ceNII Bala M.S. Chouhan WE REL ORGANIC CHEMISTRY _ JEEo gogaao0 SHR! BAN ee aTHGUTORSI FEDUGATIONAL PUGLISHERS & DISTRIBUTORS) | 6, Gulshan Vinar, | Opp. Mahalaxmi Enclave, \ Jansath Road, Muzaffarnagar (U.P.) | Phone : 0131-2660440 (0), 2600503 (R) | website : www.shribalajibooks.com i NL Published by: ' SHRI BALAJI PUBLICATIONS - ‘email : sbjpub@gmail.com First edition: 2008 " Second edition : April 2008 : Third edition: April 2009 Seventh edition: April 2013 Eighth edition: April 2014 ©All Right Reserved with Author Price : = 480.00 Typeset by : Sun Creation Muzaffarnagar All the right reserved. No part of this publication may be reproduced, stored in 2 retrieval system cr transmitted, in any form or by any means, electronic, mechanical, photocopying, recording of otherwise, without the prior permission of the ‘authors and publisher. Any violationfbreach shall be taken into legal action.Dedicated to the Lotus feet of Revered Guruji SHRI KESARAM JI MAHARAJAdvanced Problems in ORGANIC CHEMISTRYIt is a matter of great pleasure for me to present the eighth edition of “Advanced Problems in Organic Chemistry for JEE” before JEE aspirants. During my teaching experience, I felt that the facts may be made more and more clear to the students through problematic approach. Although an ‘ocean of material in Organic Chemistry is available with the students, yet the approach to design the problems has been changed in recent years and if one tries to swim in this ocean, it will be a very difficult task. To make the students more familiar with trends and tricks how to solve problems, the present problem book has been presented. In the current scenario of stiff competition especially for JEE, one must be clear that almost all the sincere applicants are well equipped with the facts of subject, yet the winner is one who knows how to use these equipments with accuracy and efficiency. AS an experienced teacher, I would like to suggest students three golden rules toscore high in OrganicChemistry: 1. Don'tgetbehind 2, Workoutanumber ofproblems of differenttypes 3. Revise through short notes / learning chart. Thope that the present book will cater to the needs of JE aspirants & as, a matter of fact, they will enjoy the present venture and I would feel rewarded if this book is found helpful to the students and teachers in real terms. All attempts have been made to make the book error free however a few misprints may inadvertently creep. J acknowledge the blessing and support of my mother Smt. Raj Kanwar, father Shri B.S. Chouhan, brother Dr. VS. Chouhan, my wife and daughter, They inspired meal the time during the preparation of this book. The support and valuable suggestions from my colleagues especially Mr. N. Avasthi, Mr. VX. Jaiswal, Mr. Nitin Jain, Mr. N.K. Sethia, Mr. Vikash Gupta, Mr. Pankaj Joshi, Dr. S. Kothari, Mr. Vineet Khatri, Mr. Ashish Mishra, Mr. Manish Arora, Mr. Govind Khandelwal, Mr. Rahul Pareek, Mr. Rahul Malav, Mr. Akshay Choudhary, Mr. Hanuman Sahay, Mrs. Neha Joshi, Mrs, Neetu Jha, Mr. Kamlesh Gupta, Mr. Kumud Ranjan and Mr. KD. Tiwari are highly acknowledged. I also pay my sincere thanks to all the esteemed members of M/s Shri Balaji Publications in bringing out this book in such anice form. In the last, constructive criticism and valuable suggestions from the readersaremost welcometo make the bookmore useful. M.S, CHOUHAN email: mahen_chouhan@yahoo.com Mob.(Only for SMS) : 09828025625A few words to the JEE Aspi Dear JEE aspirants, | hope that this collection of problems will surely help you during your preparation for JEE. In this book, each chapter consists of two levels : Level 1 - includes the problems having only one option correct. ‘These problems are based on different facts and their twists. Level 2 - includes unique approach which may be used to solve the problems altogether different from the prevailing trend followed by JEE, These approaches will undoubtedly help you in the quick revision of the key facts and their applications. 1 wish all of you a grand success in the ensuing Joint Entrance Examination. Your valuable suggestions and constructive criticism for the betterment of the book are welcome. M.S, Chouhan e-mail : mahen_chouhan@yahoo.comeneral Organic Chemistry ~~ Isomerism (Structural & Stereoisomerism) [547 TAllo Hatides (substitution Reaction) Alkyl Halides (Elimination Reaction) ——————[—[—_———— Alkyt Halides itheir Derivatives’ ‘| S05] —— awa] CEN Practical Organic Chemistry "ear [Ga Taoneeais [is JuuracNames ss O™OC~—SSHow many 2° Hydrogen atoms are present in the given following compound ? Son @2 5 oO7 @s Identify which functional group are Not present in the given following compound ? 9 NH oO (a) Ketone (b) Ester (¢) Amide (@) Ether Correct energy profile for amine inversion and hybridization of nitrogen in transition state is: tt = wh b T= WUT (a) ®)@ 0) @) “o ®B @ L____, L_____, 4 s A se © @ /\ ® ) a ® L___, L___, o Gio Gi Compare the heats of combustion of above compounds: @ O >> Gi) ©) @>G)>G © G>@> Gi @ Gi) > Gi) > 0 Which of the following is not a resonance structure of the others ? 9 9 9 Z . = @ © o @ Rank the hydrogen atoms (Hq, Hy, H) in the following molecule according to their acidic strength. HH @a>b>c (b)b>a>c © b>e>a @c>b>a ° I CHy —C—0-— CH; ‘Compare the bond lengths a and b. (@a=b @) b>a @b © cf @) Dun Diacone lactone frlactone Sclactam ‘The functional groups present in Cortisone are : HOH, ©. is och, 9 Cortisone (a) Ether, alkene, alcohol (b) Alcohol, ketone, alkene, ether © Alcohol, ketone, amine (© Ether, amine, ketone Select the acid with the highest K, ((e., lowest pK). Oo Oo Oo (@) W367 “OH py Cl ©, Oa Most stable carbocation among the given example is : CH @ @ L—F © ANY e © CO-% (@ cH, Set the following in increasing order of their pK values. ° ° I II @) Cs 0-H @) CH; —C—O—H — @) CH; —OH oO @y 99 a}xdst0 racine rofsssilig os “0 fir om msl < Td) vo 19. Circle represents most tbat, atoms,in these molecule. Which of. che llowine 5} correct Gree anne i ft 27. Se ted bond angl hevcarteo ase! urd: to their ok trot the lowest ee (3 Sa “B: a 4 beat) ¢ Bites oc a KO) “ ie) ia oy N @ oe at f < Ay tig Qxeons nojeorh)s cod wash ko ayameo = aad2>4>310'° * ()3>%4>2>1 ese oD ©2>4>1>3 2 meres LPR I> 24 ov, cosy 33. Which of the following has lowest pK, value ? 1m {78 OME oh Onno @) @) CH ? sow Ye . me * chon Farene ins saetusb oA +35. 36. 37. 38. Arrange the following (w, x,y, 2) in decreasing order of their boiling points: ODO 1H ow) oo) ” @ @w>x>2>y Owox>y>z Ow>z>y>x @wos>x>y Arrange the following in increasing order of their acidic strength. QO ‘OCH; o a O am a c $ ‘Oo ‘O” @mx>y>z (b)w>z>x>y (z>w>x>y Warx>wry Arrange the following alcohols in decreasing order of the ease of ionization under acidic conditions. TP OLD OLD am (a) 1>M>1 . wisnem @ U>M>T @u>i>m ‘Among the isomeric amines select the one with the lowest boiling point. H | CHy N i NH, N, @ O o ‘o © O @ O CHy Which one of the compounds shown below, is not an isomer of the others ? @ C) O) o-~ Arrange the anions (p) CH3, (q) NHg, (r) OH™, (s) F”, in decreasing order of their basic strength, (@p>q>r>s (@)q>p>r>s ©r>q>p>s Wr>p>q>s One among the following compounds will not give effervescence with sodium carbonate: 1H OH NOz, NO. (@) CeHsCOgH = (b) {© CeHsOH @ NOg The carboxylic acid which has maximum solubility in water is: (a) phthalic acid (b) succinic acid (© malonic acid (@) salicylic acid46. 47. 49. 50. 51. 52. 53. Among the following compounds, the most basic compound is : me) 0) { * ol 3S wh) H oO H aa H Arrange the (C-H) bonds x, y and z in decreasing order of their bond dissociation energies in homolysis. @y>x>2 (b) > x>y (@ z>y>x @y>z>x 23 g of sodium will react with methyl alcohol to give : (a) one mole of oxygen (b) 22.4 dm? of hydrogen gas at NTP © 1 mole of Hy (@) 11.2 L of hydrogen gas at NIP Which of the following is most polar? O © © fa) (b) (©) d) . ° o < NH; < N-H: € ™N; © The correct order of decreasing basic strengths of x, y and 2 is : @x>y>n (b) x>2>y © y>x>e @y>z>x Which of the following is the strongest Bronsted acid ? NH, NH, Which of he following i the strongest Bronsted base ? NH, H # | k N. @ o AV o¢ 7 @¢0 > H H Which of the following is polar aprotic solvent ? (@) DMSO (b) Crownether —() DMG (d) Alllof these OH55. 56. 57. 58. 59. 60. ‘Some pairs of acids are given below. Select the pair in which second acid! (@) CH,CO3H and CHFCOjH (b) CH FCO 7H and CH,CICO2H (©) CHyCICOH and CHyBrCO2H (@) CHCH,CHFCO 2H and CHyCHFCH2CO 7H stronger than first H—cCmctc=aclcny; ‘Compare the bond lengths a and b: (@a=b ()a>b (Ob>a @a>>>b Which (isomeric) amine has lowest boiling point ? (@) 1° amine (b) 2° amine (© 3° amine (@) cannot predict cl ‘ed 280, P ; Pwill be: i @ (b) 2sbel? © OC (4) mixture of (a) and (b) Which of the following substances is not an isomer of 3-ethyl 2-methyl pentane ? @ ~~~ ) © (d) All are isomers Which of the following is an isomer of compound 1 ? oO CH3CH2CHO CH3 —tocay CH, —CH=CH—OH CH,—CH—CH, a) @ @ NoZ% w (a) 2 0) 4 (c) 2and3 (d) all are isomers Br Which statement is incorrect in respect of the above reaction ? (a) Product is aromatic (b) Product has high dipole moment (©) Product has less resonance energy (d) Product is soluble in polar solvent61. 62. 63. 66. 67. Some pairs of ions are given below. In which pair, first ion is more stable than second? @ ® (a) CHy —CH—CHg and CH; — CH—OCH, 8 ® () CH3 — CH — CH CHy and Cy = CH—CHy —CHp Cay CH, (Oo a CH, CH, —N —CH, @ and | Hy —by- cr, cH, —c®—cH, Among the given pairs in which pair, first compound has higher boiling point than second ? (@) CHy —CH,OCH, and CH, — oH —CH3 OH (0) CHy —CHy —CH2 —CHg andCHy —CH, —CHy 3 3 2 Si cH, (c) CH3 —CHz —CH2 —CH2 —CH3 and CH; — CH —CH,—OH (@) CHs —CHy ~-CHy — CH and CH, —CH, —CH, —Cl Which of the following alcohols is the least soluble in water ? (@) Ethanol (b) 1-Propanol (© 1-Butanol (@) 1-Pentanol Which of the following alcohols is expected to have a lowest pK value ? (@) Ethanol (b) 1-propanol (© 2,2, 2-trifluorethanol (@) 2-chloroethanol Which of the following alkenes is the most stable ? (a) G o me © “U @ L Bond X is made by the overlap of which type of hybridized orbitals ? (a) spand sp? (b) sp and sp? (©) sp? and sp* (@ none of these Increasing order of acidic strength of given compounds is : ea Co Oe" HCO a70. nn. 72. ‘@m1>3 (b) 1 >2>3 () 2>3>1 @)3>2>1 Decreasing order of acidic strengths of following compounds is : A ‘N @ QO oy oO @ (@x>y>e )y>x>z (z>y>x (djz>x>y Among the given pairs, in which pair second compound is more acidic than first ? t i I (a) BrCH,NO» and CH3CH3 (b) CH3 —CCH,CN and CH, —C—CHg OH 1H H H o O & @ & cH,—C =0 CH75. 76. 77. 78. 79. ‘Which of the underlined atoms in the molecules shown below have sp-hybridization ? (u) CHCHCH; ——_(v) CH CCHC! (w) CHy CH @ H-C=Cc—H (y) CH3CN (2) (CH3)2CNNH2 (a) xandz (b) x, y, and 2 (© uwandx (d) v, xand y Which of the following, is the product of the reaction between AICI; and CH OCH ? a a a A CH 1, __ CH, @ ad—Al—o () C1—AI— |” SCH | “cH; a a cl ca a ae os a ls © (@ Cl—aAl— CH;OCH, on | a a Which of the following compounds contain atleast one secondary alcohol? 2 HO” “4 HO “on HOY ‘4H HO* oe H a a) aD yy wo @ LILW,V @) Lm (© LI t,v “eo 1,0,V Which of the following has the most negative heat of hydrogenation ? S @ Cr ) CY © co @ Cr Which of the following options is the correct order of relative stabilities of cations I, II and III as written below (most stable first) ? cu, Ts + + oO cr (ID H2C == CH —CH, —CH—CH3, ap Hye C— CHa CHg @i>m>m (b) 1 >>I (© Wl>1>0 @i>m>u What is the decreasing order of stability (most stable —> least stable) of the following carbocations ? AAAKA OC 1 @3>2>1>4>55 () 3>2>5>4>1 © 1x4>2%5>3 (@) 3>124>2=580. 81. 85. the hydrogen indicated by arrow will be easily removed as : (@ Ht (b) H® @H (@ H? Rank the bond dissociation energies of the bonds indicated with the arrows. (from smallest to largest). @1<2<3 (b) 3<2<1 @2<3<1 (d)3<1<2 Rank the following compounds in order of decreasing acid strength (most acidic > least acidic) . OH OH OH OH On, O QO O NO 3 4 1 2 (@2>4>1>3 (b)1>3>4>2 ()3>1>2>4 @3>1>4>2 Rank the following compounds in order of increasing acidity (weakest acid first). 1 fH 10 ly NO, (a) 2<3<1 @) 3<1<2 (1<2<3 @2<1<3 Which of the following phenols has the largest pk, value ((.e., is least acidic) ? @ a_\-or ©) on Lyn (© HC ) WB WA (©) SA SB (@) SB SA (©) WA WA The hydrogen bonding is strongest in which one of the following set ? (a) F—H---F (b) O—H---S (©) S—H---F (d) F—H---O Intermolecular hydrogen bonding is strongest in : (a) methylamine (b) phenol (c) formaldehyde (d) methanol A _H a H ‘SH iH sS ‘ A OH © b Identify most acidic hydrogen in given compound. @a (b) b Oc @d Which of the following compounds would you expect to be strongest carbon acid ? ° ce o&) 0 (©) CH,(CO,Et) (d@) CHyCOCH{COOC,H, 5-Bromo-; 2-eyclopropy cyclohex-2-enol have correct structure is: OH Br’ Br (dd) ‘OH93. 94, 95. 97. + Rearrange the following in the increasing order of acidic strength: + @ benzoic acid (ii) pmethoxybenzoic acid ii) o-methyoxybenzoic acid @ i-04 = () K+ EtOH == 08 © Mech? + 1,0 == @ O® +CHOH === Which compound posses highest dipole moment ? (a) naphthalene (b) phenanthrene (c) anthracene (d) azulene GFO+O%O (E = activation energy) Relation between activation energies of above reactions is : (@)E_>E,>E3 (0) Es > Ey > Ep =) Eg>By> By (A) Ey > By > Ey Rank the following solvents in decreasing order of ability to dissolve given compound. Solvent Et,0 me | EcOH Solute (a) Bt,0 > H,0 > EtOH (b) H,0 > EtOH > Et,0 (©) H,0 > Bt,0 > EtOH (@) Et,0 > E1OH > H,0 MeN: :NMe2 OD) 1, 8-Bis (dimethylamino) naphthalene is after referred 30 a8 (Proton sponge) Its basic strength is 10° more than 1-dimethyl amino naphthalene. Reason for high basic strength is : (@) resonance (b) steric inhibitation of resonance (© ortho effect (@ hypereonjugation99. 100. 101. 102. In the given pair of compounds, in which pair second compound has higher boiling point than first compound ? @ on and Co ) =o and > (©) HO— CH, —CH, —OHand CH, —CH, —CH, —OH Dipole moments of given compound will be ; Me’ "Me NO, NO, “ © (@) (A) = 6.87D, (@B) = 4.11D (b) (A) = 4.11, (8) = 6.87D © @ =411D, @) =4.11D (@) (A) = 6.87 D, (8) = 6.87D Order of decreasing basic strengths of halides is : @ Fo >Cr s1 > Br (&) F >clr > Br or (©) > Bro >Cl >F> (d) 1 >CP >Br >F™ Among the xylenes, which is thermodynamically most stable ? (@) @) © @) Allare equally stable Heat of combustion of two isomer x and y are 17 kJ/mol and 12 kJ/mol respectively. From this information it may be concluded that : (a) isomer x is 5 kJ/mol more stable (b) isomer y is 5 kJ/mol less stable © isomer y has 5 kJ/mol more potential energy (@) isomer x is 5 kJ/mol less stable103. 104. 105. 106. 107. 108. Rank the following substances in decreasing order of heat of combystion (most exothermi — least exothermic) LIN AKA wo @) © (a) B>A>C (b) A>B>C (0 C>A>B @C>B>A o 2 o cy Choose the statement that best describes given compounds, (a) 1, 3,4 represent same compound (b) 1 and 3 are isomer of 2 and 4 (©) 1,4 are isomer of 2 and 3 (@) All the structure represent the same compound Decreasing order of acid strengths is : ® Ph—OH, Ph—CH,—OH, Ph—CO,H, Ph —CH, —NH3 wy (a) © (0) (@B>A>C>D @)C>A>B>D ()C>A>D>B (@)C>B>A>D Rank the following in decreasing order of basic strength is : (A) CH, —CH, —C = (B) CH, —CH, —$” - (©) CHs —CH, —CO3 (D) CH; —CH, —O7 (@B>A>D>C (b)D>A>B>C (A>D>B>C WA>D>C>B ‘Among the given compound choose the two that yield same carbocation on ionization, ‘Br Br @ac () B,D AB (@) B,C Oxalic acid pK; Malonic acid PK Heptanedioic acid PK, where pK;, pK, PK are first ionization constants. Incorrect order is : (a) pK, > pK, > pK3 (b) pK, < pK, PK > PK, @ PK > pK; > PK109. 110. 111. 112. In sets a - d) oly onie of the'set is incorrect regarding basic strength. Seléct it NH (a) Ph —NH — Ph, < Ph— NH, < (strong base) H a ol < oO O H 'N’ J} N, ot > 4 > L> $-6.§ Dipole moment of which ketone is maximum ? fel oO @ ch o) GO © A @ CL ° ‘Oo Correct order of basic strengths of given amines is : (@) MegNH> MeNH, > MeN > NH (Proticsolvend) ° (b) PeaNH > Begtt> BIN 12 >NH3_ (Protic solvent) eS (©) MesN > Me,NH > Me~ NH, > NH; (Gas phase) (@) All are correct NH, CHS, Order of basic strength Ph—NH», Ph—-NH—Me, Ph—N—Me, ic) @) i Me © ) @A>B>C>D (b)B>A>C>D ()C>B>A>D ()C>B>D>A113. 114. 115. 116. 117. 118. Carbon-carbon double bond length will be maximum in which of the following compounds ? (@) CH, —CH = CH, (b) CH, —CH =CH—CH, (© CH —G =¢—CHy (@) CH; = CH CH; CH3 Which has maximum dipole moment ? @ BQN «i A Git) cA Compare the basic strengths of compounds given: @ @ > @ > Gd () Gi) > @ > Gd © Gi) > Gd > O @) Gi) > G) > @ For the following two reactions, which statement is true ? a a Ae Tactonk Tecion 8 (@) Reaction A is faster and less exergonic than B (b) Reaction Bis faster and more exergonic than A (©) Reaction A is faster and less endergonic than B (@ Reaction Bis faster and more endergonic than A Identify the site, where attack of H* is most favourable. @a (b) b Wc @d Rank the following alkenes on order of increasing Amex. (a) 1<2<3 (b) 1<3<2 @ 2<1<3 @2<3<1120. 121. 122. 123. 124. 119. Which of the following cyclic amine has lowest AG* for inversion ? @ Dw ~ CHy-Me o Dy -nBu © [Dy-eau @f>n-Ph Rank in the order of increasing acidic strength: 9 CO,Et Et0,C. CO.Et OgEt °. "COEt (A) (@) © @A propane (®) cyclobutane +H, + butane (© eyclopentane +H, —> pentane (@) cyclohexane +H, —> hexane oO 8 Compare basic strengths of the above compounds: (@A>B>C @)B>A>C (C>A>B (@C>B>A On reaction with acid, 4-pyrone gives a very stable cationic product. Which of the following structures shows the protonation site in that product ? 4-Pyrone A H @ Hwa © @ 48 0" H 0" bh125. 126. 127. 128. 129. 130. 131. Which of the following is the most stabilized carbocation ? OMe OMe te OMe © SN oe ote o Ae oo Ae Which carbocation is the most stable ? ak © ares © AK : @ Ak Consider a positively charged C,H; species in which the positively charged carbon is sp- hybridized, the uncharged carbon is sp’-hybridized and an empty p-orbital is perpendicular to the x system. What it the best description of this cation ? (@) vinyl (b) allenyl © alkyl @) allyl Which of the following reactions is not exothermic ? (a) CH —Cl + CH, —CHy — > CHy + CH, —CH, —Cl (b) CH; —Cl+ (CHs)3C—H = —+ CH, + (CH,),C—Cl (©) CH,;—Cl + CH, =CH—CH, —> CH, + CHy =CH— CH, — Cl (d) CH, —Cl + CH, = CHy — + CH, + CH= CHC) List the following carbocations in order of decreasing stabilization energies. + ' o ay on ay CK m™ oO (@) LLY (b) MTV, U1 © ULV, 40 (@ 1, 0,1, For the following two acid-base reactions, which statement is true ? (DCH,CH; + CH;NH, = <2 — CH,CH, + CH,NH™ pk =35 ke =80 apr + HO = HF + HO" pK, 715.7 PK 32 (@) Lis favoured to the right, IT is favoured to the left (b) Lis favoured to the left, 11 is favoured to the right (©) Tis favoured to the right, ITis favoured to the right @) Tis favoured to the lef, Il is favoured to the left Rank the hydrogen atoms (H,, Hy, H,) in the following molecules according to their acidic strengths: Ss TFS f@a>b>c ()b>arc @b>c>a @a>c>b133. 134, 135. 136. In which of the following reactions, backward reaction is favoured ? (a) HC =C—H + Lit-cH.CH, == H—CmC:9Li* +Hj,C—CH, 9 A = ©) pyc Son + “OCHaCHs = ae A, + HOCH,CH, + _s 2 (© CH,CH, SH, +CHyCH,OH = cH,CH,SH + CHyCH, 0-H H + rs NH, OH NH OH, Which carbocation is the most stabilized ? “CO “OO © CO: oD ~ % ‘Taking into account of hybridization and resonance effects, rank the following bonds in order of decreasing bond length. oO wae ay (@) I> =m @) > m>1 (© 1>m>0 (@ U=m=1 Which one among the following carbocations has the longest half-life ? @ bic 06 OHO) © CK) @ iy Ech, cH, Rank the following alkenes in order of decreasing heats of hydrogenation (largest first) AZ “yr NYO 1 2 3 4 (a) 2>3>4>1 (bl) 2>4>3>1 (© 1>3>4>2 @1>4>3>2137. 138. 139. 140. 141. 142. Which of the following reactions is most exothermic ? (a) » + chs ya + HC! o> + Bags ar + HBr © Ye cl, séa +Ha = @) ws Br, For 4+ HBr Which energy diagram best represents the given reaction ? Cty f—~ & = Hy SHC ‘CH; E E E E @ ) © @ Br H, HH @ 1 Which one of the following is most stable ? Which of the following is strongest acid ? a Si Kd Compare ee stability of the following resonating structure. ao i i ~ ai Il t (a) G) > Gi) > Gid (b) Gi) > @ > Gi) (©) @) > id > Gi) @) Gi) > Gi) > © Compare relative stability of the following resonating structure. wow ah oe tl I144. 185. 145. 155, a 147. 153. 148. 159. Which of the fi\ lowing orders pr beat Which of the following has thé lowesr barrie to'rota wo oes sa ay @ pot $ raxorbydaibjs eam aerizhauoamon gniwollais cdi? OBL ON Re in Spt aniwollets ~o { i Cfo ( Sto Use al Fe As ‘answer ai question below. L-o~ a as an Which of the 2 Ges} = =28. 6keal molt) > there cau Cee BON > (© We Maly cH, & noe oy Ny ‘OOO a wns Sones is pracnea sor monn A FUe2keal ml) 4. + “Anger w «Calculate the resonapce:eneray of anthracene!) hg ast 1a09, HO) .bive sitsoA .FeL iis or(@) 84 ‘kcal/mét pbs gb) }200 )Kéal/ rho 2i(o) 1 ¥110 ke cal/ mol 9jos (a) 216) amok How many double bond equivalents does a compound gh, pojectan ‘ria Geis posseis?'gHO,HO Bar “OgHie HD ie cat. cry HQGQPEHO bas Hc03,HD (6 (a) 0 HO,HO,HO bas .OD,HO (b) " (b)‘1 =O, Ho bac Hy 09,HO (9) ©2 ama 3 tates Js 0 wont Su Hows a nest be bend al Niosd amonellin Gi (asin below) possess 2 .H.. -S2E les 6 NH, oi H y Agate! Xo levinonss older r20rn oft 3 0” pe fasta” 7 pat O order of 12? Oxy 32 the given ca()163 Hacuares rs % ZG ut 33) 8 >) @ IG) ) ‘WMiat is thé oxidation stat€ of d$mium in 7B aifd:7C}) ppoetively? 7 CP we y ee sear 358 patie corn Safin Sang US arw-ae i ‘onesie Tame con meee eed) all are equally sta tSo nin einen cp anitinst & (6) 160. Zi Za Zi. ono, ox “sane & (8) tity 149. For the sive ‘compounds the correct order efesonance energy is : (a) I> 1>0 st Lo) > 1 > wo BEL ©! aitan I o(@) M>1>1, F ebapogras seaeit to 35; 180d ral toenian 2 29/oq priwollo odo rit aa 2? mig ati A EAP ey One Cine <1 (4) 161. Gi, by fi'cH, - CN" © ‘city -¢ =NC fred Cs tg como hesYCHs acidic hydraren ? “CHs HO. The Fonds stability order ofthe givetr canonical structifes is ]_$ zat G@) 1S M5 mH a Ones _ . @ism>n Yo a @ usm 3 s w $ sbavo P igo sand to nobanazerby 0 sth pene abo wot adi to dist IL ety (b) Nhs Ml< 1 (0) ay < a ae i o § sbytah pr) wl aurertteleniaan rbd § abuiahreap aie compe HN ee Si 0 WvSilabie Tor the aataeck OF CHO" AY 153, (a) 1: acid, (CA, CONIC); 2 aad if 4.8. Et(c)13 (CHyCH,O1, b@): ated 0 What 163. CH; CHit HCHO Zone Ci ge cao! HA CH COE! eS HCAS NSE aduusct'to J07 (2) ©),60,H and QO a DY Clay yO wht DH-CH{OH Which of the following ofdefs'of otation Barrie¥ abGut the C'= C bond; as indicated, is correct ? (a) a2, @ 15> 10 | $ swouwe Esoitonso E(b)‘I11 >I > Tutsurte sesd Yo dain TONE Seo MO), @ urd % . \ () i 164. 50 in. OrstieaO’, ~ a Oxkso- oe o raw, + Wore Ipe, whic of the following orders of BR barrier about ae CC. bond, NS i indicated, is 153. correct? Nentitl energy diagrem to the (@)1>1>m fone) | (© M>I>0 f *\ \@.N> 1 > I eer 165. Which of the follo fesenomal isnot etonan ge sabned 8 tai bunee Fans snaibe of apa 'soinonn to olden ay Qronte @ Drove Cee @ C2 fsre so as ot . : oe 4167. 168. 169. 170. 171. 172. Homologous compound have same: (a) General formula (b) Emperical formula (© Structural formula (@) Molecular formula Most acidic is: OH OH OH OH @ O ) QO © Qh, @ QO CH, NO, Which of the following substituents will decrease the acidic strength of phenol? (@) —NO, (b) —CN (© —CH, (@) —CHO Which of the following structures possesses a cross-conjugated system? (a) CH, =CH—CH =CH—CH, (b) CH, =CH—C =CH, | CH,CH, (©) CH, =CH—CH—CH =CH, (@) CH, =CH—C =CH, | | CH= CH, CH=CH, Examine the following resonating structures of formic acid for their individual stability and then answer the question given below. { - - r H—C—OHe—sH—C= 64 —5 HC 0 ot + I u uw Vv Which of the following arrangements gives the correct order of decreasing stability of the above-mentioned resonance contributors? @ I>I>m>V ) I> 1>m>1V (© Weil>I>n @ W>il>t> Which of the following is not resonating structure of each other? (@ CH, —N=C =SandCH, —S—C =N (6) CH, —G =OandcH, —C =O ° - (© CH; at omanace, —c @ CH, =CH—C = NandCH,—CH =C =N- OH 6-H In the molecule CH,! linearly is: @) 2 () 3 @4 @s5 =CCH =CH,, the maximum number of carbon atoms arranged173. 174. 175. The stability order of the following carbocations is: + + : + ARAB 4 I I I WV (a) I>IV >>I (b) IV >> D> © U>m>1>v (@) I> tl>n>1V Total number of a-hydrogen in given compound is: @)4 ©) 5 © 6 @7 In which pair second ion is more stable than first? VV OO Oo co or a wa Gi) (iv) (a) G@ and (ii) (b) (ii) and (iii) © Gi) and Gv) (@) Gii) and (iv)|GENERAL ORGANIC CHEMISTRY ANSWERS — LEVEL 1 49. | cb) | 50. | () | 52. | (a) | 52. | (a) | 53. | @ | 54. | @ 1 55-] © | 56.| © 41.] © [42] @ | 43-| @ | 44-| © | 45-| © | 46-| @ | 47-] o | 48.| @ 57. & {58. @) | 59.| @ | 60.| (©) | 61.| ) | 62] o | 63.| w | 64.] © | 73. | (a) | 74. | @) | 75-| @ | 76- | (a) | 77-| @ | 78-| @ | 79-| & | 80-| @ @) | 84. | | 85-] @) | 86 | (a) | 87-| (@ | 88. | O) 97. | (b) | 98. | (d) | 9% | (a) |100.| 205.| (<) |106.| () |107-| ) |108.| @) 113] «© [114] |245-| (@ 116. (a) -| @_|103.| (@) 104. (a) | f112.| @ |122,] (@ [229.] (@ _[220.| () .| (b)_|127.] (a) |228.] (a) 135.| (a) |136.} (a) 129.| (b) |130.] (ay |132.| (<) |132.| (@) |133.| () ]134, 1—T 137, [ise (d) |139.] (©) |140.) (c) [141.] (a) [142. 145.| (a) |146.| () |147-| (a) {148.| &) |249.| (a) |150.| 144, (©) 151.1 (a) |152.] (b) 156.| (¢) [157-| @ |158-| @) |2159.] « |160.| (0) 164,| (a = a a je 166.| (a) |167.] (a) |168.] (c) 172.| (a) |173.| « |174.| @ |175:| (){34 —_ : ORGANIC Chemistry for IIT-JEE — | Tay HN newer 2 of 1, Rank in order of radical stability (1 = most stable). © Oo »O oY? oa Oo 2, Predict the acidity order for the three phenols shown below : Acidity order : 1 (most) to 3 (least) NO, NO, CH OL HAN. NH NO2 EN.|GENERAL ORGANIC CHEMISTRY A. Which of the phenol derivatives above is the strongest acid ? Compound A © Compound B © Compound ¢ © Compound D © Compound E Compound F B. Which of the phenol derivatives above is the weakest acid ? CO Compound A CO Compound B CO Compound c CO Compound D Gi Compound E © Compound F C. Which of the mono-nitrophenol derivatives above is the strongest acid ? O Compound A O Compound D D. Which of the carbon-substituted phenol derivatives above is the strongest acid ? © Compound c © Compound F 4: The following questions refer to the twelve compounds given below. You may enter as many as six choices in each answer box. 1 OD pl eae td) HF () Oe: oO L\ 0 @ or 5) CO, @ Co 6 oO” a “et ® Co Oo A. Which compound may serve only as H-bond acceptors?» [______] B. Which may serve both as H-bond donors and acceptors? = ("____] €. Which compounds will not participate in H-bonding? = [1] 5. Consider the following compounds and answer A and B. i) ( a OA, ao Ch av) ' A. Which of the compounds is the strongest Bronsted acid ? @1 o) 0 © m @iVv10. In the two questions below, you are asked to rank the relative strengths of illustrated acids and bases. Use your knowledge of resonance and inductive to.answer this. ‘A. For the series of bases shown below, rank the set from strongest to weakest. com TOES N loolacls N N’ N H H @ ) © @ Weakest ~ Ay Strongest a 'N Me N’ N’ x7 le Me, {sd} @ ) © @ 1 Weakest B. For the series of acids shown below, rank the set from strongest to weakest. Stronges ® ine} "Che. “oH a ai @ mol 1096 ; Own ) : eS HO,C, HO,C. NO, ol Oo a oy © @ Weakest Strongest (ey © @ Weakest 11. In each of the following sections four compounds are listed. (Decreasing order of acidic strength, 1 is strongest & 4 is weakest). (ay | SSOLatise | crycocHcoeati | (CHsCo)y Cte RC ea CH wo RCH2NOz RSOLHs (CelHs)3CH RCOCHs (9 LS CHa(NO2)2 HC aN RCHLOL HsGENERAL ORGANIC CHEMISTRY H; @ oO 2 “pd Oy SO o?¢ A [ QD () w © ‘ | ° ¢ eg H HH HN H H H ? Nn? nw 3 c. I i i} é i OL > © Ly DS H)N “NH, HN “CH, HIN’ OH HjC CHs 13. Compare acidic strength of the following (Write your answer in box). ANZA IAA LAO o @) {b) © OH OH OH . FC @) ©ORGANIC Chemistry for IIT.JEE Q @) F wr Br o) © QO oO QO E. 0 0 @ © H H HOH eels @ | @) © 14, Arrange the hydrogens in increasing order of their acidic strengths. 9 0, FOF HY A. BH Ha i o. Hy H H’ Ib, ib Nie Ong H15. The compounds whose structures are shown below, incorporate a variety of functional groups. The question on the right ask you to identify which compounds have a specific functional group. For each compound that has the designed group, enter the appropriate number. The aromatic rings should not be counted as double bonds. SosO8 Se OH ‘toners 2, munconn A. alcotine 4. ibuprofen 5. camphor ° HC. ote 4 Oe ‘O Heo HyC7 SCH 7.aspirin 8. geraniot 9. acetaminophenol O—CHy a Which have carbon-carbon double bonds ? Which have a ketone carbonyl group ? Which have an aldehyde carbonyl group ? Which have aromatic rings ? Which have a hydroxy group ? Which have ether groups ? G._| Which have an ester group ? f H._| Which have an amide group? I,_| Which have a carboxylic acid group ?[[Probtem ‘A = £ 0 ona oe CY Cy ‘O. OR OH OCH, OH Sr O _— N—-H | ew | Om] Cit [Oe ‘0 oO H i I H Cl Cc C. ScoH Cc. 4 CX Peon Cy oot Cy 2 FS conH ca ‘cl ‘A. Which is the strongest acid in 1? @a (b) B ac @)D B. Which is weakest acid in 1? @a ) B amc @D C. Which is the strongest acid in 2? (aa )B @c (@)D D. Which is weakest acid in 2? @a (b) B @c ()D E. Which is the strongest acid in 3? @aA (b) B @c @D F. Which is weakest acid in 3? (aa (b) B @c (4) D G. Which is the strongest acid in 4? @A (b) B @c @p HH. Which is weakest acid in 4? @a ©) B @c @D}GENERAL ORGANIC CHEMISTRY 17. For each of the six structural formulae (A through F), shown below, five questions are posed. The answer to each is a number that should be entered in the appropriate answer box. CH, O-sc~c03 " N . (i) Number of sp? carbons : B. Number of sp? C. Number of sp? “ . carbons : carbons : (ii) Number of sp? carbons: Number of sp? carbons: Number of sp? carbons : (iii) Number of sp carbons : Number of sp carbons : Number of sp carbons : (iv) Number of carbon-carbon Number of carbon-carbon Number of carbon-carbon o-bonds : o-bonds : g-bonds : aesonse (v) Number of m-bonds to Number of xbonds to Number of r-bonds to carbon : carbon carbon D. (i) Number of sp? carbons: E. Number of sp? F. Number of sp? carbons : carbons (ii) Number of sp? carbons: Number of sp’ Number of sp? carbons : carbons = Gi)Number of spearbons: Number of spearbons: Number of p carbons : (iv} Number of carbon-carbon Number of carbon-carbon Number of carbon-carbon o-bonds : o -bonds : o-bonds = (v) Number of zt bonds to Number of bonds to Number of x-bonds to carbon : carbon + carbon :....oO ~~ ORGANIC Chemistry for ITT-JEE , 18. Match the column (1) and (11). (Matrix) Molecule Property TL @ @®) cis-compound PL ) PF @ trans-compound © CO @ Highest heat of combustion _ I san — 19. Match the column (1) and (II). Molecule pKa of Conjugate acid Ch @ wo ©) os H @) G3 @ 5.33 Gy oy © o 10.65 N. @ N © 1095 220. joGENERAL ORGANIC CHEMISTRY : 45 20. The junctures centred on atoms A, B and C on the given structure. | ‘A. Which juncture has the greatest deviation from planarity ? A ) B oc (@) Cannot be predicted B. Of the carbon-carbon bonds, (shown above) numbered from 1 to 4, which represent the most favourable site for Ha addition ? @1 @)2 ©3 @4 21,_ Select the most stable structure in each of the following Part (A) 4 “GO PO FO fO Part (B) O@AZT- jorRy |onw le ANF Part (C) (@) H& = CH—CH = CH—CHy (b) HE. = C = CH—CHy—CHy (©) HyC—CH = C = CH—CHy @HE =CH—CH,—CH = cH, 22._Match the column I and II. (Matrix) @)_f=no: Kp) __|-meffect [07 q)__|+metfect [=o — cH, ie) | reffece @ [-con te) [-vefiect 23,_Match the column I and 1. (Matrix) (@)_ [HC —CH = CH—CHy (6) _ [HC —CH = CH—CN Dipole (trans > cis) © _|ry¢—cH = cH [Melting point ((erans > cis) ce ae __ [Boiling point (cis > trans) |24. Identify the most stable structure in each of the following : [[rare A) CH, CH3~ + @ > t—H < a (b) cH, ©) Part (B) HY + N Oy" Nome HO “a Cy 4. c. OG Nox ch, Ho [rare © Fe (d) Part (D) x + @) ie ) aa © “T @ aa Part (E) CH, CH, os aK 0 > =cO . o = HZ Nau H H —- CH — CH. H oS aco _ @ Neel ua Nu Hy Nu Part (F) + + CH CH, CH @) Cow © cr o Or +p oo a7} Part (G) 1 HOH ‘ H HoH H H & SeK' | fF + £ ot # lo Hu lot or ° 4 H H ° ° i. HOH a H a HoH Hou | HOH 25, Identify the most basic compound in the following. = Part (A) 0 oO NH NA (b) " ‘NH NH A NH @ Ko) @ ‘° Part (B) NH NH, NH — CHy @ © o) ca) ‘N Part (C) (a) NaOH (b) NaQOCCHy (©) NaOcHy (a) NaNHy fo | Part (D) | NH NH NH, NH, @ ©) © @ O NO3 OCH, a — ail48 a a ORGANIC Chemistry for IIT-JEE 26. Identify the most acidic hydrogen containing compound from the following. Part (A) —— @ @ ) 6) » QO QO) O 1S in, [OO Part (B) ° ° ° ©, CO,Bt @ © © i ° C—O—E ° —____L Part (©) OH OH OH on @ “© © @ NO, CH,CHg NO, NH — CHg Part (0) ° ° Oo 9° 9 0 eA JU fe |@ RA Part (2) a) ° oH CH, — NH| CH,OH or ao © @ or o @|GENERAL ORGANIC CHEMISTRY Part (F) —_ (a) CHyCHOH (b) CHyCHNH2 (c) CH3—C == CH | (4) CH3 —CH = CH, Part (G) + NH ts (0) CHy —COgHt NHS (a) CH —COH ay 6 () wo L Part (H) OH OH OH OH No, Jo ) a) @ : NO, No, NO, NO, No, Part (1) or alSno ys @ @ o o =: been ee ard zoo e I Na,—C—H Nu Give the type of hybridization present at each atom. @ No (iv), — Gi)e2 — Wi)C3 —.fo ORGANIC Chemistry for IIT-JEE 28. Predict the direction of the following equilibrium. Write your answer in the box given below. : x a> @ Phy CBr = 4 BIT oe + Ph3CH oO . & (@) © @) ; _ °. oJ co = OD. te Hm KF H H 29, Match the column J and IL. (Matrix) 0. ‘OH (a) | NaHCO, will react with | oO ‘OH (b) | Na will react with Squaric acid | o @ Cc—O—H (c) | NaOH will react with (4) | Nant will react with Oj {s) S—O-H 30, Match the column I and I. Acid PKa (a) | CHs Coat @) 5.69 + (b) (CHla):NCHLOH @ 4.27 {o) (CH), N(GH)4O3H @) 1.83 ~ —T [ © |Sac—cx,—coz ®) 4.80[GENERAL ORGANIC CHEMISTRY 31._Match the column I oO I (a) Opes 0- 1+ nat (s) Ha & _ i CO2H | | $03 te 32.) COO) —REESOD 5 (A) + (B) MEO (C) 4 (D) : on * = } CH—OH | tl | : CH . Sum of molecular mass of gas (A + ©) is: (@) 88 (b) 90 (© 92 @ 40 i Oo 33. ph—C 9 — 400s 54) gas | Ph —C = CH—*2_(B) gas Ph —OH—N2MH2_4(C) gas 1 R—O—H—‘#_,(D) gas | ‘Sum of molecular mass of gas A +B+C +Dis :34, Match the column I and M1. ORGANIC Chemistry for IIT-JEE o co @ He Molecule Rotational free energy barrier ° Ph (a) | Ph @ 180 kJ/mol ° Ph__Ph I (b) I @ 88.3 ki/mol I Ph7 Ph Ph Ph l a Ui cl © cl ci o) 21 ki/mol I Ph~ Ph | © vi ¢ ~) Negative barrier