P1: OXT/SRB

JWDD052-14

P2: xxx
JWDD052-Solomons-v2

14

Printer: Hamilton
May 1, 2007
14:10

AROMATIC COMPOUNDS

SOLUTIONS TO PROBLEMS
14.1 Compounds (a) and (b) would yield only one monosubstitution product.
14.2 Resonance structures are defined as being structures that differ only in the positions of
the electrons. In the two 1,3,5-cyclohexatrienes shown, the carbon atoms are in different
positions; therefore, they cannot be resonance structures.
14.3 Inscribing a square in a circle with one corner at the bottom gives the following results:

We see, therefore, that cyclobutadiene would be a diradical and would not be aromatic.
14.4 (a)

The cyclopentadienyl anion (above) should be aromatic because it has a closed bonding
shell of delocalized π electrons.
(b) and (c) The cyclopentadienyl cation (below) would be a diradical. We would not
expect it to be aromatic.

(d) No, 4 is not a H¨uckel number.
14.5 (a) The cycloheptatrienyl cation (below) would be aromatic because it would have a closed
bonding shell of delocalized π electrons.

271

6 If the 1. 14.7 (a) Br Br heat −HBr (b) Br + Br− Tropylium bromide These results suggest that the bonding in tropylium bromide is ionic. that is. we would expect it to be unusually stable.5-cycloheptatriene is not unusually acidic (it is less acidic than 1.5-cycloheptatrienyl anion should not be aromatic.3.10 (a) The cyclopropenyl cation (below). Br 14.P1: OXT/SRB JWDD052-14 272 P2: xxx JWDD052-Solomons-v2 Printer: Hamilton May 1. + or + SbF6− (b) Only one 13 C NMR signal is predicted for this ion. The fact that 1. that the 1.5-heptatriene) confirms the prediction made in the previous problem. 2007 14:10 AROMATIC COMPOUNDS (b) No. 14.9 The fact that the cyclopentadienyl cation is antiaromatic means that the following hypothetical transformation would occur with an increase in π -electron energy. (c) No. This would mean that 1.11 (a) 3 (b) 4 (c) 7 (d) 5 .3. 14.5-cycloheptatrienyl anion were aromatic. 14.8 It suggests that the cyclopropenyl cation should be aromatic.5-cycloheptatriene should be unusually acidic.3.3. π-electron energy increases HC+ + + H2 14. it consists of a positive tropylium ion and a negative bromide ion.3. the cycloheptatrienyl anion (below) would be a diradical. 8 is not a H¨uckel number.

16 Br A Br B Br C D A.P2: xxx JWDD052-Solomons-v2 Printer: Hamilton May 1.13 Major contributors to the hybrid must be ones that involve separated charges. which by virtue of their location are strongly shielded by the magnetic field created by the aromatic ring current (see Figure 14. 14. D. Br (a) (b) (b) (b) (a) Br Two signals (c) (b) (b) Br (a) (a) Br Br (b) (c) (d) (b) (a) (b) Br (c) (c) Three signals Four signals CH3 CH3 CH2Br CH3 14. Very strong absorption peaks at 693 and 765 cm−1 are characteristic of a monosubstituted benzene ring. . − − P1: OXT/SRB JWDD052-14 + + etc. − + SH 14. 2007 14:10 AROMATIC COMPOUNDS 273 14.14 (a) OH N N (b) N N N N N H N H 14. p-dibromobenzene would give two 13 C signals. o-dibromobenzene would give three. Strong absorption at 740 cm−1 is characteristic of ortho substitution. Strong absorption peaks at 680 and 760 cm−1 are characteristic of a meta substitution.and sevenmembered rings.15 Because of their symmetries.8).12 The high field signal arises from the six methyl protons of trans-15. A very strong absorption peak at 800 cm−1 is characteristic of para substitution. C. B. and would have aromatic five.16-dimethyldihydropyrene. and m-dibromobenzene would give four. Contributors like the following would have separated charges.

P1: OXT/SRB JWDD052-14 274 P2: xxx JWDD052-Solomons-v2 Printer: Hamilton May 1. 2007 14:10 AROMATIC COMPOUNDS Exercises CO2H Br Br 14.17 (a) (c) (b) NO2 Br CH3 NO2 CO2H OH (e) (d) NO2 (f) NO2 O2N NO2 OCH2CH3 (g) SO3H (h) SO2OCH3 (i) Cl Cl CH3 NH2 CH2Br CH3 (k) ( j) (l) CH3 NO2 O (m) C OH C(CH3)3 CH3 (o) (n) Br CH3 OH OCH3 C6H5 (p) C6H5 (q) HOCH2CHCHCH3 CH3 (r) Cl .

2.18 (a) Br Br 1.5-Tribromobenzene OH Cl Br OH Cl Cl (b) Cl 2.3.4-Dichlorophenol Cl Cl 3.2.5-Dichlorophenol OH OH Cl 2.5-Dichlorophenol NH2 NH2 NO2 (c) NO2 NO2 4-Nitroaniline ( p-nitroaniline) SO3H 3-Nitroaniline ( m-nitroaniline) 2-Nitroaniline ( o-nitroaniline) SO3H SO3H CH3 (d) CH3 CH3 4-Methylbenzenesulfonic acid ( p-toluenesulfonic acid) 3-Methylbenzenesulfonic acid ( m-toluenesulfonic acid) 2-Methylbenzenesulfonic acid (o-toluenesulfonic acid) 275 .4-Dichlorophenol 2.3-Dichlorophenol OH Cl Cl Cl 2.P1: OXT/SRB JWDD052-14 P2: xxx JWDD052-Solomons-v2 Printer: Hamilton May 1.4-Tribromobenzene 1. 2007 14:10 AROMATIC COMPOUNDS Br Br Br Br Br 14.6-Dichlorophenol NH2 Cl Cl 3.3-Tribromobenzene OH Br 1.

) The stability gained by becoming aromatic is apparently large enough to overcome the extra strain involved in having the ring of the dianion become planar.21 The bridging CH2 group causes the 10 π electron ring system (below) to become planar. CH2 . This allows the ring to become aromatic. 2− + 2 Li + 2 BuLi − = − Pentalene dianion 14. (The highest occupied molecular orbitals may become slightly lower in energy and become bonding molecular orbitals. Neither 8 nor 12 is a H¨uckel number. and this apparently gives it the stability of an aromatic compound. therefore. 14. 14. 2007 14:10 AROMATIC COMPOUNDS (e) Butylbenzene Isobutylbenzene sec-Butylbenzene tert-Butylbenzene Problems 14. Moreover.19 H¨uckel’s rule should apply to both pentalene and heptalene.P1: OXT/SRB JWDD052-14 276 P2: xxx JWDD052-Solomons-v2 Printer: Hamilton May 1.7). is not a diradical. The dianion. causing them to become filled. Heptalene’s lack of aromaticity can be attributed to its having 12 π electrons. an aromatic dianion. (b) The strong base (butyllithium) removes two protons from the compound on the left. This acid-base reaction leads to the formation of the 10 π electron pentalene dianion. the cyclooctatetraene dianion has 10 π electrons (a H¨uckel number).20 (a) The extra two electrons go into the two partly filled (nonbonding) molecular orbitals (Fig. Pentalene’s antiaromaticity can be attributed to its having 8 π electrons.

IIA O O 14. O− O + (a) I IA O− O + II (b) Contributors like IA are exceptionally stable because they resemble an aromatic compound. [16] annulene becomes an 18 π electron system and therefore obeys H¨uckel’s rule. Similar contributors to the hybrid of II resemble the antiaromatic cyclopentadienyl cation (see Problem 14.3-cyclopentadiene would produce a cyclopentadienyl cation. Any contribution they make to the hybrid is destabilizing. They therefore make large stabilizing contributions to the hybrid.23 Ionization of 5-chloro-1.9) and thus destabilize II. Contributors like IIA are exceptionally unstable because they resemble an antiaromatic compound.P1: OXT/SRB JWDD052-14 P2: xxx JWDD052-Solomons-v2 Printer: Hamilton May 1.24 (a) The cyclononatetraenyl anion with 10 π electrons obeys H¨uckel’s rule. 2007 14:10 AROMATIC COMPOUNDS 277 14. .22 (a) Resonance contributions that involve the carbonyl group of I resemble the aromatic cycloheptatrienyl cation and thus stabilize I. Cl SN1 + + Cl − Antiaromatic ion (highly unstable) 14. _ 2 Cyclononatetraenyl anion 10 π electrons Aromatic _ Cyclohexadecaoctaenyl dianion 18 π electrons Aromatic (b) By adding 2 π electrons.9) would be highly unstable because it would be antiaromatic. and the cyclopentadienyl cation (see Problem 14.

C10H14 (d) (c) CH (b) CH3 (a) CH3 (a) (a) CH3 (d) (b) (c) TMS 3.2 5 4 δH (ppm) 3 2 1 0 .27 A 1 H NMR signal this far upfield indicates that cyclooctatetraene is a cyclic polyene and is not aromatic.9 (b) quintet δ 2.35 quartet δ 4. on the other hand. readily losing all aromatic character in the process. 14. its π electrons are not fully delocalized. 1 H NMR assignments are shown in the following spectrum. 14.05 (c) multiplet δ 7. Benzene.3 CH3 (a) H (b) NH2 (c) (a) (b) (c) (d) (d ) H C (a) H H (c) (a) triplet δ 2.3 H (a) 14.0 8 7 6 2. Strong IR absorption at ∼ 800 cm−1 indicates para substiution.8 1.4 1.25 As noted in Problem 13.1 singlet δ 1.28 Compound F is p-isopropyltoluene.25 (b) septet δ 2.28.7 multiplet δ 7. 2007 14:10 AROMATIC COMPOUNDS 14.9 (c) multiplet δ 7. furan can serve as the diene component of Diels-Alder reactions. F.26 A (c) B CH3 (a) H (b) CH3 (a) (a) doublet δ 1.P1: OXT/SRB JWDD052-14 278 P2: xxx JWDD052-Solomons-v2 Printer: Hamilton May 1. is so unreactive in a Diels-Alder reaction that it can be used as a nonreactive solvent for DielsAlder reactions.1 (b) H H doublet δ 1.

1 (2H) or (b) Multiplet. We can make the following assignments in the spectra.4 multiplet δ 7. 14. C H bendings of C6 H5 group The UV absorbance maximum at 255 nm is indicative of a benzene ring that is not conjugated with a double bond. . C H stretching of benzene ring 3020 cm−1 . 2007 14:10 AROMATIC COMPOUNDS 279 We can make the following 1 H NMR assignments: (b) CH3 (c) CH (d) (a) doublet δ 1.1 14. CH3 (c) (d) CH2 (b) (a) (b) (c) (d) CH3 (a) triplet δ 1.85 (d) multiplet δ 7.30 Compound M is m-ethyltoluene.8 Multiplet. δ 4.3 (a) CH3 CH3 (a) (c) septet δ 2.6 singlet δ 2. δ 3.1 (5H) (e) The following IR assignments can be made. H (a) (c) H C CH2 (d) C H (b) (d) (a) (a) (c) (e) Doublet.4 quartet δ 2.1 Multiplet. C H stretching of CH CH2 group 2925 cm−1 and 2853 cm−1 . δ 7.8 or (b) Multiplet. C H bendings of CH CH2 group 740 cm−1 and 695 cm−1 . δ 5. C H stretching of CH2 group 1640 cm−1 .29 Compound L is allylbenzene.05 Meta substitution is indicated by the very strong peaks at 690 and 780 cm−1 in the IR spectrum.25 (b) singlet δ 2.P1: OXT/SRB JWDD052-14 P2: xxx JWDD052-Solomons-v2 Printer: Hamilton May 1. 3035 cm−1 . C C stretching 990 cm−1 and 915 cm−1 . δ 5.

2 Singlet δ 3. We can make the following assignments in the 1 H NMR spectrum: (a) (b) (c) (d) C6 H5 CH CH OCH3 (a) (b) (c) (d) Multiplet δ 7.6 8 7 4.8 4 δH (ppm) 3 2 1 0 . 14. Putting these pieces together in the only way possible gives us the following structure for Y.6 Doublet δ 6. The upfield signal at δ 2. and the two bands at 720 and 770 cm−1 suggest a monosubstituted benzene ring.9 and 7. C9H12O (c) CH (b) CH2 (a) CH3 (a) OH (d) (e) (b) (e) (c) (d) TMS 4.1–7.6 0. OH Y.3 arises from the two equivalent methyl groups. There is a complex multiplet at δ 1. The 1 H NMR spectrum also shows a triplet at δ 0.9 0.4 6 1.P1: OXT/SRB JWDD052-14 280 P2: xxx JWDD052-Solomons-v2 Printer: Hamilton May 1.1–7. this is confirmed by the strong peaks at ∼ 690 and ∼ 770 cm−1 in the IR spectrum. The downfield signals at δ 6.5 (1H). The presence of these groups is also indicated by the peaks at δ 4.4 and δ 7.7 14. The absence of absorption peaks due to O H or C O stretching in the IR spectrum of N suggests that the oxygen atom is present as part of an ether linkage.85 indicating a CH3 group coupled with an adjacent CH2 group. The (5H) 1 H NMR multiplet between δ 7.6 strongly suggests the presence of a monosubstituted benzene ring. Meta substitution is indicated by the strong IR peak at 680 cm−1 and very strong IR peak at 760 cm−1 .33 The broad IR peak at 3400 cm−1 indicates a hydroxy group.8 5 1.2 in the 1 H NMR spectrum.32 Compound X is meta-xylene.1 arise from the protons of the benzene ring.7 and there is also a triplet at δ 4.1 Doublet δ 5.31 Compound N is C6 H5 CH CHOCH3 . 2007 14:10 AROMATIC COMPOUNDS 14.

36 Ph Ph O Ph t-Bu + Ph Ph A 14. and C O groups.34 (a) Four unsplit signals.P1: OXT/SRB JWDD052-14 P2: xxx JWDD052-Solomons-v2 Printer: Hamilton May 1. (d) CH3 (a) CH3 O N N O (b) H N N CH3 (c) (b) Absorptions arising from: C H. CH3 . 2007 14:10 AROMATIC COMPOUNDS 281 14. Challenge Problems 14.37 − Na+ Ph Br− B Fe C D (a “sandwich compound”) 5.0 .0 δH (ppm) 14.35 The vinylic protons of p-chlorostyrene should give a spectrum approximately like the following: Jbc (c) (a) (b) Jac Jac Jbc Jab Jab Jbc 7.0 6.

39 Third unoccupied π MO (five nodal planes) Second unoccupied π MO (four nodal planes) First unoccupied π MO (three nodal planes) Highest energy occupied π MO (two nodal planes) Second highest energy occupied π MO (one nodal plane) Lowest energy occupied π MO (no nodal planes) QUIZ 14.1 Which of the following reactions is inconsistent with the assertion that benzene is aromatic? (a) Br2/CCl 4 /25°C (b) H 2 /Pt/25°C (c) Br2/FeBr3 (d) KMnO4 /H 2O/25°C (e) None of the above no reaction no reaction C6H5Br + HBr no reaction .38 Ph C C C C Ph 14.P1: OXT/SRB JWDD052-14 282 P2: xxx JWDD052-Solomons-v2 Printer: Hamilton May 1. 2007 14:10 AROMATIC COMPOUNDS 14.

14. 14.P1: OXT/SRB JWDD052-14 P2: xxx JWDD052-Solomons-v2 Printer: Hamilton May 1. 2007 14:10 AROMATIC COMPOUNDS 283 14. .5 Give the structure of a compound with the formula C7 H7 Cl that is capable of undergoing both SN 1 and SN 2 reactions.4 Which of the following molecules or ions is not aromatic according to H¨uckel’s rule? (a) (b) (c) (d) + (e) All are aromatic.2 Which is the correct name of the compound shown? NO2 CH3 Cl (a) 3-Chloro-5-nitrotoluene (b) m-Chloro-m-nitrotoluene (c) l-Chloro-3-nitro-5-toluene (d) m-Chloromethylnitrobenzene (e) More than one of these 14.6 Write the name of an aromatic compound that is isomeric with naphthalene.3 Which is the correct name of the compound shown? OH F (a) 2-Fluoro-1-hydroxyphenylbenzene (b) 2-Fluoro-4-phenylphenol (c) m-Fluoro-p-hydroxybiphenyl (d) o-Fluoro-p-phenylphenol (e) More than one of these 14.