Answer Key

Department of Chemistry
SUNY/Oneonta
Chem 322 - Organic Chemistry II
Examination #1 - February 12, 2001
INSTRUCTIONS
This examination has two parts. Part I is in multiple choice format and the
answers should be placed on the "Test Scoring Answer Sheet" which must be turned
in and will be machine graded.
Part II requires your responding to questions by writing answers into the
spaces provided in this booklet. This Exam Booklet must be handed in and will be
returned to you with a grade. Write your name in the space above NOW.
On the Test Scoring Answer Sheet, using a soft pencil, enter the following data
(in the appropriate places): your name, instructor's name, your student (Social
Security) number, course number (30032201) and the test number (01); darken the
appropriate bubbles under the entries, making dark black marks which fill the
bubbles.
You may use a set of molecular models but no other aids during the exam.
Answer all questions. The questions on Part I are worth 2 points each.
You have 90 minutes. Good luck!

February 12, 2001

1.

Chem 322 - Exam #1

Page 2 of 15

Methylbenzene is also known as

(a) phenol. (b) xylene. (c) naphthalene. (d) anthracene. (e) toluene.

2.

Hydroxybenzene, Ph-OH, is also known as

(a) phenol. (b) xylene. (c) naphthalene. (d) anthracene. (e) toluene.

3.

Consider chlorobenzene shown to the right. The ring positions 1, 2, 3

are called, respectively
(a) meta, ortho, para. (b) ortho, meta, para. (c) para, meta, ortho.
(d) ortho, para, meta. (e) para, ortho, meta,. (f) meta, para, ortho.

4.

Cl

chlorobenzene

Which of the following formulas can be used to calculate the number of of -electrons
that would be found delocalized in conjugated monocyclic rings that are aromatic?
[n = 0, 1, 2, 3, ...]
(a) 2n, (b) 2n+2, (c) 2n+4, (d) 4n+2, (e) 6n

5.

Which of the following skeletal structures is an accurate and complete representation of

benzene?

(a)

(b)

(c)

(d)

(e) None of the above structures accurately

represents benzene.
6.

The compound shown to the right is known as prismane or Ladenburg benzene. What
relationship does this compound bear to benzene?
(a) It is a (poor) resonance structure of benzene.
(b) It is an enantiomer of benzene.
(c) It is a diastereomer of benzene.
(d) It is a constitutional (structural) isomer of benzene.
(e) It bears no relationship to benzene.

February 12, 2001

7.

Chem 322 - Exam #1

Page 3 of 15

Which of the following characteristics is not associated with aromaticity?

(a) downfield shift of protons in the NMR spectrum owing to a "ring current",
(b) ring undergoes electrophilic addition,
(c) ring undergoes electrophilic substitution,
(d) there are no sp3 hybridized atoms in the ring,
(e) stability

8.

Which of the following is a representation of the energy levels and electron occupancy of
molecular orbitals in benzene? Energy increases in the upward direction in the diagram,
so bonding orbitals are below the non-bonding level and anti-bonding orbitals are above
the non-bonding level.

non-bonding
level

(a)

(b)

(c)

(d)

(e) none of the above

9.

According to simple Huckel theory, which of the following rings should not be aromatic?

Note: In these structures, each carbon holds one hydrogen.

(a)
10.

(b)

(c)

(d)

Which of the following is not a valid resonance structure for phenanthrene?

February 12, 2001

Chem 322 - Exam #1

(a)

11.

(b)

Page 4 of 15

(c)

(d)

Compound A, C8H10, yields three monobromo substitution products (one major, two
minor), C8H9Br, on reaction with bromine in the presence of iron. The proton NMR
spectrum of A shows a complex multiplet at = 7.0ppm and a singlet at = 2.3ppm.
Which of the following is the structure of A?
CH3

CH3

CH3

H3C

C2H5

CH3
CH3
(a)

12.

(c)

(d)

Which of the following compounds would most readily lose a proton (H+) to give a
carbanion on treatment with NaNH2 (ie which is most acidic)?
(a)

(d) CH 2

(c)

(b)
CH2

13.

(b)

CH2

CH2

(e)

CH 2

Which of the following compounds reacts most slowly with HNO3/H2SO4?

(a)

(b)
OCH 3

(c)
NH 3 Cl

OH

(d)

February 12, 2001

14.

Page 5 of 15

Which of the following compounds reacts most rapidly with HNO3/H2SO4?

(a)
SO3 H

15.

Chem 322 - Exam #1

(b)
CH3

(c)

(d)
OCH3

Chlorobenzene is reacted with an equimolar amount of nitric acid in the presence of

sulfuric acid. What is(are) the major product(s)?
Cl
HNO3
H2SO4

major product(s)

Cl

Cl

Cl

Cl
NO2

Cl
NO2

NO2

O2N

NO2

NO2

NO2
I

II

III

IV

(a) I, (b) II, (c) III, (d) IV, (e) V, (f) I, III, (g) no reaction takes place
16.
NO2
+ (CH 3)2CHCH 2Cl

NO2

NO2
II

AlCl 3
0o C

major product(s)

NO2

NO2
CH2CH(CH3)2

NO2
NO2

C(CH3)3

III
I

CH2CH(CH3) 2
CH2CH(CH3)2

VI
IV

C(CH3) 3

C(CH3)3

February 12, 2001

Chem 322 - Exam #1

Page 6 of 15

(a) I, III (b) II, (c) IV, VI, (d) V, (e) I, III, IV, VI, (f) II, V, (g) No reaction takes place.
17.

C(CH3) 3
CH3COCl
AlCl3
C(CH3)3

C(CH3) 3

major product
C(CH3) 3

C(CH3)3

CCH3

CCH3

CCH3
O
I

H3CC

CCH3
II

C(CH3) 3

CCH3

O
IV

III

CCH3
O
V

(a) I, (b) II, (c) III, (d) IV, (e) V, (f) no reaction
18.

Which positions in these molecules would be good sites for electrophilic substitution?
NH2
OCH3
(a) 1,3,4,5,6,7,8, (b) 2,6,8, (c) 1,3,5,7,
Br
5
4
(d) 2,4,5,8, (e) 1,2,3,4,5,6,7
1
6
8
2
Br
7
3

19.

Which products would actually form in the reaction

shown to the right?
(a) I, (b) II,
(c) III,
(d) I & II,
(e) I & III,
(f) I, II & III,
(g) There would be
no reaction.

CH3

CH3

CH3

CH3

OH
NaOH (aq)
300oC

OH

Br

OH
I

II

III

February 12, 2001

20.

Chem 322 - Exam #1

Page 7 of 15

Which of the following synthetic procedures would be likely to be successful in making pbromobenzoic acid from benzene?
(I) 1) Br2/Fe, 2) HCOOH/KOH.
(II) 1) Br2/Fe, 2) CH3Br/AlCl3, 3) KMnO4/heat.
(III) 1) HCOOH/KOH, 2) Br2/Fe.
(IV) 1) CH3Br/AlCl3, 2) Br2/Fe, 3) KMnO4/heat.
(V) 1) CH3Br/AlCl3, 2) KMnO4/heat, 3) Br2/Fe.
(a) I & II, (b) I & III, (c) II & IV, (d) III & IV, (e) V

21.

Rank the following compounds in order of decreasing reactivity toward electrophilic

substitution (most reactive first):
(I) chlorobenzene, (II) 4-nitrochlorobenzene, (III) 2,4-dinitrochlorobenzene,
(IV) 2,4,6-trinitrochlorobenzene.
(a) I > II > III > IV, (b) I > III > II > IV, (c) III > I > IV > II, (d) IV > III > II > I,
(e) none of the above answers

22.

Rank the following compounds in order of decreasing reactivity toward nucleophilic

substitution (most reactive first):
(I) chlorobenzene, (II) 4-nitrochlorobenzene, (III) 2,4-dinitrochlorobenzene,
(IV) 2,4,6-trinitrochlorobenzene.
(a) I > II > III > IV, (b) I > III > II > IV, (c) III > I > IV > II, (d) IV > III > II > I,
(e) none of the above answers

23.

Which point on the reaction diagram to the right

represents the transition state for the slow step in the
aromatic electrophilic substitution?

(b)

(d)
(c)

G
(a)

reaction progress

(e)

February 12, 2001

24.

Chem 322 - Exam #1

Page 8 of 15

Consider the four compounds shown below. Which of these compounds could not be
synthesized in good yield by carrying out a Friedel-Crafts alkylation on benzene?
I

II
CH2 CH 3

CH 3

III

CH 3

CH

CH 3

CH 3

CH 3

IV
CH 2 CH 2 CH 3

(a) I, (b) II, (c) III, (d) IV, (e) I&IV, (f) II&III, (g) II-IV
25.

Consider the four compounds shown in question #24. Which of these compounds could
not be synthesized in good yield by carrying out a Friedel-Crafts acylation on benzene,
followed by an appropriate reduction?
(a) I, (b) II, (c) III, (d) IV, (e) I&IV, (f) II&III, (g) II-IV

DIRECTIONS: Questions 26-28 are of the type where a statement is followed by an explanation:
<Statement> because <Reason>. For each of these questions select the correct response
from those immediately following:
(a) Both the statement and reason are correct and the reason justifies or explains the
statement.
(b) Both the statement and reason are correct but the reason does not justify or explain the
statement.
(c) The statement is false but the reason is true (although it does not apply to the
statement).
(d) The statement is true but the reason is false.
(e) Both the statement and reason are false.
26.

Benzene reacts much more rapidly than cyclohexene with Br2/FeBr3 because benzene has
aromatic stabilization. (c)

27.

Benzene tends to undergo electrophilic substitution reactions rather than electrophilic

addition reactions because electrophilic addition would produce a molecule that no
longer has a cyclic conjugated 6 electron aromatic system. (a)

28.

FeBr3 acts as a catalyst in the bromination of benzene because it reacts with bromine to
produce something like FeBr4+Br. (d)

February 12, 2001

29.

Chem 322 - Exam #1

Page 9 of 15

Which of the following resonance structures is least important to the stability of the
intermediate that is formed when aniline undergoes electrophilic attack in ring chlorination
at a position ortho to the NH2 group?
(a)

(b)

Cl

(c)

Cl

NH2

(d)

Cl

Cl

NH2

NH2

NH2

30.
Cl

OH
NO2
+ KOH

NO2

heat

NO2

NO2

The mechanism for the above reaction involves

(a) SN1 substitution of Cl by OH.
(b) SN2 substitution of Cl by OH.
(c) an elimination-addition sequence involving a substituted benzyne as an intermediate.
(d) nucleophilic attack by OH - at the chlorine-bearing carbon, resulting in the formation of
a carbanion that subsequently loses Cl-.
(e) electrophilic attack by OH - at the chlorine-bearing carbon, resulting in the formation of
a carbocation that subsequently loses Cl-.

February 12, 2001

31.

Chem 322 - Exam #1

Page 10 of 15

Which method is most satisfactory for the conversion of 2-butene into 1-butanol?
(a) Reaction with water and sulfuric acid.
(b) Reaction with water and H3BO3.
(c) Reaction with B2H6, then reaction with hydrogen peroxide and potassium hydroxide.
(d) Reaction with B2H6, heat the reaction mixture, then reaction with hydrogen peroxide
and potassium hydroxide.
(e) Reaction with Hg(OAc) 2/H2O, then NaBH4.

32.

Which of the following procedures could be used to prepare 1-phenyl-2-methyl-2-butanol?

O
(I)

CH 3CH 2COCH3

C6H 5MgBr

H2O
H3O+

C6H 5CH 2MgBr

H 2O
H 3O+

CH 3CH2 MgBr

H 2O
H 3O+

O
(II) CH 3CCH 2CH 3
O
(III) CH 3CCH 2C6H 5

CH3

(IV) CH 3CH 2CHMgBr

OH
CH3 CH2CCH2 C6H5

H 2O
H 3O+

C6H 5CH 2CH

(a) I&II, (b) II&III, (c) III&IV, (d) I&III, (e) I&IV, (f) II&IV
33.

What reagents would you use to bring about the following conversion?

CH3
CH 3CH2 C

CH3 OH

CH3
CH 3CH2 C

CH 2OH

CH3

(a) LiAlH4 in ether, then H3O+/H2O (b) CH3MgBr, then H3O+/H2O

(c) NaBH4, then H3O+/H2O (d) KMnO4/KOH, then H3O+/H2O
(e) Na, C2H5OH

CH3

February 12, 2001

34.

What reagents would you use

to bring about the reaction to
the right?

Chem 322 - Exam #1

O
O

OCH3

OCH3

Select the major product(s) of the following reaction.

CH3CH2 OH

+ Na

(a) CH3CH2O - Na + + H2 (b) CH3CH + NaH

O
(d) CH3 CH2OCH2 CH3 + NaOH + H2

36.

HO

(a) LiAlH4, then H2O/H3O+,

(b) NaBH4, then H2O/H3O+,
(c) NaH, then H2O/H3O+,
(d) PCC, then H2O/H3O+,
(e) LiAlH4, then PCC
35.

Page 11 of 15

(c) Na + -CH2 CH2OH + H2

(e) No reaction takes place.

Which product would be formed, after work up with dilute sulfuric acid, when an excess
of phenylmagnesium bromide, Ph-Mg-Br, reacts with methyl benzoate, PhCOOCH3?
(a) Ph3C-OH, (b) Ph2CH-OH, (c) Ph-CO-Ph, (d) Ph3CH,
(e) Bogus query! Phenylmagnesium does not react with esters.

37.

Which of the following procedures could be used to prepare a primary (1o) alcohol?
I: Reduction of an aldehyde. II: Reduction of a ketone. III: Reduction of a carboxylic
acid. IV: A Grignard synthesis using formaldehyde. V: A Grignard synthesis using an
aldehyde other than formaldehyde. VI: A Grignard synthesis using a ketone.
(a) I, III, IV, (b) II, IV, V, VI, (c) II, V, (d) I, IV, V,
(e) None of the above answers is correct.

February 12, 2001

38.

Chem 322 - Exam #1

Page 12 of 15

Which of the following functional groups cannot be present in a halogen-containing

compound you wish to react with magnesium to form a Grignard reagent?
I: -COOH, II: -COCH3, III: -NO2
(a) I, (b) II, (c) III, (d) I&II, (e) I&III, (f) II&III, (g) I - III,
(h) Yo! Bogus question! Any of those three groups could be present.

39.

Which of the following reagents would be most successful at converting 1-pentanol to

pentanal, CH3CH2CH2CH2CH=O?
(a) KMnO4, (b) CrO3/H2SO4, (c) Na 2CrO4/H2SO4, (d) C5H6NCrO3Cl (PCC)/CH2Cl2

40.

Which of the following alcohols would undergo acid catalyzed dehydration to give an
alkene most easily?
(a) methanol, (b) ethanol, (c) 2-propanol (isopropyl alcohol),
(d) 2-methyl-2-propanol (t-butyl alcohol)

41.

Which starting material would be appropriate for synthesizing p-methylphenol?

OH

o
1. NaOH, 300 C

2.

H 3O+
CH 3

(a)

NH2

CH3

(b)

NO2

CH 3

(c)

COOH

CH3

(d)

SO3 H

CH3

February 12, 2001

42.

Chem 322 - Exam #1

Page 13 of 15

Ubiquinones function within the mitochondria of cells to mediate the respiration process in
which electrons are transported from the biological agent NADH to molecular oxygen.
Although a complex series of steps is involved in the overall process, the ultimate result is
a cycle whereby NADH is converted to NAD+, oxygen is converted to water, and energy is
produced.
What are the chemical functions of the quinone and phenolic forms of the ubiquinones?
O
H3 CO

OH
CH3

H 3CO

CH 3

NADH + H+ +
H3 CO

O
ubiquinone,
quinone form

H 3CO

H 2O

phenolic form
O

CH3
R
OH

OH

H 3CO

CH3

1_
O +
2 2

H 3CO

NAD+

OH
H 3CO

H 3CO

R
O

(a) The quinone form is an oxidizing agent and the phenol form is a reducing agent.
(b) The phenol form is an oxidizing agent and the quinone form is a reducing agent.
(c) Both forms are oxidizing agents.
(d) Both forms are reducing agents.
(e) None of the above answers is correct.

February 12, 2001

Chem 322 - Exam #1

Page 14 of 15

Part II. Enter your answers in the space provided. If there is inadequate
room, continue on the back of the page and clearly indicate on the front of
the page that you have done this. Hand in this entire exam booklet when you
are finished; it will be returned to you with your grade. Make sure your name
is on the front sheet.
1.

Synthesis. Draw an outline for each of the following syntheses. More than one step
may be required. Show all materials and any special conditions employed as you write
the reactions which constitute your outline. Do not balance equations or show
mechanisms.
(a)
Starting with 1-phenylethanol, and using any other materials you need, synthesize
2-phenyl-2-propanol.
O

OH
CH CH3

OH

C CH3

CrO 3

1. CH3MgBr
+
2. H3 O

H3 O +

CH3

CH3

(b)
Starting with benzene, and using any other materials you need, synthesize
1-phenylethanol.

H3C

C Cl

C CH3

AlCl3

OH
1. NaBH4
+
2. H3O

CH CH3

February 12, 2001

2.

Chem 322 - Exam #1

Page 15 of 15

Mechanism.
Show the mechanism for the reaction shown below. Draw all important resonance
(a)
structures of the intermediate -complex and indicate which makes the greatest
contribution. Do not show transition states.

OH

Br2

OH

Br

OH

FeBr4OH + FeBr3
+ HCl

OH
FeBr4-

OH

Br

Br

Br

OH

FeBr4- Br+

Br2 + FeBr3
FeBr4- Br+ +

Br

FeBr3

H
Br

OH

February 12, 2001

Chem 322 - Exam #1

Page 16 of 15

(b) Testosterone is one of the most important male steroid hormones. When testosterone
is dehydrated by treatment with acid (Ouch!), rearrangement occurs to yield the product
shown. Propose a mechanism to account for this reaction. Show intermediates, not
transition states.

H3C

OH

H3C
CH3
O
H3C

H3O+
H3C

OH2
H

+ H3O+
O
+ H2 O

H3C

H2O

O
H3C

CH3
H

H
H3 C

H3 C
O