MCQ Organic Chemistry PDF

Hig} = Himanshu Pandey BOOKS CEE] ADVANCED PROBLEMS IN __ For JEE (Main & Advanced) & All Other Engineering Entrance Examinations Check ; Lucky *, id ey wi eS Pair reat .4 a ay aa wheD Distribution Office : G. R. BATHLA PUBLICATIONS PVT. LTD. (An 180 9001 : 2008 Certified Establishment) ~ EDUCATIONAL PUBLISHERS & DISTRIBUTORS. “Prakash Building’, Opp. Nayyar Palace, Lal Kur, Meerut (U.P) . Phones : (0121) 2640303, 2640304, 2660802, 2660709 + 9760235126 (Enquiry Dept). . . (0121) 6482119, 9219404920) 9267164022 (Sates Dept) + (0121) 6452010, 6452126, 9219515310 (Order-Booking Dep.) + 8760327805, 9897275667 (Customer Care Dept) Fax: (0121) 2649956, 4059720, 2664539, 4031412 ‘e-mail: wor bathlabooks.com ‘website ¢ grbathla@roditimall.com SS © Author . ISBN : 978-93-82314-46-2 “ Q First Edition : 2010 O Sixth Edition : 2014 Q Price: % 452.80 0) Printed at: Aryan Press, Meerut (U.P) © No part of this book may be reproduced in any form or by any means without the prior written permission of the author and the publisher. * The author and the publisher have made every effort to provide authentic, accurate and ‘up-to-date information in this book. However, they do not take any legal responsibility for any misinterpretations or errors inadvertently overlooked. .PREFACE to the Sixth Edition ‘An excellent response to previous edition, I fee! great pleasure in presenting fully revised edition of the book “GRB Advanced Problems in Organic Chemistry for JEE” according to latest pattern of examination. This book deals with objective problems of each chapter which include Single Choice, Multiple Choice, Matching Type, Comprehension Type and Integer Type Problems. Exercise-! in every chapter contains two levels, Level-I is for JEE-Main and Level-2 is for JEE-Advanced. “This book is highly desirable that students, particularly those who: work very much on their own, should have a mean of achieving confidence in organic chemistry”. The study of Organic Chemistry requires at least three processes : Learning, Understanding and Application. A very good way of achieving it, is through solving the problems. : 1 do hope that the new revised edition of the book will be more useful to the students and leamed teachers. Suggestions for further improvement of the book will be gratefully acknowledged. I wish to acknowledge my indebtedness to all the faculties across the india for their enthusiastic support and their useful suggestions given from time to time for improvement of this book, . : J would like to thanks Mr, Manoj Kumar Bathla and Mr. Vishvnath Bathla, Directors of G. R. Bathla Publications Pvt. Ltd. for their effort in bringing out this February, 2014 Himanshu Pandey Note : Students and honourable teachers may feel free to give valuable suggestions on the mail suggestionsgrb@gmail.com to improve the quality of book. nePREFACE to the First Edition “New Pattern Advanced Problems in Organic Chemistry for I'T-JEE” has primarily been written with the aim of meeting the needs and. interests-of student secking admission to professional courses especially in engineering and medical, The present book on organic chemistry is designed especially in accordance with the new examination pattem and syllabus of IIT-JEE. The main objective of preparing this book is to keep pace with the changing trends of entrance examinations. To make the students more familiar with trends and tricks, how to solve problems, the present problems book has been prepared. The other salient features of the problems book are summarized below. . a 3 The problems are based on basic concepts, Preparations, properties, structures and usefulness of organic chemistry. : 3 Due considerations have been given to mechanism and stereochemical aspects of chemical reactions. 3& Maximum problems in this book are designed by combining two or more concepts, Answering them need thinking and deep knowledge. : I wish to acknowledge my indebtedness to Mr. Amresh Sharma, Mr. Amit Mishra and Mr, Vivek Pathak for their enthusiastic support. 1 acknowledge the blessings and support of my mother Smt, Kalindee Pandey, father Dr. 8.N. Pandey, uncle Shri Sudhakar Pandey, brother Sudhanshu, Saurabh and my wife Jaya They supported me all the time during the preparation of book. I would like to thank Shri Manoj Kumar Bathla and Shri Vishvnath Bathla, Directors, G. R. Bathla Publications Pvt. Ltd., for their effort in bringing out the book. The author will be grateful to teachers and students, if they be kind enough to offer criticism and suggestions for its improvements and to point out the inevitable errors which, inspite of all efforts, creep in. April, 2010 Himanshu PandeySie Chapters Pages GENERAL ORGANIC CHEMISTRY bss § Exereise-] : Only One Correct Answe Level-1 : . 1 Level-2 : : 9 § Exercise-2 : More Than One Correct Answers’ oo 46 § Exercise-3 : Linked Comprehension Type . 56 § Exercise-4 : Matrix Match Type - 62 § Exercise-S : Integer Answer Type Problems 65 > Answers 67 ISOMERISM ers, § _Exercise-1 : Only One Correct Answer : Level-1 69 Level-2 . 8 Level-3 . . 86 § Exercise-2 : More Than One Correct Answers 110 § Exercise-3 : Linked Comprehension Type . 119 § Exercise-4 : Matrix Match Type 123 § Exercise-5 : Integer Answer Type Problems 128 Answers 128 2 EM Nays ecer cin ek Cesta ie ac Ne nL) ray § Exercise-1 : Only One Correct Answer . . Level-| ; : 130 Level-2 137 § Exercise-2 : More Than One Correct Answers 182 § Exercise-3 : Linked Comprehension Type 192 § Exercise-4 : Matrix Match Type 202 § Exercise-5 : Integer Answer Type Problems 206 2 Answers mors 209 Ce a) 211-278} § Exercise-1 : Only One Correct Answet > : Level-1 7 : 21 Level-2 nee : : 218 § Exercise-2 : More Than One Correct Answers 252(vi) § Exercise-3 : Linked Comprehension Type 263 § Exercise-4 : Matrix Match Type 270 § Exercise-5 : Integer Answer Type Problems 214 3 Answers . 277 ERE at eet nai) ee § Exercise-1 : Only One Correct Answer Level-1 219 Level-2 : 289 § Exercise-2 : More Than One Correct Answers 318 § Exercisc-3 : Linked Comprehension Type : 329 § Exercise-4 : Matrix Match Type : 337 § Exercise-5 : Integer Answer Type Problems . 340 3. Answers : 343 AIT moo nels Eee § Exercise-1 : Only One Correct Answer Level-1 345 Level-2 354 § Exercise-2 : More Than One Correct Answers 394 § _Exercise-3 : Linked Comprehension Type 404 § Exercise-4 : Matrix Match Type 417 § Exercise-5 : Integer Answer Type Problems : au > Answers 424 7. CARBOXYLIC ACIDS AND ITS DERIVATIVES 426-490) § Exercise-1 : Only One Correct Answer Level-I 426 Level-2 433 § Exercise-2 : More Than One Correct Answers 465 § Exercise-3 : Linked Comprehension Type 476 § Exercise-4 : Matrix Match Type . 484 § Exercise-S : Integer Answer Type Problems 486 2 Answers . . 489 8. AMINES ere § Exercise-I : Only One Correct Answer Level-1 401 Level-2 497 § Exercise-2 : More Than One Correct Answers 518 § Excrcise-3 : Linked Comprehension Type $24 § Exercise-4 : Matrix Match Type 530 § Exercise-5 : Integer Answer Type Problems 532 3 Answers 534(vii. Prete h ee aceneau enous § Exercise-1 : Only One Correct Answer Level-1 Level-2 Level-3 Exercisc-2 : More Than One Correct Answers Exercise-3 : Linked Comprehension Type Exercise-4 : Matrix Match Type Exercise-5:: Integer Answer Type Problems Answers Comma 10. BIOMOLECULES § Exercise-1 : Only One Correct Answer Level-1 Level-2 § Exercise-2 : More Than One Correct Answers § Exercise-3 : Linked Comprehension Type § Exercise-4 : Matrix Match Type 2 Answers 11. PRACTICAL ORGANIC CHEMISTRY § Exercise-1 : Only One Correct Answer § Exercise-2 : More Than One Correct Answers Exercise-3.: Linked Comprehension Type § Exercise-4 : Matrix Match Type Answers: > 12. NOMEN eit Section-I Section-IT Section-IIL Section-IV Hints & Solutions Bowmmm KER ye 535 545 553. 599 606 615, 617 621 xe ys 623 626, 634 637 640 64: TRE) 12 643 | 647 650 651 654 TAY 655 660 662 662 663at[ auave< 1. Which of the following belongs to +/ group ? (a) —OH ()—OCH, © ()—COOH = @) —CH, 2. Which of the following is the strongest ~ group ? ' (@)—N*(CHy)3 ()—*NH; —— (©)—"*SCHs)., @—F | 3. Among the following compounds, the strongest acid is : (@HC=CH —O)CgHe ()CrHg (®CH,OH 4. Carbocations may be stabilised by : | (@)m- bonds only at allylic position : (b) n- bonds only at vinylic position (©) x- bonds at allylic and benzylic position also ‘ @-Leffect | "5. In the anion HCOO”, the two carbon-oxygen bonds are found to be of equal , length. What is the reason for it ? i | @) The C=O bond is weaker than the C—O bond. : i (b) The anion HCOO™ has two resonating structures. | (©) The electronic orbitals of carbon atom are hybridized. | (d) The anion is obtained by removel of proton from the acid molecule. | 6. Which of the following resonance structures is the major contributor to the {resonance hybrid ? aa 1 i CH,;—CH,—CH—@Me = CH,;—CH,—CH=OMe ; ” ay { @l ) I i | {Both have equal contribution _(@) They are not resonance structures | 1 | 7. The species CH, CHCH, is less stable than : : + * i (a) (CH3)3C* (b)CH3CHy CH, = (c)CH;CH2 (d) CHS i «8 Amange inthe order of decreasing pK. | | @)F—CH,CH,COOH (Q)cl—GH —CH,-~ COOH ' a t _@)F—CH,— COOH __(S) BCH, CH," COOHt 2 GRB Advanced Problems In Organic Chemistry for JEE Correct answer is : - 7 (a2) O>S>P>R (bl) P>R>S>Q (c) R>O>P>S (d) S>Q>P>R 9. The strongest base is : HN NH *\4 (@)CH, rs ) € CH; NH, (CoH Nols (CH,—NU—CH, Cols 10. Consider the following species : : 8 2 @ | (AyOH (a)cH,—8 = (CE, (D) NH, Arrange these species in their decreasing order of nucleophilicity. ! (a)C>D>B>A (b)B>4>C>D ()A>B>C>D (@C>A>B>D 11. Consider the following carbanions : 2 g @ #,00-{O)— cH, ano.n—(O)- CH, g . 2 an) cH, avy) 5e-{O)- CH, ! Correct decreasing order of stability is : @)>M>1V>1 (ey > 1V>1>0 ()IV>I>1> I (@1>>m>IV i OH OH OH NO, 12. | NO} i NO; ‘ I n a : Arrange the following phenols in increasing order of pKa, value. @IH>M =) M>M>1 = @M>I>@)IN> HoT |. Arrange the following in decreasing order of the pKa value. ee ee Sa ee ceGeneral Organic Chemistry 3 CH, ==CHCH,NH,CH;CH,CH,NH,, CH==CCH,NH; @I>t>l ‘@)N>I>m = © W>u>t ~ @uuIVIV>I> >I ()1> > HI>IV>V (@V>Iv>Ml>n>1 17. Arrange the following in increasing order of stability. Oo an aD @i<0I >1>IV {b) I> 1 >1>1V ()MlU>H1>IV () I> 1 >T>I1V (}1>1V> > (@IV>mM> > 20. Which of the following molecules can act as a nucleophile and an electrophile ? (2) CH;NH, (b) CHCl ()CHCN (@)CH,OH“4 GRB Advanced Problems in Organic Chemistry for JEE 21. Which of the following molecules has the shortest carbon-carbon single bond length ? (@) CH, =CH—C—CH (b)CH, (©) CH, =CH—CH=0 (CH, 22. Give the correct order of decreasing basicity of the following compounds. CoHsNH, (CoHs)2NH = (CsHs)3N 9 CgHiNHz oO ay ay, av) (a)I>M>m>tv (b)IV>IN>>T ()IV>I>I>I0 (d) > >1>1V 23. The correct order of stability of the following carbocations is : (a) CH,CH, CH, >CH, =CH—CH, 3CH, =CHCHCH, > + CH, =CHCICH,), (0) CH,==CHCH, > CH,CH,CH, >CH, =CHC(CH;), >CHiy=CHEHCH (och, =catcH, ).> CH, =CHCHCH, >cH, =CHCH, >oH,CH,CH, (@) CH, =CH—CHCH, > CH, =CHG(CH,),> CH,CH,— b> =CHCH, 24. The order of decreasing stability of the following cations is : CH,CHCH,, CH,CHOCH,, CH,CHCOCH, Ww . aby ap. (a) I> U>1 (b) I> > OE () I>1> 01 @I>m>u 25. What is the decreasing order of strength of the bases ? (OH- (I) NHZ (my)H—C=c- (IV) CH, CH; @Iv>I>m>1 - (b) I> IV>>T ()1>1>M>1V (@)U> H>1> IV 26. The decreasing order of nucleophilicity among the nucleophiles is : CH; aan (i) CH," vo t (uy en" ay) wef S20” ° (a)I>T>>IV . (b) IV >>> .. ©U>m>1>1v (@M>1>1>1V 27. Different hydrogen in Booc. Dp UE OF cer CH—CH,—CH,—CH(CH,), cfGeneral Organic Chemistry 5 are represented by alphabets. Arrange them in decreasing order of reactivity towards radical substitution. (@)C>A>E>D>F>B (b)F>B>A>C>D>E ()B>C>A>F>D>B (@) A>B>C>D>E>F 28, Consider the following: - / O=C—NH, g CH,CH,NH,, CH CNH, o a (mt) Correct order of their basic strength is : @I1>M @WI> > 0 (@U>1>M>1V Consider o es The correct order of their acidity is : @U>I>m>v @IV>M>n>1 om ay NO;—{O)—N @) I 1>1V>11 (@ I> > I> Iv (I) NN ANN 9 ww) sh A (b) >I >1>1V (d) none of these (ay a0) NH) ayy NE N ‘The correct order of decreasing basicity of the above compounds is : (a) I> I> > IV (@)MI>IV>0>1 . Select the correct order of basicity. () > 1> I1V>0 (@U> I> IV (a) CHCH3 >CH,=CH™ > HC=C” >OH™ (b) CH,CH3 > HC=C™ >CH, =CH™ >OH™ (0) CH,CH; > OH > HC= (@) OH" > C=C” > CH, = ~ > CH, =CH™ CH >CH,CH3 eg- General Organic Chemistry 37, The acidity of the protons H* in the following is : Oo ll th (0) CH,CH, CCH, (11) CH,CH,OCCH, q 1 (If) CH,CH,OCCH, COCH,CH; (a)1>U> 1 (b)1>l> it (o) I>1> (d) 11>1>0 38. Which comparison is not correct as indicated ? “(a) € \-on >CH,OH (acidic nature) , o€ Swi, >CH NH, (basic nature). e ® © ( \-&, >CH, CH, (stability) ° ° @ € Son > cu,lou (acidic nature) 39, How many rr electrons are there in the following species ? YX 2 (a2 4, (0) 6 8, 40. Which of the following is not correct ? “ (a) A sigma bond is weaker than m bond. (b) A sigma bond is stronger than % bond. (c) A double bond is stronger than a single bond. (@ A double bond is shorter than a single bond. 41. ‘The length of the carbon-carbon single bond of the compounds (i) CH, =CH—C=CH (i) CH=C-—C=CH (I) CH; —CH=CH, (IV) CH, =CH— CH=CH, is expected to decrease in the order : (@) HI> 1>1>1V (b) I> I> > 1V (co) I> Iv >1>T (d)1>IV>1>1n 42. Which of the following involves no displacement or shifting of electrons ? (2) Zeeman effect .~ (b) Inductive effect (c) Resonance (@ Electromeric effect 43. Which of the following exhibit electromeric effect ? (a) Alkanes : : (b) Aldehydes (©) Alky! halides @ Alkyl amines8 . GRB Advanced Problems in Organic Chemistry for JEE . 44. Point out the incorrect statement about resonance. (a) Resonance structure should have equal energy. (b) In resonance structures, the constituent atom should be in the same position. (c) In resonance structure there should be the same number of electron pairs. (a) Resonance structures should differ only in the location of electrons around the constituent atoms, , 45. Resonating structures of molecules have (a) identical bonding () different bonding (©) identical arrangement of atoms and nearly same energies (d) the different number of paired and unpaired electrons 46. Shifting of electron of multiple bond under the influence of a reagent is called: (a) Leffect (b) M-effect (© E-effect (d) T-effect : 47. Give the correct order of increasing acidity of the following compounds. © OH a OH ay (coon avy) C=CH @lu1V>1>1 (b) I> 1>IV>1 (I< UU>1> IGeneral Organic Chemistry” ** 9 49. Resonance energy of these compounds will be in the order as : ofS mS mMAN~ ~ N 0 H a | H @M>I>n >> (]U>mM>I @u>1>m 1, Which of the indicated H in the following is most acidic? H | @ HN N H ” n” HHO ” . (@) X &) ¥ @Z @p 2. In which of the following compounds is hydroxylic proton the most acidic? F @ LA, OAA, ow a) we 3. Which of the following pairs does not represent the resonance contibutors of the same species? o t | (=) CHy—CH” and cy 7 @ oN (b) CH, CHa and CH),—CH, on © i | >ot—Gis and t / AC 0 pp ay! a @ CH NC, and HNC 4. Which of the following is not a planar molecule? (a) H,C=C=CH, (b) H,C=C=C=CH, (©) HyC=C=0 (@) NC—HC=CH—CN . Which ofthe following pairs does not represent resonance structures? @ @ CH ComN—O and Hy C= NO . ee of (b) cian and CH>—NC Ge Py10 GRB Advanced Problems in Organic Chemistry for JEE on @ cat.—Ko e Sgn CN 6. In which of the following pairs is the structure on the right major resonance contributor? : : e 3 oO a Z (@) CH;—C <> CHy—C aan b—CK 9 - ° {b) CH, =CH—Cl) <— CH,—CH= op-o pes Ci CH go © nm’? — Jo 9 Tn whieh of the following pairs of resonance contributors is the structure on the right a important contributor? o eo se @ ° (») CH,—N=N <> CH,=N=N o 6 (c) CH;—-CH—-OH <> CH;—CH=OH (d) All of the above 8. Examine the following resonating structures of formic acid and arrange them in decreasing order of stability : op ety cw la cul H—C—OH ‘H—C=0—H H—C—OH <> H—C—OH a ay i) aw) (a) W>1>Ul>Iv (b) [> 1>I1>Iv (c) I> 1>IVet (d@) IV>MI>1>1 9. Which of the following compounds will not show resonance? b : °CH: @) CO (b) CH==CH—CH=CH—CH,General Organic Chemistry 1" i HN—H © @ OO 10. Which of the following compounds will exhibit d-orbital resonance? 7 20H Cz @ Os ) o © Co @ O 11. Which of the following represents resonating structure of ? ~~ QO C4? “© Ce <(d) All of these 12. Which of the following is not a permissible resonating form? e 8 e ° @ CH —¥—0 (b) CH, =K-0 CH; cH; ® ° (c) CH, “y=0 (d) CH —N=0 _CH, CH; 13. Less contributing stuctre of nitroethene is : o e 8 (a) CH cr 8G (b) CHC NCs : 3 . 9 @ ‘e409 . © Giy-Gt-KK @ Cc ae . 0 14. Which will be the least stable resonating Structure? oO + (@) CH, =CH—CH-CH—NH, (6) CH,—CH—cH CHNA, e eo (©) CH,—CH=CH-CH=NH, (@) CH =CH—CH—CH=NH,12 GRB Advanced Problems in Organic Chemistry for JEE 15. Which will be the least stable resonating structure? ae) 0 9 KS w (nt ° © Oye @ O86 16. Which of the following pairs of structures is not a pair of resonating structures? (a) H—C=NHand H_C=N—H (b) CH; —-CH=CH—CH, and CH,CH,CH—=CH, © CHy—P=CH—F— CH, and cH, pC —e—c, s ° @ olde % 17. Which of the following pairs of structures does not_represent resonating structures? oO OH A ll | { (a) CH; —C—CH, and CH, —C=CH, oOvoml 4 ®0—H OH (c) CH; —C—CH, and CH; —C—CH, ° 0 0 ° e (@) CH, =C=0 and CH, C=O 18. The most stable resonating structure of p-nitrosobenzene is : { t t { Ne Ne N® en ® () © © 0 @ () : N e Ng ° \ és oN 3 o ‘8General Organic Chemistry 13 19. Which of the following molecules has longest C=C strength? (a) CH, =C=CH) (b) CH; —CH=CH, CH; | © CH, —E—CH= CH (@) CH; —C=CH, | CH; CH; 20. The decreasing order of bond length of C=C in the following compounds is : OO OO Tl O) neisaveim ) tit> >> (©) > >1> 0 : @ IV>t> i> 1 21. In which of the following molecules all the effects namely inductive, mesomeric and hyperconjugation operate? oC a _ ©) (ls ° © Cpe of . CHs : 22. There. are three canonical structures of naphthalene. Examine them and find correct Statement among the following : . 1 1 . 1 2 2 2 <> _ 4 4 4 {a) All C—€ bonds are of same length (b) C,—C, bond is shorter than C;—Cy bond (c) Cj —C, bond is larger than C,—C bond (d) None of the above ‘NH NH} “0 S J ave it IV14 GRB Advanced Problems in Organic Chemistry for JEE Among these compounds the correct order of C—N bond length is : (a) IV>1>i> Tl - (b) M>I>T>1V (c) I> 11>1>1V @ ML>1>1V>0 24. C, —C, bond is shortest in : 2 2 : C=CH | CH=CH, ® ©) Cy 2 2 | CHr—CH, | C=sCH © @ 25. Among the following three canonical structures what would be their relative contribution in hybrid? Ci; =CH—CH—CH—CH=CH, I =CH—CH—CH=CH—CH) re eo e CH, —CH=CH—CH=CH—CH, m @Pn>M @)M>m>I @I>M>n @m>1>-n HOH il 26. CH" CH “CHB (CH, —H C\—H, C)—H, C,H and C, —H the homolytic bond dissociation energy is in the order : (a) C,—H>C,;—H>C,—H>C,—~H (b) C; -H>C,—~H>C,—H>C,—H (¢) C, —H>C,;—H>C, —H>C,—H (@) C, -H>C,—H> C,;—H> C,H 7. Which of the following bas longest C—O bond? “oY cy oct « o 28. In which of the following molecules electron density in ring is smaxinom? NO, 6 wl 96 8 3 ® H,C—N=N -H,C—-Ne=N -H,C_N=N a amy ayyGeneral Organic Chemistry 15 (a) I> > IV > (b) I> W>M>IV (©) > I> l>Iv @ M>1>Iv>0 30. What is correct increasing order of bond lengths of bond indicated as I, 1, III and TV in following compounds? 1 Wow : WY oll (a) << I2>3 (b) 1>3>2 ©) 3>2>1 (@2>3>1 33. The C—CI bond length is shortest in : (a) CH, =CH—Cl; (b) CH;—Ch (c) C6Hs—CH,—Cl (@) CH,=CH—CH,—Cl 34. Which of the following pairs of structure are resonance structure? CH;—O? CHy—O® a | es and Il yc CHs—C=NC H3C—C-NC Nou . ‘CH e 0 @ ,OH . @& (Calig,CU-NE and (Catt, C=NC 8 3 (a) Land 4 (b) 2and3 (©) Land 2 @ All of these16 GRB Advanced Problems in Organic Chemistry for JEE | 35. Which of the following is pair of resonance structure? @ @) iol () AC and oS oO OH ©, jo] . (@) AA oe AR 36. The most stable diene is : —s a @~wVv oA ovcnsdar~~~ 37. Which of the following cation would have greatest stability? CH we @ @ o ® N—CH, (c) CH; O—CH, (d) 3F CH, cH,” o a 38. Which of the following is not valid resonance structure of polyene? a”AY oY © AY @ NY 6 4 39, Most contributing structure in nitrocthene is ; o (a) CHs—S—CE) (b) e 0 e 2 eS (@) CH,=CH-NZ 5 () ben SZ ‘6 3 . e 20 * « 0 <3 @ CHy—CH=N 9 40. The most stable resonating structure of CH, —O—CH=CH is: @ 8 (b) CH; -O=CH—CH, e ) (@) CH,—O—CH—CH, & "OD OO . ‘aGeneral Organic Chemistry 17 42. The correct stability order of following species is : ow / i ey A! Om mM ®. (a) X>¥>W>Z(b) ¥>X>W>Z() X>W>Z>Y ® ) z>x>y>W 43. Choose the correct statement : (a) [effect operate in both o and x bonds () effect create net charge in molecule (©) [effect transfer electron from one carbon to another (d) J effect create partial charges and it is distance dependent 44, Which carbocation is most stabilised among following? aC ID #OD . Which one of the following is most stable? $284 OH 46. ‘Which of the following cations is most stable? ma oh, “OQ. Oe, : 3 Hy s 17. Which of the following cations is most stable? CH; CH; . @ Cy / CH, . ) CH” c/o i 8 3 CHs an os © Cv / CH: . @ Cc Ho“BY Ob wc/8 on 48. Which of the following carbanions is most'stable? 8 e: (a) CH;—CH, (b) CH;=CH—CH, ° “NH Il Il (©) CH;—C=CH, | @ CH;—C—CH,18 . * GRB Advanced Problems in Organic Chemistry for JEE 49. In which ofthe following 2nd anion is more stable than frst? * (@) 0,N—CH, and F—CH, (6) Cy and CCl, ° Ile 8 () F,C—CH, and cc—CH, (d) CH;—-C—CH, and H,N—CH, 50. Arrange the following carbanions in decreasing order of stability : 2 e ° e CH,=CH © Ph—CH, CH, =CH—CH, ) @) ® © (@) P>Q>R>S (b+) S>Q>P>R © S>Q>R>P @) Q>S>R>P 51. Arrange the following cations in decreasing order of stability = ° : . e eo oe CH,=CH—CH, Ph—CH, CH,;—CH, ® ~ @) @) (S) (a) P>R>Q>S (bl) R>P>S>Q (c) G>R>P>S (d) P>Q>S>R 52, Among the following which is most stabilised cation ? . ; INE, INH By ony oN, «T 6 53. Which of the following anions is most stabilised? @ jl » ff Aa, AA 900 . © Jel . (@) All have same stability os 54. Arrange the following anions in decreasing order of stability : ° ° ° ° Atl so I le Il H—C—CH—C—H CH; —C—CH—C—H e) @) ° ° lo Il os CH,—-C—CH—C—0—CH, @®) (@) R>Q>P (b) O>R>P (©) P>R>Q (@) P>Q>RGeneral Organic Chemistry : 19 55. Which of the following is most stabilised by ech ‘ os CHCH; wa Hy0-b-CH, 6 Se Ged =. The decreasing order of stability of following cations is (Question No. 56-60). °CH, Ha Hy ‘Hy 56. : : OH NH CH; fol (R) S (@) P>Q>R>S (bt) Q>S>R>P (©) Q>P>S>R @ Q>P>R>S “O a 21, o :0H * hat cw, “ (Q) ' (@ P>R>Qrs (o>Rss>P (c) R>S>Q>P (9 Ponere ®CH, : ord 56 ” @ . : (@—) Q>R>P>S © ay S>Onn>P (©) S>R>P>Q Ores CH: . gh, (e) P>O>R>S o P>S>Q>R ©) PoR>0>8 (d) S>R>Q>P20 GRB Advanced Problems in Organic Chemistry for JEE H, = °CH, °CH) 60. 7 CH; CH,CH; Cs HC—F—ely ba, bu, 2) @ ®) o (®) S>R>Q>P (b) P>O>R>S (0) Q>R>S>P (d) R>S>P>O => The decreasing order of stability of following anions is (Question No. 61-65). $6 Ss : @®) () O>R>5>P @ArgsPos (s>PoRr>0 (d) P>Q>R>S ease ( P>0>R>s DO>aapss. e) P>R>Q>8 (d) S>R>Q>P oO Bo: or ich gb z @) P>O>R>s @ S>R>Q>P "O>ssR>P (@) Q>R>S>PGeneral Organic Chemistry . 21 fe : ecH, Hy CHACHs Hs me—F—CHs ba, CH; P,Q? ®) © (a) R>S>Q>P (bl) P>S>R>O (0) Q>P>S>R (d) S>R>Q>P 66, The most unlikely representation of resonance structure of rnitrophenoxide i is: 8. 8 Re ah RP aap Dog Df 67. Which wa be least stable resonating site? (a) cH cE Ct |5 (b) ch, —¢ H—CH=CH—OCHs (© tf, —CH=CHCH—O—CH, (4) CH =cH—Cu—cH-0—cH, 68. Which of the following acids has lowest value of dissociation constant? @ CHy—CH—COOH by GHa—CHl,—COOH F . *F (c) CH, CH, COOH @ CHy—FH—COOH Br . Br 69. Arrange t the following acids in decreasing order of acidity : ° 1 i Woon H—C—OH CH, —C—OH > Ow . w) @® @) X>Z>¥ ) X>¥>Z () Z>X>¥ (@) Z>Y¥>X 10. Which of the following acids has towest pK, value? o . . oO ool I @ Gia C—OH ~ (b) oH, — CH, --C—OH , . | + .NO2 : NO,22 GRB Advanced Problems in Organic Chemistry for JEE il © Gta —C—OH @ CH C—On cli 71. Write the order of basic strength : SS 9 @ H H H " @ (a) © (8) Q>R>S>P (b) P>R>Q>S (c) R>P>S>Q (d) P>Q>R>S 72. Write the correct order of acidity: - : ‘COOH ll CooH /SOOH CH,” H-C—on _ | cH | . coon ‘COOH CH, ® @ ® OOH (a) P>Q>R>S (b+) O>P>R>S (0) Q>R>S>P (d) S>R>Q>P 73. Write basicity order of following : NH . ° ll lo. CH; —C— Nig; CH —CHl,—NH (Cit), NH CH —-NH @) (s) @ PasoRsg () R>S>O>P © PoR>g>s @ Q>S>R>P 74. Among the following compounds the strongest acid is : @) HC=CH — (b) CoH, (©) CoH, (@ CH,OH 78. Find out correct order “— ofthe following ‘compounds : NE cy CH,CH.NH, ®) @ ® (a) R>Q>P>S (b) P>Q>R>S (c) R>Q>S>P @ posoo>n 176. Find out strongest acid among the following : (® CHy— 11> >IVv (b) >> IV>T yc) W>IV> Hl @ Iv>Ml>l>1 79.: Which of the following has most acidic hydrogen? ° Il (a) CH;—NO, —(b) CH; —C—H (c) H—C(NO,); (@) Ph3CH 80. Which of the following compounds can react with base to form salt? ° oO-t 0 Ops 9 () N—-H (d) (ie 81. Arrange the following compounds in decreasing order of acidity = O° OH cumin ® @ ®) © (as) R>O>P>S (b) Q>R>P>S (6) S>R>Q>P (A) O>P>R>S 2, Which one among the following is the least basic? (=) CH;NH, —(b) NH (©) CH,CH,NH, (4) (Nib "83, Which of the following compounds contain most acidic H? 4 (a) CH, =CH, (6) HC=CH © OO , _ @ Ch, =CH—CH, CH=CH‘ 24 GRB Advanced Problems in Organic Chemistry for JEE 84. Which of the following reactions does not proceed in forward direction? (@) Ph;C—H+CH; (CH,);Na —» Ph,CNa +CH; (CH,),CH, NO; NO, . . ee ®) on (Cpa +NaHCO;—. on {Oph + CO; + HO ‘NO, 4 NO, Oo oO : lt - ee | : {c) CH,—C—CH,—C—CH, +C,H,ONa : ' eo ° ONa il | — > CH;—C—CH=C—CH, +C,H,OH “ oe @ ye) + Nati00,—14¢-()) Sa +C0)+H,0 85. Which of the following reactions does not proceed in forward direction? (@) CH,CH,SH + NaOH —> CH,CH,SNa +H,0 (b) CH;CH,OH +CHjMgBr —+ CH,CH,OMgBr +CH, + (©) CHjCH,OH + NaOH —> CH,CH,ONa +H,0 (@) CHCH,OH + NaH —> CH;CH,ONa +H, 86. Which of the following compounds is strongest base? il NH NH—C—CH, OOmwOO-moLy eC : NO, ° : 87. Give the correct order of decreasing acidity : " C)H.SH ‘C,H,OH C,H,NH; CH,CH,CH, a @) eB) a) (a) 251>3>4 (bl) 3>2>1>4 "@)1>2>3>4 : ()3>4>2>1 - 88. Which of the following is the strongest base? NH; HC,! Genera! Organic Chemistry | : : 25 - NER \n7 ON. NO; (a O% NO2 © NO, NO; 89. Arrange the following compounds in decreasing order of basicity : Et Sen ax @ Qn N’ Me3C’ “in ® (@) P>Q>R>S wosrsass © pesso>P. (@) O>P>S>R 90. Which of the phenol derivative is most acidic? OH OH . OH HH @ 9 ) O © O @ 3 F cl Br ‘ 91. Arrange the following compounds in increasing order of acidity = S & HH QL, CH; Oy . @ : 6 @ poorars (0) S>Q>R>P & So n>P>0 (@) R>S>P>Q 92. Arrange the following compounds in increasing order of basicity : Me Me. Me NH NH) N\ N~ . \nZ Oo o “Oo” : NO, @) @ «R) (Ss) (a) S>R>Q>P : _ &) S>R>P>Q : (©) P>Q>R>S (d) R>Q>P>S26 GRB Advanced Problems in Organic Chemistry for JEE => The decreasing order of acidity of following phenol derivatives is (Question No. 93-100). 1H OH HH HH 93. CO : CHy cl “OCH; NO, e @ ®) (sy (a) S>P>Q>R (b) Resepre | (c) Spooner (d) P>Q>R>S HH ot ‘NO? 94. : NO. (P) (R) @ R>P>Q>S ® P>R>O>S (0) nogspes (@ S>Q>P>R ent OCH, @ @) P>o>R>s ® S>R>Q>P w soRsP30 (@ Q>S>R>P HH OH 1H 1H CN F NH J ” @ ® © @ P>S>Q>R ©) S>Q>P>R () R>Q>P>S @) P>Q>R>S ) @* 0) © (a) S>O>P>R (b) S>O>R>P (c) P>Q>R>S (d) R>S>Q>PGeneral Organic Chemistry 27 OMG OCH; P) a) (a) P>Q>R ( R>0>P ()Q>P>R @) P>R>O 2%, G8 Hs CHCH3 ime Hye—6— CH : us bus ey @ ® . © (@) P>Q>R>S (bd) Q>R>P>S () S>R>O>P () R>S>Q>P 1H Il oo 100.CH;0H H—C—OH CH;—NH;: { ici) @ ®) © (2) O>R>P>S ) R>O>P>S (0) S>R>Q>P (d) Q>P>S>R => The decreasing order acidity of following benzoic acid derivatives is (Question No. 101-108). 2 EG @ o @ P>g>R>s (b) Q>P>S>R S>Ro0>P (d) R>S>P>O COOK 1H OOH OH NOz 102,| ‘NO2 NOz @) @) ®- (a) P>Q>R>S (b) P>R>Q>S (2) R>P>Q>S : (@) S>R>O>P ~28 GRB Advanced Problems in Organic Chemistry for JEE COOH " COOH coon (OOH H SS 3 SS SS 103.[] | I fH a a ‘OCH, OCH ” @ @) o (a) S>Q>R>P (b) R>O>P>S (c) O>R>S>P (d) P>Q>S>R COOH COOH COOH COOH 104 ( SY * ( SS i > Va 2 Zo es Noun, CH; ” 1 © @) © (@) P>R>Q>S (bt) S>R>O>P (c) P>S>Q>R (d) O>S>P>R COOH COOH cooH COOH SS S ~S 105.{[ f ( eo a Le F a Be ” @ ® % @ P>Q>R>S (b) S>R>Q>P (0) R>Q>P>S MO>P>S>R COOH COOH COOH 106. a | yn es ~ LD 2 l ° oe ® »Q) ® () P>Q>R @)R>P>Q_- (| O>R>P_—) PSR>O I i il 107, H—-C—OH (Seon CH;—C—OH : ” -@ ® @R>O>P —(b) O>PSR_ (©) P>Q>R.- @) Q>R>P Oo oO Oo ° tl ll - 108.0,N—CH,—C—OH Me, N—CH,—C—OH. NC—CH,—-C--OH @) (Q) @) HO—CH,—C—OH: : és) (@) Q>R>PXS (db) R>O>P>S8 (c) S>Q>P>R(d) S>R>O>PGeneral Organic Chemistry 29 => The decreasing order of basicity of following aniline derivatives is (Question No. 109-117). HC. 3 :NH) NH-CH, = \N” S mm O CO NF wo ® @ () X>¥>Z (b+) Y¥>Z>X =) Z>¥>X @ X>Z>¥ INH, NH) NH) b CHy 0. [ >: ( : 3 ‘NF Hy Hy ) @ @) o (@) S>R>P>O 0) S>R>O>P ( (©) P>Q>R>S (8) Q>S>R>P NE} NH, NH L | Petts a Te lo a cx oct x @) @ ® , @) S>R>Q>P (bt) P>Q>R>S © S038 (@ S>P>O>R NH * We NH, ~ 112. [f \A Uo . NOx ” @ - ® (a) P>Q>R>S' (b) P>R>S>O @ R>Q>P>5 (@) S>R>O>P NEb NH 2 2 SS SS 13. [ i ge a. CH, CH,CH; oo HCE CH CH; * CH ” @ @®) 6) (a) P>Q>R>S (b+) O>S>R>P (c) S>R>Q>P @) R>S>Q>P30 GRB Advanced Problems in Organic Chemistry for JEE NH, IH, NH, NH, 14, CG. C.. cy : Hy HCH 5 eCity cH, * CHy ”) @ @® © (a) P>Q>R>S (b) S>R>Q>P (c) S>P>R>Q (4) R>Q>P>S NH NE, NH NH) Ts. : F a Br I (P) @ ®) © (a) P>Q>R>S (b+) R>Q>P>S (c) S>R>Q>P (d) O>R>S>P 116. Ph—N H, Ph—N—Ph, Ph—-N—Ph : w | | H Ph . . ” @) . (a) Z>¥>X =) X>¥>Z ()Y>Z>K —@) Z>X>Y HC CH; = CH, CH / \w7 NH ?NH—CH, N’ N’ HC CH; 17. . ot (a) © (a) R>S>Q>P (b) P>Q>R>S (©) R>Q>P>S (4) S>R>O>P => Arrange the following compounds in decreasing order of asi@ity (Question wet No. 118-125). 118.CH,CHACH COOH, CH,CH, HCOOH, qa —CH,—CH,—COOH, Br a . (@) 3) cl © @ P2Q>R>S (b) Q>R>S>P () S>Q>R>P W@) S>R>O>P 119. CoH sGH OH, Coll ,COOH, CoH OCH, CeHsOH: ® (2) (a) @) @) Q2S>P>R (b) P>Q>R>S (c) Q>P>S>R (d) R>Q>S>P» General Organic Chemistry 31 oO COOH ocr oa OG ) @) © () poorsok Oy Q>R>S>P (©) Q>P>R>S (4) R>P>Q>S NH? 121. of Ow Orr Hy Cu ® 6 © p>a>Res %) R>Q>P>S (0) S>P>R>Q @) S>P>Q>R 9 aN NO; 122, CHL cH H—-C=N poy locas: \csen ‘NO, } © @ ® 9 (@) P>Q>R>S (b) Q>P>R>s (©) O>R>P>S (@) S>Q>P>R 123. CH, (COOC;H;)2, CH;COCH,CO,C;H,, (CH,CO),CH,, R—C==CH: a) @) ®) ) (a) R>Q>P>S (b+) P>R>O>S (0) S>R>Q>P (d) P>Q>R>S 240 . I 124. R-CH;—N© -R-S—CHy(CiHy)CH R-C—CHy: oO : (oa @ @) © (a) P>Q>R>S ) O>P>S>R PrQ>s>R (@) R>S>P>O “Od OF Ce @ cc) : @° @ S>P>R>0 (b) P>S>R>O () R>P>S>Q (@) P>Q>R>S => Arrange the following nitrogen containing compounds in decreasing order of basicity (Question No. 126-130). 9 Ord Ca) @ ®) (a) P>Q>R>S (b+) Q>P>R>S © OsPosoR (d) S>P>Q>R32 GRB Advanced Problems In Organic Chemistry for JEE Oro © e ?) @ S>R>0>P ~) rer © Pog>ns, (@) R>Q>P>S NMey 128. NH N—CH: CS ON O ”) @ & 8 (a) R>S>P>Q (b) Q>P>R>S (©) S>R>P>Q (d) R>S>O>P 29 oy A A sN—H 17S Sy Ik om @ ® 6 (0) R>Q>S>P (b) P>Q>R>S (0) Q>P>S>R (d) S>Q>R>P 130. ®» Si (Sin, : a CH) ) @X>Y¥>Z QW) Y>X>Z @Z>X>¥ W) X>Z>¥ => The correct order of decreasing acid strength of following carboxylic acids is (Question No. 131-1 133) 0 COOH COOH ern HO. ion H3 131. . . \H ” @ «®) 6) @ R>S>P>Q (b+) Q>P>R>S () Q>R>P>S (d) Q>P>S>R (00H COOH COOH COOH . or NO, cl NO? 132, : NO2 NO; NO; NO; ” @ ® oO @ R>P>S>O (b) P>R>Q>S (©) Q>R>P>S @) S>R>Q>PGeneral Organic Chemistry OOH 1H , COOH COOH : WC CHy 133, » HBC Hy NO, NO, NO, SO3H @) @ ® © (b) S>R>P>OQ (a) P>O>R>S (c) S>Q>P>R => Among the following compounds which is strongest acid (Question No. @ S>R>O>P 134-139). : O—C—CH 135. (@) OL ‘COOH OOH ©) O—CH; oH 136. (a) on NO2 c Ml N ou on : ) oy NO2 - © on NO? : CHO34 ‘ GRB Advanced Problems in Organic Chemistry for JEE HC. CH; Hy CH; 139. @ (b) OH © © @ NO, NO) => Arrange the following compounds in decreasing order of basicity (Question No, 140-145), 140.Mes@ Me,N MeO MeO: eo. ta ® 6) @) P>Q>R>S (b) R>S>Q>P (c) P>Q>S>R (d) Q>S>R>P Oo ° ° ° : N e oO ° (@) Q>R>S>P (vb) S>P>Q>R (c) S>P>R>Q (d) P>R>S>O NH; NH; NH; FING Me BINS MB HINGIS NB ” _ @ © @) Q>P>S>R () R>P>S>Q (c) RSS>P>Q (d) O>S>P>RGitieral Organic Chemistry Q>R>S w orn>s>hoy © O>R>P>s Boo @) S2R> OP Ces rm He umesits alduie aol Sve 8 ”) ® OA, @ Ao soeStlageien (S>Q>R>P. @): SeR>0> <2 Mole NaNHp “AG. os > A; Product A will be @) . © 0 . ‘oO 8 1H : eSch hy P RENT GO) | He TES (eh BeVeh wh36 GRB Advanced Problems in Organic Chemistry for JEE (@) None of these e NMe,CI® 147. In the compound CH, —CH, —CH—CH, attack of base occur onB, not on, : B . © @) By is sterically hindered (0) C—-H of B, is more acidic thanB, (©) B, will form stable alkene (d) All are correct NED . NH, * HsCo, Hs 148. is more basic than Y Hs Hs : . NO; | NO, : Oo } 4 (2) (a) —NO, in P is poor inductive group (6). —NO, in P is stronger inductive group (©) —NO, in Pis stronger ~M group ; (d) —NO) in P is weaker —M group ” 149. Steric inhibition is not applicable in : : ao / NH, 1H @ i; 1H; 'N’. : CH, ) ' HyC_ "CH, ON : - NO; HAC. q HC. As © iO @ 150. Correct order of acidic strengths . : Zz COOH : © x ° 3 : HAN Nb jg; ¥y. (@) X>Y>Z '() Z>¥>X (VY >Z>X (ad) X>Z>¥General Organic Chemistry 37 151, The comect order of basics of following compounds is : cH i w 'NH2 CHLCHLNH (CH,).NH CH;-——C—NH) @ “ (a) 2>1>3>4 (db) 1>3>2>4 ( ivto2>4 (d) 1325394 152, The abstraction of proton will be fastest inwhich carbon i the following compound? ° x Fhe . HCA SCH @ x (b) ¥ Zz (d) P 53, What is the increasing order of bond lengths of bonds indicated as p, q, rand sin following compound? , fv 4 ~S P| (@) pQ>R>S (o) O>P>S>R ©) “Ro 5>Q>P (@ O>S>R>P 165, Arrange the following in decreasing order of heat of hydrogenation : ® @ ®) (a) P>Q>R>S Deg7 keer? (©) Q>P>S>R (Ad) R>Q>P>S Soy ~ OOO HO ‘COOH OH ) ” ‘The correct acidic strength order of acidic hydrogen P, O and R is respectively : Oe ()P>R>Q (©) R>Q>P— (d) Q>R>P wo 4 NH (1) 167. ‘The correct basicity order of atoms X, Yand Zis: & ‘ . G@)X>¥>Z 0 ()Z>¥>X (Z>X>Y GD Y>X>Z40 GRB Advanced Problems in Organic Chemistry for JE 68. Which of the following compounds do not have all C—Cbonds of same length? . 3 -@) on eof}. © O 169. Find out correct order for the energy required for heterolytic cleavage of indicated CCl bonds forming carbocation : 4 Se we o (a) X>¥>Z ( zovex wo zoxeY. (@s¥ >X>Zz 170. Find out correct order for the energy required for heterolytic’ cleavage of i indicated c—Br bonds forming carbocation : . CH): Br LP esa Teena { ot. 7 Zz H x (@) Z>Y¥>X @)X>¥>Z OY>xX>zZ ° W@ Z>X>¥ 171. Find out correct representation of singlet carbene : a? onal QP , osecw (b) Oy (© Both (a) and (b) (@) None ofthese - 172. Find out correct representation of triplet carbene : QF «o XZ. (@ HOCH (>) H—C—H ostas (@) None of these OR 9G ogi « 173. Which of the following orders is correct order of these anions? © CH; e 2 CHS CHs Le) : @)Q>R>P (0) O>P>R = (©) RSQ>P_— (Ad) P>O>RGeneral Organic Chemistry 4 174, The barrier for rotation about indicated bonds will be maximum in which of these compounds? ¥ x ! AE 29) am @ (a) X (b) Y OZ (@) Same in all 175, The most stable canonical structure of this molecule is : o (@) None of these 176, Find out stability order of following compounds : C a [ I : ~ . @ @® () Z>X>¥ (0) Z>Y¥>X =) ¥>Z>X @ X>Y>Z 177. Find out correct order for heat of hydrogenation of these compounds: . ‘ 2 ~ im | a oO A} fa) Y>X>Z (b) ¥>Z>X |) X>¥>Z (d) Z>X>¥ 178, Find out correct order for heat of combustion of these compounds : C7) @ (2) X>¥>Z° )Z>¥>K @) Y¥>Z>X ~— (@) Z>X>Y 179. Which of the following orders is correct for hyperconjugation of these radicals? is C A H: C ®” @ aw (@) P>Q>R (b+) R>Q>P =) O@>P>R_— (d) P> ROO] -42 GRB Advanced Problems in Organic Chemistry for JEE 480, Which of the following effects of —NO, group operates on —NH, group in this motecute? NH, HAC Hy NO, (a) Only =1 effect (b) Only = effect (c) Both -/ and ~M effect (d) Only +M effect 181. Which of the following is the correct order for bond energy for C—H bonds in these compounds? : ‘che z 2. a" @ Yoz>x" (b) X>Z>¥ (@)X>¥>Z @ Z>X>¥ 182, Which of the following orders is correct for the magnitude of +M power among these compounds? CH; w C) @ : (@ Z>¥>X (W)¥>X>Z © X>¥>Z_—(@) ZX >. 183, Which of the following orders is correct for heat of hydrogenation of these compounds? w We" AC CHs @ (@)X>¥>Z. (b) Z>¥>X. (| Y>Z>X (@) Z>X>Y 184, Which of the following orders is correct for the stability of these carbocations? 3 eu NH) =NH2 Qh < Oe . ae ” > @OQ>R>P (bd) P>Q>R “QO>P>R. @ R>P>Q‘General Organic Chemistry 43 185. Which of the following anions is resonance destabilized? acy oO. oi old 3 «(ae HOS x, 1x will be: “a 1G) ©) o@ oO (@) None of these ne cio. 187. Hyperconjugation occurs in : CH, @ Oo TIO @ © ao (d) None of these 188. The most stable resonating structure of the following molecule is : @ Crk () Crk © Cofen N 189, The decreasing order of nucleophilicity among the nucteopile: fl 2 cHy-C-8 cHy-8 tn nO }8 a 2 (a) 1,2,3,4 (b) 4,3,2,1 vo aan ‘wo 3,2, 1,4 190. Which of the following compounds have a dipole moment? NO, CH @ ) © @ @44 GRB Advanced Problems in Organic Chemistry for JEE 491. Which of the following is the least stable? NH NH NH NH @ o) Ch i) Cr @ Oo . ‘NH ‘NH HN NH NH 192, Among the following which is more reactive toward AgNO,? @ Ch, ) oO © ay @ cH 193. Identify the compound which contain most acidic Fiydrogen : OL ° oro | ® é 5 © as ® a 194. Identify the most stable structure among the following : %cH, CH; . : @ $ °C . oO ott of) q t t "6 wane (| wo] . we | ww mM . @ ‘The correct stability order of the given canonical structure is : (@) X>Y>Z (be) Z>X>¥ () X>Z>¥ (d) Y>Z>XGeneral Organic Chemistry - 45 196. Arrange the following in increasing order of basicity : NE Ke HN’ “NH; H;N* ‘CH; H,N* “OH HjC” ‘CH; () @ (Ry ) (@) SQ>R (b) O>P>R (©) R>P>O (d) R>P>O 198. Select the most stable structure among following : oO od 0X oD 199. Identify the compound which is not aromatic : o SS . oto} eC «GQ yy . H H 200. Find out anti aromatic compound among the following : at i Sy @ WZ i © | 3 ; @l 5 | “Hy 201. Choose the non aromatic compound among the following : ° ° ‘ @ ) @ OQ eA 06D 0B wh’ Sa 202. Identify the compouiids in which all bond length are equal : @ ) O © &» @ CO . | H46 GRB Advanced Problems in Organic Chemistry for JEE 203. Which of the following alkene has highest value of heat of hydrogenation? nh dy ed adh 204. Which of the following compound will not liberate CO, on reaction with NiOH? OH OH COOH Q, OH (a) ©(O © Jt @ ~~ o ‘OH NO, 205. Which of the following will not react with Na metal? ef oi fT J © Oo @ (\-on [RGSS MORE THAN ONE CORRECT ANSWERS i 1. Which of the following are electrophiles? ® (a) BF, - (b) 3CCl, (©) NHy @ 1° 2. Which of the following statements are correct for butadiene? ch, =CH—OH= =CH, (@) TheC, —C; and C—C, bonds are larger than carbon-carbon double bond (b) TheC, —C; and C;—C, bonds are shorter than carbon-carbon double bond (©) The C,—C; bond is slightly shorter than C—C bond (4) The C)—C; bond is slightly larger than C=C bond 3. Br has low reactivity in CH, —CH—Br because : (a) the C—Br bond has a partial double bond character (b) of the +M effect of bromine (©) Bris electronegative (@) None of the above 4. Which of the following statements are correct? (a) RO® isa stronger nucleophile than °OH (b) RCOO® is a stronger nucleophile than POH (c) RCOO® is a stronger nucleophile than ROH @ (a) RO® is weaker nucleophile than OHGeneral Organic Chemistry a7 “5. Dipole moment of which compound is not zero? ~ Z ® oO « @ © LJ 6 CI 6. Which sof following compounds can exhibit free rotation? op><] o DS of @l- 7. In which of following pairs the first one is the stronger base than second? ee (a) CH,COO®, HCOO? (b) OH, NH, e e (c) CH, =CH, HC=C (d) CH;NH>, CH;OH 8. Which of the statements are incorrect about the following compound? NO; ON "NO; Br (a) All three C—N bonds are of same length (b) C, —N and C; —N bonds are of same length but shorter than C;—N bond (©) C,—N and C;—N bonds are of same length but longer than C,-—N bond (@) C\—N and C;—N bonds are of different length but both are longer than Cs—-N bond 9. Choose the correct statements = ‘(@) O-hydroxybenzoic acid is much more acidic than m., p-isomers and benzoic acid itself . (b) -M or ~R group increases acidity of phenol if they are present at oand p-position (©) For resonance to take place structure should be planar (@) Resonance involve change in the position of atom 10. Which statements among following are correct? (a) Hydration effect stabilise dimethyl ammonium ion more than trimethyl am:onium ion . oO Il (6) R—C—NH, is more'basic than fon “ Oo e e 2 (©) CH; (@ x, —cH—C=0 ©) CH =cH—cH= 8 () CH, —CH—CH=0 (@ CH, =cH—cH=6 32. Which among the following statements are correct? (@) CB, is more stable than CCl, (b) CCI, is more stable than CBr, (c) Singlet CH, is more stable than triplet CH (@) Singlet CH, has planar geometry 33. Which among following statements are correct? (a) Energy needed for homolytic bond fission is less than that required for the heterolytic bond fission (b) Homolytic bond fission gives neutral species which is paramagnetic in nature (©) Homolytic bond fission takes place in non polar solvents (@) Cation and anion is produced by heterolytic bond fission82 GRB Advanced Problems in Organic Chemistry for JEE 34. Which of these statements are correct? (a) Stability of alkyl carbanion can be explained by hyperconjugation 0 e Ils ©) €%-&, is more stable than CH;—C—CH, OH OH . 1 . F © is more acidic than (@) B.pt. of onitrophenol is less than p-nitrophenol 35. Which of these statements are correct? Oo a I (2) Dipole moment of A ig greater than Ph—C—Ph (b) Acetone behaves as electrophile as well as nucleophile (©) CH an show geometrical isomerism NCHy (€) RO® is better nucleophile than RS® 36. Which of these statements are correct? (a) 1, 3, S-cycloheptatriene is not acidic while 1, 3-cyclopentadiene is acidic in nature (b)_p-chlorophenot is less acidic than p-fluorophenol © Dipole moment «“( is greater than () Mesomeric effect is temporary effect 37. Which of the following are nucleophiles? : ' os * @cn® (b) BF, (©) R—O—R = (a) NH, 38. Which ofthe following ae clestrophiles? ® (a) BF, ) aici, (© H;0 @) RN 39. Which of the following are less basic than H;C—=NH? (@) CH;—C=aN w) | 9 H ow. : (©) CH,—-C—NH, @ e : 7 x { HGeneral Organic Chemistry : 53 40. Which ofthe following compounds are not linesx? @ a ee) oO @ Ct 43 5 An: 2 Ans-Ani wey Ge At oS? Ni oN NA? ie I | 3 H H Pyrimidine Imidazole Purine Among the following which statements are correct? (a) Both N of pyrimidine are of same basic strength (b) In imidazole, protonation takes place on N—3 {c) Purine has 3 basic N (d) Purine, Imidazole and pyrimidine all are aromatic 42. Pyridine is more basic than pyrrole. Which of these following statements explain this fact? (a) In pyrrole lone pair is involved in aromaticity, in pyridine lone pair is not involved in aromaticity it is free for donation . (b) Conjugated acid of pyridine remains aromatic but pyrrole does not remain aromatic. ® Q N > . e\ e Hn ! Non Aromatic Aromatic (©) +1 power in pyrrole is greater than pyridine (d) +M power of pyrrole is greater than pyridine 43. HO, ‘c=0 _ on 1 i ‘Among the following which statements are correct? (a) Conjugate base of (1) is more stable than that of pheno! (11) (b) Conjugate base of (II) is more stable than that of benzoic acid (1) (©) Magnitude of positive charge on H atom of —OH group is greater in (1) than (IN). (@) None of the above 44, HSC. H H ‘ W gon nc «08 I : Cy @? . ‘Which of the following statements are correct about this pair of geometrical isomer?54 “ GRB Advanced Problems in Organic Chemistry for JEE (a) —/ effect of vinylic group on the —COOH group is same in both isomers, 50 there is no role of -/ on the strength of acidity - (b) +M power of vinylic group is operating effectively in érans isomer (4) but not in cis-isomer (B) because of steric repulsion in cis-isomer causing loss of coplanarity of —COOH gp. with C—C bond. Therefore, cis-isomer is more acidic than trans (©) +1 power of CH; — is greater in trans than cis (d) None of the above 45. In lew of the following molecules —NO} group is not coplanar with phenyl " On 4? s N’ @ oO. / ) aC cH On on N N- HG Hs I © @ 46. In which of the following molecules both phenyl rings are coplanar oO Or oO ww, ou Den eS . “OO aan 47. Find out correct statements regarding resonance energy ! (@) Itis equal to energy of resonance hybrid - () Itis equal to the difference in energies of the most stable canonical structure and resonance hybrid : . (©) Itis energy released by the molecule (@) AAtis equal to the energy of least stable canonical structureGeneral Organic Chemistry : - 55 2 43.7 WAS 2 4 Which of the following statements are incorrect about this molecule? (a) C, —C; and C;—C, bonds are of same length (b) C,—C; bond is shorter than C,—-C, bond (c) C,—C; bond is longer than C;—C, bond (a) C;—C, and C, —C; bonds are of same length 49. Which of the following compounds will create electron at ortho and para greater than “0 . CH; H Nik HON GA @ Oo © é © OQ @ oO 50. Which of the following compounds have electron deficiency at ortho and para position? . ine_c—cH, Sw” Ox Nib ‘@ OQ ) Q © 51. Identify the cations which are less stable than : @ @ . He" CH, . ot™ ow . CH, “9 ' oo oS 52. Which of the following alkenes have more vatue of heat of hydrogenation than 2GRB Advanced Problems in Organic Chemistry for JEE 56 @ CK ) Cl © Cl (d) CL 53. Which of the following compounds exhibit aromatic character? “oy oO och “2 54. Which of the following solvents are aprotic? oO : ll (a) H;C—S—CH, (b) CH, —-C—OH : i a pis ©) H-C-NC (4) H—S—H CH, 55. In which cases, free radicals can be formed by homolytic fission? oO I (@) H,c—c—cu, , (b) R-N=N—R , . oO Il. © CSc, 0-4 — (@ cH,—0—o—cn, [STSRGS LINKED COMPREHENSION TYPE Tl Passage-1 Electron deficient species are known as electrophiles. All positively charged - species are not electrophilic. Covalent compounds having complete octet but if central atom has unfilled @-orbital also act as electrophiles, All electrophiles are not always lewis acid. . "L. Which of the following is not electrophile? ° ® ° @H (®) CH, (© BX; @ NH, 2. Which of the following electrophile is not lewis acid? (@) BCI; () BeCl, (c) CH, @ CH, 3. Which of the following is ‘electrophilic in nature? @ co, _ ©) H,0,° 8 (©) CH, @ AIC, 'x General Organic Chemistry 87 Passage-2 When (C—H)c electrons are in conjugation to pi bond, this conjugation is known as hyperconjugation. For any compound to show hypereonjugation : (® Compound should have one sp?-hybridised carbon. Gi) a-carbon with respect to sp” should be sp? (iii) cz-carbon should contain at least one hydrogen atom. No. of a-carbon & stability of cation and alkene. 4, Which of following eations is hyperconjugation destabilized? 3 2 2 I Oh —CH, cH —FH (oC —F @ 1% ' cH; cH, 5. Which of following alkenes is most stabilized? CH (a) CH, =CH, @) Sc=cH : CH, . Bs © d) CHy—CH=C com K @) Cs \cHs 6. é wae of following alkyl benzene has maximum electron density? 5 HCH; : “O *O CH; HyC-—-CH—CH; HyC—C—CH; © @) Passage-3 Inan aromatic ring, a functional group with lone pair of electron exerts +M effect, some functional groups like, —NO, —NC —CH=CH, etc., can function both as electron donating (+M) or electron withdrawing (—M) groups. More extended conjugation provide more stabilization. 7. The most stable carboéation is : ° OOO OOO © @ OO (_» OO58 GRB Advanced Problems in Organic Chemistry tor JEE 8. The most stable resonating structure of compound ON- i i \ is: e e 8 y Ss (a) b-n-{_9-{_)-R-o (b) O-N: CS c) N—O e © ® ° . wrt OO8S whe Oe oe 9. The most stable resonating structure is : CH, CH, CH, Sy uo u*No a7 “o Passage-4 The process whereby a hydrogen atom attached to the a-carbon of carbonyl compound moves to the carbonyl oxygen atom is known as enolization or keto-enol tautomerism. Isomeric carbonyl and enol structure are tautomers. H . oO OH ALF cach w_let to~ 7 ‘\ 7 fearbonyl] Carbonyt Enol Normally, the carbonyl forni is favoured but structural factor marked affect Ky. 10. Which of the following compounds will not exhibit enolization? ° . ll () O-cwrts (b) CH; —-C—CH, ° ~ RC CH; ll G : (d) Ph—C—CH, © isc ‘CHs @ > 11. Arrange the following compounds in decreasing order of Ky : 9 9 i. li ll ll CH,—C—CH,—C—OEt CH, —C—CH,—C—CH;| (Py (Q) ® O° (a) P>Q>R>S (b+) S>Q>P>R (0) Q>R>P>S (d) S>P>R>OGeneral Organic Chemistry 59 12. Which of the following has least value of K;? Oo : 2. ® ) Ck 0 ° : ° ° Il ll © Cay —C—F—CH, (@) CH; —C—CH, —C—CH, ° Passage-5 ‘Under common reaction conditions, a carbocation rearranges to another carbocation of equal or greater stability. For example, secondary carbocation will rearrange to a tertiary carbocation. It will not rearrange to a less stable primary carbocation. This generalization is not absolute, and because there is not a high energy barrier to the rearrangement of carbocations, rearrangement to a less stable cation can, occur if it offers the chance to form a more stable product, ‘ 13. In which of the following cations rearrangement takes place? ° ° ar oY © om, @ te 14. In which of the following cations rearrangement takes place most rapidly? iH 4 |e | @ @ oO ) cin 6 Ch CH CH « CH @ 74% @ 15. In the following cation, H/CH, that is most likely to migrate to the positively charged carbon is : H H Loe | Hc! —’c— aha SCH OH H’ CH3 (a) CH; atC—4 (b) HatC—4. (©) CHy atC—2_ (d) HatC—2 Passage-6 Type of anions in which delocalisation of negative charge occur on more electronegative atom are highly stabilized. If negative charge delocalisation occur on same element then stability is decided by number of resonating structure. Cyclic anions60 GRB Advanced Probiems in Organic Chemistry for JEE which are aromatic are highly stabilized but if cyclic anions are antiaromatic, they are highly destabilise due to presence of unpaired electrons in antibonding molecular orbital. “ 16. Which of the following anions is highly stabilized? 6 CH, e (a) CH)»=CH—CH, (b) (©) CH 2° (@ CH. on © b—C_o — ° Ney > ™ CH 17. Whith of the following anions is most destabilized? oG eQ eH » Qy ‘ \ 18, Find out most stable anion among following anions : o. 9° ‘Ch e ® Cj © a © Q @ QO N 8 Passage-7 In a substance that are resonance hybrids, the measured length of given bond usually differs from that predicted from any one of the contributing structures. Chloroethylene is found by measurement to have a C—CI distance of 1.69A. This is shorter than C—Cl bond in such compounds a methyl chloride (1.77A), an indication that in chloroethylene the C—Cl bond has some double bond character. 19. Which of the following has shortest C—CI bond? (a) CH;—Cl (b) CH, =CH—Cl cl (c) CH, =CH—CH=CH—CI @ 20. Arrange the following in decreasing order of C—N bond length : CH,—NH, CH, =CH-NE, ¢\-na, x ¥ Zz (@) Z>Y¥>X = (b) ¥>Z>X | X>¥>Z | X>Z>¥General Organic Chemistry 61 21, Arrange following in increasing order of C—N bond length : NH NH os : OR oS CH,=NH — CHj—CH, NH, P : a (@) OH,0 () Et,P>Et, 8! B eo @ (©) 19 > Br? >cl? > Fo (d) OH>SH> SeH 23, Which of the following negatively charged species has maximum basic character? CH; e ° (a) CH30 () OPO CH, CH: © Scu-6 @ ¢\-8 CH’ 24, Amony, “he given pairs, in which first has lower nucleophilic character? 3 . e °e | e (a) CH, and CH,OH (6) CH,CH,0 and CH; —CH—O “ . . () Agi and CH —N—CH (a) PH, and NH, |62 GRB Advanced Probtems in Organic Chemistry for JEE Passage 9 Benzoic acid is more acidic than acetic acid, formic acid is more acidic than benzoic acid, among monosubstituted benzoic acid derivative, the ortho derivative is more acidic than meta and para substituted acid due to ortho effect, Acidity of an acid can be explained by the stability of conjugated base of acid. 25. Conjugated base of which compound will be most stable? NO, (@) CH,CH,—NO, (b) CH;-——CH— CH, (©) 0,N—CH,—NO, (@ NC—CH,—CN 26. Which °c of the following i: I most acidic? oO @ on hon © on An NO, 21. comer acidic stength of the flowing: ono g Fs (a) R>Q>P () P>oer () Q>P>R (d) P>R>O EXROSaee MATRIX MATCH TYPE Tl 1, Column (1) Column (I) CJ (a) H;C—CH, P. Resonance (b) Hy,C—CH, Q. Hyperconjugation © ofa R. +Teffect S. -Jeffect 2. Column (1) Column (II) ° (a) CH; —CH—CH, P. Pyramidal structure e (b) CH; Q. Planar geometry5 General Organic Chemistry (©) CH;—CH—CH, (@) Singlet carbene 3. Column (1) i (a) H}C—CH=CH—C—H @ ) pee DB @ (©) F—C—F (d) H,C—CH—CH, \o7 5. Column () Compounds Oo I (@) HyjC—C—CH,—C—OEt ° o- ll (b) Hyxe—C—CH, —C—CH, ° ° {I (©) H—C—CH,—C—H R. Electrophile 5. Nucleophile Column (11) P. Resonance Q. Hyperconjugation R. Inductive effect S. Non planar Column 1) P. Blectrophite Q. Ambident nucleophile R. Ambident substrate S. Electrophile as well as nucleophile Column (11) pK, values64 GRB Advanced Problems in Organic Chemistry for JEE 6. Column (1D) 2 Compounds or SS © CO N [.. | (@) % H Column (1) ° oA 2 of “O cH, | @ Hee CH; ‘Column (1) (a) NaHCO, will react. (b) Na will react with, . (©) NaOH will react with. (@) NaNH, will react with. Column (11) pK, values P. 13.60 Q, 6.21 R. 3.35 S. 8.80 Column (11) P. Hyperconjugation — Q. All carbon atoms are sp? -hybridized R. Aromatic S. Diamagnetic Column (U1) 2. Du ‘ =o °General Organic Chemistry 65 9. Column (1) Column (1) HAC. o® © . @ CoNSN Ay P. Free radical is formed HC : c=0 | co) CY “4, Q.N; will liberated () R—-N=N—R > R. Carbene will formed y 8 °N==NCI @ FPO. S. Nucleophilic aromatic substitution reaction GRC INTEGER ANSWER TYPE PROBLEMS || 1, Find out number of aromatic compounds or ion from following. OG ES o D> Ss 2. The purine hetrocycle occurs mainly in the structure of DNA. Identify number of ‘N? atoms having localised lone pair of electron. "OD A (Purine) ik 3. How many resonating structures are possible for the compound. t. | Q” furan) 4. Find out mimber of compounds which are more stabilise in ionic structure, from following. Ab b.04-0%3 OE“4 66 ‘GRB Advanced Problems in Organic Chemistry for JEE 5. Find out number of benzylic hydrogen in 6. How many alkenes, from followings are more stable than aa aa eS 7. Find out number of compounds which ate more acidic than benzoic acid, from following. COOH COOH, COOH COOH 90 Loven , oO , a) Hy NO, N(CH3)) CFs 8. Identify number of compound from following. Which liberate CO, on reaction with NaHCO, Oo ot O- on “Sf HO ‘0 ° ‘Si fl ll C—OH-0N: OH: CH;—C—OH-H;C—C==CH %. How many compounds from following exhibit d-orbital resonance. NHS PH, a-t-a » = : O > FACE d I PR > G—G—-a + Br—$—sr - 10. Among the following, find out number of ions or molecules that can show backbonding. de meteGeneral Organic Chemistry e7 . 2a? > 1S -N=c=s J ve by Sms Exercise-t : Only One Correct Answer 1d) 2) &@) 4.) 5. (b) 6 (b+) 7% @) Bc) 9% Cb) 10 Ga) 11. (@) 12. (a) 13. (@) 14 (by 15. (c) 16. (d) 37. (c) 1B.) 15. (@) 20. (0) 21 (b) 22, () 23. (c) 24 (©) 25. (a) 26. (c) 27. (a) 2B. (c) 29. (a) 30. (A); BL. (a) 33. (b) 33. (d) 34. (a) 35. () 36. (a) 37. (d) 3B. (b) 39, (Cc) 49. @); AL. (©) 42. (a) 43. (b) 44. (2) 45. (c) 46. (c) 47. (b) 48. (b) 49. (6) 1.@) 2@ 3@ 4@ 5@ 6) ZW BO) % © 10.0} 11. @) 12. ©) 3% ©) 14 (@) 15. (©) 16. (b) 1% (@) 28. ©) 19. @) 20, “4 2k. (6) 22. (b) 23, (c) 24..(d) 25. (a) 26. (d) 27. (b) 2B. (O) 29. (b) 30. (a BL. (b) 32, (a) 33. (a) 34. (c) 35. (a) 36. (a) 37. (b) 38. (d) 38. (@) 40. ()) G1. (>) 42. (©) 43. @) 44. (a) 45. (0) 46.) 47. (©) 4B. fc) 49. (b) 50. (0) 51. (2) 52. (6) 58. (©) 54. (8) 55. (@) 56.) $7. (@) 5B. (B) BB. (e) 60. (O), 61. (d) 62. (a) 63. (c) 64. (b) G5. (d) 66. (c) 67. (a) BB (c) 69. (a) 70. (4), FA. (db) 72. (€) 73. () 74. (6) 75. (@) 76. (d) 7% (A) 7B. (b) 79. () BO (c)) 81. (a) 82. (d) 83. (c) 84. (d) @5. (C) BE. (b) 87. (c) 8B. (d) BD. (a) 90. (b) ST. (c) 92 (b) 9B. (c) 94. (2) 98 (6) 96ES)WOFR(b), 9B. (d) 99. (c) 100. (a) 102. (a) 102. (b) 103. (d) 104, (c) 105. (2) E06. (b) 107. (c) 108. (c) 109, (¢) 110. (a) R12. (d) 122. (b) 143. (8) 124, (b) 225. (c) 126. (b) 117, (A) 118. (c) 129. (a) 120. (0), 22. (d) 122. (6) 123. (@)-124, (b) 125. (a) 126. (b) 127. (c) 128. (a) 129. (4) 120. (b) 32, (b) 132. (6) 133. (c) 234. (b) 135. (c) 236, (c) 137 (a) 138. (a) 139. (c) 140. (a) 1 (B) 142. (2) 143, (c) 244, (b) 145. (6) 146, (2) 147. (6) 148. (6) 149. (@) 150. (8), 151, (b) 352. (a) 253. (d) 254. (b) 155. (c) 156. (c) 157. (c) 188. (@) 159. (c) 160. (a) G1. (b) 162. (a) 183, (d) 164, (c) 165. (a) 166, (a) 167. (d) 168. (a) 169, (b) 170. al (72. (0) 172. (bo) 173. (a) 174. (b) 175. (a) 178. (b) 177. (b) 378. (c) 179. (a) 280. (a) 181. (c) 162, (2) 183, (@) 184. (b) 185. (c) 186, (b) 187 (c) 188. (c) 289. (d) 190. (a) 191, (d) 182. (b) 193. (b) 194 (c) 195. (b) 196. (2) 197. (6) 198. (b) 199. (6) 200. (b) 4. (c) 202, (d),203. (d) 208, (b) 205. (c),68 . GRB Advanced Problems In Orgartic. Chemistry for JEE Exercise-2 : More Than One Correct Answers 1. @b) 2 ed) 3 (ab) 4% (ae) 5b) (Oc) 7. 6,0) 8. (a,b,d) 9% (abc) 20. (acd) IL (ac) 12, (a,b, d) cd) 14 (be) 15. @d) 36 (bc) 1% (c,d) 18 (0) -}19.(0,b,c,d) 20. (ac) 21. (@€) 22. (6,4) 23. (a,d,4) 24. (@d) 25. (b.c,d) 26. (bd) 27. (a,b,d) 2B. (a,b) 29. (bed) 30. (6d) 31, (a,b,c) 32. (abd) 53. (@,b,d) 34. (bcd) 3f. (a,b) 36. (a,c) 37. (@,¢,d) 38. (ab) 32 (a,b,c) 4. (@,b) 41. b.c,d) 42 (a,b) 43. (ac) 44. (a,b) 45. (c,d) 46 (abd) 47. (bc) 48. (a,c, 4) 49. (a,b,c) 50. (b,¢,d) 57. (a,b,c) 52. (b,c) 53. (a,b,c) 54. {a,¢) 55.(2,b.¢.d) Exercise 3 : Linked Comprehension Type .. id) 2 3@ 44 5@ E€@ 7) 8B) Fc) 10. (c) UL. (b) 12. (6) 13.) 14. (@) 18.) 16. ©) 17. (b) 18. (@) 19. @) 20.) 2% (©) #6. (0) 77. @) Exercise-4 : Matrix Match Type 1. @) OR; ©) OR; (>P, OPS 2@70 ©) PS; (> Q, HOR 3. @ POR; OR PR: @+s 4 QP 0) 0 ©) S; OMAR 5. @70 ©) Ri ©) 8; M>P 6. @)> 9 OR 8; @3P 7. @> QRS; ©) ORS; © O.R,S: O7P,S 8. 4 P,0,8: O)>P.ORS — OFP.QRS: — (D-PLO,RS 9. @)> O.Ri MIR OP O79 OS _ Exercise-S : Integer Answer Type Problemslsomerism [EQGNGSS4) ONLY ONE CORRECT ANSWER I 1. Which of the following compounds is optically active ? i | (a) 1-Bromobutane (b) 2-Bromobutane i (©) 1-Bromo-2-methylpropane (4) 2-Bromo-2-methylpropane ; i CH; : 2. Which of the following operations on the Fischer formula af OH does not C)Hs change its absolute configuration ? : (a) Exchanging groups across the horizontal bond (b) Exchanging groups across the vertical bond (6) Exchanging groups across the horizontal bond and also across the vertieal bond (4) Exchanging a vertical and horizontal group 3. Which of the following compound shows optical isomerism ? | (@)CH,CH,CH, (b) CH,OHCHOHCH,OH (©) CH;CHOHC,H, (4) CCIE, 4, Total number of stereoisomers of the compound 2, 4-dichloroheptane are : ; @2 (b)3 ©4 6 5. The structure of (S)-2- chtorobutane is best represented by : a | ch i (@) CH,CHCH,CH, | oN | 'CH,CH3 | H, oH | © —cl @o-tn we” CH,CH | » ‘CH,CH3 a3 | 6. Which one of the following is chiral ? (a) 1, 1-Dibromo-I-chloropropane _(b) 1, 3-Dibromo-1-chloropropane (c) 1, 1-Dibromo-3-chloropropane —_(d) 1, 3-Dibromo-2-chloropropane a a . — 470 GRB Advanced Problems In Organic Chemistry for JEE | 7. What is the maximum number of stereoisomers that could exist for the compound below ? a oa a cl (a6 )8 () 10 (d) 16 8. Which of the following compound are meso forms ? CH, CH, CHa : OH Hcl | OH CiI4-H : CH,CH; CH; CH, \ 1 2 3 (a) J only (b) 3 only (©) land 2 (d)2and3 9, Among the structures shown below, which has the lowest potential energy ? oLLt ord or? oC 10, Assign double bond configurations to the following : CHO NC ‘CH,OH H,N—H,C CN @E )Z ©)EE ZZ 11. Among the following, the most stable isomer is : [pT ome L=T>ome OMe | HO HH HH . © OH @) 12. Which of the following molecules have non-zero dipole moments ? (1) Gauche conformation of 1, 2-dibromocthane (11) Anti conformation of I, 2-dibromoethane (QM) Trans-1, 4-dibromocyclohexane (IV) Cis-1, 4-dibromocyclohexane 1 (V) Tetrabromomethane ' (V1) Dibromocyclohexane (a) land Ii (b) land IV (©)DandIv (I, [Vand VIIsomerism 71 13, An aqueous solution containing compounds A and B shows optical activity. A and Bare stereoisomers. Which of the following possibilities cannot be correct ? (a) A has two centers, but B does not liave any because it has a symmetry plane. (b) A and B are enatiomers. (c) A and B are distereomers. (d) A and B are not present in equal amounts. 14, How many stereogenic centres does it contain ? XB } (@)1 (b)2 ©3 @4 15. The molecular formula of diphenylmethane, c#{O)i Cita How many structural isomers are possible when one of the hydrogen in replaced by a chlorine atom ? (a6 (b)4 8 @7 16. Which is the correct structure of D-glyceraldehyde ? CHO H @ xt-on () no—-cHo CH,OH CH,OH CH,OH ©) no--H (d) All CHO 17. Total number of isomers for the molecule, CH .DClis : (3 (b)4 6 (a8 18. Which is the metamer of the compound P ? P= ‘OMe CH; @ OMe () uc—{_\—ove72 GRB Advanced Problems in Organic Chemistry for JEE 19, if degree of unsaturation is three, then a compound shows : (a) one triple bond and one double bond (b) one double bond and two rings (©) one ring and two double bonds (d) all of these are correct 20. Geometrical isomerism is possible in : . of] oC) of] oC a. we and aX Xa H H He {a) Identical (b) Diasteromers — (c) Conformers (d) Homologs 22. Which of the following is correct set of physical properties of the geometrical isomers ? 1 ROH ; se : - = an = Ww Ng Ww Na 1 Bit Dipole Boiling point Melting point —_‘Stability (a) I> ro >t Tell (b) >I >t W>T MI (@I>u I> I> I> (@)I>1 We. I> I> 23. Which of the following statements is true ? (a) A mixture of enantiomers can be separated on the basis of difference in their boiling points (by a method called fractional distillation). (b) A mixture of enantiomers can be separated on the basis of difference in their solubility in any solvent (©) A mixture of enantiomers can be separated by converting them into diastereomers by reacting them with an optically active reagent (@) A mixture of enantiomers can be separated by passing plane polarised ~~ through their solution 24, Compound t u is projection formula of : _ @Cyclohexane (6) Cyclopentane (c) Cyclobutane (4) Cyclopropane 25, Which of the following compounds may not exist as enantiomers ? (a)CH,CH(OH)CO,H (b) CH,CH,CH(CH; )CH,OH (©) CgH,CH,CH, (©) CH CHCICH,Isomerism : 73 26. Outs oft the following which are chiral ? BCL HC, 1 ® ay CH; CH; H,¢, CH: 3 oN 3 ay A ay) , HC’ "CH, HC ‘CH, - @1L1,m (b) I, HIV () I, Ut (@ Il, HIV .27, Identify number of chiral carbons in the following compounds. H oH i) HjC—CH—CH—CH, mo “2 HH OH OH cad ou (un H,C—CH— CH CH, — CH Hy CH; (@)1,2,1 (b) 1,1,2 (c)2,0,1 @2,1,1 28. Which of the following compounds are optically active ? {a) CH, -CHOH-CH, -CHy (b) HyC=CH-CH, -CH=CH, . Cl ‘ @* Nexcac’ ow Nu 29. Which of the following combinations amongst the four Fischer Projections represen the same absolute configurations ? . . 1H a uLon (iy H- CH=CH, CH=CH, CH=CH, H an ujc—-on cwpHo—t-cu=cH, H CHs . (a) If and HI (b) Pand TH (c) Land IV (d) I] and IV -74 GRB Advanced Problems In Organic Chemistry for JEE CH; H-—Cl 30. HO—H Gols The compound with the above configuration is called : (a) (2S, 3S)-2-chloro-3-hydroxypentane (b) (28, 3R)-2-chloro-3-hydroxypentane -chloro-3-hydroxypentane (a) QR, 38)-2-chloro-3-hydroxypentane 31. Select the correct statements. (a) Eclipsed and staggered ethanes give different products ‘on reaction with chlorine in presence of light. (b) The conformational isomers can be isolated at room temperature. (c) Torsional strain in ethane is minimum at dihedral angles 60°, 180° and 300°. (d) Steric strain is minimum in staggered gauche form of n- butane. 32. Which of the following statements regarding the projections shown below is true ? . CH: Hy vl a H’ “CH; it cl cl” ‘cH, H A) @) (a) ‘4’ and ‘B” both represent the same configuration (b) Both ‘4’ and ‘B’ are optically active (©) ‘B alone is optically active (@) ‘4’ alone is optically active 33. The Newman projection formula of most stable conformation of 3-Hydroxypropanal is gauche. It is stable due to : (a) minimum torsional strain (b) intramolecular hydrogen bonding (©) minimum torsional strain and intramolecular hydrogen bonding (@ minimum steric strain, 34. The following two compounds are : (a) ideritical (b) conformational isomers (©) geometrical isomers (@) structural isomerstsomerism 5 35. Among the following, the optically inactive compound is : (CCH, TO ) "TS HC ( \ Ph a Neec= © —Yo=c=cC @ HAC ‘Br H. ‘COOH 36. The following pair of compounds are best described as CH; CH; t Qe CH; CH; (a) identical (b) diastereomers (©) enantiomers (d) none of these 37. A natural occurring substance has the constitution shown below. How many isomers may have this constitution? = / QO * “ HO’ ‘CH==CHCH= CHCH;CH;CH; (a2 (b)8 (©) 16 (d) 64 38. Which of the following will not show optical isomerism as well as geometrical isomerism ? HAC. Hy CH; CH, (@) () _ H ‘CH BC, Hy H: CH; CH; () = @ = H ‘CH; Hy Hs 39, Which of the following have the same value of optical rotation ?76 GRB Advanced Problems in Organic Chemistry for JEE Me a @H be : Det spa . : Et Me : al cl (il) Me pH . ay apn . Et CH,CH,CH, @ LIV (b) 1,1 (c) I, 1V @ Lu . 40. The correct decreasing priority of ligands —NO,,—C==N, NH, and —CH,NH, in absolute configuration of an enantiomer is : (a) NO, >NH, >C=#N>CH,NH, (b) NO, >C==N>NH, >CH,NH, (©) NH; >NO, >C==N>CH,NH, (d) NH; > NO, >CH,NH, >C=N 41. The two compounds which given below are : : D D HBr I~ H-y+—-Cl D- H Br (a) enantiomers (b) identical (c) optically inactive (@) diastereomers 42. The compound which has maximum number of chiral centres is: Cl OH Hi Cl OK (@) @: cl 43, Identify number of chiral carbons in the following compounds. oT mor mer) ay) (@) 0, 2, 2,4 (b) 2, 2,0,4 (1,224 (d)2,2,2,4 44. Which of the following statements is/are correct ? . (a) A meso compound has chiral centres but exhibits no optical activity (b) A meso compound has no chiral centres and thus are optically inactivetsomerism 7 () A meso compound has molecules which are superimposable on their mirror images even though they contain chiral centres. (a) A meso compound is optically inactive because the rotation caused by any molecule is cancelled by an equal and opposite rotation caused by another molecule that is the mirror image of the first. 45. Which of the following will not show optical isomerism ? (@)CI—CH=C=CH—Cl (b) Br-—CH=C=CH— Br coon cow ton H——OH (©) @ H—-{-0H » Me cl COOH Me , 46. What is the full name of the following compound’? CHs HO: H a GHs. (a) (2R,3R)—3—chloro—2—pentanol (b) (2R,35)—3—chloro—2— pentanol (©) Q5,3R)—3—chloro—2— pentanol (@) (25,35) —3—chloro—2— pentanol 47. Which type of symmetry is present in the following molecule ? ca cl i: (@) Plane of symmetry (&) Centre of symmetry (c) Both ofthese. (d) None ait ae ae H, with Dand Hy with yy a. b- wns itwix stoi «) CoHs Relaticn between (X) and (Y) is : (a) enantiomers (b) distereomers . (c) Eand Z isomer (d) constitutional isomer 49. Among the following, the Newmann projections of meso-2, 3-butanediol are : Me Me H. OH Ht OH (@) b) HO H be ‘OH Me Me78 GRB Advanced Problems in Organic Chemistry for JEE Me Me HO. | Me Me H (d) 0 ‘H @ a, H OH (@ P,Q QO) PR © RS @OOQs 50. Which of the following compounds is most stable ? oT of7 ofp oT 1. Compounds having the same number of atoms of the same elements but differ “ only in the arrangement of the atoms are called : (a) isobars (b) isosters (c) homomers “” (d) isomers 2. How many alkenes are possible with molecular formula C,H? {a} 2 (b) 3 (©) 4 @6 3. Total number of isomers having molecular formula C,H, : (a) 2 (b) 3 ©) 4 @ 6 4. The number of isomers possible with molecular formula C>H,Cl; is : fa) 2 (b) 3 (4 (d) 6 5. Which of the following pairs of compounds are not position isomers? (Non ana AY OF wy LA and Xv COOH COOH A008 and) ® CS and C j 6. Which of the following pairs of compounds are > Keeton isomers? ody and on woo and OH OK oO ° #2 am and ve og Ke ad YO 00 oO 7. Which of the following compounds is isomeric with methyl vinyl ether? (a) Propanal (b) L-propanol {c) Ethyl methyl ether (d) Ether 8.2-butyne and 1, 3-butadiene are : (@) chain isomer (b) position isomer (c) functional isomer (d) tautomerstsomerism 79 9. Compound which is not isomeric with diethyl ether is: (a) methyl-n-propyl ether (b) |-butanol (©) 2-methyl-2-propanol (4) butanone 10. Which of the following pairs of compounds may be regarded both as functional isomer and position isomer? (a) Benzyl alcohol and methoxy benzene (b) o-cresol and p-cresol (c) Benzyl alcohol and o-cresol (@) Benzyl alcohol and benzyl methyl ether 11 Which of the following compounds can exhibit enantiomerism? {a) 3-hydroxy propanoic acid (b) 3-hydroxy butanoic acid (©) 4-hydroxy butanoic acid (@) none of these 12. The functional isomers of ethers are : (@) ketone (b) aldehyde (©) alcohols (@) esters 13. Which of the following conformations of n-butane is least stable? (@) Gauche (b) Anti (©) Eclipsed (4) Fully eclipsed 14. Total number of conformation of ethane is : (@) 2 (b) 3 @4 (d) Infinite 15. Which of the following conformations of butane is most stable? (a) Skew (b) Anti (©) Gauche (d) Eclipsed 16.Maleic acid and fumaric acid are : (2) position isomer ~ (b) geometrical isomer (©) enantiomers (@) functional isomer 17. Which of the following is a chiral molecule? (a) 1-chloro propane (b) 2-chloro propane (©) 1-chloro butane (8) 2-chloro butane 18. Which of the following molecules has 4 meso stereoisomer? ca Br | | (a) CH; —CH—CH, — CH— CH, (b) trans-2-hexene © CHy—FH— Ol, CHa CH a (@ Ch3CH, (a —FH—CHLCH a a 19. The number of meso form of the given compound is : Cy — CH CHF CH, OH OH OH (@) 2 @) 3 4 @) 8ee 180 GRB Advanced Problems in Organle Chemistry for JEE 20. Number of stereo center and stereoisomer of the given compound : amo) 78 . tyd-t (et CH3 torts Fequrqtelydiont (0) . st OH lom.qorg: Slgtiern-$ (9) fanoromi 8 diet Saat od to ameg ariwolfor oft to doit at ae! anisieng his 1mod (@) Land 2 orrasis 0),2 and 4 ns fontoste. Fysaofl (Lp (©) 3and 8 (@) 3and 6 na. bis fovaro (A) ” 21. Find out relation between I and II: furs bits forioali Iyyao8t ty CH ts trem Ivan Cust lodouln besto€t (0) Seen py atin | ns dide ‘ent | ores H Sod) to dy'W UE bros sonstoa geet ott (an brat fiiemeqar: yowed-E (a). saa] on 0) va] orem OF rronbyd- (2) H OH :HOsazpesacH lenontogut oT $16, stoyyble (ay anos (6) | ayes (bY dlodoots ay . fst re tran ed sausdudn Yo enor Ht ato Hod (a) en: ” “ bse'(c)‘homomers baeqiaa (2) (@ stfichual isomers 242uti) (8) 22, Total number of stereoisomer of give conipotid all be 7 edu ot " Waldo SED SAC CHSC CH Savwollot aifWo dou AL boeqila! (L) ove lo gy uaa td wok? (65 , Sr pion onemil bea vgs atolch’ BF @ 2 pour thO Asien a © 6 wane) Beoq ds! 23. The given pair is :1 etrangavt bs agenotinen (a) - BE stysalont lauds BY, garvoltcl oft to dod’ TT entqong owls. 6 dy oeqesq ovolda-E (1) cnatud (7A and NS cnolda-t (ah sro C2Hs CHS 9 4 a2 est sion Cl sottot adt'to dard Wm. {a) enantiomers (b) homomers + (©) constitutional isomer (@ diastereomers “| : mo, 24, The given pair are : HD HD = HY HOH (8) . : Br Br gasvad-S-unerm qh) Ly + HOLS HDHD (2) CHCl CICH;CH SCH; CiHs . {a) enantiomers £(b) diastereomers’) tH'2,-19 (b) (©) homomers . (4) constitutional isomer + . stereoisomers of th nd 25. Number of iS Gre nO oD te art ocan todmen ATL HOW] H- 1 AD (CH; —CH=+CH—CH—CA; i @2 yy o4, iO oa 6 S tertsomerism 81 26. Which one of the following statements regarding the projection shown below is correct? i cl Ph’ cl cl oie Pho yy Ph 1 1 (a) Both the projections represent the same configuration (b) Both (1) and (Il) are optically active (©) Only (1) is optically active (d) Only (11) is optically active 27: Which of the following is erythro form and optically inactive? cool : CH @ Ho—|—a () H—{—on HO—}—H Br—|— CH; CH CH3 CH3 u—{— br no—|—x ‘ © yt © y—f-er CH CH; 28. Which of the following would exhibit cis-irans isomerism? (a) CH,CH,CH—=CH, (b) CICH=CHCI (c) CICH=CCl, (d) CH,=CH—COOH 29. Which one of the following compounds does not show tautomerism? 3 (@) CH,CH,NO, () CH; —-C—N=O : cH, ’ IL Il () CH; —NH—C—CH, (a) CHs—C— Ge —C-0C;Hs CH, 30. The structures A and B represent : _ COOH COOH H OH = CHy oH HO: CH; HO- H COOH COOH @ (8) (a) enantiomers (b) diastereomers (g) homomers @) racemic mixture [-82 GRB Advanced Problems in Organic Chemistry for JEE 31. The compound has : , Br F CH; HC iF Br (@) plane of symmetry (b) axis of symmetry (©) center of symmetry @ no symmetry 32. Which of the following compounds is chiral? Hod HCl HO Br CL Br (a) (b) © (©) cS @ A Yr. 33. Which of the following dienes is chiral? (a) CH, — (b) CH; -CH=CH—CH=CH, (©) CHy— (d) CH, =CH—CH,—CH=CH, 34. The simplest alcohol that can exhibit enantosnevism ¢ (@) I-propanol (6) 2-butanol_——(c) 2-propanol__—_ (4) I-butanol 35, The following structures represent a pair of : : ; CH cl nfo mo CHy Br (a) enantiomers (b): diastereomers (©) meso compound (@) homomers 36. Tautomerism is not exhibited by : j (ay (\--c-cron ) oo © oO : @ ° 37. The two compounds may be conor as: iT PR “| CHy—-C—C—CH, and CH=CH —C—CH,CH, : CHa,isomerism 83 (a) position isomer : (b) chain isomer (c) stereoisomer (4) tautomer 38. Which of the following pairs of compounds is a ring-chain isomer? © (a) CH;—CH—CH—CH; and OH OH o ‘OH CHCl Cl oF = Of CH, (©) CHy)=CH—CH,—OH and [>-on : ? ® x. and [>—cu,cH, 39. The most stable enolic form of 2, 4-pentanedione is : mR en (a) CH, =CH—CH,—C—CH, (6) CH, —C=CH—C—CH, (4 CH, = GACH CH (@) CH;—C=C=C—CH, OH OH . OH ‘OH 40. Which ofthe following compounds can exhibit tautomerism? (a) CgH,CHO (b) CgH;—C—CMe, “oO 9 ° ll I : (©) CH; —C—CH, —C—H (d) CoHs—C—C,H 41. Among the following compounds, the one which will not: show keto-enol tautomerism is : wy SX wo dey 6s 42. Which of the following pies oteructures does not represent tautomers? @ and ‘CHO HOH oO 9 ‘OH id . H~ ~OH 0 :84 GRB Advanced Problems in Organic Chemistry for JEE 0D “—€ his (b) H—+—-OH HO OH Me Ht »OH Br H © HC CH @ AY Hf H Hw Br 56. Compound X can exist in how many orientations? GH CH,CH, X= H-C—CH=C | CH; oH (a1 (b) 2 (©) 3 @4isomerism 97 57. Which of the following will not have any stereoisomer? cl I q / (@) Ye =c &) cr 59. Which of the following structures represent meso compound? Br H OH H Me a “2 Bt “ OH ® we ©) c ©) a) “CH, Metin, a u ace 60. How are the following compolunds related? CH; HSC, Br See Seen < Br”. HY Br uf CH (a) Diastereomers (b) Enantiomers (c) Meso form (4) Identical 61, Which of the following pairs of compounds is a pair of enantiomers? “ye "SE98 GRB Advanced Problems in Organic Chemistry for JEE 62. Which of the following compounds are meso forms? CH; CH; CH; H—\—oHn H1~ci HOH cL 1-H GHs cH; CH; ay @ °% : (a) Lonly () 3 only (©) Land 2 (@) 2and 3 63. How many isomers are possible for the following molecule? i. ‘CH—CH=CHCOOH CHS : @1- (b) 2 © 3 @4 64, What are the correct designations for the structure below? (a) BE 0) Z,£ yy ‘COOH, (c) E,Z (@) No stereoisomerism is possible 65. The following compounds differ in respect of : HO ONO HOM” ON a OF HO OH | HOM on OH “OH (a) their chemical and physical properties (b) the direction in which they rotate plane of polarized light (6) their interaction with molecule @) all are correct 66, How many structural isomers are possible when one of the hydrogen in compound given below is replaced by chlorine atom? CHy @ 6 (b) 4 (8 @7 67. Assign double bond configuration to the following : : “COOH OH on CHy H)N—Hy CN: @ Ez (be) Z (c) E,Z (d) ZZIsomerism > : 99 68. Whieh ofthe following pairs dre = isomers? BCL 5 ee \ @ C=C=C=C. and =C=C= Pa - a oe BGC. CH; BGC. H ~ ) ‘pec=c% and eed H a NH ‘H ‘CH; (c) Both (a),and (b) : (d) ‘None of the above : ‘ 69. The configuration of 1 and 2 carbon atom in the following compounds is : “YQ mQ cl. ‘ey @, aR, 2k (b) 1s, 8 (c) 1R, 28 (d) 18, 2R 170 T H GN we: . EN: and |\/ pg? Me = Cl (a) dand lisomer (b) cis and trans isomer (©) functional isomer (@), position isomer 71. Bh of the following conformers’ of 1, 2-diol cannot form intramolecular TSE 72. Which oft following compounds does not haves any geometrical isomer? cl (a) &) cl oC a i el . © @ Jf : a cr . 73.1f a mixture of 2-bromobutane has’ enantiomeric excess of 50% of (+)-2-bromobutane, the stereoisomeric composition of the mixture with respect to (+) and (-) enantiomer respectively is = (a) 75% (+) and 25% (-) (b) 70% (+) and 30% (-) {c) 80% (+) and 20% (-) (@) 25% (+) and 75% (-)100 GRB Advanced Problems in Organic Chemistry for JEE 74, The following compounds ¢ differ in : axe o cr (@) configuration (b) conformation (c) structure (a) chirality 75. How many-stereomers are possible for following molecule? cl —\_ pe (a) 4 (b) 8 (c) 12 (d) 16 ‘6. Which of the following molecules have dipole n moment? a Nox cmc( “a yo ay F “ ® 6 ) © (@) AandD (b) BandC (© CandE (@) BandE 77. Which of the following molecules is expected to rotate the plane polarized light? ° : OH * 1 CH: @ Sy / ®) cK © CX oly” a ‘OH 78. Which of the following is the enantiomer of the compound shown below? H = oi r est Me—{—pr : Br—t—H Me—j—oH Et Me H H—}+— Br Me—{—Br @ -q—|~p5, () y—t+—Br Me—|— OH Et H Br—l——Me @ w—sr Et —}—"Me 79. Geometrical isomerism is possible in : Ca © '@) © OC @ Caisomerism =a DO (a) enantiomers (©), conformers 101 (b) diastereomers (a) homologous 81. Which of the following compounds will be optically active? aad ° a we Br pe GAs ) . HyC—-N—G3Hy F F @ “oo CH a——}—cl 82. If optical rotation produced by¢j__| yy is 36° then that produced by a. H——CH; . CH; c—;—H_ CH (a) -36° (b) 0° (©) +26° (a) Unpredictable Me Me (a) conformational isomers (c) constitutional isomers CH: “a bey ' mo @) contrmaional isomers (©) constitutional isomers 85. (a) position isomers: (c) functional isomers H Me. Me Me H 83. Bt and are: M Me Me“ | NH H (b) configurational isomers (@) identical (b) stereoisomers (d) identical 5- 5... "So ~ (b) chain isomers (@) metamers102: . GRB Advanced Problems in Organic Chemistry for JEE V | 86. CH;—Cl and CH;—CH—O—S. are: Br O CH ‘CH; Pci, Hs (a) functional group isomers _ (b) metamerism (c) optical isomerism (@). geometrical isomerism ON ox " Ce : C3 H CH HY “CH; HY “cH, I Ir ll Which among these are stereoisomers? . (a) Land It (b) Tand HI (©) Wand - — (@) all of these 0 ‘ OLX . ‘Which among these can exhibit tautomerism? . @) Tonk (&) Tonly (©) and I (@ Wand WI \H H 89. = + wo ro) ® Stability order among these tautomer is : @X>¥>Z _WY>X>Z (©) Z>X>Y¥ @) YSZ>X ( ° 9 0 90. : ‘ ° T Ht ati) Among these compounds, the order of enol content should be : (a) >>I @)I>H>M ©) M>n>l = @ I>m>n ede dei Which of these compounds wilt exhibit geometrical isomerism? @I ‘ (b) (© ur (d) None of theseIsomerism 103 92. v Cy © o Oo ° 1 un a ‘Among these compounds the order of enol content should be : @ 1>0>1 (b) > 1>1 (©) W>i>m °@ > I> 1 93. Which ofthe following conformers of n-butane has torsional strain? ith / ia ! he Ba (@) Both (b) and (c) CH H 94, Which one me of the following is most petened conformation of 1, 2-dimethyl cyclohexane? CH; . . a) — © rh CH; CBs CH; : ©) : (@) Allare correct 95. Which one of the ee is the most stabilised conformer of 1, 4-cyclohexane diol? OH OH ” DM 4-0 io ao “ OH 96. Which of the following compounds is optically active? CHs CH, u—_+—al Hota by BT @ y+ © y+ —cH, CH; . ca104 GRB Advanced Problems in Organic Chemistry for JEE CH; H H a ct—}—cu, © neo § Cr at cH, 0. 97. Which of the following is Homomer of ofa 2 cH oa HC cl @ Vo A © Ls @ xy 98. Which one of the following structures is puciyenidet ie? ‘CHO CHO @) H- OH ©) He H CHLOH CHOW Ou CH,OH © wone—| —n @ fon CHO cHo 99. Which of the following compounds does not contain the plane of symmetry? ci a cl “Cd cl HCH; 4 @ ©) © ™ @ a ct 100. How many chiral centers are present in tetracycline? yes HOH H Ncw; j ;—-OH x fon o FF 6 (a) 6 4 8 @) 5 101. How many chiral centers are present in-cholesterol? (@7 @ 5isomerism . 105 102. Which of the following is the most stabilised conformer of @ oF 103. yn X, Compound ¥ is projection formula of : (a) zs ) ro () CO @) CO H OH HO. H H—+-OH 0 HOH 104. HO--H | 4 HOH |! Hon Hon # H “CH,OH CH,OH (@) diastereomers (®) enantiomers (©) tautomers (4) conformers 105. Which of the following is the least stable conformer of cyclohéxane? oy Lt oS (Chair) (Twist boat) “Half chair) 106. Which of the following pairs is wi eomecy matched? {a) CHy—CH=C=CH;; optically active COOH ) XK s optically active106 GRB Advanced Problems in Organic Chemistry for JEE CH ; Optically active cl COOH NO; : 107, Which of the following nomenclatures can be used for given conformation? COOH H—+—Br H—;——0H , CH,OH (a) Only D, L (b) Only erythro, threo (c) D/L, Erythro/threo (d) DIL, RS, Erythro/threo 108. Find out relationship between following two compounds Me “COOMe . (@)Enantiomer _(b) Homomer (c) Diastereomer (d) None of these 108. Kdentifycorest 2-D representation of following molecule. CHO HO! : OH OH . CHO cHO CHO. - CHO HO. H. 4H OH oH OH H OH @ H OH ‘(b) HO: H ()H OH (a) HO H H—}—0H H OH H OH HO. H CH,OH CH,OH CH,OH CH,OH 4120- dentify the molecule which is meso. . H (b) Hooc® ‘COOH CHO @H — OH CH,OHIsomerism 107 111, Find outmost stabilise conformer of a molecule. ® aR et © - 4 112, Identify stabilise chain conformer of. following molecule. Me, . on ‘isopropyl . (by Me OH () , @ None of these Mé ‘ “ome Me ‘OMe Ph Me 114. Find out correct representation of trana-decaine “Ny108 GRB Advanced Problems in Organic Chemistry for JEE ° LPT © (d) None of these 115. Calculate no. of stereogenic center in following molecule. 8 (b)7 (©) 10 @9 116. Assign the configuration of C-2 and C-4 of following molecule. H, HH OH ou ¥ CHO @SR @)R,R OS (@)R,S 117. Identify the relationship between following molecules. Y, Br, 1, Br H, OW % %n, a, “ny on n and 4, (a) Enantiomer - (b)Diastereomer (c)Homomer (4) Both are meso 118. How are the following two compounds related? aa and mex @) Enantiomer (by Diastereomer (©) Homomer (@) Racemic mixture 119. Find out enantiomeric structure of following compound : Pho COOH ‘oO ® oN ® om PhS ‘COOH . Phi OOH Ph, COOH Ph, COOH © Sr @ %——f 0Isomerism 109 120. Find out no. of sterogenic center in following compound : NH, y ome of! S. HO . COOH - @) 4 (b) 5 © 3 d) 6 121. How are the following two compounds-are related? H CH; Be Jesichon Hotkcm HT CHs Br (a) Constitutional isomer (b) Diastereomer (c) Enantiomer (d) Homomer 122. Choose incorrect statement regarding following compounds : ~ and Hy 7CH Hc {a) The boiling point of both compounds are same (b) Both are optically active (c) Equal mixture of both compounds are optically inactive (@) Both are diastereomers 123, Which of the following is not diastereomeric structure of given compound? CH; - . CH,CH, Hin} H ‘CHy Bri Br CH, /iaCis CH,CH. CHs ©) pru%)—Km © ww>—&, pen neg ean Br CH,CH, BH () wey aad (d) None of these 124, Identify the set of compounds which are enantiomers ? H H110 GRB Advanced Problems In Organic Chemistry for JEE BH HO, Sm SE ae HAC” yy Son HC” yy MOH oan COOH hoy ( WL * nC HO “a 125, Which ofthe following molecule have (2R, 3-Z) configuration? (©) we HG om cc —CHy ® ’ no” ‘HH. H H. © a @ ne no [pcatelsised MORE THAN ONE CORRECT ANSWERS HL 1. Select ‘cis’ isomer among the following : c a “ o( Ex Cte © CEs «OSs 2. For which of the.following pairs of compounds are the correct notations given? (a) PR PB and Ph N=N N= ™, igiazotenzne Syn szobenont HC, OH o and My ? ~ OHH ‘Syn-acetaldoxime Anti-acetaldoxime . ot iC. CH,CH,CH: CIH,C- CH: is — oe 2CH:CH; BO og BrCHy Z-isomer E-isomer H COOH H, H @ cace and cacy coon ‘NHp NH, Trans-o-amino cinnamic Cis-o-amino cinnamic acid : acidIsomerism 111 3. Which of the following compounds will exhibit geometrical isomerism? (a) CH; -CH=CH—COOH (b) Br—CH=CH—Br 9 (©) CsH;—CH=N—OH @ 4, Which hf ie following compounds exhibit optical isomerism? NO, @ ~ A}6 (0) HyC=C=CH, (d) ne cif CH 5, Which of the following represents a pair of enantiomers? HOOC H H COOH (a) a) &) “— H cooH HOOC . H H HOOC boon (©) YN @ | HOOC COOH H H 6. Which of the following represent correct matching? II I (a) CH; —C—OH and H—C—OCH, Metamers (b) CH; CH, —C=CH and CH;—C==C—CH, _ Position isomers (c) CH,CH,CH,NH, and CH, —TH—tH, Tautomers NH, (@) CH;CH,OH and (CH; ),0 Functional isomers 7. Which cf the following cycloatkanes will show cis-trans isomerism? CH; CH; HC. CH; 0) ) Ker © J @ Ky HC12 GRB Advanced Problems In Organic Chemistry for JEE 8. Which of the following are correctly matched? Compounds Number of geometrical isomers (a) CH; —CH==CH—CH= CH—Ph 4 (b) CH; —(CH=CH),—CH, 2 (©) H,C=CH—CH=CH, 10 (@) HjC—(CH=CH),—CH, 20 9. Which of the following will have a frans isomer? Hy H cl cl @) Some ) | >o=c H < H < H HAC, CH © * Yo=cg @ H H . H3C CH; 10. Which of the following is chiral? cH; | HC. (@) CHs—P=O @) | >s=0 | Ph CoH : CH; | HAC. (©) CH; —N® —H @ "Ss—0 | IC Hs i 11. Which of the following compounds show tautomerism? ° s (a) NH,—C—NH), (b) NH, —C—NH, 0. Il (c) CH; —C—CH, @ wo \-n~o 12. Keto-enol tautomerism is observed in : oO (a) C,H; —C—H (0) CsH;—C—CH, °O 0 oO ll iI (©) Ph—C—Ph (@) Ph—C—CH, —C—CH,tsomerism 113 13. Tautomerism is exhibited by : (@) € \-ci-cr—on () o_o ©) cre d) Cy ° oO 14, Cis-2-butene and trans-2-butene are : © (a) geometrical isomers (b) diastereomers (©) enantiomers (@) position isomers 15, Which of the following can exist in syn and anti form? (a) Ph-——N=N—OH (b) Ph—N—=N—Ph (c) Ph—CH =N—OH (d) Ph,C=N—OH 16. The Z-isomers among the following are : HC, H H3C. H ch Br cl Br \e7 \e/ \c7 Ne’ @ i] (b) ll © i @® | IN, LN, LN, LN, HC; GH; Ws, GH, HH: F F 4H 17. Which of the following statements are correct about tautomers? {a) They possess different electronic and atomic rearrangement (b) They possess different electronic but same atomic arrangement (c) They have different atomic arrangement but same electronic arrangement (@) They exist in equilibrium 18, Which of the following compounds would be optically inactive? (@ 1,c=c—cH, ©) »{O)-{O)-F CHs H--—}—OH (d) © o,—t—a . OH . 19. In which of the following the enol form is dominant over keto form? . Oo Oo oO (@) Ch () Ct ©) OO) @ ¥% OD , ° H NH114 GRB Advanced Problems in Organic Chemistry for JEE 20. Which of the following are optically active? a Cs HC H @ ~ >c=c=c=c=¢ ® xO*« w Si H CH HC ‘CH3 © Clls—CH—COO @ poemeneneK D 21. Which of the following compounds do not have the plane of symmetry? of Jo of J"* © co @ om v oY a c a cl 22. Which of the following are optically active? 10H Br Br © non ) WW’ CH, ‘0 H3C. pa CH3 (Cc) (d) Cc=C= © Ho” H CH; . 23..Which of the following are identical molecules? cooH COocH, u—t—on u—t— on ©y—|_on © y—1— on coocH; COOH : COOCH; H HO: H 4% COOH © Ho. H © ycooc H coon ou 24, Which of the following are identical molecules? H.O.H xc ,0. CH; CH; CH, HC ,O. H z wo ZN o Zoho LA i CH; CH; H H H O H H CH;Isomerism 115 25. Which of the following compounds can have superimposable mirror image? CHs CH, H—-+—OH H———-OH (a) HOH. (b) HO——H H—}—OH H—+—OH CH; CH CH CH; H—|}—H © H—;—— 0H (©Br—}—H (@) HO——H H—}—OH HO-——}—H CHy CH; CH CH; CH; CH; 6H OH HO HH OH HO H H OH HO H HO H H OH Cos Cos Hs GH; | I i i Iv Which of the following statements are true about these isomers? (a) Land II are a pair of enantiomers (b) HL and IV are a pair of enantiomers (©) Tis the diastereomer of Il and IV (d) and III are homomers oO 0 OH HH H aL 7 \ ? | | “A HH HO oO oH I Ir I Iv Which of the following statements are correct about these molecules? @) Lis ameso compound (b) Land TI are identical (6) Wand IV are a pair of enantiomers (d) IL and Il are diastereomers 28, Which of the following compounds are optically inactive but exhibit geometrical isomerism? CHMe | CH—Me me & Clay CHy C =C=C=C a Sc—c=c Oy H OW < cu :116 “GRB Advanced Problems in Organic Chemistry for JEE 29, Magnitude of specific rotation of a compound is independent of : (a) solvent (b) concentration (c) length of tube (d) temperature 30. Enantiomers have: . (a) all physical properties same except their action on plane polarized light which is equal in magnitude but opposite in direction. (©) all chemical properties samo except when reagent is chiral in that case, reactivity of enantiomer will be different, (c) opposite configuration of all chiral centers according to CIP. male, (a) superimposable image of each other, 31.-Which of the following plots are correct for potential cierey of butane as a function about C, —C, bond? (a) Energy’ (b) Energy 0° 60° 120° 180° 240° 300° 360° ‘ -180°~120°-60° 0° 60° 120° 180° © (@) All are incorrect 0° 60° 120° 180° 240° 300° 360° 32. A pair of enantiomers is : (a) a pair of non superiiposable mirror image of each other (b) a pair of superimposable image of each other (©). always optically active if one is dextrorotatory then other will be laevorotatory’ by same magnitude (@ compounds having same boiling points 33. A racemic mixture is : (@) always equimolar mixture of a pair of enantiomers () always equimolar mixture of a pair of diastereomers (©) always optically inactive (@) always optically active H onH H aad | 6 | O-/Ph Ph Ph I U dl Which of the following statements are true about these molecules? (a) Land I] are a pair of enantiomers (b) IIT is metamer of t and II aisomerism 117 (c) Ul is diastercomer of I and II (@) IITs not stereoisomer of I and I 38, Which of the following compounds have the plane of symmetry? cl @ © © oZ2L0 cl 36. Which of the following compounds can exhibit geometrical isomerism? OH . Hl © c= c=C= ac (@) GHs—CH—=CH—CH=CH—CH; 37. Which of the compounds shown below are isomers? 38. Identify the compound which has a stereo center. H Et Ww © co @ ” co HN 39. Which of the following will show optical isomerism? Br, cl (a) a CH, (b) rien Cl Br . HC. cl = C=C=C. © OO). (0) POACMOCE HO3S $O3H 40. Which of the following molecules are chiral? HO: H 7 = ©) @ CH. @ ) eect © x bs HL CH Ou .118 GRB Advanced Problems in Organic Chemistry for JEE 41. The correct statements about the compound given below. ‘ Cl CH; “Uy, HAC “any a (a) Compound is optically active (b) Compound possesses center of symmetry (c) Compound possesses plane of symmetry (@) Compound possesses axis of symmetry 42, Consider following compounds: 8 HH, OCH, CH,OCH, & a & 6 y CoHs Choose the correct statements from the flowing (a) I, Hand IIf are functional isomers (b) I and IT are position isomers (c) IH and IV are chain isomers (d) ITT and IV are metamers 43. whieh of the following are correct statement regarding these molecules. COOH COOH Ph 00H Ph, £ uN . 7 LS v7 s mC (@) Compound Land Il are Siatereomers (b) Compound Il and IV are enantiomers (c) Compound I and III are enantiomers (4) Compound Il and 1V are homomers 44. Which of the following are correct regarding these molecule, HC. H3C Be mon HC a HC HC {a) Both compounds contain plane of symmetry (b) Both are enantiomers (c) Both are diastereomers of each other (@) Both are homomers 45. Find the correct statements regarding following molecules. HH OH OH RERERE ut i$‘ 119 ‘somerism (a) I, Hand II are meso (b) Hand JI are enantiomers {c) Land IV are diastereomers - (d) Ill and IV are diastereomers LINKED COMPREHENSION TYPE ll Passage-1 Presence of chiral center is not an essential condition to show optical isomerism. Essential condition is, compound should show non-superimposable mirror image. Allenes do not contain chiral center but show optical isomerism when different groups are attached on double bonded carbons. Biphenyls also show optical isomerism when both rings are perpendicular to each other and any ring should not contain plane of symmetry. {Which ofthe following compounds is optically inactive? 3 @H Os 1 H—}+-—oHn @u—}—c © yo} — a HG Bs ©) | (d) All are correct 3. Which of the following compounds can be resolved in enantiomeric form? CH Hcl Br ct iP @y la oon c=cC CH, : cl 208s cl 6 ——O . dowc=ce, @ BC NHs ~~ 9 7lO120 GRB Advanced Problems in Organic Chemistry for JEE Passage-2 _ - + Cyclohexane exist as two chair conformations in rapid equilibrium at room temperature. “Each carbon atom on a cyclohexane ring has one axial arid one equatorial hydrogen. Ring-flipping converts axial H’s to equatorial H's and vice-versa. In substituted cyclohexane, groups larger than hydrogen are more stable in the equatorial position. down he eis isomer has two groups on the same side of the ring, either both up or both wn, The trans isomer has two groups on opposite side of the ring one up and one wn, 4. Find out most stable substituted cyclohexane among the following : (b) © Kye 5. Which of the following is most stable conformer of 1, 2-dichlorocyclohexane? cl (@) aa (b) <2 _ (d) All have equal stability @ Jisomerism 121 Passage-3 Conformations are different arrangements of atoms that are interconverted by rotation about single bond. In eclipsed conformation, the C—H bond on one carbon is directly aligned with C—H bond on the adjacent carbon. In staggered conformation, the C—H bond on one carbon bisect the HC—H bond angle on adjacent carbon. The angle that separates a bond on one atom from a bond on a adjacent atom is called a dihedral angle. A staggered conformation with two larger groups 180° from each other is called anti. A staggered conformation with two larger group 60° from each other is called gauche. 7. Identify the most stable contarmer of 2-fluoro ethanol among the ‘llowins: H. t H HO, H H OH wc OH 8. Which of the following is gauche conformer? CH; we" ri rhe z 9. Which ofthe following conformer of butane has rinimam omer CHy H. H S*Scu, @ ay o On. © n- H’ CHs Passage-4 ‘A line which bisects a compound in two equal parts and both parts appear to be the mirror image of each other, such kind of symmetry is known as plane of symmetry. Any molecule that has a internal mirror plane of symmetry cannot be chiral, even though it may contain asymmetric carbon atoms. 10. Which of the following compounds does not contain plane of symmetry?122 GRB Advanced Problems in Organic Chemistry for JEE CH3 a Cl, CH; al @e yO ae © © H ‘OH bs, a cf ci 11. Which of the following compounds is s optically active we wl. ome on o | om ® Ne H—-—CL CH; 12. Which of the following compounds is not chiral? . Br Cl CH @ Br—|—ou . oO cH; Cl Che CH ees c= —ce @ ‘Se Passages R, S-configuration is a useful tool for determination of enantiomers, diastereomers and homomers. If configuration of all chiral centers are opposite then structures are enantiomers, if all chiral centers have same configuration then they are homomers and if ‘some have same configuration and some have opposite configuration then they are diastereomers. CH; CH; CH; H H. cl ch A H Cl ch (CH; H- ‘NH, H3C: NH, H3C: NH2 H3C- H CHs H H NH 1 i . m Iv . 13. Among above structures find out enantiomeric structures : (a) Mand TI (b) Jand Il, I and IV (c) Land IV @) Wand IV 14. Find out homomers : (a) Land (b) Hand Iv (c) land IV (d) Mand IV 15. Which of the following is not diastereomer? (@) Land Uf (6) Mandi == (©) MandIV—(@) Hand IVIsomerism 123 Seeseey MATRIX MATCH TYPE a 1. Column (1) Column GD) @) Ms come P. Plane of symmetry cHy Cl CH, Br oO Q. Meso CH; OH mC CH; © Y CHCHCHAC heey R. Optically active CH; @ H——cl S. Geometrical isomerism Hj;C—+—_H a 2. Column (1) Column (ID) OH HC. H @ P. Meso H CH; OH : Br ) Q. Anti conformer Br Me Me Ou R, Cis-isomer H Me (@ P8704 S. Eclipsed conformers Ph———OH Me 3. Column (1) Column (I) ‘CHO (a) ODN and P. Ring chain tautomers ‘OH124 GRB Advanced Problems in Organic Chemistry for JEE Be (b) wy me and ‘eu O Faneoml isomers () Et Me and MON R. Tautomerism Bt” Pr” Me: @ OH and yo ‘S. Metamerism ‘oO 4, Column (1) Column H3C Br HO CH: o CHP. Cis-compound BY CHy ome ©. ‘S (0) 0: tenesmoid ch; Br OH x (& Ch R. Optically active Cl Cl @ S. Optically inactive cl 5. Column ()) ° Column (11) cl H (a) =c=c=c P. Polar molecule perenne b) AN cee Q. Optically active Promem CK, (©) cq net R. Optically inactive BR, F 0) S. Symmetry element H H :Isomerism . 125 (ESEGSRSSS INTEGER ANSWER TYPE PROBLEMS HL 1. Total number of stereoisomers possible for the following compound is. OH CH; CH—CH; ©) CH3 2. Find out number of stereogenic centers present in following compound ‘simvastatin’ 0 xs " 3. Find out number of compounds those have ‘S configaration from following, , \s TL cm och é # HCO” H CH,CH;NH—CH; OH a oH Hom . ont (unit CH3CHs + Hyc—-cHt0n CH,CH; — CH,CHY- CH; jr H oo 4. Identify number of compounds which are meso. 7 Br OH CH; a COMe neo OO cH,0H BF126 GRB Advanced Problems in Organic Chemistry for JEE ~CH3 Br OH CH : TN, Sis re OHOOpem + OES HC ‘cl HO ‘Br CH; Br CH . H——OH : H;C-+—-H OH 5, Total number of stereoisomer possible for the compound H,C—CH = CH—CH =CH—CH ==CH—Ph 6. How many stereogenic centers have ‘R’ configuration in following compound zocor. *ZOCOr’ 7, Find out number of conformation those have Cis geometry. CH, cl me =X oh > cH,’ rif ac CHs 8, Identify. number of compounds that can show geometrical isomerism. HC, CH, Cl Hy » cl CN ec Se’ / \ / \ CH H H B Br a f irtsomerism 127 HAC. J I > \ HC ‘cH 9, Find out number of structural isomers possible for C,H, 4- 3 Caan a 10, Identify number of carbohydrate that have L-configuration , from following, HO: Ht Ht HO--CHp- CHO re CHO H——OH non HO--H >» H-+-oH + HT OH on i 2! ¢H,0H — HO-7—CH,OH OH H gre CHO cH H HH HOH _ H+-OH | H—+-OH neow H——OH * H-+—OH ” Oy H+t-oH = not | HO~CHh-y-OH CH,OH CHO H 11. The following compound may exist in two or more stereoisomers CoHs COOH Co ‘COOH (a) Total number of stereoisomers. (b) Number of enantiomeric pairs. (c) Number of meso compounds. 12. “A pair of stereoisomer might be classified in various ways depending upon their exact nature” CH,OH OH H CHO ‘HO ‘OH ‘OH A OH How many following terms could properly be applied to a pair of stereoisomers, assuming their nature permits ? (a) They might be meso isomers. (b) They might be tautomers. () They might be enantiomers. (@) They might be diastereomers. (e) The, might be conformational isomers. (f) The; might be constitutional isomers. (g) They might be configurational isomers. (h) None of the above statements are true.128 GRB Advanced Problems in Organic Chemistry for JEE SSC Sms Exercise-1 : Only One Correct Answer Level-L" 1.0) 2 2 4x) 5.0) 6b) 7.() 8b) 9. (@) 10. fo) 41.) 12. (4) 23. (a) 24. (d) “15; (b) 16.) 17.) 18. @) 19. @) 20: @) 21. (0) > 22.(c) 23: (Cc) 24. (4) 25. (0) 26.(0) 27. (c) 2Bifacd) — 29. (bc 30. (a) 31. (c) 32, (c) 33. (c) “34. (c) 35, (a) 36. (d) 37, (d) 3B. (d) 39, (d) 40. (a) 41. (a) 42. (c) 43, (a) 44, (a,c) 45. (c)” 46. (a) 47 (b) 48. (b) 49: (b), Level-2 7 * 1.2) 2i(0) 3.0) 4) BCC) 6D) 7 (a) -B(c) 9 (0) 10. (0) 11.(6) 12, (©) 13. (@)" 24. (d) 15. (b) 16. (b) 17.) 48, (d) 1B. (@) 20. (©) 21. (b) +22. (c) 28. (a) 24, () 25. (b) 28..(d) 27. (c) 2B.(b) 29, (d) 30. (c) | BU. (c) 32. (b) 33. (c) “34, (b) 35. (d) 36. (b) 37; (b) 38. (c) 39. (b) 40, (c) 41, (db) 42, (d) 43..(d) 44. (d) 45. (b) 46. (c) 47, (d) “AB, (b) 49. (2) 50, (b) 51. (b) 52. (4) 53. (c) 54.@) 55. (b) oe at 2@) 2.) 3.) 4(a) 5. (by) 6a) 7 (bY BKC). (2) -204 () IL. @) 12.) 13. () 14. ©) 16. (b) 16. @) 17.) 18. (2) 19. (@) 20. 0b), 21. (0) 22. (9) 23,(c) 24. (2) 25,(d) 26. () 27. (d) 28. (d) 29. (c) 30. (a) 31. (d) 32. (b) 33, (A) 34. (a) 35. (c) 36. (b) 37. (a) 38. (b) 39, (2) “40, (b) 41. () 42. (6). 43. (€) 44.) 45. (d) 46, (c) 47. (2) 48.(d) 49.(a) 50. (2) 52. (b) 52. (b), $3. (c) 54. (a) 55. (d) 56. (c) 57. (c) 58. (b) $9. (b) ~60..(2)) 61. (bd) 62. (bd) 63. (@) G4. (d) 65. (6) 66. (d) 67. (c) 6B. (a) “69. (2) 70. (b) TL,(b) 72. (6) 73. (a) 74. (c) 75-(d) 76-(d) 77. (d) 7B, (a) 79. (d) 80: (d) BL (c) 82. (b) 83. (a) 84. (C) 85. (d) BB. (b) 87. (C) BB. (b) 89. (a) 90. (b) 91; (c) 92. (d) 93. (d) 94. (c) 95. (b) 96. (b) 97. (b) 9B. (a) ‘99. (c) 100. (d) 101. (bd) 102. (c) 103. (a) 104, (a) 105. (a) 406. (c) 107. (4) 108. (b) 109. (c) 120. (a) 11. (b) 142, (a) 113, (b)124, (b) 115, (d) 116, (2) 247. (c) 118. (b) 119, (a) 120. (b) (9).22, (4) 128, (b) 124, (b) 228. (c ~ Exercise-2: More Than One Correct Answers 1 (@,b) 2, (0. a) 3 (ab.c) 4. (a0) 5. (a,b) y 6. (a,b. a) 7. .d) 8. (a. d) 9.(b.c.d) 30fa,b.c) 12. (a,b°e.'d) 42. (bd) 33. (2, c,d) 44. (2b) 15. (@,b,c) 16. (ac) «AA (ad) "18. (a,b. d) 29. (ab) 20. (a, b,c) 23. (b,c, d) 22a.) 29: (a.c,d) 28. (a, bc) 25. (a,b,c) 26. 27. (a, b, ¢, d) 28. (a, b,c) *29. (b,¢,d) 30. (a,b, c} 32. (a, b) 33. (0c) _3A3(a,b,d)_ 35. (a,b. d)2 36. (a,c, d) 37. (b, c,d) 38. (a,b, d) 39. (ac, d) 940. (0. cfd)" 42. (a, d) 42. (a, d) 143. (a,b,c) __44. (a, c) AS; (a, ¢) : a“tsomerism 129 Exercise-3 : Linked Comprehension Type 7@ 20) £@ 46 5) &@) 7) 8) 9 @. 10.) 19. (©) 23. (b) 14.) 15. @ Exercise-4 : Matrix Match Type LaF: 37.5; TOPOS: P.O 2 APO > PRE oo CAPS GPS % @>e (6) QR; (4S (oP 4. BOP. (0)+ 0. S} (40,7; WoPS DPR S B_ QRS (0), Ri (RS. Exercise-5 : Integer Answer Type Problems 1@8) «7 +4 64 5@) 63) 703) &@ 95) tw (5) ps A-10,8-4,6-2) 12,8, 4,6, 0,66) 000Hydrocarbons (Alkane, Alkene and Alkyne) Lindlar’s Na/NH3 1 BREE R—CaC— RD A and B are geometrical isomers ( —CH—=CH—R) of which type ? (a) 4 is trans, B is cis (b) A and B both are cis (c) A and B both are trans (a) A is cis, B is trans Pp . Which is most easily dchydrohalogenated ? o€ a ay C)-a ay (ja (a)! () 0 © (d) all with same case i 3. The relative stability of the compounds given below is in the order. CH, CH; CH ()CH; ~C=C—CH, (il) CH; —C=CH—CH, (iu) CH;—CH=CH, (IV)CH, =CH, (@1>1>Ml>1V (by IV>M>1>1 (I> > 1>IV (@U>1>1v> I 4.2 ee Aand Bare : CH; I NalOx 5. CH; ~C=CH—C—CH, S$. CHy —C=CH—C—CHs ~ pra? Products CH; The products are :Hydrocarbons (Alkane, Aikene and Atkyne) 131 II (a) CH; —C—OH'(CH;);C—COOH {| (e)CH;—C—CH,, (CH;);C COOH cocn,—b—cn,, (CH;);C—CHO (d) None is correct . 6. The compound formed when 2-butene is treated with hot alkaline KMnO, is : (a) Acetaldehyde (b) Acetic acid (¢)CH,OH-CH,OH (@) CH ‘CH, -CO-CH, 7. Relative stability among conjugated dienes (i), alkenes (ii), alkynes (iii) towards electrophilic addition reaction is in the order : (a) (i) > (i)> Gi) () (i) > (iii) > Gi) (©) Gil) > Gi) > (Gi) > Gi) > @ BbyTHF a 8 Cr —ROTTE Product A, Ais CH; CH; wo Fros of fo oC Kou oC ‘OH D D 9. Arrange the following alkanols 1, 2 and 3 in order of their reactivity towards acid catalysed dehydration. . OH (1) CH; —CH—CH,—CH, (2)CHy —b—cn, —CH; da, ou bu, OH (3) (CH;)2CH. bu CH; * (a)1>2>3 - (b)2>1>3 ()2>3>1 (d)3>2>1 10. An organic liquid (4), containing C, H and O with the boiling point 78°C and possessing a rather picasant odour, or heating with concentrated H2SO, gives'a gaseous product (B) with the empirical formula CH, (B) decolourises bromine water as well as alkaline KMnO, solution and takes up one mole of H, (per mole of B) in the presence of finely divided nickel at high termperature. (A) and (Bare: (@)C)H,OH,C)H, (0) CH,OH,CoHs ()C,H,0H,C)H, (@) (CH; ).CHOH, CH uw ©) +Brn—>A Awill have configuration : seme132 GRB Advanced Problems in Organic Chemistry for JEE Ont oc {©) both true (@) none is true 12. CH,;CHO+ HC==cD tes P (major), Pis: 9p Ocho on (6)CH,— CH—C=cD ()CH;—C—c=cD (d) None of these Br 13. cr, product » The product can be : CH; CH; Cs CHs CHs of Kor, OC Koy, © ol ‘CH; 14. Consider the following reaction. CH; cH. CH. CH,CH H,-—C—CH,CH, => Nea’ << ™ 3-~ C- —CHCH ~ on, + CH, =! Br on” MA cH, 1 a ay Which of the following base will give the best yield of the alkene Il as the thajor product ? : (a)CH,0- (b)C,H,07 {©} (CH3)3CQ™ — (d) (CpH5);CO™ 15. IUPAC name of Il is: (a) 4, 5-Dimethyloct-4-ene (c) 4, 5-Dimethyloct-5-ene (b) 3, 4-Dimethyloct-5-ene (d) None cone. 16. CH;-—CH— CH, —CH, TBO product (I) + Product (1) OH What is not true regarding the products ? (a) Product-I and Ii are position isomers, (b) Product-T and IE contains the same number of sp? and sp” carbon atoms (c) The yield of the product I and II is same . (d) Reaction obeys Sayizeff ruleHydrocarbons (Alkane, Alkene and Alkyne) 133 17. 18. 19. 20. 21. 22. 23. 24, 25. Which of the following is not true about geometrical isomers ? (a) They have different physical properties (b) The have different orientations in space (c) They have different connectivity of atoms or groups (d) They are non-interconvertible —- 2-nethyl propene is isomeric with But-I-ene, They can be distinguished by : (a) Baeyer’s reagent (b) Ammonical AgNO; (©) Br, solution . (d) 03, Zn/H,0 Which of the following is the structure of propylene chlorohydrin ? @ CH; —CH —H, : ) CH CH, — Ca f cl OH cl OH (c) CH; CH (CH — CHCl OH OH CI , Which alkene on oxidation with acidic KMnO, gives only acetic acid ? (a) CH; =CH—CH; (b) CH; —CH=CH— CH, (ce) Ethylene (d) Pentene - 2 Ethylene reacts with osmium tetroxide to form an osmic estér which on hydrolysis gives : : : (a) Ethyl alcohol + Osmic acid (b) Glyoxal + Osmic acid (c) Ethylene glycol + H,Os0, (4) Glycollic acid + H,0s0, Diborane reacts with terminal alkenes to form trialkylboranes, These react with alkaline hydrogen peroxide to form : (a) Secondary alcohols (b) Tertiary alcohols (c) Isobuty] alcohol (d) Primary alcohols Kharasch effect operates in which of the following ? (a)CH\CH,CH=CH, +HCI (b) CH,CH,— CH=CH, +HBr ' (c) CH;CH==CH — CH, + HBr (@) CHjCH>CH=CH, + HI ‘A hydrocarbon X adds on one mole of hydrogen to gives another hydrocarbon and also decolourises bromine water. X reacts with KMnO, in presence of acid to give two moles of the same carboxylic acid. The structute of X is : (a) CH;CH==CH-CH,CH,CH, (b) CH,CH,CH==CHCH,CH,, (c)€H,CH,CH,—CH=CHCH, * (d)CH) =CH—CH,CH,CH, Identify Z in the sequence sr/ -Na* CH,—cH,— CH=CH; 2 y BO 7 (@) Hs —CH— CH, — OCH —CHs CH, : (b) CH; = CH, —CH—-O— CH, — CH, le CH,134 GRB Advanced Problems in Organic Chemistry for JEE ; (©)CH;— (CH); —O—CH,—CH, (CHs— CH =O CH, 26. CH; CH=CH, —™3 _,, product X, Yis: H20/0H7 (a) CH; —CH—CH,D (0) CH, —-CH—CH,OH bu {c)CH;—CH—CH, (4) none is correct ép co1sbr 27. CH, =CH—CH=CH, ———> product. The major product is : (a) Br —CH, —CH=CH—CH,—CCl, ()CH, =CH— CCH, CCI, Br (0) CH, =CH—CH— CHa —Br CCl; (d) none is correct 28. ‘CHs (1) Hg(OAc)9/H20/THF * @)NaBlig/NaOHQO” A Ais: OH ‘CH; ‘CH; ‘CH; ‘CH; ® CSon ) © ofS ‘OH 29. 2-Phenylpropene on acidic hydration gives : (a) 2-Phenyl-2-propanol (b) 2-Phenyl--propanol (©) 3-Phenyl-1-propanol (4) 1-Phenyl-2-propanol : 30. cis-2-Butene on reaction with Br, in CCl, produces mainly : {@) 1-bromo-2-butene (6) 2, 3-dibromobutane {&) meso-2, 3-dibromobutane (4) (£)2, 3-dibromobutane 31. Which of the following reaction will lead to the creation ‘of two chiral centres in the product ? cog (a) CH;CH=CHCH, +Br, “45 (6) CH,CH,CH=CH, + Br) 4s (2) CHyCH=CHCH, +HBr-——> (4) CH,CH,CH=CH, + HBr ——> 32. The reaction of ethylene with Br, in water in the presence of NaCl gives : (a) 1, 2-dibromoethane (b) 2-bromoethanol (©) I-bromo-2-chloroethane (@) all of theseHydrocarbons (Alkane, Alkene and Alkyne) 135 33. AhydrocarbonC,H,, consumes only one mole of H, on catalytic hydrogenation. The hydrocarbon when heated with hot and concentrated alkaline KMnO, gives cyclohexanone and acetic acid (after acidification). The hydrocarbon is : (a) 1-ethyleyclohexene (b) 1, 2-dimethylcyctohexene (©) ethylidenecyclohexane (d) cyciohexylethene 34, Dipole moment of which compound will be maximum ? HC OH HC | OH HOH HH @ -X ) y=¢ © .@ xX Hoo HoH Hoa HoH 35. Correct order of reactivity towards electrophilic addition reactions is : (a) CH, =CH, >CH;—CH=CH, > (CH;),C=CH) (b) CH, =CH, >CH; —CH=CH <(CH;),C=CH, (©) CH, =CH, < (CH;),C=CH, (b) CH, =CH, +HOBr—> 10; (c)CH,CH,CH=CH, +HBr —> (4) CH;CH,CH=CH, + HBr—> _ 49. One mole of a hydrocarbon on ozonolysis yields one mole of glyoxal and two moles of formaldehyde. The hydrocarbon is : @) chy =C— C= CH, (e) CH, =CH+-CH=CH, CH, CH (c)CH,=CH—CH,—CH=CH, (d)CH,CH=C=CH, 50. A hydrocarbon (4) on chlorination gives (B), which on reacting with alcoholic KOH changes into another hydrocarbon (C). The latter decolorizes Baeyer’s reagent and on ozonolysis forms formaldehyde only (4) is : (a) Methane (b) Ethene (©) Ethane (@) Butane Alkane 1. The smallest alkane which can show optical isomerism possesses : (a) 5 carbon (b) 6 carbon (©) 7 carbon {d) 8 carbon 2. Which of the following alkanes has a meso stereoisomers? @ YY &) Av © An @ an 3. Among the following, the compound which has highest boiling point is : ANA () My @ANY. ox 4., Propane can be best prepared by the reaction : (a) CHACHjI+ CH +Na 222, 20. (b) CHyCH,COONa +CH,COONa z Electrolysis . : bo (©) CH,CH,Br + (CH) Culi 27> NaOH (@) CH,CHCH,COONe > , ws . 5138 GRB Advanced Problems in Organic Chemistry for JEE 5. MesCMgClon reaction with DO produces : (a) Me,CD (b) Me;COD —(c) (CD3);CD_—(d) (CD),COD 6. Which of the following carboxylic acids undergoes decarboxylation most easily on heating? 0 ll (a) CH,;CH,COOH (b) CH,-—-C-—-COOH ° o.. ° ll i Il (© CH,—C—cH,—c—on @ H 2 a-ak Product, find the product : @ ax<>—<-a ) mB © OOo @ & a —aig? Product : @ BR A /MeBr ¢o) BME. MeBr (©) CHy—CH=CH OLN 9. Which of the following alkyl bromides may be used for the synthesis of 2, 3-dimethyl butane by Wurtz reaction? 1 @Ar () A (©) Isobuty! bromide (@) s-butyl bromide 10, Which of the following methods of alkane synthesis involves the electrochemical oxidation of alkanoate ion? (a) Kolbe’s method (b) Wurtz method (©) Frankland method (d) Corey-House method 11. The reactivity of alkyl halides for Wurtz reaction is : (a) 18>2°>3° (b) 3°>2°> 1° (e) 2°>3°> 12 (Ad) 19> 3°>2° 12, Which of the following is planar and cannot form conformational isomer? @) OQ wo ZN © @ CO 13. Which of the following reactions has zero activation energy? _ @ CH, +c —> CH, +HCL — @) cl-cl 5 2c"3 Hydrocarbons (Alkane, Alkene and Alkyne) : 439 (©) CHS + °CH; —> CH;—CH, (a) CHS +CI—Cl —> CH,—CI+CI" 14. Photochemical fluorination ‘is explosive while iodination is too slow to occur. The reason for this is : . (a) bond dissociation energy of J, is minimum. (b) formation of CH; —F is most exothermic. (c) formation of H—F is most exothermic while formation of HI is endothermic. (a) Fy has lower bond dissociation energy than Cl, and Bry. 15. Which statement is incorrect about free radical halogenation of alkanes? (@) The number of product molecules formed by one photon i (b) If0, is added, initially the rate of reaction decreases, the (c) Inhibitors combine with free radical and terminate the chain reaction (d) Presence of Ph—f—O-—-0—F— Ph inhibit the free radical reaction. oO Oo 16. Which of the following is not the chain propagation step in the chlorination of alkane? (a) R* +80,Cl, —> (b) “SO,Cl —> SO, +CI* (©) Cl’ +R—H —> (@) R—O—O—R +2R—H —> 2ROH+2R° 17. An alkane cannot be chlorinated by using which of the following reagents? (a) Cl,/hv (b) HCI (©) SO,Cly (d) ¢-Bu—O—CI 18. The correct order of heat of combustion of the following hydrocarbon is : Pent-t-ene Pentane neopentane isopentane () @ (R) ) (a) P>Q>R>S (b) Q>S>R>P (©) P>Q>S>R @ S>R>Q>P 19. Formation of free radical takes place with absorption of minimum energy in the formation of : 7 Or, OY © XL @ be 20. Formation of free radical is easiest in = @® “ec ©) “pr © A¢ @”~, 21. The correct order of relative density of following alkanes i LIN DAR NYY NG @) @ (Ry © (a) P>S>Q>R (b) R>S>QO>P (c) R>Q>S>P (d) S>R>Q>P -! 140 GRB Advanced Problems in Organic Chemistry for JEE 22, What is the chief product obtained when n-butane is treated with Br, in the presence of light at 130°C? ay o> © +s @ 7s: Br 23. The number of possible enantiomeric pairs that can be produced during monochlorination of 2-methyl butane is : (3 (b) 4 @2 @1 24, For the given reaction how many products will obtain (all isomers)? Bry/hv SKK 2, products @1 ) 6 @4 (a) 3 25, How many total products will be obtained by monochlorination of 2-methyl butane and how many can be separated by fractional distillation? (a) 6,4 (b) 5,4 _ ©) 62 (@) 4,2 How many monobrominated products will be obtained by above reaction? os ) 4 5 @3 cH; , Hp 27. cH Ba, Products : C)Hs thc CH; CH; H-—D H-—D ucts © ete, (©) Both (a) and (b) (4) None of these CoHs GHs CH; R20; - 28. HCE +CCly, > Product: . v CH; , CH; | (a) mee cl () CHI, CH, (©) Both (a) and (b) (d) None of theseHydrocarbons (Alkane, Alkene and Alkyne) 141 HC. 1 cu; Bry, hy, 29. —“—> Product : hu CH, CH | | ©) HyC—F— Coie ) oe cH; H Br | x @ A / @ 30. How many alkane of molecular weight 100 are chiral? @ 1 (b) 2 © 3 @4 31, Which one is the correct energy profile forCI* +Cl" —> Cl,? a. 2 ° (a) | (b) | Reaction co-ordinate Reaction co-ordinate © | (a) All of these Reaction co-ordinate _ 32. Which of the following is the correct statement regarding relative acidic character of cyclopropane and propane? (a) Cyclopropane is more acidic than propane (b) Propane is more acidic-than cyclopropane (c) Both are equally acidic (@) Both are neutral Che Fractional - 33. Ph—CH—CH,—CH, ——> Products —————> Fractions, | hv Distillation : CH; No. of producis and no. of fractions are respectively : (a) 6,5 (b) 6,4 (©) 5,4 d) 6,3142 GRB Advanced Problems in Organic Chemistry for JEE 34. Which of the following cycloalkanes has lowest heat of combustion per —CH,— group per mole? @\F oD} © O © CO 35. Which of the following alkyl halides is not suitable for Corey-House synthesis of alkanes? @) CHa OA, OAN OX Br 36. The relative reactivity of 1°H, 2°H and 3°H in bromination reaction has been found to be 1 : 82 : 1600 respectively. In the reaction, ' Arias + Jn : ir wo & The percentage yield of (A) and (B) are expected to be : (@) 99.4%, 0.6% (b) 50%, 50% (©) 0.6%, 99.4% (@) 80%, 20% 37, The relative reactivity of 1°, 2° and 3° hydrogens in chlorination reaction has been ~ found to be 1 : 3.8: 5. In the reaction, ALA ye OLY cl ” ® © o The ratio of the amount of the product (4), (B), (C) and (D) is expected to be : (a) 1:38:5:1 (b) 3:7.6:5:6 © 3 . @) 1:76:5:1 38. Which of the foltowing is the free radical chain reaction? (@) 2CHyI+2Na —» CH;—CH, +2Nal @) cH, +cl, SS cH,cl+Ha ee (6) 2CH;COONa —*> CH,—CH, +2CO, +2NaOH +H, (@) All of the above . 38. /\ + HBr — Product : 7 @ aA MOA © id ar 1: BrHydrocarbons (Akane, Alkene and Alkyne) 143 40. ~~ Sets, Major product : @) CO 0) AWA) ANY @ oO 41. AANA 22a, ao —Al03, Major product : @) & (ey J © A @) AA 42. Consider the following reaction : D AY +t xe Identify structure of (X) anon following : ® hie ® by © i @ why Na/EtOH 43. oe 1 —Togae —? Product : - @A*™ oo) A OLN (@) HyC=C=CH, 44. The bond dissociation energy of the C—H bond for the compound Hy;C—H H,C—CH,—H uc—cu—cn,—af Vn (P) (R) decrtaes in the orde ® © (a) P>Q>R>S (b) S>R>Q>P (c) S>P>Q>R (@) Q>P>S>R ‘45, Which of the following carboxylic acids is difficult to decarboxylate? - . 1H @ J ©) “ae © ae @ ony 46. The method of estimation of active hydrogen in a compound by reaction with CHMgl is known as : (a) Zerewitinoff method (b) Hinsberg method (c) Zeisel method (@) Victor Meyer's method144 GRB Advanced Problems in Organic Chemistry for JEE dH i a. Y= 9 HOY, ni, The end products of the reactions are : (a) DSH and Aggy (b) >—S—CH;—CH,—SH Ss SH © xX and HO @> and“ 48, Consider the following reaction : PhyC—O—O—CPhy + CCl, The major products formed in this reaction a @ Xa and CHC; (by end CHC! () + and a (a) No reaction ‘ . Claity 4. Ar Find out number of monochlorinated products (including stereoisomers) which are possible in the above reaction : (a) 2 b) 3 (4 @s5 Ha Products of the above reaction will be : (a) racemic mixture (b) diastereomers (e) meso (d) structural isomer “Oe [rat (a) Both (b) and (e) - D . CH Hy Hy HI & {a) (b) (©) @) Hal Hy HC HC CMe; - CMe; CMe CMesHydrocarbons (Alkane, Alkene and Alkyne) 145, 53. On catalytic reduction with H,/Pt how many alkenes will give n-butane? @ 1 (b) 2 © 3 @4 Hy D ; 54, ‘= < H)Ni. Hs; Product of above reaction will be : (a) racemic mixture _ _ &) diastereomers. (c) meso {d) constitutional isomers 55. He _ 7 pani Product of above reaction will be : (a) racemic mixture (b) diastereomers (©) meso (@) constitutional isomers 56. Cees ta(t ete, Mole) @) et (b) cx (©) ant (@ None of these ARON, Product: @) “oct ), CL (©) CH (d) None of these Bra CH) —Br 58. SA Nether _, Major product : a Br—H,C cH—Br Br ‘Br OK wb Br: Br Br. Br 0 XY @ X i : Br. Br 59. Arrange the following alkanes i in decreasing eden of their heat of combustion : ofan WM - w @) (a) X>Y¥>Z- )Z>X>Y¥ © Z>Y>X @)X>zZ>y¥146 GRB Advanced Problems in Organic Chemistry for JEE Alkene and Alkyne 60. Which of the following is the major product when I-butanol is heated with concentrated H,SO,? (a) "t-butene (b) Cis-2-butene (©) Trans-2-butene (@) All of these H a. Cone, HsPO4 ‘OH ‘ Hi ) A ®) X © xX @) Hy 62. In the reaction _Calis0°, “Gion” The major product obtained is : HH. @ Ay ) YY ©) Av @ KK . «ou 6 yk one 12808, Major product : @ >< o> SK @ None of these 64, [ )-cu,—on EEE TROL, Major product : »@) [ ecu. (b) [ Sex, () CY @® ~> 65. The major product of the following reaction is : Na/Ether Br, hv Alc. KOH Br cp i, Se KON ) O of © @ cr iHydrocarbons (Alkane, Alkene and Alkyne) 147 66. ()- cc c{ HINO , Product : @ (©) Both (a) and (b) "Or? COOH 7. KOH 6 Cangas fore? Product : cook? coo°K® © Kos oy oY : ol 00K ¢ “en * ei Electrolysis, Major product : PNa® oo oC LT) 3. Com © @) | ou 0. b-4 reagent used. for the reaction : (a) LiAIH, (b) Ha /Ni _(©) NaBH, (@) Hp, Pd—BaSO, 00°K® ; 70. Electrolysis, product : ba 00°K® oO oO ol Il } (@ None of these72. B. 5. GRB Advenced Problems in Organic Chemistry for JEE dn ds ot Which reagent will be used for the above conversion? (a) Na/Lig. NH; (b) H, Po—CaC0; (©) Li, Ph—NH, @) H,, Pt H - Li Lia NHS, Major product : “9 0 a ie, 14.3, Major product : Hs H; . Hs C of 6 (8) None of these i. Which of the following has zero dipole moment? CHsCHa _ Hs © CHsCH2 - yt @ a? # vo chy 1% os H © —< “y= 7 HS Ny ‘cry Which of the following is correct order of stability of alkene? - (2) CHy—-CH=CH, < \=/ < eX < SS (b) CH;—CH=CH, < \=/ < SAX < >< o-X<< Ney <2/ < CH CH=CH, (@ N=’ < CHy—CH=CH, < =X < NA aHydrocarbons (Alkane, Alkene and Alkyne) : 149 76. Which of the following alkenes is most reactive towards electrophilic addition reaction? (a) H,C=CH, (b) CH; CH=CH, HG © =CH, (@) H,C=CH—CI HC’ 77. Propene reacts with Br, to give 1, 2-dibromopropane. The anti-addition takes place duc to the formation of intermediate + Br i J (a) CH; —CH—CH, (by) HyC—CH—CH, N37 BY : ° ° (© H\C—CH—CH,—Br —(d) None of these 78. Consider the following reaction : CH, : | Hxe—F-— CH=CH + HCl —+ CH; t The major product obtained in the reaction is : cl CH; CH; Cl “ I | | : @ Hye CH—CH &) Hct CH—CH, ‘ CH; CH; CH; ‘ : © HyC—F— CH, CHCl (@ None of these CH; 79. Which of the following reactions is expected to give a fairly good yield of : Cnc at : (@) BC. ‘ (b) H3C- “tao pe I_ 150 GRB Advanced Problems In Organic Chemistry for JEE 7] tac Pouce, . 7 HENS HBr © ay I—CH @) HC bic, 2 Hs {Su4 CH [voe8 80. O11 [=CH—CH; —> Major product . 1 @ on \-cr, I—CH; (b) orf) Li-cron ©) on—f_\—c1.—cr,—cn (d) None of these 81. H,C- H=CH—CH;, 185 Major product : ir @) wco( ci Laon ir 9 1400 4)on-en (©) Both (a) and (©) in same amount ‘@ Nonc of the above 82. HYC=CH—C=SCH+HCl —o X3X7 is: ca | @) HjC—CH—C=cH &) Hyc=CH—E— cH, a a a | | (© C1,—CH—C=CH @) CH, CHE, a 83. Arrange the following reactions in decreasing order of electrophilic addition Teaction > CH: ” @ Co) @ P>Q>R = W)G>R>P_— |W) R>O>P_— A) P=Q=R 5Hydrocarbons (Alkane, Aikene and Alkyne) 151 84, 7 HBO Mol), Major product : bf jr @) wy ® eI © Cf (d) None of these 85. The reactivity of alkene Hs, HC, HyC—CH=CH, RaOte WyC—E CH=CH, HC Hy wm ” @) towards hydrogen is : @):X>Y>Z° ()Y>X>Z (@) Z>X>¥ =) ¥>Z>X CH, Hp, Pd-BaSOs Product: Tsoquinoline 86. H;C—C=C— ‘CH; (a) an optically active compound (b) an optically inactive compound (©) aracemie mixture (@) a diastereomeric mixture 81.2 CS Cone. Hy804, PUHD, » A and B respectively are : BH. THF Hg(OAc}, HzO 38, p Sts THE CH, OAR, 4 H0,/0H NaBHy, OH A and B are respectively : Hy @ CK both ©) (-cr0H both ©) CX, and € )-exton @ ( ) cision oa( X, H Hf152 GRB Advanced Problems in Organic Chemistry for JEE 89. What reagent is needed to accomplish the following synthesis? HC: ois HC 3 =C! —_ Ht “a Hq ° {a) HfO (b) KMn0,,0H (c) 03, Zn/HO (d) Ph——CO,H 90. Which compound will yield 5-keto-2-methyl hexanal upon treatment with 0? 92. Concer EB, £83501 , Major product : wtb @ YY c=cl © H H . © OX (a) None of these u Hy 93. HyxC—CH=CH, + Het Pe, Product, the intermediate of reaction is : @ CH,—CH—CH, (&) CH,—CH,—CH, (9 ‘cH, —CH—CH, (@ CH,—cH,—CH, CHBrs+ Ale. KOH 94, —— > Major product : r ’ Br Br of >< of Svea Br Br IrHydrocarbons (Alkane, Alkene and Aikyne) 153 95, [|__|] CHC +Ale. KOH Major product : H 1 al > We oS of (a) c) a Aq Ne N SWAG HyCH3 96. NBS x Alc. KOH, y. Hg (OAc), Ph—CH,0H Z5 Zs: NaBHy, OH Hy—Ph H=CH) -H—CH3 @ . o Hy-—CHy—O—CHy—Ph H=CH, ©) @® CH)—Ph Hy, Ni . 97. WI Moley Product : “© “O “OO nonsien 98. Fastest rate of electrophilic addition takes place in : @H a V4 c= CH; (b) on \-¢ Nc CH,154 GRB Advanced Problems in Organic Chemistry for JEE (©) HC. -) (\ CH=CH) 99, Which of the following will be the correct product of reaction? Cl Cone. HsPOz —T OH HH oO oy . : OH 100. Give the reagent that would best accomplish the following reaction : Hi s <= OH nd aH 0 {a) Cold KMn0, (b) CP;CO3H, H® /H,0 8 (©) 03, Zn—H,0 (d) KMnO,, A,OH 101. Arrange the following alkenes in increasing order of their enthalpy of hydrogenation (—AH) : OO Of CF OF @ R, NaOH @) YO 0, NaOH 104. Give the major produet of the following reaction BEN, Major product : én Bs (ont fans mCN H ‘CN . H ‘Br HC Ph . Ch, CCI 105, ya ec, . i H : Ph . Ph ogee. ome CH Hs Ph - 1 (©) Ph—C=C—CHy @ HES, Hy 106. Give the major product of following reaction BulCCls, Major product : 1H we ir cai Br @) mp © (d) o156 GRB Advanced Problems in Organic Chemistry for JEE 107. Which of the following products is not formed in following reaction? (S<« HBr Hg (Ae), Hz0 oY Namo .ton ? Malo product: (@) for () Che © Ce. @) ioe Phy ‘ Hg (Ac);, CH3OH eee 1 Mi t 0s, Ye=c—cHy ajor product : cus Hs Ph Lia—CHs H—CH @ \ b) cH’ Now cay Ph, —CH, (d) None of these Soca; om Hg (OAc), 20 2 (OAes, 110. =CH, > Major product : cu NaBD,OH CH. cHy—p cH. . CHY ‘oH CHY ‘oH cH. = CH, cHy—D @) @ x cay p cH’ Sop Pa y=cr, p22. Major product: * ey Ph. HH Ph, @ SC ) a CHS Nowci CHY \cH;—OH 5Hydrocarbons (Alkane, Alkene and Atkyne) 157 me oe «© (d) cay’ or cay “a Phy BD 112. Se=cu—c oo Major product : * cH H;0,/0H H Ph CH)—-CH; @ ‘\ Non, on ” on HH a 113. Which of the following reagents will bring about following transformations? HQ, H tf (a) C1,/H,0 (b) PBr,/H® Ph Tec © xX @ , cHy “p CH: iy 2 e (c) Hg(OAc)2, H,0/NaBH,,0H (d) BH,.THF, H,0,/0H 114. Which molecule will give following dicarboxylic acid upon treatment with acidic solution of KMnO,? oO Ht «oS whpaB 115. Which of the following reagents would best accomplish the following transformations? Ak os, AL‘ 158 GRB Advanced Problems in Organic Chemistry for JEE (@) Excess BH; NaQH/H,0, followed by Os0, 8 . (b) Excess Hg(OAc), /H0; NaBH,, OH followed by conc. H,SO,4, A ° (©) 03, Zn/H,0 followed by Hg(OAc), /H,0; NaBH, OH (4) 0804; NaHSO; followed by NaOH 116. What is the product of the following sequence of reaction? =CH NaNHy/NH3 Hp, Pd-BaSO,. BH. THF SSS SS = H,0,/0H OFT WSS 0 Oe OE” 117. Which would produce chiral molecule after treatment with Lindlar: catalyst? aX w Aw ort= @ ay 118. Which of the following compounds was starting material for the oxidation shown * below? Comp KMn0,/H® yee roy oC “ 119. How is the following transformation best carried out? ky (@) 0s0,; NaHSO, (b) H,S0,/H,0 (©) HgSO,/H,S0, (a) HIO,Hydrocarbons (Alkane, Alkene and Alkyne) 159 120. The product of following reaction can be best described as : HBr (@ a racemic mixture (b) a single enantiomer (©) a pair of diastereomers (d) an achiral molecule 121. AF NBS, y BB, y Ms, 7. 735: H202, 4 a CH; } @ ) ev ef 122. Product of following reaction can be best described as : BryCChy, ——> s Br (a) meso product (b) a pair of enantiomers (c) structural isomer (d) a pair of diastereomers . 123.Which of the following reactions results in the formation of a pair of diastereomers? Ho ff . BG ff @ ey HBS ) i, HQ Ho ff HBr SY BHy. THF © SY ho, bv” @ . noba 10.)0n 124, \ oy SESS Major product: Br Br o y a 2) CX (b) XAA,,O nn (d) Wz r jr A oth 125, OK HBC, Major product : 00K, Ose OCEa CL Br an Br160 GRB Advanced Problems in Organic Chemistry for JEE sas (YO tc, HBCCly HBECC , Major product : Se ody oct oY ©) 0X @ cr Br Hy, (1 Mole) 127. Product : Pro oh, “ca,” x . Stereochemistry of the product are : (@) diastereomers . (b) meso (©) racemic mixture (d) pure enantiomers 129. CY oon ARINHCO, Major product : @ o) C1 Soon OF © @Hydrocarbons (Alkane, Alkene’and Alkyne) 161 Ch, 2NaNHz |. Hp,Pd-CaCO3 130. Ph—CH=CH—Ph on xX ——> ¥ 7 4 ey product (2) ofthe reaction. A : Ph @ cme (by at o « Ww "\=cr (d) Ph—C=C—Ph F3CO; wi Excess CF;COsH of of oof fo @ wf I m-CPBA(1 Mole) YH ot oC © 0 ‘0 ott Ch 133. ay —__, ‘NaHCO; @ OH162 GRB Advanced Probiems in Organic Chemistry for JEE 135. Which of the following is major product of reaction shown below? Hy ch CHOH. ‘ (b) @ 136. A triene treated with ozone followed by CH; —S—CH, to give following three products. What is the structure of triene? 0 0o°0 rote he wha Ph, 00 oD 9D 9D 0D 137. If the following compound is treated with Pd/C in excess of H, gas, how many stereoisomers of the product will be obtained? @1 (b) 2 (©) 3 @ 4 cH, Hy 138, a EN, Product : 5 . CH CH, cH, @eTe were OEP @ allofthese chy CH oH He H Bz Dg 139. a H,0,°0H CH; : CH . H H H of, o@il, Gt 0 Gil 18 \ HH ‘OH DHydrocarbons (Alkane, Alkene and Aikyne) 163 140. An organic compound C,H, on reductive ozonolysis gives HCHO, CO, and CH,CHO. Find structure of compound. (a) H,C=CH—CH=CH, (b) CH; —CH=C=CH, ©) a : . (@) H,C—C=C—CH, HCHO, H® “Ck Fao Mar product: 1H (he weary 4 ot Reagents (4) and (B) in above reaction : (@ CF,CO;H, H,0; (b) CF;CO3H, HIO, (©) CF,CO;H; 03, Me,S (d) All of the above 143. Which reaction will occur at the fastest rate? HH 1, Hg (OA | 1H. 1H . @ oO © © Q } HBr we «Comment on optical nature of product.164 * GRE Advanced Problems in Organic Chemistry for JEE (@) Racemie mixture (b) Enantiomer (©) Diastereomer (d) Optically inactive . 146. Arrange the following compounds in decreasing order of rate of electrophilic addition reaction. : H=CH) H=CH) é > ¢ CH; 2N. oN y nS Me Me &) @ @) So (a) O>S>P>R (b) S>O>R>P (©) P>Q>R>S @ R>Q>S>P H3 . 147. BONED, y OMENS y 7 Identify products ¥ and Z. Hs Hy Ss SS B 0 ‘0 oO (a) and @ [Cand GO Hn” So H’ SO H CH; (c) Both are See : (d) Both are H ‘0 HLHydrocarbons (Alkane, Alkene and Alkyne) 165 HL (exes) 19. aA oo I @) MV ) A ©“ ‘ @ (Y ' I 150. What isthe final product of the following reaction? Orr = 03, A8;0, 151, Which of the following is not formed in given reaction? NBS CCl, Br : r ® oy © Cy © . , Br - . 152. Which of the following is major product? __HEI( Mote) “Tow Temperature” oF Oo th 153, elect the reagent for following transformation : OH , +-c=c—-1— a @ H,-Pd,HCHO,H;S0, () Ha, Pd-BaS04; Hat OA)2, HO, NaBH,,O# (©) BH3, H,0;,0H, Pac, . (@) Hg", H»SO,, H,, Pd-BaSO,168 z GRB Advanced Problems in Organic Chemistry for JEE 154. Select the starting material for following reaction : fo _He (Achy, HO (OAC), H20 + ~NaBHSOH @ ck oO © x (d) Both (a) and (b) 155. Select the best starting material ‘for the following reaction : . H & H 9 0 20-H20 hic cH ace 156. Choose the best reagent to carry out the following transformations H;C—C=C—H —> ST H H (a) Lindlar catalyst; NaNH, /NH; (0, 1-bromopropane (b) NaNH,/NH; (), I-bromopropane; Lindlar catalyst! (©) NaNH2/NH; (D, |-bromopropane; Li/NH; () (@) All ofthe above 157. Which of the following will be most reactive in the addition reaction with HBr? {a) CH;—C=C—CH . &) AF © Co @ SI. 158. Consider the a rearrangement reaction. yOHydrocarbons (Atkane, Alkene and Alkyne) 167 | Which of the following reaction co-ordinates best represents overall reaction? * @ | © —n 159, Compound (¥) WV \ Reaction co-ordinate Jn Reaction co-ordinate 05,2040, Fh = Find the structure of (X). WS H)>—CH;—Ci Oo Oo t © | r (b) mcr int © Coen) (d) Both (a) and (b) 0 0 [ Reaction co-ordinate pine Reaction co-ordinate “Wr H worvy ow ol a TS HC), sfajor product:168 GRB Advanced Problems in Organic Chemistry for JEE 162. The product of following reaction can be : Agr HBr Z > (a) nai ) OH © @ <9 7 cH, HC Cs oy 163. yed FF Product : bi H @ O) ~~, H H H H Ay : HC,Hydrocarbons (Atkane, Alkene and Alkyne) 168 Sat? CHB 5 Product: Me: CO” K® Bi @) ) Xe . ir Br Br ‘Br 7 Hs an Br) +H; eee oe Hy CH; Hs © nan oe 0 mee o HEEB H CHy CH; Product : 168. Rates of hydration of the following alkenes are : CH;—O—CH=CH, F—CH=CH} CH,—CH=CH, (P) @) ) ¢ S-cr=cu, (s) (a) P>Q>R>S (b) S>R>Q>P () P>S>R>Q ‘ @) R>S>P>O 169. Rates of hydrohalogenation of the following alkenes are : &\-ci-cr¢ cn—cr=cr) © (2) CH;—C—CH=CH, CH;—CH=CH—CH, 1H; . @®) ) (a) P>Q>R>S (b) O>P>R>S (0) O>P>S>R (@) P>Q>S>R170 GRB Advanced Problems in Organic Chemistry for JEE 170. Rates of addition of Cl, /H,0 of the fotlowing alkenes are : i H,=CH, CH,=CH—C—H CH,—CH,—CH=CH, CH;—C=CH, ) @) ®) ® (a) S>R>P>O ‘ (b) S>P>O>R (©) P>Q>R>S (@) P>Q>S>R Red hot hot Cu tube, Hy Hy ; Hi, (a) oO (b) ©) (a) HC Hy . NaNHz/NH3() CH3CH2Br Li, NH3(/) eS CH; 171.3CH;—C=scH —", 172,CH,CH,C=CH (@) CH,CH,CH=CH—CH, (®) CH,CH,CH=CH, CHCH ' ft o ae () as =C, cH,CHs | . ‘Na, NH3(D) y 173. CH;CH,CH, —C—H +CH,—C=cH 3", OH C : c @ ne, ‘ony o NA ‘cu, 1H © (NF Hy @ 4 OH 58 174, The products of the following I and II sequences are related as : H), Pd-BaSO,, CHy—C=C—CH, (a) diastereomers (b) identical (©) enantiomers . (d) geometrical isomersHydrocarbons (Alkane, Alkene and Alkyne) 171 '=CH Bry, HO 175. ———— ir Br = cael ® © or i Br Br C=CH © @ Yor KNH He Br/CCly KNH) > 176. HC=CH —--—_———> 4 ————> B ——5> C -—_4 D ‘Cl—(CHg)p—Cl Pa-CaCOs (Mole) Na, NH3(I) Nant “CO 8CO (c) CA (d) None of these 177. Which is the most suitable reagent among the following to distinguish compound (3) from rest of the compound? 1.CH,—C=C—-CH, 2. CH; —CH, —CH, —CH, 3. CH,CH, —C=CH 4.CH;—CH=CH, (a) Bry inCCl, (6) Br, in CH,COOH (©) Alk.KMn0, (@) AgNO, /NH,OH 178. Two gases P and Q both decolourise aqueous bromine but only one of them gives white ppt with Tollen’s reagent. P and Q are likely to be : (a) H,C=CH, and CH,—C=sC—CH, CH and CH,—CH,—C=CH CH and CH;—C=CH (4) CA; —CH, —C=CH and CH, —GRB Advanced Problems in Organic Chemistry for JEE ®) Asn © Ay @ un 180. Which of the following hydrocarbons should be choosen as a starting material to prepare 3-hexanone by the hydration? '=C—CH: @ AF 8 OANA €. (AA WAY Bi Br on aut Wi. SCH—CI —T Bi ‘Br Br Br yA Bi Br / @ x= ®) () H—C=C—H (4) CH;—CHE a er ae Nor 182, Among the following compounds which one cannot decolourise alkaline KMn0 solution? (@) HC=CH (b) CH; —CH,—OH oO Il (© CH;—C—H (@ CHy—CH, '=CH NaNH D2 183. De > 4 Sapaso; B _ End prodiict B is : €D=CD, Ph D ‘ VS” oor ) Sexe < . vp Ny mY” © — (@) Ph—C=CD Dp Sp H NaNH; isa, oac® ME, Pr Nr The major product is : Ph H @ ScHc% (b) Ph—C=C—Ph Pr NH (©) Ph—C=sCH (@) None of theseHydrocarbons (Alkane, Alkene and Alkyne) : 173 (Sia)z, BH P and Q are respectively : ° (@) Ph—C—CH, and Ph—CH,—C—H oO 4 (b) Ph—CH,—CHO and Ph—C—CH, ° ° ll ll (©) Ph—C—CH, and Ph—C—CH, (a) Ph—CH,—CHO and Ph—CH,—CHO BH3.THF 186.CH,;—-C=C—CH, —————> Major product : _ CHS ;COOH i (a) CH;—CH,—C—CH, (b) CH3CH,CH;—C—H : oo, cH Ch . Ah © omc @ Kay H” CH; H H 187. Which of the (lowing: molecules is not linear? @ (b) HC © Homc-cscH _ @ HC=CH 188. Which of the following reagents can be distinguish propyne from properie? (a) Bro, CCl, (b) Dilute KMnO, (c) Conc. H,S0, (d) AgNO, in NH,OH 189 Which alkyne gives 3-ethythexane on catalytic hydrogenation? S S @) of ill © oC (d) All of these 190. Which revction yields the major product shown? HH H,0 _He"?, 1,0 , @) >= ESO,” () — ee, jr __2HBr © = “1h © >= aa ont 1 [174 GRB Advanced Problems in Organic Chemistry for JEE 191. Ph—C=C—H 2, + Major product: | | (a) Ph—C=CH* (b) Ph—CH—CH,—I (©) Ph—C=C_I (@) I-C=C—H “ ew c=C—CHy ‘Br wa — ey To carry out above conversion which reagent will be used? (@) CHBr,/NaOH, Na/NH3(J)_—_(b) Na/NH,()), CHBr, /NaOH (©) H,/Pd-BaSO,,CHBr,/NaOH' (4) H,/Pd-CaCO,, CHC], /KOH 193. ( \acin +CHCI,*, Major product : H @) (b) CHCl, ‘CH;CH,Cl 1 1 cl _. HaPd 194, CH=CH—NO, =r Major product : (a) PhCH, —CH,—NO,, (b) Ph—CH, —CH,—NH,, (c) PhCH, —CH,~-NH—OH @ (cto, . H,0/H,SO, 195.CH,; CH, —-O—CH=CH, —~—-—*» ‘The product/s formed in the reaction is/are : (a) CH; —CH, —O—CH,—CH, —OH OH | (b) CH; —CH, —-O—CH— CH, {) CH, CH, —OH and HO—CH=CH, ° . Il (@) CH,CH,—OH and CH,—C—HHydrocarbons (Alkane, Alkene and Alkyne) 175 mY Hy te H Hf ok 0 0 0D on : / 197. CVY An NaHOOs, Major product : T 1 1 ‘OONa © (Coots ©, ‘OONa 1 1 HCL . . 198. Sa,” Major product . ct @ ©) oe © Cr @ i 199.Which of the following compounds ‘ produces-1, 5-cyclooctanedione on ozonolysis? 0D OD 0D ok H x mC) —BnICCh , Major product : H i : N: N : .@ (b) CY © Se (d) All of these 1 : Sr 1 BrGRB Advanced Problems in Organic Chemistry for JEE ny sje poet: “ey . ‘OH 202. Lilian, BELG Mele) , Major product : © @ Ay &) Ns 4 @ Vv 203. O) Br (1 Mole)“ Major product : Br . Br Br Br . 0 9 O oe O ‘Br ‘Br Bi ‘Br Co2(Co)g 100°C, High P OH wA ® a op=o an oO CH,, 205. CHy CH. CH;—OH CH; CH,—Cl ) “ ) Hy” Nc cas” Non CH CHy—Cl CH3, . CH,—OH © S< @o YS. CHY Ny cH” 2 2 204, H,C—=CH, +CO+H, = CH, HOC, Major product : HHydrovarbons (Alkane, Alkene and Alkyne) pcp hh Z 207. Ci Comair product : *OB 9 OO eC eC Ha mm O> +I —45 Major product : 7 0 oO @) Hw Ys © oy (@) No reaction Ohm A, IyNaHOOs, y. yi, he 2 L I © 3, ° NB. of : oO” CH 4 20[ + Ne H_ —45 Major product : OCH; OCH; ICH;178 GRB Advanced Problems in Organic Chemistry for JEE Hg Pr 21h. XY +4 on —4, Major product : bud 5 oh 212. YY + CHyL, 22-4, Major product : , b ors xs © wr @ »y~ Ip OCH; 213; On — a2, Major product : OCH, @) CH, . © Ha OCH; OCH I CHAI © (d) ‘ ‘CHI 1 214. Find out nature of product obtained by selective bromination of following reactant : Hs Br, ey hy = HC CH (a) Meso. (b) Diastereomers, (c) Enantiomers (d) Homomers.Hydrocarbons (Alkane, Alkene and Alkyne) 179 215. Devise a synthesis of following compound from cyclopentane : oe ff ‘Br Cl, ale KOH Br Br C2H;0° Br, CCly @ 3 > ae (b) 3 = hy Clq hy Bry alc. KOH NBS Br © = az? ~—«@ None of these v 216. Which of the following alkene will give enantiomeric product on reaction with HBr? oahrn © me OA, OO 217, Draw the product of following reaction with stereochemistry : on —se* H202,0H nC ‘CH; @ pee (by Jou HC “H HAC “OH OH © tt CH @ 7 Os “ HC H A3C A : On OH 218. Devise synthesis of following compound from cyclohexene : oO - HBr N (a) Addition of HCN (oy 85, MC i, NBS HCN H®/H,0. ome os 2Hcl | 219, 4a cl Cl Reactant ‘A’ is180 GRB Advanced Problems In Organic Chemistry for JEE coy (@) Alllof these CFs (@) None of these HN } HN HL , @ COOH ) CF; Ola cl OH 221. Suggest the product of following reaction : 1 He(OAea ea » 2. NaBH, oO) oo () core OHgOAc oH e) © d) All of these _ fe) Oe 0; zn|>- uN >, sfajor product : Q O a) ® oe NY on ) oe _ (@) None of these HHHydrocarbons (Alkane, Alkene and Alkyne) 181 HOOC. ‘COOH 3. > on BD;.THF 3 H7O2, OH coou coo COOH cooH u—}+—p nt-p utd H Oy op © pou © on, © yo it coon cooHu Coon COOH 224. Find out major product : i o—c—0—C(CH); hb ae oy HG, @ © rye ° y (© | 0-C—oH (@) No reaction As . ° CHy—C=C—cH my re 9 2 Product : ‘NH—Ph { ° o- I : - (CH,—C == C—CH3 ‘CH)~~C==C—CH; wx WN” ® a t 1 Ano : NH—Ph ° I () I<, (d) None of these N |182 GRB Advanced Problems in Organic Chemistry for JEE | SCS “MORE THAN ONE CORRECT ANSWERS I 1. Which are correct regarding boiling point? fe ABR A @ v= > C Ww NY WwW Noy Asc fo nN JA (b) C=C. < c=C Hw OME Ww No 1 a 1 ©) > 2, Which of the following orders are correct regarding stability? (OQ oO) A — Ais BA © . =on> — =e > bee HC” Te Nan Ww oO Hy HG Br a eet c—cac—cn, Bf cH; Which of the following reagents can be uséd for above conversion? (®) Za/A (b) Mg/A (©) Nal/acetone (4) Alc. KOH 4. The correct basicity oders are: . ° (a) CH oH, Hj,C—CH °° e (©) CH; —CH,> HO=C (@) H,C=CH> H—C=C CHs Hy 5. Pip Products : eeHydrocarbons (Alkane, Alkene and Alkyne) _ HC. (b) Be () my ? aC 6. Choose the correct comparisons : cl. Sat .o +H: @ va * ero ec oF Bes 7 (CH3 (b) =C. > (M.pt) HH ‘cH, w =e Ch AGC © > (Reactivity toward HBr) ‘CH; H 3 HjC._/CH; HC. _/H @ °K Xo pt HH H nu, 7. Which of the following reactions give meso product? sS A Hs! Bry, CCly 7 = C. Pg PK H a4 n 7 © bac Cold KMnO4 @ (ess | Bra, CCl 3 Cold KMnO, .- LEI RMA 5 HO ‘CH; 8. Which of the following reactions give diastereomeric products? HC Hy Ke “ @ C=C Brg, H20 (b) Bry, CCl4 SON H H CH, CH3 HG H 7 © A, ya. 0 iH ‘CH; HC’ ‘CH,CHs 9. Mark out the correct comparisons. (a) 3°H > 2°H > 1°H (reactivity for bromination) () Ay < S= CH, (stability) (©) A < S=CHh (reactivity toward HBr) »@ AQ < S=CHy; (reactivity for catalytic hydrogenation)184 GRB Advanced Problems in Organic Chemistry for JEE p> Products are : OH apy oob<, © Xn oU- H3C. _CH)CH3 ® 1. wn mCPBA, 4 HO, p Choose the correct statements regarding above reaction : (a) Product. 4 is optically active (b) The conversion of alkene to product B is a stereospecific reaction (©) Product B has chiral molecule (@) Formation of “’ is syn addition reaction 12, Which of the following reactions are not feasible? (a) HC==CH + KOH —> (b) HC=CH+NaNH, —> 8 (c) HC=CH +NaOH —> (d) HC=CK® +(CH;);C—Br —> Hy HHO, 13, The féllowing synthesis cannot be carried out by : I (CH=CH, CH=CH, Oo - cl T = Clz_— ICVCH3;COOH —ICVCH3COOH_ Zn, dust Se @) HOCVH® —Chy/Fe ICV/ZnCiz NaOH, 4 () —— > 5 (excess) HOBr,H® —Ch/Fe — ICV/ZnCl,__Zn dust, CH;COOH ©) —, oS . (excess) . Bry/CHyCOOH Cla/Fe ICV/CHyCOOH. NaN. @ 2! 3 i Fe 3° JaNHz (excess) + 14, 1-butene is formed i in reactions : as ) AAys SO I ot Kons @ anyve Ss I_Hydrocarbons (Alkane, Alkene and Aikyne) 185 NaNHz — Ph—CHO. Mn02 15. Bu—C=CH ——> 4 —no? 2 — Cc 2 Compound C of the reaction cannot be : HO CHO C=C—Bu @) ) =C—Bu HO © @ =C—Bu c=C—Bu 16. Acetone is the major product in : . HPO 1 H,c=C=cH, —> Hg"? /H,SO, Ht H,C—C=CH ————> BH, -THF I H,C—C=CH s H202/OH (1 () (© m (d) None of these 17. Which of the following can be prepared by Wurtz reaction? (@) CH,CH, (b) CH,CH,CH;CH (c) “oe CH; (a) CHhy— Cll CH CH; CH, CH; nA x CHyCH,CHy (a) Compound 4 i sf > eas (b) Compound A is H,;C—CH,—CH, —Br () Reagent B is H, /Niat 120°C (d) Reagent B is LiAIH,186 GRB Advanced Problems in Organic Chemistry for JEE 19. Which of the following molecules of alkane will give only one monohalogenated product on reaction with halogen in presence of sunlight? @) HyC—cH, (&) HyxC—CH, —CH, (©) (H3Q)4C @ (O)-er-XO) 20, Which of the following methods yield saturated hydrocarbon? BH; CH2N2 —CH= CH= CHDN2 () RCH CH, Gai (b) R—CH=CH, —2 OOH © RAAB Melcher, @ cr Non Ca 21. Which of the following reactions will give result as alkane as major product? r HH. AA Hilt, oy A ats NaBH, © >a 48h, LiAlHy @ AA Rabi 22. Which of the following alkanes cannot be synthesized by the Wurtz reaction in good yield? aye © yk Ox @OXA 23, Which of the following reactions produce tie same product? (@) A Baby, _Nelether (b) ro NaOH, _Electrolysis (OOH COOH © »~, _Mafether, _ CHsBr @ >< Red P+ HL coou 24, How will you distinguish compounds 4 and B by using laboratory reagent? ° : HC=C’ oO “ @) (a) A reacts with AgNO; /NH,OH (b) A reacts with CuCl, /NH,OH {c) B does not react with AgNO; /NH,OH . (d)-B reacts with CuCl, /NH,OHHydrocarbons (Alkane, Alkene and Alkyne) 187 25, Predict the products of following reactions : i Hp, Pd-C Vr 2 a) | . S h HyLindlar catalyst py (a) Ais Ph—CH, —CH) —CH, —CH, (b) Bis Ph —CH=CH—CH—CH, (¢) dis Ph—CH=CH—CH—=CH, (4) Bis Ph—CH, —CH, —CH==CH, 1.NaNH2 Hy 26, H,C—C=CH > A 2 BB 2. CHyCH2Br Pd-BaSOq (a) Ais HyC--CH, —C=CH (b) 4isCH;—C==:C—CH,CH, HC _/CHCHs BO (©) Bis Yo @ Bis ‘ é wa Hu” NCH,CH Hg*7/H)SOs KMn04, 27, HyC-—-C=CH > X ou ° , | i (a) X is HjC—C=CH, (b) X is H;C—C—CH, 0 | (©) ¥ isHyC-—C—-OH (6) ¥ is HCOOH 1H; ‘Acetor . H; 28. H,c—c=acH ME, xy “Sy mens Z: (@) X is HyC—CH=CH—CH, (b) X is HJC—C=C°Na® OH | (© Yis Hyc—CmC—E— CH @ Zis#yC—C=C—-6= cH, CH; CH; te 42 pq ». ASCH Bali, y CL, y Hg!H50_, 7. gs @ xis AKU & vis AK 0 (©) ZisVO _@ A, Oo4 188 GRB Advanced Problems in Organic Chemistry for JEE 30. Which of the following solubility orders in water are correct? (@ H,C—C=CHCH,—O—CH, (©) H,C=CH—CH, CH,CH,CH, Bry KCN, (ron can 4 B: : CH;—C=N CHy—Br was xX! wan( x ‘OCH ‘OCH; CHy—Br CH,—C=N . A w( @ Bi ‘OCH; ‘OCH; 32. Write the products of the following reaction : CHN2, 4 A rats HCCI; + OH B (@) 4 >< (b) Ais [><}e d © ><] @ ais) ><] ct ‘cr HC. H 33. Yad’ D,INi H NcH, cH; cH; Hy GH D. H H D oD H H D @» Hw. Oy H Oy dn @ | D 3 CH, CH; CH CPB, 0° 34. Cyn. AO 8 (Majon): : in NaOH + 08 5c (Major)Hydrocarbons (Alkane, Alkene and Alkyne) 189 CH @A wf Eo (b) B Chu a iow : CH CH; @B oc @ ce Kon Pou OH . Which of the following carbocations would you expect to rearrange? *H, CH3 Ae “0 CH; ys CH ‘ \e ©) @) Hic” ‘CH—CH3 8 36. Select the correct statements : (a) addition of Br, on frans-2-butene gives erythro product (b) addition of Cl, on cis-2-butene gives threo product (c) addition of Br, on cis-2-butene gives racemic mixture (@) addition of D2 on cis-2-butene gives meso product 37. Which of the following will give allyl halide? Se 1: Ci, 800K _(@) H,C=CH—CH, aS (b) H,C=CH—CH, 25 0; (© H,c—cH—cH, SS, @ HyC—cH=cH, +HBr —= > 38, Which of the following reactions will give least substituted alkene? ~ OH Cone. H2S0, IT MesC—OK® @ 3 of. > ° ‘AgOH Ale. KOH, OANA AE? eK =A | . Br 9. Which of the following reactions will give alkyne? @ vo NaN, (b) x, _KNib,190 GRB Advanced Problems in Organic Chemistry for JEE Br Br Zo,4 | 2 so ©) HCC C— ce, 28, H,c—c=cH HE H2804, Br Br 40. An organic compound on reaction with O; followed by Zn and HO gives e CH. ert, on ten, ‘The structures are : ® Kay “OO « | @ 41. Which of the following reactions are correctly represented? (a) R—CH=CH, + HCl —> Racin ca H,0, () R—CH=CH, + HI —*y R—CH,—CH,—I Hy02 (9 R—CH=CH + HBr ——> R—CH,—CH,—Br I H20, | (@) R—CH=CH, +H] > R—-CH—CH, 42. Which of the fllowing give allylic substitution product? A S00 @ ARSE, OH A SO, OAS MARS by 3. Which of the following reactions are correct? oN Bry/CCl. @ (_) 2's Br “Br CHACOSK, = ®) HnZO OH © fy . Br Me. . Me, @ HALO - @ me es 0 Me Me MeHydrocarbons (Alkane, Alkene and Alkyne) 191 44, Which of the following are correct for the addition of X; on alkene? (a) Reaction involves cyclic halonium ion as intermediate (b) Reaction involves carbocation intermediate ” (©) Addition is anti addition reaction (@) Trans alkene (Symmetrical) gives meso product 5. Which of the following will react with 1-butyne? (a) AgNO, +NH,OH (b) CuCl, +NH,OH e (©) Na (@) KMnO,/OH 46. Which of the following do not give rearrangement of carbocation in the addition reaction of alkene? . (@) Bry/CCly (b) HBr (©) HBr/H,0,, bv (€) 050, 47. Which of the following will give acetone? Hg", H2SO. He @ H,c—c=acn 2 $ (CH; —C=mCH ot on, H2,0 KMn0. 4, ‘d) HC==CH+CH;,0H —~ OK ae @ ‘ 48. Which of the following compounds can exhibit geometrical isomerism? (@ HC—CHy—CH=CH—-CH, 0) HC OH HO Scan” @ | oak HH” HC CHS 49. Which of the following products will form by given reaction? AW SS, @ 7YS (b) HBr © daw @ BAA Br 50. In which of the following reactions the correct product is given? CCl, H,SO, Hes) w/ MS 9 OECD Br H®/,0 HBr © °s vs ao ON ete VV192 GRB Advanced Problems in Organic Chemistry for JEE dS eka LINKED COMPREHENSION TYPE I Passage-1 Conjugated diene reacts with unsaturated hydrocarbon in presence of heat to produce six membered cyclic product, this reaction is known as Diels-Alder reaction, For this reaction conjugated diene should be in cisiod form. Aromatic hydrocarbon do not give Diels-Alder reaction : Oo oO A | i Z Qs Diene —Dienophile Intermediate 1. Which of the following conjugated unsaturated hydrocarbons will give Diels-Alder reaction? oy Zz 2 @ © Cc © Can @ Ct 2 iw S 2. Which of the following Diels-Alder reactions is fastest? A 102 On @ +i + ) Ce 4% eN NO? 2 02 © | i oA“ @ Cue a Ay 3. Find the product of following reaction : On + CN CN (a) (>) ‘CHO ‘CHO COOH, {c) (d) No reaction COOHHydrocarbons (Alkane, Alkene and Alkyne) 193 Passage-2 Addition of Xz on alkene is electrophilic addition reaction. Reaction proceed through the formation of 3-membered cyclic halonium ion. Nucleophile X° attacks from backside of cyclic halonium ion hence total reaction is anti addition reaction. [f this reaction proceed in polar solvent then solvent itself acts as nucleophile. . x \ VV roe +X — A x Y< x th i Vl we ATS xe x 4. Which of the following statements is incorrect? (a) Symmetrical trans alkene gives 2 products on reaction with Br>/CCl, (>) Symmetrical cis alkene gives 2 products on reaction with Br,/CCl, (c) Trans alkenes give erythro product (d) Cis alkenes give threo product Mechanism : s Ch (1 Mole) * CCl, CH. fans 6 ~ LETHON, Major product: He H Ph u——cr H ® oy,—t—a On194 GRB Advanced Problems in Organic Chemistry for JEE Ph Ph H——c1 é H——y-— OCH; H,cO—+—H @ qty CHa CH; © Passage-3 Addition ofFLX on alkene proceed through the formation of carbocation. This reaction is also known as Markowniko! ction. According to Markownikoff’s rule addition of electrophile occurs on that carbon of alkene which have more number of ‘H’ atom. xX | Ph—cH=cH, 5 ph—CH—CH, +Ph—CHa— CH, — Major Mechanism : H—X =P H°+X° Ph He Pig 6 =CH—> — SC—CHy+ Ph—CH,—CH, Hw He More stable Less stable Po aN ve wm OI cay yes H ¥ cH, Hy Enantiomer 7. Which of the following alkenes can produce diastereomers? (@) CH;—CH=CH—CH; () € \—cimcn—cn, H, CH; "Hs . © : (d) CH;—CH=CH, 8. Which of the following alkenes will give Markownikoff reaction? (@ Fc—cH=cH, 2S (6) HeN—CH=cHy 2S CH, (© 0,n—cn=cu, 15 @ ps —cr; BB, cH 9. Arrange the following alkenes in decréasing order of reaction with HBr: CH CHs CH Ca cC=CH . =CH, |, C=CH) eat CH; CH mc" - CHy—0—cHe H : ) ®) ) (a) P>Q>R>S (b) R>Q>P>S (©) S>R>Q>P W@) Q>R>P>SHydrocarbons (Alkane, Alkene and Alkyne) 195 Passage-4 Alkene and alkyne both undergo electrophilic addition because of m electron density, they behave as electron rich species, alkenes are more reactive toward this reaction because the intermediate formed when an E® adds to an alkyne is a vinylic cation whereas the intermediate formed when an E® adds to alkene is alkyl cation, which is more stable. Ne 6 R-C=C—H 45 R-C=CH ‘Vinyl cation ze a R—CH==*CH, — R—CH—CH3 Alkyl cation 10. Ch, HCI (I Mote) ; . ° Yo ©) a” ch @) Y . 0. Y Oo ‘OH OH + 12. In the reaction : Oxn Ig, NaHCO3, aes“196 GRB Advanced Problems in Organic Chemistry for JEE f 1° ‘—OH OH OH ® Ay ) bey I oO I 0 I ©, @ a) oo Passage-5 Hs CH,=CH—C_Br CH:MgBr CH, p HDPEBISO4 rel 2CH=ECH Sep A 03-THE. ,_H®, He"7/H2S0q Mes © D 13. Find structure of compound A: ca ! | * (@ CH,—CH—CH—cH, () HyxC=CH—CH=CH, | (©) HC=C—C=CH (@) H,C=CH—C=Cu 14. Find structure of compound E : : Jibs (@ HyC=CH—C=C—CH,—CH= ‘CH, CHy () HC —CHfy—Cmc chy CCC ‘CH; Hs H,C=CH. X CH,—CH=' ©, Sent Cis H H H,C==CH. H @ dome fib H CHy—CH=K ‘CH;* Hydrocarbons (Alkane, Atkene and Alkyne) 197 15, Find structure of compound D : . oO HO, (0 H. H 0G HO, Va b) (d) oY Y o YY) © Kon 00 H3C” “oO O OH H3C Passage-6 P(CsHoBr) NaNH2 v Decolourise Br; water 95 Q and cold KMn0, 2—¥ye,5 (No reaction with Na) Lindlar catalyst ‘Na/NH() R s (Ho) (Csi) 16. Which of the following is compound P? . @A ®) 7 ©) ae @ eo Br Br . 17. Rand S are: (a) position isomers (b) enantiomers (c) geometrical isomers (@) functional group isomers 18. Identify structure of compound T : “oO I (a) CH; —C—OH ) Aa © cH, —CH,—F—O1 @ csp H I : ° ° Passage-7 Hydroboration oxidation reaction is a process of addition of HO according to Anti-Markownikoff’s rule. 'BH3.THF ~ . CH,CH=CH, —————> CH —CH, —CH,—OH H2Q),0H Reaction is regioselective. Regioselectivity of reaction is increased by using hindered boranes. THF (Tetrahydrofuran) is used to control reactivity of borane. . a198 GRB Advanced Problems in Organic Chemistry for JEE* CH;—CH=CH, — CHy—CH==CH, + — | °—> CH,CH,CH,BH, H—BH, H—BE, 2CH;—CH=CH SS (CHsCH,CHY)s B or RB R=CH;CH,CH;— 6 8 H—O—O—H+0H —> O—O—H+H,0 ~ : R R . oR | I : | anal 0—0-H—> a0 R—B—OR OH R R 3R—OH + BO}? —BD: THF THF . — air Major product : H202, OH CH cry CH, @) “ce ) Che Of fon © Chi 8 4 4 x r fou OH iD 7, OH HOOC " BD3.THF on 20. Nowe eS ie x” coon 2:02.80 COOH COOH COOH COOH H; H- oD D: H ae D © nto © 4 p Oy op © 4 OH COOH , COOH cooH coon BH.THF 21. CH —C=CH = + Major product: . H,02,0H > ° . (a) CH; —C—CH, (b) CH, —CH=CH, I OH OH | (© CH,—CH=cH, (@) CH, —CH, —C—H 3Hydrocarbons (Alkane, Atkene and Alkyne) 199 Passage-8 ‘Alkane may be prepared from alkyl halide by Wurtz method where alkyl halide reacted with Na in presence of ether. 2R—X Ay ROR + INA, Mechanism : 2Na —> 2Na® +2c7 a 2e + RX — R°+ X® i Ret GS RR+X? 2Na® +2x° ——» 2NaX Na/ eth 22, CH,CH, cl “", Which of the following products may not be formed? : (@) CH; CH, ~ (b) CH;—-CH, CH, —CH, (c) CH, =CH (@) CH, CH; | ether 2B. oy Br Aeleter, Major product : cH; CH, CH, fis . (a) HC=C (b) CH; —C—C—CH, NH - 1] CH; CH; CH; © ye CH,CH, (@) No reaction CH; 24. Which of the following compounds is most reactive for Wurtz reaction? Br Br | . - (a) CH; —CH,—CH, @) Br CH; | © @ CH, + Br CH,200 GRB Advanced Problems in Organic Chemistry for JEE Passage-9 Hydrocarbon 4 (C,H,2) was treated with BH,.THF; H,0,, NaOH to produce - B(C;H,40) as only product. Reaction of B with TsCl/pyridine followed by KOH gives C (isomeric with A) in addition to the olefinic products. Treatment of C with ozone followed by Zn/ AcOH produces only compound shown below : 0 CH 25. What is correct structure of ‘A’? (a) o) Q © @ cy 26. What is correct structure of ‘B’? . OH On (a) (b) ©) @ ‘OH OH 27. What is correct structure of compound ‘C”? 3 9 0 a Passage-10 Oxymercuration demercuration reaction is process of addition HO according to Markownikoff’s rule without any rearrangement. : ou Hg(OAc)2, HO ao) | CH,—CH=CH, CH,;—CH—CH, 5 ‘NaBH4, OH Mechanism : e e- Hg(OAd), =* Hg(OAc)+ AcO- OAc f Hi cHegren Hy 2CH—CH; —"5 CHy;—CH—CH, ~ CH;—CH—CH3, Me a, on (RH OH ; H .H a Onc’ * a NaHydrocarbons (Alkane, Alkene and Alkyne) 201 ° Base OH is used to neutralise H® produced during the reaction : CHy | Hg(OAc)2, H2O 28, ( \-c=cr, TEOAD: TES, Major product : NaBD,, OH CH; | @ Pe CH, OH CH; | ro) oo CH,—OH CH, | 0) me CH,D OH CH; | (d) Ph—C—CH,D ~ D op CH; | Hg(OAc)}z, CH30H 29. CH —C—CH=CH, “SOAS THF product: | NaBHy, OH CH; OCH, CH; CH; on @ Cy —F— CH—CH, CH, CH, OCH; to © CHO — CH—CH, CH; ~~ 3NH2 — Hg(OAe)y 30. ——_s..? NaBH,COH OH NH; TF H | N 0 | | ) cH — CH—CH, CH, (@) No reaction ) or (4) Both (a) and (b)202 GRB Advanced Problems in Organic Chemistry for JEE Passage-11 Free radical substitution chalcogenation is shown by the compounds having at Teast one H-atom an sp°-hybridised carbon atom. Here substitution is due'to free radical formation in presence of sunlight or heat or peroxide. The abstruction of H-atom is on the basis of stability of free radical formed. norte 2 Tey | 5 Q P 31. Which of the above hydrogen can be abstracted easily by halogen in presence of sunlight? @ P 0) @ OR @s 32, In the above reaction how many monobrominated products are possible? (a) 3 (b) 4 © § (@)7 33. Which of these H-atom can be substituted to get an opticatly active halide? (@) P 9 OR @s STaNa MATRIX MATCH TYPE li 1. Column (1) Column (H) @ PARKA, = O P. Red P+HI B 5 © © ch Q. Nalether OH OH . t ° © “y aA R. NH,—NH,/OH COOH . @ oy — oo” S. 2n-He/HCI 2. Column (1) Column (II) . CH. 3 | (20H, FH a — CH, FH CH CH, P. LiAlH, CH; ~ CH; CH,—x cH, ) | — Il Q. Na, dry ether * CH; —x cH,Hydrocarbons (Alkane, Alkene and Alkyne) 203 © CH Hx — CA, FH CH; CH; 1H: CH; oo (d) CH;—C—¥ —> CH)=* \ bn ‘CH; 3. Column (1) “Os met (b) AQ Seb Clay Br CH,OH © st = >< HoHO on @ ws am 4, Column (I) * »O-e-O) HH &) C=CH (©) (Oy-c=c—encrt @) H-C=C 5. Column (1) HC, (a) H;C—C==C—CH; —> Jo H HC (b) Hy3C—C=C—CH; —> c= W Z™, H a “No, R. Mg, dry ether S. Zn/A Column (11) P, Rearrangement Q. Carbocation R. Free radical S. Cyclic transition state Column (II) P, Reacts with H,-Pd/CaCO, Q Trans alkene will form when reacted with Na/Lig. NH R. Reacts with ammoniacal AgNO; S. On oxidative ozonolysis produces CO, Column (1) CH; P. Hy, Pd-BaSO, Q. Li, Lig. NH,GRB Advanced Problems in Organic Chemistry for JEE (©) HyC—CH=CH—CH, —> . H,C—CH,—CH, —CH, CH; CH; ® 7 O 6, Column (1) \ ‘HBr @ ‘C=CH, —> CH,CH, ) H- \ HBr (d) Ph on” Ww 7. Column (1) HC 9: _ A {a) HS Tee” aC Hg", W804 (b) H;\C—C=cH ————, oO ll Red P+ HI (©) H;C—C—CH, ———> e il NoH4. OH @ HC—eHl— cH, —C—CH cl 8. Cohumn (1) (a) Markownikoff product P. CH; CH=CH, R. HN=NH,A S. ByH,CH,COOH Column (1) P. Free radical Q. Enantiomer R. Diastereomer S. Carbocation Column (11) P. Reduction ° ll Q. CH;—C—CH, R. Oxidation reaction oN Column (I) — H202, hv205 Hydrocarbons (Alkane, Alkene and Alkyne) (b) Anti-Markownikoff product BCS Ob cuca + KOH : aN , H H i HCl (©) Peroxide effect R (O)-cn=cm (d) Mixture of stereoisomers 5S. CF;——-CH=CH, —> 9. Column (1) Column (11) (a) Conc. H2SO4 a P. Hofmann’s alkene ‘OH 10. can a e CpHsO/CJHsOH {b) Av ° ‘MesCOK” wre ‘1 Br Q. Saytzeff’s alkene R. Transition state Alc. KOH . OA —_ S. Carbocation Column (1) Column (IT) CH; . $ 0: Oy P. 3 different products @ Me2S erent PI HC. Os . : ©) = CH—CH; CH=CH “7g,0” Q. CO, will produce HC’ 0: (c) HyC—C=CH a R. Oxidative ozonolysis 0: (d) HyC—CH=C=CH, maw? S. Reductive ozonolysis Column (1) . Column (I) HCY Hs Cold KMn0, @ a’ P. Racemic mixture H H HC. CHs Br, CCly Q. Erythro206 GRB Advanced Problems in Organic Chemistry for JEE AsCy 78 _cRCOH : © =O OE, R. Threo H - \cu; HeHO S. Meso product - Column (I) P. Dicarboxylic acid will be formed when reacts with not alkaline KMnO,. (b) > Q. Decolourise Br2/H,0, R. Dicarboxylic acid and will be formed when reacts with O3/H,0). 5. Number of allylic hydrogen is odd. INTEGER ANSWER TYPE PROBLEMS || 1, Find out number of dimerize products obtain by following reaction. H,C—Cl + H,C—CH,—Cl + H,C—CH, —CH, —CI. wis 2. How many mono chlorinated products may be obtained when the alkane shown below is heated in the presence of Cl, 3. How many of the following reactions, leads to the formation of diastereomers. Pho HH ae ACI HBr ® vo CCly ® SecHydrocarbons (Alkane, Alkene and Aikyne) 207 CH3 Phy Ht D — cp, Hee net @ =o a © a a, CH | Ph sCH3 Ph, © co Hel () Hct och, cc, ‘CH CH3 4. Identify number of chiral centers present in product obtained by following reaction. Br, cc CH; “H 5, How many of the following addition reactions are syn addition réaction. CH; Hy CH; 7 Br oy mc’ TNi Na Dp Dd — Cy BPE B84, (4) yo C= . : , BH3:THF Cold KMn05 © Cyr oe « Cr Lae Kn, CH, _1-PRCOSH Br, +H,0 ® Qa mo” OCT 7 CH; 6. Of the following reactions how many reactions are considered as ‘oxidation reaction. 0; @ > _o (b) SS KMn0,/08 Ph “A820 A oO ~ OSE @~ 2S, 90 © Cr ae, cy) AA esate,208 GRB Advanced Problems in Organic Chemistry for JEE ) In this reaction which ring will be reduced, by hydrogenation. 8. Of the following compound, find out numbers of conjugated unsaturated hydrocarbon those would not show Diels alder reactions. a ¢ oo ou S S 9. How many different products (excluding stereoisomer) can be obtained by following reaction. Co HCI,CCly 10. Examine the structural formulas of following compounds, and firid how many compounds will produce CO; on oxidative ozonolysis. > Hj3C—C==CH » Ph—CH=CH, » -\Zrn SSne, Alkene and Alkyne) Sn SS =0 €xercise-1 : Only One Correct Answer Level-1 2. @) 2.(b) 2 (a) 4.) 5.) 6.(b) 26) Bb) 9. (C) 20. (0) 11. (b) 12. (b) 13. (a) 14 Wd) 15. @) 16. (©) 17. (©) 18. (d)_ 19. (@) 20. (0) 24, (6) 22, (d) 23. (0) 24, (O) 25. (©) 26. (b) 27. (2) 28. (6) 29. (@) 30.) |B. (@) 32. (d) 33. (c) 34. (2) 35. (b) 36. (2) 37. (c), 38. (b) 39. (@) 40, (A) $2: (4) 42. (c) 43. (d) 44. (2) 45. (@) 46. (©) 47. (b) 48. (d) 49. (0): 80.0) level-2 1 ©) 2%) 3 4£© 5) 6 72) &@ 9.) ‘20. ) AL (@) 12, (b) 43.) 14. ©) 15. @) 16.) 17. (6) 38. (b) 19. 4) 20. (4) 24. (C) 22. (@) 23. (6) 24. (b) 25. (2) 26. (d) 27. (©) 2B. (©) 29. (b) 20. (A) 31. (©) 32. (@) 33. (a) 34. (6) 38, (d) 36. (a) 37. (b) 38. (b) 38. (0) 40. (A)} AL. (@) 42. (b) 43. (0) 44. (€) 45. (©) 46. (a) 47. (A) 48. (2) 49. (©) 50. (b); 52. (¢) 52. (d) “53. 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(4) 170. (a)) 171. (c) 172. (c) 173. (2) 174. (b) 175. (c) 176. (b) 177. (d) 178. (d) 179. (b) 160. (A); 81. (c) 182. (d) 183. (a) 184, (b) 185, (b) 286. (A) 187. (b) 188. (6) 189. (6) 190, (b) 91. (c) 192. (c) 183. (c) 194, (b) 195. (a) 196. (b) 197. (@) 198. (c) 199. (b) 200. (c! 101. (d) 202. (a) 203. (c) 204. (d) 205. (b) 206. (b) 207..(a) 208, (c) 209. (c) 210. (2! 12. (C) 22, (a) 223. (b) 14. (c) 215. (c) 216. (b) 217, (a) 218. (b) 219. (4) 220. () £ (6) B22, (2) 223. (0), 224, (0) 225. (0), Exercise-2 : More Than One Correct Answers 4h (abed) 2 @c) 3 @bo 4 ad 5 @bO 6 @ 7% (bd) 8 (b,c) (bic) 20. (bc) “AL (bod) 12 Ca 23. (@,b,d) 14. (4.b,c,0}48. (@,bic) 26. (ab) 17, (@b) iB (bic) 38. (@,6,d) 20, (@, b,¢,d) 22, (@.b,d) 22, (@,c,d) 23, (@, b, 6d) 24.6, ©) | (2, B) 26. (Br ©) nn PP in (By ©) nan Bines (B,6:.4) 2B inn (2,.0,.)210 : GRB Advanced Problems in Organic Chemistry for JEE 1nd) 32 eo) 33. We) 34 bd) 35 (bd 2.G@bod) 37, (b,c) 38, (b,c) 39. (b,c) 49. (ab.c) 41. (ed) 42 (abd) 43. (2,0,0) 44. (a,c,d) 45.(2,b,6,d) 46. (c,d) 47. (a,c) 48 (26,0) (2,2, 30. £4, b,c) - a Exercise : Linked Comprehension Type 1 @ 2@ 3) 4) 50) 6@ 7© 8) 9.() 10.0) Al. ©) 12. ©) 3 (@) 14 (c) 15. (a) 16 (@) 17. (c) 18 (b) 19. (b) 20. (c) BL. Cd) 22. (Gd) 23. (a) 24. (b) 25. (c) 26 (d) 27 (@) 2B. (db) 29. (c) 30. (b)) 32. (Q)_ 32, © 33.0) - ne vl Exercise-4 : Matrix Match Type 2b 1. @349; (b)>R; “OP, W498 i 2. 40; (b) + QRS; (P; @)>P.Q ' 3, @aS; | (YR: (7P.0; P.O i 4, P,Q; ()—+ PRS; (?.0; GPRS 5. APRS: 0) 0; (ARS; @3e { 6 70,8; ()>RS; ©3P,0; P.O “7. SOR: ) OR: (P: @P.S | LB AR: WPS; (oP: 40,8 2. 40S; ©) O.Ri (O-P.R; IPR | 20, @)P,S; W)P.OR: (OR: ()>P,0,5 ' AL. (2) Q, 8; O)>P.R: (79,8; @7O5 12. ()->P.Q.R: POR OPLOR, Si or | Exercise-5 : Integer Answer Type Problems Gel20.2O 4el4@ 10 16326 26 ve Q00ONLY ONE CORRECT ANSWER 1. Which of the following statements are correct for nucleophile ? (a) All negatively charged species are nucleophiles (b) Nucleophiles are Lewis bases (©) Aikenes, alkynes, benzene and pyrrole are nucleophiles (@) All are correct 2. Consider the species. 2 @ ° (6H aycH,—6 amen, ay Nu, Arrange these nucleophilic species in their decreasing order of nucleophilicity : (@yMi>1V> i>} () > 1> I> 1V (c)1> >> 1V (a) WL>1> > 1V 3. The nucleophilicities of CH7, NH3,OH™ and P~ decrease in which order ? (a) CH3 > NH3 >OH™ > F- (b) OH™ > NH3 >CH3 > F7 (¢) NHJ > OH >CH3 > F> (@)CH3 >OH™ > F> > NHS 4. Arrange the following nucleophiles in the order of their nucleophilic strength: (@) OH” >CH,COO* > OCH} > C,H,O7 (b) CHyCOO™ Br” >Cr > F- (b) F" > > Br> 17 (c)CI” > Fo > Br oT (d)I7 >CI” > Br7 > E> "6, 2-Chlorobutane — 24% soutien ofc weohel : : In this reaction 70% racemisation takes place. % of inverted product would be (a) 30 (b) 70 (c) 35 (d) 65 . “2, tm reaction CyH OH + HX "2 +C,HX +H,0 the order of reactiy HY is: (a) HBr> HI > HCI (b) HI> HCI > HBr (©) HC}> HBr> HI (@) HI> HBr> HClsyne oe ee 2 GRB Advanced Problems in Organic Chemistry for JEE 8, Which of the following leads to the formation of an alkyl halide ? ()C, HoH, ()C,H,0H (€) CH,OH SO, (d) All of these 9. Which reaction is termed as Darzen’s reaction ? (a) ROH+HC! =) ROH+ PCI, (¢) ROH+SOCI, (d) ROH+ PCI; 10. The Sy2 reactivity order for halides is : (2) R—F>R—Cl>R—Br>R—1 (b) RI > R—-Br >R—Cl>R—F () R—Br>R—1>R—Cl>R—F (d)R—Cl>R—Br>R—F>R—I 11. In Syl reaction, the first step involves the formation of : (a) free radical (©) carbanion (©) carbocation (d) final product 42. The rate law for the reaction, RCI + Na(aq.) —> ROH + NaClis given by, rate = K, {RCI}. The rate of the reaction will be : (a) doubled on doubling the concentration of sodium hydroxide (b) halved on reducing the concentration of alkyl hatide to half (c) decreased on increasing the temperature of the reaction (d) unaffected by increasing the temperature of the reaction 13. Acctaldchyde reacts with PCls, to give : (a) ethyl chloride. (b) ethylene chloride (©) ethylidene dichloride (@ trichloroacctaldehyde 14. Vinylic halides are unreactive towards nucleophilic substitution because of the following except : (a) C-halogen bond is strong (b) ‘The halogen is bonded to sp carbon : (©) A double bond character is developed in the carbon-halogen bond by. resonance (d) Halide ions are not good leaving groups 8. An alkyl halide may be converted into an alcohol by : : {a) addition : (b) substitution | (c) dehydrohalogenation (@) climination i 16. The given reaction is an example ofC,H sBr + KCN(aq.) —> C2HCN + KBr: | {a) elimination (b) nucleophilic substitution ! (c) electrophilic substitution (d) redox change :Halides. . 213 17. Which of the following will not undergo nucleophilic aromatic substitution ? D cl Cl © CL a D D cl cl D. CH; HAC. CH * dll) qv) -CHy CH; ~ 19, 20. 2 22. (a) I, Mand IT (b) and IV (c) Mand IV. (d) only IV . Arrange the following alkyl chlorides in order of decreasing reactivity in an Sy! reaction : (D isopropyl bromide (I) propyl bromide (I) tert-butyl bromide (IV) methy! bromide {a) (111) > ()> (t) > (rv) (&) © > GM) > @v)> aD (©) (Vv) > GI) > i) > @) @ @)> @)> Gp > dv) Which one of the following is most reactive towards nucleophilic substitution reaction ? . (a)CH, =CH—Cl (b) CoH Cl (¢) CH,;CH=CH—Cl (d)CICH, —CH=CH, ‘What product would be formed from the Sy? reaction of (R)-2-bromobutane and hydroxide ion ? (a) 2-butanol (b) (S)-2-butanol (c) (R)-3-hexanol_(d) 3-pentanol Which is not correct about Sy2 ? (a) Rate of Sy2 is directly proportional to the dielectric constant of medium. (b) Rate of Sy2 is directly proportional to the nature of leaving group. (c) Rate 7 inversely a7 to the steric hindrance present in substrate. (d) Rate Rate : (base) (substrate) The reaction of 4-bromobenzyl chloride with NaCN in ethanol leads to : (a) 4-Bromobenzyl cyanide (b) 4-Cyanobenzyl chloride (c) 4-Cyanobenzyl cyanide (d) 4-Bromo-2-cyanobenzyl chloride214 GRB Advanced Problems in Organic Chemistry for JEE 23. 24, 25, 26. 27. 28. 29. 30. ‘What product would be formed from the Sy2 reaction of (S)- 3 -chlorohexane and hydroxide ion ? : (@) 2-butanol —_—_(b) (S)-2-butanol_(c) (R)-3-hexanol (4) 3-pentanol In which case racemisation takes place ? C,Hs CaHs (a) Hj\C—CH—CH, —Br a (b) CD; —CH—CH,Br = of ener = (d) All of these When ethyl iodide is heated with dry silver oxide, the product formed is : (@)CH,CH,OH , HAG ()CH;CHO (@)CH,CH,OCH,CH, Alkyl halides can be converted to ethers through : (a) Ranktand reaction (b) Williamson synthesis, (6) Fittig reaction (d) Grignard reaction ‘What is the product of the reaction of ethylbromide with the nucleophiles CH ,OH ? (@) CH,CH,OCH, | (®)CH,CH,NH, (€)\CH,CH,N* (CH; ), Br™ (d) Noné of these The order of decreasing stability of the cations is : (QCH;CHCH, (I)CH,CHOCH, (ll) CH,CHCOCH, @MI>>T (I> >M — @I>I>l I> > Which of the following two carbocation is more stable ? we eM me o a o a) . (a) A-Il, B-IE (b) A-I, B-I (c) A-I, B-IE (d) Al, B-T @ rearranges to : ; , wp LQ oZO 0A.Halides: 215 31. Which of the following reactions will go faster if the concentration of the nucleophile is increased ? CH: pr Bock, @) +CH;0° —> ) Bt CS DNA SCH Br ° OCCH; oP Juande. 0 (4) No comparison between these reactions 32, Suggest the suitable solvent for the reaction given below. CH)Br CH,OH NaOH, (@)H,0 ° (b)C,H,OH (QHCONMe, — @) CH 33. What is the principal product of the following reaction ? CH CH CH; H--N; Nj-+}—-H Ny——H H—--N; @H-+H =) HH @ H+ @ HH i—Cl -CI4—-H Hc, CI-++-H CH; CH; CH; CH; 34. Which of the following reaction is possible ? (@) CcH.OH + HBr —> C,H;Br + H,0 (b) (CHj),CCI + NaOCH; —> (CH;);COCH, + NaCl a OMe © ANg + CH;ONa —THH, AN, @ \/ < + CHsMgBr AES CsA Cth : ‘ oH216 GRB Advanced Problems in Organic Chemistry for JEE en 35. HyC—-CH—CH—CH, E> (2) 5 (C) b [or (A) D Correct order of rate of Sy2 for 4, C and D will be: (a)A>C>D (b)C>D>A4 (c)A>D>C ()C>A>D 36. The order of reactivity of alkyl halide in the reaction R—X +Mg —> RMgY is: . (a) AT> RBr > RCI (b) RCI> RBr > RI (c) RBr > RCI> RI (@) RBr > RI> RCI 37. The reaction of HC CH with RMX, leads to the formation of: (a) RCHOHR = ‘(b) RCHOHCH, —(c) R,CHCH,OH_ @) RCH,CH,OH 38. Which of the following compounds on reaction withCH MgBr will give a tertiary alcohol ? (a) CgH,CHO (b)C,H,CO,CH, (¢) C,H COOH @ CHSCH—CHICH, 39. RMgBr + 42° CHCH,CH,OH,R and A are : (a) CH,CH,— and HCHO (b) CH; — and HQ (c) both are correct (a) none is correct tl 30% 40. CH,MgBr +CH, =CH—C—H—~"> Product (1, 4 addition). It is : OH @CH,=cH—¢—H (b) CH, CH=CH—CH, &, bu (c)CH,CH,CH,CHO (d) none is correct 41. The product obtained on treating acetone with ethyl magnesium bromide followed by hydrolysis is :Halides 217 42. 43. 44. 45. 47. ou (a) CH,CH,CH,CH,OH () Hc—¢—c—cH, HOG Hs CH,CH; © ine—-on @ uc—Lon CH; ‘CH Consider the following reaction, OCH,CH, CH,CH,OH +CA,CH,MegBr —> CH,CH,H" +Mg U>U > m>t = (@M>1>n @u>i>ml Select the correct order of decreasing reactivity of the following compounds towards the attack of Grignard reagent. (1) Methyl benzoate (il) Benzaldehyde (IID) Benzoylchloride (IV) Acetophenone (@) 1>M>I>1V (b) 1> 11> T>1V (©) W> > Iv>l @ U>IV>1>I CH3Mex (pe Waa? Product What is the product ? (a)Enantiomer _(b) Diastereoisomer(c) Meso (a) Achiral (CHIEN RMX he « RMgX waa”? (4) —hHal? (B), (B) will be : (a) 1° ROH (b) 2°ROH (c) 3° ROH (d) Alkene218 GRB Advanced Problems in Organic Chemistry for JEE a) oC Oo oe GSLs ©), product Cis : {aco () “co, () CO, (a) A mixture 4CO, andCO, 1. In the given reaction PhMgBr +D,0 —+ (X); (X) will be: @® Hb) D ©) © @ Oy» 2. Find the product of the following reaction CH,CH,MgBr + HgCl, —> (X);(X)will be : (@ (CH,CH,),Hg(b) CH;CH; (©) CH,CH,Cl_—(@) CH,CH,HgCh PhM; CO) a Product Mess the structure of product : °F | OH Ph. OH (CHs),CuLi 4 SS Product H',0 Identify the structure of product : ° , OH, Ci ° OH 0b, 0 OF ah, 0, CH; 3 He 5, Find the product of the following reation (©) @ HBr, bv | H,C—CH—CH,—Br + Mg—22, 4 __# 85 _, No! Br + Mg. a 0 ¥c—_0—o—cu,’ 3Halides 219 Find out ‘B” : ‘Br | (2) HO—H,C—CH,—CH,—Br (b) HO—CH,—CH—CH, eo (c) HO—H,C--CH=CH, (d) BrMgCH,—-CH=CH, 0 0 IL IL CetaMeBr (excess) 6, H—C—C—H —-———-—> Product : HPO (a) Hyc—¢—6—H by HyC— GH CHC . O° . OH OH : () Hsc—F Ec (d) CH,OH 0 0 COOH 0 . . Banyyv CHyMgBr Mol) auct': HO. Oo @ XAPVO day © @ wow oO oO 8. Find the product of the following reaction, 0 JL Maoty product: 150 avy ons ong © [He ons oO OH ou 9. Find the product of the following reaction, Br Br Li Cul =. ASS AB c Find out the final product (C) : (a) (A), cui (b) (cic © oO (d) None of these220 GRB Advanced Problems In Organic Chemistry for JEE 10, In the given reaction HyCMgBr —s > Product H/H:0 Find the product of reaction : 1H Orn O= © ae @ a on SOCh, Mg, A. 0" aL 0H pyane” “ano” — ys Produc Product of reaction is : O. CH Sf 3 ® oH ©) GK ° cH. ° % © 3 @ HH ON cH, CHO © Nc, —cHy—C—cH CHs CH 12, The end product of the following reaction is : 0. 0 WW H3CMgBr PhMgBr 90 ——— ———> ——— Product : ‘O a @ @ (a) a, Budiketone - (b) o-hydroxy acid (6) 1. 2-diol (@) Bhydroxy acid h - PoMgBr, 4, _HOOs, 5 ° HO. 0 Find out the final product‘? Ph Ph © ZT ©) Vn Ph 3 Ph Ph © () Ph—-C—C—CHO Ph on 0 OHHalides 22. 14. A> B= C_— D> Et,0 2.H90 A Find out the structure of * 4’: 1 ‘O Bryhy Mg. [> Cone, Ha804 ,. Os ° Zn/H0 CHs @ Oo (b) C © CO) @ Cy ° HyC—CHyMgBr_ 1, CH3CH0. . —c—9 eer, ples 15. (\-v c=0 HZ0 Prt 2 Find out P and Q : OH O—CH, s | | (a) P is Ph—N-=C—CH,CH, and Q is Ph —N=C—CH,CH; 9 Il : . (b) P is Ph—NH—C—CH,CH, and Q is Prov C—CH,CH, CH; (0) P is Ph—NH—C—CH,CHy and Q is Ph—N= qoerncn 5 OCH, (@) P and Q both are same 0 0 ll H3CMgBr 16, Ph—C—C—Ph —{— Heo How many products will be obtained and how many can be separated by fractional distillation method? : @) 3,3 (b) 2,3 ©) 3,2 (d) 2,2 17. Which of the following reactions will give 2° chiral alcohol as major product? a ® (a) Pe fener 22, 8, CHs a e (b) CH Mgl + }—C--O—CH,CH Bs (excess) z222 GRB Advanced Problems in Organic Chemistry for JEE H a @ ©) Php meer HW), CH 9 e lt 130 (@) PhMgBr +CH,—C—-Ph —> ° 18, A+ fx] 2885 CH, OH : ~~ MgBr IA, — @ xo cr) 8 ono [9 @ Ho” “ots 19. R+ A/BE 4g SAN : @>As, > A Mer 20. (HsC—CH,CaLi + (0) —> >< @ >< o >< ©) >< MeBr (@) DX Br MeBr Br om +Mg —Eiher, F @ O-r ) oO) mer © PO) Mews (d) (Oy HC, e N\ H;O 22. Hy3C—CH—CH, + \‘CHMgBr—> : No” f HC ah OH OH MAADAGy OA oh ok i Tc 23, \o Mg/Ether F The final product of the reaction is ;Halides 25. O- @(O “or MeF F Mgl cy . T Mgcl e({O] } @ ( I F Mgr H3CM 1 Mok EMBLEMS, Pre Oo ¥30 » Find the structure of product : OH 0. OH (a) | © A @) 0 0 =o —>—0H » cl METHE, (py Br Identify (P) : MgBr Br MgCl MgCl oDe oF So oS COUN MgBr + So xtY SO3H224 GRB Advanced Problems in Organic Chemistry for JEE X and Y are respectively : 8 COOMgBr @) oO only (b) and oO | COOH SO3H © and © (a) None of these SOsM e % e Br MgCl Cl 27. & + On Compound (P) is : "Do "OOROO*O a CHsMeBs ‘ WX CH: Hy0 OH 3 Find out the value of “X @e . b) 4 ’ ©@3 @2 PIMEBEMOl®), product (P) : of . PhHatides 225 on Ph () Ph (d) None of these Ph ° ° | PhMgBr (excess) | 30. C-C—cl = (x); Product (X)is : nfo 1 i (@) Ph--C—cl (b) Ph—-C—Ph OH | II © Pao Ph (@ Ph—C—O—Ph Ph ° 31. HyC—Mgpr+ 9 9 8 (99; Product (0) is: a i Ko (a) HyC—C—CH (b) to a Hs o HC I () (d) HyC-—-C—CH3 CH, 2 Cl Mee oy Lone HaSOu 0 HS A 9 %o Identify ‘Y": HOP Ph 07 Nph Ph oh226 GRB Advanced Problems in Organic Chemistry for JEE t PhMgBi 33. wef cnt en, 2 HCH, ‘How many products will be obtained and what is the relationship between them? (a) 2.and enantiomers (b) 3 and all are diastereomers (c) 2 and diastereomers (4) 3 and all are homomers BE Mg, THEA 34, ——* 5 Major Product : N 2. Ph—CHO ' 3.30 H on oor » OO N I fo, Ph 9 Ph © @ Cen h 35. Which of the following compounds is not suitable solvent for Grignard reagent? 0. @) @) C © O @ no’ oO 36, AZP! ve. THF, (2 Mole) . Find the major product : @ AWS OANY O44 @ AW I PhM¢ 37, CL-C—ort MEO product : HPO ou | i (=) Ph—e—Ph (b) Ph—C—cl Ph ° ll Il (©) Ph—C—o8t (@) Ph—C—PhHalides 227 Ph Mg HCHO, 38. | Se MB, y BOD, Br Ether” Product ‘Y'is : Ph PAN, @ p< 0) pS ch;—on pi’ on ©) Py AH (a) None of these Ho 39, PhMgBr +H,C—C==N ——> Product: Pee AA A Ph—C—CH. d) i) i BO a ph © aac’ cH, © px cH Ph ° ll PhMgBr 40, H,C--CH, —C—-H —-—~ Products HPO Products obtained in the reaction are : {a) Meso (b) Racemic (c) Homomer (@) Diastereomer OH (1) PhMgBr ou. . 41. as >> (A); Product (4) in this reaction is : ‘OEt ou” @) 42, Which alkyl halide will react fastest with aqueous methanol? (a) Me;C—Br (b) MexC—Cl - (©) Me,CH—Br (d) CH, —CH, —CH, —Br 8 43. HjC—SNa® +CH,CH,—¥ —> The reaction is fastest when X is : (a) —OH (b) —F : ° Il {| (c) —O—C—CF, (d) —O—C—CH, O oO @ Ch ) © on ® oo On OH ol228 GRB Advanced Problems in Organic Chemistry for JEE 8 44, When the concentration of alkyl halide is triple and concentration of OH is reduced to half, the rate of Sy2 reaction increased by : (a) 3 times (b) 1Stimes (©) 2 times (d) 6 times 45, The compound which undergoes fastest reaction with aq. NaOH solution is : (a) Ces =F H—OCH, @) Cols CHC a a (©) C.Hs —CH,—CH,—Cl @ Ces FH CHACH, cl 6. The rate of Sy! reaction is fastest with : “Orp-O) ‘OF O) “OF Oy @O) (OKO): 47. In the tatlowing reaction the most probable product will be : Br u—t-cH; HCH Sy? on GH CH CH, H eon u—tcu, ,, HoH outs * © ine -H © inc HO we H GHs on Hs 48. The folowing, reaction is described as : Ao 08 8 C OH | ‘CH; (a) Sy! reaction with racemisation (b) Intramolecular Sy? reaction with walden inversion (c) Intramolecular Sy2 reaction with retention of configuration (@) Intramolecular Sy2 reaction with racemisation 49. In the following reaction find the correct product : OH H—-7—GHs _Nal/Acetone, H—+—CH, chHalldes 229 OH 1 OH 1 H CaHs H ‘CHy H ‘CoHs, H ‘CoHs é Oyta, ato © wets © yen, a on I on aca cl ci 50. Cl KOH (aq), ca & cl HO. OH HO. OH OH OH OH oH (a) HO- (b) Ch oH HT OH OH a On Q HO ,OH \ cl cl OH OH (© Ct @a a cal a OH a HH 51. The correct decreasing order of relative reactivity of the following chlorides toward aqueous KOH solution : fol cl co Ag ~~ wo” MV ” @ ® © (a) P>Q>R>S WY R>P>O>S (0c) S>R>Q >P (d) R>S>Q>P 52. The relative reactivity of following halides toward Sy? reaction follows the order = oO Ag Aa (Py @ (@) Q>S>R>P () P>S>R>O (©) S>R>Q 53. Rate of Sy! reaction is : PE (Op-an—a ® “ >P (4) P>R>S>O SCH3 O-G@-a-2G)-r-a-eO-0¢ Br ) (Q) @ eS (a) S>Q>R>P (db) S>R>P>O (c) P>O>R >S (d) S>R>Q>P230 GRB Advanced Problems in Organic Chemistry for JEE 54. In the following compound, arrange the reactivity of different bromine atoms toward NaSH in decreasing order : Br(R) Br(S) Br(Q) Br (P) 0 (a) P>Q>R>S (b) S>Q>P>R (©) O>S>P>R (W) P>S>O>R 55. Rate of reaction with aqueous ethanol follows the order: Br CH; Goats OO {P) (0) (R) (a) P>Q>S>R (b) O>P>R>S (c) P>R>O>S (A) RePsssg 56. The reactivity of PhMgBr with the following compounds is : PhOH =CH,CHO R—C=CH H,C—C—Cl @) @ ®) il 0. oO (s) (@) P>Q>R>S (db) S>R>O>P (c:) P>R>S>O (d) R>P>O>8 = Arrange the following in decreasing order of Sy? reaction (From question no. 57-65). cl ‘ | 57. CH;Cl CH,CH,Cl CH,CH,CH,Cl_ CH,—CH—CH, Py (@) (® ‘S) (a) P>Q>S>R (b) P>Q>R>S (0) S>R>O>P (d) S>Q>R>P cl 58, Ye dag nw AY @ ® () @ P>o>nes (b) R>P>O>S (c) Q>R>P>S (d) R>Q>P>S 9% D>A RD Dea Aa Ag a) @ ®) o @ SzRoP>g ) S>R>O>P ©) R>S>0>P (d) S>P>R>O 65 ry @ (Ry @! P>R>S>Q (b) P>Q>R>S (c) por >Q>S (d) R>Q>S>PHatides 231 a. 6" wxc—cH—cl Y “a cl a (P) @ (®) @) (a) P>Q>R>S (b) Q>P>S>R (0) O>P>R>S (d) R>S>Q>P 62. pe ZA/BE HyC—Br HyC—=CH—Br (Py @) ® SS (a) S>P>Q>R (b) Q>S>R>P (c) Q>R>P>S ) R>Q>P>S 63. HyC—O—CH,—Cl Hyc—F—CH,—Ch HyC—CH,—Cl H,C—Cl oO ) (2) ® cc) (a) Q>P>S>R (db) P>Q>R>S (c) S>R>P>O (d) S>R>Q>P 0 II 64, C\-on HjC—CHy—CI HC —CH;—CH;—C1CHs—C—CH,—Cl ) @ @ % (a) P>R>Q>S (b) S>P>O>R (c) Q>R>P>S (d) Q>S>P>R Go ' 5 5 “gem cH @ OER apes ) neQeseP (c) P>O>R>S (d) S>P>R>O = Arrange the following in decreasing order of reactivity toward Sy? reaction. (From question no. 66-76). cl 66. CH—Cl “Ng AS “ @ ® “ (a) S>R>Q>P (b+) S>Q>R>P (c) R>S>Q>P (a) PHQ>R>S a oA" ~Y A +c ” @ ® % (a) P>Q>R>S (b) S>R >Q>P (c) S>Q>R>P (d) R>Q>S>P 68. a Ag Ne aA cl 2) @ ®) O) (a) S>Q>P>R (b+) S>P>Q>R (0) Q>P>S>R Md) S>R>Q>P232 GRB Advanced Problems In Organic Chemistry for JEE Br ow ay a) ~ ® @ ® o (@) P>Q>R>S @Orkosoe (©) Q>P>R>S' (a) O>R>P>S it Tol OL Hse—C— CH a on ® @ wo. © (@) 2 0>5>R () Q>Posor (©) Q>P>R>S (d) R>S>P>Q A pace hp (R) @ P>o>R>s “o S>R>P>Q (0) oosepor (d) Q>S>R>P 20,9 o CH; CH,GH Guo HYC—C oC das, by @) @ ® ) (a) S>R>Q>P (bl) R>S>Q>P (c) Q>R>S>P (d) P>Q>R>S 08 O6 CH; OH NO, @) @ @ o (a) S>P>Q>R (b+) R>Q>P>S (0) O>R>P>S @) S>Q>P>R Br Br ‘Br 4. ?) (Q) (Ry (@) P>Q>R>S (b) S>P>Q>R (c) R>Q>P>S () R>P>Q>SHalides 233 Ph | 15. €) Ph——C1Ph—CH—Cl A Ph ) @ (R) ‘s) (a) P>Q>R>S (b+) Q>R>S>P (c) P>R>Q>S (d) R>S>Q>P a 76. H;C—O—CH,—CI Hecht c1 (Sci 0 H ) @ 3) ) (a) P>Q>R>S (b) R>Q>P>S (c) Q>P>R>S (A) Q>P>S>R OH 7. BCL y AIS , y. identify major product ‘Y” : “OO 960 96D #OL) 78. Qk 4+ Nal (1 moley A222, Major product : ISTE KE o A, 79. Find the major product of the following reaction : CH,—Br oC = Br (CHy—SH CH,—SH 2) CL (d) OL SH Br A OTs CN CN (a) or” (b) * (c) Both (a) and (b) (d) None of these234 GRB Advanced Problems in Organic Chemistry for JEE a CH3 RL. NBS, 4 KEN, 2p. product Bis: {2Mole) (1 Mole) Cres 2-239 Oe ‘NaBr/DMSO — Ab Oe OG, «Oy, 83, The reaction H, OH H, Cl Xe +soch —+ ASK +s0,+HCI proceed by the mechanism : (a) Sy! (b) Sy2 (0) Se2 (@) Syi 84. The reaction H, OH (O} CL H AX +80ch 43 SK +80, +HC1 proceed by the mechanism : (a) Syl (b) Sw2 (©) Se (@) Swi 85. Consider the following reaction ERO 7K sucatne 23 BY “H Which of the following products is not expected to form? by AY ~~ Q ® rcmcn OA © @ HC=C 4H 86. The product formed in the reaction : Br Broa br ae?Halides 235 Xe a OS ope Xo 87. Consider the following sequence of reactions ale, KOH Bog aq. KOH Sp Sg ae. CHCl, A 1H202/0H a The compound 4 is : (a) ve ) “Se © La @ oY cd cl cl 88. Which of the following reactions will go faster if concentration of nucleophite is increased? Br EtOH e CHyCOOH, (a) AP xen 208, () Se + CH,COON? ———> Ph. (©) >—Br + ,0 — @) HBr +H0—> Ph 89. Consider the following sequence of reaction CH3CH,MgBr PBry {> 2 A 8B \o/ 2 H;0, The product B is : Br (a) nv (b) “_ © AAg, @ Ar Br Br 0 AgNO: 90. xe sno 3° Product Find the product : OH 2 OK MOOK, OA ‘OH ‘CHa 91, The order of decreasing nucleophilicities of the following species is : ° e 3 (a) CH,$>CH,0>CH,COO> CH,OH ° ° 8 (b) CH;COO>CH;$>CH,0>CH,OH ——236 GRB Advanced Problems in Organic Chemistry for JEE e 8 ° (©) CH,OH> CH, $>CH,COO>CH, 0 e ° e (@) CH, O>CH,OH>CH,COO>CH, § 92, The order of decreasing nucleophi ° ° ° e°8 e (@) H,0>OH>CH,COO>CH,O —_(b) CH;0 >OH>CH,COO > H,0 ty of the following is : 2 090 8 8 8 (© CH,COO>CH,O>OH>H,0 — (d) OH>CH,0>CH,COO>H,0 93. Consider the following nucleophiles lle Ile lle ° AO, MEO, Ph—O, CH;—C—O ° I TT cue iv when attached to sp?-hybridized carbon, their leaving group ability in nucleophilic substitution reactions decreases in the order : (@) I> H> I> IV (b) I> I> IV> © I> I> I> mM @ Iv> >>I 94, Find the product of the following reaction : cl H,0, OH OS ©) yA on™ Oy OH 95. Find the product of the following reaction : Br CH,OH Och; aH se ° i ox 96. Find the major product of the following reaction : Che . : 7 ok o( © (Kou ot OHHalides 237 97. Find the major product of the following reaction : Br _CaNg0H1, OCHs OCHS w(CTF oC © eats ay (YS OCH; 98, Find the major product of the following reaction : Cys H,0, OH OH OH om oC yom << © ok 99, Which of the following reactions is not feasible? @ oe © fo es a Sn, (TY ge (C)HsOH_ OL SCY @ nena A HC CH; ‘Br CH 34 2 100. Find the major product of the following reaction : cd auen OCH; ot, ox or otX 101, Find the major product of the following reaction : Cr. +2, eC ol oct ocY 102. Find the major product of the following reaction : ()HsOH 4 BrGRB Advanced Problems in Organic Chemistry for JEE @) ack () CL © Cr @ CX 103, Which of the following cannot undergo E, reaction? ‘Br (a) XAg (b) »”y Ox (d) None of these Br 104. In which ofthe following reactions, regioseleetvity can be observed? ox, oh ott axe fa KOH fat KOH [xe KOH [ae KOH 105. The most probable product in the following reaction is : Br 28 Cr CH,CH,OK eG eB, @) CO ©) O © Ch @ Ol Br 106. Major product of the following reaction is : ‘Br CS Hse NH—CH3 NH) @) OO ®) 0 © CS @ 107. Major product of the folowing reaction is : Br EGh A — ‘NEt; © oO 0h) 0 cl cl 108, alc. KOH, cr cl aHalides 239 1 cl (a) (b) © O. (@) No reaction cl cl or cl a a 109, Which of the following will undergo fastest elimination with alcoholic KOH? ir ir Br H3C r - @ cr co) cy © oy @ ioe cH ch ne 110. Which of the following is B-elimination reaction? ‘Br \ / (a) HO +NaOH — 0 (0) CHBr; + Me;COK°—> CBr, CH; © HxC—C—Br+ KOH (ale) > A CH AWA" oH Br +NaOH ° 111. Arrange the following in decreasing order of £ reaction : cl Cl gl a ca ch Poa ch F oc I cI cd (ol re) ‘a oct cl Cl cl cl w (3) ® (@)X>Y¥>Z )X>Z>¥ =) Z>X>¥ GY >X>Z 112. Which of the following reactions will undergo an elimination reaction and an alkene will be formed in the product? Br Br 4 Br in ou, ny @) > ) as OH Ve Cone. H2SO4 No Sua of |) @ O as240 GRB Advanced Problems in Organic Chemistry for JEE ae Hofmann product product In the above reaction, maximum Saytzeff product will be obtained where X is : (a) —1 (b) Cl (c) —Br (d) —F 114 Inthe above reaction (Question no, 113) Hofmann products major when bases: 3 ° e i HC 8 (a) CH,O (b) CH,CH,O ~ (©) H,C—C—O @ ‘CHO | HC” CH, 115, Find the major product of the reaction : Cl MescoPK® rn > @ =~ (b) >~ © S\ (a) Both (a) and (b) al Me se ae ° w(K © _4, Major product : CH @ Ch ) Ch () Oo (@) None of these Me «| Me NP NB mf —54 Major product : Non, {a) Ch - (b) Ch © CL (d) None of these e 118. Sey a? Major product : off oY off of Gs i Br CHyONa 119, “Gioat? Product HsHalides . 241 @ Oo ) cl © a (@) No reaction CH; Ph——H alc. KOH, . 120.5) [pp > Major product : CH; @ Pog? ) Pr CBs Paes @ Py gts HyC’ ‘CH; HC” “ph Ph” SCH CH, NaNH; . EEL, Major product: SC. CH: HC. D D. (CH3 HC. @ KO XK OK D D D ‘CH D ‘CH3 ‘CH; 122. Identify the major product of the reaction : CH AVA, facat, BaAA OA (©) HyC=CH, . (d) “\% CHI CHsl, AgOH,A “" AgOH, A I CH, Identify the major product ¥ @ m (b) an © r- @ oo aX °NMe; CH; —C—C1Q2 Mole) aA"), xX 44 B+ CH,COOH pyridine 124, OH242 GRB Advanced Problems in Organic Chemistry for JEE Product B of the reaction is : Oo Oo “0D 0 06 CH ga e, “eo . ° 0 OPK = 00 eae poaer: OH HC, D D D 1 OCE OLL OCS 197, x LH at excess), _ CHa] (oncess), Oy ‘AgO/H20, A” Agx0/H30, A Identify “x” : @ o ) o © fo @) O ¥ H Product (Z) is :243 a Yr 129, 224, Major product Br cl a y i oO of CH, Ph—}—c1 Zn. po a cH Ph Me @ Some” Me“ = Ph Ph Me N © c= Ph” Me Ph 131, FBC HCL _Navacetone * CI-}-CH; a Ph @ Na’ m HC’ ‘CH; . nae ks on” NH © Ch (@) None of these ‘Br Ph. * Ph © Some Me” Me (d) No reaction Ph: CH3 (>) Ncacé HC” \ph (d) No reaction H3C—CH2 132 A801. Major product : ime @ ~, ><" CHs () H (a) #H pe cH, PK244 GRB Advanced Problems in Organic Chemistry for JEE CH,CH, . on 133. Ph—CH, —CH, —® N—CH, > Major Product : CH,CH,CH, (@) H,C=cH, () Ph—CH=CH, cH, (©) H,C—CH=CH, @ Ph—C=CH, BON? 134, mc 8 a“ CH, o> o> ©™ H \ (@) No reaction cH, ns ale, KOH, 443 Br orrr wark orrc ort ay AY, Ag.O/,0 136. —r A Major product : @ x (b) A. © = (@ H,C=CHy 137. Arrange the ‘own in decreasing order of £, reaction : g x Br ct @xoren wxsnr. rene (@) Z>¥>XxHalides ne 245 138, Which of the following is the correct option of reagent for the given conversion? CH,—> > COOH (8) Bra/hv, /\ MgC, Bry/hv, HCOOH (b) Cl,/hv, “\ MgCl, Br, /hv, KCN/H, O (c) Br)/hv,/\ MgCl, Br /hv, NaNH, HCN, HO (d) Cl,/hv, CHsMgBr, Br, /hv, CH;COOH a oO Oo woffa yn Which ofthe followings the correct option of reagent for the above conversion? (a) Mg/Et,0, CHCl, Br /hy, ale. KOH, KMn0,/OH, 4 ° () OH, H,80,/A,0,/Zn, H,0 (c) CHjMgBr, Br, /hv, alc. KOH, KMn0,, A @ MgvEt0. CHCl Br, /hy, alc. KOH, O3 /Zn, HO MOK “Gee? CH; KX ) ye oe" Oe Mg/Ether LALA (CoH) ee, hexane. 2. CH30H ‘Na/Ether * 4, $- diethyloctane Deduce the structure of ‘4’ : Br @) WS (b) WY (©) AV @ xX 142. Treatment of 2-bromobutane with hot alcoholic KOH gives a mixture of three isomeric butenes (A), (B) and (C), Ozonolysis of the minor product (4) gives HCHO and another aldehyde in equimolar amounts. Both (B) and (C) gave the same single product (D) on ozonolysis. Find structural formula of): @) A (b) A ©) a qd) A oO alcoholic KOH Bro/CChg NaNH [Ag(NH3)2 143.4 (CyHaCl) ——> B ——5 C ——3 D ——— ppt. Find structure of *C’:246 GRB Advanced Problems In Organic ChemIstry for JEE Br Br Br "Br Br @) oy «b) 3 () Vs @) AK, r . Br Br 144, 4s Major Product : i cH; or mt EJ? ® ~~ N’ | CH; Br a of TI (@ No reaction Sy i cH, 145. Find the nature of following reaction : i. H Bi ‘NaCN * ROH (a) Sy2 (b) Swi OF (a) Exeb Ic. KOH. 146. Cott 284, 2 Cth) as CsH0) 4 (Noisomers) Bro, CCl Br OC, Negative test Positive test which of the following is the structure of A? 1 @ A ae oa © <>-a @ O* 147. Consider the following reaction Br K,CO: Ph H 3 Major product: Br O FoHalides 247 : ° OHO . : Br H @ wr, ©) wr © YY @ mai OH BrO ° 148. Which reaction take place at the fastest rate? . NaSH AA, st ® ‘Cl CyHsOH, 25°C As NaSH eae 5 ©) a (CyHsOH, 25°C . ©, see. Br C,HsOH, 25°C . SH @ AW, St Br CHsOH, 25°C 149. What are reactant X and product ¥ in the following sequence of reactions? HC. S—Cl I u AC. of Sen, 4° Il : H HO NaN Reactant “X* Product ‘Y* ethanol-water Ok Oe Product ‘Y” No reaction 150. What is the major product of following reaction? CHy Sct + CH, =CH, 25 CH; HHOGRB Advanced Problems in Organic Chemistry for JEE ll CH Il HSC. CH, c @ » CH—C—on () eu” Neca cH HAC fl (c) CH; =CH—C—: (@) All are incorrect 151. Find the major roduc of following reaction : H SRG sai. © Ca @ No reaction i Me Me 152, Ss SUT, 4, Major product: OH Me 4H Me. l ©) L I os CH; Me CH) a ol | @l | 153, Identify the major product of following reaction CaN ‘MgBr Ox HHO NE; HCO’Halldes 249 NMgBr oO @ () OCH OCH; © (d) No reaction HCO 154, Identify the major product of following reaction : H zee %Y S—CH, oy on oO @ low 4155. Find the major product of following reaction CH; HCO: 429, Major product : Heo . Bro CH; (a) H3CO- (b) HyCO- Br OH H3CO’ H;CO 5 OH 3 (©) HyCO 0% (A) Elimination reaction ou HCO 156, Predict the major product of given reaction : ‘OH __PhSO2CI OH NaCN, DMSO. OH NH) ‘OH ‘NH:250 GRB Advanced Problems in Organic Chemistry for JEE © & @ Cr 157. Predict the major product of given reaction : Ox® (CH) ;COK' {CB sCOK, CH; @ Go ) (Ses ‘ | HC’ CH; Ci CAs © es qd) \ ‘S—CH CH; CH 2CH3MgBr. .. Maj : 158. “i d —Higo ” Maior product ° OH OH (a) why (b) wry OH 0 9 (©) why (d) No reaction Oo : a H,0 159. Ph—CH—=N—CH, + Ph—CH,MgC] —25 Major product : @) pot . (b) PhCH, HCH . CH,Ph (©) Ph—GH—CH,Ph (d) None of these HjC—NHHalides 251 160. Find the major product of following reaction : S Phi ‘CO; CH COOLI _ S 0 oft) o> N N CH; ‘OLi Oro | (d) No reaction CH; ° 161. Find major product of following reaction : Hy CH; Hy CH; CHL, BY Br Hy CH. WC i 3 mC fib a) oo . ) LOS B a Br on By cH, e 3 © Sc=c=% (@) None of these Hy NcHy 162. Predict the major product of following reaction : Br _Ag® Bi H20 OH . OH Br oOo” eG) Cl Br Br OH Br 163. Predict the major = of following reaction : Aa, _CHCHENa ° ll @ My ) AX e ‘OC2Hs252 GRB Advanced Problems In Organic Chemistry for JEE se ONa {| ©) Ax @ No reaction ‘OPh 164, Identify the major product of following reaction : OX er 23 Xo OX Ny © X%ouy 165. Find out the major product of following reaction : 9 Il B/S _, CHy3—C—OH SS cl ° I ote 3 @ ANS on, o> © (d) No reaction x, —C—CH; eiaitei=24 MORE THAN ONE CORRECT ANSWERS li : 1. Which of the following will not form Grignard reagent with Mg/dry ether? Br Br ® C—O, 6) BAB CH @ ‘Br Br Br Br 2. Which of the following will not give addition reaction with RMgX? (@ Co, () CH CH, —Br i (c) SO, (a) CH; —C—OH 3. In the given reaction, H®/H,0 (X) + RMgX (excess) ———2"> 3° Alcohol (X) may be: 0 ll | (@) R—-C—Cl ) nt ocu,Halides 253 ° Il I (©) R-C-R (a) R—-C—H CH, 4, Which of the following combinations give C,H; —C—OH? CH,CH, II (a) PhMgBr and HyC—C—CH,CH, I (b) CH,MgBr and Ph—C—CH,CH, i (¢) CH;MgBr and CH; —-C—OC,H, oO Il (@) CH,CH,MgBr and Ph—C—CH, 5. Which of the following compounds will give acid base reaction with RMgX? i (a) CH, —C—Cl (b) HS fe} ° Il (©) H-C—O—H @ 6. Find out correct statements about Grignard reagent : (a) TheC—Mg bond of the Grignard reagent is covalent but highly polar carbon being positive relative to electronegative Mg (b) RMg.X give nucleophilic addition with carbonyl compound (0) RMgX give 3° alcohol on reaction with esters (d) Mg give nucleophilic addition elimination reaction with acid derivative ‘H30H 7. R—X +Me —2 R—Mgx OH, n-butane ‘What can be R in the above reaction sequence? (@) n-propyl (b) n-butyl (©) sec- butyl (d) Isopropyl254 GRB Advanced Problems in Organic Chemistry for JEE 8. Point out the following incorrect Grignard synthesis : OH” Br !-Mg, ether 2. Ph—CHO @) nn Ph 3.H30. | I H H Oo CH;CH; OH. 1. CH3CH)MeBr os ® 2.HF0 som 1. Mg, iter “OP BE ce” aH HOH,C; MeBr oy few Oi HO 9. _Mefether sme l-aw p NBS AmO (eis, Ose . 2.80 3.4 Zn +H20 NY r ‘OH (@) Product Cis (b) Product D is Q ‘OH HY {c) Product Eis t=O (a) Product Fis co HW 10. Which of the following reactions are correct? _ 9 CH3MgBr H20 (a) +CH;—C=CH > . 9 ™ comet b) ‘CH oO T,0 orHalides 9 Il PhMgBr (©) CH; —C—cl ———> H®/H,O 0, Il (@ PhMgBr ——*— Ph—C—OH H®/H,0 255 9 I CH,;—C—-Ph 11. Which of the following compounds give aleohol on reaction with RMgX ? 0 (a) O7 Ii (&) R—C—H (©) R-O-H @) Lr 12. Which of the following ketone does not react with CH;MgBr? Il (a) CH;—C—CH, CH;Q CH; © Hyco c—o—CHs CH, CH; Il | 13. R—C—Cl +Z —>» R—C—R The reagent Z is: (@) R,CuLi (©) (Ph3P);RbC1 ° Hy ¢ CH; @) C—C—CHy 1H; CH3 lL (@ Ph—C—CH, (b) R,CA (4) H,—Pd/BaSO, Bi ON Hy CMgBr yy HsCMabr Hee ir 14. H oO (@) Zis OMgBr BrMgt yz; then (b) Yis ‘OMgBr Bry256 GRB Advanced Problems in Organic Chemistry for JEE oO 9 a s . O- (©) Yis OMgBr @Xis OMgBr Suu, Li 6 N\ Zar Tout x¥— 2, T-dimethyl; then : fa) Xis eat (b) is) Y/| cutie) Tis VO Yis AZ 16. Choose the correct among the following statements : (a) AA will react more readily than. >—I for Sy2 reaction (>) A/C will react more readily than /A./Br for Sy2 reaction (&) “Nbr will react more readily than ~ Br for Sy2 reaction () € \-cin will react more readily than Br for Sy2 reaction 17. In which product formation takes place according to Hofmann’ 's rule? oo (a) Av MesCOK ) yy ae “OWCHOK Br 8 CH;CH; OK e/ OH oHsCHOK G — @) © h- > @ yO 18. Consider the following statements and pick up the correct statements : (a) MeO: CH)—Br will react more readily than on—(O)—cniar for Sylreaction Br Br ® lwill react more readily than for Sy1 reaction cl cl . . A , (Off, }] will react more readily mi) for Sy1 reaction SN | H (4) Sy! reaction occurs in polar protic solventHalides 257 19. Which of the following compounds will give syn-limination reaction? Me (a) vv ) wo © AN Me @ ANS a Oo: %0 8 20. Which of the following compounds will not give Sy2 reaction? * cl (a) oO {b) Hy»C=CH—CI(c) (\-» q@) —bBr 21. Which of the following compounds will give Sw! reaction? (@) HyC—CH,—Br ) (\ Ph @ wet CH,CHy 22. Which of the following are correct for the given reaction? (ls 20.120, H,0) (2) Major product of reaction is || —N (b) Major product of reaction is Ck . NS PN (©) Hofmann’s alkene is major product of reaction (@) Reaction is unimolecular 23. Which of the following halides undergo E, elimination? Br (@) Lr (b) Lf ‘CMe; cl © LPwfrow © [7 ‘Br CMe;258 GRB Advanced Problems in Organic Chémistry for JEE 24, In which of the following cases, the major product has been correctly shown? 1 eK, “NH oCO#®COD Orr MeCO°K . jr Br e oo BST ow )—€ nr 08, eh 25, Pick the correct orders of reactivity : (2) Syl! — wa > ~, >a av °o () Sy2 — va > co’ Sct > pS > AAT i OB —> Aq> >a > La | @ Sy —> Aw Lay Me 26. Which of the following reactions are not feasible? cl Br KNAp NaNHp (@) Oo Tig. NH3 (b) lig. NA Br 'NaNH @ Hi ra _NaNHa © Tig. NH @ “Tig. NHS” 27. Alkyl iodide can be prepared by : CCly acetone (a) R—-CH,COOAg +1, 4s () R—CH,—Cl + Nal ——3 (c) R—OH + HI —> (d) CH, + 1, =, 28. Which of the following are Sjy2 reactions? cl 4 6 MOAN +P (6) >—Br+cN—s 8 e (© >—Br + OH (aq) —> (@ >—Br + BH (ale) —> 29, Which of the following reagents can be used to prepare an alkyl halie from an alcohol? (a) NaCl (&) Soct, (©) PCI; (@) HC1+2nCl,Halides 259° 30. H,C=CH—Cl ean undergo (a) addition reaction (b) elimination reaction {c) substitution reaction (d) electrophilic substitution reaction 31. Aryl halide undergo : (a) Fittig reaction (>) Ulmann reaction (c) Wurtz reaction (d) Grignard reagent synthesis 32. Which of the following reactions take place by Sy2 reaction? 0. OTs @a VY “(Ow S_ Nal oO acetone acetone cH . ft ‘Nal © Ix “alone? @ ON ae” HCP Br > CH; OTs 33. Which of the following reactions involve free radical as intermediate? (OC) wo JL, Be 9 AS () AX _XBS, @ Ao B BrfCCk, 34. Which of the following are possible intermediate in the following reaction? Qac-Qu @ QO (b) ©) £2 @) C2 . 35. Which of the following compounds will give racemic mixture by Sy1 reaction? A, Hy, @ oe () nemcH_o ‘Br © (Oy-ete @) nee Hy—Br260 GRB Advanced Problems in Organic Chemistry for JEE 36. Which of the following compounds will give £, reaction? » Br @ Dy CH,CHs (b) Pr—ba—cHy, f (©) H;C=CH—CH—CH; @ Cha 37. LY ]] +cuci, S28, yond ¥: | H @ xis ) xis 1 cH 1 SCH, 4 H cl i © nS @ ris ([ ae a Wi Nw eo ce 38, RCH, —CH,—ONa "5 —*s gives: a (@) RCH, —CH, 1 (b) R—CH=cH, (© R—CH,—SH @-H,C—sH 39. For the reaction ®NMe; 8 CH) —CH,—CH—cH, O84, AZ + AY Major Minor Choose the correct statements : (a) The reaction is £, elimination (b) The reaction is £; elimination (©) Transition state has carbanion like character (@) Transition state has carbocation like character 40. Which of the following can give E,cb reaction? OF Oo CN NO» @ BA (0) BA ©) ~ (@) Nv ir Cc 1Halides 261 41. Identify the compounds which may give NGP reaction : Hy is3 (@) Cs (b) HAC’ NAB Hy © (a) HyC—CH—CH,—C1 Hy—CH2—Cl 42, Which of the following reactions involve benzyne intermediate? ‘IL KNH2 Meter, THF ® NF liquid) ® OC NH, 6 ‘NaNO; + HCI _CHBr anes © - a @ AIC? c Il oO 43.fF | CHSOH , Product ON cH cl Which of the following products can be obtained by Syi reaction? Hy @ oe ©) Hy—OCH Hy o » I ‘CH; HCO’ ‘ H3CO” Ch 44, Among the following pair of reactions in which pair second reaction is more reactive than first for y1 reaction? (a) Me;C—CI+H,O and Me,C—Br + H,0 (b) Me;C—CI+CH,OH and Me,;C—CI+H,0 (c) Me;C—CI1+H,0 and Me,C—CI+H,0 @M) @M) (@) Me;C—C1+CH,SH and Me,C—CI+CH,OH 45. Which of the following reactions produce the same product? (a) A Beaty, Nether (6) S—coou #04, NaOH. Blectrolysis ><, sets Myftiher, CinBr, gy soon Red P+ HI cooH262 GRB Advanced Problems in Organic Chemistry for JEE 46, Which of the following are correct order of nucleophilicty in CH,OH? (@) Nu o8i>cH,—c-8 (c) F°>cl® > Bre 1° ’ } ® sco \8> 16; 8 47,, Which of the following can give E, cb reaction in basic medium? OH H i | | (a) CH;——-CH—C=N (b) C_—c—cF, © OH I ct (©) (@) HCF,—ccl, 48. Choose the correct comparison of reactivity toward E, reaction : Br oO OY mtr Ay Br °O- Q. . Orsay 49. Which ofthe following compounds cannot give E, reaction with strong baso? OTs F wy oS Br © - of Son CY be 50, Which of the following are better leaving group than 9Halides : 283 SERS SY LINKED COMPREHENSION TYPE HL Passage-1 Optically pure (S)—(+)-2-bromo octane [a]}"C =+36°, react with aqueous NaOH in acetone to give optically pure (R) — (-)-2-octanol [a]}}"© =—10.3°. With partially. racemized bromo compound whose [c1}}/"° =30°, the [a.]}” of the alcohol product is 60°, 1. Calculate the per cent optical purity of partially racemized bromo compound : (a) 58% (b) 83% (c) 20% (d) 30% 3. Calculate the percentage of racemization : (a) 58% (b) 83% (©) 70% (a) 30% 3. Calculate the percentage of frontside attack : (a) 15% (b) 85% (c) 30% (d) 58% Passage-2 Ether,d 58> 3+ R—X+Mg ———> R—Mg—X Grignard reagents may be prepared from 1°, 2° and 3° halides as well as from vinyl and aryl halide.’ Vicinal dihalide and those halide which contain acidic tail do not form Grignard reagent. 4. Which of the following halides is most reactive for the preparation of Grignard reagent? arr ona oO oe 5, Which of the following compounds can form Grignard reagent on reaction with Mg/Ether? (@) Hei (b) CHy—CH—CH,—C} No” rc ‘0’ Br . © Bro @O Hse Bi 1 . 6. o4 METH, Product Br Identify structure of product : . MgBr MgBr oC OC OCD) Br _MgBr :264 GRB Advanced Problems in Organic Chemistry for JEE Passage-3 Since, Grignard reagents resemble carbanion, so they are strong nucleophile and strong base. Their most useful nucleophilic reaction is addition to carbonyt group. Se & lee fa | RMgx+ Sc =P Ro 0 Mer B= Olb neon Mg | I Nou 7. Which of the following compounds will not give acid-base reaction with RMg. X? (@) CH; —CH,—Cl (b) CH,OH 0 a © BN @ RS 8. Which of the following compounds give racemic mixture on reaction with HyC—MgBr? Il ll (a) H—C—H (b) CH, —-C—CH, 9 9 il Il (c) Ph—C—H (@) CH,—C—c 9. Arrange the following compounds in decreasing order of nucleophilic addition reaction:: 9° 9 9 9 tl Il Il Il —H CH,—C—H CH,—C—CH, cl—C—cl ) 2) {R) o @ R>P>S>O (0) P>O>R>S (©) Q>R>S>P @ R>S>P>O Passage-4 a (X); Identify correct structure of (X): 2c H: SCH; Sor » Cn OX Ren Passage-5 Williamson synthesis is an important method for the preparation of symmetrical and unsymmetrical ether. In this method halide is allowed to react with alcohol in presence of Na or K metal. NaorK R—OH+R’—X ——> R—O—R’ Mechanism : ‘Na or rs | R-O—-H > R—ONa/K4+5 HT SVN ° R—O + R'—X — R—-O—- BR’ 3° halides and aromatic halides do not give this reaction. 13. Find out the product of the following reaction : Con + CHy-—CH,—Br Mr, ee (@) Na () (> 0-ancns © > (d) HxC=CH2 Find out A and B: {a) (O)-erana CH;OH (b) (Oy-on and CH;—F (©) (O)-on and CH;—Br @d) © + CH;0H _266 GRB Advanced Problems in Organic Chemistry for JEE cH, 15, CH,CH,OH +CH,—C—ci Ks Major product : | oo CH; cH, cH . (a) HyC=C (6) H;C—C—0—CH,CH, CH | CH, ee (©) CH,CH,OK (@) None of these Passage-6 > Aliphatic nucleophilic substitution is mainly of two type Sy! and Sy2 . Sy2 reaction proceed with strong nucleophile in polar aprotic solvent. 3° halides do not give Sy? reaction. Inverted products are obtained in this reaction and mechanism of reaction occurs through the formation of transition state. Swi reaction proceed through the formation of carbocation in polar aprotic solvent. Solvent itself acts as nucleophile in this reaction. Racemization takes place in Sw! reaction. 16. Which of the following compounds will give Syl reaction? CH; @) Me CH,CH, (b) H,C—cl cl 1 (c) H}C—CH,—Br (@) 17, Which one of the following will give racemised product in C,H,OH? cH; (a) HsC— FH Br “(by Pre cl CH; a CH; CH; HG Br © Moc @ ~Halides 267 18, Which one of the following will give Sy2 reaction? 3 @) nota () (S-c1,-a CH; CH; © Br (@) HC=CH—C! Passage-7 Type of elimination reaction in which least substituted alkene is major product known as Hofmann’s elimination. Such reaction occur in following conditions : (X) when base is bulky @ (Y) when leaving group is very poor such as fluoride, ammonium group (—NR3) ete. (Z) when alkyl halide contain one or more double bonds, 19. What is the major product of the following reaction? CH, CH, | Me;CO®K® Hse FH— CH CCH Maco Br CH, CH, CH, CH, CH, | | . | (a) H,C =CH—CH— f CH; (b) HyxC—CH==C— e CH; CH, CH, CH, CH, | (c) HxC—H,C—C— - CH, — (@) None of thesé CH, 20. Which of the following will not produce Hofmann’s alkene as major product on reaction with strong base? ® e wu cates © © @ XL . — 3 “| HC Nou, Ph CH3 | C2H0° 21. HFCs a Br268 GRB Advanced Problems in Organic Chemistry for JEE CH; vai / (a) Oypcmaot () ¢ \-c1,—cn=< H; ‘cts CH; Ms | (c) Oren grat, (d) CQrarmanpnen “Hs vHs CH Passage-8 There are number of organic compounds including esters, xanthate esters, amine oxides etc., that undergo pyrolytic elimination with heat in the absence of added reagent, either in inert solvent or in the absence of solvent. In general these elimination follow the rate law. Rate e [Substrate] However reaction is different from E, elimination by the degree of sym-stereoselectivity that they exhibit. These reactions are also known as E; elimination and the degree of syn-stereoselectivity reflect the extent to which they proceed via cyclic transition state. 4 oe FO “TP 1076” PI ae Me ‘Noe A wns] . Ph oh oh Ph Ph () CH, (d) None of these PhHalides 269 | O—C—CH; H 23. —4, Product. i Find the structure of product : @ Cx ) CL © Cl @) CL CH; a4 EPROP A Product. Ph-—O—C— CH; H Find the major product of reaction : H Ph onan onan HC HAC Hy Ph, © aPo (d) None of these Passage-9 ° HBr c Bro i J cf Mg. 4 CBE CH;—O—CH3 H°7,0, D, . Cone. Bal a E HyS044 "4,0, OH 25. Which one of the following is correct structure of ‘B’? OH OH ou @) (b) (©) @ ‘OH270 GRB Advanced Problems in Organic Chemistry for JEE 26. Find the major product ‘C” : Br Br Br ) ) © C4 @ . Br 27, Identify the structure of *E” : D CH. D OH OH “ye 46 0H @) (b) Cy (©) (d) Sesaed MATRIX MATCH TYPE I 1. Column o Column (1) Ph. fis (a) Ph- — FHC ha, C. P. Elimination ni Hy Hs 2, HsC ys () HC - cth—che Hea Q. Rearrangement He7 Non, © Y ale. KOH, R. Unimolecular jr A “\_4 it () “\9”N\—> H,C=CH, + CH;—C—OH ___ S. Bimolecular 2. Column (1) Column (11) H -@ ~~, ao, P. Beclimination Ph 1 CH, SOCl, . Sy2 (b) spon — 2. Sw : b Hy ©” N—cH, NeOH, R. a-elimination O CH3 ‘HyCHCH; : e . . (d) HyC—N—CH,CH, 5. Sy; —CH)—Ph. Halides 3. Column (1) (a: oO + Ph—CHy—cl “4, (b) Oo + wha ACh, Bry, hv @ Hye—F— CH, a4 CH; 4, Column (1) Ph H->-Br 2n,CH,OH Ont as Ph CH H—}—Br _Nal, acetone Opty a CH; OH Cone. H2SO; © — Cone W801 , Hy Ph ir EtO° Na® @ A a CH; H 5. Column (1) CH; | (@) Ph. cH CH,0H , ‘Br cH, | NaNB () Hye Br ——> cH; Column (If) P. Nucleophilic substitution Q. Electrophilic substitution R. Cation intermediate S. Free radical substitution Column (11) P. Anticlimination + Q. Rearrangement R. Carbocation S. Transition state Column (It) P. By272 GRB Advanced Problems in Organic Chemistry for JEE Ph HS cas © Br > R. Ist order kinetics CH50? a) ov —, 5. Ind order kinetics 6. Column (1) Column (11) ‘3 MexC—-O0°K®. (@) me HCH; P. Saytzeff’s product 1H; Br CH;CH,O°K® cy AY, sete, F e © NY CH3CH,O°Na' cl Cone. HzS0x @ HH x 7. Column (1) (@) HyCimm 122, Et ‘Br eo OH () CH, —cH—a1 OH a), D CH,CH,CH. ees CHOH ae cl CHy Et 8 (@H,c—cH—cH—cl —SL, | Acetone CH, 8. Column (1) (a) PhMgBr +Cl~NH, (b) PhMgBr + CI—CN Il (©) PhMgBr + H,C—C—C] Il (@ PhMgBr +C,H,—C—OC,H, Q. Carbocation R. E; elimination S. Hofmann product Column 1) P. Inversion Q. Racemisation R. Ist order S. IInd order Cotss.ze a), P. Ph—CN Q. Ph—NH, Il R. Ph—C—CH,CH Il S. Ph—C—CH,Halides 9. Columh (1) Column (11) HeO (@) PhMgBr +CO, > P. Nucleophilic addition reaction ° ! HPO (b) CH;MgBr + Ph—-C—Cl —2-> —Q. Nucleophilie addition elimination reaction OH ll HgO \ (c) CH,MgBr + Ph—C—OC,H, -=> R Profs CH, Il HPO (a) PAMgBr +CH;—-C—CH, —> 8. PhCOOH 10. Column (1) Column (11) ang 4 CHs—CHe—Cl, we m ®>4 = 2, On © one Li) _CHCH-Br, ~ @ S i 2 CH3CH,—Br. s XK 41, Column (1) ‘Column (11) Hs ch @ Ph—F—CH GOH, P. No reaction cl ‘CH CH; i) —cH, Shot, Q. Rearrangement ct CH; ©) (Oo peor OF Gale, Hofmann alkene 4 Non (d) CH;—CH—CH,—CH ROH, 'S. Product can exist in stereoisomeric form274 GRB Advanced Problems in Organic Chemistry for JEE 12. Column (1) HC. () HOH S0Ch, Hs 13. Column (1) (a) CHCL— CR SOE, a CK aq. KOH a cl ° cHRCH,O ot = F alc. KOH, @ Av = Column (1D (P) Nearly total inversion (Q) Nearly total retention (R) Two step mechanism (S) Syl reaction Column (11) (P) Carbanion (Q) Two step process (R) Carbocation (S) Transition state PEERS INTEGER ANSWERTYPE PROBLEMS ||} 7 RM RX NHI : SH SH AA 0 () 8 CHyMgBr 2. HO HO’ 8 @) B90 HO’ Find out value of +X”. 9 (‘4° PhMgBi cl eB ao . a 3. onan 3° Alcohol Il 1, CI—C—0C,H, 3° Alcohol. Find out value of “X”.Halides: 275 4, How many set of carbonyl compound and RMg.X can produce 3° alcohol. . OH 5, Find out numbers of possible £; products from following reaction. ee HOB a. Br 6. Identify number of substrate those can give Syl and Sy2 reaction both. CH; €S-cu,—a: : Heel CHs Br gO , HC ct Br 7. Examine the ten structures shown below and select those that satisfy each of the following condition. Br CHs B (a Cr ) nye—Lor © Ce Ta) CHA CHy a © cr 0 CY @ <4 w ya cl (i) How many compounds give Sy2 reaction on treatment with NaSH? (i) How many compounds give E, reaction on treatment with alcoholic KOH? (iii) How many compounds do not react under either of the previous reaction conditions?276 GRB Advanced Problems in Organic Chemistry for JEE 8, Examine the ten structures shown below and select those that satisfy each of the following condition. Cl (a) Cy (b) (Sena («) CH; Hy Ci @ Na ©) on a) 9 H;C ‘H).—Br (e) Shea (h) i" om By CH; CH, ee (i) How many compounds give substitution reaction with CHy$Na? (ii) How many compounds give elimination reaction with NaCN? (iii) How many compounds do not react with NaOH? 9. How many substrates will show rearrangement during Sy! reaction? ealeeueanores Or ot oe OO 10. Find out oe of reactions those proceed with retention of configuration. CH; oe yy HOH, ) 7 OHH, Sur0, Pr e 4 Br otk Ph ©) eH, @ po #5 ron :Halides: og ps _ ‘ep ~ cH, Hc a? aes ot on Se CH, = S ESE Ky Exercise-1 : Only One Correct Answer (a) fa) 4c) 5a) 6 CD) 7) Bla) 9) WG) 41.) 12.(b) 13. (2) 14. (c) 15. (b) 16. (c) 17. (a) 18. () 19. (a) 20. (by BL. (c) 22. (4) 23. (b) 24. (a) 25. (c) 26.(b) 27.) 2B. (a) 29-(b) 30. (| } 31. (d) 32. (b) 33. (c) 34. (bd) 35. (c) 36. (b) 37. (a) 38. (c) 39.() 40 (0) 41. (©) 42. (@) 43. (6) AB. (by 45. (2) 46. (2) 47. (0) 4B. (0) 49. (6c) 50. (c) 51. (b) 52. (d) 53. (a) 54. (c) 55. (a) 56. (c) 57. (b) SB. (d) 59. (a) 6D. (c) G4. (b) 62. (c) 63. (a) 64 (b) 65. (G) 66. (@) 67. (c) 68. (b) 69. (a) 70. (b) TL. (©) 72. (d) 73. (b) 74. (c) 75.) 76. (c) 77. (b) 78. (b) 79: (4) BO. (c) 81. (b) 82. (a) 83. (d) 84. (b) 85. (d) 86. (<) 87. (a) BB. (e) 89. (c) 90..(¢) 91. (2) 92. (by 93.(b) 94. (a) -95. (b) 96 (d) 97. (c) 98. (2) 99. (d) 100. (6) 101, (a) 102. (d) 103. (c) 104. (2) 105. (a) 106. (b) 107. (2) 108. (c) 109. (a) 110. (c)} AL. (by 112. (4) 143. (a) 124. (c) 115. gb) 126. (c) 197-(b) 118. (2) 119. (a) 120. (by 21. (a) 122. (¢) 123. (p) 124. (Gd) 125. \(c) 126. (a) 127. (d) 128. (b) 129. (c) 130. (a) 34. (9) 182: (c) 133. (b) 134, (c) 135. {by 136. (d) 187. (d) 138. (b) 189. (d) 140. (¢); 141. (¢) 142. (b) 143. (a) 144, (c) 145. (a) 146. (c) 147. (d) 148. (c) 149. (b) 150. (6) 51. (c) 152. (a) 153..(b) 154. (c) 15§ (a) 156. (c) 187. (d) 158. (@) 159. (c) 160. (by|_ 61, (c) 162. (b) 163. (2) 164. (6) 165..(0) a278 GRB Advanced Problems in Organic Chemistry for JEE Exercise-2 : More Than One Correct Answers . ee @be) 2 da 3 @bq * @be 0) +. bed)’ 7 (he) Fc) 9 bed) 12 (abd) I? (bd) (bc) | 13. (@.b) 14. (abd) 15 (Be) 15 ad) =? (acd) (ed) 19. (bcd) 20.fa,b,c,d) 27 (ed) 2. (be) Eb) ES (be) | 25. (@b) 26. (bcd) 27. (a,b,c) 2% fc) °°. (ed) 3 (a,b) 31. (@,b,d) 32. (a,b,c) 33. (b,c,d) 34 (ac) (ab) @ b,c. d) 37. @c) 38. bd) 3% (bc) 49. @b) 42 (Dc) 2% (b,c) 43. (@ bic) 44. (a,b,c) 45 (a,b,c, d) “6. (a,b, d) f@b.c) 4% (@,b,d) 42. tb, c.d). 5Q. .(2,.b.0), ee wenn ee ed Exercise-3 : Linked Comprehension Type ee ee 40 2@ 2@ 46 >@ ©) 7@ FO 3@ 1 Oo 4A Ge) 12) 13. (b) 14. () 35 Gy (a) 32. ©) 7H () Se G@) 29)! De (0), BBs dL 23.46), 244 (a), 23. (d)_28 (6) 2” oo Exercise-4 : Matrix Match Type E (@P.0, WORK PS @ OAR | 2. IR: 0) 5; O30 dar 3, @)70.R: () > QR; ()>P @>9s 4 @9P.S; (0) P, S; ©>0R: @P.S : 5. @IP.R: (2) 0,8: (4 R; @70.8 | 6. @) RS; WARS; OPK )>P,0 t 2. (2)40,R; (0) P, S; () QR; MaP,S : 8 99; () 5 P; Ons; Qk 9 (PS; (b)-9.0,R; (0.2: (PR i 49. @) 30 0) +P; Or aR | LL (@S; 0) 9.5; ()9R,S; @aP ! 12. (a)-+R, S; ©) 8,8; oP, MOR BBA@2AG WOR eS. OPS Exercise-S : Integer Answer Type Problems L@ 2@ 34 4@ 5@ 3 @ 4 @50D65RH Gi) 3, B,C, F i) 4,4,6,45 8. 5,AB.CHI (ii) 2,G,J (iii) 3,0, EF 9.) 104 ACESAlcohol and Ethers | (EXERGRS4)) ONLY ONE CORRECT ANSWER I J 1. Analkene obtained by the dehydration of an alcohol (4), on ozonolysis gives two ' molecules of acetaldehyde for every molecule of alkene. The alcohot (4) is : (a) CHjCH,CH,OH (b) CH,CH,OH 1 @ CH;CH=CHCH,OH (@) CHCHACHCH OH 2. R—COOH > R—CH,OH. This mode of reduction of an acid to alcohol can be, effected by : (a) Zn/HCl (b) Na—aleohot (c) Aluminium isopropoxide and isopropyl alcohol (@) LiAIH, 3. Wood —Desmetiesisilation , y+ ¥ +2; products X,Y, Z are: (@) CH3OH,CH;COOH,CH,COCH; (b) CH;COOH, HCOOH,CH,0H (©) CHjOH.CH;COOH,CH;CHO ~~ (d) CHyCOOH,CHCOCH; ,CH CHO: 4. Which of the following reaction(s) will yield propane-2-ol? i) CHyMi () CH =CA—cH, +#,0—* & cH; —cHo OE Gi) H,O © cro ONE, (@ CH, =CH—CH, SEs, PCle Alc, KOH 1 Cone, HySO, . 5. Z —> X ———¥. THO. bail Z;Zis: (@) CHy;—CH, —CH;—OH @) H3C—CH—CHs OH (©) (CzHs)3C— OH (d) CH; — CH=CH 6. 1-propanol and 2-propanol can be best distinguished by : (a) oxidation with alkaline KMnO, followed by reaction with Fehling’s solution (b) oxidation with acidic dichromate followed by reaction with Fehling’s solution (6) oxidation by heating with copper followed by reaction with Fehling’s sohution (d) oxidation with conc. SO, followed by reaction with Fehling’s solution280 GRB Advanced Problems in Organic Chemistry for JEE i 7. On heating glycerol with KHSO,/A, a compound is obtained, which has a bad j odour. The compound is : (a) Acrolein (b) Formic acid 1 () Allyl alcohol (d) Methyl isocyanide | 8. A compound X with molecular formula C3 HO-can be oxidized to a compound Y $ with the molecular formula C3H 40. is most likely to be a : | (2) primary alcohol (b) secondary atcohol | © aldehyde (d) ketone Identify (Z) in the following series, : PBry Alc. (KOH {i) H,80,/Room temp. Ethanol —> () 9 (9) ionea > 2) ' @ cH, =CH, (b) CH3 CH —OH { (©) CH3—CH)—O—CH,—CHy (4) CH; —CH, —SO3H {10. Which one of the following is not the characteristic of alcohols ? + (a) Their boiling points rise fairly uniformly with a rise in molecular weight (b) Lower members have a pleasant smell but bumning taste and the higher ones ! are odorless and tasteless i { @) These are lighter than water : ' ; \ (a) Lower members arc insoluble in water and organic solvents bot the solubility goes on increasing with the rise of molecular weight 1 Dil. H,SO,/Hg”* DLSOWHiE” 1—~Methylcyclohexanol. Here 4 is: | A (@) (b) OQ © QO (4) (@) or(b) 12. Predict the nature of P in the following hydration reaction of alkenes. i | i ! ' ~ Dil HySOyHe’* P . ' 4 : , | OH (@ () ‘ © An ® a i 13. 2-Phenylbutan-2-ol can be prepared by which of the following combinations ? 1 (@) CoHsCOCH, +C,HsMgBr (b) CyHsCOCH, +CyHsMgBr (c) CgHsCOC) Hs +CH3 MgBr @) All of these 14. Predict the nature of reducing agent in the following reaction. LOR +Alcohols and Ethers 281 (a) LiAIHy (b) NaBH, (c) Hp /Pt (d) Both (a) and (¢) . The correct structure for compound B will be : ( PBr CH;CH,CHO OT a Ie on oO OH OK © aN @ a Hi . An industrial method for the preparation of methanol is : (a) by reacting CH, with steam at 900°C with a nickel catalyst (b) by reduction of HCHO with LiAIH, (c) by catalytic reduction of CO in presence of ZnO —Cr,03 (@) by reaction of HCHO with NaOH(aq.) Absolute alcohol cannot be obtained by simple fractional distillation because (a) pure CyH;OHis unstable (b) C)H5OH forms hydrogen bonding with water (c) boiling point of C,H OH is very close to that of water (d) constant boiling azeotropic mixture is formed with water . The product when glycerol reacts with PCls is : (a) 1, 2,3 —trichloropropane (b) glycero monochlorohydrin (c) glycero dichlorohydrin (d) all of these Glycerol RHSOu A Aand Bare : (a) acrolein, allyl alcoho! (b). glyceryl sulphate, acrylic acid (©) allyl alcohol, acrolein (d) only acrolein (B is not formed) 9 MgBr il HO* . ). H3C—C—C14+2 Ais: 9 OH (a) uc (b) noel \ & OH OH282 GRB Advanced Problems in Organic Chemistry for JEE CH,OH a. on is changed into oa cH N Ce (a) (i) Cu, 300°C (ii) CHyCH2MgBr, H,0* (b) (C105, (ii) CH3CH,MgBr, H,0* (©) () KMn0g (ii) CH3CH, MgBr, Hj0* (d) (i) NaCr,07 + HSO4 (ii) CH;CH)MgBr, H,0* 22, The conversion IL oe H;C—C—CH,CHCO,CH; > H;C—CH—CH,CH,CH,0H can be effected using : (a) LiAlH, and then H* (b) NaBH, and then H* (c) Hp /Pt carbon @ All HC, i 23. ocr, “AE 4, dis: HC 6 ) CHyCHCH,OH (b) CH;CHCH,CH,OH CH3 ots (©) CH;C—OH (d) no reaction I cH; 24, ce 8 a Ais: ou o oe © Or OH on © Cr . © ‘OHAlcohols and Ethers 283 25. Which of the following can be obtained from a mixture of ethanol and concentrated sulphuric acid, if the composition of the mixture and the reaction conditions are suitably adjusted ? (a) CoHy (b) (CoH )2804 (c) CH;CH,OCH3CH; (a) CH;CHHSO, 26. An aromatic amine (X ) was treated with alcoholic potash and another compound (Y), a foul smelling gas was formed with formula CgHsNC. (Y) was formed by reacting a compound (Z) with Cly in the presence of slaked lime. The compound Z)is : ( cgHtant () CoH;0H = (¢) CHJOCH, — @) CHC; 27, An alcohol (4) on debydration gives (B), which on ozonolysis gives acetone and formaldehyde. (B) decolourises alkaline KMnO, solution but (4) does not. (4) and (B) are respectively : (a) CH3CHCH ,CH,OH and CH,CH,CH=CH b) Ceci, —CH—CHe and CH) —CH=CH—CH) OH (©) (CH;)3C—OH and (CH; ))C=CH (@) (CH; );CHCH —OH and (CH )2C=CHy, 28. Absolute alcoho! can be obtained from rectified spirit by : (@) fractional distiflation (b) azeotropic distillation (c) vacuum distillation (d) steam distillation 29, If phenyl magnesium bromide and acetaldehyde are the reactants, the product formed after hydrolysis would be : (a) benzyl alcohol (®) 1-Phenylethanol (©) 2-Phenytethano! (@) Acetone 30. Which set of the following reagents (4 to D) would you select to convert CHsCOCH; (acetophenone) to the following alcohol ? CH; CH; CgHs— C—CH—CH3 bu (a) CHyCH CH, MgBr and hydrolysis (>) CH3CH(Br)CH; - AICI; (©) (CH 9 CHMgBr and acid hydrolysis (@) CH;CHCHCH3, Zn He 1. ByHy BI. CpHyg0(X) Es Cy Hyp (FP) a CH OZ) (4 3alcohol) 2UOOR lan isomer of) oO 1.05 samp? NN Zcan be: a284 GRB Advanced Problems in Organic Chemistry for JEE CH, cH, @ oH ® CL oH CH; CH; CH; © @ LX ‘OH Ho CH3 ge Me—CH—COOH 32. Me Bis: MeMgBr(wocgu), p #8 (a) Me;CHCOMe () MexCH— CMe, oH (c) Me,CHCOCHMe @) Me,CHCHCHMe, . OH 33. Which of the following reactions is possible ? (a) CgHs0H + HBr — Cg HBr + 1,0 (b) (CH )3CCl + NaOCH3 —> (CH3)3;COCH; +NaCh ay ‘CH,OH ( ALA + cHyone is S cl (@ CoHsMgBr @ Wr ean eee CgHsCH CCH), Gi H,0 I OH CH; CH, 34, yc—b—cr=ca, +. u,c—¢—ca—cH, X can be: én, cn, ou (@) BH, /THF,H,0, /OH7 () Hj0* ({c) Hg@Ac)2/NaBH4, NaOH (d) All of these*Alcohois and Ethers 285 cl A ys H,0 35. HC=CH—C—Cl-— > 4, Ais : ~~, cl (@) CCl; CH—CH.CL (b) CClyFH—CH,OH On cl ©) CChCH— CHC {@ CCls68 — CH a OH OH NaBD, . 36. CH;CH=CHy = 5 oq? Product X, X is: (0) CH CHCH,D (b) CH CHCHAOH OH D © CH GHCH, (d) none is correct oD 37. Identify end products 4, B and C of the following : CH;CH=CH, a A;CH3CH=CH, 24 B;CH;CH=CH a c (@) CH;CHCH inall cases bx (b) CHyCH(OH)CH,D, CH3CH(OD)CH;,CH3CH(OD)CH,D (©) CHACHCH, in all cases bo (d) CH;CHCH;D in all cases | OD . _ __BHyTHF H,0,/0H7 38. RCH=Uky Ge-coon? ty] co D In this sequence of reaction 4, B, C and D are respectively : (a) (RCH,CH) )3B, RCH)CH{OH, RCH,CH3, HI286 GRB Advanced Problems in Organic Chemistry for JEE (©) (RCH,CHa)3 8, RACH, RCH,CHs, Fl oH © (RCH CHa) B, RCH CH CH RCH CH Ou (d) none of the above " " 39. HyC—€— CH=CH, — HxC—C—CH— CH, This change can be CH; CH, OH done by : (a) acid catalysed hydration (b) oxymercuration-demercuration (©) hydroboration-oxidation (d) any method mentioned above ile KC BBr/ ide CH,ONa 4. CHCACH KON, gS gp Br In the above reaction sequence, the final product is, (a) diethyl ether (b) 1-methoxypropane (©) isopropyl alcohol (d) propylene glycol 41. Sodium tertiary butoxide forms ether only with : (a) CH; —CH)—~ Br (>) CH; —X x x I {c) HyC—CH—CH, (@) HyC— oH —CH; CH; 42, In the given reaction HC. , — (i) Hg(OAc),/CH;OH_ _Do=CH— CHs 5 eB xd, H3C [X]will be: OMe Me (a) HyxC—C—CH,—CH (b) HxC—CH—CH— CH CH; CH; (©) Hxe—0H— CH, CHs @) HyC—QH— CH CH CH; CH3Alcohols and Ethers 287 HC HAC. SN NS 4. ocr, — CH, a ‘C—~CH—CH; HAC HC 3 OH 3 oO | w HC. NS —CH—CH. “ | 3 H3C OH (X)and (¥) are respectively : (@) LiAIH, and NaBH, (b) LiAIHy/AICL; and LiAIHy (c) LiAIHy and LiAIH,/AICly (@) Hy/Niand Hy /Pt 44. >» +HI —— Product, Product is : . @) () HO~ 1 1-OH © on rv “I © ore «CT Vuno Cis: 2 ~_-CH—CH CH)—CH @ PTT? ) i SS OH | OH ~~ CH—CH) () yo 1 (d) none of these SS 1 OH 46. Which of the following reaction is possible ? (@) CgHsOH + HBr —> CgHsBr +50 (b) (CH3)3CC1 + NaOCH; —> (CH;)3COCH +NaCl i OMe CH,OH (0) Sch CHONa AN ho" @ wy + CgHsMgBr 2 CeHsCHsCICHs ou cl288 GRB Advanced Problems in Organic Chemistry for JEE (i) CHyMgCl (i HO X. The product obtained in this reaction is : af 47. HyC—CH. KY 2 (a) CH;CH,OH (b) (CH; )2CHOH { (©) CA;CH,CH,0H (dé) HO—CH,—CH,—CH, —CH, — OH 48. What i in the following sequence of reactions ? PCs alc. KOH () Cone. H3804 ea Sy z x Yap ioba 7 (a) CH3CH,CH,0H (b) CH;CHOHCH3 (c) (CH3CH, )CHOH (a) CH3;CH=CH . fi) CH= C 49. HyC—CH—CH wan Product ? Ne Product is : {a) H;C—CH—CH,—CH=CH;—CH3 dae (b) H3C—CH—CH)—C=C—CH; bMe (c) HyC—CH—CH,—C=C—CH, ou — CH—cH—c=c— (@) H3C aoe C=C—CHy 50. In the reaction 210 (C2Hs)20+H20 alumina acts mainly as : (a) an absorbent of water (b) a provider of hot solid surface (c) a Lewis acid to coordinate (C)Hs)20 formed () a Lewis acid catalyst to increase the leaving group ability of the — OH group by coordination at oxygenAlcohols and Ethers 289 o eA PRCHI PHCH:—I, CFCH;OH, DMSO A and B are respectively : Q—CHy—Ph OH oO «OO CH,Ph OH OCHPh (b) A= H2Ph : QCH2Ph ° () A=B= : 5 @ 4=b- CI CHPh oe a : Which of the following is the best set of reagents to perform the above conversion? (@) ThO,, A + (0) HyPO04,4 (c) Cone. HyS04 ; A (d) Al,O3,A &290 GRB Advanced Problems in Organic Chemistry for JEE e 3. 9, Product Zz The main product is : HH 20H (a) Q (b) 0 He HT HO ‘CH; ° HH )H Cr HO CH; H,C CH; ll Mg-Hg Cone.H,SO, KMn0,,H® a > 4. 2Ph—C—CH H,0 The final product is : Ph Ph 1 @) en OH OH (©) Ph—C—C—Ph Hl oo Mg-Hg 5. 2Ph—C—CH, —=—"> Il H30 ° The main product is : @) Ph—C—C—Ph al oo Ph | © Ph—-E-—G—CH “CH; 0 MesC—Cl CH; 6. —— AIChs Dil. H,S0, Ch, FeCls —Ees (b) CH; an ie oOo Ph | () CH;—C ~f- | Ph O Product (b) CH; —C—C—CH, oll o 0 Ph | @ Pr—e— oo Oo cH, HBr, A. na A.Alcohols and Ethers 291 - 2 The final product A is : OCH; Br ; » Or Me;C Mey cl H0__NaOl Batt, NaOH, NAS product or (HOB) By The product is : i. HO, HOw Hitwe © pycwmd > © cram FQN’ HyN' Which of the following sets of reagents would accomplish the following conversion? i te ( e-em ()-c1—ar—cncry bs (a) CH3CH,CH, MgBr ; H® /H20, PCC,CH)Cly (b) CH3CH CH, MgBr ; H® /H20 ; H)SO4, A; PCC,CH2Cl) 8 () Ph3P =CHCH,CHy ; ByHg, H202,0H (@ Ph3P = CHCH,CH; ; HyS0,,H,0 . An organic compound 4 (Molecular formula CH,204) on treatment with Na metal liberates Hp gas and on treatment with HIO, gives 2 moles of CH CHO, HCOOH (1 mole) and CO, (1 mole). Find out structure of 4. CHy Le CH;—-OH ‘cH—oHn C—O CH ‘CH-—OH CH—OH CH—OH CH—OH | CH—OH (2) (CH), b) oe © CH—OH (d) { ’ c=0 CROW CH—OH CH—OH | CH—-OH Hy;—OH | CH;-OH CHy-CH; 40%292 GRB Advanced Problems in Organic Chemistry for JEE 10. An organic compound A (Molecular formulaC¢H30) does not change the colour of acidic dichromate solution. Compound A on treatment with H,SO, produces alkene, which on oxidative ozonolysis gives a molecule (C¢H 903) which gives positive iodoform test. Find out structure of (a) [)-ocus (b) a (c) OH (d) CH; Ca on Prt Hy CH3CH2 & CH; \n 87 Cone. HBr coe Sone HBS Product Hw? Non h HC’ : —OH group is substituted by —Br. The slowest step is dehydration. Which of the following is correct comparison of rate constants k,and ky’? (@) ky = ky (b) ky > kp © kP>S>Q (b) R>S>P>Q (c) P>R>S>Q (A) R>S>O>P F294 GRB Advanced Problems in Organic Chemistry for JEE 17. Which of the following alcohols will show positive iodoform test? OH OH oO | | (a) CH;—CH—CH, —NO), (b) CH; —CH—CH, —C—OH OH (©) ICH, —CH—CH,CH, (d) None of these 18. In the given reaction, 3 Px? BoHs TsCl_ Me;COPK' oincnaaary B) H,0, °OH ® (4) The product B is: (a) Identical to B (b) Chain isomer of A (c) A positional isomer of ‘4’ (d) Reduced product of A soct. Mj oO 19, ae, Ms Product Pyridine, A” Etj0 He ON cH,0H ‘The final product is : ‘OH @) ) oO ° LAH © @ OH o ‘OH oO ° 2. wy Jano, 1H OH @) (b) © @ iH He .CH,0HAlcohols and Ethers “he Qe & ot ol ce 23. LN pu, © 9D 9 # LX ° ° SH ‘on gy, CHsCH:OH. 24. ()—cricn, EE, CH;,CHs (a) b) Cree ‘OCH,CH; ‘OCHCHs H2CHy CH:CH3 () @) H{CH3, OCH,CH3 wm‘, tt 25. GENO: ON 0. @ (b) Br (c) CL (@ BY 1 Br —oH ° Conc: HyS04 , 4 _(CHsCOO , ,_KMnOVOH Cone HaSO4 (HCO, g ew 26. a “AIC: a HO—~ —OH296 GRB Advanced Problems in Organic Chemistry for JEE CH; COOH COOH - COCH, @ &) ©) «) CooH COOH COCH; COCH 27. C3 +CH,CH,oH HCL, 0 OCHCH; CH,—O—CH @) (b) Cy 0 O © Ch @ ‘07 SOCH.CH; ‘07 SCH;—O—CHh 28, Which of the following reacts fastest with HBr? CH,OH CH,OH CH,OH CH,OH @) oO ® GC © QO @ NO, cl 29, The order of reactivity of following alcohols toward HCI is : é on ey YX, pn’ Son 1 2 HH 3 4 OCH; (a) 1>2>3>4 (b) 1>3>2>4 (©) 4>3>2>1 @ 4>3>1>2 30. The order of solubility of 0. 1h” ‘cx, wea HCY NH T U m in water is : @I>I>M @&)I >t @) > I> 31, Dehydration of following alcohols will be in order : Ce Onn Ove Ore (a) 1<2<3<4 (b) 4>3>1>2 (©) 4>2>1>3 (d) 1>3>4>2Alcohols and Ethers 297 32, Which of the following reactions proceeds with retention of configuration? je le (a) H—+— 0H Na CH,Br, (bh) OH TsCl | CH3ONa Et Et Me Ph PCs, CHxONa SsOCcl, KCN (© H—+—on SS SH 08 Ss | Et CH; 33. Find out correct product of reaction : HBr (Excess) Br AN Br Br Br Now 34, os Mafeher, HCHO, 4 4g. He @ o—<>—crk08 ~ &) o> —cH.08 ) HoHc—< ci, —0n @ onc —<>—cHo a3 ees E01 KMNOS, 5 C03, 4 and Bare: Act “Kew” oe he Chey CL ow OK " (©) HH OH @ OH 36. MnO, Product The main product is :298 GRB Advanced Problems in Organic Chemistry for JEE . oH ° ° oO OH @) (b) (c) (d) O OH 37. oh seme Major product : oy ) =< © >< (d) None of these O OH : ° se YB ss Bre tan Identify product D in this reaction : 0 0 oO 0 oO oO ) cy ‘OH () CHI, ol ye 39. In the given reaction 9, O—CH,CH, 129, (py Pwill be: woe Ons © > @ (con 40, H,0/H® oa 0-0. Hs *X? will be : . Ho” 07 ~CHN o& CHS cio © JE (@) All of these 0 H ‘OH 41. OH _MnO2, CHsCH2OK, vjaior Product : ‘CH3CH30HAlcohols and Ethers oO oO oO vs 1H ®) cr ) oe © Cre ® : oS oS OH 42, LPP OAC ww ‘O- 2. OH/H,O° HH (X) will be: 0 (a) O o 9 e || I {b) O—C—(CHz);—C—(CH);—COOH ° Il i} (c) HO—(CH2);—C— (CH2);—C—OH i (d) HO—(CH;);—C— (CH2);—CH,0H t i :NH—-C—CH NH—C—CH, 43. NaNHA ‘The above reaction is known as : (a) Clemmensen reduction (b) Birch reduction (©) MPV reaction (d) Wolff-Kishner reaction 44, In the following reaction @ H30 — > Product ‘The major product is : OH OH @) CY ©) CY © @ OH OH 299GRB Advanced Problems in Organic Chemistry for JEE 300 < 45.C CHsoyy B2 CC The major product obtained in this reaction is : CH; (CH)Br CH, Br Br, CH3. Br NC Br ot o¢ 9 © 2 a ® \ on => Find out major products of following reactions. (Question No. 46-50) CH; CH; 46. nti Le HiB04, f OH OH tt ie (a) Ph—C cH, ©Pr—C—E—Ph CH, nd CH g CHy : e Ph © ctf @ fm Ph OH OH OH a. Cone.HyS04 , “0” 9 ° ? @ ) LA © An (a) None of these H OH OH 48. Oo J, 9 ° 0 ° ~ @ oo ) cx © Ax @ OA, OH OH 49. Ph cH,Alcohols and Ethers w1 ° OH 9 H @ mt ll ©) why Ory @ wf 4 3 0 CH; 50. OH HyS0, OH CH; CHy CH; LA @ CL ® LX © Ck CH q O “Ct = Find out major products of following reactions. (Question No. 51-55) 51. 7A __, Conc. H3PO4, OH — @) AZ (b) N= O\~\ OH 52. , Cone. 1804 Kody 0% @) () ©l | (d) None of these oe qd) CH,—OH : Ha 53. —— HOCH; ‘CH; —OH ~~ @ A (b) tA of | @- OH _Cone: HS04 - Gone. HaSOe , A ~ @ on o Co © 0 54. ss. (( W) —ome B80 a @302 GRB Advanced Problems in Organic Chemistry tor JEE 56. 37. 58. 59, 60. 61. OH OH OH OH “Gh “Gy “Q @l | When ethylene glycol is heated with oxalic acid in the presence of conc. H)SO4, the product formed is : oO 0. oO 0. oC ft » Yt oo o Oo °. 9 ‘Os © C) © se fo Oo An organic compound having molecular formula C3H,0 does not react with 2, 4-dinitrophenyl hydrazine and does not react with Na metal. The compound is expected to be: (@) CHyCH,CHO (b) CH;COCH; (©) CHy =CH—CH,—OH (d) CH, =CH—-O—CH Which of the following statements is correct? (a) Phenol is less acidic than ethanol (b) Phenol is more acidic than ethanol (©) Phenol is more acidic than p-nitrophenol () Phenol is more acidic than acetic acid The vapours of an alcohol (X) are passed over Cu heated at 300°C whereby an alkene is formed as product. The alcohol (X) is expected to be : © oe @ +-on b) aA ‘OH (b) AlOs = OH OH 350°C The major product formed in the reaction is : oO ok, ©) xox ok @ >—éon Aol is prepared best by the reaction : (a) (CH )3C—Br + (CH3 )3COK— ‘OH ) (CHy);C—OH 2, —Ol (b) (CH3)s TarAlcohols and Ethers 303 6: 63. 64. 65. 6 8 x CH ),0—on “22 © oH, (©) (CHs)s are Cone. H, SO, (CH;);COH (@) (CH3 )2C=CH, ———3 ———> . When 2-chloroethanol is warmed slightly with dilute NaOH, the major product formed is : (a) Cl—CH, —CH —O—CH, —CH) —Cl (b) HO—CH, —CH,—CH,—CH, —OH () HOCH) —CH; —OH © \o7 Bthylene glycol (HO YOH)on heating with cone. H)SOq gives mainly : @ Ho” So” on ) \o/ 00 2 ws Which of the following reactions would give the best yield of ¢-butyl methyt ether? H, SO, (@) (CH );C OH (b) (CH3)3C—Br +CH;OH——> ee (©) (CHy);C-—Br +CH; ONa®—+ (d) (CH )3C—OK +CH Br —> Consider the following reactions fe Pea Bt geo (Ha ——€ 20,4 Br Br The product (Cis: “™N, “on, (@) OH ‘OH (>) Br “o io ou (©) HO @ C 5 H)SO, ° ti 4, In the ree-:tion HOC AA OH — The major product formed is : @) HO A AA ‘CH (&) O (a) HO, OH 0 MoO304 GRB Advanced Probiems in Organic Chemistry for JEE 67. The major product formed in the reaction is: 1H NaxCOy Chon +CHSCH—1 Te 0: (d} @ Ory © on om 0OLo Ol, 68. Consider the following reaction, Br /CCly Dil. KOH HC = CH—CH,CH, OH —4 4 3 B The product B is : Br @ A on 1 So” Yon ‘Br © Dé Br wd 5 0" 69. Find out correct product of following reaction : 0, CH,CH)Br “20 @AV* — ) Ch=Ch © Ag — @ CHCHOH 70. The major product (1) of he eaction: #3804, Wrekin? ¥ 0; oC ©) 0° OMA OD AAYAAG 71. In the reaction, CH;OH C—CH, — (X) Ihe 4 H® The product (X) has the structure : CH; CH; (a) Hy3C—C—CH,OH {b) H3C—C—CH) —OCH3 OCH, OH vs os (©) H3C—C—CH, (a) CH; —CH—CH, —OCH OCHAicohols and Ethers: 305 72. Consider the following sequence of reactions cc, H,C=CH—COOCH, +Br, —*> 4 ou (Cl Babe ‘OH The end product (B) is : 9, A, COOcH: Ol cooctt, ° ao yu 0%“ . 0” “coocHs Non “OL “On > oO ° ro) 73. in the reaction : A Mex;C—O—CH)CH; + HI —> (1Mole) (a) Me3C-—OH +CH ,CH)I (b) Me3C—I +CH3CH,OH (6) Me3C—1+CH CHI (@) Me ;C—OH +CH3CH,OH 74, Which of the following ethers is the most unreactive to cleavage with cone, HBr? (a) Ph—CH;—O—CH3 (b) Ph—O—Ph OAL’ @ >—0-< on O. BB. ue Major product : oT A OF WM 76. The product of the reaction is : ° KH. Ww ae OH 0 on s Sy ott (b) CY @ ast}o™ @ as OH 77. Which of the following reactions will not result in the formation of anisote? fa) (O}-on + (cHy);80, 4, (b) (O)-on +CHisI—GRB Advanced Problems in Organic Chemistry for JEE (©) “oO +CH,N,—> @ (Open +CHj;MgI—> 78. Consider the following sequence of reactions. 28 HO, pH p-Tsct AcOK p—KOH c x Pyridine AcOH Hj0, A The major product (C) is : HO, yH Hi ,OH OS, OS, (©) AY (@) ()-2-butanol 79. 9 4, 9 Ais: 0 ‘0 COOH (CH,OH (a) ByH¢/H,0 {b) LiAIHy (c) CH3;OH/Na (d@) P/HI . 9 . 80. OA . Ho” on OH 0 Reagent A used in this change is : (a) BH (b) LialH, (c) Sn/HCl (@) NaBH, 81. ah on oe &) >— © foo No reaction 82. The major product formed in the reaction is : One =? ONS @ Cj + CH;CH,OH ) toh ‘0 He oO” of) “A ® Soho: ‘CHO OH ‘OH HO’ Hi ‘COOH 33. Ort “L 804, HIOs c TiAl, 5 coon ‘excessAlcohols and Ethers : 307 oH (a) HO” HH (b) HO HO HI OH OH HO. OH © ry (@ HO ‘OH oH ‘OH oH ‘OH ou ‘TsCl LiAIR, 84. Pyridine” A—— > B Product (B) of the above reaction is : L 85, Find ot the product when compound reacts with NaBH, ® lope () HO ‘OCH; © ah @ pn 0 COOH KxCr07 86. oH Find ou): COOH COOH COOH ocr oy ot oly308 GRB Advanced Problems in Organic Chemistry for JEE fi 87. \o-d Product HO, i Py @® o © OK @ ox oO \_/ *o- H;CO. OCH, 88. NaBH (4), Product (X) is : “an HO, ‘OH _H3CO. ,OCH; 28 OCH; ! fl 2 i 89. EtO—C. C—cH; > Bto—C Which of the following reagents will be used for above conversions? (@) LiAIR, (b) NaBH, (©) K2Cr,07 (@) Jones reagent 90. KSI, : product of the reaction is : *CH—CH,—1 * (@) Ph—CH)—CH,—SH () Ph—CH, —CH, —SH (©) Both (a) and (b) (@ None of these oH OH 1. Cy — CO ; This conversion can be carried out by : (a) Hp804/A, HIOg (b) NalO4, H®/A (c) HIO4, NaBH, (d) H®/A, Zn(Hg - HC)Alcohols and Ethers 309 92. Which of the following alcohols will not give iodoform test? OH @ nw (b) CH;—CH;,—OH on oH © Ke . @ A OH 93. HH) ———> Major product obtained in this reaction is Ph 8 O) ) Ph Br HH Ph Q COOC.Hs 94, ‘tf LAIN, : Products of the reaction is : (@) racemic (b) diastereomers (©) meso (2) optically pure 95. Reduction of R—CH,OH—> RCH; can be carried out by : (@) LiAIHy (b) Hy>—Ni—(¢) Red P+ HI (d) NaBH4/AICI; OPh OPh 96. _HI(exce8s) . hich of the following is major product? ‘OPh E . OH I OH @) (b) © iS (d) None of these T ‘OH 97. Which of the following ethers will get hydrolysed by H® /H,0? “OrOQ OS wOrecea poe310 GRB Advanced Problems in Organic Chemistry for JEE 98. Which of the following alcohols will not react with Cu/A? Ph (a) CH; —CH, —OH (b) Pht on bs vs on (©) HyC—C—on (@ Ph—cH bs, Hs OH Oo Oo OH oO @) QO ©) Cl @ Ch @ O Br 00. Which of the following can give purple colour with neutral FeCl3? OH Hl CH, OH COOH (O) oO CH; (i (ii) (ii) {iv) (a) (ii) and (iv) (b) (i) and (iii) (c) (ii) and Giiiy — @) Gi) and (iv) HRC CH; H 101. The hydrolysis ormco{O)-+ + +(O)-no ; ; H C1 CH in aqueous acetone gives : . (a) KandL () Only K (©) Land Mt (@ Only ar HCH CH; where K=CH,0—C) } O)0,;; H OHCH; HCH CH; L=H;COXC) | O)}-4oz. OW H CH;Alcohols and Ethers 3 HC CH CH: M=H,CO: NO2 H CH;OH OH HSO. 102. Pe 1280+ , «p> Identify ‘P* in the reaction : ‘CH=CH, if 0° {a) —CH; (b) ° ll © @ [>-cm eo OH 103. on dehydration gives : H ox @l | ~ CH—CH, ol oct m(O} + CH;—CH=CH, As pO, 2 g HHS ns | Identify R and S : on ° o—0—H @ ana JL 0) and OH OH ° © ane A @ and >—OH JY ° . QH _He(OAc)2, HO/H™ 1 y,, evrig « 105. Cs —— NaBH, 1X; Ais: on i OH ® Cr wo © o « CS312 GRB Advanced Problems in Organic Chemistry for JEE 0 HALO | HBr Mg HCHO 106. CO + CHMgBr ——">P 5 9 Eo R Tino > Sis: OH OK oD 9" oC La 107. Identify the major product of the following reaction : Cx Cone, H7SO4, A OH () A ) Cy © Cy @ Cr 108. Find the correct method for the following conversion : on = =—BN oon VI US e (a) OH, HBr () Conc. HyS04, A () H®, HBr (d) None of these 109. Which combination of reagents will bring about the following conversion? CT -OK (a) MeMgBr/H®, H)S04/A, HBr/H,0> (b) MeMgbr/H®, H.S0,4/A, HBr (c) MeMgBr/H®, HBr/CClg (d) HBr/H)0>, MeMgBr/H® OH | 110, C CH,OH is converted into Cc CH—CH,—CHj by : (a) Cu/A,CH CH) MgCV/H,0® (b) CrO3,CH,CH,MgC/H30® (c) KMnO4,CH3CH)MgCV/H,0® (d) NazCr07/H®, CH3CH2MgCl/H,0°Alcohols and Ethers . 313 111. Which of the following alcohols will undergo easiest deydration? cr (© Br, Br OO 6 Bi 113. In the following reactions Me,C=CH—CH, —CH = CH) + CgHsCO3H (lequiv.)—> X, X is: oR © <8 o> 0 114, The most steam volatile species is : OH OH (a) OL &) NO> NO, NO; 115. In the Libermann nitroso reaction, changes in the colour of phenol occur as : (@) Brown or red-green-red-deep blue (b) Red-deep blue-green (©) Red-brown-white (d) White-red-green3t4 GRB Advanced Problems in Organic Chemistry for JEE 116, The alcohol which is most readily dehydrated is : (a) 2-butanol (6) 14 phenyl 1-propanol 9 © Aun @ Ae 117. A compound P (C7Hg0) is insoluble in water, dilute HC1, NaHCO, but dissolve in dilute NaOH. When P is treated with bromine-water, it is converted intoa compound of formila C7H ,OBr. Compound P is : OCH; OH OH OH ‘CH: oO oC ‘oe om “2 Hs 118. In the following sequence of reaction CH,OH CH=CH—CH; + Hg (CH;CO0), am XXis: ia t (@) & S-cr—cxcs @) (Sacco gers ©) Orteavnoy @ € \-cu,—cu—cn, CH3;CO: 19. & COST. Product of the reaction is : (Excess) “Dap Ona 120. When SA is treated with proton acid, a resonance stabilized cation is produced. Which diene listed below when treated with acid will give the same carbocation? OH arn. a ony @ OH OKAlcohols and Ethers 315 121, Which of the following would undergo most rapid hydrolysis with aqueous NaOH to furnish the comesonain | hydroxy derivatives? (one “G0 NMe; 9 Ag ‘OCH; 2 b _LiAIH, H)0 @ Find out ‘A’ of the reaction : H OH HO. (CH,—OH Hi (CH,OH @) oT O° “SO 123. Identify the major product of reaction : OH %, TS-Cl KSH TL, HSH, wD dine SH SH D @ OP, OO AKRQ @ Norenetion o% Fy wn 124, Find the product of following reaction with stereochemistry. H, a 2 HyC —ZC—Com CH, Nat, ‘ oH 4 ' “tp A Vt H @ recs eC — Cam Cs ©) HC C—Clonu Ht Ne HO cH, Me Cl CH; © HC me os . @ HC Soe H 0 -316 GRB Advanced Problems in Organic Chemistry for JEE 125. Select the major product of following reaction ; 0. 2 Py CHCH,0. ae a @ DY 6) > OCH;CH; Pre OCH,CH; o 8 @§ @ cn, a CH3CH;—OCH2 : 126. What would be the major product of the following reaction’? oO e cy al oO CH;OH Ph Ph H CH, OH OH «= Ph a, @ HC n> tb) Photc—choant Pi ‘OCHs OCH, Sh Qa Ph © Hc 1) —$ Goad (d) None of these Phe ‘OCH3 127. Find out major product of following reaction : Ph 8 CH;CH,O ¢ : CCH H OTs (a) Cm ) On (©) Onn (@) No reaction OCH2CH; CH; ee WOH PBry KCN CHj;CH, YH CH; CH: (CH: (®) am © Someg cHCH, Yon Hq H 128. — > final product. H @ eattt CH NC SCH,CH;Alcohols and Ethers 317 129, What would be the major product of following reaction? HyC. CH; CH3. Cone. HpSO4 eee ‘OH 4 CH, CH; CH: Cc /CHy b) ‘CH; CB CHE en Or, CHChtNOH, | gg (Expected) (Unexpected) The unexpected product B is : @) (b) on CHC, H | _é ‘OH 4s) ‘OCH; H Il oO . . _ <> 131. The final product in following reaction is : - jr H 1. Mg, ether 2. HOP 0 HC” ‘OH Ss @ () CH CHGRB Advanced Problems in Organic Chemistry for JEE 318 ‘MgBr H © ° @ CHy cH, 132. How many structure of final products are possible? Conc, H2SO4 BryCCly Lone. HaSO4, _ BrICCh Ion - CaHgBra @2 (b)5 6 @3 tag MORE THAN ONE CORRECT ANSWERS {a 1. Choose incorrect statements regarding the following reaction : BoHe 0H, Hz02 {a) Syn addition of —H (from BH) and —OH (from solution) occur. (b) Syn addition of —H (from BH) and —-OH (from H0>) occur. (©) The product is optically active. (d) Addition follows anti-Markownikoff orientation. HBr 2 [> 13. C)HsBr can be converted into C7 H; —O—C Hs by: (a) reacting by Cz HsONa (b) heating with moist Ag 20 (c) heating with dry Ag,O (d) treating with C)HsMgBr 14. 1°, 2° and 3° alcohols can be distinguished by : (a) Cw/S73 K (b) Victor Meyer test (c) ZnC}9/HCI @) Br, +H,0 15. Alcohols can be replaced by —CI group by the following reagents : (a) Cl, (b) soci, (c) PCls (d) HCl +ZnClyAlcohols and Ethers : 321 16. Glycerol can be converted to acrolein by dehydration in presence of : (a) Conc. H,S0, (b) KHSO, (©) CaCly (@ Anhyd, ZnCly 17, CH;CH)—OH can be converted to CH;CH,CN by the following reactions : A A (a) CH;CH,OH + KCN —> (b) CHyCH,OH + HCN —+ ‘TSCl KCN SOC], KCN (©) CHyCH,OH——>» > (¢) CH,CH,OH 4 > 18, Which of the following will oxidise to salt of acid by Br) + KOH? OH | (a) CH;—CH;—OH () | S—cu—cu, o (xe ® [ cron c ‘CH Yo one NaBr 19. So“ HC OH Pyridine H. H H Br (a) Ais (b) Bis HC OTs HC H H . H (e) Ais (a) Bis BC ‘OTs HC Br 2 Cone, H2S04 Os OK 20. — A—>R >Y Cc OH ° CH; (@) Ais Bis (©) Cis o@ Cis ° ‘CH; Y H3 i PBry Mg CH;—CH—-C—H a. < >on 3 4p SS on 4 ERO B H°H,0 c (a) Ais oer : (b) Bis ase CH; OH | fe | ©) cx Gat @ ce cect, Neu { 3 . OH322 ‘GRB Advanced Problems in Organic Chemistry for JEE ». CY Cone. Hr80s, 4 OH Q H u V 0 NH @ Ais ©) ay © Bis @ uy ‘OH . OH 2 C103 CH3MgBr H;S04 Baie 4 EE pp dil. acetone 4 HeH,0 B a ce HOF OH D oO. N OH OH : @ Ais ) Bis CS © eC @ ol ‘OH o Me SO, ti 2, Me — 180, Lilly 5 OH Me Me Me @A fore : wis 0 OH Me Me os Oh . © Bis . HH OH Me 2s. Cone. HI Mg, ether Excess)” f CO, HF Son KMn04 Cc——D 1 COOH (@A ? ©) a 1 COOH on ‘COOH © cw @ Di OH : COOHAlcohols and Ethers 323 2 CHJ—C=C | CHI _Hz,Pd-BaSO4 26. \ Gf A A Bn () Aisg S—CHy—C=C—CH; @) Bis S—CH,—C=C—CH; 0 OCH; “CH. (©) Cis HyCO HC} NaHCO: Mn0; 27. ASB SS? ces (@) A A ) “ _Nalether PCls 28. CsH20 (A) ether {pe-xon NaBH, Hg(OAc), _ BH:THF Fg Pa 2 H,0,/04 (a) DisCH;—CH = CH, © FisCity—CH—Cg OH 1. Mg 29. HyC=CH—-CH,Br +MB_, 4 2. HCHO -3.HPO (a) 4 is H>C—CH—CH,CH,OH Br CH, CH; worry @ Cis Hi: H CHy wr Or, CH; (©) ond (d) “i ic Delether 2 (b) Eis CH; —CH) —CH)--OH (d) Bis CHCHZCl Bry KOH alc. KOH /f a pe SS | (b) Bis CH) — (HCH Cth, —0n Br324 GRB Advanced Problems in Organic Chemistry for JEE (©) Cis AD Br Br, @ cis yD ‘O” 30. CH;—(CH,);—CH)MgBr 1 i) A [6 Ho” B K,Cr:07 CHy (Cth) —CmcH Ds 7 - i 6 (i) H30 @xK OH ti) #30 Bh OH 9 @ zis AAA © (6) Jis PhMgBr MgBr (©) Cis Hg’/H,S0, (d) Kis| 31. Compound A is an optically active alcohol. Treatment with oxidising agent converts it to a ketone B. In a separate reaction 4 is treated with PBr3, converting it into C. Con reaction with Mg is added to B to yield . Identify the correct options. OMgBr (@) 4 is 2-butanol (b) A is 1-butanol (c) Cis 2-bromobutane (@) Cis 1-bromobutane 32. Alcohol 4 (CjgHj0) is converted into mixture of alkene B and C on heating with conc. H3PO,. Catalytic hydrogenation of B and C yields the same product. Assuming that dehydration of alcohol 4 proceed without rearrangement. Alkene B on ozonolysis form cyclopentanone. Identify the correct options.Alcohols and Ethers 325 33. 34. 3 a (a) Ais (b) Bis Ott Y © Cis | @ Cis Acompound*X"(C)4H 40) on mild oxidation yields C)4H,20 (1). [fis treated with a dehydrating agent, it loses a molecule of HO and resulting product on vigorous oxidation yield two molecule of benzoic acid. Identify the structure of X and ¥. {a) Xis (orem HO! oH (b) Xis Ph——CH—CH,—Ph Il () Yis Ph—C—CH,—Ph (d) Yisph—cHh cs {Yo Compounds 4, B and C are isomeric alcohols with formula CsHj20. 4 on oxidation gives ketone, B gives acid while Cis not oxidised, A gives test with 1y/ NaOH. The three isomeric alcohols react with HBr with decreasing rates C > A > B. \dentify A and B. OH . OH w@ 4 b) Ais () Bi d) Bis cH; ¢ Hon (c} is @ Bis xy ‘An optically active alcohol 4 (CgHy¢0) on oxidation gives B. A on heating gives C (CgHhy4) a8 major product. C on ozonolysis produces D (CsHy0) and CH CH. Don reduction with LiAIH, gave | on Identify correct oO answers. ‘ . CH; @D if Yeo (by Bis [+008 A CH; © Ais | foomon (@) Cis [x H326 : GRB Advanced Problems in Organic Chemistry for JEE 36. Compound A (C7H,4) decolouriges Bry in CCly and reacts with Hg(OAc)) followed by reduction with NaBH, to produce a resolvable compound B. A undergoes reductive ozonolysis to give A/S ss one ofthe compound, ° Identify 4 and B. @ 4is wis OH (ae PBN 1H 37. A3° optically active alcohol CyH, gO ‘A’ on dehydration with conc. HSO 4 produces B (Co Hg ) which exists in two stereoisomeric forms, For ozonolysis of B followed by work up with Zn- HO produces CH; —C—H and C (7H; 0). C on treatment || Hy /CH; Oo with LiAIH, produces D (C7H 40). D on dehydration produced Identify the correct answers. CH; (a) Ais ‘CH—CHz—CH;—OH CH3 @) Ais Cp ovcn OH I © Dis (>on ; OH | @ ox bic, 38. 4 (CsHj20) ether, on reaction with PCls form alkyl chloride B and.C. B and C both on reaction with aqueous KOH form alcohol D and £. Both D and E give iodoform test. Identify the correct answers. CH; (@) Ais CH;CH)—O—CH. (b) Cis Cus FH, ‘CH; ° : cl (©) CisCH,CH,CH,CI @ EisCH; — FBO OHAlcohols and Ethers 327, Cone. H2S0. 39, } PH SES: Products can be: Why WA whe wr 40. Among the following gemdiols which are stable with respect to corresponding, carbonyls : 1H ? OH (a) cney—H (b) nec OH HH 0 © ou @ CH—On _ CH;—OH CH;—OH | CH,—OH 45. Which of the following esterification reactions are unimolecular? Oo ll H®/H,0 (a) CH; —C—OH +CH;0H —— CH30. 1 fl H®/H,0 (b) CH, “+ C—OH+C,H,OH 5 CH; Ph {| | H®/HLO (c) CH; —C—OH + Ph FH Ph 0. OH HO. HOM, os . J LO Zz oO ‘OH HO: 46. Which of the following reactions involve rearrangement? . Ph 0}. 8 Ph ct0 @) \Z\ = (b) oa —_4, HC C S i OH Ph o-CH © Cone. HyS0s @ as? AIC SfAlcohols and Ethers . 329 47. Which df the following pairs can be distinguished by using Lucas reagent? (a) ¢ S—c1,-on, CH3CH,OH (b) ¢ S-cu-on, CS-on © D-H Ao, © Aon, on 48, Which of the following compounds are soluble in NaHCO}? OH SO3H OH COOH (a) No, ©} © {Nor @ NO2 le NO; 49. Which of the following reactions are correctly interpreted? —skC_, KSH (@) >—OW Sine” —S >sn He(OAc (by +See OAD tu 1,0, NaBHy CH,CH; oO CH Ll it (©) Ph——C—ph AE, CH—C_C Ph OH CI Ph @ ¢ \-cu ony (Som 50, Which of the following reagents can be used for identification of phenol? (a) Nedtral FeCl; (b) NaNO + HCI (6) (NH4)a[Ce(NO3 6] (@) ZnCl, /HCL daa Sey LINKED COMPREHENSION TYPE a Passage-1 Although epoxides do not contain a good leaving group, they contain a strained three-membered ring with polar bonds. Nucleophilic attack’ opens the strained three-membered ring, making it favourable process even with the poor leaving group. Ae. & om, S—leaving group inde — Chia gc — a ° Ne Nu This reaction occurs readily with strong nucleophile, and with acids like HZ, where Z is nucleophilic atom.330 GRB Advanced Problems in Organic Chemistry for JEE Reaction with H. O CNM,O. at OH strong nucleophile H CN \t ‘Nucleophile Reaction with va mS OH opens the 1, Find out correct product of the reaction : 7 membered ring ° 1. CHO 2.H20 cH, = OH @ oe ©) HI ‘OCH. “ino JH: eno nos qa © 70H @ Cue Oe 1H 2 ZX ee What would be the major product of reaction? 1 7 : 1 @ << © vx © ~~" @ xX YH H 1 1H PI He 3. tH.» a 2 GOH H: Find out major product of reaction : Ph ou @ —CH,—CH,—OH . Sn abu, HC”) ° ac CH; CH; OH Hy © ‘H—-CH—CH) _ (d) -None of these sue? S “Alcohols and Ethers 331 Passage-2 1, 2-diols are oxidized to ketones or aldehydes by periodic acid HIO4. Periodic acid reacts with diol to form a cyclic. intermediate. The reaction takes place because iodine is in a highly positive oxidation state, so it readily accepts electrons. When the intermediate breaks down, the bond between the two carbons bonded to the OH groups break 4 t ; HIOg { * mG HyC—C—CH—CHy 5 41,0-—C-—CH-CHy — - =O bub Oey WC on, HN +0=C +HIO; HO Nu “Cy Ba A LEKOH, yp 0504, HlO4, py Identify D. Oo @) Cr ©) CY © © HH H HOG =o 5 HIOy 5. ron (Excess) Re H,OH Which of the following will not form by above reaction? oO oO @) H-C—H_— (b) CH,OH (©) CO, (é) H-C—OH 6. Whicti of the following compounds will not react with HIO 4? OH OH @) ©) oe “yy A OH “on OH rs . — © @ xi ™ “ou (CHC! “oH (CH).332 GRB Advanced Problems in Organic Chemistry for JEE Passage-3 Carbon-oxygen double bond are easily reduced by NaBH, or LiAlH,. The actual reducing agent in these reduction is hydride ion (H” ). ft 9 OH | ow | oe gq? —c— ge +OH VA ‘The metal-hydrogen bond in LiAIH, is more polar than metal-hydrogen bond in NaBH. As a result LiAIH, is strong reducing agent than NaBH. Esters, carboxylic acids, amides cannot be reduced by NaBH. The carbonyl group of amide reduced to methylene group by LiAlH. 7. Find the correct product of the following reaction : wot (O) i LiAlHy, f i @) Hy3c—C- CH,—NH, (0) HCH C—NH ou on © + H—>CgHs (d) Product of reaction is carbonyt compound. Passage & Compound (4) CjgH2,0, is insoluble in ag. NaOH but not in NaHCO, I Treatment of (4) with DMSO (CH;—S—CH,) in alkali give (B) Cy;Hy403- Treatment of (4) with strong alkali alone give an isomeric compound (C). When (4) is refluxed with HI, CHI is obtained, compound (B) is insoluble in alkali and decolourises Br)/CCI,. (B) on treating with strong base gives (D), an isomer of (B). Ozonolysis (C) of gives (E).CgHgO3 and isomer of vanilline. Ozonolysis of (D) gives (F) CoHyo03, which is identical with product of methylation of vanilline (4-hydroxy-3-methoxy benzaldehyde). 22, Structure of compound (A) is : ~S BsCOr CHO @ (b) OCH;Alcohols and Ethers 337 © ) OH CHO OCH; OCH; 23. Compound (B) is : a OCH. @ > @) OCH; OCH; OCH; OCH; © @ HCO’ OCH; O—CH;—CH=CH, 24, Compound (6) and (a are respectively: OCH, (@) None of these ‘CH,OH OCH; StaNeR=Y MATRIX MATCH TYPE Ht Column (1) Column (1) OH 1. @ P. White turbidity with HCVZnCl, (b) CH3CH,0H Q. Violet colour with FeCl, (©) CH; — Fon R, Colour change of NazCr,07, H t : 7338 GRB Advanced Problems in Organic Chemistry for JEE ao (d) CHE —ON S. 1, /O°H, gives bright cH, yellow ppt. ° on 2. (a) CH3 —CH, —C—O—CH— CH,CH; —=> P. Involve carbocation | formation . CH3 ° H®/H;0 ) Cy —C—O— CH Ph $$ Q. Acyl cleavage cH, . HE . (©) CH;CH)—-O— e—cH 5 cone, R. Racemic mixture cH, : D I HI . (d) CH. NO, —~ S. Product gives haloform test 3. (a) Fries rearrangement P. Acid catalysed rearrangement (6) Claisen rearrangement Q. Concerned with ester (c) Bayer-Villiger’s rearrangement. Involve electrophilic substitution (4) Pinacole-Pinacolone S. Intramolecular rearrangement rearrangement Hy fy 4, (a) > P. Hofmann product q P=0 1 (b) H3 mets, Q. Saytzeff product D 1H CH; cH——O © ch, R. RearrangementAlcohols and Ethers 339 CH; on , Cone. HyS0, ° @ Phe CH—CH,—CH; 74. Bimolecular elimination T : ° 5. (a) Oxidation of 1° alcohol in aldehyde P. KMnO4; A,OH ) Qo HCl. CrOs Q. Collin’s reagent ©) ( O C103 R. Jone’s reagent Noh, (@) Oxidation of alkyne into acid S. pee 6. (a) Identification of 1°, 2° and 3° P. Oxymercuration ‘Alcohol demercuration react (b) Identification of 1°, 2° and 3° Nitroalkane Q. Cw/300°C, A (©) Formation of alcohol by anti-Markownikoff’s R. Victor Meyer test addition (@) Formation of alcohol by Markownikoff's S. Hydroboration oxidation addition T. Lucas test 7. (a) Phenol + Neutral FeCl P. No reaction () Phenol + Br (aq.) Q. Violet colour (c) Phenol + NaHCO; R. White ppt. (@ Pieric acid + NaHCO; S. CO gas is evolved oO Ph I asauo 8. (@) CH; —C—o— ¢ —Ph——, P. Unimolecular Ph CH, O tl H°/H,0 (b) CH — EC —O—Ph ——s — Q. Bimolecular CH; CH; | 9/110 (©) CH;—-0O—C —cH, ——> R. Alkyl oxygen bond | cleavage CH; (® CH;—o—cH—cH, 1, S. AcyLoxygen bond | cleavage CH;340 GRB Advanced Problems in Organic Chemistry for JEE CERCA INTEGER ANSWER TYPE PROBLEMS || 1. How many compounds A through G are enol tautomers of 2-butanone. PEE (a) © wee ‘OH ©) ®) @ 2. Consider the pairs of ethers A through F show below. To the right of each pairs is a description of reaction conditions to be applied to each. One compound of the pair will react more rapidly than the other. Find out number of reactions in which first ether more rapidly cleaved than second. Ether pairs Conditions HAC, : Treated with HBr i @) €S-o-curcri, and O—CH; CH CN, aC FAC Hy ; — Treated with HSO, ® <> C(CHs)s and, in CHSCN, 40°C F CoHs, neon CHS Treated with H,SO, oO-E = O-Q mw CHy He 4 Treated with 5% ant aqueous H2SO4, 25°C ‘OH CH : CH(CH:). and CH(CH3)2 Treated with 5% z SS a ONS 07 SZ 07 aqueous H)SO4, 25°C ®© (S-cn—0—cm, and Treated with H°/H,0 € \-cy,—0—cn,Alcohols and Ethers . _ 3M 3. Find out number of moles of HO, that will react with following compound. CHO bon HOH CHOH HOH CH,OH OCH OCH 4, How many moles of ‘HI’ will react with ‘OCH; CH;—OH =O H—OH suio, ws ; OH ——*» HCHO + ‘X’ HCOOH + C03, find out the value of ‘x’. ‘OH > —OH 5. 6. R—CH,—OH— R—CH,—C Find out number of reagents that can be used for above conversion, from following, HCl, ZnCl, PClz, PCls, POCI;, SOCIz, NaCl, TsCl 7. Identify numbers of alcohol those will show rearrangement during dehydration with concentrate H2SO4. OH HH xy XS AY Cr on” oon , CH,CHs oo op otto -342 10. GRB Advanced Problems in Organic Chemistry for JEE . Find out number of reagents that converts 1° alcohol to aldehyde. KMn0,{H°|A , KCr07}Dil, #280, , Ceric ammonium nitrate “ ®) © ° I H,C—S—CH, (DMSO) , (( WW ) eno : ¢ \,| cr03 ) a A =—/ h i—H «) (Fy . Find out number of alcohols that can give positive iodoform test. A t " “oe by—cwy or ©) OH @ @) @) on HO. CH;—CH,—OH CH,—OH CO () o () (h) How many moles of HI reacts with glycerol to give 2-iodopropane.Alcohols and Ethers = ANSWERS fee 0} Exercise-1 : Only One Correct Answer 1@) 2G) 3.) 4(b) 5 (o) 6) 7.(dy BC) 9. (b) 10. 22.) 12, (bd) 23,(0) 44. (©), 25. (b) 16. (c) 27. (d) 18. (2) 29. (2) 20. (c)) 21, (@) 22. (2) 23. (¢) 24, (b) 28. (ab,c) 26. (0) 27. (c) 2B. (c) 29. (b) 30. (c) BL. (b) 32. (dD) 33. (0) 34. (c) 35. (b) 36. (b) 37. (b) 3B. (2) 39. (b) 40. (b) 42, (b) 42. (2) 48. (c) 44. (b) 45. (©) 46: (d) 47. (C) 48, (d) 49. (6) “50. (A)! 1) 2@ 30) 4@ 5 6) 7@ 8) 94) 10. (dA) 11, @© 12.) 13. (©) 14, () 15. (a) 16 (@) 17. (c)_ 18. (c) 29. (b) °20. (0) 21. (d) 22, (b) 23. (c) 24. (2) 25. (a) 26. (b) 27. (c) 28. (d) 29. () 30. (c) BL. (©) “32. (a) 33. (b) 34. (6) 35. (2) 36 (c) 37. (b) 3B. (a) 39. (b) 40, (a) 41, (b) 42. (6) 43. (bl) 44. (d) 45. (@) 46. (c) 47, (2) 48, (0) 49. (c) 50. ) 85. (b) 86. (c) 87. (a) - 83. (c) 89..(b) 90. (cj 94. (©) 92. (6) 93. (b) 94. (b) 95. (c) 86, (a) 97. (d) 98,(b) 99. (@) 100. (a) (01, (a) 102, (c) 103. (c) 104, {c) 105. (d) 106. (b) 207. (a) 168. (c) 109, (2) 110. (a) 41. (4) 412. (b) 123. (c) 114. (a) 135. (b) 126. (b) 217, (c) 118, (©) 119. (6) 120. (6), 1. (a) 122. (c) 123, (b) 124. (c) 225. (d) 126. (a) 127. (b) 428, (c) 129, (b) 130.(c) @. 0) . ca) 4. Gc) 8. fab.d) 6 (ord) (a, bc) . . (add) 10, (bd) 42. (ad) 12. (a,c) (a,c) . . tb,e.d) 16, fab) 17 (cd) 1B, (a,b) (a,b) 20. » (2,b,c) 22, (b,c) 23. (cd) 24 (a,c) (a,c,d) 28. (a,b, ¢,d) 28. (a,b, d) 30. (a, b,c. a 33. (b,c) 3% (ac) 38. (a,b,c, d) 36. fac) 39, (a,b) 40, fa, b,c, d) AJ. (a, c,d) 42. (a,b,c) 45. (b,c) 46. (bcd) 47. (a,b,c) 4B. (@.b.d) Exercise-3': Linked Comprehension Type 2) 2) 3. @) 4.) 5.4) 6. (0) 7. (c) Bb) 8, ) 20. (0) 13. (©) 42, (6) 13. (6) 14. (@) 15. d) 16.) 17%. (a) 28 (D) 19.) 20: (A); 22. (0) _ 22. (¢)_23.(b)_ 24. (@)344 GRB Advanced Problems in Organic Chemistry for JEE Exercise-4 : Matrix Match Type 1 @)30; (b)-9 RS; (c)-9 PRLS; (dP 2. (a) 0,8; (db) PRS; ()3P,S; GPR 3. ()>P.O.R,S: — (bIWRS ()>P.0.S; MPS 4. @)P.S; (b) O0.R; WoP.S 3 0,R 5. (a) OR. S: (b) $; C)90; (dP 6. (a) O.R,T tb) Ri (> S; - MP 7a 0; (b) > R; Ps amas 8. @)>P, MPS; ORR: MOR Exercise-S : Integer Answer Type ProblemsCarbonyl Compounds (SYSHGRS0) ONLY ONE CORRECT ANSWER “1 Ewe . Which of the following reagents may be used to accomplish the conversion ? CgHsCH=CH—CH,0H —>C,H,CH=CHCHO (@) [(CH3)3CO}; A, >—O8 (&) (OH cicoy (c) MnO» (d) All of these 2. The major product obtained from photochemical chlorination of ethylbenzene (in excess) is hydrolyzed with aqueous KOH and the product is then oxidized with PCC. The final product formed is : (a) PhCH,CHO (b) PRCOCH; ~—(¢) PhCHO (@) PhCOOH | 3. A compound (A), C4HgClz, on hydrolysis gives a product (32) which forms a 2, 4-DNP derivative, but does not reduce Tollen’s reagent. The compound { 4) has the structure : (a) CH3CH,CHCICH,CI (b) CH3CH2CCI,CHy (c) CH3CH CH CHCl, (d) CH3CHCICHCICH, 4, Which of the following compounds does not react with NaHSO, ? ! © (@) CgHsCHO (6) CgHsCOCH3 (4) CHjCOCH3 (4) CH COC pHs! 5. Which of the following will not undergo aldol condensation ? (a) Acetaldehyde (b) Propionaldehyde (4) Trideuterio acetaldehyde (d) Benzaldehyde + 6. in the Cannizzaro reaction, which is the slowest step ? + 2PhCHO—“> PhCHOH + PhCOO™ (a) The attack of OH” at the carboxyl group ! (b) The transfer of hydride to the carbonyl group (c) The abstraction of proton from the carboxylic acid (d) The deprotonation of PhCH OH A cyanohydrin of a compound (X )on hydrolysis gives an o- hydroxy acid which shows optical activity after resolution. The compound (X )is : : (a) acetone - (b) formaldehyde (c) diethyl ketone (6) acetaldehyde x346 GRB Advanced Problems in Organic Chemistry for JEE 8. Acctaldehyde on treatment with a few drops of concentrated H»SO4 gives : (a) CH;CHOHCH,CHO. (b) CH;CH=CHCHO HyC_ Lo. LCH; oO om 0 CY : ° 9 CH; 9. Phenylglyoxal, CgH sCOCHO, on lieating with concentrated NaOH gives : (a) CgHsCOONa and CH;0H (b) CgHsCH,0H and HCOONa (c) CgHsCHOHCOONa (a) CgHsCOONa and HCOONa 10. The most appropriate reagent for the conversion of 2-pentanone into butanoic acid i 1 @) chromic acid (b) acidified KMnO, } © alkalineKMnO, - (d) sodium hypochlorite 1 11, 2-Methyleyclohexanone is allowed to react with metachloroperoxobenzoic acid. ‘The major product formed in the reaction CH;COCH; Ga? A a B96 ° ° ' CHO ' ° > ) (b) i CHs ! HC OO | oC? @ ( 0 CH; { £2. Consider the following sequence of reactions. ' Ba(OH), H,S0, NaBH, ' The final product (C) is : (a) (CH3)2C(OH)CH,COCH; (b) (CH )2C==CHCOCH, (©) (CH3),CHCHCHOHCH (d) (CH3)2C-=CHCHOHCH; 13. Among the following compounds, the one which can undergo both aldol condensation and Cannizzaro reaction is : (a) (CH; ),CHCHO (b) HCHO (©) CgHsCHO (d) CH;CHO 14. Consider the following sequence of reactions. L.GHsMgBr | H,SO, Heat 1.05 Ay : Ketone 4 S75? 8 ng Cte “Ot SS oO The ketone (A) is: + ‘Carbonyl Compounds 347 @ vr & aa © @ 15. The reaction of CgHsCH=CHCHO with NaBH, gives : (@) C6HsCH)CH,CH}OH (b) CeHsCH=CHCH,OH (c) CgHsCH,CH,CHO (d) CgHsCH,CHOHCH3 Cee CH POKES, p 16. — ‘HgSO, Gt The principal organic product P is : @ Sr ooctnn ®) J cocnp: @ Pe CHD—CHO Mé 17. Which one of the following is mixed ketone ? II I (a) CH; —C—CH (b) CH; —CH, —C—CH3 ° Ii It (c) CgHs—C—CHs - (a) CHy—CHy—C—CHs 18. Which one of the following alcohols cannot be oxidized by K2CrO, ? (a) Ethanol (b) Tert butyl alcohol (6) Isopropyl alcohol (@) Allyl alcohol 19. In the given reaction : OH OH HIO, CH, CH CCH ——+ (A) + (B) CH3 (A) and (B) respectively be = (a) CH;CHO and CH;CHO (b) CH3COCH, and CH;CHO (©) CH;COCH, andCH;COCH; —(@) CH;COOH and CH3COCH 20. Acetophenone can be obtained by the distillation of : (@) (CoHsCO0) Ca (b) (CH3CO0),Ca (c) (CgHsCOO) Ca and (CH3COO)Ca (a) (CeHsCOO) > Ca and (HCOO); Ca348 GRB Advanced Problems in Organic Chemistry for JEE 21, Arrange these compounds in decreasing order of reactivity for the nucleophilic addition reaction. (1) Acid chloride (11) Aldehyde (III) Ketone (IV) Ester (a) I> >> Iv (b) IV>>0>1 (c) HI>>1>1V (@ [> 1V> > O1 22, Two isomeric ketones, 3-pentanone and 2-pentanone can be distinguished by : (2) 1) /NaOH only (b) NaSO3H only (©) NaCN/HCI (4) Both (a) and (6) 23. In the reaction sequence Cots — CH OHH PS oy), py pwill be: 9 Il tl (a) CsHs—C—NHCH, (6) CH; —C—NH—C,H, i (©) CgHs—CH, —C— NH (d) Mixture of (a) and (b) 24, Schiff’s base is prepared from : (a) carbony! compound and primary amine {b) carbonyl compound and secondary amine (c) carbonyl compound and tertiary amine (d) all of the above 25, Schiff’s reagent is used for the differentiation between : (@) HCHO and CH,CHO (b) CH3COCH, and CH;CHO 9 (©) CeHs— CH — son, and CgHs— bon, —CHy, (@) HCHO and C,H,CHO 26, Fehling solution gives red precipitate with : (a) aromatic aldehyde (b) saturated aliphatic aldehyde (©) unsaturated aliphatic aldehyde (4) both (b) and (c) 27, Silver mirror test with Tollen’s reagent is given by : (a) CgHsCHO (b) CH, ==CH—CHO (©) CgHs—-CH=CH—CHO (d) all of these 28. Acetone can be converted into pinacol by : (a) Mg/Hg/H,0 (b) Zn/Hg/HCI (c) Na/Hg/H,SO, (@) all of these pcHaCHs TX 29, Comowna’ S ; formed by the reaction of furfural ie \N ‘0% ~CHO, with ethanol is :Carbonyl Compounds 349 (@) an aldol (b) an acetal (c) aketal (@) ahemiacetal 30. Perkin reaction is catalysed by : (@) NaOH (b) HCI () NHC! (d) Pyridine 31. Product of Perkin reaction is : (a) 0, B- unsaturated aldehyde (b) B- cyclohexyl, ,B- unsaturated aldehyde (©) B- Aryl-c, B- unsaturated acid (d) all of the above 32. In the given reaction OH (i) Zn I a CoHsCHO +X see C6Hs— CH—CH2—CO0C2Hs, [¥ ] will be: (a) CH; —CO0C2Hs (>) CH — CH, —COOCAHs Sr (c) Br—CH, —CO0CHs @ CH—C00C;Hs Br 33. Cannizzaro reaction is example of : (a) redox reaction (b) disproportionation (©) both (4) and (B) (d) only oxidation 34. Cross Cannizzaro reaction is an example of : (a) redox reaction (b) disproportionation (c) both (a) and (b) (d) oxidation 35. Which will give silver mirror test with Tollen’s reagent? (a) C6HsCHO (b) CH;— CHO. (c) HCOOH (d) All of these 36. Acetaldchyde cannot give : (@) Todoform test (b) Lucas test (c) Benedict test (a) Tollen’s test 37. The reaction in which NaCN/C)H OH/HOHis used is : (a) Perkin reaction (b) Benzoin condensation (©) Reimer-Tiemann reaction (d) Rosenmunds reduction 38. Which one of the following reactions is used for the conversion of ketone into hydrocarbons ? (a) Aldo} condensation (b) Wolf Kishner reduction (©) Reirser-Tiemann reaction (a) Perkin reaction 39. Schiff’s r-agent gives pink colour with : (a) acetaldehyde (b) acetone (c) acetic acid (d) methyl acetate350 GRB Advanced Problems in Organic Chemistry for JEE 40. Consider the structure of given alcohol, This alcohol can be prepared from : OH C6Hs— be CH; bas . Oo (2) CoH — CH andC)HsMgBr I (6) CH; —CH, —C—CH, and CgHsMgBr i (©) CgHs —C— CH and CH; MgBr (@) all of the above 41. In the given reaction, [X']will be : Colts eH MEO, ° (@) only syn oxime (b) only anti oxime (©) mixture of syn and anti oxime (4) secondary amide 42. In the reaction sequence, [X ]is which keton ? CH, I pxy temo, HOOC—(CH,); —CH— COOH 9 ° CH; (a) (b) 9° CH; HAC, CH3 () @ 43, In the given reaction, [X ] will be : 9 CH;Carbonyl Compounds 351 9 ° cHO °. cH, (@) (b) or) 0 ©. CH, CH, © (d) : ‘0 0 44. What is the given reaction known as ? I GHsCOSH tl CH, —C—CH; > cH, —C—O—CH, (a) Bayer-villiger oxidation (b) oppenaur oxidation (©) Periodate oxidation (d) Peroxide oxidation 45. In the given reaction, (X') and (Y) will respectively be : OH x+y cu,—bi—cH—cHO (iy (a) CH; — CH, — CHO and CH, —CH, —CHO (b) CH; —CHO and CH; —CH—CHO (©) CH; —CHO and CH; —CHO os (@) CH;—CHO and cHs -¢—cHO CH3 46. Which of the following compounds are in their most stable tautomeric forms ? | SS @ wc S roa CH; (b) Ch ‘O " ) \ H 0 HO H. oH ad cr352 GRB Advanced Problems in Organic Chemistry for JEE 47. Which of the following compounds have higher enolic content than keto content ? 9 9 ol (a) CH; —C—C—CH, (b) oO oO © @ 48. In which of the following pairs, the first one will have a higher enol content than the second one ? . COOEt ? (a) CH, and Scoort chy ‘city ° oO 00k i (e) CH, md Ok COOEt CH; CH, OCH; ° 0 o 0° ood ool © ¢ ¢ ZNLN CH; “CH, CH; Cli, CH, OCH; ° 0 o 0 od ho @™ ce c oN ZNZY oN CH; “CH, CH; Ph CH, Ph 49. Tautomer of the foliowing compound is : Oo ll Oba)Carbonyl Compounds 353 oC ge = at) 0 Ee one{) OH 9 WBN on. 50. —aarsene? PP willbe: 9 9 Bro, OC6Hs @) (b) OBr OC6Hs OC 6Hs © @ , $1. Which of the following is an example of aldol condensation ? (a) 2CH,;CHO—SL MOH _, CH,CHOHCH,CHO (b) HCHO —#2N208_, cH,0H (c) CeHsCHO + HCHO SE MOH 5 CgH;CHOH (® 2cH,CocH, —S2%-S08_, C11, C(OH)(CH3 )CH,COCH, 52, Which of the following would undergo aldol condensation ? * CH (a) CCl;CHO (6) H3C—C—CHO bs (©) CH,CH,CHO (@) HCHO354 GRB Advanced Problems in Organic Chemistry for JEE 1, Mark out the correct order of dipole moment for the following compounds : 9 ° ° Il ll ll H-C-H H;C—C—H H,C—C—CH, I Wt oe @I>M>m — (b) W>M>1 ©) MI> >I @) W> I> 2. Arrange the following compounds in decreasing order of nucleophilic addition reaction : ° ° ll ll H-C—H HyC—C—-H nyc ca CH, I {a) I> 1V> I>! () I> 1> > IV (©) IV>M>1>1 @ U>ml> Ive 3. Arrange the following compounds in decreasing order of nucleophilic addition Teaction : 0 ° ° i I il It CH;—C—CH, CH;—C—Cl CH;—C—NH, CH,;—C—OH I at I Iv ° ° ll ll CH; —C—O—C—CH, v (a) [>V>I>IV> (b) I>IV>I>Vv>l (©) U>I>V>mI>IV (@) IV>M>V>I>t 4. In the given reaction sequence H,N—OH PLO. . C6HsCHO ea A 3B A A and B respectively are : (a) CgHs—CH=N—OH, CgHsCN- (0) CgHs—CH=N—OH, Cottg oN (0) CsHs—CH=N—OH, CoH CHO (a) C6Hs—CH—N—OH, Cy; —COOH 5. Consider the following reaction 0 OH Won a, C3 ‘The above reaction is an example of:Carbonyl Compounds 355 (a) intermolecular hemiacetal formation (b) intramolecular hemiacetal formation (c) intermolecular acetal formation (@) intramolecular acetal formation 6. In the given reaction 1. HCHO/A® CO) “tne * X is: OH Teuret Ne@ren ‘OH ‘OH 7. Secondary amine react with carbonyl compound to give : (a) Imine (b) Schiff’s base (c) Hydrazone —(d) Enamine 8. In the given reaction 0 HCN LiAIHy —> A > B H,0 A and B will respectively be : 1 OH Hi OH . OH @) Chen and Sere (b) Kew and (Kens OH CX aC 9. Arrange the compounds in order of decreasing reactivity for nucleophilic addition reaction : oO 0 oO ll ll Il CHy—C—CH,—Cl_ CCH, —C—H_ HCH HyC—C—CH I iia (a) 1>1V>T1> Ih (b) I> >> IV (c) W>HI>1>IV (d) U>1>il>IV 10. In the given reaction 6 HOM, H+O Identify P and Q: . 5) C1 and on€ | ) Ch and [ on °. ‘ ‘OH CHO356 GRB Advanced Problems in Organic Chemistry for JEE HOCAA and [)—onw All ofthese ll 11. Which carbonyl group of the given compound is most reactive for nucleophilic addition reaction? 9 1 0 2 3 0 @)1 b) 2 ©3 (@) All have equal reactivity 12. Which carbonyl compound has maximum dipole moment? oO Oo oO oO ) A 8 oO © A @® A Br 13. In the given reaction the main product will be : CH3MgBr t NCU 0 aw) 14. In the given reaction the main product will be : CH3MgBr/Cuply ¥, H,O/H® a OO ole °C OQ 15. Arrange the stability of given gemdiols in decreasing order : OH be xX ‘OH On ‘OH 1 qt ttyCarbonyl Compounds 357 (@) M>1>T >> = @) M>I> =) >>I 16. Which one of the following compounds would form most stable hydrate? Oo Il I {a) Cls;C—C—H (b) HxC—C—H 9 il (©) FxC—C—CF, @ nH 7. Which ofthe following structures contains a hemiacetal group? o_ /0H HC. OCH oy ey OH oc! (©) H3C—C—CH (@) CoHs—CHe ‘oc OCH, 18. Which of the following compounds would give positive Fehling’s solution test? 9 oo ACHs {I (a) CoHs—C—CH, (b) HCO. OCH OH ‘0. © CY @ Cy 19. Which of the following carbonyl compounds when treated with dilute acid forms a stable cation? @ wot on, ©) U oO 0 © oO @ © ~O) 20. In the given reaction . O—CH,CH, BO, (P) P willbe: acm ee © (> (d) ()-cH.08368 GRB Advanced Problems in Organic Chemistry for JEE (X) will be : Mase ee 22, In ae given reaction (X) will be : @) Ph () Ce ‘OCH, oe OMgBr Ph @ KAA, @ AAG 23. In the given reaction ether H®/H0 (X) will be: CHO a oO) 0 eh ‘coor 24, What are A, B and C in the given et aN Pk esa, Hd se [sate B OH @) on in all cases o on inall casesCarbonyl Compounds 389 OH © in all cases oO OH OH eCOCD = OO (4) (8) . © Il “Aw 25. CéHls—C—CiH; “ERS p TPO H°/H,0 A CH—CH; CH, mn CH=CH, (@ Ph—C—Ph (b) Ph—C—Ph (©) Ph—C—Ph (4) Ph—C——Ph CH,CH; OH 26. Which one of the following combinations gives compound (XJ? ) oO @ mw ro HN © BW YY@ vA oO 0 HO: 5 H® 1. LiAlHy, 27. + — A— BB J 2.130 sey guruture of B: 9 @ oOo 0 L/ - 1. BuLi He 2. HyC—Br 28. nc “ A—— B 3. HgCh/H$O Identify structure ae :360 GRB Advanced Problems in Organic Chemistry for JEE 9 ° ° A ll ) © © (@ H#—C—H oO 0 , H2Pd—BaSO, Isoquinoline OH 0X ‘C=C—CH; (d) on CH: 3 C=C H” i Oo NaCN 2 * O “ra? ©) (X)is: HO. CN CN oO OH @) CS ) O © Ch, ® CL ‘N CN 31, In the given reaction a’ YY 1. CH3MgBr ~% oO 2.190 (X) will be = ° @) Ba OME wm AJ 0 © Ox @ ar OH PCC CH3NH; H2/Pd—C 32, PCG CEN, HPC py Ht P will be :Carbonyl Compounds 361 HCH Nn7 NH—CH; ° HO. ,NH—CH, of) (d) CS 33. In the given reaction 6 Co eS mrt: 34, Find the product of ee following reaction : CH, Nitz=-NHaKOH CH; CH;—CH,—"N—CH,—CH; CH; oO °F (b) © (d) None of these SN K c oO oy wis 35. ———> Product: HCL HO ° ~ @) oa jan [te SN cr cd HO ch [362 GRB Advanced Problems in Organic Chemistry for JEE NO, 36. ATH, product: 0 NO, NH N=O NH “SL “OY L “ i : © ll NjHy, OH 37. Cis CH CHa —C—CHly A Product: Br Br 9 @ Ma 0) AN OAX qd) AA 38, Find the product of the following reaction : Ne e On NoHy/OH aS A NH, e Sexo ys fii, 42M, Product CH3CH)—Br ws) Find out final product of reaction : Ph. oS Pho |S Ph. @ Xe) w PA © _X_ ) @ _Ye=0 O Ch+HiO (pyCarbonyl Compounds 363 P will be: OH cl ° cl cl {a) ) © @ cl ‘OH Oo ‘OH 42, What is the product () of the following reaction? oO ° 8 OH/A ¢ x) 0. fe} oO Oo oO @ CO ©) ool © @ 'O 0 oO Oo CH; KOH a, x HOH, ae oO Find out the structure of “X° : o 0 ° o 90 @ AA o Anny © AAJ. @ None ofthese ° 44, Find the product of following reaction = ° oo |W NaOH Ph—CH,—-C—CH,—Ph + Ph—C—C—Ph ——>364 GRB Advanced Problems in Organic Chemistry for JEE ° 9° Ph. Ph Ph, Ph @ (b) Hi OH Ph Ph Ph Ph f () Ph-C—C—CHy—Ph (@ None of these Phe —Ph 45. Find the major product of given reaction : oO ll O- 0 + CHj—CH;—C—H om, H oO ° ll ll (@) Ph—CH=CH—CH,—C—H —() CH,CH, CH= {~ CH CH; ° ° ll (©) CHjCH,CH=CH—CH, —C—H (@) PhCH C—H CH; What is (4)? Oo ° 0 we os ows ora 7. Which of the following is an example of aldol condensation reaction? @) oo +HCHO a8, Ph—CH,—OHCarbonyl Compounds 365 © K + MeNH —> vo @2 J cin, Exot 48. Consider the following sequence of reaction 1, Cold KMn0, NaOH A> B 2. HIOg, A The product B is : Oo oO whrry OQ 9 eS Loy ce} 49. Consider the following sequence of reaction 1.03, MeOH, 2. Zn, HO a Product A and B respectively : OH ° ° Oo. ompy and kos wryay and a ou 0 ° oO 90 OH © Lysy and neo" @ REY ant PRPRY oO oO OH 0 oO CHC . Liaw. 50. cy =o, 4 2A Reactant (A) and product (B) are respectively : CH—Ph () Ph—CHy and Cr Ph (©) Ph—CHy wa OY366 GRB Advanced Problems in Organic Chemistry for JEE OH q CH—Ph © Oe and| ©! CH—Ph oO —H acy t _NsOH, P will bee 9 ° @ OH On? b Shy “OL ° ©) OL (@) None of these i 2, (Crary 2, x Oy Identify final product ‘Y” : OH O ° (a) Ph—-CH—C—OK® (b) Ph—CH, —C—OH oO 00 tt A (©) Ph—C—C—H @ PI HH. “Qe Ge Identify “X" and ‘Y* of the above reaction: : H. ,O HH. ,O (@) 05/Ag,0 and X (b) 0x/Zn—-H,0 and, t H’ *O H *OCarbonyl Compounds 367 HO, 0 HL 0 (©) KMnO, and (d) KMnO, and X HO” So H” ‘oO 54. How many products will obtain in the following reaction? O Il Ph—CHO+ + C—H NaOH, (2 (b) 3 ©4 @1 55. Find out no. of products produced in following reaction : ° ° Il ll | 4 Kon CH+ (1 @)4 (©) 3 @2 CHO oon 86.2 | 5 P+Q COOH P and Q are respectively : CH,—OH —COO®Na® CH,OH CH,OH () | and | ) | and | COOPNa® COP Na® COO®Na® == COOPNa® COOPNa® CH,OH © | both @ | both COO®Na® COO*Na® 9 57. OC) + PhjP==CH,—> A Ais: CH CH; CH; @ CO) (b) CO (©) CO @ O 0 {I e8 CH—CH, S Ba Li 58. H3C—C-—CHy —CH, —CH)—CH)— PPh — (X) 5 Major product (X)is: CH CH; CH; ® CO) ®) a © O @ OS368 GRB Advanced Problems in Organic Chemistry for JEE H “So 0 t L.2PhP. H n a, 4 1 59. a 4 z B Find out structure of. mL 8D 9S #CO cl 2CH: I, 60. PhP BCH TET H y PhLi ch Identify structure of ‘Y” : CH=CH—CH, CH=CH—CH; @) (by Hy —CH=CH CH=CH CH; CH= PPh; CH)—PPh3 : ©) @ e CH=! rhs CH;—PPh; now a (X); Major product (%) is : oy orZz on or 62. Which halide will give Wittig reaction? @+a ©) (So @ >S-a (0) HxC=CH—CICarbonyl Compounds 369 63. Find the product of following reaction : ns > i] CHO 2CH;CH) —C—OC,H; ——> (X) Ho “x? will be: QO ll ll (@) CH,—CH 2 C—0CHs CH oO oO ll il (b) CH; —CH, —C—CH, —CH, —C—OC2Hs oO . (c) 2CH;CH, —C—OH °O @ CHy— CH-C—OC>Hs ChFC aH oO t e ® 64. (Open —c—o0at CH, ay) ya z 30 A Find final product + ° A ° ll @ Ph—CHy—C—FH— C—0C>Hs Ph . tl (b) Ph—CH,—C—CH—Ph ° ° Il ll (©) Ph—C—CH, —CH, —C—OH ° 9 Il ll (@ Ph—CH, oF -C— 0H . Ph370 GRB Advanced Problems in Organic Chemistry for JEE ° ° : lle 6. OCH; cao. HHO Ph—C—H, On CH oo > oer ~ 4,0 . oO Identify *x° : 9 / 9 @ OO OL : 0 o- 0 9 © Olean @ Oe 5 \ 2 Hs0 66. XS Ho ro 0 Find correct re of “X? = : oO . O= C—CH; : ° Identify name of reaction : : (a) Aldol condensation (b) Cannizzaro condensation (©) Crossed Claisen condensation (d) Tischenko reaction uCarbonyl Compounds 371 HCN II 68. CH, HO, coc CH imo, 5 HC” It oO Identify structure of final product B : og ° i : CHO @ Hye CH CH @) CHO CH(CHO), ° Il HCN ll 0) ‘CH—CH,—CH,—C—H @) None of these HC” | ° 9 . oH HID 0. ESS X+ CHy= CH—C=N —yr Mentity final product ‘¥" : ° UN CEN Nc @ ) NN * | (@ Nove of these ° ° 1 HO. 0. A+B 2.130, Ment Aand B: (a) rh i © O + Bo (d) None of theseGRB Advanced Problems in Organic Chemistry for JEE “ 5 ba, 72. In the given reaction : Of ‘eo! (P); (P) will be = 73. In the given reaction : t KONIEIOH all olen eo? Product: er) @l ; | LSet Tl -cuoa on 2 | Cn d=02 ot Lig. @ Chto) : bn MnO, Ke 4. (O)-cm0n nce ona (will be: o=0Carbonyl Compounds 373 oO lle (@) Ph—C—CH—Ph (b) Ph—C—OK® and Ph—CH,OH OH ° ll il (©) Ph—C—H (@) Ph—C—C—Ph 75. Compound ‘X” C4Hg0 which gives 2, 4-DNP derivative and negative iodoform test is : 9 . wl , a (6) [con OH ql © (@) HyC—CH—C—H CHy 76. Compound ‘X* C4HgO which gives 2, 4-DNP derivative and positive iodoform test is : oO oO @ XX ) AA, Oo © tweet @ [>on CH; Oo ll i 7. C—CH p+ NaOH X+Y Aga Z (yellow ppt.) Identify final product ‘2 = : (@) Cs (b) HC=CH eo . © PoC —ONA® (@) HyC=CH, KoBr, LH? Ke rs Z;Zrwill be :374 GRB Advanced Problems in Organic Chemistry for JEE . 0 : COOH @ , ® or oO . . oo I cooK® © > @ § ‘CH,0H ° . I] 79. (Oye: BCs, yey Sy z CHM, (yellow ppt) 10 Identify final product “A” : ou @ CH; ® PEP > CH 9 . ° ll Il (© Ph—C—Ph @ C—OH - CHO © oO . , OH Cl; + Ca(OH) + 80. Pa. J SEOs, pg pW 5, It ©) par (b) [Ph—CH,-C—0},Ca “29 : . 9 ° + COO” © @ | CH,OH i oo CF: . , 81. CH; —C—H EICO3F ox will be: ° ° ll . Il (@) CH; —C—OH (b) CH; -O—C—H | |Carbony!.Compounds = : 375 9 9 I (¢) HHO—CH, —-C—H (¢) H-C—OH 0 CH; ll |. PhCO3H 82. CHls Cp CF CH 5 40 w CH; 0 CH; ° CH; | (9) hy CH; —0—C Ey (9 Cy CHa C—O FC _ Hs : CH; © CH; || © Cis ~CHly=-C—P— O= CH (4) none of these CH; 83. © EACPBA, p -prwill be: @)' a (b) A © by _ @ J wo PCPA, Product; Find the product : bh ob . i CF,CO3H H © 1420 : 85. Ph—-CH-C—Cs OS x 5 4Z Ph Y and Z are respectively :376 GRB Advanced Problems in Organic Chemistry for JEE Oo I pu (a) Ph—CH—C—Offand CH, OH ) Phe both Ph Ph (©) CHOH both (4) none of these 00 ou cH,CO,H 86. CH; —C—C—Ph —3—5, Product; Product will be : oO Oo Oo ol fh Ul (2) CH;—O—C—c—Ph (b) CH; —C—C—o—Ph 0 oO oO | ll ll Il (©) CH; —C—O—C—Ph (d) Ph—C—O—C—CH,0H 87. Which of the following compounds contains most acidic hydrogen? ° q i @ H;C—C—H - 0) H3C—C—CH, —ccH 3 °. oO 9 Il tl i il (©) HyC—C—-CH,—C—OCH, (a) HyC—C—CH, —C—NH, 88, Which hydrogen of the given compound is least acidic in nature? 9 1H 2 ow ‘CH33 H 4 @1 (b) 2 © 3 @4 9. Which hydrogen of above compound (Question no, 88) is most acidic? @ 1 b) 2 (©) 3 (d) 4 90, Compound (X)C4H,0 gives Positive haloform test but does not give 2, 4-DNP derivative is : OH May ©) AA, OAC @ on 0 ° II Ni 91. Ph—C—C—Ph ——- Product, find structure of product :Carbony! Compounds a7 , 9° OH oo . | 4 (a) PhCH Ph (b) Pree ° ou ph (ONS! OH LC | ©) Ph—FH—CHOH @ Ph + CH,0H Ph Ph 92. In the given reaction sequence oO OF Br 4154 ne: 2.H80 COOH (@) ) "eS . "oy 3 ee 1 Ba HO 2 ou 3.H9O oO . oO ov 0) ANH @ A Br Te ° COOH 94, 0 | , KOH » Zn—H0 Compound B is : Q @) Ob (b) Cr OH CHO © (>= a) Oro.378 GRB Advanced Problems in Organic Chemistry for JEE 2 1.NaOH ‘NHy—NHY/OH i. une 4 9: COD Zm—c—n* y I . o . 0 Compound (¥) is = (@ CH—Ph (b) 0 ° CH—Ph © Ciro @ CI -cun ° 6 ll 1 CoH ONa® 96. CH3—CH, —C—CH)—Br ———_—3 (X) . 2HPo (X) will be : (a) CH; —CH, —CH, —C—0C;H, (b) Ory — FCs CO0C)Hs (©) Mixture of (a) and (b) (@ CH;CH, —C—OH 9 Me CuLi . 97. Wo” Product; Product will be : 3 ‘Me on | GUS OH oO Nemromeurel CH, CH; 98, In the given reaction 0 cH, | ASSET, (x); 4 will be : 2. CH3I * . OH 9 "9 9 oY LY WK 0XCarbonyl Compounds 379 9. Which of the following compounds would be most reactive for Perkin condensation with acetic anhydride? oO 0. @ on (Ot w cro) oO (©) we) (d) o{O)-co 100. Cinnamic acid from benzaldehyde would be prepared by which of the following reactions? (a) Perkin reaction’ (b) Reformatsky reaction (¢) Knoevenagel condensation (@) All of these 101. The given conversion can be performed by which of the following reactions? 90 O-O (a) Aldol condensation (b) Michael addition (c) Perkin reaction (@) Reimer-Tiemann reaction Oo ° ° Il ( -ecaicasoe, 1. C3H0/C,Hs0H oxen 102. aR (R) would be : (a) HCHO (b) H;C—C—H . Oo l (©) (COOC;Hs) . @ H—C—OCpHs oO wo) —- ‘OH ‘OH ‘Above conversion can be achieved by : (a) Wolff-Kishner reduction. (b) Clemmensen reduction (c) LiAlH, (d) NaBH, 104. Predict the caer product of reaction : cl “ok J RABUKON (4); Product (A) is : [380 GRB Advanced Problems In Organic Chemistry for JEE OH a (@) od °) NO, NOs cl oO oO © @) NO, NO, @ 30 105, =, o A, 2S 4+; Compounds A and B can be differentiated by : (a) 2,4-DNP (b) Febling solution (©) Lucas reagent (@) NaHSO; oc a 106. , these compounds can be differentiated by : @ ry 4-DNP (b) Tollen’s reagent (c) Lucas reagent (d) NaHSO3 Oo O 5 (1 moie) 1 _HO- (CHsMgBr 107. ~e a” Product : Mg—Hg, 108. 35 Ss X;; Find out final product (X) : OoCarbonyi Compounds 381 a OH. OH one 109. ca CCH, ECPBA, (9 ; find major product (X) : 9 cH, 2 II sll @ mo as (6) ph—t+-o—C—c, Ob H cH f CH; t © mf boon @ Ph+—c_—cu, OH 9 i ll mo ated HF ep 0 2, oC © welin (€) Both (a) and (6) LiAlH, Conc. H2SO, oi Rs Sone TESOF , (4) Product (X) of reaction is: cw ‘OH OH @ll 1) ol] @ cy . ‘0 [~382 : GRB Advanced Problems in Organic Chemistry for JEE 9 Il Il 2 113. —H + Br—-CHy—-C—-OEt — 5 A Product (A) of the above reaction is : OH ° oH 9 ll | ll (a) Ph—CH—CH, —C—OH (b) Ph—CH—CH —C—OBt (© Ph—-CH=CH—CHy—OH_—_(@) Ph—CH=CH—CH, me GRD BRS 44 2Glycerol Product (AY of the reaction is : 090 090 00 9O KA wo JIU © KA @ Jan - oO oO H,C=N=I N CF; HH 1s. eax et y; Prod Vis: oO oO @ C3 6) 9 © Ay @{_p> 1s[ =o ENOH, y POS y Final product Fis om 45 @ Dew ) CO © Ch @ 0 N’ NN : : | | . ‘N—OH H H . 9 0 OEt wo du (1Mole) .2PhMgBr 17. ——P — YC Ho Find ont final product of reaction : 9 y oo HO, PhO Ph’ OHO ry [Ph 0) Et () Cy oe Ph NS+ Carbonyl Compounds 383 a, oO KOH 118. wr + CH,=CH—CH,—Br ——> Major product (X) Find out (X) of the reaction : CH,—CH=CH, oO Q, 0 CH; 1H=CH Q 0 Q ‘H-—CH © @ We CHy-CH=CHy N—OH 119, Cone. 504 LAI iy) ‘Y’ will be: H | N: i . N. OH 0 120. HEN, (A); Product ‘A’ will be: 2. LiAIHy 3, NaNO2 + He Oo (@) ct ® ic © O (@) none of these m. Ly ses ee, 9 ° ody wh © je. @ A OH OH384 GRB Advanced Problems in Organic Chemistry for JEE oO mg \ + tha AS, (x Xwill be: oO @ O-4 ) Oy © Or~« @ © ‘C=0 oO ee 123, ori MeONaMeOH, (4). sind out major product (A) : ‘on ° 9 oO 0 ° ° O 0 > CH : AcON® _H110 124, +(CH,C00),0 “> {> Product : ‘OH 9 @) On} , Aldol condensation O “Or ; Perkin condensation oo tl cu~cr—l_on © Oo, , Claisen condensation @ , Cannizzaro reactionCarbonyl Compounds 385 COOH 125. Reagents required for o conversion is : (a) LiAIH4, H®, A(b) Ow, H® (©) H®,OH/A —(d) NaBHy, H’ 126. Consider the following carbonyl compounds H ) (Q) ®) o Which of the following is correct decreasing order of their dipole moment? (@) P>R>Q25, (b) S>R>O>P (0) S>Q>R>P (8) Q>S>R>P | ll 127. of \-c—cn, CERN A, Oy ecu {O)—« Which of the following is correct decreasing rate of homologoation with various G? (a) —O Me>—CH, > NO >—H>—F (b) —NO, > —F>—H>—CH; > —OCH; (c) —OMe>—CH, > —H>—F>—NO, (d) —OMe> —NO, > —H> —F>—CH) ° | 128, CH; —C—H react most readily with : (@) H,N—NH, ~ ) HyN—NH—€—NH (c) Ph—NH—NH, (d) H)N—OH 129. The possible number of stereoisomers of the product of following reaction would be: H,N—OH Ph—CH=CH—CH— C=O | I po=4.5 CH; H (a) 2 (b) 6 () 8 (d) 4 130. The final product (C) of the following reaction would be = HN—On PCls Bry/Fe Cols Felts ee)386 GRB Advanced Problems in Organic Chemistry for JEE H “OO »~OylO= N—OH oO » OLO « OL-O-« Br 131. Give the correct Sequence of reagents for the following conversion : it i o-{ cH, 4 Ho—cH cH) C—CH, 0. eo CH3OH (excess) Me/ether Zn H,0/H3 0. ® “Taso, ; 2 . 12804 @ ether H,O/H30 CH,OH/H® ) My/ ZN 203 3 0, So CH,OH (excess) Mp/ether H,O/H- ( 2 (excess) Mp/e ZN 20/3 H,O/H$O_CHOH (excess) Mgyether | ZO\. ae OO SESS ees #50, 132. Ou Buti pt ° Buli, p RK, 5 Hee T * > x nes ‘al product ‘T” is; ” 9 ll aS (b) ca () oa (d) R°-—C—R” RY OR” 133. In the following reaction the major product ome is: oO eo PhCO3H CHCl, oO. O ‘or “Oly CHCOOH @)Carbony! Compounds 9 e = ] CHO 134.) ) +H,C—C—CH, > x ® © © Dx , of oO . —o 0 138. cts — >| )-(Cih)s—CHy La Ld Which of the following reagents is suitable for above conversion? (a) Zn-Hg/HCI (©) LiAlH, eS (6) HyN—NH/OH (@) NaBH, 9 ll CHCHBR 26 (OY Oe product : 9 OH 0 Il © | lle (@) Br,CH—C—O (b) Ph—CH—C—O o 0 9 oll lle (©) Ph—-C—C—-H (@) Ph—C—0+CH,Br, ° 1. NaOH + Bi 137, wore AOSTA, Product 2.H®, A 9 { HN 9 i @ ©) oO388 GRB Advanced Problems in Organic Chemistry for JEE BoHe 4 2 HCN H5O _H,S0. 138, =O 5 5 AES, FE Product : ~ H,0/0H ‘Oo : 0 @) WA, ®) nO >< 139. © — LD : oH ° oi @ Ap \on O° Which of the following sets of reagents is the most appropriate to perform the above conversion ? So (a) HIO4; OH; 2n-Hg/HC! o (b) Cold KMn0,; Pb (OAc)4; OH; Li/NH3 8 (©) 03/MeS; OH; Li/NH, e oS (d) KMnO,; OH/A; N>H4/OH, 4 . 8 140, Reactant 24 r- —CH; The suitable reactant is : 0 I. (@) +CH;—C—H : oO of +aK — Oo Oo me) “ANOCMer, CO oO ‘The above reaction is known as : (a) Kolbe reaction: (©) MPV reduction: oO oO ll o cn teu 3 () Oppenauer oxidation (@) Tischenko reactionCarbonyl Compounds 389 142, The product formed in the reaction is : i) Il ox )-C—00H NaBiy ° -@ (toon, ) wo—(_) cho 0 © o={ cH —oH @ (boc 143. Which of the following reactants on reaction with cone. NaOH followed by acidification gives the following lactone as the only product? 9 0 OCH; * CoH oO ® COOH 7" ° ° 3 I I A ¢—On 6K CH C--OH i : | ° 144. a or Liall H ‘CH; OOH, LAI, Product fee OH ®) 07 Pony © yo“. oO390 GRB Advanced Problems in Organic Chemistry for JEE H H H 146, The structure of major product of fottowing reaction is : ‘CHO _CiHSO1CH,08 | ae oh 147. Which of hese pair ofreactants compound may be used to make this given acetal? ° oN 0 + or) HO @) eo ° wo HS + wt ode 148, Identify the major product of following reaction : 2.NaOH mA, Bali 9 9 Oo { oO worry ow © px] 0 dAnCarbonyl Compounds 391 149, Find the major product of reaction : OH HO. O CH3CH20H. H® HO OH OH HO. ° (CH3CH;0 ° (@) &) CH3CHy HO OH OCH,CH; HOY Ay HO. ° © OH. @ HO HO 150. Which of the following is major product of reaction? oO OH y® Dy tH HO, 0: f™ @ coon @) a of 5 © Aw on @ loa SS 451. What would be the major product of following reaction? oO CE Ota + —H OH OH CH—CiHs | OH O—-CH—Ph_ Toure OH ‘OH Se © Cr Hs (a) No reaction oO 152. What dicarbonyl compound is needed to prepare the following compound by aldol reaction? : OH392 GRB Advanced Problems in Organic Chemistry tor JEE To oy («© oY (a) Cannot be prepared OK MOH Product : “KY oO (d) No reaction OH CoHsO 154, smc N at, Caray Product : HO, ,CH(CN), ou “Oo ‘CH(CN), 9 Q—CH(CN); Oh »S ‘CH(CN)2 oO 07 ofa H3CO' 0 o 0" HCOCarbonyl Compounds 393 (d) None of these ~Gi,coon DMF ” ° 9 ou jc (a) (b) (©) @ ° Br, (excess) ist a ° ° @) ys + CHBrs 0) Khe Br Br o oO Br © wh ® ow COOH, - Ba, ale: KOH tS . GycooH COOH Oo oO COOH Oo oO Br “OD (OOH394 GRB Advanced Problems in Organic Chemistry for JEE 8 ee C2HsO Br (CH3)3;C—OK 15s =o oe Product : 0 j;COOH ch, oom wo oe 0 re eer CHOCO . 160. sar BBO? Major product: Cols Calls Cis CH o ty ©) oO, ohy CeHs MORE THAN ONE CORRECT ANSWERS || 1. Which of the following do not react with Fehling solution? (a) CH;CHO —(b) Ph—CHO-_—(€) Glucose @ A 2. Which of the following form Schiff’s base with CH; —NH,? 9 . oO Il I (a) HjC—C—H (b) H,C,—C—H i (©) CH,;—CH, —OH (@) H-C—OH ll {I 3, H—C—OH and H;C—C—OH can be distinguished by : {a) NaHCO, (b) H,SO, (c) AgNO; /NH,OH * @ Febling solution ° ll II 4. HyC—C—H and (Ope can be distinguished by : (@) Tolien’s reagent (b) Fehling solution (©) Benedict solution @ H,N—-OH 5. Which of the following give N-substituted amide from ketoxime? (a) PCI; (b) SO, (©) BF; (d) NH;Carbonyl Compounds 395 6. Acctaldchyde can be obtained from which of the following reactions? (a) CH,CH,OH 24; ° Pd-BaSO4 ll b) CH, —C—cl (b) CHs id (©) (CHyCOO);Ca + (HCOO), Ca 2s for (@ HyC—CH= ad —_, Zn-H0 CH; 7. Which of the following do not give Cannizzaro reaction 0 . ll (a) C,C—C—H ) HoH ° © P—o—# ° 8. Which of the following yield yellow precipitate on reaction with I, and NaQH? oO @ “YC ) ° O rt (©) Ph—C—C—CH _@ vy Ph OH 9. Which of the following compounds exhibit acid base reaction with NaOH? oO ocy™ ©) oO 0 \-ton oy” © - 0396 GRB Advanced Problems in Organic Chemistry for JEE 10. aut ‘OH ‘CH, CH, CH In the reaction X and ¥ may be : (a) pec and Ph;P—=CH, (b) PDC and Ph,P—=CH, (c) pec and Ph ,P—=CH—CH, (d) pec and Me,S—=CH, CH; 11. The synthesis of Ph—F—OH can be achieved by : C,Hs H® 1,0. (a) PhMgBr +CH,--C—C,H, ——> I H®/H120. (b) C)HsMgBr + Ph—C—CH, ———> H®/H,0 (c) CH3MgBr + Ph—-C—-CH,CH, ——> I H®/H,0, (a) PhMgBr +CH,;—C—cl ——>5 12. Which of the following are correct for reaction? 0 oO ° CH; BatNeOW, 445 » C+CO2 . 9 So @ di me wei oe a) Ais . is Br 0 Oo 9° © of @ ol) ° ° os To. cmd 13. + CHy=CH—C—CHy >Carbonyl Compounds 397 Select the reactions involved in the above reaction : (@) Michael Addition (b) Aldol Condensation (©) Dehydration (d) Perkin Condensation eC oor Which of the following reagents can perform this conversion successfully? J. (@ HS SH, H) and Ni (b) Zn-Hg/HCl 8 (©) Mg. THE/H,0 (@) NjH/OH 15, Sclect the correct combination : e ] ou @ HyC—C—H —> HyC—CH=CH—C—H ° _ 0 ll KOH ‘lle (b) Ph—C—H ——> Ph—-C—OK® +Ph—CH,—OH ° IL. anon; i (c) Ph—-C—H ———> Ph—C—-O—CH,—Ph i @ H—c—H , H-C—on + CH,OH ° 16. or NDS, products ‘The possible products are : ‘NaOH I CMe; CMe; ony () my . ° Yl 9 g 0 Mes ® or 17. Which of the following reactions involve hydride ion transfer? ° fe) I ou Ilo (a) 2H—C—H ———> H—C—O + CH,;—OH398 GRB Advanced Problems in Organic Chemistry for JEE e | (b) 2H;C—C_H as H,C—CH=CH—C—H i i AIOEt (© 24,c—c—H MOS, cy, —c_o—cH,cH, 9 Al(OCMe3)3 a @ vk sean, wipe A t 18, Which of the following statements are correct? (@) Carbonyt compounds give nucleophilic addition reaction while alkenes give electrophilic addition reaction (©) >C=0 bond has larger dipole than C=C (6) Aldehyde and terminal alkyne both react with Tollen’s reagent (@) Aldehydes and ketones can be distinguished by 2, 4-DNP 19. Which of the following may be classified as an acetal? ® CO ) Ch ©) [ oa @ 3 20. Which of the following pairs are not correctly matched? @) Doo EEE cH, (©) Dao NAWOH, sain, cu—on °: ee AE PABSOs, por 0 @) —C=I en setno, f NH, + Which ofthe following compounds wil not show enotsaton? < “OOL | © AA @ o= 3 NH2OH PCI; dil. NOH ~—N3H («¢) —~ -———> — — H,N—OH A @ 25. Which of these carbonyl compounds on reduction with Zn-Hg/HCl will give the same product? 6 li Hs {i CH @ H€-(O) cH (6) HC —(O)-t-en ‘CH; CH) Hi c=0 oO | 7a (©) HC H,—CH—CH, (d) H3C. C—C—CHs Nou. ey COOH 1. PCls H)N—OH H2S04 26. h > x > ¥ FZ Et ‘2. CH3MgBr HCI X,Y and Zare: COCH f@) a Ph Et400 GRB Advanced Problems in Organic Chemistry for JEE II ll NH—C—CH; NH—C—CH © urn @n-rr Et ° H50. , HjCMgBr , HS. 21. + aes 5 4 RE pg Bc Product ‘A’ and ‘C” are : OH H;C_ OH HO, °K ©) © OY @ CL 28. Which of the following alcohols can be oxidised by K,Cr,0;? (a) CH; —CH, —OH (b) —bon © >-0H : (@) HyC=CH—CH,—OH 0 29, Da and “CN can be distinguished by : 0 @I,+NaOH (6) NaSO,H_~=— (©) NaCN/HCL_—(d) 2, 4- DNP 30. Which of the following reactions will produce aldehyde? Oy H _ cO+H, @ >= Zn-Hy0 () HsC—CH= CH ZcOP BH, 42. () HyC—C=CH = (@ HyxC—cascH B+ H280«, OH/H,0 31. In the given reaction : HN—On PCis Ph—C—CH, —*—— (4) —S (7) 1 7c 2 ° ill be : ¥ wil ° I . (a) Ph—C—NH—CH, (b) HjC—C—NH—Ph It ° I] (c) Ph—CH,—-C—NH, (d) Ph—CH,—CN eeCarbonyl Compounds : 401 32, Fehling solution gives red precipitate with : (a) Aromatic aldehyde (b) Aliphatic aldehyde (©) Ketone (d) o-Hydroxy ketones 33. Which of the following compounds will give positive Tollen’s test? ° : | @ cu; . () Ch oe oon Hy Hy ory @ cca ou : ‘OCH; 34, Silver mirror test with Tollen’s reagent is given by : (a) Pao () PhO H oy Ph— CH; —€— CH —O8 (@ Hj;C—C=CH 0 1. PhP. 384, ()=cHcrs In the above reaction 4 and B will respectively be : . cl . @ CX and HCHO ) cA“ and HyC—CHO ‘CH; 0 | © on and uct (@) HyC—CH,—Br and Co oO 36. Mixture of Ph—C—H and HCHO is treated with NaOH, then Cannizzaro reaction involves : (a) Reduction of HCHO (b) Oxidation of HCHO (c) Reduction of PhCHO (a) Oxidation of PhCHO 37. Which of the following form stable hemiketal? t f (@) Ph—C—Ph (b) HO—(CH,);—C—CH,, 0 Il (©) HOH,C—C—(CHOH),;—CH,OH oO \| . (d) HO—CH,—(CH,),—C—CH, * .402 GRB Advanced Problems in Organic Chemistry for JEE 38. Among the following compounds which will react with acetone to give a product containing >C=N—? (a) CoHsNH,, (b) (CHy)3N . © Ph—N—Ph @ Po—N—NH A H 39. A new C—C bond formation is possible in : (a) Aldol condensation (b) Friedel-Crafts alkylation (©) Clemmensen reduction (d) Reimer-Tiemann reaction 40. Which of the following will undergo aldol condensation? ° 9 9 H Il Il @ oO” © -—H (d) D30—C H ° : 41. Which of the following will not react with H,O? (@) CHCl, (b) C,C—CHO (©) CCl, @a’%vo 42. Grignard reagents produce carbonyl compounds with : i i (@) CO, () R—C=N (@) R—C—Cl_ @) R—-C—O—R’ 43. The given imine cai be preparéd from which of the following reactions? H CH; I CH; @ cl ) ‘on HP 9° H . (d) “Oy +NH; oO 20 © my in® 44. Which of the following reactions would give identical product? Hi H® I a Or (@) CHs;—C—H HS me HEO. () cH,—c—n SEM i ‘ H/H,0Carbonyl Compounds 403 CH; I 0,04 HI04 (c) CH, —C=CH—CH,; ——> ——> cl | °: (@® CH,—Cu—cn, “28%, _O_, Zn—Hj0 4. \) le — € S-cr—on Identify the reagents that can perform this conversion successfully : (a) H), Raney Ni, A (b) Mg-THF, H,0 (©) NaBHy, H,0 () H—C—H,0°H 46. Which of the following compounds can be synthesized by intramolecular aldol condensation in very good yield? Oo CHO 5 @ ©) Cr © Ot ® ‘CH; * . 47, Identify the compounds that give aromatic salt on reaction with HCIO, : @ oy () A oO a @ 48. Which of the following pairs can be differentited by Tollen's reagent? Hin Qs ©) and Ag vy" . OH © AA and oO @ wy ma AK O°404 GRB Advanced Problems in Organic Chemistry for JEE 49, When salicyl aldehyde is treated with (CH3;CO),0 in presence of CH;COOPNa®, A: o camcr_ton fa) OL is major product - ‘OH : ©) 1O®) is the major product = © On™ is formed as intermediate, which finally condense and H | form the product. ? =O Hy (d) This reaction is Perkin condensation. : ll : 50. Which of the following compounds will react faster than CH: with CHyMgBr? ° ° —{ . ° ° | { @ (S44 {b) CH; —C—H t oO © CH; —C—NH, (@) CH;—C—cl (ERAS Linke COMPREHENSION TYPE Ht Passage-1 The addition reaction of enol or enolate to the carbonyl function of aldehyde or ketone is known as aldol addition. The B-hydroxyaldehyde or P-hydroxyketone so - obtained undergo dehydration in second step to produce a conjugated enone. The first part of reaction isan addition reaction and the second par isan elination reaction, jonyl compound having o.-hydrogen undergoes aldol condensation reaction. ° ll con 2CH,CH,—C—H—" CHCH,CH=C—C—H CHCarbonyl Compounds Mechanism : e th . HO + tent Tne” HyC-—CH=C—H CH oO 80 80 oO Cat rl CCE + ae — > CH;CH;—CH—CH—C—-H CH; : CH; “oe i HO. 29, cHscH—cH—cHC—H1 —, cc —cH=C—C-Ht CH3 CH 1. Find out product of following reaction : ° ‘NaOH, 5 X is: Il Ph (a) CH;—CH = CH—C—Ph (b) Ph—c=C€ ° | Ph Il Ph (c) Ph—C—CH=C—CH, (@) None of these Ph 2. Which of the following will give aldol condensation? 0 9° i i AL a ween @fcet on 3, Find out major product of fllowing reaction: a406 GRB Advanced Problems in Organic Chemistry for JEE O° 9 »OCD | OOS 0 oO Oo 0 : (CH. HC (c) CX we (d) None of these ‘C—-H ‘CH | 0 Passage-2 . The base catalysed reaction of 1, 2-diketone to a salt of 2-hydroxy carboxylic acid is known as benzilic acid rearrangement. The reaction is not applicable tol, 2-diketones containing o-methylerie group because of competing aldol condensation.: fl etl ) ; i : XO) => mi — Phe —C—OH ba Ph OHO lll e PEO Ph 4, Find out product of following reaction : °° fj Oo OH O OH OC Le 68 or Li! o-6—c08 Che of LT ] - @ None ofthese C—Ch,.Carbonyl Compounds 407 5. ow Ot te-nt OA, « Find ‘P’ : OHO | lle @ on(O)-eC—8 CH; OHO Ie ll e &) on {O06 © on {Oo (Oa (d) None of the above O L.NaOH, 6. —_— ct 2. H%H,0 0 ou OH COOH OH On ® Sevan ©) © ‘coon cy ‘COOH ‘When an aldehyde with no a-hydrogen react with concentrated aqueous NaOH, half the aldehyde is converted to carboxylic acid salt and other half is converted to an alcohol. In other words, half the reaction is oxidized and other half is reduced. This reaction is known as Cannizzaro reaction. QO 9° ll Conc. NaOH, Il ee 2 —H >—-ONa + OH408 GR Advanced Problems in Organic Chemistry for JEE Mechanism : Ce 3 CCR. o (% IL OH | ll Slow o Ph GH PROG EH Ph Ph +/H—C—Ph A J | | Sup Sot | oH | H et ov O pr, + H-C—Ph So | H 7. Which of the following will not give Cannizzaro reaction? ° ° co 0 Il II i fl iL (@) (Sc) fcr © a @ HCH a 8. Find out the products of following reaction : ° ° : Il Ih x (Sc + HoH $8 ay X and ¥ are: : ° ° ll lle (a) Ph—C—0 and CH,OH (b) Ph—CH,OH and H—C—O ° oO lle oo (¢) Ph——CH,OH and CHjOH (@ Ph—C—O and H—C—O 9. Find out ‘X” of the reaction : iis (See hoe OH | oo Ta (@) Ph—CH-C 5 . (©) Ph—c—”—5, \ ft N38. ° 6 0 (c) Ph—C—CH,OH (d) Ph—CH—CIhOH oNCarbonyl Compounds Passage-4 When two molecules of an ester undergo a condensation reaction, the reaction is called a Claisen condensation. The product of a Claisen condensation is B-ketoester. O° ° oO oO { 1. CH3CH20 Il ll 2CH CH, —C—OEt ————> CH,CH, —C—CH— C—OBt + E10H 2H . CH; Mechanism : EO nae —OEt ca ns : BIOH 9° ll ll 8 BO—C—GH—C—CHICHs + B10 on hl CH,CH3 CH fon 10. Find out product of following reaction : Il 2¢ \—cis-—c_ors sien, oO ° Il tl (b) Pa—CH,—C— FC —O8t ll (a), Ph—CH, —C—CH,—Ph . Ph ll © Ph—C#t, —C—FH—C—O8 (d) None of these Ph 11. Find out final product of reaction : O° O° 9, Pwr cHs0. 1. HHO. HC OCH; SEX a Y410 GRB Advanced Problems in Organic Chemistry for JEE : . Oo COOH CH; Te mone Oe oO © ol @ 0 0 12, Find out starting materials for following f-ketoester : ° 1. CH;CH,O on™ corset Ooh ‘X? and ‘Y’ are : 9 ° 9 9 Notgn~ a (@) + (b) + 9 °o | C—OEt © +HOX~ None of these Passage-5 An organic compound 4 has molecular formula C,,H,,0. 4 on treatment with H,N—OH yields two stereoisomer 8 and C having molecular formula C,,H,;NO. B and C on treatment with concentrated H,SO, yield D and E.D and E are respective isomer of BandC. D on alkaline hydrolysis produces optically active amine F (C4H,,N). £ on alkaline hydrolysis produces aniline as one product. 13, Find out structure of organic compound 4: . ca: f tb (@) PhCH —C—CH (b) Ph—C—cl,—CH ‘CH3 ‘CHy oO (e) Ph—CH, —C—CH, —CH, —CH, ° ll (a) Ph—C—CH— CHLCH, CH;Carbonyl Compounds ait 14, Compounds B and D are : (@) Functional isomer (©) Geometrical isomer 15. Compounds D and E are: (@) Functional isomer Passage-6 (b) Enantiomer (d) Metamers (b) Enantiomer By (©) Geometrical isomer (a) Metamers Ca(OH) +p c=CH Ph 5 ee C+D Me2S HC” 16, 4+B 24) Product : ° 9° @ (cron | () [yb creo oO oO © [foc (d) m—cu—cH——Pn , bu 17. Find correct structure of E : ° 9 @ [ y-bo Ca ) [i ° 2. © t (a) None of these 18, E ———> Product 0 : ° f@) Lo (b) %, l i @) [ )-e 9 (d) None of these412 GRB Advanced Problems in Organic Chemistry for JEE Passage-7 9 Compound having —C—CH, group reacts rapidly with halogen in presence of a base to form haloform, The reaction is known as haloform. ° $ 0 / II X2+0H lls ° R—C—CH, ———> R—C—O+CHX, Mechanism : 6 Ce } ° I {~s Gi i R Wows 11+ 0H Ss R hoa Yon C—CH)—X 9 aN i 8 @ 8 6 RO een R—C—Cx, CH OH x Re HH 'O Haloform 19. Which of the following will yield iodoforin on reaction with, + NaOH? Mes PhO L Il @O FC 0) Po—o—C—Chy 0 Ph 0 © “TT © 6\-tca 9 X:+ OH 8 20.(C) a + CH Which of the following is correct comparison of rate of haloform reaction with various halogens? : @) Fry > Fan > Tig (©) iy > am > Fer (©) Ferg = Tan = Mig @) Fay > 1p > HgCarbonyl Compounds 413 21. Consider the following reactions : 0 ll ch, OH le os Reaction 1» Ph_-C—CH, ———> Ph—C—O+CHCI, oO oO I Ch, OH Il 2 Reaction IL—> Ph—-C—CD, ————> Ph—-C—O +CDCl, Which of the following is correct comparison of the rate of reaction [and IT : @) 4 >" {b) 7 4-4-O) , oO Oo (c) 5 (d) wo) LO) ® Ons O 9 1-©)-G)- Product, Final product reacts with I 2 HO NaHCO, and liberated ° .o CO, gas 1. KOH . (4) Ph—C_—H ———-» Product S. Final product reacts with il 2H Na and liberated H, gas. ° "Carbonyl Compounds 6. Column (1) ° @ (\-cn 9 w J oO © H Ay Oo @ wy Sci 7. Column (1) »Ope H ) HyC—-E—H © inane OH ® Oo 8. Column (1) - 9 6 9 @2 Ay 2. H 9 6 ° Ou ° (b) 2yAy > CH3;—-OH + wre si Ken (c) 2Ph—C—H —> Product oO e ol @ A, 2228 product Column (11) P. Aldo! condensation Q. Cannizzaro reaction R, Benzoin condensation 5. Claisen-Schmidt reaction Column (11) P. Positive lodoform test Q. Reduces Fehling solution R. Positive Tollen’s test S. Brady’s reagent turns red Column (1D) P. Oxidation Q. Condensation R. Nucleophilic addition S. Electrophilic substitution T. Nucleophilic substitution a9420 GRB Advanced Problems in Organic Chemistry for JEE 9. Column (1) Column (i) Me Me @) oO 4 . P. NaBH, “Ny CH,OH H MnO. ® om oe ante oO Il © HH, R. H—C—H, KOH i (4) H;C—CH=CH, > L—CH=CHe S, $eO, . “H 10. Column (1) * Column It 0 : @) Oo P. Febling solution Oo; ll . (b) H;C—C—CH, Q. 2,4-dintrophenyl hydrazine test (© H—C—H R. Tolien’s reagent i —H ® oe S. Todoform test ‘OH 11. Column (1) Column IT CHO - ® Oo ‘ P. Perkin condensation eyCarbonyl Compounds : 421 CHO OH a) Q. Canmizzaro reaction . OCH; o({O R. Aldol condensation C1 cio S. Haloform reaction Saeed INTEGER ANSWER TYPE PROBLEMS tt 1. Examine the structural formulas given below and identify number of compounds which are reduced by NaBH,. > / “COO o hn: of e 2. Find out number of substrates those cannot ners Cannizzaro’s ssaton Il 1" { t t t H—C—H, Ph—C—H, H,C—C—H, Qe »H—C—C—H o-. 90 “O © I - I tl Cl;C—C—H, Ph—C—C—Ph, pre, , 3; Examine the structural formulas of compounds given below and Pas number ~ of compounds which show positive iodoform test. Re BRA Oh ote dy, wht.422 GRB Advanced Problems in Organic Chemistry for JEE 4, Find out number of products obtained by cross Cannizzaro’s reaction between . Oo - ll Il (b) PhCH + (CH; );C 0-H 5. Of the following compourids, how many would give positive test with Tollen’s reagent. t t i i fl CH,—C—H, CH, —C—OH , H~C—OH ,CH;—C—CH, , Ph—C—H HC OH HC Ponts oO , * CH;—C=C—H OGHs HC’ Noctis | OH 6. Ofthe following earbony! compounds, how many would give aldol condensation reaction. 9 90 II H noo « i CH? Hq oO wan, ores , whom CH; "7. Consider the following reactions and identify how many reactions can give carbonyl compounds as major product. Ph @ wok yo ©) ogy trou wean Kun @ NA — Rui, OH “ 0. PhMgBr Cr0; © oy a © OQ Dil. "Acetone Ay 1Carbonyl Compounds 423 8. Consider the following reactions, and find out number of reactions which are Claisen condensation in nature. 9 I. end a @)'y GHLOW” (b) 2 ‘C—CH; > OC Hs Gat 0F ° 9 9 © wn Soc, SP @ ont 2, ? 0 © pra di cca os, 9 9 ogy + ox ocgns_nsiconon, Oo CN e 0 a yo, ‘CN oO oO 9, Examine the structural formulas of following compounds and find out number of compounds which show higher rate of nucleophilic addition than Ota OOO 9.9 iQCH; Cl N(CH), :QH t 10, R—C—R—— R—CH,—R ‘Identify numbers of reagent that can be used for above conversioil. (a) Zn—Hg/ HCL (b) LiAIH, (0) CHCl, +NaOH ° CH,—SH (8) NjH,/OH ©) |. ,H,/Ni (f) SeO, CH,—SH» 424 GRB Advanced Problems in Organic Chemistry for JEE e Resse Exercise-1 : Only One Correct Answer Levelt L@) 2) 3(o) 4) 5.4) 6 () 72@ &@ % © 12. (©) 12. (a) 33. (a) 14. (b) 18. (b) 16. (b) 17% (©) 18. (b) 19. (by 21. () 22 (d) 23. (d) 28. (a) 28. (b) 26. (d) 27. (d) 2B. (@) 29. WA) 31. (c) 32. (c) 33. (c) 34. (a) 35. (d) 36, (b) 37. (b) 38. (b) 39. (@) 41. (©) 42. (b) 43. (b) 44. (2) 45. (b) 48. (ad) 47 (b) 48.(a,b) 49.(a,0,d) $0. (by 51. (a) 52. (©) Level-2 © 2) 3@ 4@ 5) &@) 7 BO) % © 41. (b) 12. () 13.(6) 14 (2) 15. (b) 26. (©) 37. (2) 18.) 19% 21 (d) 22. (b) 23. (d) 24. (@) 25. (a) 26. (a) “87. (a) 28.) 29. (A) 31. (c) 32. (@) 38. (C) 34 (b) 35 (a) 36. (4) 37 (©) 38. () 39 (b) 41. (c) 42. (@) 43. () 44. (@) 45 (a) 46. (2) 47 (@) 48. (b) 49. (0) 51. (b) 62. (a) 58. (b) 54. (c) 55 (¢) SE (a) 57 (@) 58. (d) 59 () G1. (c) 62. (4) 63 (a) 64. (b) 65 (c) OB. (d) 67 (c) EB. (c) 69. (a) ‘TL. (d)_ 72 (6) 73. (d) 74. (a) 75 (d) 76 (a) 7% (b) 7B. (c) 79. (b) 82. (a) BZ. (b) 83. (d) BA. (b) BE: (a) 26. (c) B7 (b) BB. (c) 89. (d) 2. (b) 92. (c) 93. (6) 94. (b) 95, (c) 96. () 97. () 9B. (c) 99 (a) LOS. (b) 102. {d) 203. (9) 104. (2) 105. (b)106. (b) 107. (c) 108. (d) 109. (b) V2, (d) 112. (c) 213. (b) 184 (9) 125, (b)126, (©) 117. (a) 238. (a) 219. (2) 122, (d) 122. (b) 123, (b) 224, (b) 125. (b)126. (c) 227. (c) 22B. (a) 229. (c) }4. (a) 232, (d) 133. (b) 134. (c) 135; (c)236. (b) 137 (b) 138. (a) 139) 41. (b) 142, (9) 143 (b) 144, (4) 145. (0) 246, (b) JAZ. (a) 148, (6) 149. (¢) 20. (ay, 20.-(c) 30. (d) a0} $0) 382. (2) 153, (0) 154. (c) 455, (0)255. (0) 187. (6) 358. (4)189._e)_160. (of Exercise-2 : More Than One Correct Answers L (a 2 (@b) 3 Ea) 7 @6 & (bd) % (ed) 1 (Od) I, (a,b,c) 12 3. (a,b,c) WA. (abd) 15. (be) 18 bo) 37% od) th 19. (¢,d) 20. (b,d) 21. (@,b,c,d) 22> (a,b,d) 28. (@,b,c,d) 24 28. (2, b,c) 26. (a,b,c) 27 (b,c) 28. (ac,d) 29. (a,b) 36. 31. fab) 32. (b,d) 33. (a,b,c) 34 f@,b.c,d) a5. (4) ae 87 (c,d) 38 (a,d) 3% (2,b,d) 40. (a,b,d) 42 (a,b, 6, d) 42, 83. (abc) 44. (b.c) 43. (ed) 46 (ad) 47% tbc) 4B. 4. (0) 8% (b,c) (a,b, dy (a,b, d) fa, b,c) (b, c) 0) (¢) (b,c, d) (a,b, d)Carbonyl Compounds : 425 Exercise-3 : Linked Comprehension Type Le) 2) 3.0) 4) 5. (b+) 6) FCC) Bb) 9), Me OI 32. (@)_ 42 (a) 13.) 14. (@) 18. (@) 16. (b) 27. (6) 18, (@) 19. (a) “20. ot @1.-{a): 22. (b) 23. (d) 24. (2) 25. (bd) 26. (c)_ 27. (d) 28. (b) 29, (a) 30. <0) + @AQR; ()P.,8; C)AP.RS; @)>R,S 2. @)9ORS; (vb) PS CAR; G70, 3. @)P,Q,8; W)OPQRS CAP: @IORS 4. )9P.Q, () +P: ©) PQS; @P,2,8 8. (a) P.Q,S; O)ARS; ©) Q: MaRS 6. QRS; )9P.S; (70S P.RS 7. () > P,Q,R,S8; ©+9, @P.O,R.S 8 ()9 PRT; O47OR @R,S,T % (b) > S; ©79; @3 5.0 10. (a) O.R (0) +, S; (©) P.Q.R; @>OR,T - (=P, {b)-» P.0; (R,S2" MP, Exercise-S : integer Answer Type Problems 3142.4 £6 64) 25) 84) 93) 10.3) 000Carboxylic Acids and Its Derivatives : CH) —CH. CH,—CH , \ @{? No b) | "\c=o : : CH, —CH,% CH, —CH,” : CH, —CH,CO CH, —CH,COOH : : © So @ : CH) —CH,CO: CH, —CH,COOH 2, CH;CH(OH)COOH molecule shows : (a) geometrical isomerism (b) metamerism (c) optical isomerism (d) tautomerism ' 3. Which of the following is the best representation of the structure of the carboxylate ion ? o ace 6 8 @ R-CRp (b) RCEg © RCE (d) None ofthese » 1 & : | 4. The correct order of decreasing acid strength of trichloroacetic acid (A), trifluoroacetic acid (B), acetic acid (C), and formic acid (D) is : 1 (a) A>B>C>D (b) A>C>B>D (c) B>A>D>C (d) B>D>C>A 5. Identify Zin sequence. 4i) Heat H,0(H") CHyCOONHg Gr pg YZ | (@) CHyCH,CONH) (b) CH,CN (©) CH;COOH @) (CH3CO),0 6. A halogen compound ‘4’ on hydrolysis with dilute alkali followed by acidification gives acetic acid. The compound X is: (@) CICH,CH,Cl (b) CHsCHC], (©) CICH,CHCl, (d) CHCCL, | 7. Which of the following statements are false about HCOOH ? | | (a) Itis a stranger acid than CH;COOH | | (b) It forms formyl chloride with PCls ! (c) It gives CO and H7O on heating with conc. HySO4 | {d) It reduces Tollen’s reagent |Carboxylic Acids and Its Derivatives 427 8. Inaset of the given reactions, acetic acid yields a product. Product C would be: Cah (@) GHeMgBr/ether 1H 3COOH. — A——_> 8B CHy! +PCls Fy. AICI, B to Cc (a) CH3;CHCOH)C)Hs (b) CH;COC.Hs : . . CaHs (c) CHyCH(OH)CHs, : (d) CH; —C— (OH)CgHs 9, in the given reaction final compound (L _- COOH NO) . . (O) EEN, (yO EE) (ii) Hy" i COOH) Hs CoHs—C NO, () ©) OH OH I CHs—C—CyHs CeHs—C— CoH NO, () (d) 1. The acid D obtained through the following sequence of reactions is : CpHsBr-ME KOH, 4B, (excess (@) succinic acid (>) malanic acid (c) maleic acid (€) oxalic acid 11. Carboxylic acid group can be detected by which test 2 (@) Sodium bisulphite test (b) Fehling’s solution test (©) Tollen’s reagent + @ With NaHCO, 12, Phenol is a weaker acid than acetic acid because : (@) phenoxide ion is better stabilized by resonance than acetate ion (b) acetate ion is better stabilized by resonance than phenoxide ion (c) phenol is less soluble in water than acetic acid (@) both phenoxide ion and acetate ion are equally stable 113. Which of the following is the weakest acid ? {a) C1;CCOOH (6) Cl,CHCOOH (¢) CICH,COOH (d) CH;COOH 14. Which of the following dicarboxylic acids contain the most acidic hydrogen ? (@) Maleic acid __(b)'Fumaric acid _(c) Succinic acid __(d)_Malonic acid428 GRB Advanced Problems in Organic Chemistry for JEE 15, Which of the following sets of reagents X and ¥ will convert propanoic acid into alanine (an amino acid) ? : ® bate t Lertne f HyC—CH, —C—On 5 4C—CH—C—On > HjC—CH—C—C00- (@) Bry, NaNHy (b) Bry/P, NaOH (©) Bry/P,NH3 (@) Br, /HBr, NaNH 16. Identify Z in the following reaction sequence Mg Dry _@ P+Cly CH3I Siren? © ee 7 Y (i) HO Zz . (a) CH;COOH = (b) CHyMgl_—(@) CH,COCI_—(@) CICHCOOH 17. R—CH,—CH,OH can be converted into RCH,CH,COOH. The correct sequence of reagent is : (a) PBry, KCN, H* (b) PBr3, KCN, H (© KCN, Ht (@) HCN, PBr3,H* 18. (CH3 )7C—=CHCOCH, can be oxidised to (CH )C=CHCOOHby : (a) Chromic acid (b) NaOl (©) Cuat 300°C (d) KMn04 19. The compound B is : ch, CH;CH,COOH i> A AE B (a) CH;CH,OH (b) CH3CH,COCI (c} CH; =CHCOOH * (d) CH;—CHCi— COOH red P LiAlH, . 20. A <77— CH;COOH ———> B. What is not true for A and B ? (a) Ais hydrocarbon of general formula C,,H2,42 while B belongs to alkanol (b) A can be obtained by reducing CHyCH,Cl while B by its hydrolysis (c) Ais alkene while B is alcohol . (d) A and B both belong to different homologous series ° COOH 21, In the reaction A XS p Bo inc® \coox Identify 4: Wa (@) HCC © HCC ‘CHOOH ‘COOH NH (©) HAC) ‘@) Allare correct coon 22. Give the order of sodalime decarboxylation of the following acid. @) CH;COOH (Il) CH) =CH— CH, ~COOHCarboxylic Acids and Its Derivatives 429 NQ> (I) CH, (COOH), (lV) 02N COOH NO; (a) [>> M>IV (bo) M>IV>U>I () IV> I> I> 1 @ I> M>u>1V 0 2B. Cx on saponification forms : oO ~O OH OH rd . . (a) CH, —CH, and OHC—CHO . (b) OX—CH, —CH, — OH and OHC—COOH : {c) CH —CH and HOOC—COOH : OH OH (@) HO—CH, — CH; —COOH and HCOOH 24, Arrange the following compounds in decreasing order of acidity. () CICH,CH,CH,COOH i) CHyCHCICH,COOH (iii) CH;CH,CHCICOOH @I>H>i =) M>n>1 «= @i>m>n @ Mein NaNj+Cone. H,SO, 28, H,C—CH, — COOH AE AEM, y by reaction Ry Bry/P Lee Y by reaction Ry Which is the correct alternate ? x ¥ Ry Ry (@) CHjCH)NH, HC —GHCOOH Schmidt HVZ Br {b) CH;CH,CONH, = CH3CH,COBr Schmidt. HVZ (©) CHyCH)NH CHaCH,C08r Schmidt. HVZ (d) None of the above H30® ji 26, X and Y in the reaction sequence R—C==N > X fimoretae, y, are given by the set : (a) Carboxamide, Carbonitrile (b) Carboxylic acid, Carbonitrile (c) RCODH, RCOOCH (d) RCONH2, RCOCH3, 27. Which of the following organic acid decolourises bromine water as well as forms anhydride ? (a) HOOC—COOH (») HOOC—CH,— COOH H—C—COOH H—C—COOH (c) H—C—COOH (d) HOOC—C—H430 28, 29. 30. 3. 32, 33. 34, 35. 36. GRB Advanced Problems in Organic Chemistry for JEE The compound which on reduction with LiAIH, gives two alcohols is : (a) CH3;COOCH; (b) CH;COOC)Hs (0) CH3COCH; (@ CH;CHO Consider the following sequence of reactions. B Cc D Come. 00s, oO soci, O (CH,CH,),Cd O i Identify 4, B,C and D. (a) —F,—COOH, —COCH;,—OCH,CH,CH () —CHO, —COOH, —COCI, —COCH,CH; (c) —Br,COOH, —COCI, —COCH,CH; (@) —Br,—COOH, —Cocl, — idit CH,COCI+C,H,0 =" cH,COOC;Hs + HCL The fanction of pyridine in the above reaction is : (@) to absorb liberated HC] () to catalyse the reaction (c} both (a) and (b) (@) none of these CHCOCI can react with: (@) CoH OH (6) CoH NH a © Cet (onto (@ all of these ‘COOH The end product in the reaction is : 0. CH,CONH, 255 p41, cs pS (a) CH;CHO (6) CH;COCH, (©) CH;CO0C,H, (4) (CH3CO),0 Hofmann bromamide reaction involves the intermediate formation of : (a) a species with electron deficient carbon (©) a species with electton deficient nitrogen (©) aspecies with negative charge . (@) a five radical species RCOOAg + Bry ++ R—Br + AgBr +COp. This reaction is called (a) Wurtz reaction (0) Hunsdiecker reaction (0) Friedel-Crafts reaction (a) Kolbe reaction Main product of the reaction is : CHyCONH + HNO, —> Product (2) CH;NH, —(b) CH3CH,NHz (©) CH;COOH— (@) CH,OH The reaction, CH3COOC,Hs a C)HsOH +CH3CH3OH, is called: (a) Claisen reduction (b) Claisen condensationCarboxylic Acids and Its Derivatives 431 (c) Bouveault-Blanc reduction (a) Tischenko reduction 37. The reaction CH;CONH, “25, gives: , (@) CH3Br () CHy (©) CH;0Br —(d) CH NH 38. The reaction of acetaldehyde in the presence of AKOCHs)3 produces : (a) CH;CH(OH)CH,CHO (6) CH;CH=CH—CHO (©) CH;COOC)Hs (d) No reaction 39. Methyl acetate on treating with excess of C)HsMgBr produces : TAs C2Hs (@) CH —C—0H 6) CH; —C—On CH; CoH - CoH CH; ©) GoHs—C—-OH (@) CHis—-C— 08 CoHs CoHs 40. Ina set of reactions, propionic acid yielded a compound (D). SOCI. ‘NE, CH;CH,COOH 5 (8) “5 (C) 4) 2 The structure of (D) would be : . (a) CH,CH,NHCH (b) CHyCHNH (©) CH;CH)CH NH (d) CH3CH,CONH,, 41. The end product in the following series of reaction is : cHycooH NYS (4) 2 (By 22550) (@) CH, (b) CHj0H (©) acetonitrite (4) ammonium acetate 42. The end product in the following sequence is : : Acetamide 2255 (4) 48 (8) (a) CHjNHy (6) CgHsNHp (©) CHjCN.——(@) CH CONT, 43. CgHsCOOCH, + '8OH” —> A+B In the above reaction, products A and B respectively are : 18, i i (a) C3HsC—O- +CH;0"8H (b) C)H;—C—0"8 +CH,0H 18 9 ° i Il (©) CxHs—C—O'8 +CH30H = (@) Cp Hs —C—O7 +CH3OH432 GRB Advanced Problems in Organic Chemistry for JEE oO 4 44. Thereactionot / withamixture of Br, and KOH given R—NH} asa R” NH, Product, The intermediates involved inthis reaction ar Yi ¢ (b) R—N=C=0 R/\NHBr (a) oO R—NHBi (d df (©) R—NHEr © Amr I Br 45, In which of the following reactions propionic anhydride'is not obtained ? (@) CH;CH,CooH 2:4, (b) CH3CH,COCI +CH,CH,COONa—> (c)} CH3CH,COOH + (CHjCH,CO),0 “> (@) CH3CH,COOH + (C;H7C0),0—*> 46. Z=7 for following reaction : CH;CHO MoO; _, y __SOCl CH,COONa. 2 dil, H,SO, y 2 (a) CH;CHO (b) (CH3CO)20 (©) (CH )2CHCH,COOH (4) (CH;CICO),0 47. Which one of the following is an example of Rosenmund’s reduction ? H; {a) CH;COCI FyR,59, CHsCHO + HCI — (i) SnCi,—HCI (0) CHSC N gg? CH: CHO + NHACI LiAlHy (© CH;COOK ——*> CH;CH,OH+H,0 Lay @ CH,cocl—* cH, CH, OH + HCL 48. Among the given compounds, the most susceptible to nucleophilic attack at the carbonyl group is : (2) MeCOOCOMe (b) MeCHO = (c) MeCOOMe~—() MeCOCI 49. In a reaction, (4) 85 (8) Bs (Cc) 2s CH ON (4), (B)and (C) are : (a) CHjCOOH, CH ,COONH, and CH CONE () CH3COCI,CH;CONH) and CHjCOONH,Carboxylic Acids and Its Derivatives : 433 () C)HsCOOH,C)HsCOONHy and C)HsCONH> (@) CpHsCONH,,C)HsCONH) and C;H;COOH $0. Which of the following esters cannot undergo Claisen self condensation ? (a) CH;CH,CH,CH,COOC,H; ——_(b) CsHsCOOC,H, (©) CeH,\CH,COOC,H, (4) CgHsCH,CO0C;Hs CH,MgBr CO, 1. HyC—C=sCH 1 CH, +4 >. B . HS Bwillbe: . oO . ce} ory. 6) Novepr oa @ Aon . Br iA 2. Consider the given reaction; RCOOAg car R—Br yi Which one of the following acids will give maximum yield-of R— Br in the above reaction? (a) >—COOH 0) AJOH © —fcoon (@) All will give same yield CH; Natt Is 3. Nil _, F Pe f-C00H Goneuso? PD I NH) The above reaction is known as : (a) Schmidt reaction (6) Curtius reaction (©) Hofinann rearrangement (d) Lossen rearrangement Ih 4. Ph—CH—C—OH—*> (x) | on (Xyilbe: a) Ph—-CH—C==0 + (b) Ph—CH=C=0 of ©? Ph (@) none of these Oo434 GRB Advanced Problems in Organic Chemistry for JEE nestFe(coye) |! _ 5. Ph—CHO + Ph—CHO——> Ph—_C—O—-CH, —Ph.. This reaction is known as : (a) Claisen rearrangement (b) Tischenko reaction (c) Perkin reaction (d) Cannizzaro reaction 1H, CaHs0°Na® 6. 3 _ ‘aHist +CHy—C—OCHs “Fog? (X) will be: HL tS @ CH (b) ‘CH3 i JL () nce—e ais © ox ‘OH 2 Which one of the following compounds gives carboxylic acid with HNO? 9 : a @ tN © on © hone A, OH . Ll NaBH,Carboxylic Acids and Its Derivatives $$ 44 _Lalty ii. wa wns XO ( ne LiAlHs ‘Which of the following will not form? oO (a) on >) Nou (©) AA @ ® NED 2 NH, @ HN @ ~_-0H nD ne, 2255 0s 208, p Sess, ° exon Ros S will be : i i (a) | ou (b) | -e-cn,436 GRB Advanced Problems in Organic Chemistry for JEE —piq «D ANDnA ys, 14, ‘COOH 2 KOH, By : LNHy A, 2. KOD, Bry (@) ‘Xs Opn and Yis (Op (0) “Xs (Op: and Yis Op 15. PhCOOH and Ph—CH; can be separated by : (a) NaHCO; : (b) ag. NaHCO; + n-Hexane (©) H,0 (d@) mHexane {(CH3CO),0 Lia 16 (O)-wn ee, ~“yeiine” ~ ino, ? 7 Find out structure of ¥ : i A 7 9) Ph a (©) Ph a © mh @ Pr R ‘ H _NBs , ABO, COs oo nna a ee “Prine” 7 Product = ; ° wkyy - ono, 9° y YW Okt © @ {AA ort : : OH NyCarboxylic Acids and Its Derivatives | 437 18, The correct sequence of reagents for the following conversion is : oon ‘NO? SOCI, Ag CH,N2 SOCI, CH,N, | Ag,H,O @) —> 9? o) — — —— y CH,N, SOCl, Ag Ag SOCI, CH;Np. @ SS Oe af 9 NaN3 A . 19. Or — Xx =” Product : (a) (Oy only @) ‘NH; and HCOOH i f I © ‘C—NH) (4) ‘C—OH + NH 20. Arrange the following amides according to their relative reactivity when treated with Bry in excess of strong base. i Oboe me GL senor Opto ©) @ @) Om © (a) P>Q>R>S (b) R>S>P>O (©) O>P>S>R (@) S>P>Q>R_ ‘ 21. Which of the following compounds cannot give Hofmann rearrangement? | CH,O ° : ill I @ Ph—-F—C—NHa (b) CH; —CH, —C—NH—Ph CH; oO (©) O2 (@® Ph—C—NHp438 GRB Advanced Problems in Organic Chemistry for JEE l 18 Cone, H2SO, 22, HyC—C—OH+C,H, OH———$ (x) oO 18 Conc. H,SO, . 1 HjC—C—OH + (CH; );C—OH———-$ (vr) Jn the above reaction (X) and (Y) are respectively : i iP ll (@) CH; —C—O—CyHg and CH, oO : CH; ° 9 CH, ll is loa | - &) Hy3C—C—O—C,H, and HsC—C-—0—F— Cy CH, ° ° CH, II Il | (©) CH; —C—O—C)H; and HsC—C—-0—C— CH; CH; oO ° CH, las] ll (@) CH; —C—O—CpHg and CHs—C—0—F— cH CH; The product is : oO (a) He ‘OH ‘OH ~ OH (c) He HH COO! of Me 24, SN, ‘ COOMe 4Carboxylic Acids and Its Derivatives The main product is : © o ee 1.02 4. CO, NaHCO3 " Bre 2H OH ” Product I and UL are respectively: NH, @ and : ‘COOH (00H OH Ny NH’ SH © and E ® and Q OH OH I t. HH NI Br)+KOW S0Ch_, Mb, Bat KOW product : NH) Mh. © Ee @ weet, 1 GS-0, ggg (Major) (Minor)450 GRB Advanced Problems in Organic Chemistry for JEE Product A and B are: (a) Metamers (b) Position isomer (c) Enantiomer (@) Diasteredmers 28. An optically active compound ‘X” having molecular formula C4Hg03. It evolves CO; with NaHCO}. ‘X" on reaction with LiAlH, give achiral compound. ‘X” is: OH 0 hn ©) coon ©) HH @ at HE OH 29. There are — isomeric tetracarboxylic acid. OH OOH OOH (00H 00H 00H oon *HOOC COOH Hood COOH - ) oO. thi of these form two isomeric monoanhydrides? (@) only P (b) only PandQ (c) onlyQ @ P,QandR 9 Il 30. bl on Sone H:804, GH, Vy, The final product ‘X” is : ° Il (@) Ph—-C—-NH, r() {Om oO 090 I I (©) Ph—C—C—NH, (4) Ph—C—NH—NH ° : ll cH I i a1. C—el LiAlHy Cone HNO w ad ll oO The final product (X) is : SS @_ | ) © ( @ DCarboxylic Acids and Its Derivatives 441 32, Consider the following sequence of reaction &u 4s 8+ CHyCH:CO0 (CuuFhisO2) 1. KMn04/SH 2H® OOH COOH The compound A is : “S. © Qa @ o~ 0. vw 33. Following two methods are used for the preparation of acid Mg 1.CO, ) > R—Br —-—> RMgBr ——3—>R—COOH ® aiber?” RMEB 2HfO NeCN ” H;O (I) > R—Br—> R—CN ——>R—COOH Out of these two method sehich will be suitable for following conversion? Opa Pa Op fom (a) Bothi and (b) oat I> @) Only! —@) None of these 34, Which reaction would best accomplish the following conversion? emt {a) LiAIH,, Collins reagent b) NaBH Jones reagent (©) NaBH4,CrO3, H® (d) Ci re, NaBHy, H30«Ol Hy | weontng GRB Advanced Problems in Organic Chemistry for JEE Cl ——+—S Major product ; Hy CH; Mes (b) oc, CHO é @ Mey vy ‘Mes (a) oO <—— o[O ha CSN, Product : Se man Cl b) | N @ N—CH; % HAs, 4 POC p FENINH2, O - Product Cis : HH SN SN > _o LN © A © NHCarboxylic Acids and Its Derivatives 443 8 . OH 2O~ oOo OO ‘OH od 9 39. e—-ore 26: NH — > Major product : \_/ Lo ian &. @) Hjc—C—N 9 (b) H;C—C—Q -N—H 8 ll (c) HxC—C—N (d) Ph—C—NH) A, 40. NsOH. 120, Products : R Xe R ° ° OH ° : (a) RCOO°Na® —(b) Ga dy © Both(@) and () (@) None of these 41. Find out structure of compound R : Br i ALPE NEON, p. 10 0 CHsCHLOH, uw Ph ° 0 ® iW ©) on © wr (@ None of these 2 Pt 4.) KMn04 ‘00H oy 2 R ‘OH, +444 GRB Advanced Problems In Organic Chemistry for JEE Find out structure of compound (X) : roeheehoshioe “a. Chae 11, (P); Product (P) will be : io Che C coer @ ct ‘OOH ‘0 «nee 1 hin ==> Product : 9 ore es BRON, ©; Product Cis : L i wy i) oy" «@ AY Oo 46. Which of the a compounds will undergo decarboxylation on heating? oh () COOH (@) 47. Major product formed in the following reaction sequence is : a “=i 4 CHO Cys —C2HsO2 Ne? CyHs0° Na® _HO AROCarboxylic Acids and Its Derivatives JU, JAK (a) Ph (b) Pl Ph © os @ | 48, OCS 4 4,c—C—OCHs cot Major product : OCH eno i @ OCH. oon C—OC;Hs © : @ 1 00C;Hs 0 49. Predict product formed in the following reaction : we _GpHj0°Na® HO wen ac , 50. What is the major product obtained in this reaction? CH0°Na _CH3CHyBr, 150 0” CHZOH a446 GRB Advanced Problems In Organic Chemistry for JEE i Ly ® Aon , ©) © A, no @ OH 51. What is the major product obtained from the following reaction? 0. OK Na lercess) Xylene, A CH;COOH o OH 9 OEt @ Ch (b) Cr © Cr (a) CH 0 ‘OH ‘OH ‘OFt 52. Which of the following would be the best synthesis of 2, 2-dimethylpropanoic acid? 0 CHsMgBr | SOBr, Mg/E0, CO; @ wow Tfo aS? 5 5 & oH A CHsMaBe SOBr, KCN. _H;0. H30 9 © J CHMgBr , SOBr) Mg/ij0, CO, 9 HO HO. @ JAG CikMebr, SOBs, KON, fo HjO 53. Which of the following can decarboxylated most easily? (@) CHyCH,CH;COOH (>) CH;—CH=CH—COOH COOR COOH OnN, NOz © @Carboxylic Acids and Its Derivatives 447 54. In the esterification reaction : OCH; HC CHs HSC. + Hs + CH,oH —Core HO, CH3 CH, Which of the following is formed as an intermediate? oct Xe wo—6— on, BC 7 CH; » Hs CHs aK 1 | OCH HC. ELCH3 . Fy. 5 () {d) CHy CH3 85. Which of the following will not produce benzoic acid by oxidation with alkaline KMn0,? t *(@) Ph—CH; —(b) Ph CH, —Cl (c) Ph—CH,CH; (4) Pr-O CH CH; 56. Which of the following reactions does not involve decarboxylation? a A (@) CH;COOAg + BSS ) A Nous tL OH © o°Ne®? 45 ON +B > 57. Which of the following reaction will give racemic mixture? COOH COOH @ uf-n tet, () wa ae HCOOH448 GRB Advanced Problems In Organic Chemistry for JEE cooH cooH PCs HH oa (@HotH 8, @ ER, H,COOH CH 1H HH 58 #804 , Product : OH (@) H,C=CH—CHy—CHy—C—0H ) SY fe} - © (a) ZL BN o7%o a 8 HSH et owe ¢ () LN (c) CO,andCO (d) HCOOH 60. H—COOH and H—CHO can be distinguished by : (a) Tollen’s reagent () Fehling’s solution (©) NaHCO; solution (@) HgCly solution #50 61. +HCN 34295 g aa CHO The end product B is: inn 62, C1 Tf cr BEN, 4 KON, gp HO, 6 5 excess The end product C is : |Carboxylic Acids and Its Derivatives on. @ now ON (b) HO. 1H o HO H,SO. Ss 63. x + “xr? a oO HH Product (X) is : cor IH (a) H ‘0 () HH @ CO 1, E10°Na® 1. KOH, A 65. HC (COOEt), ———____> A 5 B 2. Br—CH,—-COOEt “2, u80 The end product B will be : (®) FOOC—CH,—HC(COOED, 6) wow 0 He © on @yo Oo oO ‘OH 66. The end product of reaction is : “rn P+Ch KOH Hae) $ 1,0 4450 GRB Advanced Problems in Organic Chemistry for JEE oe hf (a) obo’ (b) (O)--0-4c, ‘cH by N\ (©) HyC—C—OH . (d) ed Hy HC 68, So Hel? M804, 4 B fo, ‘The end product B will be : H =N ® ae © “i © ie 1H. HH 69. Consider the following sequence of reaction : BaCO3 + H7SO4 —> X (gas) 5, EME rr be: Br 2X, ¥; Ywill be: 3.430 oO JH Bi H oar OA © ny " @ a 70. ned bon dite Product : os 3.130 -wneX ction no-on-( toon © po ton @ wo—o1—{_)~cioHCarboxylic Acids and Its Derivatives 451 ‘71. Consider the following sequence of reaction : A 203, p_varm Jaco (C4He03) The compound A is : @ WY ae © wh @ gn 2. noone ZP 260°, ox wie: OH yo No (@Hcoon AH oa” ok 7B. H0Y“ou ROS, (P); (will be: HH. pail LDA HH @) ®) Yoon @ ud POH @ Ny A ° Z 74. HO’ nt —H, (4); Product (A) will be : acess} , I ©) mW wY © ay ory I Hy 8. 6 Hy He, 44 obs Hy—COOH Identify correct structure of A: Hi @ no’ Son & M480 © @ Hs 20H 1H452 GRB Advanced Problems in Organic Chemistry for JEE 16. (O) i POs, 4 MoH,» Find structure of compound B ; 9 Me i Me oO 0 Oo Me Me f Me f © (Opto @ (OOP Me ~ oO 1. tw yy Sy 7 2. SOC, AICI; The structure of compound ¥ : 9 IL Il (a) Ph—C—O—Ph (b) Ph—C—NH—Ph i (©) Ph—C—Ph @ edb, Ph » a 2 a — oor of ow at 79. Consider the following sequence of reactions OH x Cron y (OOH The end product ¥ has structure : OC! 00CH; - 0) 00HCarboxylic Acids and Its Derivatives 453 © 0 oO © —on 2s, (X); Identify product (X) : 9 Oo 9 9 O O ” Identify structure of major product : i Osi ® oe O QO l I O © o @ OH 82. Consider the following sequence of reactions 9 . Paro, _LiAlHy — A B ni Son 4 HO A+B C+D(CiHeO2) The structure of compound C is : ® as © pO © py com @ nC ’ -454 GRB Advanced Problems in Organic Chemistry for JEE 1, PhMgBr (excess) 2 ‘CH, The major product formed in the reaction is : h @ wry ©) HH . 5 PI © @ 7 OH ir 90 a4. oN th ABE Oy ° The structure of product (X): @ PAN, ©) Ne A, © ya @ aa 83. CH; “ @) © (@) A 4 ———> B (Major) HSO4 H,SO, The structure of major product B is : Hq aL Hs | Ph, (@) WA (&) Ph © Hs @ ‘NH: ‘CH . _ we ne ° H 88. yew 1. CHsMgBr (excess) . 2. RO The product of reaction is : oO @ wy © wore " 89. Which of the following compounds will not liberate ammonia gas on refluxing with aqueous NaOH? (@) CoHisCN ) Se ©) iH (@) nt w_ovy oO 9 90. + CH;NH, —> (P); Product P is : Hy HQ NHCH; HH @) (b) Nowy456 GRB Advanced Problems in Organic Chemistry for JEE © Mey @ cH, CH3 91. The major product of the reaction is : + 1.08 na® 2.190 9 ; t ce) p (b) mtn Gren I 0 uh " ©) Ph @ Ol, oO Ome if 93. oO +Cl—CH,—C—cl Fes, (1 Mole) Major product formed is : @ we Oa Onry © wr 0Carboxylic Acids and is Derivatives 457 o, wry Xn +kon 2, 4+B (a) oie and nok © whan and he @ md Be and HO 95. The major product formed in the reaction : OMe. phogBr (excess) Ph — Ye Ph Ph @) a ) ~ omy © wn 96. The products obtained in the reaction wh chy OF Products: (a) Ph—CHO and CHC1; (b) PhCHO and HCOO®Na® (c) Ph—CH,OH and CHCl (a) PhCOOPNa®, PhCH,OH and HCOO?Na® 97. Identify the reaction among following which is not stated correctly = ° ° Il - dl (a) Ph—C—O—C)Hs.+NH3 ——> Ph—C—NH) + C)Hs0H ll LiAlHy (0) Ph—C—-NHy 5-9 Ph—CHgNTfg (©) CH3Li 4 CH,OH > CH 00H, +LiOH Br OH 1H @ OL +Brn— ‘COOH Br ‘Br458 GRB Advanced Problems in Organic Chemistry for JEE 98, The major product formed in the reaction : s E10° + (COOEt a> 5 NO? : 9 OEt ‘NO, NO; ° Sy oe ) ‘OFt CE sO OF NO. t ‘NO; 99. Consider the following sequence of reactions (OOH 1.80Ch Zetightct oo 2.AICh Anhydrousy 4? Bs Identify B= Hy—CeHs “CLIO “OO “COO Oe 100. The major product of the reaction :Carboxylle Acids and Its Derivatives > 459 101, Consider the following sequence of reaction 6 4 OL, B+ CH)CH,COO” (Cutt OOH 1. KMnOyOH —_= B 2.450 OOH The compound A is : oT oy nore noe or yy a 102. + CHjCH,CH,CH;—NH,——> ‘X" Br ‘S® “Br Identify structure of ‘X”: ore >< ° x9 Se ® VX oo Xa x Bi ‘S’ Bi ‘S Br ‘S rf ir Br r Bro BF SS” “Br OPh OPh -Ph Ph Ph @ 0) tH @ Me q 104. or +CI-—C—Cl —> P;; Product P will be : ‘COOH 103. -460 | GRB Advanced Problems in Organic Chemistry for JEE ‘C—OCH; ° @ H® — EtMgBr (1 Mole) OH 28tMgaH® 170 a) —> ——__5 — —— @ 5) oo Gi) © ° OH EtMgBr (1 Mole) é °OH LAI, (ce) —> ——_—_> — @ di) Os ai) 9 HL Ph w7.€ \ ~__, —_, O° 8 Nalliq NH whe LAI, | CHs—C—cl ©) Oy @ Oe @Carboxylic Acids and Its Derivatives 461 9 LiAlHy wha Zn-HyACl ota Own o @) @ a) Q) NH; 108. + C —> (X) ; Identify structure of (X) : ‘0 O o Zoo oO lo “(er 9 ove uso 109. CoHs! ‘Hs + PhMgBr (excess) —"—> Product : pe @ moo ) when h fl - (©) Ph—C—Ph @ Ph oo boats Br / no. on 120, p ; Identify structure of product P : . - H30 Oo oO oO OOH of ‘OH OH @) (by © @462 GRB Advanced Problems in Organic Chemistry for JEE 111. Find out major product of following reaction : HC NaOCHs, 0 0 #20 oo @ =, ) 0 ‘O 0 COOCH; HCO. © ra (d) No reaction 0 Oo , OCH3 0 . 112. Identify the major product of following reaction : 9 oc IH ‘Ol @ cot ©) 0 Hi ‘OH 113. Find out correct sequence of reagents for following conversion : 6. 9 ° Il ll Ph—C—OH ~—> Ph—C—H (a) PCls,CH;MgBr (b) CH,N,, NaBH, ° ll (©) SOCI,, H,/Pd, BaSO, (d) CH, —C—Cl, LiAlH, ° Il cxtis 8a Mor #1120 114. (CH);C—C—CH,—C—O—C)H — > > Final product : BrCarboxylte Acids and Its Derivatives 463 Oo . oO oO tl ll (@) (CH,);C—-C—CH,—C—OH _(b) (CH);C—C—CH, oO oO oO ll ll CH, ne—e—e H—C—OC;H; (d) (CH;),C—C—CH, —CH, —Ph CH,Ph ° Uf 1.8001 115. Ph,CH—C—OH ————> ZENA Ph. Ph. cl @ =C=0 ) >c=c me ox Son i (© Ph—C—Ph (@) None of these 116. What would be the product of following reaction? Q . tee HMO ‘CH;COOH oO HO OH. ‘CH,COOH ‘OH CH; © oe (@) None of these He ‘CH;COOH 117. Which reaction occurs at the fastest rate? 90 o @ An +CH;—NH, —> (6) An +CH;—NH, —> 9 ©) AN +H,0 — (@) Aron +H0—464 GRB Advanced Problems in Organic Chemistry for JEE 118, Find oor final pact of otfllowing sequence of reaction : BuLi. 1,0 Chon Gree Hetn® un or aca CHsBr Hg”7/H oO AL, oO @) WC (b) CH,CH; 3 (© CHCH;~ CH; @ eS 119. Which is the major product of following reaction? Oo 0 CHy CH3CH; 6 oN ae Oe 0: () oe “oO (@) None of these a S0Ck, _CHOH 20, BH in pol:Carboxylic Acids and Its Derivatives 465 daeis7a MORE THAN ONE CORRECT ANSWERS i 1. Which of the following are correct methods for the preparation of propanoic acid? HBr = Mg CO) (a) H,C—CH=CH, ——>» ——5 —5 Ether Heo BH; THF = KMnO, (b) H,C—C=CH-——_—» H202,°OH HB Mg CO; (©) H,C=CH, ——> qo 5 Ether H80 (@ Hyc—cH=c—ca, —2 CH, ——> 5 > hed” CHs 2. Which of the following carboxylic acids do not undergo decarboxylation simply on heating? (a) F,C—C—OH (b) H,C=CH—C—OH OH © @ oO ‘oHo . 7 ° 3. Choose the incorrect rate of decarboxylation in the mentioned conditions : io] oO It (@) HyC—CH=CH—CH,—C—OH > H,C—CH,—CH=CH—C—OH (decarboxylation on heating) ° (0) F,C-—-COOH > Cl;C—C—OH (decarboxylation on heating with sodalime) © on{)-coon > rco(C))-coou (decarboxylation on heating we HySO,4) “atom Com H (decarboxylation on heating) 4. Which of the following ketoesters are not likely to have been prepared by Claisen condensation?”- 466 GRB Advanced Problems in Organic Chemistry for JEE 9 ‘ ll (a) CH;CH, —C—CH— C—OC,H, CH oO . il (b) Ph—CH, —C—CH—C—OC,H; CH; ° ° ] ll (©) Ph—-C—CH, —C—OC,H, ° i] (a) CH;—CH, —C—O—CH, —CH, —C—-0C,H, 5. Which of the following reagents cannot be used for the reduction of carboxylic acid to alcohol? (a) NaBH, (b) Hy and Pt catalyst (©) LiAIH, (d) NaBH,CN clo ll PICly | fl 6. RCH, —C—OH-— > R—CH—C—OH at Which of the following are intermediate species responsible for product? ° ° . il (a) R—CH,—C—CI (b) R—CH—-C—OH oO ll (ce) R—CH= so (d) ROC cl soe cl Ox ,Ph_H,0,H° #0, IYO OE Products oO Products are : @ HH) OH (e) @) : yy “YC Ph PhCarboxylic Acids and Its Derivatives 487 8. Find out correct orders : ® Agu? —0H> ——OH (Rate of esterification) ) a > >—c-oH > ym (Rate of esterification) 9 § 0 ®0 (9; 0 9 o © A, > fe | A Hoe (Rate of nucleophilic addition) il. (@) L. ona OH COOH " coct Sabai Which of the following reagents can be used in step-1? (a) AICI; . Cl AlCl; NaxCr07 Ph VN Sx ey ea: HO. ©) vis er (a) Xis ©) Yis CL 0 H. cr (a) Xis (©) Yis Hs cr Hs C (b) HCl oO oO COOH ‘COOH (Acidity) NH Step, “cOH (©) PCI, @) zis () Xis|__ (@ Yis[_ @ Soci, ‘COOH: COOH ‘COOH COOH468 GRB Advanced Problems in Organic Chemistry for JEE CH, A ° ef ye HO, yyy. ‘CH,COOH (a) xis oa © xT a) Xis is ‘CH,COOH OH OH {I © Xis CH; (@) YisCH;—C—H ‘CH;COOH CHy oO | TsCl KSH 13. Ph—CH, —CH— OH > X >: o CH, CHs | | (a) X is Ph—CH, —CH— OTs. (b) X is Ph—CH, —CH— OTs GO). © CH; CH; | (¢) ¥ is Ph—CH, —CH— SH (@ Y is Ph—CH,—CH—SH oO o) oO i] ols 14. Ph—CH, -O—C—CH, + OH X+¥: 18 (a) X is Ph—CH, —OH () X is Ph—CH, OH (©) Yis CHs—F—0° @ Yis CHy—e— oe oO : : R—OH 15. R—COOH + (CF,CO),0 —s ¥ ——9 ¥ +Z: @yY isk—G—O-R ) x sR—-C—0-F ch, q . oY sR-f—0-8 °O . (d) Zis CF, —-COOHCarboxylic Acids and Its Derivatives : 469 oO “O) +H)CN2—> X+Y: oO CHO @x wC) @) (©) CO @ ‘0 o, a, », DA wo | Ja Aggy oe WP (@) Lis ByHg, 1.01/01 (b) Viis Red P + HI ou Vis Jones reagent (@) His SOBr, SOCI, AICI: Zn—t 18. — = ty a Zz: 1. Ag 2 Oo xX 9 19. NN? Br ae SOCh y ‘CH3NH2 Zz 3.HPO ° 9 xin &) vis Ate oon . NH © Yis A, @ Zis An’ 20. _AA/©90H when treated with cone. H380, and heated produces 4. A HO ° when treated with base OH produces 8 and consequent heating produces C :470 GRB Advanced Problems in Organic Chemistry for JEE oO 0 @a Ch ©) Bis on oO. or won) 0 OH ° LiAlH, HBr oN: 30, CaO a0, A 21. CH,0, SS yoo (x) COOH @ ra[ =o ©) rs] eo © xis @ vs[ ro 0 ‘COOH 22. Which of the following can be used for the synthesis of benzyl acetate? (a) Ph—CH, —-OH + (CH,CO),0 —> ° ll hexanedioic acid ; Lo He (b) CH; —CH,0H + CH, —C—oH—> ° | Base (©) CH,CH,OH + CH, —C—cl—> ‘NaOH (d) CgHsCH,OH + CH,COOH —> 23. In which of the following reactions is benzoic acid the major product? ° - 1. KMn04, OH I ly + NaOH i (2) CoH sCH,OH (b) C5Hs—C—CH, 2", 2.Hj0® » Ho co, KMn0,, OH (©) CsHsMgBr——» (d) CHsCH;, ———5 HFO #80 24, Acid anhydride can be prepared by : Yi (a) CsH,COOH+cH,Ccoc! Pe, (b) C5H;COO°Na® + C,H ,COCI——> (©) CsHs;CONH, +CH;COO°Na® > . COOH “OCs COOHCarboxylic Acids and Its Derivatives 471 ° 25, The oxidation of which of the following compounds with KMnO,,OH/A followed by treatment of acid will give benzoic acid? (a) CoHsCH3 (b) C5H;CH=CH—CH, oO | (©) CoH yC=C—CH (d) CgH;—C—CH,OH 26. The intermediates formed during the reaction : cc, CHsCH,COOAg + Br; ——> CoH CBE oO ll (a) CsH;—CH, —C—0" () CgHs CHa © Br* () (\- 27. Which of the following reactions are used in the pseparation of alcohols? oO . LiAIBs (@) CHCH,Br+aq.KOH—> —®) A Oo X © Nae @ ca,cH,c1 23 3 ° PCls 28. ry ——> R’—C—NH—R N—OH Which of the following statements are correct for above reaction? (a) Reaction is intermolecular (b) Reaction is acid catalysed (©) It is the crans hydrocarbon radical with respect to the —-OH group that migrates. (d) The rearrangement is intramolecular 29. Which of the following statements are correct for benzoic acid? (a) Nitration gives o-and p-nitrobenzoic acid (b) Bromination gives m-bromo benzoic acid (c) The Friedel-Crafts reaction with CH, ECAC gives m-carboxy 0 acetophenone. (@) The reaction with oleum gives 3-sulphobenzoic acid472 GRB Advanced Problems in Organic Chemistry for JEE 30. In which of the following esters the a-hydrogen is acidic? ° ll | (a) H—C—0C;H, (b) O,N—CH, —C—OC,H, ° tl © Fac (@) Ph—CH, —C—OBt CN 31. Which of the following would be decarboxylates readily when heated? ° oO 90 COOH @ Kay (b) AK © Aor Ors; 3 ‘COOH 32. cy @), 4 NaBHe , 7 Conc, HBr W Bs 1. Mg, ether waavbul 2.C0» M 3.530? Pe—CH—Cal : CcooH ou CVAICI, @) Wis “wv (b) (¥) is Ph—CH—CH, ° 1: © rir @ msl 33. Compound (4) CsH,0, on treatment with aq. NaOH followed by acidification gives (B)CgH,0, which on oxidation gives benzoic acid only : OH oO H OH {a) Ais 5 (b) Bis 6 CHO os © Bis (Coon OH (©) Ais CHOCarboxylic Acids and Its Derivatives 473 34, Which of the following will liberate CO, on reaction with NaHCO3? @) Om, () CH;COOH ” ol OH © ol HO ‘OH ‘OH 35, In Hofmann bromamide degradation reaction oO I R—C—NH, + KOH + Br, —> intermediates are : (a) RCONHBr —(b) RNCO (© RNH, (@) none of these 36. C4Hy,N +HNO, —> CyH)90 (3° alechol) w) (0 will give : (a) carbylamine reaction (6) Hofmann mustard oil reaction (©) diazonium salt with HNO, (d) base insoluble product with Hinsberg reagents 7. Which ofthe following compounds wll give HVZ rection? COOH «Or ‘oH oD (©) coon oO) 38. In the given reaction i w i R—C—0H 2s r—C—o—cH, O will be : (@) CHN, (&} CH,OH/H® = (c) MeCOOH —(d) Me,S0, OH PhMgBr | 39. P—s*" cH, —C— Ph H°/H20 | Ph Identify structures of P: ll (a) CH;—C—cl (6) CH; —C—OC)Hs ° ] (©) CH;—C—Ph (@) CH,OH474 GRB Advanced Problems in Organic Chemistry for JEE 40. An ester 4 of the formula CsH,Q) on acidic, hydrolysis gives an acid B, which reduces Tollen’s reagent and an alcohol C, which gives iodoform test. Ester A can also be converted into alcohol B by reaction with excess of Grignard reagent D. Bs @) Ais wco-c (b) Bis H--C—OH Il Nom ] CHy (c) Cis HO—CH (@) Dis CHsMgBr Nous i NeOH 41. HyC—C—O—C=CH, + H,0——> X +¥ | HPO Ph X and ¥ are : (a) X isCH;—-C—O—CH,—Ph (b) ¥ is HCHO oO l (©) ¥ is H}C—C—OH @) Xis PhCH oO oo ao AIC, 4“Y X and ¥ are: HH OH OH Oo a) (b) (c) (d) all of these tl i PHCO 1 43. Ph—C—Ph eos, Ae bec Band C are respectively : ° I (a) Ph—CH,—OH (b) Ph—C—O—PhCarboxylic Acids and Its Derivatives 475 (c) Ph—OH (@ Ph—C—CH,—Ph 44, Which of the following decarboxylate on heating? o ‘OH @ oH ) ° 9 il COOH Ph Ph .C—OH © @ {oe ‘oa © ‘COOH Oo oO 45. Which of the following will form Ph—NH—F—CH, on reaction with aniline? Oo 9 90 (@) hf (b) AA oO ° o © Opoes HC CH ° 46, In which of the following reaction phthalic acid can be formed? Os KMn04 @) tno b) — CH oC OC V205 ‘CoHs 47. Which of the following compounds cannot undergo decarboxylation on heating? oO oS @ cre ) . ‘oO co oO COOH COOH © ®476 GRB Advanced Problems in Organic Chemistry for JEE 48. Which of the following reactions can be used to prepare lactones (cyclic esters)? OH ° on ‘OH oO ° ° oH g (© HO OH, ot, NIBH , 0 Hs 49. Which of the following will give cyclic products upon being heated or being treated by an acid? OH oO oO (a) AH, (b) ay Non H O on oO (c) ALK, (d) Non OH 50. Consider the following reaction sequence : 2CH3MgBr H°/H20 OH ore Oa Ar oO OCH. (a) Compound A can be AY said oO OCH ) Compound Aan te AN 4 Cols oO (© Compound B can be ‘OH (@) Compound B can be Ar 0 datetime LINKED COMPREHENSION TYPE i Passage-1 Compound A having molécular formula C;H;NO, can undergo reduction with Sn +HCL Treatment of 4 with KMnO, gives a compound B (C7H;NO,) which has lower boiling point compared to its other isomer. B when treated with SOCI, produces C.C when treated with CH,N,, produces D of molecular formula C,H,N 303. D when treated with Ag/H,O produces E.Carboxylic Acids and Its Derivatives 477 1. Find out structure of A : CH;—-NO; CH; "Hs CH; 10> (a) (b) © @ NO, NO, 2. Find out structure of C : gor oc coct OC! CH—NO, 0, @) b) © @ ‘NO? NO; 3. Find out: structure of E : CH,COOH CH,COOH H,COOH CH; 102 (00H @ (b) ©) @ NO NO, Passage-2 ‘An organic compound 4 on acid hydrolysis produces B, an amino acid. B on treatment with HNO, gives C.C on heating with conc. H,SO, produces a lactone D. A can also be synthesised by the reaction of cyclopentanone with HyN—OH followed by treatment of conc. H,S0,. 4, What is the structure of compound 4? @ o ol. © haw @l ja i 'NO2 H 5. Find out structure of D: R LYY @ ® WY © (@ Hood478 GRB Advanced Problems in Organic Chemistry for JEE LiAlHy 6. D———+ Product : H,0 HH HH @ w Kw NH, () Ho” YY (@ HY on Passages _ ‘An organic compound (4)C5H,0> reacts with Br, in presence of phosphorus to give (3) ‘ompound (B) contaive area carbon atom and yields (C) on yydrobromination. Compound (C) does not show geometrical isonierism and on decarboxylation gives an alkene (D) which on ozonolysis gives E and F. Compound (E) gives positive Schiff test but (#') does not. 7. Identify correct structure of A : OH 1H e @ ~y 0) ~ (©) +C—OH — @) None of these 8. Find out structure of D : oA oY y= w ne OY se CH, ot oe CH, 1H Oe a ‘CH,—OH Passage-4 —— H Z g 6 Ph—C—O—CMey + pre %o cme, CH3 |[s'» @ Ph—C—=0° CMe; ino H°+Me,C—OH=="Me;C—OH,Carboxylic Acids and Its Derivatives 479 10. Choose the correct case of hydrolysis for the following molecules : ° ° ° | CH, ~C—OCPhg CH CH c—O—CPh;, Pe C—O—CPh, CHs CH; @) @ ® ° ll CH,CH,— CH C—O Chi CH; (8) @ PogoRos (bt) P=Q=R=S (6) S>R>Q>P (d) Q>P>S>R 18 1 1,0 11. CH, —C—OCMe, ——> Produets : ‘Has S04 18 ° ° ll 18 (@ CH;—C—OH+Me;C—OH —(b) CH, —C—OH+ Me,C—OH Oo ll as ll (c) CH, —C—OH + Me ,C—OH (d) CH; —C—OH + Me ,C—OH 12. Which of the following will give the racemised product on hydrolysis in presence of H,S0,? | (a) Ph—CH—C—O—CH)CH), CH; © oO" (©) CHs: oon Op @ orb og @pom480 GRB Advanced Problems in Organic Chemistry for JEE Passage-5 The decarboxylation of B-ketoacids, 8, y-unsaturated acid and geminal diacid proceed through the formation of cyclic transition state in presence of heat. ° oO ° Il ll i CH, —C—CH, —C—OH—»CH;—C—cH, Mechanism : A 4 f HsC—Cy\ C=O—>CH;—C. + C=0 Ncu, S 2 (enol) ° I CH;—C—CH 13. Find the product of following reaction : OOH A = COOH OH 0 O "LIS ogo . ef ‘00H 14, Find the correct product of following reaction : ° It a HyC—CH =CH—CD,—C—OH——> (a} H,C—CH,—-CH=CD, (b) CH; —CH=CH—CHD, (©) H;C—C=CH, (d) None of these CHD, 9 00H 15. ‘oon 5Carboxylic Acids and Its Derivatives 481 0 oO i COOH \ @ ) /o HOOC’ HOOC f 0 . © @ ‘OOH 0 Passage-6 An optically active ester ‘F” have molecular weight 186. Hydrolysis of ‘F’ gives two optically active compounds ‘G’ and ‘H’. °G’ which is soluble in NaOH and ‘7’. “H?’ gives a positive iodoform test and on warming with conc. H,SO, gives ‘I’ with no diastereomers, When Ag salt of ‘G’ reacted with Br, racemic mixture ‘J” is formed. Optically active ‘J’ is formed when ‘H’ is treated with TsCl and then with NaBr. 16. Find out structure of F : “ @ f-o-en< ® AA CHy o AY @ oy 17, Find out correct structure of J : HH @ i 6 ~ @ 7X ork 18. What would be the structure of F if H gives negative iodoform test? @ i. ° Ag ) rar, Ag © ~ oN @ yew Passage-7 (Ops + Mg Es 4 ® + LA HO, 9 (cat0)482 (GRB Advanced Problems in Organic Chemistry for JEE B+PBr, —>C C+NaCN —3D A D+H,80, —> E (CoH,,02) E+SOCl, —+F F+AICl, —>G LiAIHg | HyS04 aes G—H q 19, Find out structure of J : a @le Ie ©) OD OH 20, The compound (F) must be : a cl ‘Oo y 21, The compounds D and F must be : CN oa oC] “QD 1: on we | © < | and Cie a ‘CN @ | and Cite Passage-8 ‘The Hunsdiecker reaction is believed to proceed by a free radical mechanism and involves the formation of an acyl hypohalite. ° - oO A. R—-C—O—Ag +Br, —> R—C—O—Br +AgBrCarboxylic Acids and Its Derivatives 0 0 ll Ie. B. R—C—O—Br —> R—C—O+ Br ° I C. R—C—O—> R* +00, ° - 0 I I D. R++R—C—OBr —> R—Br + R—C—O* I a 2 22. Ph—CH = CH—CH— C—OAg —T Product CHy The major product is : (@) Ph—CH= oe H—Br CH3 Br | (6) Ph—CH—CH=CH—CH, Br (c) Ph—CH= C —CH,—CH, (@ Ph—CH= CH—CH—CH,Br CH CH;0 ves : 1 ll Br 23. Hye C—OAg —> Major product : CHy CH, Hy (a) Hx3C—C—CH;—Br (b) HyxC—C—Br 3 Hy is CH3CHy | (©) HyC—=C (d) HC —F— CHa CH)CH;484 GRB Advanced Problems in Organic Chemistry for JEE 24. The rate determining step is : (a) Step 1 (b) Step Tl (c) Step II (d) Step IV Passage 9 ° o 6 ° Co Cy cen 2S on oO 9 HO. D e OH, pO E Me2S © 25. Find out correct combination of ‘A’ : Oo Oo > dl . i (a) C,H, 0,CI—C—0C,H, (b) C,H, 0,CH, —C—Cl oO , © GH, 0,CH;—C—00,H, (@) B® /H,0,CH;—C—0C,H, \ 26. identify *C” : (a) C)Hs 8,cH,CH,—1 (b) H® /H,0, A (©) /\MgBr, H®/H,0 _ @ None of these 27. Name of the reaction which converts F into G : (a) Cannizzaro reaction (0) Claisen condensation (©) Aldo! condensation (d) Reformatsky reaction (EGRET matrix matcu TPE Tl 1. Column (1) Column (1) 3 (a) HOOC—}+—COOH _4 , P. Diastereomers H-—D 7 Ph COOH 1 1 D--+—-H |. AgOH/A wo (b) Wye 2 Bec Q. Racemic mixture Ph CH; 4 (©) Hooc—+—cooH 4 R. Optically active Et aCarboxylic Acids and Its Derivatives. 485, 4 0) PED C—OH —> oO CH; oO 2. Column (1) OH Aa (a) Ph—CH—COOH > A ) Ph— FIC —COOR—+ OH A © Ph—CH--CH,—CH;— COOH OH A (4) HO—CH, —COOH —> 3. Column (1) . HPO (a) HyC—C—O—CH,CH, ———> ° H°/H,0 (b) H,C—C—O—CPh, ——> Ph O ll H®/H,0 | (©) Ph—C—C—O—CH, ——> Ph e OH/HZ0 (d) CH,CH, —C—O—CH, ——> 4, Column () 0 (a) Ph—-C—NH, —> Ph—CH,OH oO )H He &) —_ Ph Ph (c) Ph—CH = CH—COOH 5. CO, will evolve Column 1) P. Cyclic Q. Exhibit geometrical isomerism R. Can be optically active 5. Lactone Column (11) P. Bimolecular Q. Unimolecular R, Alkyl cleavage S. Acyl cleavage Column (i) P. B;H,, AcOH, H,0 Q. LiAlH, R. Hp, Pd BaSO,486 GRB Advanced Problems in Organic Chemistry for JEE 3) oh—¢—a ° 5. Column (1) H a @ PH _quso' ® ° on CH SOH/A® 0 oOo” oO wv & 0 6. Column (1) oO (a) —C—OH —+» —CH,OH ° | (b) -C—Cl —+ —CH,OH Oy 1, (c) —C—OR’ —» —CH,OH @ >o— R-CH,OH 0 S. None of these Column (1) P. Hydrolysis Q. Esterification R. Saponification S. Acid Base reaction Column (1) P.LiAIHy Q. NaBH, R.B3H,/THF S.H,/Pa _INTEGER ANSWER TYPE PROBLEMS Ht ~ 1. Examine the structure of following compounds, and find out number of compounds that will undergo decarboxylation in presence of heat, O90 2 0 9° t - J, OH , ‘OH ° . ‘OH ‘OHCarboxylic Acids and Its Derivatives - 487 COOH COOH HOOC, OR OL ae ‘COOH ‘COOH 2. How many motes of NaOH would’ be required for complete neutralization of following compounds. f oH oO HO— HO,S HO 0 3. How many moles ofCO, will released when following compound treated with heat, HOOC, HOOC ‘COOH ‘COOH 4, Examine the structural formulas of following compounds and find out how many compounds can show Claisen condensation reaction, aoe > rhe , oe OC:Hs OCs t Rt oct Me Oyeti 5 an pr HOR “Gaon Cystic product, ‘C— Ost ‘At what value of ‘n’ the formation of six membered ring take place. ° . ‘XCCH;MgBr 7 2 ” 6 C3 ge HO AN OF, Find out value of “X’.488 GRB Advanced Problems in Organic Chemistry for JEE 9° Il ll cas8n2 7. CH;—C—OC,H, +CH;CH, —C—OC,H, oF How many different condensation products would be form by above reaction. 8. How many of following esters show Ajs-1 hydrolysis (Acid catalyzed, unimolecular and alkyl-oxygen fission ester hydrolysis) oO CH; oO CeHs i | i! | i _'! CH; —C T CH CH “C06 Cots, C-—-O—CH, Coll Pe t hs beo-ery + 0; c—0—cH < ° CH; 0Carboxylic Acids and Its Derivatives mn === Exercise-1 : Only One Correct Answer -t L© 11.) 22. (b) 31. 0) 42. . ). Level-2 Ir) -2.(0) “3. (a) A) Bb) GB) 7) BCC) 9 Ca)" 80. ) V1, (bY 22. (c) 13. (6) 14. (@) 45. (@) 26. (C) 17. (b) 18. (b) 19. (b) 20. ()) 2d. (by 22. (a)' 23. (6) 24. (6) 25. (a). 26. (d) 27. (b) 28. (c) 29. (@) 30. (6) 31. (c) 32, (b) 33. (by 34. a) 35. (b) 36. (d) 37. (Cc) 38. (b) 39. (a) 40. (c) AL. (a) 42. (d) 48. (b) 44. (0) 45. (c) 46, (Cc) 47. (b) 48. (b) 49. (2) 50. () BL. (c) 52. (c) 53.-(a) 54 (a) 55. (d) 56. (d) 57. (@) $8. (d) 59. (c) 60. (0) F61. (©), 62. (b) 63. (c) 64. (b) 65. (b) 66. (a) 67. (b) 6B. (6) 69. (a) 70. (A) 7A. (b) 72. tb) 73. (a) 74. (c) 75. (d) 76. (a) 77. (c) 78. {a) 79. (b) 80. (a), 81. () 82. (b) 83: (a) BA. (b) 85. (c) 86. (a) 87. (c) 8B. (db) 89. (4) 90. (b), 91. () 92. d) 93..(@) 94. (b) 95. (c) 96. (d) 97. (C) 9B. (a) 99. (b) 200. @@) (c) 102. (c) 103. (d) 104. (b) 105. (a) 106. (b) 207. (c) 108. (4) 209. (2) 210. -_(@) 142, (b) 113, (©) 114. () 145. (a) 126. (b) 147 (a) 118 (c) 139. (6) 120. (eo) 2 6d 3 he) GS. (abd) B (c,d) @O 8 bo) % Cd) . ac,d) 42, (a,c) 42, (ed) @o 1 (4) 15. cd) 16. @d) 17 (@,b,¢,d) 18. (@,b,d) (@,c.d) 20, (a,b,d) 21. (ec) 22, {a b,c) 23.(2, b,c, d) 24. (a,b, d) 5. (a,b,c, d) 26. (a,b,c) 27 (a,b,c) 28. (b,c,d) 28 (bd) 30. (b, c,d) 31, (4d) 32. (@,c.d) 38. (a,b) 34 (Oc) 35. (a,b) 36. (@, b,c) 37, (b,c) 3B. (a,b,d) 39. (@,b,c) 40. (a,b,c) 41. (cd) 42 (0,0) 43. (ac) 48. (2,b,c) 45. (a,b, d) 46. (b,c,d) 47. (abc) 48 (a,b,d) 49._(a,b.¢)_50._ (a,b,c). sh (c) 2(b) 30) 4 (@) 5.) 6) F.0d) BC) 9. (b) 10. (0) 11. (B) 42. @)- 13. (@) 14. (a) 45. (c) 16. (@} 17. (b) 18.) 19. (©) 26. (b) ._ (b)_ 27. (c)490 GRB Advanced Problems in Organic Chemistry for JEE Exercise-4 : Matrix Match Type L @MOPRS; )9P.R,S; ©9908: 90,8 2. @)9P.QR: 0); SOFP.RS: OaP §. @P,S; O)9O,R; ©>S; < GPS 4. @3S; 0) 0; Oas Mor 5. @)>S; 90; o> Mor 6 (a) PRS: ©) +P,0,S; > P.RS; D> PRS Exercise-5 : integer Answer Type Problems Ge 26 @_ Load 000.8 (XTSROEISJ] ONLY ONE CORRECT ANSWER (Teta I 1. Acetamide is treated separately with the following reagents. Which one of these give methylamine ? (@) PCis (b) Sodalime (© NaOH +Br, (d) Hot concentrated H2SO, 2. Reaction of RCONH) with a mixture of Br, and KOH gives RNH3 as the main product. The intermediates involved in the reaction are : i (a) R—-C—NHBr (b) R—NHBr {I aa | () R-N=C=0 @ R—C—NE ‘Br 3. Which is the best method of preparing 2° amine ? i (a) CH;Ci+ NH; —> (b) CH;CI Sa/HCL t (© cHjc1- 2S (€) CHyNiy LESMON, seven, 4. Bthyl cyanide (A) can be converted to ethyl amine (B) by : Hj0° _NHy/S (ay ASH gs (oy 4, Mle, ora LiAIH, () A—8 {d) both (a), (¢) are correct 5. In Gabriel synthesis, amine is always : {a) aliphatic primary amine (b) aliphatic secondary amine (©) aromatic primary amine (é) aromatic secondary amine 6. In Gabriel synthesis, balide may be : (a) benzyl halide (b) allyl halide {c) both (a) and (b) (d) tertiary alkyl halide . CHCI,/Ale. KOH 7. In the given reaction sequence CgHs—CH,—NH, ———~—— HOMO Fy. yw be: | \ | x1, 1492 GRB Advanced Problems in Organic Chemistry for JEE (@) CgHs—CN () CgHsNC (© C6Hs—CH,—NH, (@) CgH3—CH,0H Br,/OD~ 8. Predict the nature of the product PCgHsCONH, —2——-9 P- (a) CgHsNH) (b) CeHsNHD (©) CgHsND2 (6) All of these 9. Which of the following statements is not correct ? (a) Aliphatic amines are stronger bases than ammonia, (b) Aromatic amines are stronger bases than amnioni (©) The alkyt group in alky! ammonium ion more stabilizes the ion relative to the amine. (@) The aryl group in aryl ammonium ion.less stabilizes the ion relative to the amine. 110. The correct sequence regarding base strength of aliphatic amines in aqueous solution is: (a) R3N>R,NH>RNH2>NH; —(b) RyNH > RNH >R3N>NH3 (c) RZNH>R3N>RNH, >NH3 — (d) RNH2 > RyNH> R3N > NH3 11, Decreasing order of basicity of the three isomers of nitro aniline is : (a) p-nitroaniline > 0 - nitroaniline > m- nitroaniline (b) p-nitroaniline > m- nitroaniline > 0 - nitroaniline (c) m- nitroaniline > p- nitroaniline > o- nitroaniline (a) m- nitroaniline > o- nitroaniline > p- nitroaniline 42. Strongest base is : NHp i (a) NH CNH» H)N HN. @ Yg-on HN HN 13. Which is the best leaving group ? (a) No (b) OH (©) NH> (@) CH3COO™ 14. Which is most volatile ? (@) CH3CH,CH2NH (b) (CH3)3N CH3CEa O} NH (d) CH,OH HC 15. Which one of the following is used as phase transfer catalyst ? (a) Primary amine (b) Quaternary ammonium salt (©) Tertiary nitroalkane (G) Tertiary amineAmines 493 16. Which of the following is most basic ? \eMneereetes N H 17. Predict about the relative boiling point of the following two amines. wo ¢ NCH ay uct yn (a) Boiling point of 1> I (6) Boiling point of I> I (c) Both should have equal boiling points (d) It can’t be predicted 48. Carbylamine test is performed in alcoholic KOH by heating a mixture of : (a) chloroform and silver powder (b) trihalogenated methane and a primary amine (c) an alkyl halide and a primary amine ‘ (d) an alkyl cyanide and a primary amine 19. Which of the following statements is not correct ? (a) Replacement of halogen by NH; in alkyl halide is a nucleophilic substitution Teaction (b) Aryl halideds show more reactivity as compared to alkyl halides in the replacements of halogen by the NH group (©) During the replacement of halogen by —NH} group, ammonia is taken in large excess so as to avoid the formation of 20 and 30 amines (d) Tertiary alkyl halide generally produces alkene instead of the replacement of halogen by NH group . 20. Which of the following statements is not correct ? (a) Primary amines show intermolecular hydrogen bonding. (b) Secondary amines show intermolecular hydrogen bonding. (c) Tertiary amines show intermotecular hydrogen bonding. (@) Amines have lower boiling points as compared to those of alcohols and carboxylic acids of comparable molar masses. 21. Which of the following amines from N—nitroso derivative when treated with NaNO, and HCI? (a) CH;NH (b) € \-wn R | | R (Oty 6x : \R 22. Hinsberg’s reagent is : : (a) phenylisocyanide (b) benzensulphonyl chioride (©) p- toluenesulphonic acid (d) 0-dichlorobenzene494 GRB Advanced Problems in Organic Chemistry for JEE ® 23. Thermal decomposition of \ ine 3017 gives : (@) Swe, +MeOH () C> NMey +MeOH © € Sve, +CHy (@) no reaction o | 24. Conner yp (ects + (CH), NOH.This is called : (a) Hofmann elimination 4(b) Cope reaction (} Saytzeff reaction (@) Carbyl amine reaction 25. Cope reaction is : (@) Sy1 intramolecular (b) Sy2 intramolecular (©) &; intramolecular (a) Ep intramolecular 26. Which of the following is Hofmann mustard oil reaction ? (a) Reaction of primary amine with CHCl, (b) Reaction of primary amine with CHCl, +KOH (©) Reaction of primary amine with CS + HgCly (d) Reaction of aromatic amine with iodoform 27. CqHN + HNO —> C4H oO, X will give : (&) (a) Carbyl amine reaction (b) Hofinann mustard oil reaction {¢) Diazonium salt (as the intermediate) with HNO» (4) None of the above * 28. In the Hofmann-Bromamide rearrangement intermediate compounds are ; ° ho | (a) R—CONHBr : ) [fn Na* (© R—N=C=0 (A) all of these 29. Which one of the following amines will not give benzoylation reaction ? (@) CeHs —NH (>) ( \-a @ ( yocns (a) CgH; —-NH—CH,Amines 495 30. Which of the following compounds can from alcohol with NaNO, /HC1? HC Nia (@) NH (6) H3C— CH ‘CH; cH; () CH; —CH,—NH, (a) All of these 31. Which of the following will not react with CS» ? (a) CgHs—NHa (b) CHs—NH—CH, (©) —H @ (» R 32. In the given reaction CH, —CH) —NH— CH,— CH — Cl (@) CHI (excess) -XJis the . oduct :[X] will be : Agora? EX Tis the major produet ; [ Jwill be (@) CH) =CH, * () CH) = CHC! (©) 1: Lratio of (a) and (b) (6) CH;—CH, —Cl 33, Predict the nature of P in the following reaction. Me ,CCH,NH, !%9, p (main product) (a) Me;CCH,OH (b) Me,CCH== CH) (©) MeC(OH)CaHs (d) MeyCCH,NH(NO) 34. —— X. Here X is : ‘0 ‘OH N N H H 3s. [>On ENN: pps: @ >a (b) j>—a © || >—OHn (a) none of these496 GRB Advanced Problems in Organic Chemistry for JEE 36. Which of the following is an enamine ? oO Oy OHO © Cem, (dd) C )-necor{) 37. Which of the following amines will react with cyclohexanone to give enamine ? (a) CH3NH (b) (CH3),NH ol @ CO N N H H 0 38, The intermediates obtained inthe reaction ,¢% —S, p—Nay are: a “Hea” _— (@ R—-C—N—N=N (b) R—N 0 (c) R—CNO (d) none of these 39. Compound [¥]C4H) N reacts with p- toluene sulphonyl chloride in aqueous NaOH to give a solid, The compound L¥ Jis : (a) CH; — CH) —CH, —CH, — NH} (b) me—cn —CH)—NH CH; (©) CH;CH) —NH—CH)—CH, (d) H3C—CHy NCH CH 40. Cyclohexanol can be converted into cyclohexylamine by following two routes, Which of he following methods is expected to give good yield of cyclohexylamine ? _K:€20,, NUH, oC nse post m oH NH, | (0) both are equally suitable (@ neither of the two |Amines 497 “AL. Which of the following will give unsymmetrical di-substituted urea after reactign with CH;NH2 ? (@) COCl, (b) CH3CH,NCS (¢).CH3CH,NCO (4) all of these 1. Which of the following compounds is an amine? @ Ch ®) Ch on® OO @ Ch WN 7 ! | O° 2. Which of following compounds exists as non-resolvable racemic mixture? NH @ Y (by Aw © AV @ Ay NH) | | H H 3. Which of the following compounds loses optical activity due to pyramidal inversion? oe ony ®) 7" oy @ ys Ol NA Hp, Ni 4A, AgCN, 4 Ha Ni, The final product (B) is : H MAN OMAN, ONY © An, | H °° 1.KNH,DMF 1. KOH, 4 5 NH 2. PHCH)Br 2.80 oO The end product B of the above reaction is : Aw Ph () Ph’ “NH ORY © Wm a498 GRB Advanced Problems in Organic Chemistry for JEE AgCN ‘NaOH, A 6. CH;CH)Br > A ao? B: (B)is : 3 (a) CH;CH,NHCH3 (b) CH;CH,CH,NH, (©) CH;CH.NH, @ Ay? H NH, 6 CHCl, KOH LiAINy 1. a x is: A H,0 (a) Ph—N—CHls (b) Ph—CH-—NH) H O° Il ® 6 © Ph—N—C—H (@) Ph—N=C H 8. The. major product formed in the reaction : ae ae PETSOH (Trace), (Trace) CoH, A ,OH. (OO 9 N O i © Ons 0) e C a 9. One. itl, y CHM, H,0,, OH © Hy, Nid The final product (¥') is : N: @ py” | @ ww © pw wA HAmines 499 10. Among the following compounds which one will produce a Schiff base on reaction with cyclopentanone? | Na cn © Cy — @ or 3 11. In which of the following reactions does the amine behaves as an acid? (a) (CyHs)2NH+ HPtCl, (b) CH;NH, + H,0 (©) (Me,CH))NH+n—C4Hgli——(@) (CoH) N+ BFS 12, Consider the following seguence of ects: ie oe och 1, CHp==CH—CH)Br 1.CHa=CH—OMB, p 2. Inés ry The end ve @B)is: p ‘e OH {a) Ch ) ion 1} he (d) Cw 13. Consider the following sequence of reactions : Br, (1 Mole 1.KCN ess) HC = CH—CH = cH, PEO MO, 4 SEO 5 CCl, 2. Hp, Ni HCH; The end product (B) is : (a) HyN—(CH )y —CH = CH—(CH2 )2—NH (b) HyN—(CHp)6 —NH2 (c) NC—CH,—CH = CH—CH, —CN (@) H,c= CHC (CHa)2 NH NH, CHy Br +KOH — 1. CH;I (excess) 14. HyC—CH, —CH— C—NH — il A 2. AgOH A . ° The major product (B) is :500 GRB Advanced Probiems in Organic Chemistry for JEE CH3 (2) CH:—CH,—CH=CH, ® CH;—CH;—CH— an 3 Cth | CHs (©) H}\C—CH=CH—CH, (d) HjC—CH,—CH—N: cH b 1. Br) (1 Mole), CCl. 1. CH3I 15. EER OMI CO, 4 CNC) aioe product) 2. (CH3)2NH (excess) 2. AgOH, A ‘The major product (B) is : NMex (a) &) Me NMez oy (©) O @ ‘OH 16. Consider the following sequence of reactions : oO CH, Id HOC Cm =an—me, a B)is: CH; 9 9 @ seu © cr, HO NH AAC. - © HOHC—f—CHte Nt @) Ce Nh a CHy 17. The major product (X) of the reaction is : OCH3 BN, x ON 4 0Amines 501 @ morn N’ | H 18. Which of the following compounds does not liberateN » on treatment with HNO? oO i] (@) HyC—C—NH, © >-NE 19.. The product formed in the reaction is : os Hy o-Z »\n | CH; a © Hy0—N—(CHia)s CH H () wre oO (b) HyN—C—NH @ HyCN— CH H 1. Liat, 2.120 »© CH; @ HyC—H (CH; )s —CH0H H 20. The major product (B) formed in the reaction sequence is : dil. NaOH aa (a) lcm I 7 (©) Ph—-C—-N OO. VY ma PhoO—Cl, 4 1. CHiMebs & 2.H3®0 Ae (b) Ph—-C—CH OH ‘CH; Lo (@) Ph—C—N O | Vy CH; -502 "__GRB Advanced Problems in Organic Chemistry for JEE 21. An organic compound (4) on reduction gives a compound (B) which on reaction with CHC1, and NaOH form (C).'The compound (C) on catalytic reduction gives N-methylaniline. The compound (4) is : @ No, & ©) (Oss i © (Opt @ (Oi, 22. The major end product (B) of the reaction : ( \ HCI A 1. NaCN (excess) B _ ZnClz 2. Hy, Ni . cl © 409°. ©) ye VV BN A 7 (@ Ho“ wu, ‘NH2 23, Which one among the following is expected to form a secondary alcohol on treatment with HNO»? NH NH. NH x (a) Ay (b) ) NY @ N-4 CN oO 24, The end product (B) of the reaction sequence : ° {| Ph—C—Cl LAI, (C)Hs—N—CH; ————5 AB | ‘NaOH H,0 H Hy Hy (@) mtd’ () pec 2H aHs ou A Mh © Ph—CH— (@) Ph—N. Hs Hs 1. Bry + KOH, A as. ( N-H e The product of above reaction is :Amines oO 0 tl @{ Nor oro ©, Yn OC 8 NH ° h 26. ‘The major product (X) of the reaction is : OH cy ANS, NH; dil, HC) OH OH Kon OC )=0 © oe, ok 27. The major product of the reaction is : NH) NaNO2, sy dil. HCI, 0°C. Ni : Nc? : Nt N 2 S TO@uC@noeryod ye on ‘NE 28, The reaction of p-aminophenol with one mole of acetyl chloride in presence of pyridine gives : Lon, HO OH NH NE, "NER O 29, The major product (X) formed in the reaction : CHy (OOH 1.NGH, HySOq 2. 30°, 8 x504 GRB Advanced Problems in Organic Chemistry tor JEE : . oe Wl fy ; ® kw ory ce NH; Oo Oo (yu oC Se b II 0 30, Which of the following is the strongest Bronsted acid? N, @ Cot ) (Sun, © ts @¢ New 31. Which of the following is the strongest Bronsted base? Q O ‘N, @ Cys ® Onn @©€ Sn @f Yu 2. Which of the following is the weakest Bronsted base? 33. Which of the following is strongest Bronsted base! Ss @ (7 O) Ox fi oe 1H 34. For the following compounds, which is the strongest vase and which is strongest acid? NH,” oy tL oe CW € > Ton 1 1 ul Vv 0Amines . 505 {a) I= Strongest base, I = Strongest acid (b) IV = Strongest base, III = Strongest acid (c) Ill = Strongest base, IV = Strongest acid (a) IT = Strongest base, IIT = Strongest acid 3. Which compound is the likely product from following reaction? NH + CH; (excess) —+ Hs es @ Cor, o(X © — @{ )-cH cH, Hs 36. Which of these is the strongest base? Et, ~~ @ EDN (b) C 1D © New: NUE BY N’ — 0 37. What sequence of reaction would best accomplish the following reaction? =n, CH, (a) LiAIHg, 3CH31/AgOH, A (b) LiAIHg, P05 /A (©) 20% HyS04/A, P,05/A (d) Hp, Pd - BaSO, 38. What is the likely product from the following reaction? NZ N 1.10) 2h OH 9 YL OD 0 39. Repeated Hofmann elimination reaction (exhaustive methylation followed by heating with AgOH) will often remove anitrogen atom from an amine molecule. Which of the following compounds is the likely product in this case? Hofmann elimination ofS ox 0 6 ae506 GRB Advanced Problems in Organic Chemistry for JEE 40. Only one of the following amines will lose its nitrogen atom as trimethyl amine by repeated Hofmann elimination reactions : y CH yh © Si @ 'N: 41. The nitrogen atom in each of the following tertiary amines may be removed as trimethyl amine by repeated Hofmann elimination. Which of the following amines requires the greater number of Hofmann sequence to accomplish this? ye N(CHS)2 ys 42. The Hinsberg test of aCsH,4N2 compound produces a solid that is insoluble in 10% aq. NaOH. This solid derivative dissolves in 10% aq. H,SOq. Which of the following would best fit these facts? H 7 | \AZ @ n wn OOCAA, © ax oOnn, DYN N 74 43. What set of conditions would be useful for preparing a.2° amine? (a) 2° R—Br + NaNHz (b) 2° R—Br + NaN3, H)/Pt (¢) 1°R-—-NHp + 1° RCHO, Hand Pt (4) 1° R--Br ‘N°, H30/A . ee , 0 44, Which of the following amines reacts most rapidly with i On O—C—CH;?Amines 507 45. Consider the following sequence of reactions ; AgOH NH, BR*KOH, , CHaltexcess), _AgOH NaOH a Identify product C : @ 7 ) Sh \ / N, oO \ ee) 0X 46. The major product formed in the following reaction is; @) (b) H;C—CH=CD, (c) HXC=CH—CD; (d) HyC=N—CH3 47, The product formed in the reaction is : 2 NE + Br CH;0°Na‘ CH,OH t NH NH—C—OCH; am508 GRB Advanced Prabiems in Organic Chemistry for JEE Identify B : COOH OOH OOH %, OO, oO © on @) 2g Oh, Oy 9 WN-OH 804 49. > A> B (Major) The final product (8) is : YH ® oe © OCC, ll oO 0 OMS @ XN H 50. The final major product of the reaction is : OH | NaNO, + HCI Ph—C— CH— CH; ——+> Ph NH, PI x @) wll Sener th Pht 9 OH OR Awe | ©) Ph—-C—CH (d) Ph—C—C—CH Ph Ph CH; 51. The major product of the reaction : Hi NH Nano. + HCI —sa5Amines CH,Ci @ cr of (©) o @) 52. The end product of the following reaction is : p-TsCl A NaN; B LiAlHy Pyridine 1:0 PhO ‘OH Cc PhO NE2 PhO NH. (c) JA @ ny, HO NH) HO ‘NH NH KOH 4g NWN, Bac 2. Br—CH)—Cly_F oO The products (B) and (C) are ; 9 2 NH @ Or }) 4.NEy—-CHy—CH)—Br ~ NH AT NTE eniy—cry—ci,—F OT TU xo —ce QO 0 \=00 of Cc NE 4+ NH;—CH)—CH,—F °° i a NE2 + NH, —CH,—B oe) OME NCH —CHy— Br510 GRB Advanced Problems in Organic Chemistry for JEE 54, Which of the following compounds will react with cyclopentanone to form an enamine? . 2 ° oC ) |. © Lae oy "QD eG eG H H 55. Predict the major product ‘X" in the following reaction : HH HNO2 ys NH ° HH Ht HH © WK oXK wo Ak @ JK on 56. ao (A) ; Product of this reaction is : OO) oO) 57. wn KOBE, 44, 8: Compound Bis :Amines sit (a) (b) {c) CO @ 59.[ Nr CXOH2* Be, 0). Product (X) is : 0 0 9° ° (a) HH 0) ° of @ —Br NH) ‘NH, 0 h FO or 60. Hy KOBE, (yy ; Product (¥) of the reaction : Ph Ph Pho (a) HsC—-NH, (b) HEN, (©) Mixtureof = (d)_ HAC H CH; (a) and (b) N NZ A . . 61. aaron? Os Find 00): 9 | : CH; t @ ©) oar ‘ 9 e i © @ Chon 62. Predict the product of following reaction : cl512 GRB Advanced Problems in Organic Chemistry for JEE Ts @ o wy wha adn a opr, 0 Neg? OOF ¥ re H Ts Ts Hy, 4 3 Hl Pb (OAC). HOA os 63. a Ks 1 NH Final product M is : O @ Ch ® ©) O @ O > WS Lp WN ona crcn,6 aC Bray CHBCHRO Final product ‘O” is : NH) @ Cr ) cry © NO: (d) Ore, oO ‘oO OCH:CH, 65. Consider the following diazonium ion : wes{O)—ve ox{O)- Ne - o meo{O)—no we-{O)-nF R ‘s The order of reactivity towards diazo coupling with phenol in presence of dil (@)P>Q>R>8 © Q>S>R>P ©) P>R>S>Q (a) S>R>Q>P it Sp, Br, 66. Reaction| Ph—C—NH, ——"> 4 oO ll 6H, By, Reaction I! Ph—C—ND, ——>> 8Amines 513 Products A and B are : (a) Ph—NH, and Ph—ND, (b) Ph—ND, and Ph—-NH; (c) Both Ph—NH, (a) Both Ph—-ND, 67. An organic compound (4) CyH,3N dissolves in dil. HCI and releases Ny with HNO, giving an optically active alcohol. Atcohol on oxidation gives dicarboxylic acid, which on heating form anhydride. The organic compound *”is : Or Oy NH; © NH @ (Ol cus CH; ‘The final product is : 0 . Hy ) o~ O) or Cs oy CH; © aa @ om CH; CH; 69. Identify “inthe following sequence of reaction 3 N= ne LUN, CuCN P LiAIHy Q HNO xX (a) Benzoic acid (b) Phenyl acetic acid (©) Benzyl alcohol (d) Benzamide 710. Which sequence of steps will be able to produce 3, 3’-dinitro-biphenyl from benzene? (a) HNO,/H,SO,,Cl,/FeCl,, Na/ether . () Cl,/FeCl;, HNO; /H,80,, Na/ether (©) Cly/FeCl;, H,SO,, Na/ether (@) 1,/HI03, Cl /FeCl;, CgHsNO,514 GRB Advanced Problems in Organic Chemistry for JEE 71. 1°, 2° and 3° nitroalkane can be identified by action of : (a) HNO, + NaOH (aq,) (b) CHCI, + NaOH (aq) (©) HNO, + NaOH (aq.) @ CHCI, + KOH (alc.) 72, A compound‘ X" when reacted with PCI, and then with NH, gives‘Y’. When‘¥" treated with Bry and KOH produced ‘2’, Z on treatment with NaNO, +HClat0°C and then boiling produced ortho-cresot. Compound * X” is : (@) o-toluic acid () 0-chlorotoluene (©) o-bromotoluene . (d) m-tohuic acid ar Corton Oy For such kind of diazo-coupling reaction the suitable substituents P'and S are respectively : (a) —NH) and—OCH; (b) NO, and—C—H Oo 4 (©) —NH) and---NHCH3 (d) —OCH; and a ‘0 CH3 Hy (CH; Woe Sv 75. The final. product B obtained in the reaction is : CHCHe 07 A CH3CH;—N > 4—> B+ HC=CH, CHCA, CHCl. OH . @) ‘wt ©) (HC=CH, CH;CHy CH,CH, (c) H;C—CH=CH, (d) CHyCH,—N—OH HCH, 16. HaN—OH_, y _HxSO4 , y pH=4.5-5.5 a Find out Y of the reaction :Amines 515. (@) N—OH ) ‘N—-OH i i NP NP oy oly 8 7. O—CH)-—CH=CH A -SHAHCL, yp NaNO2+HCl, ( a HPO, A NO, + : The compound C is : . HH OH : ly CH=CH ) oOfO ‘Hy — CH=CH) ~~ HH Ou © : @{O NO 78. (NHaS. 4 NaNOo + HCl B i NOz ‘The compound B is : re) “GO, “So @ a, oH. - 1.NaNO) +HCL 79. 2. HyPO2 NOz NHGRB Advanced Probiems in Organic Chemistry for JEE FTC. 80. identify the final product of following reaction NaN3 Ha,Pt a dioxane, HzO ool oct! oC oO, 81. Consider the following sequence sot ction: : NH 1. Bry + KOH cH, ‘The final product is oO @ J ®) Co oO oO O oO © Aa @ Oo 0 82. ‘Hp, Pt, cn HP Oo ‘The product can be given as : . ee OD. 0, CHa -NEa ONE, . NH ¥ H 83. Ina sct of reactions propionic acid yielded a compound D. ol A SOCk , p NES KOH D °

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