Problems and Solutions in OTE CCIE AY Subrata Sen GuptaProblems and Solutions in Organic Chemistry Subrata Sen Gupta Formerly, Reader in Chemistry RPM. College, West BengalPreface chemical compounds ae visible to the aked eye, their constituent atoms and bonds are invisible even under a very powerful microscope. When one tres to visualize the {formation ofa compound, one has to depend on the infor ration available in related literature, confirmed through time-tested experiments. Therefore, when a student comes across a new problem, the solution can only be rationalized asa “plausible” explanation or by concluding that ‘results have to be confirmed by experiments and investigations’. Organic chemistry is a mind-boggling field of chemisty, inthe sense that nature has produced thousands of organic ‘molecules with unimaginable complexities. Fascinated by this area of study, chemists are observing and following nature to synthesize many new compounds in thei labora- tories, many of which have changed our lifestyle in unim- aginable ways. ‘Young learners must realize that to excel in any science course, they must develop the habit of solving problems. ‘To gain confidence inthis, they would initially need the assistance of books that contain a large numberof solved problems. It is with this objective in mind that Problems ‘and Solutions in Organic: Chemistry was conceived. The ‘book is designed as a self-study material, 10 expose stu dents tothe various facets of organic chemistry. ‘ABOUT THE BOOK Problems and Solutions in Organic Chemisry is primar- ily writen for undergraduate students who have opted for fan Honours course in chemistry. It wil also be useful for students pursuing postgraduation in chemistry and those preparing for competitive examinations such as the Joint ‘Admission Test for Masters (JAM), National Eligibility ‘Test (CSIR-UGC NET), and Graduate Aptitude Test in Engineering (GATE). ‘Most problems in each chapter have been discussed ‘on the basis of traditional functional groups present in ‘organic compounds. This will help students get an idea of the types of problems based on a particular elas of com ‘pounds. For example, alcohols can participate in elimi ration reactions, ethrification reactions, esterification reactions, and are reagents in nucleophilic substitutions a5 well. Therefore, if we separately discuss the problems ‘on alcohols, we can get an idea ofthe different types of reactions these compounds take part in. Similarly, the properties of aliphatic carbonyl compounds and aromatic Eatbonyl compounds differ in many reactions. Theret if problems on these compounds are individually discussed, stadents would get specific information on the types of reactions these two different classes of carbonyl compounds take part in, Such an approach to learning the subject is more pragmatic as it helps readers get acquainted with the relevant reactions within a class of organic compounds. KEY FEATURES * Problems on the nomenclature ofthe different classes Of organic compounds based on IUPAC rules, and the answers to these + A plethora of problems onthe classes of compounds With plausible mechanisms and rationalization, where necessary «Illustrative reaction mechanisms through welldrawn diagrams with supportive explanations and com- ments wherever needed + Problems on stereochemistry, spectroscopy, and per- icyclic reactions + Over 1500 solved problems addressing various topics on the subject. + Includes 700 chapter-end exercise problems 10 aid self-evaluation CONTENTS AND COVERAGE The book has 21 chapters, A short description ofthe nature of problems included in each chapters given here, Chapter I, Nomenclature af Organic Compounds, provides problems onthe naming of various aliphatic, alicyclic ro- ‘mati, fused polynuclear, spiro, heterocyclic, and bridged compounds. The nomenclature of many unique unsati- ‘ated aliphatic compounds and compounds with a variety of functional groups have been discussed. End-chopter ‘exercises discussing certain interesting chemical structures hhave also been included. ‘Chapter 2, Physical Organic Chemistry, deals with prob- Jems based onthe concepts and theories inorganic chemis- ‘ty, such as acid-base reactions, dipole moments, reaction rates tautomerism, reaction kinetics, and aromaticities. Chapter 3, Stervochemisiy, includes a large number of problems on various aspects of stereochemistry involving Drganie molecules, Problems on both stitic and dynamic. stereochemistry have een demonstrate. Chapter 4, Aliphatic and Alieyelie Hydrocarbons and thir Hades, elucidates problems on both saturated andiv Preface Uunsaturnted compounds in addition 10 those on aliphatic and alicyclic hydrocarbons. Chapter 5, Alcohols and Ethers, throws light on typical problems on alcohols and aliphatic ethers. Chapter 6, Aliphatic Cartons! Compounds, deals with a ‘wide aay of interesting problems on aliphatic aldehydes and Ketones ‘Chapter 7, Aliphatic Acids and their Derivatives, describes ‘problems on aliphatic acids and their derivative, such as ‘esters, amis, and acid halides. Chapter 8, Aliphatic and Alicylic Amines, Niele, socyanides, Vides, Diazocompounds, and Organometallic. Compounds, diseusses a host of interesting problems on these clases of compounds. Chapter 9, Aromatic Carbony! Compounds, explores the typical problems associated with these compounds. Chapter 10, Aromatic Acids, Amines, Nitre-compounds, ‘and Diazo-compounds, comprises a large number of prob- Tems on these staggering classes of compounds Chapter 11, Phenolic Compounds, Benzoquinones, and Aromatic Ethers, deals with specific and interesting prob- lems on these compounds 10 understand their reactions beter. Chapter 12, Bensenes, Polynuclear and Alieplic ‘Hydrocarbons, explains problems on benzene and substi- tuted benzenes, polynuclear aromatic hydrocarbons, and some additional problems on alicyclic compounds, which hhave not been discussed in Chapter 4. (Chapter 13, Periyelic Reactions, deals with problems on this special cass of organic reactions. These include reac- tions suchas eletrocyclic reaction, cycloaddition reaction, sigmatropi reaction, and ene-reaction. Chopter 14, Problems on the Uses of Spectroscopic ‘Methods in Organic Chemis, illustrates the problems on the application of ultraviolet (UV), infared (IR), nuclear ‘magnetic resonance (NMR), and mass spectroscopic meth- ‘ds in the identification and determination of structures of| ‘organic molecules, ‘Chapter 15, Heterocyclic Compounds, has a large array of problems on monocyclic and bieyelic heterocycles with N, (0, and $ as heteroatoms. Chapter 16, Carbolydrates, has problems dealing with naturally occurring typical monosaccharides, disacha- Fides, and polysaccharides. Chapter 17, Amino Acids, Proteins, and Nucleic Acids, deals with a variety of problems on important biomole cules such as amino aids, proteins, and nucleic acids Chapter 18, Molecular Rearrangements, analyses prob- Jems associated with molecular rearrangements encom- passing al the clases of organic compounds, Chapter 19, Conversions and Syntheses of Organic Compounds, gives & cleat picture on the mechanisms related to conversions among organic molecules and also talks about the synthesis of organie molecules from typical compounds and reagents. Chapter 20, Constitutional Problems on Organic Compounds, bas a diverse range of problems onthe iden- tiffetion of compounds based on a sequence of reactions. (Chapter21, Miscellaneous Problems, presents large num- bro interesting problems based onthe different classes of ‘organic compounds and a variety of organic reactions we encounter in organic chemistry. ‘Appendix A, Abbreviations of a Few Reagents Used in Chemical Literatare, lists out the abbreviations and the ‘coresponding chemical structures of some frequently used reagents in organic reaction. Appendix B, Reducing and Oxidizing Agents Commonly Used in Organic Chemisry, lays emphasis on the various reducing and oxidizing agents, along with their chemi composition, preferred solvent, and reaction mixture. ‘ACKNOWLEDGEMENTS express my deepest gratitude to Oxford University Press India for accepting this book for publication. !am particu larly thankful tothe members ofthe editorial team for their CHYCHL,CHLE FEATURES OF Over 1500 Problems with Solutions. ‘The book contains more than 1500 problems with Solutions to reinforce Teaming through the ‘question-and-answer format Coy, +KR= [eke I 3 Kicoordinated 1-cown-6 Numerous Exercises “There are moe than 700, enereige questions spread terse chapters for sll valuation of eoncep'sTHE BOOK 206 Theintcraction of diphenytketene and styrene results ina compound °°, C,:H,0.°A° reacts with methylma, nesium bromide to give *B, C,,H,,0. Dehydration of Exclusive Chapter followed by ozonclsis gives a ketoacid "D’, which with ‘on Constitutional alkaline hypoiodit forms triphensIsuccini avi. Identify Problems the compounds “A’, B", and "D° and show the reactions. ‘This chapter tains students to analytically think and seduce organic compounds hich are represented 35 unknown variables in 8 given reaction deseription semen mo t-¢—-o Pa-cH—CH, Presentation Based on Various Classes of Compounds ‘The text exemplifies the subject matter according tothe various lasses of oreanie ‘compounds and their associated actions. i Ph CH—CcOon, © Tiphenyevecine acid ae @ Aliphatic Carbonyl e Compounds wy @ Aliphatic Acids and thelr @ Derivativese @ LI Give the structures of the following IUPAC names (@) L-Aliy2-ethyl-(prop-1-en-2-y-3-vinyeyclobs 13diene () 34S-Amino-2-nitrophenyD-2-methytpropanal (©) Mrop-t-enybher--en-2-one (@) 4,4Dipropyleyclohesa-25-dienone (©) # Methyi-67-dimethylene-toxononanoic acid ( 2(Prop-L-en-2-3)-7ing-12.345,68-0ctahydrona- phthalene ethy-7-viny-1,2,34-tetrabydronaphthalene-2- ern op atligtihaatenencee © OeeaAieeiat 8 eee Sandee ae @ o Mh - Be " ‘NO, © 0 @ AZ © ol ApS com @) COOH (h) ° Nomenclature of Organic Compounds © caso ) ° m 8 o 7 A4 coat P oa o Fs G7 wo Oe ‘coon ® p @ Ls 7 ane He a o o Be ae ets © o ‘Ans (@) 44-Di(E-prop-t-enybeyclohoxs-2Sionone () # Methyl.6-dimethylene--oxonon-2-noie seid (©) (2RIR2- cis Buel Sdhen-251)-T-inylL 23456, 7 -octahydronapihalene (8) (E)2-(ut2-enylbenzere-L3-carborylie acid (6) (£)-24But2-eny)3-methorycarbony!)berzoic aid2 Problems and Sots in Organic Chemiry (9, (1825.48)-2-Brom-|--2-Bromo-B-chlro-E-hydroxy-2-mercaptonon- S-enoie aid (). @R:4R)-2,34-Tehydroxypentanedial (8) 252)-4.Bromo-4-methythepta-2,5-iene (). QR3RAS)-2,3,4-Teihydoxy-4-formylpentanoic acid (m) 535,48) 23,4 Teinydroxy-$-oxohexanal {n) (2R3s45)-2.3,4-Teikydroxypentanedial (6) 256,7-Teramethyldecane () (B)8-Methyberadee-3-en-13-ynoie acid (@ Etlea-1 3dien-byne (©) QEAE}4-Metiylocta2,4dien-6-yne 14 Write the TUPAC names ofthe following compounds.(@) Methanetricarboryic acid () 4-Ethyl-t-phenyleyelohexanone (©) 4Ethyl-+methyleyclobexa2,5-dienone (8) 34Prop-Len-2-yleyclopent-i-ene (©) Pestane-2,3trione (), 4.010-I-phenyleyclohexanecarbaldebyde (@) BicyeloJ22 2Joctan-2-one () Spiro AJoctane-2-carboryic acid (@ 4Vinyloct-len-T-yne (). FEthyny/-2-vinyeyeloberane (&) 14G,6-Dimethylenecyclohex-I-enyDethanone () 2Hydroxyeyelohepta-24,6-rienone (2) 3 Hydroxy-4-methylpent-enal—~ (0) Methyl 2-methy|-3-oxobutanoate (0) 4-Chloro-6-hydroxyhexan-one 1LS Are the following TUPAC names correct? If not, give their correet IUPAC names, (2) 1345,6-Pentabromo-12,6trichlorohexane (@) S-Ethoxy-2-methyl-S-oxopentanole acid (6) 2-Methyl-46-dioxohepta (@) Biacesy) (©) Butane-13-dione (, Diethytoxal (g) -Nitropentanenitrite (h) Octa-5,7-dien-1 3-diyne (@), Butane-12,4ricaboxylic acid {) #-Cyano-2-(-cyanoethy))butanote acid (0) 3 Propylldenepent-t-en-S:yne Ans (@) Incorrect (Correct name: 1,2,3.4,6-Pentabromo-1,5,6- sichlorohexane) (@) Incorrect (Correct name: 4-Carbethony-?-methylbatanoic acid) () Comect (@) Incortet (Comet: Butane-23-dione) (@) Incorec (Coret:3-Oxobutanl) (),Incorec (Comet: Diethyl ethanediowte) () Comect {) Incorrect (Comect: Octa-13-iene-5,7-diyne) @ Comect G) Correct ) Incorrect (3-Ethynyhexa-1,3-dene) 16 Givethe £,Z nomenclature ofthe following ompounds. @ = coon yooe » inde 3 lla eee wwe @ COOH © 1] ne en i a ® io (@) GESE)-Oct0-1,3,S.rien-7-yne (©) (O-But2-ene-12,4triarboxylic acid (©) (2)-+-Bromohex 2-enedicic acid (6) @-4-Cyan0-2-(E}-2- “Oy “ya 0 ) ") Oo "oo O Oao (@) Dikenzophenantiene (©) Berzantiacene (Not Benzoathracene) (@) Pemalene (@ Hepaiene (©) Octalene (© Biphenylene (Not Diphenylene; two benzene ringsare oto-fued 10 te etal rng of fur carbon stms) © Tiphenplene (ve benzene rings ar ortho Fedo the cent ring of siccarbon atoms) (2) Ditenzofajantiracene (©) Dibenzolhjantacene ©) Bicyeo(22. heptane (0) Bicyelo(22.0}hexane ( Bieylol4.2.2Kecane (@) Spio3.Ajocine (Total numberof carbons sesh) (©) Spiros secane (Not Spiro[3 decane; tot number of carbons itn) (6) Spio(3. 3p (Total numberof earbons i seven) ©) Spiof3 Show S-ne (@) Spitl$ dee--en-6yne © Spiol4Siecat ene (Not Spiro 5]ooe- tere; 16s lower than 1.9) (© Cyctohexylnenzene 1.14 Are the following IUPAC names correct? Int give the correct name along withthe structures. Cive your reat sons in brie. (2) 1,8-Dibromohexa35-dien-Lyne (©) Hexane-i,-dicarborglic acid (©) 3Ethynythexa-L¢diene (© 4 Formyoutan-2-one (©) Hepta-2-en<-ynediieackd (, SForms12-oxoheranedioi acid (@) Propane-23-ricarboxyit ackd ) Diaziridine-t-carboxslic cid (8) 7-Bromo-hept-4.6-dien-2-ynoic acid () Octa-4,6-dien-2-yndiote acid Ans (@) Incorrect (¢) Correct (D).ncomeet (©) Comect (Incorrect) Incomect (©) Comect —(g) Comet’ (x) Comroct (@ Incorrect’ (h) Comet). Incorrect ‘The corect names and the coresponding sttures ae given here, with explanations as necessary. ® (vung should sts fo the le-and side according fo TUPAC rule) ‘Nomenclature of Organie Compounds 7 (©) Hooc—cH—cH,—cH,—cH},—CooHt Hexanediic acid (lnthe case of strated siurbonylc aid with no ranching one ned ot tive any number tinct the positons ‘of COOH greups) © user, ci,—cit=cH—-CH-c: S-Etynyihera diene (Gath case of compounds having double bonds ple bonds, the tase name should inlace ‘the maximum numberof duble bonds) © ° cH,—€—cit,—cH—cit=0 4-Oxepentanal -CH=0 group ges preference over C=O soup in aumbering the cain. The position of the ‘CH= grovpneed not be given ay number) (©) Hooc—cH=cH—cH,—c=c—coont Hept 2-0-5. yeti seid (Since we hve the option of imberng the ‘ator chin te double bend gets a lower umber) 0 cu Propane-.23-ticabenivile (ON gro is mamed as ert when ‘they ar supposed to yield eater acd ‘on hyralyis ina aliphatic cain (a) NCO=CHI)=CH,-C=Neo lsoeyaatepropslyanate [=NCO aroun (eyanst) gets preference over OEN (soeyante group 0 3 cHci—cut, Propan tol (opropael is wrong me Scoot iain. arbonti ci Nunberng shot sat re he rg ore ofthe tng)“-romoepa-4.6ien-2-yni okt (Nunbesing should stan fom the sie of "he “COOH group which the prniple fictional group) © noo: ‘cout (Oat. 2 in 6 yeti acid (Since there isa coce, umbering should srt from the double bond end) 1.15 Give the names of the following heterocyclic com- pounds based on the Hantzsch-Widmann system, (@) 10t-Azirene Tae low (0) Azcte citerpoible ses "L3.5 "13, (©) Oxirane {@) Oxetene w (6) 2-Ethyl3-methylaziridine ( 14-Diphenylazetidine (2) 13-Dithiotane (i) 13.5,7-Tetroxoe 0 2tsir1 Dione @) 124-Trazine (hy 4H-1,3-Diphosphepine () 13-Oxathiolane 7 (on) 13-Thiazole Cy (0) 6H-12,5-Thiadiazine J (0) 2H,611,82-Ditiacine ss (®) 132-Diazarsetidine tortie ‘iscome) ‘Ans The structures of the aforementioned compounds are (0) siven here. @ he Wi — in wen ew 1. 135-tindiine Waar ‘ee (Coerng eg mate Cao Sinocnaieton wiocarias 3 @ 1 Tower than te set 7 rl “I38) wd we—9 ‘Oxo Osco oe 4, Ast © a ; Sn cn-neZS Ne 132 Dannie 2-Biyl3-methyaztidine (Substituents ar cited in alpbabeial ode) m—ne—ay, @ AL 1 Cy wen Ly (The tocan set 411.13.Diphospheine (Havre atoms get preference so ndieat hyerogen forthe lowest locas) O} 13-Thiazole © su 2H6141,52-Ditiasine (Rambering begs withthe sulfur tom, “Tin prefin gets preference ‘eran a at ie why the order of oan i 152 endmot 125") ba it 1A.2-Oxazaphespholitine (Not 1.42-Oxanzaphlicine) @ (rretosantact'13'islower 1:16 Give the names ofthe following isotope labelled com- ‘han 14) pounds.“cH, @ cH © oe, fo moet, ¢) WYO CHINE, GG Ds @ “ (from @ voor €Y-coon (9 HIMCIOONs Ane @ (“o)Metane @) CH) Methane (©) Dichloo?H, meine (@) 1-{Amino("C)methyTJeyelopentanol (@) 1{Aminomethyl)cyclopentan('*O)ol or 1-(Aminome- fy HOveelopetno! (0 OINPH}eyelhex enamine {@) Sodium ztyiQ3-"C,)weiate (8) SMenyif i )pent-hene ere the loeat spat of She parent bydeocarbon mame) (Bhi oF (0a ) PH,KBenzene (k) (2,27H,}-1-2H)-Naphthalenone {0 mibotCmetyeylopetanol toy (Hace acid (@) (O-tlacet ac or Ace? Hct (0) (1C}pentantjne aid ot 1"C,OHipetanoi sid (9) Cycloberane Hleaboryie it {@ #2"C]Ety ena aid {8 Sodium *C}ornate 1L17 Give the names of the following radical D cncr,cr, © cucncy, © , “y Ronee Orie Coral ©, ¢ 0 e 4 a 5 © 36. oO ay ! as o &, © cHcHen, 0 cH,eucH, o m) ., &y 8 YW oe o I" ) cot @ GH-tu-EH, fo Heer -H, cy Cy —GH-EH, dupdnpdnc ey 6 bye EE Ans (@ Prony (©) Propan-2-yl or I-Methyethyl or Isopropyl (Tradition!) (© Cyelopents-24-ene--y1 (@) 2H-2yran-6-1 (6) Bicyclo(22.1heptan2-yt (© Spir(4 Sdecan-8y1 (@) U-Phenalen-ty1 () 11-Biphenyl31 @) Mesbytium @ Propytium () Propyl-2ytiam © _Cyetobutytium (6m) Furan-2-ylium ‘Met ation ‘Propyl cation *Propan-2-l cation **Cyelabuty ation *Furan-2-y ation (6) Ethane-1.2-bis(yium) {) Cyclobuti-ene-,2-bs(livm) (Note thatthe charged carbon gets priority in numbering) ©) Cyclohexane-,L-bisGlium) *Cycloheryldene dicaion (@) Propane-t,2,ns(yium) (, Butane-1,4bis(ylium) (9) Methanide () Propan2-ide 1 *Propan-2-yl anion *1-Methyletyl anion (0) Butan-t-ide —*Butan-Lylanion (9) Buleleyie-ide *Dut-l-yo-I-y anion 1.18 What is meant by 4,8, and A conventions in naming ‘organle compounds? Give examples., , ‘Ans A-convenion: Iti a method of describing non-standard bonding numbers of skeletal atoms in pareat hydrides. ‘A non-sandard bonding number ofa neural hetero torn ina siructure is denoted by the symbol 3, where isthe number ‘of non-standard bonds. A few example ae given here HSH, (tose, brace HPPH PH, Metytaaiphae Tohen2otonione as tanoetane YSIga uth rhorporn sens THPow asestniatSdng sonst body sont) somber) 1n43.Didhepin URAC) 1.3 Diep (CAS) (CAS stand for che ‘shanti S.convenion: The presence of contiguous formal double ‘bonds ata skeletal atom in acyclic parent compound whose name normally represents the srtural unit having maxi= ‘mum number of nom-cumultive double bonds is described by the symbol "9", where ‘isan Arabic numeral dencting the number of contiguous double bonds ached to that pat= ticular skeletal atom, The symbol 8" is always preceded by the concemed locant. The heteroatom exhibiting nonstind- ard bonding number can be associated with contiguous for- ‘mal double bonds in 8 cyclic parent hydride. In such cases the symbol forthe now-standaré bonding number i ko to be incorporated in the name. Illustrative examples ae given hee. (Sulphur ator hs onstandsd bonding ‘number Cy DIB SN Thine tc iepene 106?-Benzof9}annulene_ aaastolet 22.Dicloo-H20813-bemzothadazne Arconvention: If the cyclic component and the side chain are linked together through a double bond, the locants of this bond are placed as superserits to @ Greek capital delta (@). The symbol is inserted berween the eyelic and the acy- clic companent. The loeant for the cyclic partis placed caer tt En,-coon Inne 1 In the following pair, state which name is coneet and which ist (2) Pentan-2-0l and Peotane-2-o1 (b) Pentane-24-dione and Penia-2,4dione (6) 12,NAN-Tetaaminobenzene and N,N] 2-Tetraminoben- 1,3.57-Tewoxocane and 13.57-Tetraoxacane Thialdchyde and Thiosldehyde (9, esidoamiie acid and imidamidic acid (g) Carboximidie acid and Carboximidoie acid ‘Cyclohchexanosthanal and Cyelohexethanol , Dibera{ieloxepine and Dibenzo[heloxcpine {@. Benzilmonoxime and Berzilmonooxime Benzophenone and Benrphenone © ‘Answer these questions. Inthe following sets of combinations of leant, which set wil get preference in numbering the carbon atoms of acai. (2368). 245.2 (ip 2,7 and 1,2 Gi) (1.2) ana .2.46) () What does the folowing letereters or combination of leters indicate ina stcture ofan organic compound? eri, 5, rac,m,abeo, co, nor neo, fried, Ves (©) Decide which on ofthe fllowing names ae corrector incoret in each pir according to TUPAC rules of mam ing organie compounds. Give reasons wherever neces. sy. (i) Neo-pentane and Neopentane 845.5) (Gi) N-Acetylatet aniline and W-acetylated aniline (Gv) Spiro[S decane and Spins. S Mecane (©) Methanoic acid and Methanoie-aid () Ethylthanoat a Ethyl ethanoate (vi) Ethylmethy! ketone and Ethyl methyl ketone (ui) Styrene oxide and Steyrenconide (6x) Biphenyl and Diphenst(@) Bis-2-chloromethylamine and Bis-2-chloromethy) (i) (R)Lactc avid and R-Lactic acid 13 Give structures to demonstrate the following ways of naming organic compounds. (@) Trivial name () Semi-trivial name (©) Fusion name (@) Substttive name (6) Replacement name (9, Conjunctive name () Radicofunctional name (i) Additive mame ( Subtractive name () Hantsch-Widman name of hetercycles 114 Give the IUPAC names of the following compounds. (@) cic =cHeHCHcH=cH, cuecH, ( c=cnenion=cicH=ct, cacH a cHICH,,0CH.CH,CHCH=CH, gh gsc ( casieng,ceu.cn, cuter, cu, © ou, (© caycu,crtecne=cducy,c=ccH,cr=cH, cucu, ) cHomctncn=cucr, grenpcnscnce, @ CHKCH.CH, ECHL, exgen,cn,—Leea, ( cujac=o=c=cn, cect, cryencr,c=Luce, 15 Answe these questions on statues (@) Give the IUPAC names ofthe following compounds 0 @ cuCH, Hy cu.cn.cu, cH, «i oo, ca nara orl DY (&) Draw the structures ofthe following compounds. () Triapentaulvalene (iv) BenzofSJannulene (i) Azalene (©) Annulene} Gi) 14{Anmtene) 1.6 Give the TUPAC names ofthe following compounds @ He Ct Cra hiccr eno ® He cH Crain’ hire, o a Cpancrc! ‘i Naphtaene (orthoses) chysene (orthoses) 1.7 Give the trivial names ofthe following compounds, @ o oo "dé ener cn -cH, onc cH D-H “COS Naphdacene (erthofsed) ©Solutions in Organle Chemis "OO "GD °Qe: °O eel OD (8) Give the IUPAC names ofthe following spiro hydrocar- ‘bons. Show the numbering of the carbon atoms. a) Cx) wa CX] o Cd 1110 Ieeaify the correct aumbering ofthe following pairs of, 18 Identify the comect numbering ofthe carbon atoms ofthe spiro compounds and give its TUPAC names. following sets of compounds, @ f © ® 8 oy Wy, & © ng—en, Na Ae Hany ys. cp : PNAS, 7a bts a a8 oo G. Chr aN, yey ne 0 oy . si 411. Answer these questions on TUPAC strue- “ae ua "AC names and Mao (2) Give the structure ofthe Fllowing compounds. (i) 11"-Bieyelopentadienyligene ) Bi(eyclopentylidene) ) Biphenyl ) Tereyelopropane (0 Give the smactures of alerate acpi and eye hyo- carbons and non-alernate cyclic hydrocarbons and mene - Hae sorted te i creamer ion the necessary rules for such definitions, oe # and give the conect name ofeach of (© Give the IUPAC names of the following btecyelic spiro the following bridged hydrocarbons. pape @ oO « OD wi) oO) 9 OY?) “i OOWX OX 1.12 Draw the structures ofthe following compounds. (@) Perehlor@smethyipentane) () 2(tiydroxymethyheptane-,6-dial (©) Aluminium wi2-propanolte) (@) Etoxyetylene {e) Bis(2-bromocthy ether (, 22-Oxydiethanol () 3-Formythept-2-enedial () 3-Vinythept2-en-6synal (@)Pyridine-2-carbaldehyde ) Benzenecarbothialdehyde (W) Benzenchexot 1.13 Give the TUPAC names of he following compounds cic crab cbeceno, wba Leycu fen ° ca en-cn-crc, 7 cymes bcx,-cmerot (@ c,—€-cnt—cn, cu,—cH=cit, onilata inn @ cH-cr-cn,-t tc, 9. 8 cH -€-c4, ter cH, L ( cHy=crlcacr 14 Draw the structures ofthe fllowi (@) Hepia2,dienoic aid (0) Hex-2- ® F > > © crycosba.cn, Cy eD.cn () Do—cH,—cH,—0D D=Desterian, T= Tim 1.17 Give the method of numbering the earbon atoms in the following compounds ® © oo Ho ee D-Glucarorl :63-lctone © — ox ayon fo He Me OF Methyl f-D.ylo-Hexopyranosie-4-ulose 1.18 Draw the Fischer projection formulaof(@)4-0-«-D-Glu- copyranosylcrD-glucopyranose and Haworth structure ‘of () D-Galacopyranosyl(1-+4)-<-D-glicopyranoe, 119 Draw the structures of (a) (2.22,2)-Bicos-5,8,11.3 tetracnoie acid) and (Z)-Octadec-9-enoie acid. What are the ‘wivil names of these two compounds?- 24 State whether the following molecular formulae are correct to represent stable neutral organic compounds. State the reason, @) GHC @ CHyNO,—(@) CyMtyN,FCL ©) COB) CulyNC,—H) CHO, © CHNO — O CHCIBe ‘Ans Amongst the aforementioned molecular formulae, for- smulae (2), (0), (and (g) are possible. However, (2) (©, (D, (8) are not valid formulae. The argument i that, for stable ‘organic compounds the total numberof edd-valenced atoms 2.2 Caleulate the double bond equivalent ofthe fllowing, ‘molecular formulae and give a least one reasonable struc- ture for each. (2) C0, @) GHLN (0) CyHyO ‘Ans Double bond equivalent of a compound having the meal HX, Be he enn Dae. [Note that the atoms of oxygen ave no been needed in the equation because it hasan even ‘numbered valency. On the basis ofthis equation, Dab of = 2e8t2=620-0) 24342-640-1) 5 DBE of @) 2el+2-0+0-0) 2 11042-O40-) z DBE of (c)= DBE of @)= [Note: It isto be noted thatthe value of DBE cannot be faction. The value should be 2er0 or any positive integer. ‘Any triple bond is equivalent to two double bonds, ‘Based on the DBE values of (2), (0), (6) and (the follow ing strotures may be suggested but oer structures may also fimo these values. Physical Organic Chemistry 11,01 © Oo C a3 ocr, © 23 A good base Is not necessarily a good nucleophile. Explain, ‘Ans The basicity of an anion is defined by its ability to accept a cation (usally a prton) from a reaction media, Usually, the ‘anion having higher electron density represents a stronger base By the term nueleophilcty, we mean the ability of an anon ora Lewis base to release its electron to form a covalent bond with an electron deficient atom or group by §,2 type substitution It is measured in tems of polarizability of the clettonpairand not by the charge density, Far example, Fis 8 very stong base but a poor mcleopile. On the other hand, risa weak base buta strong muclephile. Similarly, OH is¢ stronger base than HS" but the latter i stronger nucleophile 24 What is benzyne? Give chemical evidence in favour of the formation of benzyne asa reactive intermediate. ‘Ans Benzyne is dehydrobenzene, Several structures have been suggested for this reactive intermediate but the structure represented (1), shown below is commonly used to explain, the reactions of benzyne. It is normally formed when an aryl halide with at least oe iydrogen atom tthe ortho postion is ‘weated witha strong base, aC [NaNH lig, a — ao # Nays onCarin nt tin Oat Cemsry ‘That Benzyne is the intermediate in the aforementioned feaction is confirmed by the fact that when a C labelled ‘compound, as shown here, is taken, then a 50:50 mixture of ‘0 compounds is obtained differing in the position of the pose Or «Br ck [NaN ig NH W Bente sa, oom wm aye Direct substitution should have given 100% of (A) only 25 Givean example where the benzyne intermediate has Deen trapped in a reaction product ins When bromofluorobenzene is treated with sdamide in Tiquid ammonia in the presence of furan then an adduct is obtained. This adduct finally gives [-naphthol on teatment with an acid. This is accountable if benzyne intermediate is formed to react with furan, - ‘NaNH, I ‘= Sy (2 Becwoeic oc “ot [ne a 26 Thebasicity and nucleophilicty ofan anion sometimes {do not ran parallel but in certain cases they do, Explain. ‘Ans The basicity ofan electron rich species is dependent on its electron density and not on the degree of polarizability ofthe electtons. Nucleophilicity ofan electron reach spe- cies depends on the polarizability of the electron, usually ‘a non-bonded electron pair in the valence shel. Therefore, basicity and nucleophilcty do not always run parallel, that is, a good base is not necessarily a good nucleophile and vice versa, For example, between F-and I, Fis stronger base but Iisa stronger nucleophile. Similarly, between HS ‘and OH>, the former is better nucleophile but OH” is @ ote noted that an electron pai residing sive atom smote poarable va jing higher elec- stronger bse 1 ta age bu les electone {fon the electron pion smaller tr tonegatie value “Wkan in aslo anions, the native charge resides on the su mth tir Bases and uceopiiiy nn pan 2.7 Arcange the following oxyanions inorder of increas sega well ab increasing nuclei wih ea mie. () CHO” ( Ho () PhO © (CHy,Co” (© (CHy,cHo- ( CH,COO™ {Ans In al the aforementioned oxyanions, negative charge resides on the oxygen atom. Therefore, ther basicities and ‘nucleophilcity run parallel. Basicties can be easily deter- mined on the basis ofthe cities oftheir conjugate acids ‘Conjugate acids are shown within brackets CH,O- (CH,OH, PHO" (PhOH, (CH,),CHO™ [(CH), (CHOH), HO™ €H,0), (CH,),COT(CH,),CO” [(CH,),COH), (CH,COO"(CH,COOH). ‘The increasing order of acidity is as follows: (CH),COH < (CH,),CHOH < CH,OH< H,0 a) and > b). Ns © kn Lr > wo Sain ° Steric inhibition ‘ofresnance 2.11. Account for the increase in the ratio of Lalkene to 2alkene products as the base is changed from MeO™ to ‘Me,CO™ to Et CO” in the dehydrobromiaation of 2-br0- mo-2,-dimethylbutane. ‘Ans The reaction is E2 elimination. Steric factor plays role haere to decide the product compositions, When a bulkier base ‘used, less crowded hydrogen from the B position is elimi- nated. The course ofthe reaction i shown hee. ee be ont = o H H Hc ‘CHC, pad Ht In case of (D, the less bulky MeO can approach from behind to abstract the hydrogen and that leads to the form tion ofthe more stable 2-alkene. [As the sizeof the base increases, tis approach becomes smore dificult due to steric fator and E2 elimination kes rita cosl place through the conformation represented by (Il) where ‘erie factor is minimum. In this case, [alkene is formed as the majr produit. 12.42 The bond energy of which CCN bond, A oF B, Is greater? B © NEC. ‘et ‘Ans In this compound, élocalization of relectrons of the tomatic tystem with the CN (A) is not possible due to non-planarity of CN group sith the benzene ring due to steric interaction offered by the ortho Et groups. However, CN (B) can take part in resonance. This makes the CCN (B) bond ‘ssume some double bond character. Consequently, this bond has higher bond energy. ww (A) 2.13 Differentiate between polarization and polarizability ‘ofa covalent bond with suitable examples, ‘Ans The term polarization of & covalent bond means is per ‘manent distortion o a state of partial bipolar character de to slference in eleronegativity valves of the atoms and groups Joined by the concerned bond. For example, CF, is perma- ‘ently polarized to postive and negative poles duet difference inthe clectroncpativitesofcaton ad Morne toms, ft ‘The term polarizability ofa covalent bond, on the other and, means temporary polarization of the bod due tothe proximity of reagent For example, C~Ibondhecomes very ‘much dtoned compared to CF bond inthe presence of & nucleophilic reagent. Thus, wean conelue that C—1 bond is rmorepoarizable than CE bond although the late is more polarized. 2.414 Between bond polarity and bond polarizabiiy, ‘whieh one is of greater Importance in $,2-type substitu. tion reaction and why? {Ans Incase of S,2 type substitution reaction, polarizability of ‘bond is more important than that of permanent polarization. Forexample, when CHF and CHyl are treated separately with ‘Ott itis the CH! that undergoes substitution ata faster rate ‘and not the CHF. In this ease C=P bond is more polarizedpw ono in bat 1 bond ie more polrizable.Polarzailty ofa bond an create a more electron deficient cette during S,2-type subst ‘ution and thus nee ess activation energy to Feat Les polarized but ore olrzabl Faster reaction) Owe sa : Ho” “Git F, + oc, F i) More polarized bres plarizble (Stowe reaction) 2245 “CH, has a planar structure whereas “CF, appears (0 havea tetrahedral structure. Discuss. ‘Ans Inthe case of ‘CH, there is no lone pir associated with Ihydrogen atoms and consequently no bond pair-lone pit repulsion force operating hee. However, in he case of “CF, tach Fatom is thre pars of lonepair eletons. Therefore, in this case bond pair-lone pir repulsion force i very effec” tive and decreases the CFC angle o nearly the etraedral Angle. Tis isthe ceason forthe difernce inthe shapes ofthe ke Asn (4 “erahedal seve ‘Altematively, more electronegative rine atoms il try to form covalent bonds withthe less electronegative sp? hybridized carbon (Bens rule) 26 In AX,Y,,X and Y are bonded to A. Elecronega- tivity orders A> X> ¥. Draw the structure of possible Stereolsomers; if A oecaples the centre ofa tetrahedron find square. In addition, comment on the polarity of the possible isomers. ‘Ans In the case ofa tetrahedral stacture, only one structure {f possible because the structure of the molecule ofthe type ‘AXGY, would bea symmetrical one, Resultant vector of one SAY system will be balanced by anoter. In the case of guar planar structure two stereoisomers are possible having ferent plas. o ¥ oy “The tetrahedral structure 1) is nonpolar because it iy metric andthe elecronegativty order ofthe concerned atoms isA>X>¥. Berween the square planar structures, (I) is nonpolar because the bond polarities of A-X and AY bonds ar mutt aw x & it sare being symmetrical. The struc- ally compensate, te St ponds are not symmetrical oriented. Seip tecebond thc = bond eneray ss than ce a of he 2a Te remem tne CHO tnd very hl CE pon rE at fhe CO bo vere Aceount ora. fas When aos J by cova with itrent eons a din eon drs sr set creenatey fleas hrs nd 2 aaa cer ond Seength meets. Ta he eas of the sere eres Foro ig fond adhe tts come ea oe bond The cseonepvy diene & ras Aa oro=o he cewonanity val fs a etre ante eres age. Co- teomnd 28 oma bond becomes closure anda eu sey Spoepoal potas Become clone. This ceri caging efpovitals mor fective an bond aan nee hs oes forte esl sted sequsion ee ee eo & =f) tareaites) (50) Sma aiance 218 The observed dipole moment of Pk—Clis LSSD. The Ph-CI bond distance is 2.8A. Estimate % lone character of PhCl ‘Ans The theroretilly calculated value ofthe dipole moment is 2.8410-Femx4 81410 Pemel3 475 0-esuem=13.47D Experimental value is |S, Therefore, % ionic character of ss mrctbontis SS 0=12% 2.19 Given the bond Assecation enerles in Kanal as Git -t1= 2, H-Cl=103,Cl-C1= 58, and CHCl), She whether trench between methane ad ceri ‘ib endatermic or exothermic? ‘Anite convention tht bond breaking energy is alas Cris ste sin Hod ema eas Sexthemi ands negative ns. I the ently change Ofte oe chemical change Hi fnd to ave 2 Sige te econ cone tobe endemic. On te ter hand vale -ve thn the ection exer Inthe present ase, C-HandH-Cl bond a boken and the emery change 1102+ 5) = led Keane, Energy ‘leased de 1 te bod oraton (103 81)= 18 heal tol Teer vale (60-188) 28 Kata Ths theron etme 100 CHW col —> cH-c1 +H ct 220 o- and p-Nitrophenol can be separated by steam Aistillation, Explain. ‘Ans o-Nitophenol ean form intrmoleeular hydrogen bond- ing and consequently is extremely volatile to come out witheam. p-nitrophenol, on the other hand, cannot fom intrmo- lecular hydrogen bonding but can form intermolecular hydro- gen bonds and, therefore, much less volatile to come ou with i 7 CO sata N-O hydrogen bonding i oNirophenot Intermolecular hydrogen bonding \—0- NO, _PNivophesa Propel 221 Which of the two carbocations CH,=CH-CH, and ‘CH,CH,CH, is more stable and why? ‘Ans CH,=CH-CH,? isan allylic carbocation and is stabi- Tized by delocalization. CH,CH,CH, isa primary caboca- tion and is stabilized by hyperconjupative rescnance. Since resonance involving delocalization of p-electons is a more stabilizing phenomenon, CH,=CHCH,*is more sable than cH,CH,CH,, Ne : cuZou-én, —~ Gi-cu=cn, H Ww leva cnc en, — crcr Hy 2.22 What i a carbenoid? Give an example ofa reaction ‘where such compounds are used in synthesis. Ans A combination of methylene iodide (CH,,) and zine-cop- per couple is refered to as Simons Smith eagent. The active Species is iodomethylzine iodide (ICH,Za). Since (ICH,2a) ives a methylene (carbene, its commonly called carbenoid. ‘The reaction is a general method of creating a cyclopropane stem fom alkenes. The reaction i stereospecific RL lbh a, =, Rt 1 2einDinbtned ‘jlopropane Re @pakese ROR zs LSE be BO (epakere 12a Diba ‘3cloprepane 2.23 Triplet carbenes add to £ or Z-alhenes wi ‘of stereochemical integrity. Explain. rotten ceri ‘Ane Triplet carbenes react with alkenes in a noa-stereose~ lective manner and form both cis and trans cyclopropanes irrespective of the stereochemistry (E or Z) of alkenes. The ‘reaction proceeds trcugh the following mechanism. cH, Act ib wn How va Tip cree ‘Grae in elecwon spin before coafermatonl change a, Aas change in conformation before So a i an HN / cH, CH, 224 The dipole moment of aniline Is 1.S3D and that of nitrobenzene is 3.95D. However, the dipole moment of ‘p-Nitroailine isnot S48D but 6.1D. Explain, ‘Ans Due to extended resonance involving -NH, and NO, ‘roups, the distance between the poles increases and since the Value of dipole moment i a product of charge and distance, the dipole moment valve is enhanced ro os oe 225 Arulene has an unexpectedly high dipole moment Explain. ‘Ans Azulene is a bycyclic compound with 10 reeletrons. Distribution ofthese electrons hetween the two rings gener ates an aromatic system comprising a eycloheptatrieny cation (tropytium fon) and a cyelopentadienide in. Since thie aro- ‘atic system is quite sable, azulene remains mostly in bipo- Jar form and shows high dipole moment value. -OQ9 2.26 Rxplal whether thé fllowing statements are true oF (2) Enantiomers can be distingulshed from their dipole ‘moment values,ee (®) reand,ing dastereolsomers canbe differentiated from their dipole moment values. ‘Ans. (@) The statement is fale, Since enantiomers are minor mages ofeach other wih the same bond connectivities, ‘hey have the same value of dipole moments. An example oe Mee ge, gm, annem Ey Ey seid, ‘Apaicofenantomers “HHP of inte moment (©) This statement is wus. Diastereoisomers have the same bond connectvitics but they ae nt mirror images ofeach other Therefore, they have diferent dipolemoment values ‘An examples given here ea ian Semel So=e’! fowisomer™ | Tons ome™ A pair of daservsomers “These to dastereicomerscan be diferente ‘fom tr dipole moment ves, sce ‘ber diple moment values ae dierent 227 Dichlorobenzenes can be distinguished by the meas- ‘urement of thelr dipole moments. Explain. ‘Anso~ mand p-ichlorobenzenescaa be distinguished from their dipole moment values. Dipole moment values can be caleulated using cosine las fallow, Dipole moments of disubstituted benzenes may be cleu- lated by using “law of cosines given here. If and ware individual dipole moments associated with the wo substitus tents on the benzene rng and if she angle between the two ‘bond inked tothe rings, then the resultant dipole moment, is given by the equation, " bn » 08 60° For oisomer: ig = Vine 60") poet cos 120°= -} Forman: my =P 20) Cece: uy = YT tae one 180 =—L "=, when =H (@=1807) = 1-H =O. when to find out the “The aforementioned method hasbeen sed 19 fh aes tenecc, Te mein wei whe ‘AUCs are he same. The dipole moment valves of eaten dicorobenzenes ae found 1 be very clos 10 called values my " a i Ae cx CH] ae "cl me vieicbemane —mDebinbenrere ne MAE poiachmame 1228 arAminoacids have greater dipole moments than expected. Explain, ‘Ans An c-mino acid remains asa dipolar zwittr ion and that ‘cahances platy. Tits why amino aids have higher dipole ‘moment than expected. H,8—CH,—CooH == H,8—CH,—Coo” iycene Zoiter ion (ore pole) 229 Draw the energy profile diagrams of E1, E2, an Egg mechanisms of elimination. ee ‘Ans The energy profile diagrams of El, are satin F2, and Elgg 1: El eimintion i ‘ sa to-step reaction, The formation of th ebocton interment she ate doen overall reaction is exothermic. ee Racin progres — Energy profile dag of El reaction 2 F2 reaction is a ones i sep reaction with a transition comprising the substrate and the base. be sareort es BY & the fist and he hed steps. The postions inthe diagram a Br have been placed arbitral. goat, 2.31 PACH,NO, fv aliquid that dslves in NaOH. On Sa ideation with HCI, inal sli tautomer b precip t Sted, However ths sly reverts othe orginal gu a Eaplia th witha sutable energy profile diagram. E [Ans tis unig example expan Bow kinetically con- 7 = ‘rolled and thermodynamically controlled processes deter- RCH,CH;Br+ Base care cayenat mite berate of fil pret composton ery pi dag of a wo og of econ A : ae ee PRCH—N- == PrcH—N=0 cg Eley esions atwe step proces The te deemia- ive ing step i the formation of alkene from the intermediate car- ‘anion. The carbanion formation step is fst 182 In the aforementioned examples, the composition of the cauilibrium mixture is, of course, governed by the relative ‘thermodynamic stability of the forms under the particular conditions being studied. In this case the niteo-form, a yellow oil is the more stable of the two and at equilibrium, predom- 2.30 Draw an energy profile diagram of a three-step ¢X0- nates to the almost otal exclusion ofthe aciform. Despite ‘thermic reaction in which the second step isthe ratedeter~ hie tact, acidification of the isolable sodium salt ofthe car- ‘mining step and the second intermediate is more stable anion intermediate yields only the less stable aci-form (B), Reaction sordinaie —— Energy profile disgrara of Eloy reaction than the first. ‘This happens because more rapid protonation takes place on ‘Ans The energy profile diagram is given here based on the the oxygen atom having a higher electron density, that i @ ‘conditions just mentioned. ‘inetcally controlled reaction, The enerey profile diagram of the process is shown here. Energy — Reaction progress —— Energy profile diagram of El reaction ‘The activation energy of the second step is the highest; therefor, isthe rate determining step ofthe whole reaction. Between the activation energies to reach the transition ‘The second intermediate is mote stable because its position is states TS-2 requites less energy, reflecting the greater ease of Tower than that ofthe first intermediate in the energy profile cleavage of OH bond than a CH bond, Although the imme diagram, Nothing hasbeen mentioned abou the rates between dite result ofthe acidification of the intermediate sodium saltDrie son in OnmeChenr {s the formation of aci-form, it spontaneously gets ionized. ‘Thus acisform will lore ts proton fate to form the interme- diate and then reprotonation produces the more stable nito- form, When the equilibrium condition is allowed to sen the thermadynamically control product (A) would be the major product again 2.32 Predict the enol content ofthe following compounds. tnd explain: Ethyl acetoaectate (A), Acetylaetone (B), Diethylmalonate (C), and 3-Ethylexane-2,4-dione (D). [Ans In the aforementioned cases, the decreasing order of ‘enol content is B> A > C > D. Inthe ease of (A), 1 effect. ‘of the marked (bold) CH, group increases the electron den Sites of ketone oxygen atom and thereby strengthens the imramolecular hydrogen bond. Lak a clic, Loc, tiyacetacete(Ketofoan) @) On 4, od ee! oi on Intramolecular Hood ofthe eno fom (tform) ‘On tbe other band, the marked ~OBt group has—Ieffect and ‘weakens the intramolecular hydrogen bonding, In totality the enol content decreases, Another factor important heres cross ‘conjugation between the ester group andthe enol stretue ‘This resonance inhibits the resonance ofthe @B-ansaturated system within the sing. This destabilizes the enol-form with fespecttothe keto tautomer and sift the equirium towards the ketone, 7 HoT 0GH, r A wer Rac neh Age, Inthe case of (B), the marked CH, group has 41 effect and strengthens the intramolecular” hydrogen bonding Consequently, the enol content increases. Moreover resonance stabilization of the enol-form has some role in increasing the amount of enolform, ong b=cH—C—CHl, ; e on ac a @ Hyco SH, tniraroleeler H-bond ofthe cool: frm (l-form) 1m (©), the marked OEE groups have -I effect and make the intramolecular hydrogen bond very weak and enol content ‘decreases futher. Moreover, rexonance involving the ~OBt ‘roup also destablies the enol-form. a m8 so cL on, = 20 Schon aces me Dt oat e 2H Hebond oe po on, Inemoleeular H-bond ofthe eal-form (eis form) oi, er ca, eer Tn the case of (D), the enol content is minimum because the strong steric interactions amongst the alkyl groups on the ‘carbon atoms prevent the formation of enolic frm, can 9 cut poten oy be bey, snp ne coo 4 cai bcos, i Ag Hitond i aes eyypos cc, (aa-frm) Irermloctlar bond ofthe enol fom (ior)233 OF the following two compounds, which one has higher enol content? °° i ( Ph—cH,—C—cr, cH, waiter te, h ssa scat pl) ne on bce Paper ncopetetee e o Coch nmep stones posal Smear ofc pp temple Simca tsa " 2 Cs onmarck cmb yeni Ache, omey ten ; —e al i I mcr, —l_cn,—Lce, “Two difereat ook os ae poste Termin fb cea fo i ar) Fool cna, —b=c—c—a, h (rotor) \ a pa wes dpay h sacle ted ofthe elf (fom) 2.34 PRCOCH,COCH, and PRCOCH,COPh have very ‘igh enol content. Account for this ‘Ans In both these compounds, the ene form becomes sta bilize by extended resonance involving the Ph ring. The resonating stuctue ofthe hydrogen-bonded enolic form of the fist compound is given bere. meomccne Inthe second compound, there are two benzene rings and ‘both of them can participate in a similar resonance. Therefore, itsenol-form ismore stabilized and consequently enol content is more than thet ofthe fr. 235 Ina substituted Pdiketone lke R'-CO-CHR-CO-R*, the size ofthe substituents RI, R2, and RP has role in the ‘nol content of the compound. Discuss. Ans The ketone shown hee can have diferent conforma- tions having diferent orientations of C=O groups. These are shown here feed oat) nPNcyS9 oe Seu Rr R ; tia hod f om ‘The carbon bearing the R? group is sp? hybridized, hav= ing tewahedral geometry demanding more space for R! and RE Therefore, ab the sizes of the R! and RE increase, the keto form becomes less stable. In enolform, the said carbon. becomes sp? hybridized, the spatial demand for R¥ and R? decreases and the sri sain i released to some extent and the eno-content increases. Keto-frm of (ID) is further dest bilized veto dipole-dipole repulsion. For example, in ease of the stnieire R-CO-CH,=CO=R, the enolketo ratio is 1.4 ‘when R= Me, but the said ratio is 6.1 when R= + Bi, ‘When in a compound lkz R'—CO-CHR-CO-R’, R', RY, and R?, are all bully, the effet is opposite, that, the ‘etoform predominates Over the epol-form. This is because ofthe fact thatthe three groupe become closure in enolic form and strie interaction among the three grovps increases sharply and destabilizes the enol-for. Enolie form of I) s shown now to demonstate this seri interaction. 8 al ee BN ng ae PN A e wh - OA 236 The enol content of hexan-2-one is 0.11% but that of. cyelohexanone is 1.18. Offer an explanation. ‘Ans This diference in he enol corer beeen sn open chain ketone and cyclic araloge has been atributed 10 the loss of ‘entopy. The double bond in open-cain enol locks pat ofthe ‘hain nig orientation so thatthe enlization is accompanied by partial less of feedom of rotation ofthe chain This los of| entropy ductoenoizatonfavousthereteton ofthe keto- form. ‘On he other hand, cyclohexanone already has a semi-rigid structure; therefore, due to enolization, the lose of entropy ioo eee ea campasenes te ccnmaie Stesaa ame sky kg seaman glen enh ecu Te ee eile re i lar hydrogen bonding. cus stabilize the enol-form. That is why, iteains almost exclu: aria Sivly in Ketoform. Ketosform is farther stabilized by reso- ° th nance of the C=O group itself Htc, ch,— cH, Nexn2one 1 a 4 ‘Keto-form oe cH, —¢=cH,— cH, cH, cH, norm ¢ ° on nc—t-an, — ihe oe Resonating stuctes of aetone caine In case of phenol, it remains in 100% enole form. This is beoause, phenol contains a benzene nucleus with aromatic ‘ability de wo resonance. Its Keto-orm is less stable due to loss in aromatic stability. The energy diflerence between the 237 When an aci-catalysed brominationIscarried out on two forms is around 15 kcal/mole ‘an active Isomer ofthe folowing compound, then a racemic Cyclohexanone (Enol-form) ‘(Keto-form) Feros i 7 i 7 We, sd = HL Ser fama sar teat O~ Oo t Phenol (Keto-form) = & (Enotic form) Lata an aac Ans ince, roinsten kes ce dong te 232 WR af he loving we compounds wi exhibit ttn feo xed ys The al ete i Give explanation, iin the active compound is converted into an enantiotopic face (8) 2 gH tod bromine ge oubstuted rom Re-and fe egal well eerie noon "Cie : ou cH, swale | fan eh Peet ‘Ans The compound stihydionyoenzene @) is vily em mls ‘ownssphorgucnel exibis cay ket onal omer ¢ im, tnketofom s known and eae withhydoeylanis polite 4 togive atovine The low of aromatic esomnee oe of scm : se baz: nis ghia oer oan resonance energy of thee C=O groupe, which at on Witt reach C=O pip, AP NH a ° Y7 (El vi noi x) — ’ wo Sono NN Phvcuueme!—12.¢cyeoenine § ee tox om eels ¢ ¢ N11 Goch ea oo on aiont 2.38 Acetone remains almost exclusively In keteform but The compound(s) canals exhibit keto-ene ontmeri jhenol is always in 100% enole form. Explain. but the Ketosform is very unstablete ike 7‘on adjacent carbon atoms. The enol-form is stabilized by intra ‘molecular hydrogen bonding, The structures ace shown here ou 9 on 0 on Hydroxyginal (Ket-form les ible) Bab form (Mor abe) a 7, —Inamoteule ‘on Hibond on 240 Give an example where intermolecular hydrogen bonding i responsible in giving stable enolic form. ‘Ans Ithas been observed that in cetan ese, intermolecolar ‘hydrogen bonding can stabilize the enolic form. An example is given here 9 on ney HE, ac ieee DS SSDimethyIens-3-dione —Enol.fom whe wo 0--w—0' nokta stabilized by Intemolecle hydrogen bond cH, 241 The following compound remains almost in 100% ‘nol form. Offer an explanation. aa eno-Cy-or-tlin Ans This compound san tikeione.Itean also exhibitketo~ ‘enol tautomerism and the enol-form remains almost in 100%, ‘duc to extended resonance, The conversion is given here a8 enp-Cy-ent lin ‘Ketform 4 ono )-c= nol fom 1 evi kon 9 q = C-P a Physical Ors Chena BS 242 Which one of the following bridged bicyclic com- ted cnt toner? " on, on iit we we [Ans Between these two compounds, compound (b) can exist as keto and enol tautomeric forms. However, compound (a) can- not, beeaute the formation of enol involving the bridgebcad hydrogen wil volt the socalled Breas rule @ Ko X on Chi = Me Me ees ttecee! : o * 7 fi oe (QILe = 7 pee pa oes otter 2.43 tn the flloning chart, B-keto esters with different Substituents on the acearbon along with the % enol con tent in each cae is given. Account for these differences in nol contents g cH —C—cn—co,61 k R Yel content gu Et 3 Me 4 H 15 Ph 30 CO,E 4 ‘Ans Ithas been observed that asthe «-H becomes mare labile, ‘he enol content increases. Now when the elactronegativty of the ‘R” group increases, the @C—H bond becomes weaker and consequently enol content increases, 2.44 Which one of the following has higher enol conteat? Give reasons for your answer. o “or ‘Ans The compound a) i the triketo-form of phlroglusinot ‘which its enol form. The enol form of the compound (b) {is reoreinel. Now, phlaroglucinol can eadily frm it trike te-form. However esoreinol cannot readily form its dike= for. Therefore, i ean be concluded that eno-content oF ‘the compound (bis higher than that oF),Present enn organ Cheniry 9 on © ac hy Ketosom aol foe © oy “cy 1245 How do the polar and non-polar solvents affect the ‘enolcontent ofa keto-enol iautomerie system in 1,}diketo ‘compounds? ‘Ans The enolic form ofa keto-enol tautomeric system is Tess polar due to H-bonding. Consequently, polar solvents stabi- lize the etonic frm, andthe enol conteat shouldbe higher in ‘on-potarsoivents For example, in case of CH,-CO-CH,-CO-CH,, the percentage of ketonic frm in por solvents it as high as 92% bat in water iis only 158%. Again, inthe ease of CH,=CO— CH,-CO, Et, enolic form s only 5.7% inacticacd, whereas the Ketoic form is as high 5 94%. In addition, hydroxylic solvents would form hydrogen bonds sith the solute oxygen atom to compete with the {intramolecular hydrogen bonding in the enol. This would further decrease the enol content of 1, }ikecones. 246 The heat of hydrogenation of cs-but2-ene Is greater than that of trans-but-2-ene. Expl ‘Ans Heat of hydrogenation is equivalent to the enthalpy ‘change in the hydrogenation reaction, The more sabe the alk- nei, less would be the enthalpy change, Between cs-but2- ne and wans-but-2-eno, rans isomer is more stable and con- Sequently, has less heat of hydrogenation compared to the cis isomer. Energy profile diagrams of heats of hydrogenation of trans and cts iaomers are shown here, assuming the reactions tobe one-step process. Brey —= Frodt Hydrogenation of ron isomer rane But2-006 infin 206 rons-But-2-ene is more stable than the cis isomer because dhe two lange methyl groups ae Tocated far apart compared 10 the cs isomer where methyl groups are closure, Hence trans pce i less crowded and bas lesser van der Waals stain (etre stain) 247 OMe group strongly: fof the benzene nucleus ‘position. Explain. ‘Ans OMe group has pairs of non-bonded electrons. A pair of ‘etrons can delocalize with the p-electrons ofthe benzene ‘lecron and thereby increases the electron densities ofo- and >» postions to it meposiion cannot get electro-rich by this ‘elocalizatio, On the contrary, OMe group has ~I effect and that operates through bonds to deactivate the m-positon. activates the o- and p-positions ‘but weakly deactivates the 85-88 8-8 (Ortho sn para positions are activated ‘ome Q Meta postion is deactivated 2. Haloensaredncivaling yt of directing. apa ‘Anstislogen tons ive on ended eleton pais in eal ance shel Apo he lctonscan prepa ie ioe Sataatn proce along wih he preccwot athe ene sts aon tress ected oto an pare potion hepato th floes This delocalization becomes effcte athe requ ot an ekcopie eget Garg an ecepte an However, logon sons ae hplyletonepae ad therfrhavea deactivating tet on he brace nck C > A >B and for which the relative fo cn relate for ate ena seeK,> Koi Ky Watermelon sree ideas An street seria teen condo, and Ky ae ecole eacins ad HR ote corresponding reverse reaction canbe shown follows, TH e*eTBY Profile diagramKKK Ky Ks Boetey Products — Reason pages — tis tobe noted that greater the value of the rate constant, the faster would be the rate and vice versa. In this energy rofl diggram, the rate determining sep isthe formation of ‘T.S-1 inthe forward reaction andthe formation of 2 inthe reverse reaction. 250 Bromine can be displaced by iodine in H,0 medium Dat iodine ean be displaced hy bromine inacetone medium. Expla ‘Ans The nucleophilcty of an anion or electron rch neutral ‘species is found tobe solvent dependent. nthe case of apolar solvent like H,O, the smaller anion with high electron density {gets more solvated and its mobility and availability decreases. In H,0 mediam, Bris more solvated than F. Consequenty, in that medium Tis better nucleophile to aisplace Br ‘When the medium is changed to acetone, none of the halo- igen ions are solvated effectively and the Br, being smaller in size, has greater mobility compared to I and behaves as ‘better nucleophile. Therefore, in acetone medium Br can Aisplace T- oe He - wt, weno Con Gy enene " Ye a Fat Ny Geet : 2 SS eye 251 CH,CH,OH does not react with aqueous NaBr to {form CH,CH,Br but readily reacts with HBr to form (CH,CH,Br. Explain. ‘Ans Inthe case of an $,2-1ype displacement reaction, a bet- ternucleophile can displace a weaker micleophil. Inthe ease ofthe reaction between CH,CH,OH and NaB solution, Br- being a weaker nucleophile, cannot dspace a better mucleop- File OH and the reaction docs nt occur Inthe ease of the reaction between CH,CH,OH and HBr, (CH,CH,OH is protonated to form CH,CH, OH,” In this ease, Br elsplaces the weaker nucleophile H,0. (CHCHOH + Nate —~ Noseaction a Physical Organic Chemisnh 29) CH,CH,OH + HBr — cH,cH,OH1,+ BF GS cnet, cols — crear H,0 ee In addition, OF"is a bad leaving group bu 1,0 i @ good leaving group. 2152 The reaction of PhCH=CH, with H,0/H,S0, (Ai, and with D,O/D,S0, (dl) shows Kyo /Kay=3. Explain {his observation. ‘Ans The given reactions ae acid catalysed hydration of sty rene. The reaction isan electrophilic addition and takes place intwo steps, The fist steps the rapid formation of a carboca- tion andthe secon step i the slow attack by H,0 (D,0). The ‘course othe reaction is shown here. w cso. 4 ce aaa By by, H ee ou Since the slow step involves the attack by HO with con- comitant loss ofa proton in case of D,0, this step would be slower because the OD bond is about four times stronger than the O~H bond. Thats why the reaction shows deueriam, isotope effet, 2.53 What isa nucleophilic eatalyst. Give an example. ‘Ans Nucleophilic catalysts are those ncleophilic species that accelerate the rate of an S,2-type displacement reaction hich is otherwise extremely slow. Atthe end ofthe reaction, the nucleopilic catalyst i ecovered, Is such a catalyst. For example, the reaction between an aleohol and HCI is quite slow but te reaction rats enhanced inthe presence of Na. ‘The course of te reaction is shown. I is a strong nucleop- hile and at the same time a good leaving group. These are the basic requirement for a nucleophile to act as a ‘nucleophilic catlye (CH,CH,OH + HCl —> CH,CH.OH, +c baer 5% ccnscu,bn,+ oF 22% cnycu,crs 1,0 on, Fi 17 eave om, FA caycry +40 Fast PB cuycrcrs LEM cnyenersr am ene 2.54 DMF and DMSO favours S,2 reaction although they are polar solvents Explain,acc ‘Ans DMF and DMSO are polar molecules. However, they fil to solvate an electon rich mueleephil throug thei +ve end because of strong serie factor. On the other hand, Because ‘oftheir high dielectric constant values, they ean cause polar jeation of the substrate molecule and can ficilitate facile nucleophilic attack. For these two reasons, DMF and DMSO Support 8,2 substtation in spite oftheir polar character. to oh pe OF gy eine poe“ fin ot Sex, ca, paso’ 255 The addition of a nucleophile to a carbonyl com- pound leads to addition, whereas the addition of the same {oan acid chloride leads to substitution. Explain. [Ans The addition ofa nucleophile to a carbonyl compound leads 1 stale addition compound because there is no good leaving group atached tothe carbonyl eabon atom, When a rucleophilic reagent adds to an acid chloride, an iil adai- jon compound is formed but t undergoes further elimination ‘beeause the carbonyl carbon contains a chlorine stom which isa good leaving group. ow i i n-ne Ney = Roo Cuter te oes Sable ation compound 2.56 Which of the following compounds have resultant dipole moment? () C,H-0H (@ Coy (@) Me-O-Me (©) pDiacetybenzene (©) MeNH ( pDicyanobenzene [Ans CH,OH, Me,NH, and p-Disceylbenzene have result- fant dipole moment. p-Diacetylbenzene has a resultant cipole moment beeause the CC bond joing the benzene nucleus fad the acetyl group has fee rotation and the two aceiyl ‘groups can have non-symmetrical orientations, 28a result of ‘which, bond momen are not mutually neutralized ; 2 omen, 14c7S0 fe case of pianobrene, the rent dpe wag re rotation of CN groups about MeeceN bond docs no change th symmetry ofthe molecule ‘This shown here i, i i i € f i x x 1257 Compare the dipole moments of compounds in each ofthe following pais. (@) p-Toluidine and p-Anisidine (@) Vinyl bromide and Ethy! bromide (6 23:Diphenyleyslopropenone and Acetophenone (@) MeCland MeF (©) p-Chlorophenol and p-Fluorophenol ( Tropolone and 2-Hydrexytropolone Ans (@) p-Anisdine has greater dipole moment than p-Toluidine because in ease of p-anisidine, delocalization (+M) effect |smore pronounced due othe presence of an -NH, gr0up having alone pair of eletrons onthe nitrogen atom. () CH,Ci has higher dipole moment than CHF, because the CCl bond distance is much larger than the C-F bond distance in CHF, although CHF is more polar due to seater electroncgativty of F atom, We know that dipole ‘moment = charge x distance. Vinyl bromide has es dipole moment than ethyl bromide. In the case of vinyl bromide the -I effect of bromine atom is opposed by the 4M effect due to pi-lectons delocalization. In ease of ethyl bromide, -1 effect of the ‘bromine atom is reinforce by the 4 effect of CH, group. Meftect © SBr-cH=cH, — si Let, ‘Ving bromide CH) cH, Be ‘Hettet ty bromide 2.3-Diphenyleyclopropenone has higher dipole moment than aeeiephenone. Cycloprepenone syste ean assume ‘vomaie stibilty due to delocalization. The generated tyelopronenium ion is further stabilized by the resonance involving benzene nucleus, ‘chil, “Het ©¢ ni Ng NS, (©) p-Chlorophenol bas higher dipole moment than p-luoro- Phenol, The reason is thet in case of p-chlorophenol, extended esonanceis possible due tothe avaiable vacant on Mo’ w | _£9-0o- = o bs ao ‘Stbilized molecule So = Sa~ wo cent compounds (i) and (0, ) i more pol Sed nuble Terns it as rete dipole moment 8 X- Ox. 7 ‘Mor onic and “ stable ducto some On wo Lest onic ©) Inthiscase the compound () hs ier dipole moment i In compound (v), extended resonance is possible along Witte srloemen of roma Chance othe re Tenteredang The compound (wi) azslene and totic dno eoalunon of pele; however aeoeatta ste Oyy.O-7.. 6 Go-Q0-©> co © (© In this case, the compound (vii) has higher dipole ‘moment valve. The ionie forms of both the compounds have an aromatic system comprising cycloheptatrienyl carbonium ion, However, in the ease of (ii), itis further stabilized by intramolecular hydrogen bonding. ° on Ot ii) ‘Stable ionic system. e=8 (i) Less subleioni system 2.4 Which of the owing So compounds hs hgher dipole moment? : ae ee ae Ph ° ° o o‘Ans Compound (a bas higher dipole moment than compound (@). Compound (a) can assume fone aromatic character due to delocalization and that state further stablized by the con- jugated Ph group. Tis isnot possible in case of compound {(@), Since the compound remains in more ioni form, it has a higher dipole momeat value, o- {cytoprpeniu fn (Aromat) notes 2.66 Acid catalysed addition of methanol to S_0 produces, 'O and not ‘0 Give an expla- ‘OMe MeO" nation and the necessary mechanism. Ans Protonation ofthe parent compound can produce two cat ions (and (), pena reed SS Ss ae a a SJ w ale OF the two carbocations shown, it apparently seems that (9 should be more stable because the lone pir of electrons on the S atom is more polarizable but the produ obtained by the sci catalysed methanol addition shows tht carbocation (I) isthe reactive intermediate, This stability of (I) compared t0 () may be poor overlapping ofthe lone pair of electrons or Syothich resides i an p> hybrid ovbtl arising fom principal ‘quantum level 3" tin case of O in the carbocation I) the Tone paris in sp? orbital involving principal quantum level 2 ‘Therefore, in ease this carbocation (I i more stabilized by delocalization; consequently this carbocation takes par in the reaction. The bigger size of sulphur atom and great bond Aistance ofthe C~S bond might also be pul responsibie for this poor ovedpping Physiol Orgone Chemis 31) i Le ‘one ze that Y reacts with LAIN, Me Me ‘whereas Et,C=CMe, does not. ‘Ans LiAlHl, nommally doesnot reduce olefinic double bond. However, thi cyclic compound is found to be reduced ‘because it generates a strong carbocation centre due to deo: «alization ofthe exocyelic double bond leading to the forma tion of an aromatic cyclopentadienide system. However, in case af E,C=CMe, thistype of activation isnot posible and reduction doesnot decurin his case, Boe whee eee ase 2.66 Arrange thecompoundsin each groupin the decreas- ing order of the properties mentioned in parenthesis v= (2) CHC), C1,CH,, CHCL,, CCA, (Dipole moment) () Benz ehloride, Chlorabenzene, Cyelohexyl eMoride, Neopentyl chloride (Afinity towards ,2 nucleophilic substitution) (© Benzene, Nitrobeazene, Toluene, Anlsale (Affinity towards electrophilic substitution) BAI Ty SMe Me Ans (@) Dipole moment order is CH,CI>CI,CH, > CHCI,> CCly {() Nucleophile substiution order ($,2) ie Benzyl chloride > Cyelohexyl chloride > Neopenty elorde, Choraben- (6) Anisole > Toluene > Benzene > Nitrobenzene 267 Arrange the fllowing ions ‘order of decreasingee Deen, Deen © ns A om" w ‘Ans Inthe ease of compounds in (a), the decreasing ability order Ns tu > [ecu ae «in cu, Deen,» a ‘ ° w He (isa suble 2x leon Huck’ roma yen, (i) has the stability due to +1 and hyperconjugative resonance involving woCH, groups. A> A Antiaromate sytem Incase of 6) In this case, (iv) represents an_antiaromatic system sccording 19 Huckel’s rule. Therefore, it is less stable than (0), 2.68 CH,CHCICH, and CD,CHCICD, show kinetic isotope effect during (a) substitution reaction using CH,COOAgICH,COOH and (b) using NaOMe/DMSO, Indicate the primary/secondary nature ofthe kinetic isotope effect in the aforementioned reactions explaining the variation ofthe rate. ‘Ans (a) Reaction with CH,COOAg gives an ester through §,1 mode of subsiution. The couse of the reaction can be stow as follows. A : ane Cian Se elec ae Inthis case the stability ofthe intermediate carbocation is party doe to 11 effects of CH groups and primarily due to Fyperconjugation involving the cleavages of C-H bonds of wr st enbacton formation isthe te dete ret ena th reaction, CD,CHCICD, would et aa Miia Se pecause C-D bond is about seven times more LeSe when compared o C= bond. Terfore, te rescton roam eon seamtary Kt stoe eet 1B) Tris cue of an extalyed 2 encton. The mech nismcan be sbown 8 lows csc “The resetion sa one-step process through a transition step. “Thisthe slow sep. Ifthe substrate molecule is CD,CHCICD,, then the reaction rate willbe slowed down because the slow step involves the cleavage of C-H bond and CD is stronger. ‘Therefor, thi reaction will exhibit primary kinetic isotope cect. 2.69 Compare the basicities and nuclephilicity of the fol- lowing compounds. Explain your answer. fay, win, 8 ‘Ans The decreasing orders of aucleopilicity and basicity are ,N-NIL, > NHOH > NH, and NH, > NINH, > NH,OH respectively, In all these cases, nucleophilicity is due 1 the Jone pair of electrons on the nitrogen atom. In case of H.N— \NH, and NH,OH, nucleophilicity is enhanced ue to o-efTect ‘ofthe lone pair of electrons on the adjacent atom, a-efest ‘more effective in ease of HN=NH, because the lone par of lectrons on the nitrogen atom is more polarizable compared to that on the oxygen atom. Oxygen atom has higher eleetron- egatvity than nitrogen ator, ‘Onthe other hand basicity depends on the electron density ‘on the nitrogen atom. Flecron density of the nitrogen atom in NH, is higher than the incase of H,N-NH, and NH,OH, because of sirong -I effects of the adjacent Nand © atom respectively, where oxygen is more electronegative than nitrogen. 2.10 (Byam of 10,c~cu=cu—cO,\a a stronger bas than cerresponing ome. Hapa. Futhes Comment ot thelr elave sles, ‘Ans In the case of (E)isomer, the carboxylate anion cannot ‘orm an intramolecular hydrogen bonding, but (Z-can. That is why (Evisomer can behave asa stronger baseHL coo” Some’ noc (Strong bse) cis inmer (Weak bse) Since (2)-somer forms intramolecular H-bonding, it cane not release H* easly. However, (E)-somer cannot form ire ‘molecular H-bonding and an release H* more really. Hence (2yisomeris more acidic than (Z)somer. 2.71 Arrange the folowing amides basicity. Explain your answer. @ g wm 2 © om ey ee ‘Ans In these compounds, bascty is determined on the basis ‘of electron density on nitrogen atom. Based on this fact, the ecreasing basicity order is (B) > (=) > (@) In case of (0), line pair of electrons on the nitrogen atom cannot delocalize, ‘because in that case a double bond has tobe placed withthe bridgehead atoms violating Bredt’s rule Incate of), resonance involving a-anesturted ketone system partially inhibits the delocalization ofthe electon pair on the nitrogen atom. In case of (2), no such incidents inhibit the delocalization ofthe electron pain the itogen atom. Violates Bred’s re easing order of lati esonace involving oa pir fleas on @i Aime 2.72 Me\CH on ehlorination using Cl, in aifused sun light gives primary halide as major’ monosubstituted product, whereas bromination by heating with bromine produces a tertiary halide as the major compound. Justify the observation. ‘Ans A probable explanation may be that when a rection ‘with chlorine is cared eut inthe presence of ight, he reac- tion proceeds according to fee radical mechanism. Now the ‘compound Me,CH consis nine primary hydrogens and one terary hydrogen. Therefore, probability ofthe formation of primary fee radial is much greater compared othe formation of tertiary ftee radical, although tertiary fee radial is more Sable by hyperconjugation, but not by any inductive effets. In the reaction of Me,Cil with bromine, when it proceeds thermally, ionie mechanism is more probable, because te ‘iary cation can be formed thermally more easily than tha of| the formation of tertiary radical. This teary carbocation is ‘much more stable compared tothe possible primary earboca- arn oellly tion, because the former i stabilized by +1 effects of the CH, ‘groups as well as hyperconjugative delocalization. Ths, pho- tochericl chlorination gives a primary chloride as the major ‘product but reaction with bromine under thermal condition fives ateriary bromide a the major product em He-¢-H és, mary a Ties -Het cr, cHCL ae—C—a Primary halide “eesiary bomise Altematively, it can be concluded that if we assume the formation ofboth primary and tertiary radials from Me,CH, ‘hen the CI being more reactive and less selective ean readily ‘react with a primary radical because ofits higher concentra tion. On the ctherhand, By i less reactive and more selective, and reacts with the more table teriary radial 2:73 Write down the mechanism of the following reaction, R fs HN Account for reacts 35 times as fast a the one that has R=CH,.presen nt soon a One Chm ‘Ans It isa case of activated micleophiie substitution where piperidine isthe nucleophile, The course ofthe reaction can be shown as follows, H AQ) this extensive resonance involving “NO. group is facile, but in RCH, the steric interaction causes the -NO, _roup to move out ofthe plane ofthe benzene ring and inhib its resonance and consequently slows down the rate ofthe reaction 274 Explain the relative order of reactivity ofthe follom- ing amines with Me,B. @ oO © O ir i cH.cH.cH, (0) (CH,CHCH)N: ‘Ans The relative order of reactivity is (c) > (2)> (0). Com- pound (esa rigid bridged bicyclic compound andthe lone pair of electrons onthe nitrogen atom is more exposed to react Ivith the bulky Lewis acid, MeB. Incase of), thee propyl ‘groups bonded tothe central nitrogen atom envelope the lone pair ofelectons on the nitrogen atom in such a way thatthe bulky Me,B cannot get close enough to react withthe com ‘pound. Compound (a is paially rigid and only one propyl froup is atacked tothe nitrogen atom bearing the nitrogen stom, Therefore, iis more reactive than (b) but less reactive tan (0) 2.75 The following compounds are extremely strong bases towards HY. Give reasons. @ w ) xi—C—fn, ies, ‘OMe Meo. trivially known as guanidine. It is An iong organi tase because ofthe fast hats proto. ated for i stabilized by resonance involving three equiva- Tear mone postive resonating structures. A neural molecule ea no pive a resonating structure but tess stable because of bipolar structures. w 7 i nt cAin, — k= eA ‘Ans The compound (a) i ® iar My nic Resonaing stots of monopronated cation Incase ofthe compound (t), monoprotonated form gets ‘very much stabilized by intramolecular hydrogen bonding. ‘Thats why i functions as a strong base towards H’, but can- ‘ot do so agunst Lewis acids such as BH, or AICI, tr ; Fay b 4 ‘Subized by intamolecular hydrogen boning 276 Compare the acidity of p-hlorophenol and ‘p-faorophenol. ee ‘Ans Between chorphena nd porno the fore is more aii. In ease of pshlcophenol, the correspon ing nose ion is moe stabiied by extended resonance imine it Xr on he hte som Ine of p-vcrophenc, this type of extended resonance st 9 Sil because the fiorn tom hs mo such donbmw 8 gu =r or Extended sesnance (More stable). Er G-O-9 ‘PFlutephenl a p-Chleropenel tended repuoe: mn poutle (Less suble) 2.77 Which one of the following two compounds fs more basic and why? ® a, mn, oat, nn, ‘Ans The aforementioned compounds are rigid molecules. “The compound (b) is more basic, because is monoprotonated form gets sabilized by intramolecular hydrogen bonding. Inthe case of compound (a), such intramolecular hydrogen ‘bonding i not possible after monoprotcnation. Bah = Bs Stbiiedty Iydropen bonding iy im, My Notsilized by inamoleul yon bonding x © 2.78 Arrange the following compounds in order of ‘increasing acid strength with explanations. ) COOH oon oO on myn ou ‘Ans The decreasing acidity order i (€)> (6)> (In ase of (©): the coresponding carboxylate anion ie tabilized by intr molecular hydrogen bonding from two ortho -OH groups. In ease of (8, the stabilization comes from intramolecular hydrogen bonding fom one ortho OH group. Incase of a), carboxylate ion ie destabilized by resonance involving p-Oli group. sans ope ce tectton density increases fon the carbonate group ‘aking the aid weaker ” 2.79 Whats ortho-effecton the acidity of substituted ben- ole acd. Explain with a suitable example. ‘Ans Benzoic acid can have two sete of resonance, One is within the “COOH group and the other involving benzene sing slong with the COOH group. These ae shown her. Wri o— Resonance = 0 only © 75 Resonance involving benzcne ting D Resonance (I) has no apparent ole on the acity strenth incase of substituted benzoic acids but he resonance (1) with substitution atthe orzho-positon can inhibit this resonance {du to non-planaity of “COOH soup. This enhances the resonance (1) and inreases the acy, This enkaneement in the strength of orthosubstituted benzoic acids compared t0 benzoic acd ite is called ‘orshovefect’. A few examples are given hee,Qn nisin omen HO 2d: Hb en ed cH, on 4 We G 8, WO. 26 BV 6: wey ada 30 10 2.80 Ureais a monoacidie base and protonati the oxygen stom, Ans Urea has the fllowing resonating structures. Resonating sven of actal molecule From the given resonating structure, itis evident that elee- trom density ve maximum onthe exyzen atom. Mhetfore, pro tonation occurs onthe oxygen atom and the protonated form igalo stabilized by equivalet resonating sicirs. ao ni —C=8n, Resonating rcs of monoprscnted etan ds In order of 281 Arrange the following comp Increasing px, valves. cr, “@ ew) © ct, fl wn wn ohh ers ‘Ans The decreasing ower ofacity ofthe three compoutds {(@)>()> (a) Al the three compounds produce stable aro~ Inaticcyclopentadienide jon. However, inthe case of (this is father stabilized by very strong I effets of four ~CF, ‘Seas The caranion frm (bisa combination of 0 ao rane ring sytems, The cortesponding. carbanion in-each case, hasbeen given hee “oO Hy oh a2 x cr oh cr, 2.82 Discuss the acidity of phate acid and maleic aid iased on the fst and second dssocatons of ~COOW sroups. ‘An Phila ibenzene-.2-dcarboxyic cand maleic ‘id is ei-butenedion acid. Two eatboxyie groups exhibit Aierent aides. In ease af pili eid, pk of fist dis Socio 298 and px, of sto dssciton i 528. This diterence has een atuibted to the intamoleclar hydrogen tending in ease of Second sisociaion. This eauses second Aax | + Rt Carocstion Ally osyanide 2.86 Explain why the halogen atom of vinyl chloride is less reactive than that of ethyl chloride, Ans In the cae of vinyl chloride, resonanceinvelving the lone pair of electrons on the ehorne tom makes the CCI bond to assume some double bond character and consequently the CCl bond becomes stonger and requires more enersy 10 react. No such resonance is possible in case of ethyl ehlorde u,=cn—@i:-—@u,—c Vinyl boi é7 ene aaa 2.87 Give the structures of the isomeric alkenes having the molecular formuta C,H, and arrange them in order ‘of ercasing heats of hydrogenation. Whats the relatos ship between stability and heats of hydrogenation? When ‘ean we compare the stabilities of alkenes from thle heats ‘of hydrogenation, Ans The isomeric alkenes fom the molecular Formula Cl ae given her. cHScnenencn, cHycH=cHCH,CH, Peteene Pen-ene 0 a ot, (cy.cucn=ct, cHy=C—cu.cu, 3Metylbutt-ene 2Metfbul-ene aw o (cy.c=cuce, 2 Mayet ene ” ‘The decreasing order of heat of hydrogenation benwcen (Dana 1D i () > (MH) and that amongst (ID, (IV), and () is (U)> (IV) >(V). In case of isomeric alkenes leading tothe formation of same alkane on hydrogenation, the most stable alkene tas the least heat of hydrogenation and vice vers TE hydrogenation produces diferent alkenes then heat of hydrogenation” method cannot be used to compare thee sta- bilities. In the present case, stabilities of () and (1) cannot 'be compared with methyl substituted butuenes, because () and (I) gives n-pentane a8 the hydrogenated compound but (AUD, (IV), and (V) give 2-methylbutane asthe hydrogenated ‘compound. compounds in order of methanol Give reasons ia decreasing rate of solvolysis favour of your answers (4) Isopropyl bromide (€) Diphenyimethy! bromide () Butyl bromide (@) eBuryl chloride ‘Ans These lly bromides are likely to undergo solvolysis by S,1 pathway, In Sy1 mechanism of substitutions, the reac- tibn rates are dependent on the stabilities ofthe interme ‘carbocations. On the basis ofthis fact, the increasing order of fates of reactions of the aforementioned compounds is Isopropyl bromide < -Butyl chloride < ¢-Buty bromide < Diphenylmethy bromide. ‘Between “Buy! chloride and Buty bromide, the later is more reactive because i contains a bette leaving group (Br) ‘compared to Cin Butyl chloride. 2.89 Arrange the following compounds in order of ‘decreasing nucleophilic giving reasons: (a) Aniline, (b) Ethylamine, €)4-Nitroaniline, and (c)4-Bromoaniline. ‘Ans In these compounds, baticites and mucleophilicity un parallel because the lone pair of electons, necessary forthe Exhibition ofboth basicity and nucleopilicity resides on the nitrogen atom in each case, The bascites of these compounds in decreasing order are a cnn > Oo a QO > oO ‘Br = “The decreasing nuleophilicty is also in the same order, as showa. 4-Bromoaniline is less basie and less nucleophilic than aniline because of mesomeric and inductive effect. Eth yamine is the most basic and nucleophilic because the lone rir of electrons onthe nitrogen atom cannot delocalize. 2.90 Arrange the following compounds in order of increasing acd strength. (@) 4Nitrophenol —_(b) 35-Dimethyt--nitrophenol (6) 246-Teinitrophenol (d) Acetic acid (©) 2eDimethyl-btrophenol. ‘Ans The increasing order of acidites of these compounds is follows: on on on Soe 6 x No, No; g on NO, < cH-C—on < 291 Arrange the following reagents in order of decrease ing basicity. Give your Justiieati () BuOK (@) Naoet () aNd, (© n-BuLi (©) PhjCNa Aus Te dcr sy on of ee eg en eB )> PRENAPA,C) > NN) > B.0K(840")>NAOEL> E>) nue a cont ae nd ee sro ae of creo cana oro e EON 40H» NH,» PCH nat 292 Arrange the following ions in the decreasing order of 2 reactivity towards Mel in MeOH. support of your answer. @e (© Pho- ©) (@) CHO-ans Inthe case of 8,2 substitution, the mcleopilcty ofan ‘anion or Lew base is measured othe basis ofthe polat- Ieablity of the pair of electrons responsible for exhibiting ‘ueleopilcity. On the bass ofthis at, the aforementioned fons canbe aangedin decreasing order of auleopaiicity as follows > BOT M&O >P0"> ‘When the size ofthe atom bearing the lone pao electrons i lager and clctoncgativity vale is lower, then the lone pir of electron ie more polarzabe. When the lone pair of letons resides onthe dential atom in several sions, then the more base anion i more nucleophile. 293 Which of the following «wo carbocations is more ‘Ans Berween the compounds (a) and (6), (6) is mow stable ‘Acconling 19 Walsh model of eyclopropae, the ring behaves Tike asubstiuent having atclectroa system. Therefore three cyclopropyle rings wil sabilize the carbocation more effec- tively than two cyclopropyl ings anda methyl grou. 2294 Which compound inthe following pairs more acidic and why? ‘Ans Compound (a) is more acidic than compound (b-After ‘deprotonation of the cena carbon atom of (a, the come Sponding carbocation can assume an almost planar sructre because the rgid amu ofits structure and resonance invely= ing benzene rings become mare effective. In case of (B) he carbocation foned by deprotonation becomes partly nonpla- ar due to non-giiy ofits structure, 298 Predict with proper reasoning which member ofthe following pairs behaves a a better base towards BMey * 4 a eee aG) o o a o pared to dethylamine(). Inthe ease of diethyl teraction between Me groups of BMe, and cibyl group of the amine will prevent reactants to come close enough for Inthe cas of (), compound (i) is more basic, because the Ione par of electrons onthe aitrogen atom is more exposed Poet Orne Crome {o coordinate with BMe,. In compound (iv, the lone pair of ‘ectons on the nitrogen atom is somewhat masked by the ‘methyl group and some seri interaction may occur with the ‘meth groups of BME, 2.96 What do you mean by nuclofuga suitable example. ‘Ans The leaving group tat carries away the bonding electron pir ina substition reactions called nucleofuge and the ten- ‘eney of atoms or groups to depart withthe Bonding eleston pairs ealld ncleofugaty. For example, nthe hydrolysis of “in alkyl chloride, Cris the nucleofuge 297 Which of the nitrogen atoms in semicarbazide is inolved in the semicarbazone formation. Explain. ‘Ans Inthe ese of semicarbaide, we ean show the following resonaton structures. Explain with i ‘ 68,8, > Hh ' ef Hie. From these resonating structures, itis evident that tbe lone pair of electrons on the marked nitrogen (bold) cannot tke pt inthe resonance. Therefore, itis more available and a ‘more polrzable electron pico participate inte reaction of {he formation of semicarbazone 2.98 Nitromethane's a stronger acid than methyl cyanide ‘but tinitromethane isa weaker acid than tricyanometh- ane. Givean explanation for this, ‘Ans Its tobe noted that-NO, group ia much stronger nee- asive group (electron withdrawing group) compared to CN proup. That is why, CH,NO, isa stronger eid than CH,CN. CH —NO, = GH, at, cH. —can SS Ga can-—-er Incate of tinitromethane,carbanio cannot become sta- bitined by resonance because planarity cannot be achieved de fo interaction among the three nitro groups on sine fle carbon. In case oftrieyanomethane, CN group is Hinear Bnd steric factor i not inhibiting resenance, This is why, yenomethane elves a & Stanger ad compared 1Prosi nt ston nore chmiry on NS Beso, termes on oc 299 Each ofthe following molecules contains two halo- tens at different postions in the molecule, For each one, explain whieh ofthe two halogens wil be more reactive fn the Sy reaction oynet a © yA @ ad © a, @ cel ‘Ans The underlined halogen in each case is more reactive towards Sy reaction O > a. © on — Si, owe —O ere r 1 6 esos sbieed @ ve che np in © ge 2 BP HEN, neeQry, Mor ste ae ~nA*, ar 2 “More stable than 7 Oncth 1 cH, ridged bieyelic compound prevents + ve sp earbon tte bridgehead 2.100 The equilibrium constants for the complex forma- tion of amines with Me,B increase inthe following order. Give the necessary explanation, NH, ~CO,H >—OMe > -NRy and (b) he oder of increasing eet i MeeMeCH «Beye 2.402 Write resonance structares for the following indicating major and minor contributors (Cyl ithe phensl ring). @ lencnocnenr (© keu,cocusr © lemenocnencH,y (a IcyH,cHNn4r awe MAGS AG Major WO AgAs— Ayre Age MajorMajor(is) Major Ga) a 7 Koti, Bin 2.103 Which compound among the following pairs will hhave a higher electron density at the marked carbon Ans ® 7 . Florine has preter #M effect ‘compared 10 chlorine oH Hl (C—Hiypercanipation it more etetve han C=C hypereoniustion se hae, wc Samanta 2404 Arrange the following ions in deere ‘nucleophilety In protic and aprote solvent, cP, 8®, 19 F i order of aa ‘Ans In a protic solvent like water, the decreasing mucleop- hiliety oder is > Br > CI-> F> In ease ofan aprotic sel vent, the onder is reversed andis P'> CI-> Br-> 2.105 Write the following compounds in order of decreas- ing acidity, and explain the reason for the order. (@) cH,co.n (© cicH,co,t () HCO, (@ aicH,cH,co,n ‘Ans The order of docreasing acidity i as fllows: CCICH,CO,H > HCO.HI > CICH,CH,CO,H> CH,COOH Th case of a-chloracetc sci, “effect of chlorine atom is ‘ore pronounced because o its proximity o~CO,H. This is ‘why itis more acidic than HCO,H. Now, “effect af chlorine ‘stom in -CH4,> CHCl,» HORE é: ‘The dereasing basicity order is also the decreasing nucleop- hiticty onde. 2.4107 Which one ofthe following pars has higher boiling Point and why? HL Be () cuyeny ich, an cH,eeH, Gy, ‘Ans The explanations ae as fllows: (a) Betweencis-andirans-l.2-dibeomoethylene,cisisomerbas {greater dipole moment and consequently, intermolecularQrrires one seseninononchemy Aipole-dipoleinveractins is also more. Therefore, cis fsomer has a higher boiling point. ans-.2-Dibromeet- sere bas zero dipole moment. [Between n-butane and isobvtne, butane has higher boiling pint. The probable reason isthatn-butane, beinga smightchsin hydrocarbon its molecules can come close to each other snd van der Ws atrative force could ‘operate more effectively to keep the molecules together. In the ease of isobutane, it being a branched hydroear= ‘on, the melecules cana come close enough and van det ‘Waals fores of atraction are very feeble, Consequently, the molecules ofabutane remain less associated and it thas a lower boiling pont. 2.108 Based on HSAB theory, identity the following ions and molecules as hard and soft acids and bass. HY, BF,, Pa, CH,COO™, Ca, BH, H, SCN", OF, els, CO, Ce, NH, ‘Ans Hard acids: H", BE, CO Soft acids: Pa, Ca", BH, Pt Hard bases: CH,COO", Off, CO,*, NH, Soft bases I, SCN- 2.109 Show the direction (LHS or RHS) that you would ‘expect the following equllbria tie in. Give reasons. (@) CHLCEN+ Gy == CH () CH=CH, 0H = CH.CH 411.0 (©) OWS CHNH, == CHAN +10 © NEG @ cHsis cH HCH +1 ( CH,CH,OT + Cg1,COOH = CH,CH,OH + 61,00" (9) GHANH, + HCO; = CN,NH+ HCOOH Ans {G) RIS, Acetonitile (pK, = 35) isa stronger acid than ben- zeae (pK, = 43) and wil, therefore, protonate the benzene conjugate base, phenyl anion (@) LHS. Water (pX, = 157) is « much stronger acid than ‘ethane (pK, =36) and wil protnate the conjugate base, ‘ethyl anion (6) LHS, Water (pK, = 15.7) isa much stronger acid than the Noli proton of inethylamine (pK, ~ 36) and will there fore, protonste the methylamide anion HS, Mercaptomethane (CH,SH; pk, ‘much stronger acid than methane (pK, protanate the methyl anion. RHS. Benzoic acid (pK, = 4.2) i a stronger acid than ‘ethanol (pK, = 15.9) and wll protonateetboxde anion LHS. Form acid (pK, = 3.73) is stronger acid than the v,> W;- Therefore, HOMO is W, having a plane of symmetry. ‘Wits Vets and vy," are antibonding r-moleclar orbitals. ‘The order of decressing energy is y,* > Ws > Yq" The fore, LUMO is y,* having a C; axis as the element of symmetry. v ww 2.120 What isthe structure of ascorbic acid. Comment on Perpendicular C, axis the acidity ofthe compound. What isits IUPAC name? [Ans The structure of ascorbic acid is given here. Woy Wo Aa 00 uo“* Yon In this ease, the acidic hydrogen is withthe marked ‘OH ‘group (underlined) and this i due to vinylogous effect. The Fonizaton leads to an alkoxy ion which is stabilized by res- ‘onanee. nee ces) Fs SF ye ‘oon a To ~ST ok, city ena niientteret oesiecemees peer OW Teal i tear el uel om, Os 9 { =p 07 onan ° | ‘on ay TL mes ° o 2.122 What are isohyptle and non-sohyptle reac Explain with reactions. ‘Ans Isohyptic reactions are those reactions in which there is ‘po change inthe oxidation states ofthe carbon atoms partci- ‘ating in the reactions. Substitution reations ae found 10 be isohyptic reactions ‘i ; $2. won, Inthis reaction, the oxidation state ofthe carbon atom has ‘ot changed afer the reaction. Therefore, it an be identified asa ‘isohyptic reaction’renee ee ee Inthe case of addition and changes in the oxidation state ofthe carbon atoms involved in the reaction. Hy HO + BF ont ‘Uh £3 ean City i u ‘The aforementioned two reaction, namely addition and elimination, may be considered as fsobyptic reactions because they involve a change in the oxidation levels ofthe carbon stom involved inthe reactions. 2.123 For each of the following molecules shown, hyper~ conjugative, rather than steric factors, dictate the geome- try of the structures. Draw the most stable conformation ‘or geometric isomer and clearly label all dominant hyper~ ‘conjugative interactions, for example, C-Cand o*C-0. Me x7 Oe (@) M70 (MeO mH @ crn=i-5 ween roe Ans 2b. -Me— @ me mb Me Mos stale conformation ueto gauche effect, | f. PL coe oP Fan pone pron oxygen int of OC M 4 4 ©) ye— En — eee, as Most sale Conformation ue gach fest, | at Wy oD: en Filled 9 C—H int 9 C= F there ar two sich interactions o Front view 9 ane — 990 Oy (0-p lone pair Me! ‘Top view € 0 2 Op one pair Oi 1 C-Cmakes the mol portal lone par on oxygen into x* C—C make cule planar, 3? fone pair on oxygen into o* C—C causes ‘methyl and double bond tobe on the same sie ofthe central (OC bond © o's—0 Fie Nien oO In adion filed. 4 The three phosphites illustrated in this question ‘exhibit 750-old span in reactivity with a test electrophile (Eq, 2.1). Rank the phosphite from the least to the most nucleophilic and provide a concise explanation for your predicted reactivity ord ROP: +E + RO,P—E ‘wo anomeric interactions between the ‘ile mont and s* C=O ifthe OMe substituent is directed (axial away Hom the ing, Phosphate (b) has three anomeri interactions between the fled orb and 3* CO. This etre shld be the weakest niclephileCin ° Anomeie sailing interacions ©) beeen the fled portal ando* C—O Phosphate (c) bas one anomeric interaction between the filled p-rbital andthe o* CO, ifthe OMe substituent i of ented inthe conformation just shown. Otherwise there ae no anomeric interactions. Aa? Me o ‘This phosphate should be the strongest mileophile. ‘Therefore, relative reactivities of (2), 8), and (are found tobe 125:1:750, 2.125 “Phloroglucinol can behave as an ambident nucleo- pile but phenol cannot’ Sustiy this statement with exam Dies ‘Ans Phloroglucinol can have both enolic form (phenolic structure) as well a triketo-orm. ; ins fom eet mum a AES 0” en cu, “MOH 0° Nal +H,0 noon ‘The other two -OH groups can also undergo 2 similar In wiketo-form, phloroglucinl behaves like B-tiketone with active methylene group. The hydrogen atom from these tive metbylene groups canbe lst as Hin the presence of| a strong base forms a very stable carbanion, Therefore, C- allylation is also possible, a shown here. ° cu, 1 0 ay Physiol Orgonic Chemizayl AT) In this way, all the six active hydrogens can be substi- ‘uted by alkyl group. Thus, phloroplucino! can undergo O-slkylation as well as Ccalkylation through nucleophil attack. Therefore, phloroglucin! can function as an ambient nucleophile. Ketoform of phenol isnot observed because of its extreme instil 26 When an aldehyde reacts with NaHSO,, a bisul- Dhite addition compound is formed. HSO,” isthe neces- sary nucleophile in tis reaction. Is ian ambident nucleo Dhile? Give the reaction and structure ofthe product. Is. SO -an ambident nucleophile? ‘Ans HISO,”is an ambident nucleophile. Its structure is shown, here, 1 can take part in a nucleophilic substitution reaction (5,2) through oxygen atom a well as sulphur atom. Since the lone pai a eletrons on sulphur atom is more polariza- ble, this lone pair of electrons takes part in the formation of sodium bsulphite addition product. The course ofthe reac~ ion shown bere. on Bisulpite adston product 180," isnot an ambident nucleophile, I always attacks through oxygen atom, 2.127 Forench ofthe following pais of alkyl halides, ind ‘eate which member in each is more reactive In 8,2 reac tions. @ An © ~ an o oo to ” arm hem Ma Ae a i wi wQn arto nen ‘Ans In (a), (i) is more teactive. Compound (i) is sterically hindered foe $2. Tn (b, iv o more reactive. i) has got a branching. In (oi) is more reactive, (¥) i 4 neopeny-tike com- Tn (), i s more reactive. (vi) i wetary halide and serene reluctant to undergo §,2 reaction. 2128 The sodium salt of methylsulphinic acid reacts vith methyl fodide in methanol (o give a misture of 0 Teomerie products. What are the structures of these 70 products? ‘Ans Sodium salt of methylsulphinc acid is an ambident fcleopile. I ean attack through oxygen atom as well 35 through sulphur atom. The eaction and products are shown Metylulphinic acid ° ot cu—$-o° (and (tp are the two isomer products 2.129 Explain whether the fllowing substitution reac- tions (S,2) will occur oF not. (a) Net RCN —— Nut CX () Net RN, —~ NR NS ‘Ans Inthe case of (a), CN” isthe conjugate base of avery ‘weak (HCN) aid (9, = 10). Therefore, CN" is strong base Sint consequently isa bad leaving group. Therefore reaction (@) wil ot take place. In the case of (0) Nis also conjugate base of a weak cid HN, (pK, = 58), Therefore, iis als a bad leaving group fd the reaction shown in the problem wil not eur 2.130 fn each of the following pairs of reactons, which tives more ofthe elimination product? a ¢ @rs (Aw Ar) ® 6 a 0) (CH4,C0 & CH,CH.O) + A «i ow E g © a (A a Ayre wo” ¢ A) i expound () wil undergo bet branching slows down 5,2 © Ane ( X00 a ‘Ans Inthe ase of (8), the {er elimination reaction because Inthe ease of anion. Therefore, (iv) would reaction nthe ease of (), (> slower $,2 but better E2. Tne case af), secondary baide (vii) is slower in $2 tt better in elimination easton than the primary halie (i) 2131 2-Rromo, 2 Br > Cl bea Fis 2 beter leaving ‘op an Br and Brisa beter ning pop than Cr. The Earcation cn undergo elimination (1) a (1) sow, ‘ove mine ofthe me compound Se cn,~C=cncr, PN 2ee ou, concn, Sy! feron oh ca-tcucn, Ome 2 Mtethoxy2-methyouane i cHyac—cH.cH, 2Mehy butte (9) (etiy,cHieH,C1+ 8, —- eH,),cncH,N, +r and (Cil,cHCH +N (CH,),cHCH,N, +ot om () CHCH.CHCH,Be+ SH” —> cuycrcucn,sit +e and (CHCH,CH,CH,Be + SH —> CH,CHLCH,CH,SH +B HoH, (9 cucu en” cu,cHeN + and cicr,prsoxr CHDNCEO cy crnew ene (8) cases (eH, —= Cr ad c8e+(H4yF—e CH ror a occ, + cHc0; — of sor a occ, C1 e456; — C7 ser ‘Ans The explanations areas follows: (@) (CH)),CHCH,| reacts faster because I>, being a weaker base, beter leaving group (8) Inthis case, CH,CH,CH,CH,Br will react fase, because in the other ease substitution slows down S,2 reaction, In this cas, the restion carried out in DMF would be faster, because hyeoxylic solvent CH,OH will solvate CCN- more effectively and will educe is effective con centration as nucleophile In this pair of reactions, tihenylphosphine will eat st 3 faster rae, because the lone par n phosphorus atom is ‘more polarzable. In genera, thid perio atoms are more nucleophilic than their second period counterparts In the transition state of substitution reaction, the earbon atom undergoing substitution changes hybridization fom sp" (bond angle 109°) to sp" (Dond angle 120°). Ring strain will oppose this change in bond angle (spreading process). Incase of lower ring, the opposing process is ‘more compared tothe larger ring, Therefore, cyelobutyl chloride will eat at slower ate compared fo cyclopen- ‘ylelerid, 2.133 OF the following nucleophilic substitution reac- tions, which of these will probably aseur and which will probably not occur or be very slow? Explain your answer. © © © (a) CHCN + —+ CHL oN () (CH),COH + NH; — (cH) CNH, + OH (©) CH,080,0CH,+ cr — CHC +cH,050, (©) CHLCHL+ Nj — CHLCH Ny F Ans (@) The reaction (a) will not occur beeause CN” is 2 poor leaving group (conjugate base of weak acid HCN), Psat hn) (©) In the case of (), there wil be no substitution reaction ‘because OH" isa very poor leaving group (conjusate base ‘ofa very weak acid H,0). However, there is a possibility ‘of acid-base reaction inthis eaze withthe formation of alkoxide and NH, (Hg, COM +N; —~ (C11),CO" + NH, (©) This reaction will tke place because CH,OSO,~isa good leaving group, being a conjugate base of a strong acid, (CH,050,H, comparable to H,S0,. (@) The reaction will occu. Ii 8 good leaving group. 2.134 Give a specific example of two related reactions having different rates for which each of the following is the principal reason forthe relative reactivity. (a) The less basic leaving group is more reactive. () A nitrogen anion is hydrogen bonded more strongly ‘han a sulphur anion. (6) Steric hindrance (@) Protie solvent can form hydrogen bonds. ant ) Ny +cHyc1 S cryny vcr — Moret Fase — testa Nyse B2- cuyye r= ‘ cau ver ©) cauprescar PHESANEH Cay sen scons (Mijn) ier cpr esen” APSE Cy scx 4 CHNCS (Minor) aor) (©) cHRCH,CHL+ cH," — cus,cH,cH,SCH, +1 Fase) (CA CH CH,°—> CH,CHCHLSCH, +1 lower) @ Hers 22 Acee CHCHE +1 (Very slow) cu.crl +r CHCHEST (rate 2.135 The resetion of methyl bromide with methylamine ‘give dimethylammonium bromide i a typical 2 reac jon that shows a second-order kinetics, Second ccryprsciyn, $2 However, the analogous eyelization of 4-bromobu ‘plamine shows fistorder kin H eri nec W, SwWren on son n zane Chemiry “i trance dglcment reason ix wel snot tar ng oc ne Herr onpng Sieractna's tise dices ji ey. mech, = men ot ‘Ans Reaction cen inary hada an aoe 2 opal 82 ssbaaten easton Tn eae of cate he recon mse fis re so rl Ther Fat enon woul bee = NCB) ha ‘molecular, k= rate constant. pect ‘Compre waste inemolsea ndscond x. ts mt gation te = INICIO eect Son i ph hea eating cvs st lero sch ties ‘ inemoirlr etn fovoue te concen islow then te etn cones a compuraty more cle tot nanolclar recon ening yee computa tor vue Thee caled hgh ton eae he Sribess fy ompounde 21136 Optcaly acne -bromobutan 2s rested with Om in methane to obtain an opel nace prodoct Tang te formula C¥,O, What isthe strate of this Scnpound? Espa ‘Ans The recéon amount ofomsin fm cpeide ote Ervatve) fom broehya by intraarea tn, being enalaed y ate, The cour of he econ Par ty H Bu in cH, a, WE sanonbemtt tbe aes eons Hx diate Intramolecular S,2reactontakesplaceinthat conformation where the nucleophile and the leaving group are ant to each ‘other, The other enantiomer of the bromahydrin gives the same result 2437 In contrast to $,2 reactions, Ss reaction show rel- atively ttle nucleophilic selectivity. That is, when more sleopbie present inthe reaction mediam, ie sgn teadescy 0 deri So ees tak uclopile and strong auseopie, nae ee econ show a marked tendency tod crea SG Frode an eplanaton for tis bekay- ts for the fac Feeney show how your ansmer accounts for seen CHCHLCCH reacts nth OOIMT NaCN in thee ae ee peur CH,CHCHLCN, whereas under Fe ee ions, (CHYJCC! eats Yo gle primarily (cup,coct,ci, ‘Ans The explanations ae as follows: (@) The rae equation of an S,2 substitution is given by the following expression: Rate = [Substrate] [Nucleopile], k= Rate coastant Thus the rection is sccond order and bimolecular. The reaction is found 19 be dependent on the concentration as tvell as mocleophlicty ofthe nucleophile. 1F the reaction tedium contains 10 different nvleophiles differing in their mecleopilcy, then a sronger nucleophile will eact prefrbly. Thus, when ROH treated with a mixture of HI land HBr, the major product would be RU and not RBr. This {is becane Fis astouger nucleophile compared to Br than one Sal reactions show In cae of $1 reacton, the rate equation is found to fol- Tow th expression given here Rate A{Substate}, k= Rate constant Thus, the rte of $1 substiuion is independent ofthe nature of the nucleophile nd is concentration in the rae ion medium. Therefore, Sy1 reaction is less disenmina ing towards nuctcophils. In the case of a reaction between CH,CH,CH,CI and [NaN in ethan, the reaction proceeds according 0 8,2 pathway. Here two nucleophile species are CN” and EVOH, Sine CN" isa stronger nucleophile compared 10 EVOH, the major product is CH,CH,CH,CN. © se cuycrgenLe1 *". cu,crcnen +r en On the other hand (CHICCI reacts by $1 mechanism, ‘where the formation ofthe butyl cation i the ate deter ining step.e fig ne-¢-a er. He-E + oF by, by, {Butyl cation then competes for CN" and EXOH to form a stable product. Since the concentration of EYOH (reae- tion medium) is larger compared to CN”, the predominant substituted product is (CH,),COCH,CH,, i ne—¢—6—cnne, én, 2138 When (CHL),CBr undergoes Sy hydrolysis adding ‘common ion’ (Le, NaBr) to the aqueous Solution ha no sffet on the rate. On the other hand, when (C,1L),ClIDr Undergoes Sy1 hydrolysis, addition of NaBr retards the ‘eaton, Given thatthe (C,H,),CH cation f known to be much more table than (CH, C* cation provide am expla nation for the aitferent behaviour of the two compounds. ‘Ans In cae of Syl solvolysis, the sabiliy of eabocation Plays & very imporant ole A carbocation, during its ater Shor ie ime, is surounde bya “salvation age consisting ‘of largey water moleculs (incase of hydrolysis). Such a sol ‘ated eatboeaton prits unl it pulls a water moleute out ofits salvation eage forming a molecule of aleoho and cat ing the remainder ofthe cage to cllps, outa halide on pushes through the salvation cage to atack positively charged Carbon. In ase of elativel les stable (CH,),C* carbocation ‘ith high concentration of postive charge on a exon, the solvent cage collapses quickly and eats with «nucleophilic solvent molecule, before an extemal bromide fon can tack. ‘Therefore, the rection sno affecte by the aditon of Nae tothe reaction medium Hy ih tho no Hc— ea BO AS nc—¢—on on ony ‘Buy omit (Adsivon of Nabe as of). anton ons ‘As the stability, and hence the average lifetime, of the ‘carbocation increases, halide ion (in this case bromide ion) finds a chance to react with the carbocation and the reversal ofthe ionization step becomes possible andthe effective con- centration of eatbocation decreases (mass law effect). That is why addition of NaBr tothe aqueous medium containing (Cil1), CHB retards the solvolysis reaction " " 8, nate ise Sth et iS —s ma; Ph (arial regeneration Suble carbocation (ami eeenrai win solvent cage Soe 2.139 The order of bond lengths inthe halogen hydracids is H1> HBr > HCI> HE; the order oftheir dipole moment is HF> HCI> HBr > HI Offer an explanation. ‘Ans Dipole moment (1!) = magnitude of charge X distance ‘between the cenire of the postive and negative ples (Le. Xd). The value of eis determined by the elecronegativ- ity of X (alogen atom), The order ofelectroncgativities is F 40)>C1G.0)> Br28)> (2.5). Ife’ increases sufficiently ‘more rapidly from I to F than “a” decreases from HI to HF, then the product ofe xd increases from Hl to HF. The exper. imental dipole moment values of HF, HCl, HBr, and Hare 1,86, 105, 0.82, and 0.38D respectively. 2.140 Arrange the four halide fons in order of decreasing basicity. Explain your answer. ‘Ans The decreasing order of acidity of the four halogen hydracids is HT > HCI HB > HF. Itis known that stronger the acid, weaker isthe coresponding conjugate base (and vice versa). Therefore, it follows that the order of decreasing basic~ if ade ois Conjuate basso haope hye ids): o> Cl-> Br-> F. Pee 2.141 Arrange the acids with the following pK, values in order of increasing strength: 63, 4.7, 9.5, 2.t, 15.8. Do ‘he same with bases having pK, values 8.1, 42, 16,10, and 25, and order of acidity for the bases with pK, values 7, 114,92, 128, ‘Ans The general rules of relations of strengths of acids and bases with respect to pK, and pk, are (a) stronger the acid, sumalle the pk, values (and vice vers}; (b) stronger the base, smaller the pk, (and vice versa) On the basis of these, we ‘conclude the following: Acids, pk: 158, 95, 63, 47, -2.1 (rength increases from if to right) Bases, pK: 4.2, 8.1, 10, 16, 25 (base strength increases from left to right; Ky: 12.8, 114, 9.2, 7,427 (aid strength increases from Lf 0 gh), 2.142 Comment on the relative stabilities of the following ‘carbocations,Crs nt sso gm Cet © Deo, @@He — CHE ‘Ans The increasing stability of order is (a) < (b) < (0 ‘The carbocation (2) is partially nonplanar because of the fivemembered saturated ring. Consequently, hyperconjuga~ tion involving CH, groups ofthe ring would be dificult. the case of), earbocation is almost planar and hyperconju- {gate resonance involving CH, groups a well s delcaliza- tion involving x-eletros ofthe Ph rng stabilize it considers ‘bly (6) is stabilized by hyperconjugative resonance involving groups. nal he cases +1 eet also has some stabilizing effect bu this effets less compared to hyperconjugation and ‘eloclization of r-sletrons. 2.143 Nucleophilcty and basicity order of NH, H,N-NIly land H,N—OH are in reverse to each other. Explain. ‘Ans All the three compounds show ther basicity duet the presence of lone par of electrons om the nittogen atom. In ease of N,H,, basicity is partly decreased due to =I elect of the ater nitvogen atom, Since oxygen atom is more lectron- cezative than nittogen, basicity of NH,OH i less han that of HLN-NH, Therefore, basicity order ofthe three compounds is NII, > Ny}, > NHOH, In this ease, nacleophiliity doesnot run parallel with the basicity, In both HN-NH,, and H,N-OH, nucleop- hilic attack by Jone of electzons is enhanced by the lone pair of electrons onthe adjacent atom. The phenomenon is falled “oveffet’ This effec is more pronounced in ase of H,N—NH, compared to H,N—OH, because lone pair on Nis more poariable than the lone pair of electrons on O atom. Therefor, the ncleophilcty order is H,N—NH, > H,N-OH> NH, 2.144 Enobform of 9-formyuorene is favoured in its ‘equilibrium system. Explain. ‘Ans The siracture oF 9-formy/tNuorene is given hee eso 9-Formyuorene “The hydrogen stom attached to C9 is doubly benzylic and considerably ace, Therefor, it eolizes readily andthe planar enolic form is stabilized by delocalization involving extended conjugation, oa weSo u-Con Eno fom (Gabiized by evened conjugation witha Ph BoP) ne remains almest 2.145 Othe following iva compounds 2S jain the enolic orm but the other as Ketonic form, Tena the compounds and give reason @ X » oo S ‘Ans Bath the compounds are ietones. Te compound () aaa Saaeyn enolic frm because te enolic Form cae efunsatrted Ketone form. Compound (8 ‘Sit to form enolic form beease ofthe excesive tain {fast develped deo te buy ouP- x, ~, as nucleophile, is CSF >KP> Li. ns and anions are not 2.149 For the reaction KCN + RX —~ RCN + KX, which solvent, methanol, acetone, or dimethyl sulphoxide would be more important? ‘Ans The mode of reaction is S,2 substitution, The rate equa- tion of ,2 substitution is ar follows: Rate=é{Substate] [Nucleophile], Aerate constant. This means, the rate is ‘dependent on the concentration of the nucle Ina protic solvent ike MeOH, the nucleophilic species CN= {es solvated due tothe formation of hydrogen bonding and its effective concentration decreases, In acetone, ionization ‘is minimum, DMSO is polar solvent but it cannot solvate anionic species CN dae to stric fctor but atthe same time the substrate molecule becomes more polarized. Conse- ‘quently, ate of §,2 substintion is accelerated considerably in DMSO ((CH,),S=0)}. 2.150 Why are vinylic and aryl halides unreactive towards both Ss1 and S,2 reactions? ‘Ans Vinylc and aryl halides donot form stable carbocations ‘tough ionization; therefor, they fal to give Syl subs tions. On the other hand, resonance involving the lone pair ‘of eleezons onthe halogen atom makes the carbon-halogen ‘bond very stong (double bond character) and thereby appe- ciably increases the bond strength of C=X bond and prevents ‘S,2 reactions RCH=CH—X: —> RCH CHART Vinyic halide Unstable carbocation + x O-CO:# ae 1K: => neu—cH=k Vioyi halide Song bond b= Arle Psat Orgone Chentmfad) 2ASt CICH,OCH, undergoes Sy1 solvolysis even though itis primary halide, Explain, {Ans In this case formation of the intermediate carbocation through the heterosis of C-Cl bond is stabilized by the delocalization of the lone pair of electrons on the oxygen atom (analogous to NGP). Thus the formation of earbocation requires lest activation energy and the solvolysis reaction by Sy mechanism cccurs smoothly. ta G. “edcui—dcn, = CH, Gen, ——- cnc, HGH Gotven | Ho—cH,-dcx, — 4,6—cH,—den, 2452 Consider the ‘meat reaction: wing data for a simple displace- Hor +R—Br—=R-OH +B Experiment Thitial Relative concentration | intial reaction (Moesfitre) rate jo- | RDF T 005 | 005 T 2 o10 | 00s ' 3 095 | 0.10 2 What isthe mechanism ofthe reaction? ‘Ans Inthe reaction, doubling the concentration of hydrox ide ion (nucleophile) does not affect the rate ofthe reaction Doubling the concentration of RB doubles the rte of the reaction. The reaction is, therefore, frst order in RB and ero order in HO. This act suggests thatthe eacton is 3 ‘ase of Sl substitution. I occurs im two steps. The ist step Js the slow ionization of RBr to R* and Br. In the second step HO- rapidly combines withthe carbocation to form the product 2.153 Draw the energy profiles for a three-step reaction which (a) the rst step isthe slowest an the last step is the fastest (D) the frst step isthe fastest and the last step {isthe slowest; (c) the second steps the slowest andthe last ‘Ans The thre step reaction can be depicted a A= 2 C-2— D, Letusassume that the overall reaction is exothermis, The three energy profile diagrams can be eriten as follows. all hese energy profile diagrams, Dh lower energy content A’ Inthe gran (3), the Bist step i the RD. sep and the ast step isthe fstet (lowest atvation energy. In the dae gram Cb) the it tp isthe fastest andthe ast step isthe slow - ‘rte deterining step nthe diagram) dh second Step isthe slowest athe last tp isthe fastest.a 2.154 Consider the reaction A <== anf | °x a] 27 | 26a p| sae | 23 ‘What is the composition of the equilibrium mixture at asec? [Ans Since this problem requires an answer to an equilibium ‘constant will be necessary to determine the value of AG. Since ks postive fora negative AG, the necessary equation would be “RTInK = AG" = All ~Tas* ‘Therefore,AG" = (-25.44 +2427) 298(252.3-246.4)x10 1.17(298%5.9%10") 293K 17-176: ART IK #527 log K KS, therefore, 5:7 log log k= 2.93; (8) (al Inthe equilibrium, A=, B thereis I par A. 1 owas gag"? 3.28 son = 36 and eB = aE 100= 764 “Thus in the equilibrium mixture, 23.6% A and 764% B wie ne conption eof the resonating stracars of dipheny. ae oe cemutene, en the strata wih sete chow te mplanes af the cumsene- pe lonaingsvetare rertie equed reonangsmctte i town he. The ae i re oneave dle bons tec aan alee wi ot amber of bl ond <) (De ‘The macs of test ofthe conscivedoble tonite thow. 2is6 Ped which member of exh of the following pais compounds har higher rssnance ney andj, tify your choice, rer (Anthracene or phoantrene {© Ammontumaceate or cetamide {6 Gyuooattrant orsgrene (@) brant ecmatiiberere (© prensosinon or buat 69 Farmer tape Ans ts no ht horse sean sta ie Io welds rsonansccny and vce ee. Tee ‘evilhovet fio mre able rca nce ee othe canpoind ne stscmenioned prs of enon (0 Begeenantineene sn henner as Pier esomee nee ee mum unbe Otbeneoi irs san ese ume fang sects, Ste ohne an pea threne are given here. me ‘Anhssne Phonanbrene(©) Berween ammonium acetate and acetamide, resonance is more effective in case of acetamide. Incase of ammo. nium acetate, the negative charge on the oxygen atom of the acctate ion is not sulficiently free because of ammo- nium ion and, therefore, resonance is inhibited. There- fore, acetamide has higher resonance energy. ° cH—c—oH, cr Ln, Ammonium eat Acti (©) Cyclooctatetrane almost always remains in non-planar fub-like strcture with litle seope for resonance. Planar structure of eyelooctatetraene isan unstable ani-aromatic system. Styrene isa planar molecule with an olefinic dou- ‘le conjugated 1 a phenyl ring and gives alge number ‘of resonating structures. Therefore, styrene has higher = O cycloosaraene (ant anraromate stucte) (Tab tke nonplanar strate) cH=cH, ‘iyene (Plann) (@) Between benzene and hexamethylbenzene, hexamethylb- fenzene is more stable due to byperconjugaton. There- fore, it bas higher resonance enerty (© prBenzoauinone i a crossed conjugated system and has to aromatic stability. Benzaldchyde isan aromatic com- ‘pound with an extended conjugation, Therefore, benza- ‘dehyde is avery stable molecule having higher resonance Q pBemguinone uw enzaldebyde (0) Between furan and thiophene, thiophene has higher aro- matic character ve to greater polarizability ofthe elec- {ton pair on the sulphur atom. Therefore, thiophene is ‘more sable and has higher resonance energy. Foran (Lestefective Thiophene ‘esonance) rats nll (@) Between cyclohepta-3.Sariene and 2-hydroxycyco- hepta-246-rienone, the later is more stable, because it ‘an forma stable aromatic system by th ionization of the Ketonic group followed by intramolecular hydrogen ‘bonding. Therefore, 2-hydroxycyclohepta-?2,4,6-rienone has higher resonance energy. oO Cyelohepal 3.-iene Cycthoptatrenyl eatin form (very table det the formation ‘of somatic sysem) Oo” anaigatet, ms 22157 Which of the following hydrocarbons is expected to De the most acidie? ge a I we © ‘Ans Methyl hydrogen of compound (a) is the most acidic, because the corresponding conjugate base is a vinyl-subsi- tuted Huckel 6x-electon anion, that is, cyelopentydienide a. oy | San te Cran Vinpt-substiated Inthe ease of (b) and (c), the corresponding conjugate ‘bases cannot achieve such aromatic stabilities. a Wn lS a 7 ve Conjugate base cannot assume ‘cestton Hache! arom sem on,yaaa pal Cen, ou, Ba O ; Conjugate base cans assume ‘lecron Hckel rate syste 2.158 Sulphonation of benzene exhibits primary kinetic Isotope effect. Explain. ‘Ans Suiphonation of benzene isan electrophilic substiution involving two steps. The fist step is electrophilic atack by $0, molecule to form a o-complex It then loses a proton fiom 9p carbon to give the sulphonated compound, Study with deuterium-labeled compound (CyD,) shows ‘the reaction rate slows down abou four times, Tis enfin that sulphonation reaction exhibits primary kinetic isotope effect and the rate determining sep is the loss of proton inthe Second step. .ps0.8 2.159 Draw the resonance structures of the following Intermediates and indicate the most important contribu- tor tothe resonance hybrid in each ease. cH, cH, een-éo © oO ‘Ans Fortbe ion (2), the resonating structures ar as follows a ou tly —— cnc 0 @ owen ent Shoat op nace En ee metngeti OF these two structures, 1) sa more contributing resonst- ing strwcture because in (ll), we need to put a double bond ‘with the bridgehead carbon and that violates the Breas rule, ‘making the system extremely strained 2.160 Compare with reasons, the ease of Sy reaction of {he following compounds. os gaa en cm FA and CH, —E—E ca, cH, cn CH, » ‘Ans Between he compounds (0) ad (the compound(s tore reactive owas Sy susiitn, because ves more Sable ebay caon wht ie conjpated Hts ane Pinay eins nthe cast of), th comesponding tration i stabi lized by oly tre hyperconjgative resonating soaches. The cation ae ao partly sabized by #1 efet of be sy raps bat hypercnjtiveesonnce mor oe tant intscae Hyperonjgatoninvelved nt wast sealable 5 oH es cu, cu, More stable