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Suggested solutions for Chapter 2 Problem 4. 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