a Mee aed Org FleAbout the Author Mahendra Singh Chouhan (MSC Sir) is a renowned name in the realm of Organic Chemistry. Through a Chemical Engineer from Mumbai University, his great passion for the subject led him to impart guidance to IIT-JEE aspirants on a regular basis. His in depth knowledge and vast experience-has helped innumerable students to achieve their dream of excelling at IIT, JEE and other such tough challenges: He has launched a website to extend the benefits of his expertise beyond the geographical barriers to all those who dare to dream and seek - www.iitjeeorganic.com. The website provides expert guidance in all the areas of the subject ina most skillful manner. There are quizzes, challenging questions, notes, e- books and videos etc. This website is a complete guide in itself for ‘organic chemistry and has been designed for lIT-JEE aspirants, keeping | tomindthe various syllabi and CBSE. | Highly recommended forthe high flyers. ke callaati. BalaJi Advanced Problems in ORGANIC CHEMISTRY by: M.S. Chouhan Director Vibrant Academy, Kota SHRI BALAJI PUBLICATIONS (EDUCATIONAL PUBLISHERS & DISTRIBUTORS) [TANISO 9004-2008 CERTIFIED ORGANIZATION” ‘Muzatfamagar (U.P.) - 251001A few words to the JEE Aspirants Dear JEE aspirants, | | hope that this collection of problems will surely help you during your preparation for JEE. In this book, each chapter consists of two levels : Level 1 - includes the problems having only one option correct. These problems are based on different facts and their twists. Level 2 - includes unique approach which may be used to solve the problems altogether different from the prevailing trend followed by JEE. These approaches will undoubtedly help you in the quick revision of the key facts and their applications. | wish all of you a grand success in the ensuing Joint Entrance Examination. Your valuable suggestions and constructive criticism for the betterment of the book are welcome. M.S. ChouhanPreface It is a matter of great pleasure for me to present the eleventh edition of "Advanced Problems in Organic Chemistry for JEE" before JEE aspirants. During my teaching experience, | felt that the facts may be made more and more clear to the students through problematic approach. Although an ocean of material in Organic Chemistry is available with the students, yet the approach to design the problems has been changed in recent years and if one tries to swim in this ocean, it will be a very difficult task. To make the students more familiar with trends and tricks how to solve problems, the present problem book has been presented. In the current scenario of stiff competition especially for JEE, one must be clear that almost all the sincere applicants are well equipped with the facts of subject, yet the winner is one who knows how to use these equipments with accuracy and efficiency. As an experienced teacher, I would like to suggest students three golden rules to score high in Organic Chemistry: 1. Don'tgetbehind 2. Workoutanumber of problems of different types 3. Revise through short notes / learning chart. Thope that the present book will cater to the needs of JEE aspirants & as a matter of fact, they will enjoy the present venture and I would feel rewarded if this book is found helpful to the students and teachers in real terms. All attempts have been made to make the book error free however a few misprints may inadvertently creep. Iacknowledge the blessing and support of my mother Smt. Raj Kanwar, father Shri B.S. Chouhan, brother Dr. VS. Chouhan, my wife and daughter. They inspired me all the time during: the preparation of this book. The support and valuable suggestions from my colleagues especially Mr. N. Avasthi , Mr, VK. jaiswal, Mr. Nitin Jain, Mr. N.K. Sethia, Mr. Vikash Gupta, Mr. Pankaj Joshi, Dr. S. Kothari, Mr. Vineet Khatri, Mr. Ashish Mishra, Mr. Manish Arora, Mr. Govind Khandelwal, Mr. Rahul Pareek, Mr. Rahul Malay, Mr. Divyesh Tiwari, Mr. Omkar Kelapure, Mr. Kishore Kilani, Mr. Mayank Pareek, Mr. Gurpreet Singh, Mr. Yogesh Jain, Madam Anjana Kamal , Mr. Aneet Choudhary, Mr. Shaliwahan Singh Rathore, Mr. Akshay Chaudhary, Mr. Hanuman Sahay, Mrs. Neha Joshi, Mrs. Neetu Jha, Mr. Kamlesh Gupta and Mr. Kumud Ranjan are highly acknowledged. I also pay my sincere thanks to all the esteemed members of M/s Shri Balaji Publications in bringing out this book in such a nice form. In the last, constructive criticism and valuable suggestions from the readers are most welcome to make the book more useful. M.S. CHOUHANaa General Organic Chemistry [TZ Isomerism (structural & stereoisomerism) 1737) Grignard Reagent ak Hydrocarbons (Alkanes) (74877) Hydrocarbons (Atkenes) Ez | AC || Hydrocarbons (Alkynes) Ez | BA) Alkyl Halides (Substitution Reaction) ez Ezy =a =5) =z SBI) Alkyl Hatides (Elimination Reaction) Per ‘Alkyl Halides i | 6 | Alcohol, Ether and Epoxides [TJ Atdehydes and Ketones © 8) Aldol and Cannizaro Reaction ee Carboxylic Acid and their Derivatives i Ea Carbene and Nitrene Ceres [02M Aromatic compounds Byes) En Practical Organic Chemistry [RAM Biomotecutes [HN wrac Names [UES tearning chart f= Apr rots 342-388LEARNING CHART (AROMATIC COMPOUND) {gi = . 7 e he gay i 2 ‘S, ee Cs é S ay > fol. i cf Oy Oe oei (kO- [Or 2tlOn= | i o LEARNING CHART (ALIPHATIC) mth oll, tcp £1 | GENERAL ORGANIC CHEMISTRY i Siti A How many 2° Hydrogen atoms are present in the given following compound ? co @2 (Og @7 @s Identify which functional group is Not present in the given following compound ? o 0 o (@) Ketone (b) Ester (© Amide (@ Ether Correct energy profile for amine inversion and hybridization of nitrogen in transition state is: CN = wht DNA a) @)7 @ © @) « 3) (A) ee — t et © @ ey) ) ) @® es {____, o «wo «i Correct order of the heats of combustion of above compounds is: @ D> > Gi) 0) O> Gd >G © W>M> Gi @ > G>~O Which of the following is not a resonance structure of the others ? 9 9° 9 Z . < @ © © @ Rank the hydrogen atoms(H,, Hp, H.) presentin the following molecule in decreasing order of their acidic strength. ® HH "CH3, (@a>b>e (b>a>c (b> ema @c>b>a oO ] CH, —C 0-H: The correct relation between the bond lengths a and b is: (@a=b () b>a © b . © aw (@) Allof these Circle represent most acidic hydrogens in these molecules. Which of the following is correct. representation ? a woe A ® © n° @x) © x (@) Allof these.21, Arrange the fellowing in decreasing order of res acidic strengths. PoP Ne o o @A>C>B>D.WA>D>B>C (@A>D>C>B @D>A>C>B 2. a Cyclopropane Cyclobutane _Cyclopentane o ay a The correct order of heats of combustion of above compounds is: @I>n>m @ u>1>m © m>n>1 @ m>1>0 ~& oe Compare carbon-carbon bond rotation across A, B, and C @ A>B>C ) A>C>B (B>A>C @B>C>A 24. Which of the following acids would have a STRONGER CONJUGATE BASE ? @ ths Ws th © (@) 2,4,6 0 13,5 “© 235 13.6 25. —S1, A; Major products of the reaction is (are): Lup Cac ie26. 27. 29, (@) both ©)& (©) @ Q ) or © Which of the following compound is most stable ? CoHig veHi7 @ ) Cothy fthe oO @ ‘AcO ‘AcO Selected bond angles for six hydrocarbons are shown below. Arrange these hydrocarbons according to their pK Values, from the lowest to the highest. tS” Sor S108" 1 o ~ @v minimum). or <0 mm ‘ 2 vets = 4 Hs (1>2>4>3 )3>4>2>51 (2>4>1>3 @1>3>2>4 Which of the following has lowest pK. value ? @ §° %O- 0) ? 9 @ 2 CO Ox ASRIGRS IG Cea No 34. Arrange the following (w, x, y, 2) in decreasing order of their boiling points: | i) o o @ (@)wox>2>y (bk) wox>y>e © woe>y>x @w>2>x>y 35. Arrange the following in increasing order of their acidic strength. 9° OCH: o eL co) oO oO ™ : o @my>z Owoz>x>y (@s>woxry Wz>x>w>y Arrange the following alcohols in decreasing order of the ease of ionization under acidic conditions. @>m>n ) I> > mr (@u>m>t @u>1>0 ‘Among the iomeric amines sleet the one with the lowest boiling point. | N (Hs NH, w @ © Orme © O @ Cry Which one of the compounds shown below, is not an isomer of the others ? o() oO) °© Arrange the anions (p) THs, (@) NHz, (F) OH”, (6) F”, in decreasing order of their basic strength. @p>q>r>s O)q>p>r>s Or>q>p>s @r>p>qrs ‘One among the following compounds will not give effervescence with sodium carbonate: 1H Ost NO,, NO, (@) CgHsCO,H —— (b) © CeHsOH @ ‘The carboxylic acid which has maximum solubility in water is: (a) phthalic acid (© malonic acid[GENERAL ORGANIC crennsTAY 46. 47. 48. 49. 50. 51. 52. 53. ‘Among the following compounds, the most basic compound is oO ) 3 ol } wk S N’ H ‘0 x jt & > Hi Arrange the (C - H) bonds x,y and z in decreasing order of their bond dissociation energies in homolysis. @y>x>e W)2>x>y (© s>yrx @y>s>x 23 g of sodium will react with methyl alcohol to give : (@) one mole of oxygen (b) 22.4 dm? of hydrogen gas at NTP © 1mole of H, (@ 11.2 Lof hydrogen gas at NTP Which of the following is most polar? On QO © ste correct order of dressing basi stengis of, y ands (a) x>y>2 ()x>s>y Oy>x>z @y>z>x Which of the following is the strongest Bronsted acid ? NH, NH @ O ) O oO } @ Wich ofthe following ithe strongest Bronsted base? NH, H i i A N, &) N @ Pais oC 2 Me 7 Which of the following is polar aprotic solvent ? (@) DMSO (b) Crown ether (©) DMG @ Allof these OH55. 56. 57. 58. 59. ‘Some pairs of acids are given below. Select the pair in which second acid is stronger than first (a) CH3COH and CHFCO,H (b) CH2FCO2H and CH,CICO,H (© CH2CICOzH and CH2BrCO2H (@) CHCH,CHFCO 7H and CH3CHFCH,CO2H H—c=c4c=c’cus; ‘Compare the bond lengths a and b: (@)a=b @a>b (© b>a @a>>>b Which (isomeric) amine has lowest boiling point ? (@) 1° amine . (©) 2° amine (© 3° amine (@ cannot predict 2s P ; Pwill be: © Ou oO O (d) mixture of (a) and (b) Which of the following substances is not an isomer of 3-ethyl 2-methyl pentane ? @n~nw © © (@ Allare isomers ‘Which of the following is an isomer of compound 1? ° i CH;CH,CHO CHy—C—CH3 CHy—CH=CH—OH CH,—cH—cH a @ @ No : ® @2 4 (© 2and3 (@) all are isomers 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 _(4) Product is soluble in polar solvent61. 62. 63. 65. 66. 67. Some pairs of ions are given below. In which pair, first on is more stable than second? @ @ (@) CHy —CH—CHy and GH, —CH—OCH, 8 © cy cH, EH Gilg and cia uy Sit, Oo ae CH, CH;—N —CH, wo and 1 cH, ores, H, —C° — CH, e CH—CH, —CHy ‘Among the given pairs in which ni first compound has higher boiling point than second ? (@) CHs —CH,0CHy and Cy — CH—CHy 1H ©) City —CH, —CH —CHy and CH; — CH, — CH CH —CH, (© CHy —CHg —CH2 —CHz —CHy and CH —CH—CH,—OH (@) CHy —CH, —CHg —CHy and CHy —CH —CH2 —Cl Which of the following alcohols is the least soluble in water ? (@) Ethanol (6) 1-Propanol (© 1-Butanol (@ 1-Pentanol Which of the following alcohols is expected to have a lowest pkg value? (a) Ethanol () 1-propanol (© 2,2, 2-trifluorethanol (@) 2-chloroethanol Which of the following alkenes is the most stable ? @ ian © “t @ Zac @ “( Bond X is made by the overlap of which type of hybridized orbitals ? ARS (@) spandsp® (b) sp and sp”. (© sp? and sp* (@) none of these Increasing order of acidic strength of given compounds is : PD LO aw an68. 69. 70. 71. 72. 73. @ I1>3 (b) 1>2>3 © 2>3>1 (@3>2>1 Decreasing order of acidic strengths of following compounds is : ey QO » oO @ a @x>y>e Wy>x>e z>y>x @z>x>y Among the given pai, in which pair second compound is more acidic than first? ° ° I (a) BrCH,NO} and CHCHs (©) Cy —CcH,cN and CHy — tity oH HH oH vt O 7 @ ¢ > & S —c=o0 cH; © CH74. 75. 76. 77. 78. 79. Which of the underlined atoms ine molecules shown below have sp-hybridization ? (w) GH,CHCH, ——(v) CH, CCHCI (w) CH3CH? @) H-C=C—H @) CH3CN (®) (CHy),CNNH, (@) xandz x,y, andz (©u,wandx (@v, xand y Which of the following, is the product of the reaction between AICI and CH30CH3 ? a l ae i Ate a Az a—at Oe Nc & N° Neu, a a cd a aaatto C8 1 ar~ eH,oct, —At aa eaten, @ aA CHOCH, a a Which ofthe following compounds coma at least one secondary alcohol? Or Be oe 2 am @ i 1,1V, VI " w 1m o unny “a 10LV Which of the following has the most negative heat of hydrogenation ? Om Ch Oh Which of the following options is the correct order of relative stabilities of cations I, Il and III as written below (most stable first) ? cH, Sty o cr ({) HC =CH—CH, —CH—CH3 an Hyo—¢—Gry ity (@) 1>u0>1 ) > MM >1 @ m>1>0 @i>m>n What is the decreasing order of stability (most stable -> least stable) of the following Ws AAA O (@ 3>2>1>4>5 )3>2>5>4>1 (© 1=4>2=5>3 @3>164>20581. 83. the hydrogen indicated by arrow will be easily removed as : a @H* @) H° oH @ Rank the bond dissociation energies of the bonds indicated with the arrows. (from smallest to largest). 2 b, c least ee) 4) No, 1 (@)254>1>3 (b)1>3>4>2 | 3>1>2>4 W3>1>4>2 Rank the following compounds in order of increasing acidity (weakest acid first). ao @2<3<1 M3<1<2 @le2<3 @2<1<3 ‘Which of the following phenols has the largest pK value (i.e, i least acidic) ? @ a Yon © ox Yon © eC LY-on @ nec methoxybenzoic acid (lil) o-methyoxybenzoic acid @) i—o1 == (0) KH+ OH = ‘0° (© MescO? + 1,0 == @ +CHOH == ‘Which compound posses highest dipole moment ? (a) naphthalene (©) phenanthrene © anthracene (@) azulene Of0+O0+O (E = activation energy) Relation between activation energies of above reactions i @E,>E,>Es OYE p>E>E, (OEy>E,>E, (4) E> Ey > Ey Rank the following solvents in decreasing order of ability to dissolve given compound. nm | OO ~ |. CO 2, Solute, (@) Et,0 > H,0 > EtOH (0) H,0 > EtOH > Er,0 (© H,0 > Et,0 > EtOH (@ Et,0 > EtOH > H,0. OO) 1,83 (inedyamino) apitalene afer efered re (Proton sponge) Its basie strength is 10!° more than 1-dimethyl amino naphthalene, Reason for high basic strength is: (@ resonance (©) steric inhibitation of resonance © ortho effect (2) hyperconjugation99. 100. 101. 102. In the given pair of compounds, in which pair second compound has higher boiling point than first compound ? @ [ot ana -—o fe ©» >=0 and >= (© HO—CH, —cH, —OH and CH, — CH, —CH, —OH li wo CNS ane (Ge Mec Ae Me. Me Me, : ; Dipole moments of given compound will be : Me Me NO, NO, “ © (a) (A) = 6.870, (B) = 4.11D (b) (A) = 4.11D, @) = 6.87D © (A) =4.11D, @)=4.1D @ (A) = 6.87 D, (B) = 6.87D Order of decreasing basic strengths of halides is : (@) F >Cl 1 >Br- (be) F >cl >Bro >Ir () >Br >Cl >F (@ 0 >ch >Br >F- Among the xylenes, which is thermodynamically most stable ? “OF “O © (d) All are equally stable Heat of combustion of two isomer x and y are 17 kJ/mol and 12 43/mol this information it may be concluded that = ¥/mol respectively. From (@) isomer xis 5 kJ /mol more stable (b) isomer y is 5 kJ/mol less stable (© isomer y has 5 ki/mol more potential energy (@ isomer xis 5 1d/mol less stable103. 104. 105. 106. 107. 108. 109. Rank the following substances in decreasing order of heat of combustion (most exothermic —+ least exothermic) Www ANY OY aw co © (@ B>A>c (b) A>B>C (0 C>A>B @c>B>A LL 6 @ o Choose the statement that best describes given compounds (@) 1,5, 4 represent same compound (b) 1 and 3 are isomer of 2 and 4 (© 21,4 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, —NH, w o © ‘} @B>A>C>D QO)C>A>B>D (QC>A>D>B (@)C>B>A>D Rank the following in decreasing order of basic strength i (cH, —cH, C=C (@) cH, —cH, —s~ (cH — cH, —co3 @)cH, —cH, —0- @B>A>D>C )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. © @aAc ) B,D (AB @ Bc Oxalic acid Pky ‘Malonic acid pK> Heptanedioic acid py where pK,, pK, pK are first ionization constants. Incorrect order is : (9) PK, > PKz > PKs () PIG PK > Ky (4) pK, > pk, > pk, Insets a— d, only one of the set is incorrect regarding basic strength. Select it: : NH . (@) Ph—NH—Ph, MeNH, > Me,N > NH, (Protic solvent) z Y > ‘0 (©) EE,NH > EtyH > BINH, > NH @rotic solvent) eRe (© MeN > Me,NH > Me-NH, > NH, (Gas phase) (@ Allare correct, CH Order of basic strength Ph —NH,, Ph—NH—Me, Ph—N—Me, oO @ ® | Me 5 © o @A=B>C>D @)B>A>C>D (©) C>B>A>D (@)C>B>D>A Carbon-carbon double bond length will be maximum in which of the following compounds ? ©) CH, —cH =cH—cH, @ CH, =CH, CH CH Which has maximum dipole moment ? ° i |116. 117. 118, 119. 120. 121. ni @ EN wo A Git) oe Compare the basic strengths of compounds given: : @ O> @ > Gi) © >> Gi) © G)>Gi)>@ @ GD > d>O For the following two reactions, which statement is true ? i (a) Reaction A is faster and less exergonic than B (b) Reaction B is faster and more exergonic than A (©) Reaction A is faster and less endergonie than B (@) Reaction B is faster and more endergonic than A _ boy nt av] ay Identify the site, where artack of H* is most favourable. @a ) b OMe @d Rank the following alkenes on order of increasing 2, "OO =O) @1<2<3 @1<3<2 © 2<1<3 @2<3<1 Which of the following cyclic amine has lowest AG* for inversion ? @ [Dy-cu-me @[Sy-ngu Dy-tu © [Dy-pa Rank in the order of increasing acidic strength: E10,€. COEt CO, ‘OnE Sy wacnec’ ma propane (b) cyclobutane +H, -> butane (© cyclopentane +H, — pentane (@) cyclohexane +H —> hexane > “ Co ® b © 0d. S 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 at i @ ie oly © @ ° x © ‘Which of the following is the most stabilized carbocation ? ‘ome ome ‘OMe one @ “co ® AC © “ty @ “ty Which carbocation is the most stable ? @ mae woaak © ark Aa ge @ Consider a positively charged C,H, species in which the positively charged carbon is sp - hybridized, the uncharged carbon is. pehybridized and an empty p-orbital is perpendicular to the x system. What it the best description of this cation ? (a) vinyl (b) allenyl © alkyl (@) allyl129. 130. 131. 132, 133. ‘Which of the following reactions (@) CHy—Cl+CH,;—CH, = +" CH, + CH, —cH, —cl () CHy—Cl+ (CH),C—H > CH, + (CH,), C—Cl (© CHy—Cl+CH,=CH—CH, —> CH, + CH, =CH—CH,—Cl (@) CH;—Cl4+CH,=CH, = —+ GH, + Cll) = CHC! List the following carbocations in order of decreasing stabilization energies. © am Cr am CY wy CO @) UL 11v ) 1M, IV, 0,1 © m1, (4) 1, 11, 1V, For the following two acid-base reactions, which statement is true ? (DCH,CH; + CHyNH, = == —CH,CH, + CHyNH™ Pi =25- Pra =50 mr + HO = HR + HO™ 187 e=32 (a) is favoured to the right, 1 is favoured to the left (b) Lis favoured to the left, Ils favoured to the right (© Tis favoured to the right, I! is favoured to the right (@) Lis favoured to the left, Ili favoured to the left Rank the hydrogen atoms (H,, Hy, H,) in the following molecules according to their acidic strengths & 0 ® ® @a>b>e Wb>are @b>c>a @a>e> In which of the following reactions, backward reaction is favoured ? @ H—C=C—H + Lit-CHCH, > H—c=0:Lit + H,c—cH, ene = / oe + HOCH,CH, Fy OH (© CH,CH,SH, +cHACHOH = = CH,CH,SHy cH,CH, O-1 1 + + ‘a itty on MOH *O-O+0-°0 Which carbocation is the most stabilized ?aR oR RR 134. 135. 136, 137. 138, 139, ORGANIC CHEMISTRY E 22 a 8 @ CO © CD © Co: @ CO % 4 ‘Taking into account of hybridization and resonance effects, rank the following bonds in order of decreasing bond length, 0 oi? 2A an @i>U=m @n>m>1 ©i>m>n @m= ‘Which one among the following carbocations has the longest half-life ? @ bi wi Co o ORK) @ chy Gat, O cH, Rank the following alkenes in order of decreasing heats of hydrogenation (largest first) AF SSeS 1 2 a ‘ (a)2>3>4>1 (b)2>4>3>1 -@1>3>4>2 Which of the following reactions is most exothermic ? «> + chs a+na o> + Begs ar + HBr ra v8 Ysa hy Which energy diagram best represents the given reaction ? oC my = = me” ey JT ‘Which one of the following is most stable ? @1>4>3>2140. 141. 142. 143. 144, 148. Which of the following is strongest acid ? H q | toute o ac" © CO @ O H Compare relative stability ofthe following resonating structure. + @ Gy Git) tl @ @> w >a Oa> >a © o> Gi > @ @ Gi) > Gi) > @ Compare relative stability of the following resonating structure. o ° oF CH = @ AY 07 tl ti N N 1 @ p>q>r © a>p>r © a>r>p @ p>r>q ‘Which of the following isomeric hydrocarbons is most acidic ? “OD »OX "CD “CQ Which of the following has the lowest barrier to rotation about the indicated bond ? @ QO ORF OA @ ay Use the following data to answer the question below. OO O00" OOO (Ni) (QH = ~1162kcal mol“) ‘amhracene 28.6kcal mol")146. 147. 148. 149. 150. 151. - ae Caleiilate the resonance energy of anthracene: (@) 84 kcal/mol (b) 100 kcal/mol (¢) 110 keal/mol__ (4) 116 kcal/mol How many double bond equivalents does a compound of molecular formula CeH;.05 possess? @o 1 @2 @3 How many double bond equivalents does amoxycillin (shown below) possess ? NH, OH ¥ Kx amoxycillin CO,H @s (b) 6 O7 @9 ‘What is the oxidation state ‘osmium in 7B and 7C, respectively ? 3 | + “S02 NZ et : ra SS of @) 6,8 (b) 8,6 (©) 6,6 @ 8,8 9 oO Hy Hp NTP, | Ha | Identify most acidic hydrogen present in the above compound: faa @)b Oc @a ‘Which of the following compounds has most acidic hydrogen ? aan oOL < oOL 2 o cat J +Ohacly wlQhac®?> Sy } Acetic acid, (CH,COOHD, has a pK, of 48. Ethanol, (CrIgcH,019, has pK, of 16 What are the major species present, when acetic acid and ethanol are added to water and adjusted to 7.0? (@) CH,CO3H and CH,CO,0H (©) CHjCO;H and CH,CH,O~ () CH,CH,0" and cH,CH,OH (4) CH3CO3 and CH,CH,OH152. 153. 154. 155. 156. 157. ‘The most stable canonical structure of given molecule is: 6, ( } C) C ; @ ) © e @ In the potential energy diagram to the right, the point X represents : lv \ leone Reorganiation (@) a transition state (b) a reaction intermediate (© a resonance hybrid @ areactant Po Dew © @ ‘Which of the following orders is correct for heat of hydrogenation of these compounds ? @i>m>0 @m>m>1 (© M>IS0 @ W>1>m Oe ce (ee CH, CH, CH, o 7 o a? Which of the following orders is correct for heat of hydrogenation of these compounds ? @i>n>m = @M>u>1 |] M>M>1 — @ mt >1271 CH, =O <> ®cH,—0° +—> °CH, —0® o w am Which of these structures is practically nota valid canonical structure for formaldehyde? @ om © m (4) None of these CH,=CH—CH=CH—®NH,; — "CH,—CH=cH— °cH— ®NH, ® ay cH, —CH=CH—CH=NH, ay(ECR eee ee Which of these structures is not a valid canonical structure ? @1 () om (@) none of these c oe oF I I 158. oO oO ‘B f Neu, 4 a x Now, ® a an ‘The correct order of stability for the given canonical structures is @I>m>n &m>i>n = © m>M>1 — @u>1>m : O-O+¢ : ~O-O-6 ‘The most stable canonical structure among the given structure is : @t ou (© ml (@) all are equally stable 160. A\AAroan, SAYS Fors o a OCH; un For the given compounds the correct order of resonance energy is: @ m>1>m @u>ism (@i>0>m @m>u>1 = H on 0 H on, Ais ets 161. cay CNC Gy-goNC a- C= NS @ ~CHy ® ay “CHS ‘The correct stability order of the given canonical structures is : @ i>u>m @m>i>n @1>mM>0 @m>m>1 162. In the above compound, how many sites are available for the attack of CHO" ? @1 2 ©3 @4 163. CH +tyCH, — CHy0-CH ty CH, CH,0 ~ CH ty CH - § ~~ OEt o m a a Which of the following orders of rotation barrier about the C = C bond, as indicated, is correct ? @i>n>m () > m>1 © M>1>0 @u>1>m165. 166. 167. 168. 169. 170. Which of the following orders of rotation barrier about the C correct? @i>u>m — @m>n>i @ maton @ W>t> Which of the following compound is not resonance stabilized ? @ Cr o Ch eo Qh, @ CO Homologous compound have same: C bond, as indicated, is (@) General formula (&) Empericalformuia (© Structural formula (@ Molecular formula Most acidic Ht H oH H @ © © ou @ No, i No, Which of the following substituents will decrease the acidic strength of phenol? (@ —No, @ oN © cH, (@ —cHo Which of the following structures possesses a cross-conjugated system? (@) CH, —cii—cH —cH—cH, () cH, =cH—c =cH, | cH,cH, (© CH, =CH—CH—CH=CH, (@ cH, =cH—c = cH, | | cH— cH, cua, Examine the following resonating structures of formic acid for their individual stability and then answer the question given below. Se o y Js 5 H-C_OH HC 0 He C0 0 on 1 in m1 v Which of the following arrangements gives the correct order of det above-mentioned resonance contributors? (@) M>I>Ml>V (b) I> >> IV (©) We ll>150 creasing stability of the @ W>m>i>n172. 173. 174. 175. 176. 177. ‘Sand CH, —S—C =N (b) CH, —C =oandcH, —c =6 i , IPP (©) CH; —C—OHand cH, — C =O—H @ CH, =CH—C = Nand¢H,—cH = In the molecule CH, linearly is: @2 ) 3 o4 @s ‘The stability order ofthe following carbocations is RRA 1 m oN @ I>WV>M>1 &) WV>i>i>1 © l>M>I>V @ I>M>n>v ‘Total number of a-hydrogen in given compound is: =n CCH =CH,, the maximum number of carbon atoms arranged @4 ms 6 @7 ln which pair second ion is more stable than fist? 7 OO Oo ch ot wo Gi) (wy @ ‘ iv G) —— ®) WMandGiy) © GandGv)—(@) Gil) and (iv) Which one is the most stable cation in the following ? “O 9 9 «GO ‘The most reactive amine towards dilute hydrochloric acid is_____ HANH, CONE, fin NH OO 8 ti178, 179. 180. 181. 182. 183. 184, 185. rn ‘How many resonance structures are there for anthracene ? Co @ 6 @) 5 oF (a2 Which bass srong enough to convert (CH), COHinto (CH )sCONain a reaction that goes to completion ? (@) NaNH,, (b) CH,CH,Na (© NaOH (a) CH,CO2Na (©) More than one of the above Based upon an understanding of product stability, predict the product formed when the following dianion reacts with one equivalent of acid once Chenin oF EEE eof a ao OH OF On oe 9 o oF oad oA oAK wAA Rank the following alkyl radicals in order of increasing stability (least < < < most). Ph ¥ % 3 % @4<2<1<3° 0 W)3<1<2<4 = (1K63<4e2 Md) 2< 431 ‘Among the given cations, the most stable carbonium jon is ? (@) sec-butyl (b) tert-butyl © wbuyl (@ None of these Cyclohexadiene contains __vinylicand__ allylic hydrogen atoms ? (@) 2and 2 respectively (©) 4 and 4 respectively (© 2and 4 respectively @ 4and 2 respectively ‘The dipole moments of halo compounds are in the order (@) CHCl, > CCl, > CHL, > cis~CHCI =CHCL (b) cis-CHCI = CHCl > CHCl, > CHCl > CCl, (© cis~CHCI = CHCl > CH,Cl, > CHCl, >Ccl (@) CHCl, > CHCI, > eis -CHCI =CHCI > CCl, ‘The pka value in HO of piric acid, acetic acid and phenol are in the order: @) Picric acid 0.4, acetic acid 4.75, phenol 10.0187. 188. 189. 190. (b) Acetic acid 0.4, picrie acid 4.75, phenol 10.0 (©) Picric acid 0.4 phenol 4.75, acetic acid 10.0 (d) Phenol 0.4, acetic acid 4.75 picric acid 10.0 ‘The preferred sites of protonation in the following compounds are: cH, CH XH @o ai) (@) land3, (b) 2and 4 (© land 4 @ 2and3 ‘Among ivi HH Ce 1H Tis @ i) « the boiling point follows the order @ @<@ < Gi) © GD<@<0 © <<) @ W@ << @ ‘The number of C —C sigma bonds in the compound coo (a) 16 (b) 14 () 18 @u ‘The correct order of dipole moment for the following molecules is GS OG x P ° o ay a a (@ W>i>M> @)l>V>M>1 © M>t>n>Vv @u>m>Wwet Curved arrows are used in Organic Chemistry to show the movement of electrons in the ‘mechanism of a reaction. The correct product of the following reaction is ee34 ORGANIC Chemistry for ITJEE tlolz}@ls/@}4}/@ls{/@}e{@]7|o|*® |o 9% | wb) | 10. | @ | 11. } oy | 12-| cb) | 13. } ca | 14. | @ | 15+ | od | 26-| 17.| @ | 18.| (© | 19.| @ | 20.} «@ | 21. | @ |22-| @ | 23-| © | 24 | @ 2s. | @ | 26.| @ | 27-| «@ | 28.| @ |29.| @ | 30} @ | 31-| © | 32| 33./ @ | 34.| @ [35.| @ | a6. @ | 37-| o [38-| @ [39] @ | 40.| | | 43-| | 42.| a) | 43.| @ | 44] ce | 45] ce | 46-| @ | 47-| © | 48: | @) 49. | (b) | 50. | (b) | §1-| (a) | 52.| (a) | 53.] (a) | 54] @ | 55-| © | 56 | © 37.| w |58.| m [59.| @ | 60.| c@ | 61.| @ | 62.| w | 63.| @ | 64] 65. | (d) | 66. | (©) | 67. | (a) | 68. | (a) | 69.} (a) | 70.] cb) | 71-| @ | 72-| @ 73.| ca |74.| a | 75-| @ | 76.| @ |77-| w | 78-| @ | 79-| @ | 80-] ca | | e1.| ca [92.| cw [9s.] @ [es] co | 8s.| o | 96.| @ | 7.| @ | 88.| o 89.| (a) | 90.| a | 91] @ | 92-| @ | 93-| @ | 94-| @ | 95-| cw | 96.| @ 97.| () | 98. | @ | 99. | (a) |100.| cb |101.] () |102.] (a) |103.] (ay |104.| (a) 105.| (<) |106.| ¢<) |107.| (@) |208.| @ |209,| ce) |110.] ( [raa.] ca [r12] co 113.| ¢ [114] © |115.| © [116] c@ [117] ca [218] @ |119.] (@ [120] ( 121.| (©) |122.] ca |123.| (©) |124.| co |125.] @ |226.] 0 [127.] @ [128] «a 129.| ) |230.] c [131.| « |132| @ [299 (© [34] @ lass] cw fase] @ 137,| @ {138 @ |139.| © |240.| co [1414 c@ [2421] ca [143,] @ fraal ) 145.| (a) [146.] cw [247- ca [248.1 & |249.| ca [a50.] 0 |as1.] @ |as2, J153.| c@ [254] cw [ass] co [156] c [157] [ase ay [i591 @ |a60. 161] co [262 co |r63.| c [rea] c |265.| co [266.] «a [67.1 cw [268 © © 169.| (a) |270.| «by |173-] c@ [172-1 © |273-| co [174] @ |275.] a [276 cw | | [178] co [179] ce) |180.] ca |181.] ) [182 wo) |183.] @) free, (a) © 187,| ca) |188,| (b) ) [190] ()1. Rank in order of radical stability (1 = most stable). @ o a 7 leans ere Oo Oo Predict the acidity order for the three phenols shown below : Acidity order : 1 (most) to 3 (least) 5 Acidity order : Ht OH On ON, No, ry ® © NO, NO, CHy oH OH oH HN, NH © © ® NO2 NH, \,ORGANIC Chemistry for UT-JEE | ‘Which of the phenol derivatives above is the strongest acid ? Compound A Compound B Compound ¢ Compound D Compound E Compound F Which of the phenol derivatives above is the weakest acid ? OD Compound A Compound B 1D Compound © 1D Compound D Compound E (0 Compound F Which of the mono-nitrophenol derivatives above is the strongest acid ? © Compound a 1D Compound D D. Which of the carbon-substituted phenol derivatives above is the strongest acid ? C. Compound ¢ 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. | @| He Gis @ ne © Ofte © OY chy 5 @ Cy en) COX @ { ‘OH NH @ Cr wo] me ® Cu oO D ° 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? [—] 5. Consider the following compounds and answer A and B, i i i ‘A. Which of the compounds is the strongest Bronsted acid ? @t wu om @wvIRGANIC CHEMISTRY > _ < 37 B. Which of the compounds is the strongest Lewis base ? @ on © ml @yv 6. Rank the non-bonding electrons indicated by the arrows in order of increasing energy. eT Isc, N— cH, ° 7. In each of the following sections four nitrogen containing compounds are listed. In the box under each formula write a number (1 to 4) indicating the order of base strength, QO w| GQ [Ores on pm ®) N(CHy)2 © Cc O-« aes Oyo i HC | 2 TON38 x ORGANIC Chemistry for UTJEE 8. For the two sets of acids shown below, rank their acidity most acidic to least acidic. oO) ao w 3 pr opha ahee apn ®) Br Br @ Co) ww In each of the following sections four compounds are listed. In the box under each formula entera number (1 to4) indicating the order of acid strength (1 is strongest & 4 is weakest) cucrcugosH | ciyccuprco,H | coucncico.n | casccico.4 @) CaHsCHOH GHC nH C@H.OCHiy CatigoH ) OH 02H 9 fe xv | © © NHy Co —H ‘N—H @ Cc > aos Cis iil[GHNERAL ORGANIC CHEMISTRY | 39 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, 2 5 i Strongest ‘N 'N’ y z — “lO| O N Me 'N’ @) &) © @ Weakest B. For the series of acids shown below, rank the set from strongest to weakest. = 0 HO, ‘HO, ei eS — = HO,C. ™ HOC, of Of ke) | cy™ ‘OMe 102 11. Im each of the following sections four compounds are listed. (Decreasing order of acidic i CH,(CO£7Hs)2 CH3COCH LO £2Hs (CH3CO),CH, RC ==CH (a) RCH:NO2 RSOLHy (CelHs)sCH RCOCH (b) (©) C |“ORGANIC Chemistry for ITJEE| 12, Rankin the order of increasing basic strength. © ja My H NH, A@ a © w ° ‘& o © oC @ « @ \ HN NH, HyN CH HN OH HC CH, 13. Compare acidic strength of the following (Write your answer in box). AW AA ANA @) o) © on A OH HN @Ie se/se] | go & sy L 14, Arrange the hydrogens in increasing order of their acidic strengths. Hy Nae REF H sa mn : I H ot,42 15. ORGANIC Chemistry for IIT-JEE ‘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. CHa © cH HyC\_-CHy HgC_CH, CH, NZ CH CH, CH, COnH ‘limonene 2. muscone nicotine 4 ibuprofen 5. camphor KO ° CH HeC, OH oH ° Ol wt) O—CH; Be H ofa HycSOHyC7 CH 6. vanitin aspirin 8. geraniot 8. acetaminophenol A. | Which have carbon-carbon double bonds ? B._| Which have a ketone carbonyl group ? i C._| Which have an aldehyde carbonyl group ? D._|_Which have aromatic rings ? E. | Which have a hydroxy group? F._| Which have ether groups? G._| Which have an ester group ? i H. | Which have an amide group ? 1. | Which have a carboxylic acid group ?A c rE ° o elo i at Cr penton ‘Which is the strongest acid in 1? @A ‘we Which is weakest acid in 1 2 @A ) B ‘Which is the strongest acid in 2? @aA () B Which is weakest acid in 2? @aA os Which is the strongest acid in 3 ? @aA @)B ‘Which is weakest acid in 3? @a wes Which is the strongest acid in 4? @aA (b) B Which is weakest acid in 4? (aA (b) B oc oc oc oc oc @pD @b @pD @pD @pD @p