CHEM 2425. Chapter 15.

Benzene and Aromaticity (homework) W

Short Answer

Drawing Instructions: Draw structures corresponding to the given names.

1. Draw: m-fluoronitrobenzene

2. Draw: p-bromoaniline

3. Draw: 3,5-dimethylbenzoic acid

4. Draw: p-chlorobenzaldehyde

5. Draw: 1-phenyl-3-methylpentane

IUPAC Naming Instructions: Provide proper IUPAC names.

6. Name:

7. Name:

8. Name:

9. Name:

1 CHEM 2425. Chapter 15. Benzene and Aromaticity (homework) W

10. Name:

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.

11.

12.

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

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

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

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

2 CHEM 2425. Chapter 15. Benzene and Aromaticity (homework) W

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

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

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

16. 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.

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

3 CHEM 2425. Chapter 15. Benzene and Aromaticity (homework) W

18. 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.

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)

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

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

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

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

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

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

C9H12; 1H NMR: 6.65  (singlet, 3H)

2.25  (singlet, 9H)

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

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

C7H7ClO; IR absorption at 810 cm1

4 CHEM 2425. Chapter 15. Benzene and Aromaticity (homework) W

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

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

26. Refer to Exhibit 15-7. What is the significance of an IR absorption at 810 cm1?

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

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

29. Draw the resonance structures of cyclooctatetraene.

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

5 CHEM 2425. Chapter 15. Benzene and Aromaticity (homework) W

CHEM 2425. Chapter 15. Benzene and Aromaticity (homework) W

Answer Section
SHORT ANSWER

1. ANS:

PTS: 1
2. ANS:

PTS: 1
3. ANS:

PTS: 1
4. ANS:

PTS: 1
5. ANS:

PTS: 1
6. ANS:

6 CHEM 2425. Chapter 15. Benzene and Aromaticity (homework) W

 m-nitrotoluene or 1-methyl-3-nitrobenzene

PTS: 1
7. ANS:
(1-methylethyl) benzene or isopropylbenzene or cumene

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

PTS: 1
9. ANS:
1-methyl-2,4-benzenediamine or 2,4-diaminotoluene

PTS: 1
10. ANS:
(E)-2,3-diphenyl-2-hexene

PTS: 1
11. ANS:
This compound, [16]annulene, appears to be a cyclic, planar, conjugated molecule with 16 pi electrons.
However, 16 is not a Hückel number, so the compound is probably not planar, and is not aromatic.

PTS: 1
12. 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.

PTS: 1
13. ANS:
There are six -electrons in the sulfathiazole ring.

PTS: 1
14. 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.

PTS: 1
15. 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 4.56.5 ppm).

PTS: 1

7 CHEM 2425. Chapter 15. Benzene and Aromaticity (homework) W

16. ANS:

PTS: 1
17. ANS:
The conjugate bases of Compounds Q and Z are both resonance stabilized. Let's examine all resonance
structures for both conjugate bases:

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.

PTS: 1
18. 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.

PTS: 1
19. 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.

PTS: 1

8 CHEM 2425. Chapter 15. Benzene and Aromaticity (homework) W

20. 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.

PTS: 1
21. 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.

PTS: 1
22. 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.

PTS: 1
23. ANS:

PTS: 1
24. 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.

PTS: 1
25. 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.

PTS: 1
26. ANS:
An IR absorption at 810 cm1 indicates a p-disubstituted aromatic ring.

PTS: 1
27. ANS:

PTS: 1
28. ANS:

9 CHEM 2425. Chapter 15. Benzene and Aromaticity (homework) W

 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.

PTS: 1
29. ANS:

PTS: 1
30. 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.

PTS: 1

10 CHEM 2425. Chapter 15. Benzene and Aromaticity (homework) W