Solutions manual to accompany Clayden, Greeves, Warren, and Wothers aoe TASTUPaMElacae W)INNINSolutions manual to accompany Organic Chemistry by Clayden, Greeves, Warren, and Wothers, STUART WARREN University of Cambridge OXFORD UNIVERSITY PRESSOXFORD Geet Clarendon Set, Oxford OX2 6D? 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Diste ened cing nt sim rine sttccounon: wech Srer arzar:atares Haag (ea, Imarened, ard ic} pee tances, Draw molecule hased an gach framewors toni bath ketone and garbotnllc aolsrunctional grou, Purpose of the problem ‘Te: go me drewing Simple atiseines well and re ster yon seep Pom neles arc marras towns dealive sunita ica Suggested solution ‘me inesr atoratedlfyeicarhon witk sever esrhon atotrs hu there iy a wld chalice offer seme nexiilitias hut pac may-~wall have thocght of ether, Ther fr fi the rez. Ar ste Aa RAR sengel onus CoO Pre po fad & fe ye el ee Oe art CC Om Problem 2 ‘Scnay tn stucuoe of breselanih op 2. 33, hla a feo? ne ena pans oF mmiserag ‘evop tee ala Frage ia here er metry es aa of fa: enters a rus ot Sines, Finely, sendy che sabe areswees branche2 Organic Chemistry Solutions Manual Purpose of the problem ‘To petsuade you that functional groups are easily recognized even in complicated molecules and that, say, an ester is an ester whatever company it may keep. You were not expected to see the full implications of the carbon framework part of the question. That was to amuse and surprise you, Suggested solution ‘The ethers are all the unmarked oxygen atoms in the rings all are cyclic, seven in six-membered rings two in seven-membered rings, and one in an eight-membered ring, Tere are two carbonyl sroups, one an ester and one an aldehyde, and three alkenes. ‘The carbon chain is branched because it has seven methyl groups branching off it and the aldehyde is also a branch. Amazingly, under this disguise, you can detect a basically linear carbon chain, shown with a thick black line, although i twists and turns thoughout the entire molecule! Purpose of the problem To shock you with two dreadful siractures and to try and convince you that well drawn realistic structures are more attractive to the eye as well as easier to understandChapter 2 Suggested solutions for Chapter 2 Suggested solution The bond angles are grotesque with square planar saturated carbon, alkynes at 120°, alkenes at 180°, ‘onds coming off benzene rings at the wrong angle, and so on, The left-hand structure would be slearer if most of the hydrogens were omitted. Here are two possible hetter structures for each molecule, There are many other correct possibilities. ea ce Problem 4 Z Draw structures comesponding to these names. In each case sugges altemative names that might corwoy the strture more clearly to someone wo is istening to you speak. (a) 14-di(2.2-dimethylethybenzene (©) 3{pr0p-2enyoxyjorop-t-ene. (©) eyclohexe-1.3.5:riene Purpose of the problem ‘To help you appreciate the limitations of names, the usefulness of names for part structures, and, in the ase of (c), to amuse. Suggested solution (a) I-di-(1,1-dimethylethyDbenzene, More helpful name para 1 di-ter-butyl benzene, an equally helpful name. i--butyl benzene. It is sold as = the LL dimenicty soo b) 3+( prop-2-enyloxy)prop-I-ene. This name does not convey the simple symmetrical structure nor that it contains two allyl groups. Most chemists would call this ‘diallyl ether though it is sold as ‘ally ether’ (©) cyclohexs-1,3,5-trione. Tis is, of course, benzene, but even IUPAC has not tried to impose this ‘correct’ name for such an important compound, Pe, Problem 5: Draw one possible structure for each of these molecules, selecting any group of your choice ‘or the ‘wild card’ substituents.Organic Chemistry Solutions Manual Purpose of the problem . ‘To help you appreciate the wide range and versatility of general structures with X, RI, Ar!, ete ‘These become more important when you stata database search fora pat structure Suggested solution ‘There are, of course, many possible solutions. X could be a heteroatom or a structural fragment while Ar could be any of a very large number of substituted benzene rings or even other types of aromatic rings. Our frst two solutions in each case are ones you might have found and the rest are mote inventive. The four-membered ring could have X = NH or CO (a Ketone) while the substituents R! and R? could be the same (both methyl groups) or differen (a benzene ring and an ether) In the last two structures X itself cartes extra groups ~ the two oxygen atoms in the SOs group oran alkene while R' and R? could be ina ring orbe diferent highly functionalized groups Of course, there are also some things that R!, R®, and X cannot be. R’ and R® cannot be N or CH; while X cannot be Ph or Cl ‘The three aryl groups in the second example might all be different or some might be the same. In the last two structures we show some unusual aromatic rings including some linked together and. fone with a nitrogen atom in the ring A AL “yy Problem6 Bee Translate these vow poor ‘alagrams of molecules into more realistic stustues. Try to get ‘the angles about right and, whatever you do. don't include ary mua) Planar carbon atoms - “oF oter bond angles of 90: _ Saeco ton ene O(CH:CH;)20 _—~_(CHy0),CHCH=CHCH(OMe}2 Purpose of the problem [An exercise in interpretation and composition — this sor of ‘structure’, which i used hen sHructures must be represented by ordinary printing, gives no clue to the shape ofthe molecule and you must decide that for yours.Chapter 2 Suggested solutions for Chapter 2 Suggested solution ‘You probably needed a few tral and error drawings first, but simply drawing out the carbon chains ‘5 you the answers, The frst is straightforward though you may not previously have sen the dot ‘9a the mile ofthe formula. This does not represent any atom but simply shows thatthe atom aamediately belore the dot is not joined to that immediately after it The (OH) group is a substituent off the chain, not part ofthe chain itsel- The second has no ends (Me groups etc.) and © must be an unbroken ring. The third gives no clue as to the shape ofthe alkene and we have shosen tras. It also uses two ways to represent MeO. Either is correct but i is best to stick to one ‘representation in any given molecule. ‘CaMeCH(OM).(CH,),00CMy OfCH:CH.I:0 ——_(CHs0),CHCH=CHEHOMe, Scam aga cfferent stuctures that woule ae emia Cite. Make 3000 realistic diagrams of each one and say which functional groups) ae present Purpose of the problem ‘demtification and naming of functional groups is more important than the naming of sompounds. This was your chance to experiment with different functional groups as well as u= Purpose of the problem Just litle practice in converting verbal descriptions into {thea naming thetn is justified. We hope you agree that the diagrams are more the description in the question and more easly understood than the name, Suggested solution ‘The structures are uniquely described by the rather verbose conn [Naming the compounds requires (1) identi ‘goup, (2) numbering the skeleton, and (3) locating the functional group by name amd = The aromatic compound is 4 ketone with (wo carbon atoms ~ an ethanone ‘evem ‘eannot be 2 two-carbon Keetone!). ‘The carbonyl group is Cl. The aromatic vy its Cl at Cl and is numbered so as to give the smallest possible numbers to the I is (2.5-dichloro~ nitrophenyl)ethanone. “The aliphatic compound is a carboxylic acid which === CL The rest is straightforward. Groups are usualy named in alphabetical order. It is 2==— {6-triluorohex-4-ynoic acid. Ifyou don't agree with our names, don’t Worry. Ht gent => matter. What does mater is: did you draw clear comprehensible structure? Problem 9 Draw full structures for these compounds, displai-g v= ~c"3c=con framework clearly and ‘showing all the bonds present in the functional gowns. Name =e Functional groups. ‘AcO(CH NOs meo;0.0H,0c08% ‘cp=CH.CO.NH(CH):ON Purpose of the problem ‘This i rather like Problem 6 except that more thought is meeded forthe details of the functional {g70ups and you may have needed to check the ‘organic ements’ Ac, Es, and so on in the chapter. Suggested solution For once the solution can be simply stated as no variation & really possible The tricks for the ist ‘one ate to see that ‘AcO” represents an ester and to have only four bonds to nitrogen in NOs. The second has two ester groups on the central CH: group but nei joined to it by a CO bond and theChapter 2 Suggested solutions for Chapter 2 sxher by a CC bond. The las is straightforward except for the dots used to separate the substituents ‘explained in the answer to Problem 6). ‘AcO(CHaaNOs ‘me04e.cH, 0coet CHiz=CH.CO.NN(CH EN DAG RS doy Ay, Problem 10 Purpose of the problem TES important exercise is one you will et used to very quickly and, before long, do without ‘Hanking I you do, it wll sve you from many trivial erors. Remember that the oxidation state of ‘atbon is +4, oF C{1V), in all these compounds. The oxidation level of a functional group tll you ‘wih which oxygen-bosed functional group iti interchangeable without oxidation or reduction. Suggested solution vant the number of bonds to heterostoms. These can range from none to fou. The only tricky es ae alkenes and alkynes, which have no heteroatoms but are formed by dehydration of -deabols, aldehydes, or Ketones. There isa summary chart on p. 36 ofthe textbook, but brie: ‘eras to nerrostoms Oxdaton lve “pe struct ° ycrocarbon| a ‘eonot on In these cases we have examples ofall oxidation levels, Check the answer against yours and the ‘able. In the case of the alkene, formally a dehydration product from an alcohol, either but not both ef the C atoms is atthe alcohol oxidation level.Organic Chemistry Solutions Manual ea seo ce ils eee Be e ne iar rraneaeene ASAIN . ncrocaton etcne Seonat ten ane reise on pp. 23 (drawing ai es) 4 44 (ening soon re 1 ‘common compounds an three common solvents). Purpose of the problem These compounds are important so drawing them again is not just a useful exercise: it also helps reinforce your knowledge of these structures. Suggested solution Hire are the drawings we suggested for the amino acids on p, 23. There are other ways. sot yes Oe aie stents Qe. te te ‘The ‘ten common compounds’ and ‘three common solvents’ are specially important and we recommend that you learn these structures. We generally pour scorn on the idea of memorizing, things, so take note when we recommend itl plier ty td a) seston er sectcence mio ete acd (erp) dete ‘ahora neoursscmy ears acy Owego Coe ein ebera) ‘The three common solvents below join ether, acetone, ethyl acetate (ELOAc), toluene, and pyridine as commonly used solvents for organic reactions. One or other of these will dissolve almost any organic compound. e ple seem aimetrtomanice OME) sired (MSO)Suggested solutions for Chapter 3 Problem 4 é oe : 5 How doos the mass spectrum gives evidence ef isotopes in the compounds of bromine, hlorne, and carbon? Assuming the molecular jon of each of these compounds is of 100% sundance, what peeks (and in what intensity) would appear around that mass number? (a) C:HsBrO, (b) Ceo, (c) CoHuBrCI? Give In cages (a) and (o) a possible structure for the ompound. What compound is (b)? Purpose of the problem "9 ve you practic in spotting the important atoms that have isotopes and in interpreting multiple ‘Seiecular ions, The molecular ion isthe most important peak in the mass spectrum and is often the eiv peak to interest us. ‘Saggested solution Beomine has two isotopes, "Br and "Br, in about a I: ratio, chlorine has two, °°Cl and "Ch in about a 31 ratio and there is about 1.196 °C in normal compounds. Hence the molecular ions of ‘Se three compounds will be a fllows 2) GHsBrO, MW 124/126, There will also be weak peaks (2.2% of each main peak) at 125 and Compaunds containing Bor 127 forthe same ions with °C. seuss have thei ole ons Ca as a molecular ion at 720 witha stong peak at 721. The chance that one C atom is Cis Sosa ei. Te st ee simply 60 x 1.1% = 66% so the M + 1 peal more than half as strong as M* itelé The Shy, hance of two atoms i small <) GcH,BrCt is more complicated a the molecule ton will contain tl rata of Br and "ie, and a 3:1 ratio of $C and Cl. The molecu in consists of four peaks (ctios in brackets): CH BP"CL (G), CoHY"BC (3), CQHYBP"C (1), and Cele" Cl (1), The masses of these peaks are 190, 192, 182, and 19, The molecular ion wil therefore have thee peaks at 19, 192, and 194 in a ratio of Sl with peaks at 191, 193, and 195 at 6x 1.196 = 646% ofthe peak before it So the complete Picture is 190 (759%), 191 (59), 192 (L008), 195 (6.6%), 194 (259), and 195 (1.73). Compound (b) is of course, buckminsterfllerene and the other compounds might be isomers such as these o omar ene Sl lee le Problem 2 : : : i i The C NMR spectrum for ethyl benzoate contains these peaks: 17.3, 61.1, 100-150. oo ‘.p1m. (four peaks), and 166.8 p.p.m. Which peak belongs to which carbon atom? Purpose of the problem To familiarize you with the four main regions of the BC NMR spectrum: saturated carbons at 0-30 ppm, saturated carbons next to oxygen at 8 1-100 p.pam. alkenes and aromatic compounds1 We have ignored the effects of the c atoms on tho othe ¢ atom, but tay wil algo erase he ‘Shama! sit toa lesser extent, Organic Chemistry Solutions Manual with unsaturated carbon at 100-150 p.p.m., and unsaturated carbon next to oxygen (usually C=O} at 150-200 ppm. Suggested solution ‘There are four different types of carbon atom in the benzene ring (don't forget the ‘ipso’ carbon joined to the substituent) and it is not easy to say which is which. The rest can be deduced from the four main regions. Problem 3 The thinner used in typists comection fds a single compound, C2HsCls, having #C NVR ‘peaks at 45.1 and 95.0 p.o.m. What its stricture? A commercial paint thinner gives two spots on chromatogrephy and has 3¢ NWR pecks at 7.0, 27:5, 35.2, 46.3, 95.6, ond 206.3 p.pm. Suggest what compounds might be used to make up this thinner. Purpose of the problem To start you on the road of structure identification with one very simple problem and then some deductive reasoning. It is necessary to think about the size of chemical shifs inthis case. Suggested solution ‘There are only two possible structures for a compound C;HsCl ~ it must be trichloroethane and the chlorines can be distributed in these two ways. meh “ye ‘The frst isomer would have a peak for the methyl group in the region 0-50 ppm. and one for the CCls group at 2 much larger chemical shift because of the three chlorine atoms. The second jsomer would have a peak for CHCl in the 50-100 p.p.m. region and one for CHCl at a langer shift Dut the two shifts would not beso far apart. The observed shifts are 50 p.p.m. apart and, in fact, the ‘compound is 1,1,l-trichloroethane. The NMR specirum of the 11,2-richloro isomer has peaks at 50.5 and 70.7 p.pam. ~ much closer together. ‘The mixture probably contains the same trchloroethane as the peaks at 45.3 and 95.6 ppm, suggest (the chemical shifts of the mixture need not be quite the same as those ofthe pure compound. as each compound is effectively dissolved in the other). The remaining peaks at 7.0, 27.3, 35.2, and 20633 p.p.m. definitely belong to a carbonyl compound, probably a ketone since 206.3 p.pam. is so large. Butanone fits the bill a t has one methyl and one CH group on the carbonyl group and one ‘methyl away fom any electronegative atoms. There are other possibilities Problem 4 ‘The ‘normal’ O-H stretch (Le. without hydrogen bonding) comes at about 3600 em-. What Is the reduced mass (u) for 0-H? Wnat heppens to the reduced mass when you double the ‘atomic weight of each atom in tum, that is, what Is 4 for O-D and what isu for $-H? Infact, ‘both O-D and S-H stretches come at about 2500 om. Why? Purpose of the problem To get you thinking about the position of IR bands in terms of the two main influences ~ reduced mass and bond strength. The relationship between the frequency (v) of the vibration,Chapter 3 Suggested solutions for Chapter 3 a Se force constant f(more or less equals bond strength), and the reduced mass (j) is given by ‘aes cquation. eV Seggested solution ‘Tbe redaced mass) ofa vibrating bond i given by this equation, Se reduced mass of OH is 16/17 oF about 0.94. When you double the mass of H, the reduced ‘as of OD becomes 32/18 oF about 1.78 which is roughly double that for OH. But when you deste the mass of O, the reduced mass for SH is 32/33 or about 0.97 ~ hardly changed from O81 The change in reduced mass is enough to account forthe changed frequency of the OD bond ~ amps by about 2 — but cannot account for the change from OTT to SH as the two reduced ‘mmmees are bout the same. The only explanation of this can be thatthe SH bond is weaker than the 5 {OH bond by 2 factor of about 2. There isan important principe tobe deduced fram this problem. Very roughly, the reduced masses € a bonds involving heavier atoms (C, N, O, 5, et) are about the same and the differences in IR seething frequency are mostly due to changes in bond strength. This s most dramatic in comparing siege. double, and triple bonds. Only with bonds involving hydrogen does the reduced mass become ‘he more important factor, though i is also significant in comparing, sy, C-O with C-CL ‘wre: are their structiires? Without +#C NMR cata, it may be easier to tackle this: problem by. ‘es! Hriting down all the. possible siuctures for C3HaNO: In what tanec aye nou SAR eta help? i | One sharp band ave 3000 em ane ston bard at bout 1700 ei "= Two sharp bands above 3000 em” twa bands between 4600 and 1700 om“! “=! One strong broad bak above 3000 én~'; a hand at about 2200.m—" Purpose of the problem 2 Sow that IR alone has some usefulness in the identification of molecules but that NMR is ‘tecesy even with very simple molecules In answets to examination questions ofthis type itis «0 show how you interpret the data as well sto give a structure you get the answer right, tation is not so important, but if you get the answer wrong, you should still get some Se Sr your interpretation Seggested solution 4 Ore sharp band above 3000 cm“ must be an N-H and one strong band at about 1700 em~! is probably a C=O. That leaves CH, and so we might have one of these (there are other ls likely | ‘sractures). °C NMR would help because a(i) would have a carbonyl group and two signal for saturated € while ali) would aso have a C=O but only one signal for saturated carbon as the : sommpound is symmetricala2 Organic Chemistry Solutions Manual {h) Two sharp bandh above 3000 cm © must be an NIL, group ant wo bands between 16 ae 7mm ern! sugges C=O aad a C=C. This leaves jst three hydrogen atoms and yives us seu EE NMR would help because the -0 shift would show whether the compouend sos an amide or a aldshyde and the alkene shitis would reveal the presence of the NHe grou in i Ws, ~~ a wa ° 4c) One strong broad hand! shove MiOO emt mnast e an OL aids baad at about 2200 cm must hea tiple hond, presumably CX as there woul esherwise be NHS as well, That leaves CoH. again hut ke de nol need & rig and we hae suet two double bonds, presumably Tike thess Problem 6 Four compouncs having the molecular formuls CaMlsOr have the IR and "*C NMR spectra fiven below, How many OBEs (Double Bond Equivslents) are thore in CaHO2? What are the ‘structures of the four compounds? You mignt again find it helpful to draw aut some or all possibilities before you stan, NMR: 214, 82, 58, and 44 p.pm. 1300 (broad) cm’: "C NMR: 62 and 79 p.p-m. {e) IR: 1770 cm™': “C NMR: 178, 86, 40, and 27 p.pm. {@) IR: 1720 and 1650 (strong) cm '; “C NMR: 165, 131, 133, and 54 p.p.m, Purpose of the problem rst steps in eal identification using two diferent methods. Because the molecules ate vo small fonly four carbon atoms} drawing ut fee trial structes gives you some ideas 28 10 the 1ypES of -ompounds key to be fou Suggested solution Here are some posible structures for C.MQ.. I and a ring are likely wo feaure, The double bonds nave pot to be C20 or C=C tor both these isn ring’. Fanetional groups ae likely to ipdude alcohol, ldebyde, aid amd ketone °. ° WAA, Poo TS ‘oH Me Ile ot ketone). 82 and 58 one saturated carbon Bot next dear that two double bonds or one double bond Ga) METAS em oop: BC NMR: 214 ppm ppm, (to saturated atbons nent wo oxygen? and Al pspan twonygen bur nea some es must be a € tron: wtharawcing proxy. The secon! ase does not show Up i the IR so i must be an ether. As thete i only one double hond. there mst be a ring. This {yy He S00 rand cay mest ean OH, CNMI 92 aad “0 gay mest he a symmetrc anolecie with no alkenes and no C nana saturated carbon next to oxygen. Tica gies one struts. Nos 6 she ane des nat in the 18 because itis spmmetrica so it mast bea eipie borChapter 3 Suggested solutions for Chapter 3 {6} IR: 1770 cm! must be some sort of C=O; !°C NMR: 178 p.pm. (C=O of ac derivative), 86 p.pam. (saturated C next to 0), 40 and 27 ppm. (saturated Cs not next to 0). Again only one double bond so it must have a ring 100. Looks lke a close relative of ( 4) TR: 1720 and 1650 (strong) em must be conjugated C=C and C=O; "C NMR: 168 ppm, (C20 of acid derivative), 131 and 133 p.p.m, (alkene), and 54 p.p.m. (saturated C next to). ‘This defines all the carbon atoms and it must be a simple unsaturated ester. Notice that we cannot tell which signa corresponds to which alkene carbon but thet this does not affect our conclusion. Problem 7 Three compouncs of molecular formula CyHeO have the IR and *C NMR spectra given below. Suggest structute for each compound, explaining how you make your deductions. ‘compound AR: 1730 om; #9C NMR: 13.3, 15.7, 45.7, and 201.6 p.p.m. compound BR: 3200 (broad) cm”; °C NMR; 36.9, 61.3, 447.2, and 134.7 ppm. compound CIR: no peaks except CH and fingerprint; #0 NMR: 25.8 and 67.8 p.p.m. ‘The rest of the problem as stated in the text is given below in the ‘Suggested solution”) Purpose of the problem More practice in the same essential skill. Notice that we have two more H atoms in tis formula so = have either a ring or a double bond but not both. In adltion, a bit of chemistry is added. Suggested solution scpound A IR: 1730 cm” (C=O of some sort); C NMR: 13.3, 157, and 45.7 pppam. (three saturated carbon atoms with one next to some electron-withdrawing group but not oxygen), and 201.6 prpam. (aldehyde oF ketone). No symmetry. A ketone would hhave two Cs next to C=O so this is just butanal. Serpound BR: 3200 (broad) em™! (OH); #C NMR: 369 ppm. (saturated ©), 613 ppm. {saturated C next to 0), 117.2 and 1347 ppm alkene). There are two possibilities here eae aarzyssar ssempound CIR: no peaks except CH and fingerprint (oxygen must be ether; °C NMR: 258 ppm. (Gaturated © not next to O) and 67.9 ppm. (saturated C next to 0). Note symmetry. As there are no double bonds, there must be a ring and it can only be THR, Xow the extra bit of the orginal problem, which may resolve our doubts on the structure of Sepound B Compound A reacts with NaBH, to give compound D. Compound B reacts with hydrogen gas seer a palladium catalyst to give the same compound D. Compound C reacts with neither reagent. Seggsst structure for compound D from the data given and explain the reactions, (Note: He ‘Sikes alkenes to alkanes inthe presence of a palladium catalyst) ‘empound DIR: 3200 (broad) em! (OH); #C NMR: 15.2, 20.3, and 36.0 ppm. (three saturated Gs not next to O) and 62.9 p.pam, (saturated C next to 0). Must be n-butanol NaBH reduces the aldehyde to the alcohol and Hy/Pd would reduce the alkene in ether of our OH > NH > CH. Why? Purpose of the problem To encourage you to think about the energies of orbital as well as just about their quantum description. Suggested solution + orbitals and p omits can combine t frm o bonds. Inthe chapter (p. 108) we discussed the structure of PH, which has bond angles of about 90" and is made of bonds beoween Is) and 5p(P)onitals. There sno special problem in overlapping ether 2p or p oxi with Is orbitals though the 3p orbital are larger. a WA ‘The difference comes in the energy of the orbitals. The 2p orbitals are much closer in energy to the 1s orbital than the 3p orbitals and so the energy gain is greater on a bond formation. 2920 is wee otra’ to omar 1840 Sect 180 Bonds between H and C, N, O, and Farell stronger than bonds between H and Si , S, and CL ‘Thisisparly because 2p AOs ate used fr the fist but 3p AOS forthe second group. The ul story Includes the fat that CH, NHs, and H;0 are hybridized (so the lower energy 2s orbitals are used as wall wile PH, and H,S ae not hybridized. Sif, is, ofcourse, tetrahedral whl itis dificlt to ay ‘whether linear HP and HCl are hybridized or not ‘Within the group C, NO, and F, the energy ofthe 1s orbital stays the same but the energy ofthe 2p (or of the sp hybrid orbitals) drops as the elements get more electronegative. These orbitals gt closer in energy tothe 1s obital and the gain in bond formation is corespondingly grater.Chapter 4 Suggested solutions for Chapter 4 Problem 4 ‘Though no helium ‘molecule’ He> exists, an ion Hej does exist. Explain Purpose of the problem To encourage You to think aboot the filing of atonnx orbitals and to accept surprising conchasions. Suggested solution The orbitals of the He atom ans the fact that 0 Hes molecule exists sre diwused in the book an pp. 97-8, The prablen is that the 1s orbitals overlap te form a bonding tc) and an antibonding {e* orbital but hoth would be filled in the Hey molecule and the bond order i 70, If there sone fewer electron, only one cletrom need go into the antibonding order of oneshalf The ion Hey loos exist, orbital (a) and there isa boc Wes Ah emtsoning at He sreoning ot " On 9G +O tenses tb sews Problem 5 You may be surprised to know that the molecule CH, with divalent carbon, can exist tis, of ‘course, very unstable but Its Known and it can have two different stuuctures. One hes an H-G-H bone angle of 180 and the other an angle of 220°. Suggest structures for these species and say which orbitals will be occupeed by all bonding and ronbonding elections, Which structure is likely 0 be move stable? Purpose of the problem To demanstate that a simple MO treatment can be applied to strange and unknown molecules, Suggested solution The hasie arrangements of the orbitals w yet the H80 and 120° bond angles rust be an sp hybridized «case but ust one p wtbital and an sp* orbital in the second. oom for 1900 and am sp? carton for 120 . Thi leaves over two g orbitals im the fies “The orbitals for the @ structuse aze straightforward wg sestamsat tA) 18 There will he fru electrons in cach of these «bonds leaving exited (civalent cazbon has any’ valency eect {wo electsons to make up the six os and cannot achieve « noble pas structre) Inthe 18D case, the two remaining p orbitals are degenerate so we can pu one ebetzon in each, It lhe 120° case, the remaining spt orbital af lower ener ecto than the p orbital and will have bath 19Organic Chemistry Solutions Manual 1m You shoud nate tht onygen hae four 2 eectons ana wil have wo Ione portal an ene each nthe ‘other two fo avis repulsion, PR can, Gores Ay Sieh ta enon p ob Structures with unpaired degenerate electrons ate usually more stable than those with a full and an empty orbital. However, we have told you only part of the story and we shall return to these ‘carbenes” in Chapter 40. Problem 6 ji i “Consiruct an MO Giagfam for ne molecule LiH and suggest what typ of bond & might have. Purpose of the problem ‘To demonstrate that a simple MO treatment can be applied to ionic as well as covalent structures Suggested solution H has, ofcourse, only one electron ina 1s orbital Liha thtee~ a falls shell and one elton in the 2 orbital. Li isalso ver electroposiive so its 2 orbital is hgh in energy (much higher than that ‘of F~ see the answer to Problem 3) The results that lithium gives its 2s electron tothe Is orbital of 1H and an ionic compound results with both ions having the same electron configuration: 1s, The hhydrides of the alkali metals ae useful sources of hydride ion (H). un? 4O- 4O- “OF "Ot Problem 7 Deduice the MOS forthe angen molecule, What is the bond oe in onion and where are “the 2p electrons? Purpose of the problem To let you try out your sil in a simple diatomic molecule that has a curious structure. ‘Suggested solution Simply dock two oxygen atoms side by side and overlap the orbitals. The Is and 2s (only the shown below) interact as usual but both bonding and antibonding MOs are occupied so there is no bonding. When we overlap the parly filed p AOs we find we can make three bonds ~ one 2pcr and ‘two 2pm bonds. Now we have two electrons left over and they have to go into antibonding 2pm” (MO. The first two up are degenerate so itis better {0 put one electon in each and avoid the ‘repulsion from two electrons in the same orbital.Chapter 4 Suggested solutions for Chapter 4 Abin buenos Bie nc ke bya 0 td lw nh ese oped Sree stboig MO. The ek ht ond or snd espace Fees orks aed on oncck O nom Th eed Sues take oa ay wae ines neato, Parpose of the problem = 2ec easy to find molecules where you can construct MOs from AOs without hybridization but s=h v= = one such, You should not be ashamed if you failed to do this problem and you should be sseuily proud if you succeeded. We shall not in general construct MOs in this way a5 it is too ‘Sica bur if you simply set up an energy diagram ofthe AOs, in ascending order as usual, you can ee setstacory MOs. ‘Seggested solution ‘Etre (acctylene) has a C-C triple hond, Each carbon bonds to only two other atoms the other C ‘ax: -=: of the Hs, Using MO theory, we can see that only the carbon 2s and 2p, have the right s=meetr to bind to two atoms at ance which leaves the 2p, and 2p. to form & MOs with the 2 saris on the other carbon atom, —@ fh ot: = {0-Q-O-0 gos 2s 2s ts combination of As in ety tra he rise to bending MOsOrganic Chemistry Solutions Manual ‘The thre lowest orbitals are o MOs because they ae symmetrical about the line H-C-C-H. They are all bonding and al filled but they do not correspond to particular bonds in the molecule. The lowes is bonding right through, the second is bonding for both C-Hs but antibonding for C-C, and the third is ‘again bonding forall three bonds. The two top orbitals are x MOs because they have a node (zero clectron density) passing through the atoms. They are degenerate and correspond roughly to the two (CC mbonds. The total number of electrons (10) is right for $ bonds (2 CHs, 1 6 CC, and 2 x Cs). Purpose of the problem ‘To give you practice in selecting the right hybridization state for carbon atoms in molecules. ‘Suggested solution ‘Simply count the number of « bonds and hybridize that many AOs: if two, then the C atom is sp hybridized (linear; if three, sp* (trigonal); and, if four, sp? (tetrahedral). A simple statement of the answer should be enough. The atoms marked with an arrow are most likely to give you trouble: make sure you understand why they are as shown, oe 4 predet r ee ay te answer tothe Don’ se these sorts of rains in your answer. Purpose of the problem ‘To give you practice in selecting the right hybridization state fr carbon atoms and translating that information ino three-dimensional structures for molecules. Suggested solution ‘Carbon dione is linear as it has only two C-O o bonds and no lone pairs on C. The C atom must bbe p hybridized and the only tick sto get the two x bonds orthogonal to each other. They must be like that because the p orbitals on C involved in the two x bonds are themselves orthogonal (2p, and 2p.). Most people would draw the O atoms as sp* hybridized, rather than sp or even unhybridized, bur this is unimportant as you cant realy tll tetoobonds —— tietwoxbande sifu ge oe |e eco oe=0 = oes ecoChapter 4 Suggestec solutions for Chapter 4 The imine has a C=N double band so it must have sp! hybridized C and N. This means that the Jone pair on Nis in an sp orbital and aot in « p orbital, the molecule is planar (except for the oup which is of cours, tetrahedral) and bent atthe nitrogen ator, 4 wo “nN es so tetrahedral wih an sy! hybridized © atom, The serangement of rhe lone pairs stound the fluorine atoms imor shown! is also probably teteahedra x ‘Thifluoromethane is, of sours ‘he next molecule, CH, C2CH- is alone and it has the same shape as COs and for the same ‘eas, except that ve ean now be sure shat the end carbon atoms are 9p? ybridized as they are slanat. However, the ta planes are arthagonal so the mole as whole is mot planae Finally, (CH:),0 must be a three-membered ring and therefore the C-C-O skeleton of the snolecule must he phinat three paints are always ina planet, However, she two carbon atoms are 1p hybridized (four t bonds) and are approrimately tetrahedral with the H atoms above and below he plane. The oxygen atom might also be sp hybridized, but whe knows?Suggested solutions for Chapter 5 Problem” z een ee Eich of these molecules (s electootlé. loentiy the eletiopnilc, tom ena dana. __ Mechanism for action win a generalized nucleophile Nu”, gir ihe prot in each case. ee a ie 4 oer ese oe Purpose of the problem ‘The recognition of electrophilic sits is half the bale in starting to understand mechanisms. Here is some practice: later you will o this automatically. Suggested solution Here we have two cations, two compounds with x bonds, and two with nothing but & bonds. One ofthe cations has only three bonds to positively charged carbon soit will react by addition of the nucleophile. The other has thre-valent oxygen and so cannot add a nucleophile (four-valent ‘oxygen would have 10 valency electrons and is unknown). The nucleophile must attack the proton instead. Some nucleophiles might attack the carbon atom next to the oxygen “ “ r some — she s r Ys The ro carbonyl compounds will be atacked atthe carbon stom with clesvage of them bond. In general, x bonds are more easly broken than o bonds and negative charges end up on electronegative atoms. If you proposed that each compound reacted further, you were right, but the expected answers do not include these extra steps shovn in square brackets. A full discussion is found in Chapter 12 of the main text. et fe een Pel Ne [oe J - tam A at Re ss LU we ‘The last two molecules are forced to break o bonds. n the case of chlorine, the two ends are the same so you can attack either Cl atom. In MeSCI, the S-Cl bond is weaker than the C-S bond and (Cis the most electrophilic atom in the molecule. The $-Cl bond is broken and the negative charge ends up as chloride ion. oN mi Sel oe worse we,‘Chanter 5 Suaaested solutions for Chaprer 5 | tach of these molecules 1s migopiic, ently the muciopniic stam and craw a ones Tor reaction wih a geneaize lecvonie E, mina product lye Purpose of the problem “The recogion of micleophili sites isthe other half ofthe bt in starting to understand mechanisms. Here is some practic: later you wil do ths too automatically, Reactions occur when the two meet. Suggested solution, ‘This time there are three anions but only two of them (the alkyne and the sulfur anions) have lone pair electrons. We can start our arrows from these and they are the points where the electrophile will atach itself c i fe gt ie a potas Le oh ‘The last anion is like the BH, anion we discussed on p. 125 of the main text. The negative charge does not show a pair of elecizons on Al but just an imbalance of protons and electrons. ll the valency electrons are in the bonds and we must use these o electrons in the reaction. The arrow should stat halfway along the o bond and emerge through the Hf atom. roe ib = TT meoNome - E ‘One nucleophile has a x bond from C to N. The nitrogen atom also has a lone pair of electrons and you could stat your arrow either there or halfway down the t bond ~it doesn't matter which, ae " ner a Me me Me “The ening two nclophies have lone pair One syminetiel(NEy-Ny hyde) and will tack trough one nitrogen stom, You may have drawn the product sa cation or you may Ive removed «proton fom i Eder ane is correc F = Hani, “2 a we ri, | Finally, the phosphorus compound has four atoms with lone pits! There ate three OMe groups and the phosphorus atom il, However the lone parson the oxygen atoms are probably in 2sp* orbitals (and are certainly in some kind of orbital with the principal quantum number 2) while that fon the phosphorus atom is in a 3sp? orbital and is of higher energy. I eats, ae ad 1 Ts pois exred in Craper 7.Organic Chemistry Solutions Manual Purpose of the problem First practice in interpreting curly arrows and drawing the products. Once the arrows are drawn, there is no more scape for decision-making, You must draw the products. Suggested solution Just break the bonds that are being broken and make the bonds that are being formed. sas simple as that, though you might straighten out the products a it so that there aren't any funny angles. Ve 5 Purpose of the problem First practice in considering different posible reactions. One ofthe eatin might seem tivial but itis’ Suggested solution In each case one ofthe electrophilic sites isan acidic proton. There is also an electrophilic x bond in cach case (C=O of C=N+), We might as wel use the same abbreviation (Nu”) for the nucleophile that we used in Problem 1. For the frst case, we draw the two reactions separately Me meme me” MeChapter 5 Suggested solutions for Chapter 5 ‘The last compound also has an electrophilic P atom so there are three possibilities. Don't worry if you missed this last one but phosphorus comes below nitrogen in the periodic table and, unlike 2a ‘am have five & bonds as in PCI “wy mm pm wt Q, Problem 5 ‘Putin the arrows on these structures (which have been drawn with all the atoms in the right lacest) to give the products shown, A508 ‘oD — CKO Purpose of the problem To encourage you to draw arrows for unknown reactions and to show you how easy its Suggested solution ‘you have todo isto see which new bonds are formed and which old bonds are broken and draw “sows out ofthe one into the other. Which way should the arraws go? Take them from an eectron- ==nating atom (an anion in both these examples) towards an electron-accepting atom (O and Br ). In the fist example, a hydrogen atom has moved from the left- tothe righthand molecule 4 this is best shown by an atom-specific arrow. A ow | ee Don't worry if your arrows are not exactly the same as ours ~ as long as they stat and finish in the right place and move the right H atom, they're allright. The notes on the mechanism are for sour guidance ~ you should not usualy include them. The second reaction looks more complicated, but the problem is easier — just move electrons through the molecule, ear 7Organic Chemistry Solutions Manual Eide et ace nese tn wg ma have i ees ‘drawmin a ee a. Purpose of the problem To encourage you to draw arrows for unknown reactions without help. This time you have to decide how to draw the molecules so that reaction can occur. The compounds and the reactions are ‘much simpler than the last set. Suggested solution In the frst example, OH has replaced Br. The reagent NaOH is salt so the reactive species is the hydroxide anion, We can draw the mechanism in one step with HO as a nucleophile displacing stable Br from the organic molecule A» = ape goalie ‘The same reagents are used in the second example with the adltion of EtCH;SH’. This change is ‘obviously important because the product contains this unt rather than OH, We should first drave ‘out this compound and use NaOH as a base to remove a proton from the SH group. The second step is example (a) with a different nucleophile Bie IN A Example (6) uses HBr as the reagent. This isa strong acid with an electrophilic proton. The best nucleophile inthe organic compound isthe oxygen atom so the fist step isa proton transfer and the second step uses the bromide ion, as « nucleophile for the methyl group. Direct attack at O* ‘would give impossible four-valent oxygen. & on RCH SH = =Chapter 5 Suggested solutions for Chapter 5 Purpose of the problem "To develop your arow-drawing cil n a more dificult example. Suggested solution Best to follow the advice given in the hint, First, draw the molecules better. If NaHCO. isa salt we need draw only the anion, 2s the very table Na* won't do anything Ifthe anion is a weak base it can remove only the most acidic proton feom the organic molecule and that ‘must be the CO,H proton. ohhh Now we need to lose one Br atom ~ the one nearer to the benzene ring - and the whole CO ‘group which must falloff as CO,. We start our arrows on the negative charge, form the new x bond, and lose Bras the sable anion.Suggested solutions for Chapter 6 Problem 4 "Draw mechanisms for these reactions. — eo oe i OF Purpose of the problem Rehearsal ofa simple but important mechanism that works for all aldehydes and Ketones. Suggested solution Draw out the BH, or AIH, anion, and the compound if necessary, and transfer the hydride ion. A ‘second protonation step is also needed ~ during the work-up inthe second cas, It is not necessary to draw out the whole metal hydride anion but you must draw out one metal-hydrogen bond es you need to take electrons from that bond. ON = Og Purpose of the problem To get you thinking about equilibria and hence stability of compounds rather than reaction -mechanisms,Chapter 6 Suggested solutions for Chapter 6 34 Suggested solution Hydration isan equilibrium reaction so the mechanism isnot strictly relevant tothe question. If you have drawn the mechanism, you should be proud rather than ashamed because it isan important mechanism. To answer the question we must consider the effect ofthe theee-membered ving. All thre-membered rings are unstable because the ring angles are about 60” instead of the usual angle. Cjclopropanone is very stained because the trigonal (5p?) carbon would lke an angle of 120" and there is‘60" of stan’. Inthe hydrate the trigonal carbon setrahedrl (sp) and theres only 49! of strin'. The hydeat is more stable than the ketone The second casei totally diferent. The hydroxy-aldehyde isnot strained but the hemiacetal has 48° of strain at each corner. Even without strain, hydrates and hemiacetals ae normally less stable than aldehydes or Ketones because one C=O bond is worth more than two C-0 single bonds. In this case the hemiacetal is even less stable because of strain, Problem 3 (One way to make cyanohycrins is ilustrated here. Suggest a detaled mechanism forthe process. meson Purpose of the problem ‘To help you get used to mechanisms involving silicon and to revise an important way to promote Additions to C=O groups Suggested solution The sill eyane isan electrophile while the cyanide ion in the catalyst is a nucleophile. Cyanide adds to the carbonyl group and the oxyanion product is captured by silicon so liberating another cyanide ion for the next cycle. “Den oN en H oN Jo BO ge i Se Problem 4 There ate three possible products from the reduction of this compound with sodium. HW borohydride. What are their structures? How would you distinguish them spectroscopiclly, ‘assuming you can Isolate pure compounds? Purpose of the problem To et you think practically about reactions that may give more than one product Suggested solution The three compounds are easly drawn: one ot ther C=O of both may be reduced, yo eronyhtone aa15 0. Wians ana Fleming (1995), Spectroscopic methods in ‘ganic chemistry (Sted, MeGranis, London, Organic Chemistry Solutions Manual ‘The diol has no C=O group in the ""C NMR or infrared and has a molecular ion in the mass spectrum at two mass units higher than the other two products. Distinguishing them is more tricky. ‘The hydroxy-ketone has a conjugated carbonyl group (about 1680 cm! in the infrared) but the Ihydrony-aldehyde is not conjugated (about 1730 em™* in the infared). The chemical shift of the (C-OH carbon atoms in the 100-150 p.p.m. region will ls be different because the benzene ring is next to this atom in the hydroxy-Ketone. Calculations from tables in Williams and Fleming suggest about 80 ppm. for the hydroxy-ketone and about 60 p.p.m. for the hydroxy-aldehyde, The mass spectra will also be different ~ simple accleavage gives quite diferent fragments Problem 5 ‘The triketone shown here is called ‘ninhysrn’ and is used forthe detection of amino acids. It exists in equeous solution as @ monohydrate, Which of the three ketones Is hydrated and wy? Purpose of the problem ‘To start you thinking about why some carbonyl groups are more stable than others. Suggested solution ‘The two Ketones next to the benzene ring are conjugated with it and thereby stabilized though they ate also destabilized by the mide carbonyl group ~ two electron- withdrawing groups next to each ‘other is bad thing. The central carbonyl group has no stabilization from the benzene ring and a double dose of destabilization from its neighbours. Problem 6 ‘This hydrow-ketone shows no peaks in Is infrared spectrum between 1600 and 1809 em: * ‘butt does show a braad absorption at 3000 to 3400 om”*. Inthe “#C NMR spectrum, there ‘are no peaks above 150 p.p.m. but there is @ peak at 140 p.p-m. Suggest an explanation, Purpose of the problem Revision of Chapter 3 with & reaction from this chapter ‘Suggested solution ‘The evidence shows that there is no carbonyl group in this molecule but that there is an OH group. ‘The peak at 110 prp.m. looks at frst sight ike an alkene but that isnot possible (try to draw any alkene structures and you will see why) so it must be an unuswal saturated carbon atom (pesheps ‘one with two oxygen atoms). You might also argue that an alcohol and a ketone could react to give a hhemiacetal, and that, of course, is what its. The compound exists asthe stable cyclic hemiacetal ~ stable because ofthe ring size, MR heChapter 6 Suggested solutions for Chapter 6 Purpose of the problem ‘To give you practic in seeing the underlying structure of a hemiacetal Suggested solution Each OH group represents a carbonyl group in disguise (marked with a black blob). Just remove the ‘other oxygen atom with whatever i attached to it and you have the two components an alcohol and. an aldehyde or a ketone. The fist example shows how it is done. oaks on es eee ‘The next is similar but the alcohol is from a different molecule, So-7-70 Do not be deceived by the next: itis not symmetical. There is one hemicetal (two oxygens on te same carbon atom) but the other end of the molecule isa simple tertiary alcohol lege Similarly, the last two examples are not quite the same, The first is indeed symmetrical but the second has one oxygen atom in a different position, There is only one hemiscetal34 Organic Chemistry Solutions Manuel Reamer ao ome Bar BR & Oo ree Wan Purpose of the problem To help you detect bad mechanisms and find concealed good ones Suggested solution rere ‘The wrong mechanism, the one the question warns you to avoid, is shown in the margin just to clear the decks. If NaBH, doesn't displace like tis, then what does it do? We know it attacks carbonyl groups to give alcohols and to get trchlorocthanol we should have to reduce chloral and ‘we have chloral hydrate. Hydrates are in equiliorium with their carbonyl compounds, so this isthe “ fenas not deen allel pa pare the adducts ae simple lochs nt wre of Such ping cle onl Sow Purpose of the problem ‘More revision of equilibria to help you develop judgement about stability. Suggested solution “This time we need a mechanism so that we can work out what would be formed, Protonation of the carbonyl group and then nucleophilic addition of chloride ion gives the supposed product. Se — ‘There’s nothing wrong with the mechanism; it’s just that the reaction is an equilibrium that wil run backwards. Hemiacetals are unstable because they decompose back to carbonyl compound and alcohol. Chloride ion is very stable and this reaction will run backwards even ‘more readily.Chapter 6 Suggested solutions for Chapter 6 35 Problem 10, \What would be the products of these reactions? In eacn case give a mechanism to justify your predictions,» nach emer Nabi —-1 ee —+1 40, wet 0 Purpose of the problem “To give you practice in the at of predicting products, more dificult chan simply jusiping a known Suggested solution Each ofthese reactions is straight out of the textbook and each is simple addition tothe carbonyl soup. The ist is cyanohydrin formation and you need to draw out the aldehyde group to make a 00d job of the mechanism. AF" Jost we Ao ‘The second is a standard Grignard reaction and you just need to remember that the aqueous work-up step is not usualy written down but is still needed, e oes y aes ene ing none ‘The only tap isin the reduction of the eylic keto-ester where you need to recall that NaBHy reduces ketones but doesn't reduce esters. Correct identification of functional groups matters. Seu Pe on ath 0 aert. re Problem 44 i “The equilbxium constant Ko, for formation ofthe cyanohycrin of cyciopentanone and HCN is 667, while for butan-2ane and HON it is 28. Explain Purpose of the problem More revision of equilibria this time with some numbers,