HCO3H & H,C~G-CO,H are formed o (b) 2 equivalents of HIO, consumed & HCO,H, HCH = 0 & CH, ~CH = O are formed © 3 equivalents of HIO, consumed & HCO,H (2 eq.) & 1 €q, of CHCOH are formed (@ 2 equivalents of HIO, consumed & 2 eq. of HCO;H & 1 e9, of CH3CH = O is formed °° ‘ hei CH3-CO._,C- OCH, UNH (4); Product (A) of the reaction is WOH,O (96%) OW on OU ct, - OH OW cH,OH S108. 106. 107. 108. 109. I 2 I R-C-O-R'+R"OH ESR -C-O-R"+ ROH Above reaction is/an example of : (@) esterification (b) saponification (© trans-esterific (@) hydrolysis ‘What is the major organic product of the following sequence of reactions ? (CH,),CHCH,OH— "Me, HSC, _0"_, > H (a) (CH3)2 CHCHCH,CH, (b) (CH3),CHCH,CH,0H oH (© (CH), CHCH,CHCH, (@) (CH,),CHCH,CH,CH,OH ‘The structure of the product formed in the reaction given below is DX) CHO bon —282* Products obtained in the above reaction are : CH, -OH (a) HCHO, HCO,H (b) HCHO, 2HCO,H (© CO;,2HCO.H (@ CO, HCHO, HCO,H HO (CH-OH), + 4HIO, —> Products obtained are CH, -OH io pentose (a) 4HCO,H, HCHO. (>) 4CH,0, HCO,H (©) CO;, 4HCHO (a) COz,3HCO,H, HCHO 0 CHO @ (CH-OH), 82 Product (i) (CH-OF), "2, Product CH, -OH CH -OHALCOHOL, ETHERS AND EPOXIDES : "Ey 369 110. 111. 112. 113. 114. Ratio of moles of formic acid obtained in reaction (j) and reaction (i) is (a) 3/4 © 45 ©1 ws Which ofthe following compound gives 2HCHO,CO., HOD,H when oxidised by periodic ackd? cH, -OH cHo CH) - OH CHO I I ee i c=0 c=0 (@ CH-oF, — 0) (CH-O, = | @| (CH-OH), cH-oH 1H, -OH CH, -OH : 7 i CH, -OH cH, -OH Hydration of 3-phenylbut-1-ene in dil. H,S0, will give mainly (a) 3-Phenylbutan-1-o1 (b) 3-Phenylbucan-2-0 (© 2Phenylbutan-2-01 (a) 2-Phenylbutan-1-01 Decarboxylation of sodium salicylate with soda lime forms : (a) Salicylic acid (b) Phenol (©) Benzene (a) None of these Meo - CH Gu -OH CH -OH © —%#2+ >What is the maximum value of (x) ? I Gu -oH Ei CH, - OH @1 2 3 @4 Gih-o8 by-on unt n° SS (4) > @) > ©. Product Cis Gil - COate " Cy ) CL 16 Cit,- GH-OH Gail; 08 City City @) oC oC TCH, CH, - CH, - OHus. 116. 117. 118. 119. 120. ORGANIC Chemistry for HEE gpe= 08 +441, 011 tain § (te Gti, - CHy-OH Reactant A of the above reaction is : ° I IL Il (@) CH, -C-CH, —_(b) Cocl, (©) CH, -C-cl (@) CH, -C-OEt 9° g § ak ° a” @” @ o CO,CH3 CO,CH3 CH, - OH CHO CHO Identify correct combination : CH, -O# @ A) =| (b) @)= NaBH, — (© (C)=KMn0, —_(@) (D) = H,0® CH, -SH In the Libermann’s nitroso reaction, sequential changes in the colour of phenol occurs as : (a) Brown or red —> green —+ deep blue. (b) Red —» deep blue—> green (© Red —> green —> white (@) White —> red —> green Ethanol when reacts with PCI, gives A, POCI; and HCL. A reacts with dry Ag,O to form B(major product) and AgCl. A and B respectively are : (a) C,H,Cland C,H,0C,Hs (b) C,H, andC,H,0C,H, (© Cpl, andC,H,0C,H, (@) CH, and C,H.NO, ° ~ (CH); -OH 8 (A), (HB, ©) Product (C) is : (a) CH, ~(CH,), -CO,H (b) CH, ~ (CH); -*CO,H I (© CH, -CO,H (@ cH, -¢-o-n Choose the best synthesis of phenyl n-propyl ether. OH Name OH @ Tanai? ©) yc pola dprote savene121, 122. 123. 124. 125. SS 4 ee Na meal, OH EONS. The product obtained is = CO,H What wa true vo the aint reaction ? I I CH ~C-OH + CH, ~on SS cH, -C-0-CH, +H,0 (a) The use of equimolar quantities of CH,OH and CH,COOH will give the greatest yield of the ester at equilibrium (b) Removal of water will increase the amount of ester at equilibrium (© Addition of CH,COOCH, will cause the formation of equal an equal number of moles of ‘water (d) Application of pressure increases the amount of ester at equilibrium. jum chloro chromate) is a good reagent for which of the following transformations ? ae ol How many primary alcohols (including stereoisomers) are possible with formula CH,,0? (@) Two (b) Three (© Four @ Five 1 -Phenylethanol can be prepared by the reaction of benzaldehyde with the product obrained in the reaction between: (@) CHgLand Mg (©) C,Hsland Mg (©) CH,Br and AICI, (d) CHjOH and ZnCl,372, 126. 127. 128. 129. 130. 131. 132. 0.092 g of a compound with the molecular formula CyH,O,on reaction with an excess of CH,Mglgives 67.00 mL of methane at STP. The number of active hydrogen atoms present in a molecule of the compound is : (@) one (b) wo (© three @) four Migratory aptitude of the following in decreasing order is Soo OMe Me @ © @ (@a>c>b>d ()a>d>b>c © a>d>c>b @b>c>a>b ‘The major product formed in the reaction is : CHR tee, 2 OM @ O + RCH,OH o Cm ‘0 HO: an wo (CO]+ nase oan Ho CHO i Ho offSo7 Reaction of R-2-butanol with p-toluenesulphonyl chloride in pyridine then LiBr gives : (@) R-2-butyl bromide (b) 5-2-buty! tosylate (© R-2-dutyl tosylare @ S-2-butyl bromide Optically active 2-octanol rapidly loses its optical activity when exposed to : (@) dilute acid () dilute base © light @ humidity If (+) 2-methyl butanoic acid were esterified by reaction with (+) 2-butanol, how many optically active compounds would be present in the final equilibrium reaction mixture? @2 3 o4 @6 ° oH Oy Me ov ota sw Es x SOU, y Sart, cr wae * amor? z Nace, y Product Z of above reaction is :133. 134, 135. ° il 9-C-chy oO a O-C-CHy ola the product : (a) Noreaction w H NZ @ \ © or oe (@) Ph—C—Ph (Et) ,CHCHO + CH Mg "+ (a) Product obtained in the above reaction is : if : (a) CH; —C—C—H (b) CH, —CH—CHO I (©) CH; —C—CH, —OH @ aE cn, on Ht Reaction - (1): CH, —CH = CH—CH, 0 (a) Ss (8) 2 mate Reaction - (2): CH, —CH = CH —CH 8 () 2 mole Product (B) and (C) respectively are : (@) CH,CHO, CH,COgH (©) CH,CHO in both reaction (b) CHACOAH, CH,CHO (@) CHCO,H in both reaction374 136. 137. 138. 139. 140. ORGANIC Chemistry for IT-JEE OH Bel 4 tle —_ Pyridine, 25°“ “Pyridine, 25°¢ a oO CO OO oO oO —— HO ~ (CH), - OH, this conversion can be achieved by (@) Oz, Zn, then LiALH, (b) 05/H,0,, then LiAIH, (© cold dil. KMnO,,HIO,, then LiAIH, (4) All of these Which of the following alcohol on treatment with HCl give 3-chloro-3-methyl cyclohexene asa product ? ‘ cH, Gti Ho (@) (b) OO. © (d) All of these on on (onc ace sy —__ > (A) Product of t : Seam A Hp” ()i Product of the reaction is NOH on |sOH @ ct © ‘oe © CO @ ‘CHy CH “oH Esterification (shown below) isa reaction converting a carboxylic acid to its ester. It involves only the carbonyl carbon. Esterification of (~) -lactic acid with methanol yields (+)-methyl lactate. Assuming that there are no side reactions, what is true about this reaction ? B; product (B) is : CH OH on oH i cot eee © @ (a) An yz process has occurred, inverting the absolute configuration of the chiral center (b) AnS,,, reaction at the chiral center has inverted the optical rotation (©) A diastereomer has been produced; diastereomers have different physical properties including optical rotation @ Optical rotation is not directly related to absolute configuration, so the change in sign of rotation is merely a coincidenceALcoHoL, 141, 142. 143. 144, 145. 375 Which of the following sets of reagents, used in the order shown, would successfully accomplish the conversion shown ? 9° CHy I I C)-Kx— .CHCH,CH,CH3 (@) CH,CH,CH,MgBr; H,0"; PCC, CH,Cl, (0) CH,CH,CHMgBr; H1,0°; HS04, heat PCC, CHCl, (©) (Cells) P-CHCH,CHy, ByHg; CH,CO.H (@ (gH), P-CHCH,CH; H,0 ° .CO,Et 2 he Product 3 Product of the reaction is : 9 ° ° CHO CH @ © © © Which of the following compound on hydrolysis followed by heating gives a product, which gives positive iodoform test? OnE I (@) CHy-GH-C-cH, -cHl, o Gets Coxe ° 9 i (©) CHy-GH-CO,Et “ry ~O-Et Co,er Treatment of a 2° OH with Cr /H,50, yields an/a: (a) aldehyde (b) carboxylic acid (©) ester (2) ketone Esterification of the acid P with the alcohols Q will give : HL cis OH cH, or (9 (a) only one enantiomer (b) a mixture of diastereomers (©) a mixture of enantiomers @) only one diastereomer147. 148. 149. 10,C ea ‘major product of the reaction, when the given compound is hydrolysed and heated strongly: i = cOnH 02H @ &) © @ HO,C ° OH COnH ° RO. e © _ find out the reactivity order with LIALH,: tio ®cocl () A>B>c>D () B>c>D>A (© D>C>B>A (@)B>D>C>A4 Find out the reaction in which obtained product give positive isocyanide test: ° @ On ts © orx.,. Se pa, NH, 0 On yo Oy pen OH ° - oro In the above given compound how many functional seh aluminium hydride ) and SBH (sodium borohydride) respectively sce by LAH (Lithium @44 b) 4,3 © 3,4 ~ @a2150. An unknown compound (A) (molarmass = 180) ‘on acylation gives a ‘produet (molar mass =390) than find the number of hydroxyl group present in compound (A). @s m6 (0 10 @1 151. Which of the following compound is differentiated by NaHCO, as well as by NaOH ? OH oH CHy—OH O80 OO Con y~O# « TORO) 152. Arrange the following compounds in order of their reactivity toward LiAIH, ove (@) icii B 5 Aqueous _ Make base with “H layer 10% NaOH tetrahydro- np fsequinoline Aqueous _Bvaporate, ¢ layer (a) A =tetrahydroisoquinoline, B =naphthalene and C =inorganic ions such as Na* and e iphthalene, B =tetrahydroisoquinoline and inorganic ions such as Na” andl” jorganic ions such as Na* andCl”,B =naphthalene andC =tetrahydroisoquinoline organic ions suchas Na* and Cl”, B =naphthalene‘andC =tetrahydroisoquinoline378 154. 155. 156. 157. z : "ORGANIC Chemistry for ITTEE ieOOg © CHy—OH _ #8 value of xis: Scx, O-cH, @2 ) 3 o4 @s co;H OE 8 ‘CH, —CHO a Compound (B) is : ° : fe} o (@ (@) and (c) both oO 1-Phenoxypropane is treated with excess of conc. HI at 0°C and the mixture of products is treated with thionyl chloride. The products formed are (a) m-propanol + Chlorobenzene (b) Phenol + n-propyl iodide (© mpropyl chloride +Chlorobenzene (4) n-propyl chloride + Phenol ‘Amongst the following compounds, the compound having the lowest boiling point is @ Non ©) \~\ox © om (dd) “on 1HALCOHOL, ETHERS AND EPOXIDES ra (@) 4. lo | s. | o wm | 7 | o @ | 9. [ow () | 11. | &) | 22. | ow | 13.| @ [14] @ | 15-] @ @ | 17. [cm] a8. | @ [19.[ @ 20] [21] @ [22] @ [23] @ [24] @ 25. |(b) | 26. | (b) | 27-| (o) | 28. | w) | 29. | @ | 30. | @ | 31-| @) | 32-| 33. || 34. | w | 35.| @ | 36. | | 37-| @ |38.| | 39.| | 40.| 41. |b) | 42. | | 43.| a | 44.|@ | 45.| o | 46. | c@ | 47-| o | 48-| 49. {ca | 50. | @ | 51-| @ [52] |53-| © [54] | 55.| m [56] @ 37. |@|58.| @ |59.[aa 59. |e» | 59. [ca [60.| @ | 61-| @ [ 62. [av |_ 62. |p-b| 63. | >) | 64. | (@ | 65. | cb) | 66. | (@) | 67. | (a) | 68. | (a) | 69. | (a) 70. |¢c) | 71- | @) | 72-| @ | 73. | @ | 74.| @ | 75-| w | 76. | @ | 77-[ 0 78. |co | 79. | w | 80. | @ | 81.| @ | 82-| @ | 83.| @ | 84.| w | 85.] o 86. |<) | 87-| @ | 88-| @ | 89. | @ | 90-| @ | 91.| @ | 92.] w | 93.] aw Toa. | f9s-[@ [96.10 197-1 [98] @ [99-1 @ hoolw hort a 102.]¢o) [203.| «@ [204.] « |105.| @ 109.| «| 110.|ca [112.] «@ [112-| w) [113.| © 117,] 118.|¢a) |119.| (o) |120.] (a) |121.| @. 125.| (a) 126.|(c) |127.| oy |128.| (@) |129.| ca, 133,] ( 134.| [135.| @ |136.| co [137.| @ 241] «© 142.| ) |143-| (o) |144.| @)_|145.| o) '149.| (a) 150.| a) [151.| © |152.] (a) |153.| 157,|380 ORGANIC Chemistry for IIT-JER 1. Consider the pairs of ethers, numbered I through V, shown below. To the right of each pairis a description of reaction conditions to be applied to each. One compound of the pair will react more rapidly than the other. Which ether of the two will be more rapidly cleaved? Write your answer in box. HG | ( Hy CH,CN, 40°C | me o-c(ctis)s @ OCH, Fe Hc wae Gai 3) Treated with HxS0,, iy in CH{CN, 40°C 0. C0 < ¢\- ao, ‘Treated with H,S0, im. inCH,CN, 40°C ciH,0 on eck W. ‘07 oH 2 | CH(CHs)2 & CH(CH,), | D072 CH(CHa2 & SN o-' 3? _| Treated with 5% aqueous H,S0,, 25°C Treated with 5% aqueous | oct, H,S0,, 25°CALCOHOL, ETHERS AND EPOXIDES 381 Mace n (2) CHy CH, ~CH, CH, ~CH,-OH —(b)_CHy ~CH, ~CH,~CH-CH, 2 5 ~CH 3 OH CH; (ah gta won, -cH,-4-on 1H dn, cH, cH, © cit, -bH-cHt, ~CHy -OH o crt,-b-crt-crt, on CH, CH, @ HO-CHH,-CH-cH, -CH @ city -b-ctty -OH oy ‘Above compounds (a) to (h) are isomers of Cti;.0. Based on the above isomer answer the following (A to F). Which isomer is most reactive towards dehydration by conc, H,S0,? Which isomer will undergo rearrangement when treated with conc, H,S0,? Which isomers on dehydration with conc. H,SO, give alkene which is capable to show geometrical isomerism ? Which isomer is least acidic ? Which isomers on dehydration give most stable alkene ? Which isomer on dehydration with cone, HPO, undergo maximum rearrangement ?(382 ORGANIC Chemistry for ITJEE xeon to) fo) {oy R— GH, |= >= [R— GH, — On RCH] ———=[_RCOAH (alkane lowest alcohol TT aideryde] | (acid highest tration wo) oxdation 109 [0] = Oxidation (H) = Reduction: Consider the above sequence and answer A to F. ‘A. Conversion (CH ~CH—> CH, ~CH, -OH) alkane —> alcohol is achieved by: (@) Br,/hy, alc. KOH (b) Br2/hy, aq. KOH © Br,/CCl,, LIAL, @ Br,/CCl,, NaBH, B. Conversion R - CH, -OH—>» R -CHO can be done by: (a) PCC/CH,Cl, (b) Cu, 300°C (© Gro; @ Allof these . Conversion R ~CHO—+ R -CO,H can be done by: (a) KMno, (b) H,Cr0, (©) K,Cr,0, (@) All of these D. Conversion R -CO,H—> R ~CHO can be done by: (a) LiAlH, (b) NaBH, (©) DIBAL-H (d) Alll of these E. Conversion R -CHO —» R-CH, ~OH can be done by: (@) LiAIH, (@) NaBH, (©) Hp /Ni @ Allof these F. Reduction R -CH, -OH —> R ~CH, can be done by: (a) LiAIH, (b) NaBH, — AICI, (© H,-Ni (@ Red P + HI 4._Which of the following is true for 3-methylbutanal ? This compound may be classified as an aldehyde. ether solution. a b. is compound may be classified as a ketone €. | An aldol reaction takes place on treatment with NaOH solution. a. ‘An excess of CH,MgBr in ether reacts to give 4-methyl-2-pentanol, Wolff-Kishner reduction gives butane, ‘This compound is an isomer of 3-pentanone.ALCOHOL, ETHERS AND EPOXIDES 5. 383 This problem isan introduction to the planning of multistep syntheses. For use, you have six reactant compounds (A through F) ; and eight reagents (1 through 8), shown below. Following these lists, five multistep syntheses are outlined, For each of these, certain Teactants or reagents must be identified by writing an appropriate letter or number in designated answer boxes. Write a single letter or number, indicating your choice of the best reactant or reagent, in each answer box. Reactant Compounds : ° ia ° Oy Kw A AA AR (A) @) © @) ® © sag (2) Jones’ reagent [Na,Cr,0, in HO") (3) Sodium hydride Nati (S) Thionyl chloride SOC, (7) Aluminium trichloride AIC, (2) Reagent) ip- OH Reactant Reagent 2 {cl agent{), (2 Reagent] Reagent oT? CaH6O2 “Gy Reaecane (2) PCC [C105 in pyridine + HCI] (4) Sodium borohydride NaBH, (©) Phosphorus tribromide PBr (8) Magnesium turnings in ether ° ee (2) regen] ecan 3. Oren Baste), gio, Ss ome = 0- GH,CH,CH, (2) NaOH saution coc, Reactant Reagent() (2) Reagent) tc) CsH6O ay Reactant] ‘ococH, Reactant 4) Regen coneagee Gieden— 5. (8) oreapenecy bBo oH384 ORGANIC Chemistry for IT-JEE 6.__Which of the following is true for 3-methyl-2-butanone? Ic may be prepared by CrO, oxidation of 2-methyl-2-butanol. b. | Its reaction with NaBH, gives a secondary alcohol. S| Itmay be prepared by acidic Hg? catalyzed hydration of 3-methyl-1-butyne. a. It forms a silver mirror on treatment with [Ag(NH; )s]"- ‘This compound is an isomer of 4-penten-1-ol. Which of these methods would serve to prepare 1-phenyl-2-propanol? . | Addition of benzyl Grignard reagent to acetaldehyde (ethanal). b. | Addition of phenyl lithium to propylene oxide (methyloxirane). ¢. | Addition of phenyl Grignard reagent to acetone (2-propanone) i. | Acid-catalyzed hydration (addition of water to) of 2-phenyl-L-propene. e. | addition of methyl Grignard reagent to acetophenone (methyl phenyl ketone). 8. Match the Column (1) and (11). Reaction Name of Reaction @ (®)| _Pinacol-Pinacolone rearrangement eeeeae =ALCOHOL, ETHERS AND EPOXIDES 385 oe ee ait @ Semi-Pinacol reaction a © © Pinacolie-Diazotization @na_, @ @pna’? | ¢s) i Match the Column (1) and (11). Reactant Products ieee ll & Cre mmo |e Kees ana, ‘CH lw Cre sa lw CKes © ® cH @ pte © Cees ants386 "ORGANIC Chemistry for HT IEE 10. oh OH c= | | HO—— H | Reaction 1. | "5, on — SH | #01 cH,OH | | I cHO | ] Ho——1—u | Reaction 2. | |! OH sto, | #. OH | CH,OH | Ratio of moles of formaldehyde obtained in the reaction (1) and reaction (2) ? Di-tert glycols rearrange in the presence of acid to give a-tertiary ketones. The trivial name of the simplest glycol of this type is pinacol, and this type of reaction therefore is named pinacol rearrangement (in this specific case, the reaction is called a pinacol-pinacolone Tearrangement). The rearrangement involves 4 steps. one of the hydroxyl groups is protonated in the first step. A molecule of water is eliminated in the second step and tertiary carbocation is formed, The carbocation rearranges in the third step into'a more stable carboxonium ion via a (1, 2] rearrangement. In the last step, the carboxonium ion is deprotonated and the product ketone is obtained. H,S04 =H0. L2-shift Me Me Me Me Me Me Me Me Pinacol Me Mee ™ ee Me Me Pinatslone A. What is R.DS. of pinacol-pinacolone rearrangement ? (@) Istep (b) I step (© Mstep @ WstepCHyPh OH + HO: on CHPh How many products obtained in above reaction ? @)1 b) 2. o3 @4 on c. i poet NNO, p Product is : ° ° it a @ o © @ HCH, D. Cis a, Be OH NH, Product (A) is: © CHy ot @ cry —C—C—eh cH On OH (@) None of these SUBJECTIVE PROBLEMS Maximum number of moles of Ac,O consumed by reactant (A)is :Sard 1. 1-B; 1A; I-A; IV-B; V-B 2. A-d; B-a,cefg,h; C-a,b,c; Dd; E~de,f,gh; F-e 3. A-b; B-d, C-d, D-c, E-d; F-d 4 aceg Hy — OH (@ Reagent Ht @) reactant id] Reagent oe 5 “amor > CoHli202 Co ° T* neagent[1], (D Reagent 5) ©? CsHs02 “ayeacane far + & aspen] (2 Reagent] (2) Reagent) ) Reacami€) ‘OH “Gyco, _* CsHi02 ~Feoane with > D-OH Greer Tang with a Hoo catalytic acid CH,CH,CH, (Q) NaOH solution OCOCHs Reactant Reagent) | p49 2 Ressem) £ aFI6O 3) ReaeantE} ‘OcocH, ss (1) Reagent] Reagan cy emeenG@, Gay gy (2) Resta) @)Reagendsy ©3474 HO" On 6 bce 7 abe 8. a-p,b-r,c-5,d-q 9% a-s,b-1,c-a,d-p 10. Ratio of reaction I and il = 2 11. A~-b; B-b; C-c; D=a Subjective Problems 47 | ALDEHYDES AND KETONES ey) eS 3) i = = See oad ay i Of _NattaKOWO , (4) ; Product Ais: - (ia -isner reduc) major Noy OH 6 9 +) 2 @ c © ° ° © @ORGANIC Chemistry for UTJEE ° Il ow ono : (CH, — CH) — NMeg CH, — CH, — Nes Above conversion can be achieved by : (a) Wolf-Kishner reduction. (b) Clemmensen reduction © LAH, (d) NaBH, : il CHj —C— CH, — cH, —CH—¢H, ——> cH — (CHz)3 — CH— GH. 2 “$ is ais Sila 6 Above conversion can be achieved by : (@) Wolff- Kishner reduction (b) Clemmensen reduction (6 HS —CHy —CHlg —SH, following by Raney Ni (A) None of these C—CH3 a a —2n®_, ; Product of the Clemmensen reduction is HCl ‘NO, fr" ee CH — CH L = Gs CH, — CH L —CHy "O., "On “Oe, * fe q 5. CH; —CH—CH, — CH, —C —CH3 —> CH —CH— (CH), —CHy ‘Above conversion can be achieved by : (@ Wolff-Kishner reduction (b) Clemmensen reduction (©) LiAIH, (d) NaBH,Rr ° Il c—cH, cH, —CHy cH, — CH, cH, — CH pee @ O) 7 6. “ES & O OH OH cl a ® @ ® Identify product (A) & (8) from the given product P,Q,R: (@A=P,B=Q ()A=QB=R © ()A=Q B=P_— (d) A=R, B=P ° I C—cH, 7 — 2D (A) ; Identify the A. HO CH, —CHy @ Efe ® ee yae HO a OH o @ a ° ll C—CHy Nie 8. 2. Product (A) is : (Wet Kid ttn) CH, — CH, —Br CH, — CH, (@ &) CH, — CH, — OH@ Gch — oo Above conversion can be carried out by : (a) Clemmensen reduction (b) Wolff-Kishner reduction (©) LAH, @ NaBH, 10. Increasing order of equilibrium constants for the formation of a hydrate: ° ° ° ° CoO” ico ce NH ON © a ay w () V ‘0 0 Above compounds can be differentiated by following reagent: (a) 2-4 DNP (Brady reagent) (b) Tollen's reagent (©) Lucas reagent @ Nalts0, on on on excess 1 equivalent a OH _Poc exces), (4) A, gy CME, cy_NABHL, py Product (D) will be: ou OH OH | CH—CH, (a) © a OH OH OH © oe @20. 21. BI,THE py idnium Cro chomate FCO, (ey H0,0H Giic, CHy—CH = cH, Uis(OAd HAO (py Pyridinium Chloro Chromate (PCO), ‘NaBH,HO® (®) CH, i Relationship between products (Q) and ($) is: (@) Positional isomer (©) Chain isomer © ae (d) Functional isomer In the reaction, Dee LAG) benzene beat, ¥. the product (1) is: 2.0, heat r “OD ° Rank the following in order of increasing value of the equilibrium constant for hydration, Keyg, (smallest value first). i [=o (CH,){CCC(CHS) 5 7 2 3 @1<2<3 @3<1<2 ©@2<1<3 — @2<3<1 o “Above conversion can be achieved by: (a) Zn(Hg), HCl (b) NH, —NH3/KOH/A (© Lal, @ Hy /Ni24. 26. Which sequence represents the best synthesis of hexanal ? (CHCH,CH,CHCH,CH =0 ° exanal (b) 1. CH,CH,CH,CH = CH, +c, Goon 2. CH MgBr, diethyl ether 3.H,0° 4, PCC, CHCl (a) 1.CH3CH,CH2 CH2Br + NaC =CH 2. H,0, H,$04,1gS0, I (©) 1.CH3CHyCH.CH2CCH3 (@ 1. CHjCH)CH,CH.MgBr + Ba “oth, IL 2.CHsCOOH 3. LiAIHy 2.0" 3. PCC, CHCl oe H,0 5. PCC, CHCl, dO —HNOa_,(4) —SM©!D2_,(B), Product (B) in this reaction is | a oA odd 7 cH,OH ~ HO—j]—H - 4 HO—f— ae u—t- on —2> n—+— 3 H—}— 0H H—)— 0H a CH, —OH cH, — OH ‘Compound (x) in the above reaction is : f i (@) Ph—C—CH, (b) Ph—C—H Il (© Ph—cH, —C—H @ mh—cn,—lca,27. 29. 30. ° I , Ph —C—CH, MNO: 4a) AGO _y(5) 30" _4¢¢) Prodiict (C) of the above reaction is : Il (@) Ph—CO,H (& Ph—C—COnH 90 It I (© Ph—C—C_H (@ Ph—C—CH,OH ° i oO HEH 4¢4) MMOL 5 (5); Product (B) ofthe reaction i: (a) Ph—CH, — NO, () Ph—CH, —ONO. (© Ph—cHo @ Ph—o—N=0 ° ee ta): RvB” 07 Product (A) of the above reaction is (bromination occur not in the benzene ring) : Oo. Br ° @ oe © ° oO Il Br . C. CH “ “Orr slot test NS Tolle test 14,0 2 . —aapotes0, Positive Tollens test Compound (A) is : ° © oct, il 1 @ cH, —C—GH— Gata () at —o— 6a, OCH, OCH, OCH;I Hz —CH—OCH ; @ H—C—cit, — CH, — GH —octis OCHy OCH; BI. CigHys > (B) NN, ; Reactant (A) in this reaction is : (a Giigo HOT/a Ph, CH Ph CHy @ cmc? () me < Ph” \ coy cry Ph Phy yh © pom @ both () and (©) cus CHy : Peitiurs HL? ee, a OM. o-H | methyl -eyelohexyl sive ‘tive tive test with : Todoform 2-4 DNP 2 hydrogen peroxide test test a ‘Compound (P) is : 1 (@ cH, —C—cH, —CH, — cH, —CH—CH, OH fe () CH, —C—cH, — CH—CH — CH, —CH, ° (© CH —C—CH, —CHy — CH —CH, —CH, —OH nein (@ cH, —C— cH —C—cHy | CH CH83. © Correct order of reactivity of following compounds towards Grignard reagent? oO am @ I>u>m (b) U>1>m © U>l>1 (@ I> m> 1 it <® 34. aon —HGHO_, (4) ; Product (A) is : Tons” Sp on Ph cH, —Ph CH, CHy, @) ) oo 0 CH; | cH—Ph cH, a 3 @ oo © oT ° i] fa 35. (CH),CO—C—CH, — CH, — CH. OCH,CH,CHs “Hop,” I oH ‘ocH, Total number of products obtained in above reaction is : @2 3 o4 (@s536. 37. 38. 39. for What reagent and/or reaction conditions would you choose to bring about the following conversion? °. ORK J] — Os = 0 +HOCH,CH,OH 0: (@) 1. LiAIH,, 2,0 (b) HO, H,S0,, heat (© H,0, NaOH, heat (@) PCC, CHCl 9 Met excess : : ‘The above reduction can be best carried out by : (a) Clemmensen reduction (b) Wolff-Kishner reduction (©) NaBH, (@) None of these CH, —C = cH CH; —C =CH—EHs THE, (gy (2)H,0,/80" Product (A) and (B) is differentiated by: (@) 2-4-DNP (b) Naor (© Nametal (@) Naliso,41. 42. 43. 45. Oy ABEL sy UAL) BOL 40) End product (C) in above reaction is : HH Ooty oh oS Compound (X) C,H,0, which reacts with 2, 4-DNP derivative and gives negative haloform testis (a) CH, —C—CH, —CHy ) CH; — GH — CHO CH : oa io ET Pal eu llet When a nucleophile encounters a ketone, the site of attack is (a) the carbon atom of the carbonyl (b) the oxygen atom of the carbonyl (©) both the carbon and oxygen atoms, with equal probability (@) no attack occurs as ketones do not react with nucleophiles ‘The correct order of rate of reaction toward nucleophilic addition reaction: uo CHO Ho ° o I 1 ¢-Ph CH, -C— Et No, OMe @ © © @ © (@a>b>c>d>e Q)a>b>d>c>e (@ a>d>e>b>c @a>b>e>d>c ‘The structure Chea would be best classified as a(an) : 4 (@) Acetal (b) Hemiacetal (©) Hydrate @ Cyanohydrin Which of the following pairs of reactants is most effective in forming an enamine ? 9 I (@) CH,CH,CH + [(CH),CH] NH ) + CHy —NH—CHyi (© (CH3)3CCH + (CH ),NH (d) None of these form an enamine. 46. The reaction of CgHsCH = CHCHO with LiAlH, gives : (@) CeH;CH,CH,CH,OH (b) CgHsCH = CHCH,OH (© CcHsCH,CH;CHO (@) CgHsCHaCHOHCH, “7 Qa (A) (a) ; Product (B) of the reaction is: > @ @ OO © OQ) @lL] HH HI 48. Which of following compound is hemiacetal ? HO, OMe OH H OH @ @) cy o X (@) all of these o —+ —S4sI_, 71% 5 End product of the reaction will be : NH, N—CH, (a) Ph—CHy —CH, — NH (b) Ph—cH, (@ Ph—GH—C=N (@ Ph—cH CHs Oo i 50. Ph—CH —CH—C—CH,—> Ph —CH = CH—CO,H ‘Above conversion can be achieved by : (@) KMn0,, A followed by H" (b) Ip/NaOH followed by H* © Ha/Pt (4) LiAlH, O ve ., Son ©) HCHO (@) Both (a) and (©) si.52. 53. 54. 55. 56. O 22225 (A); Product (A) of the reaction is : ° ° HI @ ) © @ CH, COCH, —B2*M20H_, (4) + cHiBr, ; Product (C) of the reaction is : #0 ° ° ° ° r cars @ ®) © aC) OQ 0 tao, + 2 Glycol Product (A) of the reaction will b ° ° i 1 (@) CHy — CH, —C—cH, —C—CH, —CHs z i (&) CHy —CH, —C—CH, —CHy —C—cH, i i (© CH, —CH, —C—CH, —C—CH i i (@ CH, —C—CH, —C—CH, i R—C—H —2-842_5R—CH=N—R. This reaction gives best yield at : (@) pH1-2 (b) pH4-5 (© pHi0-11 (@) pH 13-14 ‘An aromatic compound A of the molecular formula CgH90 on react dilute NaOH gives a yellow precipitate. The structure of the compounc (@) Opa (b) CgHsCHOHCH, ° © city-{O)—cH,0H @ on {Oj-on CHy n with iodine and expected to be:57. 58. 59. 60. 61. 62. Compound A (molecular formula C,H0) is treated with acidified potassitim dichromate to form a product B(molecular formula CHO). B forms a shining silver mirror on warming with ammonical silver nitrate, B when treated with an aqueous solution of NH;NHCONH, and sodium acetate gives a product C. Identify the structure of C. (a) CHsCH,CH = NNHCONH, (b) CHj¢ = NHHCONH, oy (© CHC =NCONHNH, (@ CH,CH,CH = NCONHNH2 dy In the reaction, the acid obtained will be CH3CHO + HCN —+ CH3CH(OH)CN —*-°H_, CHgCH(OH)COOH (@) D-isomer (b) Lisomer © (80%D + 20%L) mixture (@ (S0%D + 50%L) mixture In the following sequence (CH3CH,Cl—™X_, (jy Milla, (jy _aeeticanbndide (i), Product (fii) is : (@) CHyCH,CH NH, (b) CH CH,CH,CONHCH, (©) CH3CHjCH,NHCOCH, (@) CHyCHCH,CONHCOCH O° eu -e ce69. 70. 71. 74. Consider the following sequence of reactions. Ketone A! COHMIEE _HyS04, test a Or ra “amo Po Bt, HO ie “A oe © Moy or ° In the reaction, o + CHigCOCtig —BONMBOH_ x, the product (1) i HC. CHy HC. CH, @ ® o™ a Cm New, Oo Ney ‘The conversion of acetophenone into benzoic acid can be achieved by its reaction with : (a) sodium hydroxide followed by acidification (b) iodine and sodium hydroxide, followed by acidification (©) hydroxylamine followed by reaction with HS04 (@) m-chloroperoxobenzoic aci In which of the following compounds the methylenie hydrogens are the most acidic ? (a) CHyCOCH,CH; (b) CH;CH,COOC,H, (© CH3CH,CH(COOC;Hs)2 (@ CHjCOCH_CN ‘Which is the major product of the following reaction ? enor Cr 7. (a) &) © (d) N OH ‘ONH, oe o> ° IL Ph—c—on 2, Ages ®) Product (B) is:75. 76. 77. 78. @ tn (®) Ph—CH, —OH © Ph—CH,—cl (@ Ph—cH = cH, ‘The presence of unsaturation in organic compounds can be tested with : (a) Schiffs reagent (b) Tollens' reagent (c) Fehling's reagent (4) Baeyer’s reagent Which of the following gives iodoform test ? (a) CH3CH,0H (b) C,H,CHO (© (CH,0H), (@ None of these ‘Which ofthe following f-keto carboxylic acid does not undergo decarboxylation on heating? COjH @ © 0 OH COgH CH © 0. (@) None of these “ft HOCH,CH,CH, —C—OCH,CH, "2 -y¢4) Ha =CiMisBe_y¢gy_NHACY/NO (cy (molar equivalend) ° I KOH, _Hy0°_, _(Cis— G0 (py mp Pyridine Product (0) is : i O—C—CH ° I Il (a) HC =CH— CH— CH, —CH, —C—OH (b) HC = CH—CH, — : —COnH OH iii (© He —ci— ¢ —CH, —CH, —C—0—C—CH, OH ° Il @ Hg —CH—-GH, — Gio CH C—O OH79. ‘The compound shown in the below undergoes racemization on reaction with aqueous acid, H, OH we ° Which of the following structures best represents the intermediate responsible for this process? oH H, OW oH H, oH NS SF fA : @ o © @ fy ° oH OH HO “OH 80. The final product of the following sequence of reaction is: (CH) ,CHCH,CH,CH Br —M&_, "9 _Ha0" i i (a) CH,0CCH,CH,CH,CH,OH (b) CH, CCH,CH,CH,CH,OH i i i (© HCCH,CH,CH,CH,OH @ HCcH,cH,CH, CH 81. The amino ketone shown below undergoes a spontaneous cyclization on standing. What is the major product of this intramolecular reaction ? ° ll sie ‘CHCHNH, i CH ° Cy N @ Co (b) i ‘CH CH CHy CH, % o Co @ y NH,82. Compound (A) CsH20 is optically active. Compound (A) give negative Tollens test and positive test with 3-4-di-nitro phenyl hydrazine. Identify A. ° i I (@) CH, —C—cH, — (0) CH, —C—CH—CH, CH,—CHs i i (© H—C—cH, —cH—cH, (@ CH, —C—CH, — CH —CHz —CHs CH,—CH, QO NO, 83. a S 08:0 (4); Product (A) ofthe reaction is : S M (H,0® 99% ° ° @ eau © aa a On Qe Br ss 5 OST +) tone 560) 84. Product oS will be : 2 2 9 85. Ph—CH, —S%S2 (4) 28X04 _ Ph —CH,OH + (B) Product (B) of above the reaction is : (a) Ph—CO2H (b) Ph—CO3 (©) Ph—CHO (@) Ph—CH,86. 87. 89. OAD, product ; Product obtained in the reaction is = H—}—0n © wor CH — OH D-(+)-Glyceraldehyde (@) Diastereomer (® Racemic (© Meso (@) Optically pure enantiomer 0 MOH cay (p) #_4(c); Product (C) of the reaction is : aes OH oo 'N’ 'N’ 'N’ ‘OH N’ ‘OH I I | I H H H H TN + cHgMgbr—5> (A) (a) + (€) Product (A) and (C) is: O° Oo I i] 4 @ -C —CHs ; CHIy o) C—CHg ; CHI t cy; ciy—cuo; © [-s—a crs @[_)-c%—¢Ho ,cm, on ° 1 Nig —NH—C—NH | Ph—CH—CH3 > (A) @) Product (B) is : ra i (@) Ph—C =N—C—NH—NH) &) a =N—NH—C—NH) CH q oO I (©) Ph—CH = N—N—C—NH (d) Ph—CH = N—C—NH, CH(© Alcohol (@) Alkane ° CH, © @ ‘OMe ‘OMe ° K, * cn pi a 92, ce + HON SE ROE ROR Reactant Kea. PhCHO @ ° Ae : Il Ph—C—CHg 7 i cH, —C—H q ‘The correct order of decreasing value Of Keg 18: @a>brcrd @) d>a>b>e (© d>b>a>c @d>a>cod93. Product (B) of the given reaction is ° ° we-0- 87 is no OF wt Sy sw) OH ai s0,0Me 'sO;Me Tone me @ u © ‘| © C5 @ . 94. End a ei reaction is : Ne AA, ~ (ay —22888 (By HP? _ cy ee does not undergo self aldol condensation 95. a Suto ~S py cao + 2b AEs onal acid Compound (A) will be: (@) Ph—C =C—C =C—CHO (b) Ph—c =¢—cH —cH—cHO (© Ph—CH =CH—C =C—CHO (@ Ph—CH =cH—c =cH—co,H 96. 9 —>—0H _ Product; Product of the reaction is : —— > eam Graycnon oc, 2h (molectlar sieves) ee eee wk ox o Ke @) é >-9 o< PQ p<|aupsnvoes. nes 97. Which pair of reactants compounds may be used to make given acetal ? Q i ° ° cH, — on on (a) + | (b) ti aie >on 9 ° on + © O >on ef.) * Aon on a Q 0 98. CHO _#°_ 0p; (4) & (B) are isomers ; Isomer (B) is : o ° CH oF (a) &) ‘o— H on chy © 4 @ AK ou oH on 9. AW, ca) AH 25 (8) (A) and (B) is differentiated by : (a) Natt () 2-4 DNA (©) Tollen’s reagent (4) Nal1SO3as 100. 101. 102. 103. i ORGANIC Chemistry for HT-JEE) Which of the following pairs cannot be differentiated by Tollens' reagent ? (a) Benzaldehyde and benzyl alcohol (b) Hexanal and 2-hexanone (©) 2-Hexanol and 2-hexanone (d) Pentanal and diethyl ether ‘An optically active compound G ¢,20 gives positive test with 2, 4-dinitrophenyl hydrazine, but negative with Tollens' reagent, what is the structure of the compound ? i i (a) CHy —C—CH, —CH, —CH, —CH, (b) H—C—CH—CH, —CH, — CH, I CH, i i (©) Cy —C— CH— Chl, Ctl, @) Gils — Gi, — CG Gis CH CH ‘Compound (A) CgH,;0., when treated with Ip in aqueous sodium hydroxide gives yellow precipitate. When A is treated with Tollens reagent no reaction occur. When A is hydrolysed and then treated with Tollens reagent, a silver mirror is formed in test tube. Compound (A) will be = ° © ocH, U1 Wl (a) CH; —C—CH, —CH, —CH—OH (b) CH;—C—C— CH, I | Oct Oc, i i I (©) CH, —C—CHty —CH(OCH)2 (@ H—C—cH, —cH, —cHOCH). bea CH, —CH, —CO,H ae 74 —MaoML gp. Ey? ©), Product (C) obtained is: | (CH, — CH, —CO,H ° (a) CH, —CH =CH—CH, ) oO OQ @ N—NH,105. 106. 107. Which of following does not react with NaHSO, (sodium bisulphite)? ° I I @ cH, —C—H () CHy —C—et IL © oboe (@) Ph—CH, —C—CH, (CH, — CH, — CH, —NH, Hy i ee Faron? (4); Product (A) is: “CO . ‘Oo N’ ‘ g = q 4+CH, = CH—CH, — Br (4) ; Product (A) is: : 4 co) ‘CH, —CH = CH, oR enact en Lo o CT 6 cy c= CH, — CH = cH, CO;H hb H - —{WMeesses)_, (4) >_> (B) + CHIy; Product (B) in this reaction is : @wcitao CO,Na CO.Na CO;Na co,Na @ (b) 4 © O @ OoBEET cnet) ° = AS — D Arrange the following reagent in the correct order in which above transformation is carried cout (@) KO0/D,0,1*/4, LAH, (&) #*/, KOD/D,0, LIAIH, (© KOD/D,0, LiAIH,,H*/a, @ LAI, H*/A, KOD/D,0 i 109. Cis —C— HE (4) 2 _4¢6) —9(¢) Hate) HL > HCHO + (E) Compound (C)can show geometrical isomerism. Product (E) of the reaction will be : g i (@) CH; —C—CH (b) CHy —cH, —C—H (© cH; —cHO (@ HCHO 110. Arrange in their increasing order of equilibrium constants for hydration ? 9 ° ° ° Il i] I I CH,—C—CH,, CH;—C—H, CH —C_cH,—cL_ H—C_-H, ww ® ~ o cc) cl—cH, —C—H @ @)A eed reactant (A) is: (a) CH, —C =CH (b) HC =cH (© CH,—C =C—CHy (@) Ph—CH = CH, ! - 118. CH,CH, —C—CHy S39; lajor product of this reaction is : i @ oe (b) CH, —CH, —C—CH =N—OH 0 i (© cH, —C—C—CH (@ CH, CH, —C—CHy hon Non(418 ORGANIC Chemistry for IIT-JEE ° 116. GO —ERPEN (A) +(B). Product (A) & (B) are Btn, 4 | N. @ & ©OO-OO.. -~G0O'GO on NAV -OH © a WH “6D CO ° I L nitromethane 9386 cH 7. o + CHyNO, M28, 4 HCl, (By, product (B) is : J 3,4 Methylene dicaybenzaldehyde CH = CH—NO, c=cH—No, (a) ) IT ieee OH 0 oH I CH = CH—NO, i © @ o Le 5 oO 9 annie : 118. Tarim —? 4). Product (A) is ()Nano,/u"120. q21. 122. 2 Soe —SSEOH (4), Product (A) is : emote) i © A wP>-c~<] © IA w@ 107 ot ° on ree me lg (catalyst) i fons Which of following can be used as a catalyst in the above reaction? i @ ar (&) CH; —C—O- (©) Er—O™ (@) HSO3 Arrange the following carbonyl compounds in decreasing order of their reactivity in nucleophilic addition reaciton. CHO COCH; CHO CH, @ a Gi) (iv) @ ii>ii>i>iv (b) i> i> iv> it © ii>ii>i>iv @) iti> i> iv> ii ‘The following reaction were carried out. H ne? 7 Ip/NaticO, OH “The final product formed in the above reaction sequence is 9 \ "ome 7,8 dud123. 124. 125. "ORGANIC Chemistry for IT-JEE) on Mec a nee le ae © Yield of each step as actually carried out in the laboratory is given above. What is overall yield of reaction? (@) 42% (b) 31% © 21% @ 60% What is the appropriate reagent to carry out above synthesis, i.e.,A, B, C respectively are : (a) Br,/H", LiAIH,,H® (b) Br,/H*,NaBH,, HO (©) NBS, AICI, HO- @) Br,/HO™, BF,, HO™ on © S14) 2) 0) ye); Oecd Product (B) is : (@) Nylon 66 () Nylon 6 (© Styrene (@) Polystyrene Methyl vinyl ketone on reaction with LiCuMe, gives a major product, whose structure is: @ a" © Kn HO oO oO om Me wA Kn126. 9 @ CAs OH H.C = CH—— cH, oO 9 9 i v7. ct, cr, cn, Lect, Product (B) of above reaction is : Which of following is in capable to show iodoform test ? on (b) Ph—CH = CH—CH—CH 8 elias > 20s, yy SHEN, py (ajo cl cl © [OL » [O lO » OL N N N’ 'N* cL 9° Cok 128. EC, A ; Product obtained is : Et0,C’ Ree ° OH co,Bt @ ©) © (@) None of these ° ° ° 129, (a) AM, (ay Hs Diastereomers, Comme Reactent (A) is : 9 I (@) CH, —C—CH, 9° Il (©) CH3—CH,—C—CH,—CH3 i (b) CH —C—CH,—CH (@) CH —CHy—CH,—CH = 0180. 131. 132. 133. 134, 4 +xLialH, Stee 5 ae, siete (900% yield) Gaobarenone Gycobutanot ‘Value of x in above reaction is : @1 &) 2 3 @4 (4) SH 4(B) —HaS04_4(¢) 12" (0) « (=) —S_pcHy —N=C Ph Ph (oy 4) aa ¢G)_H ce) aon 2 8 ‘Molecular weight of compound (A) is : @ 58 & 120 © 60 @ 182 I PhCH — C —H —#¥228588_,(4) + enol + aldehyde - a eae alte Product (A) of above reaction will be : on (&) PhjcH—CH, ° I IL (© Ph,CH—CH—OH (@) PhCH—C—CH, ‘Which of the following will form stable hydrate ? CO, IS (@) CC1yCHO (Chloral) o CL Co (ninhydrin) ‘CO 7 (©) (CF;)2CO (d) All of these ‘The pH at which maximum hydrate is present in an solution of oxaloacetic acid: 9 9 bbc, on PK, =3.98 () pH (@) pH=6 2135. 136. 137. 138. 139, EHYDES AND KETONES _ 7 423 Arrange their stabilities of given gem- diols in decreasing order. OH Oe wl fon . oO ‘OH an ay, ‘OH @l>u>m ) > >t (@l>il>t (@ mM >t> i Maximum hydration takes place of : i i i i | (@) CR CCF, (b) CH, CcHy © Hs Get (a) Cols CC Hs a The conversion, PRCN -+ PhCOCHS, can be achieved! most conveniently by reaction with: (@) CH MgBr followed by hydrolysis (b) fp — NaOH, CHI © dil. H,80, followed by reaction with CH.N, (@) LAH followed by reaction with CH1 ° jt Ss H-6 In the above reaction, product (6) is: oF co © Coen @ ite OH Structure of Ais: ? Oo © ied @ da ° 9° @ cor ©) cdORGANIC Chemistry for HT-JEE 140. =< Y=o 24> HcHo+ 4) 220) 0 Product (B) is : i i (a) Ph—NH—C—CO,H (b) Ph— NH—C—CH, —CO,H © om Seen rh @ oo oO 1 Ph COsH 141. — ‘To Carry out above conversion, arrange the following reagents in correct order. 03 /Zn EtONa / EtOH/A ‘NaOCl Ht a aw 3 (@) 1933234 @) 1523453 (1933432 @ 1323334 HOCH, ° | IL Maa, HCCC cH, Cot AEs (4) 291 — (5) + HCHO CH, -CHs Product (B) is: CH,—O\ /CHy @ n—¢-a_—a_—<¢ — 07 Ney te LON 7H () H—-C—cH,—CH,— Br” So” cu, e CH,—O\ CH ci (© H-0— Cc, =o —ah—¢ —0 Say144, 148. 146. Identify appropriate reagents for the above reaction: (@ a=Br/CCl,, —b=a9, KOH (b) a=Br,/H*, b=aq. KOH (© a=Br,/H*, b =ale.KOH (@) a=Br/HO™, b= aq. KOH OH OH DA Pet); red 09 af hs resco is: 56 Me’ Me Ph ‘ ca au go The Kg, values in HCN addition to following aldehydes are in the order = 9 ° 9 co o* : ‘Meo Me,N © am: amp @ I>u>m () > m>1 @ M>i>0 (@) U>I>m HH 9 @ eaves ts J +nen ba, oH 7 @ cy4-es ts J snen iH u lation between K and K, is: (a) Ky =Ka (b) Ky >Ka © Kp>Ky @) & =K,426 Ronee “ORGANIC Chemistry for IT-JEE 147. Which of the following is correet for the reaction ? ° 2, erie 2010 (4) (a) Ais cyanohydrin () Nucleophilic-addition reaction (©) The above reaction is not shown by alkenes (€) Allof these 148. Which of the following compounds (i through v) should not be classified as an acetal ? - H CHO: OCH 0. 0, 9. 9 ct OS 0 0 @ @) way @w (@) ii and iit ©) iv oi (@) none (they are all acetals) 149. In which of reactions final product is NOT a ketone : (@) CH, —C =C—H—™2 (4) — SELB) BE 5 (C) — HB, (¢) Stl, (p) Px{OHOa tno, ¢p) () H—C Il (© R—C— on 4(4) S58) (0 big -rHe (@) 1-butyne BMH, (4) a=, (p) Be Oy/HO"_, ey 150. The reaction of ethyl methyl ketone withClz/excess OH gives the following major product (a) CICH,CH,COCH, (b) CHCH,Coccl, (©) CICH,CH,COcH,C! (@) CHyCCI,CoctcL 151. The product obtained from the following sequence of reactions is Cy —C = CHT a Matti i504 (2) propanol (6) 2propanol_ (©) L-propanol (4) propanheALDEHYDES AND KETONES 427 ) @ © @ © oo) (b) (O} 10. © 11. © ©. 13. @) (b) 15. (oy (b) b) 18. () 19. (b) @ 21. o @) 23. o) 24, @ o 26. (O} 27. 0) (@ 29. ), o 31. @ 32. © (o) 34. (oy 35. (@ o), 37. © @ 39. ) 40. @) b) 42. @), 43. @) @), 45. @) @ 47. (b) @ (0) 50. @) 51. @ o) 53. @) © 55. @) 56. (v) (a) 58. @ 59. © © 61. © @ 63. o) 64, ) (b) 66. @ 67. @), @ 69. ) © 71. ) 72. @ @ 74. @) 75. @ @, 77. @ @ 79. © 80. © @ 82. @) 83. ), 0) 85. 0) @) 87. ) 88. © (b) 90. ) 91. ©. o) 93. (b) 95. © 96. © @ 98. @) 99. © 100. © 101, © 103. | o 104. 105. © 106.| ) 107. @), 108. © 109.| © 111.| © 112,] 113,| ) 114, © 115. o 116. @ 117. @ 119.| ) 120. | 121. 0) 122.| ) 123. Ac 123, @), 126.| © 127, 128, @) 129. © 130. @) 131. @ 132, © 134,| @ 135, 136, @) 137,| @ 138. ) 139.) @ 140. () 142.| @ 143, sey ® 145.| @ 146. (b) 147, @_ @ 150.1 o) 151,ORGANIC Chemistry for ITJEE 1, Select the best choice for example (A to L) from the examples (a to n) given below. Write your choice in the box given. [ a. An acetal derivative of a ketone, \ B. | A chiral ketone, | G. | An aldehyde that gives a aldol condensation with itself. i An oxime derivative | 1 t reduces aldehydes to 1°- alcohols | Ana, B-unsa etone, | A reagent that oxidizes aldehydes to carboxylic acids. | Hz A reagent that reduces ketones to alkanes. | |_t. | sn enamine derivative of a ketone. J. | An intermediate in imine formation. K. | A cyclic hemiacetal. | A cyanohydrin derivative, —_ a, EE i a He Oo CHg OH | «| Co |w © ‘CN OH OH | @ pwn’ © | znaigno | H 0 CHs | ° | ® oa (h)| NaBH, aq. alcohol | | HO, OCH, @] agavn,).?on™ * |) 0 on @) chy— C—OGH, CH |