CHEM 242 Quiz No.

1 February 9, 1994

1. Which statement best expresses Hückel’s rule?

A. Among planar, monocyclic, completely conjugated polyenes, only those that have (2n + 4) π
electrons are aromatic.
B. Among planar, monocyclic, completely conjugated polyenes, only those that have (4n + 2) π
electrons are aromatic.
C. Only planar, monocyclic, completely conjugated polyenes that have (4n + 2) π electrons are aromatic.
D. Only planar, monocyclic, completely conjugated polyenes that have (2n + 4) π electrons are aromatic.
E. Only completely conjugated polyenes that have 6n π electrons are aromatic.

2. All of the hydrocarbons shown are very weak acids. One, however, is far more acidic than the others. Which
one is strongest acid?

A. B. C. D. E.

3. Which one of the following is best classified as a heterocyclic aromatic compound?

H N
N N
NH2
N

A. B. C. D. E.

4. Which one of the following would be expected to undergo nucleophilic substitution via a carbocation
intermediate (SN1) at the fastest rate?

Br Br
H

H Br H Br Br
A. B. C. D. E.

5. Which one of the following undergoes nucleophilic aromatic substitution at the fastest rate?
Cl Cl Cl Cl Cl

NO2 Cl CH3 OCH3 N(CH3)2

A. B. C. D. E.

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CHEM 242 Quiz No. 1 February 9, 1994

6. All of the following substituents are deactivating; some more than others. Only one of the substituents,
however, is a meta directing group. Which one?

A . —Cl B . —F C . —CH2Cl D . —CHCl2 E . —CCl3

7. Only one of the following undergoes bromination of its aromatic ring with Br2 without the necessity of adding
FeBr 3 as a catalyst. Which one?
CH3 Cl CH3 Cl Cl

N(CH3)2 NO2 NO2 Cl CH3

A. B. C. D. E.

8. Which one of the following statements concerning a cyano group (—C≡N) as a substituent directly attached
to an aromatic ring or a carbon-carbon double bond is t r u e?

A. activates an aromatic ring toward electrophilic aromatic substitution;

increases dienophilic reactivity of C=C double bond

B. activates an aromatic ring toward electrophilic aromatic substitution;

decreases dienophilic reactivity of C=C double bond

C. deactivates an aromatic ring toward electrophilic aromatic substitution;

decreases dienophilic reactivity of C=C double bond

D. deactivates an aromatic ring toward electrophilic aromatic substitution;

increases dienophilic reactivity of C=C double bond

E. not a valid answer

9. Which one of the following gives an aromatic substitution product with 1-chloro-2,4-dinitrobenzene at the
fastest rate at 25 °C?

A. CH3CCl in the presence of AlCl 3 D . Anisole (C6H5OCH3) in the presence of AlCl3

B. (CH3)3CCl in the presence of AlCl3 E . NaOCH3 in methanol

C. (CH3)2C=CH2 in the presence of H2SO 4

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CHEM 242 Quiz No. 1 February 9, 1994

1 0 . What is the major product of the following reaction?

HNO3
CH3O CH2
H2SO 4

O2N O2N

CH3O CH2 CH3O CH2

A. D.

NO2 NO2

CH3O CH2 CH3O CH2

B. E.

CH3O CH2 NO2

C.

1 1 . What is the major product of the following reaction? (Only answers A, B, and C are valid.)

O
HNO3
CH3C CH2
H2SO 4

O2N NO2
O O

CH3C CH2 CH3C CH2

A. B.

CH3C CH2 NO2

C.

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CHEM 242 Quiz No. 1 February 9, 1994

1 2 . The figure shown is a dotted line representation of the hybrid of resonance structures written for the
carbocation formed by adding a proton to benzene. What is the distribution of charge among the numbered
ring carbons predicted on the basis of a resonance argument?

Carbon 1 Carbon 2 Carbon 3 Carbon 4 Carbon 5 Carbon 6 H H

A. +0.17 +0.17 +0.17 +0.17 +0.17 +0.17 H 5 1 H

6
B. +0.20 +0.20 +0.20 +0.20 +0.20 0
+
C. 0 +0.25 0 +0.25 0 +0.50
H 4 2 H
3
D. +0.33 0 +0.33 0 +0.33 0
H
E. 0 +0.50 0 +0.50 0 0

1 3 . What is the best choice of alkyl halide RX in a Friedel-Crafts alkylation:

AlCl3
ArH + RX ArR + HX

in order to ensure that the group R in the product is structurally identical to R in RX?

A. CH3CH2CH2CH2Cl C. CH3CH=CHCH2Cl E. CH2Cl

B. (CH3)3CCH2Cl D. CH2=CHCH2CH2Cl

+ –
1 4 . The Lewis structure shown at the right represents the rate-determining
H3N Cl O
intermediate of a certain reaction. What are the most reasonable reactants? +
H N
O
A. Chlorobenzene and NH4NO3 –

B. 1-Chloro-2-nitrobenzene + NH3 H H
C. 1-Chloro-2-nitrobenzene + NaNH 2 H
D. 2-Nitroaniline and NaCl
E. 2-Nitroaniline, Cl2, and FeCl3

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CHEM 242 Quiz No. 1 February 9, 1994

1 5 . Which one of the following is a practical synthesis of CH3 O

2-methyl-5-tert-butylacetophenone, the structure of which is shown at the right?
CCH3
A. Treat toluene with tert-butyl chloride and aluminum chloride, followed by reaction of
O O
the product with acetic anhydride ( CH3COCCH3 ) and aluminum chloride.
C(CH3)3
O

B. Treat toluene with acetyl chloride ( CH3CCl ) and aluminum chloride, followed by
reaction of the product with tert-butyl chloride and aluminum chloride.
O

C. Treat tert-butylbenzene with acetyl chloride ( CH3CCl ) and aluminum chloride, followed by reaction of the
product with methyl chloride and aluminum chloride.

D. Treat acetophenone with tert-butyl chloride and aluminum chloride, followed by reaction of the product with
methyl chloride and aluminum chloride.

E. Treat acetophenone with methyl chloride and aluminum chloride, followed by reaction of the product with
tert-butyl chloride and aluminum chloride.

1 5 . Which one of the following is the best synthesis of 2-chloro-4-nitrobenzoic acid, the CO2H

structure of which is shown at the right? Cl

A. 1. Heat benzoic acid with HNO3, H2SO 4;

2. Cl2, FeCl3, heat
NO2
B. 1. Treat toluene with with HNO3, H2SO 4;
2. K2Cr2O7, H2O, H2SO 4, heat
3. Cl2, FeCl3, heat

C. 1. Treat toluene with with HNO3, H2SO 4;

2. Cl2, FeCl3, heat
3. K2Cr2O7, H2O, H2SO 4, heat

D. 1. Treat nitrobenzene with Cl2, FeCl3, heat;

2. CH3Cl, AlCl3
3. K2Cr2O7, H2O, H2SO 4, heat

E. 1. Treat chlorobenzene with with HNO3, H2SO 4;

2. CH3Cl, AlCl3
3. K2Cr2O7, H2O, H2SO 4, heat

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CHEM 242 Quiz No. 1 February 9, 1994

1 7 . Which one of the following has the greatest number of signals in its 13C NMR spectrum? (Spectrum run
under conditions where splitting due to 13C-1H coupling is not observed.)

A . hexane C . 1-hexene E . 1,5-hexadiene

B . 2-methylpentane D . cis-3-hexene

1 8 . Which one of the hydrocarbons in problem #17 gives a 13C NMR spectrum in which none of the carbon
signals appear as a quartet when the spectrum is run under conditions where 13C-H splitting is observed?

1 9 . Which one of the following has the fewest number of signals in its 13C NMR spectrum? (Spectrum run
under conditions where splitting due to 13C-1H coupling is not observed.)

A . 1-chloro-4-nitrobenzene C . 1-chloro-2-nitrobenzene E . 1,3-dichloro-5-nitrobenzene

B . 1,4-dichlorobenzene D . 1,2-dichlorobenzene

2 0 . Which one of the compounds in problem #19 gives a 13C NMR spectrum in there are six peaks? (Spectrum
run under conditions where splitting due to 13C-1H coupling is not observed.)

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CHEM 242 Quiz No. 1 February 9, 1994

KEY TO QUIZ NO. 1

1. B 6. E 11. C 16. C
2. C 7. A 12. D 17. C
3. D 8. D 13. E 18. E
4. C 9. E 14. B 19. B
5. A 10. D 15. A 20. C

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Quiz No.

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