Chapter7 215 Solutions to Problems be al If stereoisomers are not included, 3 different monosubstituted compounds can be formed. If stereoisomers are included, four different monosubstituted compounds can be formed because the second listed compound has an asymmetric carbon, BrCSECCHCCH,CHs HC=CC=CCHCH, Br HC=CC=CCH,CH,Br If stereoisomers are not included, 2 different monosubstituted compounds can be formed. If stereoisomers are included, three different monosubstituted compounds can be formed because the first compound has a double bond that can have cis-trans isomers. BICH=CHC=CCH=CH, — CHy=CC=CCH=CH, Br Ignoring stereoisomers, § different disubstituted compounds can be formed. BrC=CCRCCHCH, = BrC=CC=CCH,CH,Br HCSCC=CCHCH,Br Br Br Br HC=CC=CCCH, HC=CC=CCH,CHBr Br Br Ignoring stereoisomers, 5 different disubstituted compounds can be formed. BrCH=CC=CCH=CH BrCH=CHC=CC=CH, BrCH=CHC=CCH=CHBr Br Br Br=CHC=CCH=CH) Br . Three of the five different disubstituted compounds have an asymmetric carbon. BrC=CCHCCHCHy Br Br Br Each of the compounds with an asymmetric carbon can have the R or the S configuration Therefore, 8 disubstituted products are possible: (2x 3) + 2 compounds without an asymmetric carbon. ‘Two of the five disubstituted compounds do not have cis-trans isomers. CIR=CC=CC=CH, — BC=CHC=CCH=CH, HC=SCC=CCH,CHBr HC=CC=CCHCH,Br 1 I Br Br Br ‘Two of the five disubstituted compounds have a pair of cis-trans isomers. BrCH=CC=CCH=CH, BrCH=CHC=CC=CH, Br Br One of the five disubstituted compounds has two pairs of cis-trans isomers, BrCH=CHC=CCH=CHBr Therefore, 10 disubstituted compounds are possible.216 2m 3. 4, Chapter 7 Ladenburg benzene is a better proposal. It would form 1 monosubstituted compound, three disubstituted compounds, and would not add Br2, all in accordance with what early chemists knew about the structure of benzene HO yy Br Boy Br Hg Br Kg Br H 1H H HOH Br iH H H H H Br Dewar benzene is not in accordance with what early chemists knew about the structure of benzene, because it would form two monosubstituted compounds, 6 disubstituted compounds, and it would add Bro. Br Br Br Br Br ox cr Br Br Br Oo Br L “Br Br a. From examination of the contributing resonance structures in Figure 7.4 on page 271 of the text, one can conclude that all the carbon-oxygen bonds in the carbonate ion should be the same length. Because the two negative charges are shared equally by three oxygens, each oxygen should have two thirds of a negative charge. a. 1, 2, 3, 5, and6Chapter? 217 2, Because the substituent is not able to participate in resonance, the only resonance structures are the two resonance structures of the benzene ring, OO <_ «pons CH;CH=CH-CH=CH-CH, CH,CH-CH=cH- CH=CH, ee “ cH,cH4CH~CH-CH=cH, \¢ resonance contributor that makes the greatest contribution to the hybrid is labeled ““A’ “B” contributes less to the hybrid than “A”, and “C” contributes less to the hybrid than a, Solved in the text. i ia T+ b. CHj—C-OCH, CH;—C=6CH, A B “ (0 (\- B A218 Chapter 7 A & B B is more stable than C because the electronegative oxygen atom is closer to the positive charge in C *OH OH lt e. CH,;—C-NHCH, CH;—C=NHCH; B A f. CH,-CH-CH=CH-CH, — CH,CH=CH-CH-CH, equally stable S+on tbs e@ CH3;—C=-NHCH; be be a. CHsC==CH™=CHCHs CH, CH, a CH,CH,C-CH, <—» CH,CH,C=CH, CH;CH,CH=CH—CH, <<—® CH,CH,CH—CH=CH, ‘more stable because the unpaired electron is shared by a primary and a secondary carbon8. Chapter? 219 i ° b. CH;C—CH=CH, —«—= CH;C=CH-CH, ° Il + CHjC—CH=CHCH, <> CH,C=CH-CHCH, more stable because the positive change in on a secondary carbon °° © CHj;CH—CH=CH, ge i CH,C=CHCH, =<—» CH,C—tHCH, more stable because only in this compound is the negative charge delocalized “NE NH, qd. CH;-C—NH, ~<—> CH,—C=NH) more stable because the positive charge is on a N rather than on an O “OH ou CH;-C—NH, ——= CH,—C=NH, a. Because nitrogen is less electronegative than oxygen, it is better able to stabilize the positive charge by resonance. \ CH, <—> CH,NH=cH, more stable Tn order for electron delocalization to occur, the atoms that share the electrons must be in the same plane. The two tert-butyl groups prevent the positively charged carbon and the benzene ting from being in the same plane. Therefore, the carbocation cannot be stabilized by electron delocalization. more stable220 Chapter 7 ¢. The compound with delocalized electrons is more stable than the compound in which all the electrons are localized + + + (CH,CH) cu,os CH, ~—= CH,Q=CH, all the electrons are localized electrons are delocalized |. The compound with delocalized electrons is more stable than the compound in which all the electrons are localized. CHCH, .CHCH; CHCH, CH CY Cy electrons are delocalized all the electrons are localized e. The OCH; group destabilizes the carbocation in the first species and destabilizes it in the second species. OCH, : x CHC Cth <— CH C= ‘The OCH; group destabilizes the carbocation by inductive electron withdrawal + + * CH, <> on6¥dH—cH=cH, —<—> cH,6=cH-CH=CH, ‘The OCH group stabilizes the carbocation by resonance electron donation. 9. a, Solved in the text. The contributing resonance structures show that there are four sites that could react with HO". cl a . a <> ¢. The contributing resonance structures show that there are three sites that could react with a bromine radical Z2INS A vw, Chapter7 21 4d. The contributing resonance structures show that there are two sites that could be protonated. ORD — OD 10. Solved in the text. LL. In each case, the compound shown is the stronger acid because the negative charge that results when it loses a proton can be delocalized. Electron delocalization is not possible for the other compound in each pair. a. CH;CH=CHOH ——» H* + CH,;CH=CHO ——» CH,CHCH=0 Il gv i * - b. CHyC-OH ——> H” + CH;C—O" —~—» CH,C=0 © CH;CH=CHOH——> H* + CH;CH=CHO <—» cH,CHCH=0 4. CH,CH=CHNH, —> H" + CH,CH=CHNH, —<—> cH,CHCH=NH, 12, a, Ethylamine is a stronger base because when the lone pair on the nitrogen in aniline is protonated, it can no longer be delocalized into the benzene ring. b. Ethoxide ion is a stronger base because a negatively charged oxygen is a stronger base than aneutral nitrogen, . Ethoxide ion is a stronger base because when the phenolate ion is protonated, the pair of electrons that is protonated can no longer be delocalized into the benzene ring. 13. The carboxylic acid is the most acidic because its conjugate base has greater resonance stabilization than does the conjugate base of phenol, The alcohol is the least stable because, unlike the negative change on the conjugate base of phenol, the negative change on its oxygen atom cannot be delocalized. 9 Cp-&on > (p-0 > (p-en08222 14, 45. 16. 1. 18. 19. Chapter 7 The y4 molecular orbital of 1,3-butadiene has 3 nodes (two vertical and one horizontal). The yy molecular orbital of 1,3-butadiene has 4 nodes (three vertical and one horizontal). a. YW, and yp are bonding molecular orbitals, and ys and Wy are antibonding molecular orbitals. b. y; and ys are symmetric molecular orbitals, and > and yz are asymmetric molecular orbitals. ¢. yy is the HOMO and y; is the LUMO in the ground state. 1d. ysis the HOMO and y, is the LUMO in the excited state. e. If the HOMO is symmetric, the LUMO is asymmetric and vice versa. a. Yj, Ya, and ys are bonding molecular orbitals, and y, Ws, and Ye are antibonding molecular orbitals. b. Wi. Va, and ys are symmetric molecular orbitals, and Y, Yq. and Ye are asymmetric molecular orbitals. ¢. ysis the HOMO and yj is the LUMO in the ground state. 4. yy is the HOMO and ys is the LUMO in the ground state. €. If the HOMO is symmetric, the LUMO is asymmetric and vice versa. a. The y; molecular orbital of 1,3-butadiene has 3 bonding interactions and the y molecular orbital has 2 bonding interactions. b. The y; molecular orbital of 1,3,5,7-octatetraene has 7 bonding interactions and the molecular orbital has 6 bonding interactions. Notice that the y; molecular orbital has one bonding orbital between each of the overlapping p orbitals, Notice also that as the energy of the molecular orbital increases, the number of bonding interactions decreases. ad, fg. i,j, Lom a.and b, 1. CH,-N=Nt <> CHG: More stable, because the negative charge is on nitrogen rather than on carbon. 2 More stable, because the negative charge is on oxygen rather than on nitrogen.Chapter7 223 Both are equally stable. Additional resonance structures could be drawn for each of these three species, but they are relatively unstable because they have an incomplete octet 20. a ANAN2N, =x AAS Ws ¥ yee f b.224 Chapter 7 21. a, different compounds b, resonance contributors ¢. different compounds d. resonance contributors ¢. different compounds Notice that in the structures that are different compounds, both atoms and electrons have changed their locations. In contrast, in structures that are resonance contributors, only the electrons have moved. 22.0 a 1. CH;CH=CHOCH; «—» cH,CHCH=6cH, major minor (CH,NH, CH,NH Oo —- the two resonance contributors have the same stability 2 the two resonance contributors have the same stability 5S + OCH OCH; OcH, OCH, OCH, major minor minor minor major ° oO” +f a7 6. CHy—NC =< HN Oo 0 the two resonance contributors have the same stabilityChapter7 225 o il Ls 7. CH;CH,COCH,CH, ~<—= CH,CH,C=OCH,CH, major minor 8 CH;CH=CHCH=CHCH) CH,CHCH=CHCH=CH, minor ~N Pad major CH,CH=CHCHCH=CH, major 8 x ‘ x HCNHCH; —@—* HC=NHCH; major minor 10. CH,CH=CHCH, ——» cH,CHCH=cH, minor major I — c <> - o oS, -0% So 0% Sor 0” No ‘=o 7 or u. c each of the three resonance contributors has the same stability ° ° o 1 = ie I 12, HCCH=CHCH, <—» HCCHCH=CH, <—» HC=CHCH=CH, minor minor major 1B. O- O- O.-- OO The five contributors are equally stable. po oO o 14. CH,CH-N’ <_— CH;CH-NS —<— cH, CHEN’ minor Oo minor ° major Oo csr226 © Chapter 7 15. ‘The electrons can move in two different direction. They can move out of the benzene ring toward the alkene group; they can move into the benzene ring away from the alkyl group. CH=CH, CHCH, cucn, CHCH, CH=CH, major minor minor minor major CHCH, CHCH, cHCH, CH=CH, rminoe pe minor mah 16. * " . A cl cl cl major minor minor minor major 1 0 q a gg 17. CH,C—CH-CCH, > CH,C—CH=CCH; ~— CH;C=CH-CCH, minor major major ° eo ~ 18, CH,COCH,CH; == CH,=COCH,CH, minor major b. 2,4, 6, 11, and 13 23, a. CHyCHCH=CH) b. CHy ano This makes the greater ‘This makes the greater ‘This makes the greater contribution because the contribution because the contribution because the positive charge is on positive charge is on negative charge is on a secondary carbon. atertiary carbon, an oxygen atom.Chapter? 227 The resonance contributors show that the carbonyl oxygen has the greater electron density. carbonyl oxygen b. The compound on the right has the greater electron density on its nitrogen because the compound on the left has a resonance contributor with a positive charge on the nitrogen. ¢. The compound with the cyclohexane ring has the greater electron density on its oxygen because the lone pair on the nitrogen can be delocalized onto the oxygen. There is less delocalization onto oxygen by the lone pair in the compound with the benzene ring because the lone pair can also be delocalized away from the oxygen into the benzene ring. ee 9° il + (onion, <> NH=CCH, a q e On <> prt, <> Cpriite 28. The methyl group on benzene can lose a proton easier than the methyl group on cyclohexane because the electrons left behind on the carbon in the former can be delocalized into the benzene ring. In contrast, the electrons left behind in the other compound are localized on the carbon. On 26. The carbocation is stable because the positive charge is shared by 10 carbon atoms (the central carbon and 3 carbons of each of the 3 benzene rings).228 21. 28, 29. Chapter 7 0 » ll CH,CH,O—C—CH=C ad CH,CH,G—C=CH—C= #1 most stable because the #2 because the negative charge negative charge is on oxygen is on nitrogen —cH— #3 because the negative charge #4 the least stable because the negative charge is on carbon ison carbon and it has separated charges ‘The more the electrons that are left behind when the proton is removed can be delocalized, the greater the stability of the base. The more stable the base, the more acidic its conjugate acid. ‘The negative charge on the base in the first compound can be delocalized onto two other carbons; the negative charge on the base in the second compound can be delocalized onto one other carbon; the negative charge on the base in the last compound cannot be delocalized. 1 . CH;CO™ the negative charge is shared by 2 oxygens nt b. CH,CCHCCH, _ the negative charge is shared by a carbon and 2 oxygens ©. tl CHCH;CHCCH, the negative charge is shared by a carbon and an oxygen a. [Hy this compound has delocalized electrons i e CHyC—CH the negative charge is shared by a carbon and an oxygen CH, oO ‘v7 the negative charge is shared by a nitrogen and 2 oxygens °Chapter? 229 30. The stronger base is the less stable base of cach pair in Problem 29, a, CH3CH,O7 i 1 b. CHyCCHCH;CCH ° -~T ©. CHyCHCH,CCH, NH, d. cH,CHCH, CH, e CHC tH én, 9 N Less stable bee: se the negative charge cannot be delocalized. Less stable because the negative charge can be delocalized onto only one carbonyl oxygen. Less stable because the negative charge cannot be delocalized Less stable hecause neither of the nitrogen lone pairs in be delocalized, Less stable because the negative charge is delocalized onto a carbon. Less stable because the negative charge can be delocalized ‘onto only one carbonyl oxygen. 31. The carbocation leading to 1,1-dichloroethane is more stable than the carbocation leading to 1,2-dichloroethane because the positive charge on the intermediate leading to 1,1-dichlorocthane is shared by carbon and chlorine. Since the more stable carbocation is the one that is easier to. form, the final product of the reaction is 1,1-dichloroethane. HCL ycscH #CS H,c=cH— — oncHcl a 1,2-dichloroethane vor HCH. HCI NS CHyCHCI a 1 L-dichloroethane CH;CH:230 32. Chapter 7 ‘The resonance contributors of pyrrole are more stable because the positive charge is on nitrogen. In furan, the positive charge is on oxygen which, being more electronegative, is less stable with a positive charge. Ais the most acidic because the electrons left behind when the proton is removed can be delocalized onto two oxygen atoms. B is the next most acidic because the electrons left behind ‘when the proton is removed can be delocalized onto one oxygen atom. C is the least acidic because the electrons left behind when the proton is removed cannot be delocalized. Bad Rvcufen, » enfemonon’ i CH,CCH,CCH; > CH,CCH,CH,CCH; > CHCCH,CH,CH,CCH, A B c Of the two possible carbocations that can be formed in reaction a, the more stable carbocation is the one formed by adding the clectrophile to the sp? carbon bonded to the greater number of hydrogens. It is more stable because the positive charge is shared by carbon and fluorine. the carbocation formed by adding the electrophile to the. sp? carbon bonded to the greater number of hydrogens CH,CH,—I the carbocation formed by not adding the electrophile to the sp? carbon bonded to the greater number of hydrogens Of the two possible carbocations that can be formed in reaction b, the more stable carbocation is the one formed by not adding the electrophile to the sp? carbon bonded to the greater number of hydrogens. The fluoro substituent is not in a position to help to stabilize the positive charge in either carbocation. In the carbocation formed by not adding the electrophile to the sp? carbon bonded to the greater number of hydrogens, the electron-withdrawing fluoro substituent is farther away from the positive charge.35. a. and d. Potential Energy —> Chapter 7 231 CH;CHCF, the carbocation formed by adding the electrophile to the sp? carbon bonded to the greater number of hydrogens CH,CH,CF; the carbocation formed by not adding the electrophile to the p> carbon bonded to the greater number of hydrogens —232 36. Chapter 7 4. The resonance contributors ine" are more stable than the resonance contributors in "b"* because in "b" a positive charge is on the most electronegatice atom (the oxygen). Therefore, the phenolate ion has greater resonance stabilization than phenol. Thus, as shown in the energy diagram, the difference in energy between the phenolate ion ‘and the cyclohexoxide ion is greater than the difference in energy between phenol and cyclohexanol €. Because of the greater resonance stabilization of the phenolate ion compared to phenol, phenol has a larger Kg than cyclohexanol. f. Because it has a larger Kg (a lower pKa), phenol is a stronger acid 2 a = 3 NH, ‘ Ons O~ > Progress of the Reaction b. NH; NH, o- «INF, NH) NH, NH, :NHChapter? 233 d. Aniline has greater resonance stabilization than the anilinium ion. Thus in the energy diagram, the difference in energy between aniline and cyclohexylamine is greater than the difference in energy between the anilinium ion and the eyclohexylammonium ion. €. Because of the greater resonance stabilization of aniline compared to the anilinium ion, the anilinium ion has a larger Ka than the cyclohexylammonium ion. f. Because it has a larger Ka (a lower pXg), the anilinium ion is a stronger acid than the cyclohexylammonium ion. Therefore, cyclohexylamine is a stronger base than aniline. (The stronger the acid, the weaker its conjugate base.) a, Ithas 8 molecular orbitals, b. Vis Va, Ws and yy are bonding molecular orbitals; Ws, Vo,¥>, and yg are antibonding molecular orbitals. Vi. Vay Vs and y; are symmetric molecular orbitals; Yo, Wi, We, and Ys are asymmetric molecular orbitals. d. Ys is the HOMO and ys is the LUMO in the ground state. €. Ys is the HOMO and yg is the LUMO in the ground state. £ The HOMO is symmetric, the LUMO is asymmetric and vice versa. g. Ithas 7 nodes between the nuclei.