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,se 36 Organic Chemistry Solutions Manual ‘Suggested solution ‘We need fist to state the problem in chemistry rather than in writing Oreos ES SS The two Ketones are very similar, the ring being the main diference. The two equilibrium constants ae also very similar as Ke isa simple rato of [eyanohydrin] to [ketone] and is not on a log scale. There is a factor of about 2.5 between the two examples. There is, ofcourse, some strain in the five-membered ring (angle 108°) but only atthe carbonyl group (ideal angle 120°). Replacing ‘the trigonal centre by a tetrahedral centre so thatthe ideal angle (109°) is almost identical to the actual angle is enough to explain this small factor.Suggested solutions for Chapter 7 Problem 4. ‘Xe these molecules conjugated? Explain your ansiner in any reasonable way, My AAR. Purpose of the problem ‘evasion of the basic kinds of conjugation and how to show conjugation with curly arrows. gested solution £5 wo are straightforward with one conjugated system (an enone) in the first example and ‘ame (2 phenyl alkyne) in the second. OF course, the benzene ring is itself conjugated in the ssxoad example. You can show either or both with curly arrows: we have done so for the first exmnple only. The last three compounds obviously form a group with the same skeleton and only the alkene ‘mene around. There i, of course, ester conjugation in all three but this the only kind inthe last ‘sempound. The firs s most conjugated with the lone pair on nitrogen delocalized into the carbonyl pmep. The middle compound just has the alkene and the ester conjugated, This time we have used ‘amcty arrow representations for all three compounds and a dottedline electron distribution smmmnary forthe frst, ae meOrganic Chemistry Solutions Manual Problem 2 raw 2 full orbital diagram for all the bonding and ontibonding * orttals in the three ‘membered cylit cation shown here, The molecule is obviously very strained. Might it survive by also being aromatic? Purpose of the problem Revision of MO diagrams for conjugated systems with aromatic. Suggested solution ‘There are only two electrons inthis simple cation but we need to mix the 2 bond (mand x” orbitals) ‘withthe empty p orbital to gie the MOs, One MO will be bonding all ound the ring and this is the ‘only one that matters to the structure. The others may have given you problems. We can mix the p- ‘AO withthe #-MO as they have the same symmetry in a three-membered ring but we cannot mix P| with 27. So our three MOs are m+ p, x — py and “Se pec oT AC fm RA Hp ‘The cyclic cation is stable and can be made because of the gain in energy in populating only the lowest all-bonding orbital. As it happens ‘sand Ws are degenerate. Ifyou count the number of bonding and antibonding interactions in cach you will see that the net result is one antibonding interaction in both orbitals. I is also aromatic, having 4 + 2 n-electrons where n=0. ‘You get the same result if you mix three p-AOs, one an each carbon atom. Then its easier if we look down on the ting showing the top lobe ofthe p orbital at each atom, The lowest, all-bonding corbizal has no nodes (except the plane of the ring) and the two degenerate, antibonding, and unoccupied orbitals have one node exeh, aChapter 7 Suggested solutions for Chapter 7 Problem 3 How extensive are the conjugated systems in these molecules? OR saptecam arene o fae Purpose of the problem A chance to delve more deeply into what is meant by conjugation. Suggested solution ‘The B-lactam has ewo clearly deined conjugating systems: the amide and the more extended ‘unsaturated acid going right through tothe sulfur atom. These are shoven by culy arrows on the first diagram. These sysems are joined by a single bonds so they really are one system: all the p covbitals on the ringed atoms in the second diagram are more of less parallel and all are conjugated. B OH FE, EG rasliihedtrnoket tie) iipenbinaber wok de oplathgene (yea arrows on the first diggram, Each benzene ring has substituents with lone pairs shown on the second diagram so this molecule has no less than six lone pairs of electrons involved in extended ‘conjugation. There are three separate conjugated systems shown in boxes on the second diagram, moo ome m ‘ome ome ome Problem 4 Draw diagrams to jtustrate the conjugation present in these molecules. You should draw tee ‘ypes of diagram: (a) conjugation arrows to give at least two different ways of representing the ‘molecule joined by the corect ‘reaction’ arrow: (b) a diagram wih dotted ines and partial charges (i any to show the double bond and charge istibution (if any; and (c) 9 diagram of the atomic oritals that make up the lawestenergy bonding molecular orbital. SAECO10 Organic Chemistry Solutions Manual Purpose of the problem ‘A more exacting exploration of the precise details of conjugation. Suggested solution “Treating each molecule separately inthe styles demanded by the question. the first compound is the guanidinium ion, a very stable cation because of conjugation. The curly arzows in the frst set of diagrams show that each nitrogen hasan equal amount of postive charge and thsi reflected in the second diagram showing exactly one-third + on each N. The thd diagram, ofthe lowest-energy ‘MO, looks down on the molecule and shows the top lobe of the p orbital on each atom. cite is its “ee ® Ls ") ee ‘The second molecule is what we shall learn to call an enolate ion. The negative charge is delocalized throughout the conjugated system but is particularly on the two oxygen atoms and, to a lesser extent, ‘onthe central carbon atom. Is dificult to represent this accurately with partial changes but the charge ‘on each oxygen atom is nearly a half. The lowest-energy MO has all the p orbitals in phase ‘The third compound is naphthalene. The structure drawn isthe best; curly arrow diagrams do rot do this molecule justice and other versions are less convincing. In particular, they do not show that the middle bond common to both rings is the shortest bond. There are no charges anywhere and al the p orbitals are conjugated. This isthe basic ten-eleetron aromatic system. 08 -€9-CO OO thy Problem 5 \Which ofthese compounds are aromatic? Justiy your answer with some electron counting. You ‘ate welcome to treat each ring separately or two or more rings togetner, whichever you prefer. SOL ee) th 0 on oH siiaone: 9 wane aeoiote c0s4 of DH ome oR Vetote rg metore “"eetus used te taat aut ciliates ature Newer pmentChapter 7 Suggested solutions for Chapter 7 Purpose of the problem A simple explor Suggested solution “The frst three compounds ae straightforward providing you count lone pair electrons on atoms in the sing and donot count electrons outside the rng such a those in the carbonyl bond in the fst compound. Nor should you count the lone pair represented by the negative charge inthe third ‘compound. They are in an sp? orbital in the plane of the ring. ion ofthe idea of aromaticty: can you count to si? at 2lona pi tcrons arse oof Seine Ue ol. wen poe ‘The rest offer variations on the benzene ring and each ring must be considered separately. Methoxatin has five- and six-membered rings with nitsogen in them. Count the lone pair in @ P orbital on the nitrogen atom in the five-membered ring but not those in an sp! orbital in the six-membered ring (pyridine). Both are aromatic. Colchicine has an aromatic seven-membered ring with six electrons (don’t count the C=O group) while cllstephin has an interesting positively charged aromatic ring with three double bonds, We summarize these answers briefly by giving the ‘umber of electrons in each conjugated ring. 2lone par evens on bon on iainone: 9 teractneaiote1 19 you notice hat on one ‘dium on is necessary ae hee ls ‘ery one sive charge onthe Organic Chemistry Solutions Manual Purpose of the problem To get you thinking sbout the relationship between conjugation and light absorption. Suggested solution Each dyestuif has essentially the same conjugated system shown here isolated from extra substituents. The positive charge is shared between the two nitrogen atoms and the whole system is symmetrical. The colour is due to excitation of the lone pair electrons, which are delocalized over the whole system, into an antibonding x* orbital of the aromatic system. There will be many bonding x orbitals and the same number of antibonding x* orbitals. The lowest (the LUMO) willbe ‘unusually low in energy and the n, x* isin the visible region. me a CT Me ‘The substituent on the middle atom is iffrent inthe wo des and is als conjugating Tis extra conjugation decides the exact shade of colour wth the highly conjugating naphthalene rin in EL42 taking the absorption all the waytheough to red ight so the dye appears green tothe eye. The OH group also helps a lone par isalso conjugated into the aromatic ings. The sulfonate groups make the compound water-solubleChapter 7 Suggested solutions for Chapter 7 43 Purpose of the problem sher thoughts on the relationship between conjugation and light absorption plus revision of Chapter Suggested solution ~e of the dyestuffs in the shaving foam, Fast Green FCF, has a conjugated system very similar to 1 we have just been discussing in Problem 6, though it has extra solubilizing substituents on the Srogen atom, Fast een For eee congo sta ‘Saree cour ans “oso¢ ‘uy in er mv sly ater Quinoline yellow is quite different. It has two conjugated ring systems linked by a single bond. However, they are also linked by conjugation from the OH group in one ring tothe nitrogen atom the other. Infact, the whole molecule is conjugated. Because the conjugation is more limited, this snolecule absorbs violet light and so appears yellow. It has the usual sulfonate solubilizing groups. he ‘quinoline’ part of the name refers to the left-hand ring system. Qunotne tor Fay _/ ? a ‘0,08 ‘Soon ‘The compounds in the ‘spectrum of molecules’ are much simpler and you may well have been surprised after reading Chapter 7 that they are coloured at all ° —~ OOF ent rete uric oto You probably found ‘red’ easiest to deal with as there is an obvious extended conjugation throughout the whole molecule The conjugation in ‘blue is less obvious but clearly more effective blue compound absorbs longer wavelength light than a red compound) and relies on a redistribution of electrons that makes both rings aromatic. This compound is called azulene (an azure alkene) as a blue hydrocarbon is very remarkable.Organic Chemistry Solutions Manual The orange and yellow compounds owe their colour to functionality. ‘Orange’ is a quinone ~ 3 conjugated six-membered ring compound with four electrons — and has a low-energy unoccupied orbital (a x* orbital, the LUMO) from the two conjugated carbonyl groups, which is easily occupied by excitation of a x electron. 'Yellow’ is diazomethane, an unstable toxic and even explosive gas hich has some conjugation in its very small framework but owes its colour mainly to the N=N functionality which again has a low-energy 2” orbital. i\efs 2 8 oH, ae GEN ‘The green compound, delightfully named 9-nitrosojulolidine, has conventional conjugation of an eflicient sort between electton-donating Nand the electron-accepting nitroso group (N=0. Nitroso compounds can be brightly coloured without any conjugation asi the case with ‘purple’. It is very unusual to have blue or purple gases and this compound has a CF; group to stabilize the nitroso group which, when not conjugated, is an odd-electron compound. The colour comes from excitation of a lone pair electron into the N=O antibonding orbital Sean Go through the list of aromatic compounds at the end of the chapter and see how many. ‘electrons there are in the ings taken separately or taken together (if they are fused}. are al the numbers of the (4n ++ 2) kind? Purpose of the problem Revision of material in the chapter explored a litle more deeply to reinforce the concept of aromatic + Suggested solution The fst two compounds are straightforward providing you put lone pais in the right orbital and don’t count C=O groups. Gas Sigmar cee = Me rghctns frnoncangand tener, ios twotrom One par lb ings tage sence noi fe inne ine teen nrg Nain oatsspied ried NaN ofan :0). It the Chapter 7 Suggested solutions for Chapter 7 45 LSD and Omeprazole have in common a fused aromatic ring system with one benzene ring and sme heterocyclic ring. You can think of these as two sx-electron rings sharing two clectons oF as ome ten-cleciron system. Omeprazole has a pyridine ring as well nsgiew 9 enon a maingpeie. rine rng OMe Aa Ea. A Awe me a l mee fi) Ns cae COE Viagra has an ordinary benzene ring and an interesting double heterocyclic ring, You can simply “Sy that there are two fused rings with six electrons eack but a couple of delocalizations show clearly sebich lone pairs can be delocalized and that the resulting system has 10 electrons delocalized round ss rim, The final example, haem, was fully analysed in the chapter as an 18-electron aromaticSuggested solutions for Chapter 8 “Problem 4 It you wanted fo separate a mixture of naphthalene, pyridine, and prtoluc acid, how would you go about it? i oe o. Purpose of the problem Revision of simple acidity and basicity in a practical situation. Suggested solution 1 Thee a contves protien - Pyridine iva weak hase (pK 5.5) and can be dissolved in aqueous acd. p-Toluic acid isa weak acid Jou cannot uaaly separate (PK, about 4.5) and canbe dissolved in agucous base. Naphthalene is neither an acid nora base and eee ‘remains insoluble in water at any pH. So, dissolve the mixture in an organic solvent immiscible with water (say ether, Et:0, or CHsCh) and extract with aqueous acid (pH < 4); this will remove the pyridine as an aqueous solution of its protonated form. Then extract the remaining organic layer with aqueous base (pH > 6) which will extract the p-toluic acd as its anion. You now have three solutions. Braporate the organic solution of naphthalene and recrystllize it to get pure naphthalene. Aci the basic solution of p-toluic acd to precipitate the fce acid and recrysalize it. Finally, add base to the pyridine solution, extract the pyridine with an organic solvent, (say ether, Et,O, or CHCl), evaporate the solvent, and distil the pyridine. Itis just as good to extract with base first and acid second. © Problem 2 ae | in the separation of benzo acid from toluene we suggested using NaQH solution. How concentrated a solution woul bo necessary to ensure thatthe pH was above the OM of boenzoieecid (0K 4.2)? How would you estimate now much solution to Use? Purpose of the problem You can check your understanding ofthe relationship between pH and concentration Suggested solution Even avery weak solution of NaOH will have a pH > 4.2 By te calculation on p. 184 ofthe chapter, fora pH of 5 we should need [Hj0*] = 10° mol dma!, We know thatthe tonic product of waters {H,0"] (OH = 10-and so for pH 5 we need 10-* mol dm! of NaOH. This is very dite! The ‘rouble is that you need one hydroxide ion for every molecule of benzoic acid so if you had, say, 1.22 g PRCOLH (= 0.01 equi) you would need 1000 lies (d=) of your NaOH solution. It makes more sense to have a much more concentrated solution, say, 0.1M. This would give an unnecessarily high pH of 13 but you would need only 100 ml (cm*) to extract your benzoic acid,Chapter 8 Suggested solutions for Chapter 8 4a ° Problem 3 i \Whot species would be present you were to clsole this hyeron-ci na) water at pH (b) aqueous alkali at nH 42; or (c) @ concentrated solution of a mineral acid? Purpose of the problem Revision of simple acidity and basicity requiring pK; values ina practical situation, Suggested solution The COsH group will have a pK; of about 4-5 and the OH group a pK, of about 10. Tis gives a comfortable margin between the two ionization At pH 7 the acid willbe ionized an a pH 12 both cups wl be ionized. In concentrated mineral acid both wil have ther protons and te carboxylic ‘i will sart to be protonated. It is more readily protonated than the isolated OH group as it gives 4 delocalized cation “oh oh Tht Problem 4 ‘What would you expect to be the site of (a) protonation and (b) deprotonation if the compounds below were treated with an appropriate acid or base? In each case suggest & suitable acié or base for both purposes. ee Purpose of the problem Progressing towards more taxing judgements on more interesting molecules, Suggested solution The simple amine, piperidine, will have a normal amine pKus of about 11 so it will be easy £0 protonate with even very weak acids. Any mineral acid like HCl will do as would weaker acids ike RCOzH. Deprotonation will remove the NH proton as nitrogen is more electronegative than carbon but a very strong base such as BuLi wil be needed as the pK, willbe about 30-3. “~ ~ sean aii eae ne hae Qe = 4 ' ‘The next example is more complicated but actually contains 2 normal tertiary amine (pK about 11) and.a normal primary alcohol (pK, about 16). Protonation at nitrogen will occur with any acid = let’s choose TSOH this time ~ and deprotonation will occur at the OH group and will need a strong, base ~ let's say NaH. °°on —O ao we 239 wee Organic Chemistry Solutions Manual The final example isthe most complicated one. There sa normal OH geoup (PK; about 16) and a slightly acidic alkyne (pK, about 32) so the OH willbe deprotonatd frst The basic group isnot a normal amine but an amidine in which the two nitrogen atoms can combine (sc arzows) to capture 2 proton It wll hae a pK, of about 12 and so would even be protonated bya phenol though most chemists would use a carboxylic acd. i ee Stati Problem 5 ‘Suggest what species viould be formed ty each of these combinations of reagents. You ere ‘advised to use pK, values to help you and to beware of some cases where ‘no change’ might be the answer. ase den A. O le Purpose of the problem Learning to compare species of similar acidity or basicity. Suggested solution In each case one of the reagents might take a proton fiom the other. In example (a), would the anion of the phenol remove a proton fom the carboxylic acid? We can answer that by considering pK, values. The answer is yes. There ate five pH unis between the two acids so the equilibrium will be well to the right. The equilibrium constant is about 10°, Tos tear” Prout preavout10 Example (b) has a similar possible reaction. This time the difference is much smaller and the oer way. The carboxylic ac is slighty stronger than protonated imidazole and the equilibrium constant is about 1072, et Sen ww Lee oa seal Example (c) aso involves @ carboxylic acid but this one is rather different. The three fluorine atoms make CFsCO,H a very strong acid, comparable to mineral acids. This equilibrium is well lover to the lel Pk stout 5 pry anauroChapter 8 Suggested solutions for Chapter 8 49 Problem 6 What is the relationship between these two molecules? Discuss the structure ofthe anion ‘hat would be formed by the deprotonation of each compound. Purpose of the problem lp you recognize that conjugation may be at the back of some related stuetures. Suggested solution They are tautomers. They der only in the position of a proton. Each is an acid ~ the frst has an NH ‘poup a part of an amide and the second has an OH group. Deprotonation may at fist appear to ‘reduce two different anions but they are actually the same because of delocalization ofthe anion, 1. =—Qe ike ‘What species would be formed by treating this compound with: (a) one equivalent; b) WO yg, ‘cqulvalents of NaNH2 in quid ammonia? Purpose of the problem 4 simple problem to help you think about the possiblity of selective deprotonation Suggested solution ae more acidic group is the OH (PK; about 16) and the les acidic i the alkyne (PK, about 35). The alkoxide wil be formed first, and then a second deprotonation is posible because the (wo ‘ezative charges are far apart inthe dianion and wil not significantly destabilize each other. Was Sp tly 5p i a i Problem 8 ‘The carbon NMR spectra of these compounds could be run in D0 under the conditions. shown. Why were these conditions necessary and what spectrum would you expect to " dee ‘eepscvum nin 0CY/0;0 $C sesamin NoO0/%0 Purpose of the problem SMR revision and practice at judging the tates of compounds at different pH, Hidden symmetry ‘20m conjugationSuggested solution Both compounds are quite pola an not very soluble inthe usual organic NMR solvents in addition, they have NH or OH protons that exchange and broaden the signals Ifthe exchange is made rapid by acid or base catalysis andthe NHs and OHs exchanged for deuterium, al these problems disappear and clean sharp spect result The ist compound isa guanidine and forms a cation in ai The cation s symmetrical and avery simple spectrum results — just tre types of carbon inthe aromatic region and ne very low feld carbon (at age 6) forthe carbon in the mide of the eatin. 0s 0-0 ‘The second compound loses a proton from the OH group in bas to give a delocalized symmetrical anion. There willbe five signals in the NMR spectrum: the two methyl groups are the same and the two CCH, groups in the ring are equivalent, Thee is one unique carbon atom jained to the two methyl groups and another in the middle of the anion and, finally, the two carbonyl groups are equivalent. Problem 9 "The phenols shown here have approximate pk, values of 4, 7,9, 10, and 44. Suggest with ‘explanations which pK value belongs to which pheno}. cee Purpose of the problem [A problem requiring detailed interpretation of electronic effets. Suggested solution Hlecron-withdrawing groups (Gland even mote so NO,) make phenols more acidic but electron- donating groups (Me) make them less acd. The nito group is very effective if it can stabilize the anion by conjugation. A pk value of about 10 is normal for a phenol, o it is pheno tsef tht has that value. The compound less acidic than phenol (pK, 11) must be the timethyl compound. One chlorine atom will make phenol slightly more acidic 30 pK, 9 must be 3-chlorophenol and the compounds with one nitro group (pK. 7) oF two (PK, 4) must be the very acidic phenols. Problem 10 Discuss the stabilization of the anions formed by the deprotonation of (a) and (b) an the Cation formed bythe protonation of (c). Consider delocalization in general and the possibilty of aromaticty in particular. @ x ird a Chapter 8 Suggested solutions for Chapter 8 Purpose of the problem ‘To get you thinking about delocalized cations and anions. Soggested solution “Fee Js only one remotely acidic proton in (a), the NH proton, Removal of ths gives an anion that “sane delocalized on to all the four nitcogen atoms in the five-membered ring. The combination of © electronegative stoms, 2 delocalized anion, and an aromatic anion (see diagram in margin) srattes this a very stable anion and the original amine is areal acid witha pK, (5) about the same a5 p2 of a carboxylic acid (RCO,HD. CA 22 =O) ‘Tez most acidic proton in (b) is that of the phenol and the anion is delocalized round the ‘Seprene ring, into the fused five-membered ring, and even out onto the ketone axygen atom so its 4 Sol: anion. However, there are only cight delocalized electrons altogether so, although the esse ring remains aromatic, there is no extra stabilizaion from any aromaticity in the “Seocalized five-membered ring or in the system as a whole, It has a pK, value of about 8.5. “OO Gogh nee diamine (c) will be protonated on the trigonal (sp?) nitrogen using the delocalized lone pair “Meera shows both rings as aromatic) as there ae 12 electrons delocalized ~ six foreach ring. The ‘eer asa whole isn't aromatic because is not ane conjugated ring stem. PAR -OVQ- 2-0 ‘Parpose of the problem ‘See. ccvsion in thinking about the acidity and basicity of functional groups ~ amino acids are gretosbely important. ‘Seggred solution “Se world expect the NH; group to have a pyc of about 11 and the SH group a pK, of about 8 so “Se ook sll right. But you would also expect the CO:H group to have a pK, of about 5 and that ‘pets al crong! We need to stat at high pH and work downwards to see what exactly we have by Se Se come to pH 5, This is what happens.Organic Chemistry Solutions Manual wey ova al its “ By the time we want to protonate the COs ion, there is an NH group next door so it will be much more difficult to make the cation and the pX, value is lower because we must go to more acidic solutions to get protonation. The structure ofthe molecule at pHs 1 (cation), 5 (awitterion), 9 (monoanion, that is, dianion and monocation in the sime molectle), and 12 (dianion) is 3s shown. Coe es Purpose of the problem To get you thinking about carbon acids, how their anions are delocalized, and what makes the anions stable. Suggested solution All dhse carbon acids give anions whose negative charge is mainly on oxygen. Similar ones are described in the chapter (Table 82, p. 193) and we expect simple carbonyl compounds to have pK,s of about 15- 20 and 1,3-diearbonyl compounds to have pKys of about 5-15. The first three compounds are all ketones on the lft and have ketone, aldehyde, and ester groups on the right respectively. The charge is ‘delocalized over both cazbonyl groups. The aldehyde is most effective asi isa simple carbonyl group. ‘The Ketone has ¢-conjugation, which reduces the electiveness ofthe carbonyl delocalization, and the «ster is worst asi has competing conjugation from the ester oxygen ator, o 9 0 0° 80 o °0 8 Ad, =A A AL AR aH 4 “ 4 o rib apt os co pp tba a uO electronegative chlorine atom — it isa proton from that side ofthe ketone that is lost. Deloclizing the charge on to the carbon atoms shows this. ° a) ° Ae fe he = é Ss rtp pe ace red ve aa a RG SE and trifluoroacety. Delocalization is very effective and most ofthe negative charge will be on one of the two oxygen atoms. 8 ise. 2 oo 0 of Jobe ick sleetChapter 8 Suggested solutions for Chapter 8 53 Purpose of the problem you thinking about carbon acis, how their anions are delocalized, and what makes the szions sable 1 Note that at no pH dose Suggested solution ‘aan ci ex Be fom wo Tee thre pK, values for glutamic acd itself must be like this (the remote COsH group is normal _fetneen 22 and 42 ts fom 0 {Se che one near the amino group is unusual as we discussed in the answer to Problem 11). eau wth the zwtein ee a poo 9428 mee oar oe eth ont ons ont Ne esanic 8 Ia glutamine, the remote CO:H group is missing and the other two pK; values are hardy ‘Sunged. The dimethyl ster has only the amino group lft and its py value isles beause we ave slaved the wo CO} anions with eleeton-withdrawingester groups. The wo monoesters are most esting. The fis is essentially the same as glutamine ~ the remote ester has tle effect on the ‘ser ovo groups. The second has, a we should expect, a remote COsH group like that of glutaric 2 iselfbut an amino group lice that ofthe diester showing thatthe neaer of the two esgrgroups the diester has the bigger eect 0 Purpose of the problem ‘Ts belp you appreciate the disastrous effects that innocent-looking groups may have because of reir weak acidity. Suggested solution ‘The OH group is the Wicked Witch ofthe Westin this problem, Whoever planned these syntheses -xpected itto lie quitly and do nothing. Bu, although an OH group is only a weak acid (pK, about54 Organic Chemistry Solutions Manual 16) it will give up its proton to the very basic Grignard reagent. Inthe first case, one equivalent of Grignard reagent is destroyed but addition ofa second would save the day. wp nen ee ‘The second case is more serious as the Grignard reagent destroys itself as it s formed with the replacement of Br with H and then nothing can be done to rescue the synthesis. The only answer is to block the OH group with something non-acidic (see Chapter 24). An mgm ok ee ° Net sy SEB mesh 2°, Hao tSuggested solutions for Chapter 9 Problem 4. pose mechanisms for the frst four reactions in the chapter. je obS os Je Pode 2m Heo Purpose of the problem ‘zhearsal of the basic reactions of Chapter 8 Suggested solution A reaction simply involves the nucleophilic attack of the + Ketone followed by protonation. You may draw the intermediate as an anion or with an O-metal 1d as you please. Note the atom-specific arrows t0 show which atom is nucleophilic. Inthe second example the alyslthium might attack through its other end, 0 organometallic reagent on the aldehyde Problem 2 i \When this reaction is caried out with allyl bromide labelled as shown with #20, the label is ‘ound equally distibuted between the ends of the aly system in the product. Expain how this is possible, How would you detect the 1%C distrbution in the product? on Py Em, bs 2. Prono » Be awe FE Fe Purpose of the problem Reminder of the way ally-metals react and revision of NMR.Organic Chemistry Solutions Manual Suggested solution ‘One explanation is that allyl Grignard reagents might reat as nucleophiles at eit system, aay Sahn = = ‘The mechanism given in the chapter (p.224) suggest that allyl Grignards aways reat atthe rem: ced by a oyic mechanism, If that isthe case, the formation ofthe Grignard must occur at both ers os. met mene, ae eee eae y ‘This could occur during the formation by attack of the metal at the other end of the ally: system, of after formation by equilibration with the aly! anion ey ao ad, mat A MM Ay AS Gun = MA In either case the two ally] Grignard reagents would have equal energies and would be forme! = equal amounts. The reaction with benzaldehyde would then follow a cyclic mechanism, end of the ea tis Ts et See ‘Your explanation may not be exactly the same as either of these ~ the only important thing is thet you should have some way of getting the eacton to occur at the other end of the alli system. The '3¢ distribution in the product would be determined by NMR spectra. Each labelled atom woule appear as much stronger signal (the natural abundance of "Cis 1.19) and each signal will be in « different part of the spectrum. The chemical shits are more accurately estimated as 115-120 and 45-50 ppm. Purpose of the problem ‘The toughest test — predicting the product. The sooner you get practice the better.Chapter 9 Suggested solutions for Chapter 9 solution a ‘on harder than explanation, you should get these right frst ime as only the last, ~ «sina I the Bist example, ethyl Grignard reagent acts a a base to remove a ‘Sayne, Whether you draw the inteemediate as an alkyne anion or Grignard reagent 1 you need not necessarily include the mechanism for the protonation step. ee Seo example just make the organometallic compound and ad itt the carbonyl group _ssssess an electrophilic ketone because of the strain of a carbonyl group in a four-membered “Grignard eagent is vinyl and not ally so the ambiguities in Problem 2 donot aise. _ cf- 6 eg ao ‘cumple raises the question of halogen replacement or orholthiation and, if the former, hen bromine is one ofthe halogens, halogen replacements usualy the reaction which + did ortho-lthiation between Cl and Br, you should not be ashamed. be 4 sows [eR “oye “Y fee — o tar i 4 ty l. z ee eee aad Seabee rt ; : (Fee 2 216) : : 4 CL “sree of the problem Ms deere

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