Chapter 15Benzene and Aromaticity

SHORT ANSWER

Drawing Instructions: Draw structures corresponding to the given names.

1. Draw: m-fluoronitrobenzene

ANS:

2. Draw: p-bromoaniline

ANS:

3. Draw: o-chlorophenol

ANS:

4. Draw: 3,5-dimethylbenzoic acid

ANS:

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Benzene and Aromaticity

5. Draw: p-chlorobenzaldehyde

ANS:

6. Draw: 1-phenyl-3-methylpentane

ANS:

IUPAC Naming Instructions: Provide proper IUPAC names.

7. Name:

ANS:
m-nitrotoluene or 1-methyl-3-nitrobenzene

8. Name:

ANS:
(1-methylethyl) benzene or isopropylbenzene or cumene

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 Chapter 15

9. Name:

ANS:
1-((1S, 3R)-3-methylcyclohexyl)benzene

10. Name:

ANS:
1-methyl-2,4-benzenediamine or 2,4-diaminotoluene

11. Name:

ANS:
(E)-2,3-diphenyl-2-hexene

Exhibit 15-1
For each molecule below, predict whether the molecule would be expected to show aromatic
character or not. Explain your answer in each case.

12.

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Benzene and Aromaticity

ANS:
To meet the criterion of a cyclic, planar, conjugated molecule, the oxygen and the nitrogen bearing
the hydrogen must both be sp2-hybridized. If this occurs, both heteroatoms contribute two
electrons each to the pi system. This results in a total of eight pi electrons, which is not aromatic
according to the Hckel (4n + 2) Rule.

13.

ANS:
The carbocation is sp2-hybridized, so if the oxygen is also sp2-hybridized then each atom in the
cycle has a conjugated p-orbital. Each double bond contributes two pi electrons and the oxygen
contributes two pi electrons, for a total of six pi electrons in the conjugated system. Therefore, this
species is predicted to show aromatic character.

14.

ANS:
This compound, [16]annulene, appears to be a cyclic, planar, conjugated molecule with 16 pi
electrons. However, 16 is not a Hckel number, so the compound is probably not planar, and is not
aromatic.

15.

ANS:
This compound has a pyridine-like nitrogen, which is sp2-hybridized and has its lone pair of
electrons in the plane of the ring. If oxygen is also sp2-hybridized, then it contributes two pi
electrons to the cyclic, conjugated pi system for a total of six -electrons. Therefore, this molecule
is predicted to show aromatic character.

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 Chapter 15

Exhibit 15-2
Answer the following question(s) concerning sulfathiazole, below.

16. Refer to Exhibit 15-2. What is the hybridization of the nitrogen atom in sulfathiazole?

ANS:
The hybridization of the nitrogen atom is sp2 in sulfathiazole.

17. Refer to Exhibit 15-2. Assuming that the sulfur atom is sp2-hybridized, how many -
electrons are there in the sulfathiazole ring?

ANS:
There are six -electrons in the sulfathiazole ring.

18. Refer to Exhibit 15-2. What reactivity do you predict for sulfathiazole?

ANS:
Sulfathiazole is predicted to have aromatic reactivity since it is cyclic, planar, conjugated and has
six -electrons.

PTS: 1

Exhibit 15-3
Refer to the data below to answer the following question(s).

The 1H NMR spectrum of [14]annulene at 60C shows two signals, one at 0 ppm and one at 7.6
ppm, with an area ratio of 5:2.

19. Refer to Exhibit 15-3. Is [14]annulene aromatic?

ANS:
[14]annulene contains a cyclic, conjugated pi system with 14 pi electrons (14 = 4n + 2; n = 3). It is
difficult to predict, however, if the molecule is planar without making a model. The 1H NMR
signal at 7.6 ppm is consistent with the presence of a ring current, which is characteristic of
aromatic molecules. Thus, [14]annulene is aromatic.

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Benzene and Aromaticity

20. Refer to Exhibit 15-3. Draw in the protons on the [14]annulene skeleton provided below
which are responsible for the 1H NMR signal at 0 ppm.

ANS:

21. Refer to Exhibit 15-3. Explain why these protons have absorption at such high fields.

ANS:
When an aromatic ring is oriented perpendicularly to a strong magnetic field the induced ring
current deshields protons outside the ring and shields protons inside the ring. Thus, the protons
inside the ring absorb at a field higher than normal (0 ppm versus 4.56.5 ppm).

Exhibit 15-4
Consider the data below to answer the following question(s).

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 Chapter 15

22. Refer to Exhibit 15-4. Conjugate bases QB and ZB are both resonance stabilized. Draw the
indicated number of resonance forms for QB and ZB.

ANS:

23. Refer to Exhibit 15-4. Which of the compounds above, Q or Z, would you predict to be most
acidic? Explain your answer.

ANS:
The conjugate bases of Compounds Q and Z are both resonance stabilized. Let's examine all
resonance structures for both conjugate bases:

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Benzene and Aromaticity

For the conjugate base QB the negative charge is delocalized into the ring. This generates a
cyclopentadienyl anion that is aromatic. For the conjugate base ZB, the negative charge is
delocalized by resonance but no aromatic ions result. Therefore, Compound Q should be the most
acidic, since its anion is the most stable.

24. Most alkyl halides are nonpolar covalent compounds and, therefore, are soluble in nonpolar
solvents and insoluble in water. Cycloheptatrienyl bromide is an unusual alkyl halide in that
it is insoluble in nonpolar solvents, but is readily soluble in water! This behavior is
consistent with cycloheptatrienyl bromide being an ionic compound. Why does
cycloheptatrienyl bromide exist as an ionic compound? Explain by comparing the covalent
structure to the ionic structure.

ANS:
In the covalent structure, the carbon bonded to the bromine is sp3-hybridized, so the ring cannot be
aromatic. In the ionic structure, the carbocation is sp2-hybridized, so the structure is a cyclic,
conjugated, six -electron system and aromatic.

Exhibit 15-5
Consider the data below to answer the following question(s).

C9H12; 1H NMR: 7.18 (broad singlet, 5H)

2.55 (triplet, 2H)
1.70 (sextet, 2H)
0.9 (triplet, 3H)

25. Refer to Exhibit 15-5. Describe the signal at 7.18 in terms of its splitting, integration and
chemical shift.

ANS:
The integration of the signal at 7.18 indicates that there are five hydrogens that are more or less
equivalent (broad singlet); the chemical shift indicates that these five hydrogens are aromatic. This
is typical for a monosubstituted benzene.

26. Refer to Exhibit 15-5. Describe the signal at 2.55 in terms of its splitting, integration, and
chemical shift.

ANS:
The integration of the signal at 2.55 indicates that it is two hydrogens that are split (triplet) by
two adjacent hydrogens, or a CH2 next to a CH2. The chemical shift indicates that this CH2
could be next to an aromatic ring.

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 Chapter 15

27. Refer to Exhibit 15-5. Describe the signal at 1.70 in terms of its splitting, integration and
chemical shift.

ANS:
The integration of the signal at 1.70 indicates that it is two hydrogens split by five adjacent
hydrogens (sextet); most probably a CH2 between a CH2 and a CH3. Its chemical shift
indicates that there is some electronegative group causing some deshielding to occur.

28. Refer to Exhibit 15-5. Describe the signal at 0.9 in terms of its splitting, integration and
chemical shift.

ANS:
The integration of the signal at 0.9 indicates that it is three hydrogens split by two adjacent
hydrogens (triplet) or a CH3 next to a CH2. Its chemical shift is in the normal range for a
methyl group.

29. Refer to Exhibit 15-5. Propose a structure for this compound.

ANS:

Exhibit 15-6
Consider the data below to answer the following question(s).

C9H12; 1H NMR: 6.65 (singlet, 3H)

2.25 (singlet, 9H)

30. Refer to Exhibit 15-6. Describe the signal at 6.65 in terms of its splitting, integration and
chemical shift.

ANS:
The signal at 6.65 indicates that it is 3 equivalent hydrogens in the aromatic region of the
spectrum. This could be a 1,3,5-trisubstituted compound.

31. Refer to Exhibit 15-6. Describe the signal at 2.25 in terms of its splitting, integration and
chemical shift.

ANS:
The signal at 2.25 indicates that it is nine equivalent hydrogens attached to an aromatic ring;
probably three CH3 groups.

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Benzene and Aromaticity

32. Refer to Exhibit 15-6. Propose a structure for this compound.

ANS:

33. What is the structure of a hydrocarbon that shows a molecular ion at m/z = 182 in the mass
spectrum and has the following 1H NMR spectrum?

7.2 , singlet, 5H
2.9 , singlet, 2H

ANS:
The molecular weight of the hydrocarbon corresponds to the formula C14H14, which indicates eight
double bonds and/or rings. Since the ratio of protons in the 1H NMR is 5:2, there must be 10
aromatic and 4 aliphatic protons. There must be two equivalently substituted phenyl rings, which
accounts for 12 carbons. Since all aliphatic protons are equivalent, and we need two more carbons
to complete the structure, the compound must be 1,2-diphenylethane.

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 Chapter 15

Exhibit 15-7
Consider the data below to answer the following question(s).

C7H7ClO; IR absorption at 810 cm1

Spectrum obtained from: SDBSWeb: http://www.aist.go.jp/RIODB/SDBS/

34. Refer to Exhibit 15-7. Calculate the degrees of unsaturation for this compound.

ANS:
The formula C7H7ClO corresponds to a base formula of C7H8. A saturated formula is C7H16 so
there are (16 8) 2 = 4 degrees of unsaturation.

35. Refer to Exhibit 15-7. What is the significance of an IR absorption at 810 cm1?

ANS:
An IR absorption at 810 cm1 indicates a p-disubstituted aromatic ring.

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Benzene and Aromaticity

36. Refer to Exhibit 15-7. Describe the signal at 3.7 in terms of its splitting, integration and
chemical shift.

ANS:
The signal at 3.7 indicates that there are three hydrogens next to zero hydrogens (singlet) shifted
by attachment to an electronegative atom like oxygen; probably an OCH3.

37. Refer to Exhibit 15-7. Propose a structure for this compound.

ANS:

38. Give the IUPAC name for:

ANS:
2-bromotoluene or o-bromotoluene

39. Draw a picture of the orbitals in furan (shown below). Is furan aromatic?

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 Chapter 15

ANS:

Furan is a planar ring and is conjugated. Furan has 6 electrons as shown above. The additional
electron pair of the oxygen atom is not part of aromatic system.

4n + 2 = 4(1) + 2 = 6

Furan is aromatic.

40. Draw the MO energy diagram for the cycloheptatrienyl anion and classify the anion as
aromatic or antiaromatic.

ANS:

4n (8) electrons: antiaromatic

41. Draw the resonance structures of cyclooctatetraene.

ANS:

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Benzene and Aromaticity

42. Explain in terms of MO theory, why systems with 4n + 2 electrons are aromatic and with
4n electrons are antiaromatic.

ANS:
Aromatic compounds exhibit greater than expected stability. Antiaromatic compounds are
less stable. If the MO energy diagram of any 4n + 2 molecule is examined, the electrons all
occupy low energy bonding molecular orbitals. This has a net stabilizing effect. Antiaromatic
compounds have some of electrons occupying higher energy antibonding molecular orbitals.
Conversely, this has a net destabilizing effect.

MULTIPLE CHOICE

1. Consider the following compound. Atoms other than carbon and hydrogen are labeled.

Which of the following is not valid?

a. parent compound in naming, benzene.
b. 1,4-disubstitution is present.
c. para prefix applicable
d. classified as aromatic
ANS: A

2. How many monosubstituted products would you expect for the bromination of naphthalene?
a. 2 c. 6
b. 4 d. 8
ANS: A

3. Which region of an IR spectrum provides information about the substitution pattern of

aromatic compounds?
a. 3030 cm-1
b. 1660 - 2000 cm-1
c. 1450 - 1600 cm-1
d. 690 - 840 cm-1
e. b and d
f. All of the above can be used.
ANS: E

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 Chapter 15

4. Which of the following does not correctly characterize this compound represented by the
molecular model shown below? Atoms other than carbon and hydrogen are labeled.

a. slightly acidic
b. named as m-isopropylphenol
c. contains aryl, alkyl and benzylic proton
d. would produce a signal due to dehydration in a mass spectrum
e. All of the above characterize this compound.
ANS: D

5. Which of the following is NSAIDs were developed to selectively block the COX-2 enzyme?
a.

b.

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Benzene and Aromaticity

c.

d.

e.
both a and b
f. both c and d
g. a, b, c, and d
ANS: F

6. Which of the following NSAIDs would not produce a peak for benzylic protons in an
1
HNMR spectrum?
a.

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 Chapter 15

b.

c.

d.

e.
both a and b
f. both c and d
g. a, b, c, and d
ANS: F

7. Which of the following aromatic compounds will have largest number of signals in a
13
CNMR?
a. 1,4-dimethylbenzene (p-cresol)
b. 1,3,5-trimethylbenzene (mesitylene)
c. 1,2,4,5-tetramethylbenzene
d. All produce the same number of signals.
ANS: D

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Benzene and Aromaticity

8. What m/z ratio range might be common to many substituted benzene compounds?
a. 72 - 77 ppm c. 81 - 88 ppm
b. 26 - 38 ppm d. less than 59 ppm
ANS: A

9. Which of the choices arranges numbered protons in the following substance in order of
increasing downfield chemical shift in a proton NMR? Atoms other than carbon and
hydrogen are labeled.

a. 1 = 2 < 3 < 4 c. 4 = 3 < 2 =1

b. 4 < 3 < 2 = 1 d. 1 = 2 < 4 < 3
ANS: A

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