FACULTY OF SCIENCE

TERM TEST #2

ANSWERS

COURSE NAME Organic Chemistry

COURSE NUMBER CHEM 2120U

INSTRUCTOR J.W. Easton

DATE 2011-03-15

TIME 1.0 hour

INSTRUCTIONS TO STUDENTS
1. A complete test includes answers to:
 PART A………………………… 10 multiple-choice questions ………………..… 10 marks
 PART B………………………... 3 questions ……………….........………...........… 10
marks
 PART C................................ 3 questions ..................................................
10 marks

2. Multiple choice questions have one and only one answer. Answer each of the
questions by circling the letter (A,B,C,D,E) on the question booklet that represents
the correct answer.

3. Please keep the Booklet intact. Do not remove any pages from the Booklet. At the
conclusion
of the test, the complete Term Test Booklet and the Seating Arrangement Form
should be submitted.

4. Unless noted otherwise, all chemical structures should be in the condensed form
(CH3-,
-CH2-, etc) and should not be in skeletal form.

5. This is a closed book exam. Rough work can be done on the blank pages at the end
of the test.
 6. Calculators are not permitted nor required.

PART A - Multiple-choice Questions

(10 x 1 = 10 marks)
Answer the following questions by circling the letter (A,B,C,D,E) on the question booklet
that represents the correct answer.

1. Given the following compounds, arrange them in order of increasing acid strength (the
weakest acid is identified first and the strongest acid is identified last):

OH OH OH OH OH

NO2 CH3 Br
H O
I II III IV V

III, IV, V, II, I

IV, III, V, I, II
I, II, III, IV, V
V, II, I, III, IV
II, I, V, III, IV

Given the following compounds, which will react rapidly with bromine (Br2) at room temperature
in the dark?

NO2 NH2 OH

I II III IV V
I, III, V
II, IV
III, IV
I, II, III, IV, V
II, IV, V

2
3. Given the following compounds, which compounds will undergo electrophilic nitration more
rapidly than benzene?
O

O
CH3 N(CH3)2 NO2 SO3H

I II III IV V
VI

A. III, IV, VI
B. I, II, V
C. I, II, III, VI
D. II, IV, V
E. IV, V, VI

4. Given the following compounds, which compounds give meta substitution under
electrophilic bromination conditions?
O

O
CH3 N(CH3)2 NO2 SO3H

I II III IV V VI

A. III, IV, V
B. I, II, V
C. I, II, III, VI
D. III, IV, VI
E. IV, V

5. The first step in the acid-catalyzed hydrolysis of an ester is the addition of

an acid which increases the rate of the overall reaction by:

A. protonating the carbonyl-carbon atom thereby making the carbon atom

more susceptible to nucleophilic addition.
B. protonating the carbonyl-carbon atom thereby making the carbon atom
more susceptible to electrophilic addition.
C. protonating the carbonyl-oxygen atom thereby making the carbon
atom more susceptible to nucleophilic addition.
D. protonating the carbonyl-oxygen atom thereby making the carbon
atom more susceptible to elecphilic addition.
E. protonating the alkoxy-oxygen thereby making the alcohol part of the
ester easier to remove.

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 6. The compound below has two aromatic (benzene) rings. The two aromatic rings are
different and are labeled A and B. If an electrophilic substitution, such as bromination, is
carried out on each compound, from your knowledge of substituent effects, which of the two
rings would be preferentially attacked and what would be the orientation of the substituent?

O
B

A. Ring A; ortho/para substitution

B. Ring B; ortho/para substitution
C. Ring A; meta substitution
D. Ring B; meta substitution
E. Ring B; all sites

7. In the classic reaction of carbonyl compounds, a nucleophile (Z) adds to the carbonyl
carbon as shown below:
.. -
:O: : O:
k1
+ :Z
R Y R Y
k-1
Z
3
An sp hybridized carbon bonded to an oxygen atom as well as to two electronegative atoms
will be unstable. The result will be the following transformation:

A. The π-bond will reform and Y- will be preferentially eliminated if it is a

stronger base than Z-.
B. The π-bond will reform and Z- will be preferentially eliminated if it is a
stronger base than Y-.
C. The π-bond will reform and both Y- and Z- will be eliminated.
D. The π-bond will reform and neither Y- and Z- will be eliminated.
E. The π-bond will reform and Y- will be preferentially eliminated if it is a
weaker base than Z-.

8. In the acid-catalyzed formation of an ester, which of the following structures is an

intermediate in that reaction?

+
OH
OH
+
OH OH O
R OH
OH R
O
R + OH R' + R OH R C+ R'
I II III IV V

I
II
III
IV
V

4
 9. Given the following Diels-Alder reaction,

COOCH3
CH3

C
+ A
C
CH3
COOCH3
And given below a list of possible structures

H H3C H H3C H H CH3

H3C H3C H
COOCH3 COOCH3 COOCH3 COOCH3 COOCH3

COOCH3 COOCH3 COOCH3 COOCH3 COOCH3

H H3C H H3C H CH3 H
H3C H H3C
I II III IV V

the structure of Compound A is expected to be

I
II
III
IV
V

10.Ethyl benzoate can be prepared by the Fischer Esterification reaction as shown below by
using benzoic acid and ethyl alcohol. A small amount of sulfuric acid is added as a catalyst.
You are working for a company where it is desirable to have as high a yield of ethyl benzoate
as possible. However, the reaction is an equilibrium reaction and the overall yield of product
is somewhat determined by the value of the equilibrium constant, K.

O O

H2SO4
OH OCH2CH3 + H2O
+ CH3CH2 OH

However, the best way to achieve a high yield is by:

Adding more of the catalyst, H2SO4.

Adding an excess amount of ethyl alcohol.
Adding an excess amount of benzoic acid.
Adding an excess of ethyl alcohol; carrying out the reaction at less than 100oC
Adding an excess of ethyl alcohol; carrying out the reaction at greater than 100oC

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PART B – Mechanisms and Related Questions
(10 marks)
Answer the following three (3) questions. Your answers should be brief and should be specific.

QUESTION B1 (4
marks)
Show all the steps in the mechanism for the electrophilic aromatic substitution reaction given
below:

CCH2CH3
O
AlCl3
+ C
CH3CH2 Cl

Clearly and completely, write each of steps in the boxes below.

STEP 1
: O:

C .. ..
+ AlCl3 CH3CH2C O: + -AlCl
CH3CH2 Cl : 4

.. +

STEP 2
O

+ CCH2CH3
..
H
+ CH3CH2C O:
+

STEP 3

6
 O
O

CCH2CH3
+ CCH2CH3

H + HB+

:B

.. ..
Base could be H2O: H3O: +
.. ..

7
QUESTION B2 (3
marks)
(a) Draw the structure of the product from the following reaction in the box provided.

Cl 1. AlCl3

O 2. H2O O

(b) Show all of the steps in the mechanism for the reaction given above.

.. ..
Cl : O :
.. + AlCl3 -AlCl
+ + 4
: O:

..
O : +

H
:O:

+ +

+ HB+

H H
:O: :O:
:B

B is some base….could be water.

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QUESTION B3 (3
marks)
The reaction below shows the addition of HBr to 1-phenylpropene.
The only product that is produced is (1-bromopropyl)benzene.
Br

+ HBr

(1-bromopropyl)benzene

(a) Propose a mechanism for the reaction.

H Br + + Br -
+

Resonance stabilized Not resonance stabilized

Br
+

+ Br -

(b) Explain (and use appropriate diagrams) why none of the other regioisomer in produced.

Protonation of the double bond at carbon 2 of 1-phenylpropene leads to an intermediate that

can be stabilized by resonance involving the aromatic ring. As a result, only one product is
formed.

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PART C – Questions on the Synthesis of Organic Compounds
(10 marks)

QUESTION C1 (4
marks)
The structure of Compound E is shown below. Benzene could be converted into Compound E in
four (4) reactions if the reactions are carried out in a proper sequence. If any reaction produces
more than one isomer, assume that they are easily separated and you can choose the
appropriate isomer to use.

Show how benzene could be converted into Compound E by drawing the reactants (including all
reagents) that are required for Reactions A, B, C, and D in the boxes below. Just the basic
reagents should be identified…….don’t include any ‘work-up’ reagents such as H3O+.

COOH

Reaction A Reaction B Reaction C Reaction D

NO2
Br

Compound E

Reaction A Reaction B Reaction C Reaction D

CH3Cl / AlCl3 Br2 / FeCl3 KMnO4 HNO3 / H2SO4

OR

Reaction A Reaction B Reaction C Reaction D

Br2 / FeCl3 HNO3 / H2SO4 CH3Cl / AlCl3 KMnO4

QUESTION C2 (3
marks)
Starting from benzene, show how you could legitimately synthesize ONE (1) of the following
compounds whose structures are given below. You have access to all inorganic reagents and any
organic compound having no more than three carbon atoms.

Br COOH
HC CH2

Br Br NH2

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 Br

CH2CH3 CHCH3 HC CH2

CH3CH2Cl NBS KOH

AlCl3 Benzoyl peroxide

The problem that we did in class started with the acylation using acetyl chloride followed by
Wolff-Kishner reduction.

Acceptable alternative reactions would Br2/uV rad’n for the bromination and any strong base for
the last reaction.

NO2 NH2

HNO3 Sn / HCl

H2SO4

Br2 (excess)

NH2
Br Br Br Br
1. NaNO2 / HCl / 0-5C

2. H3PO2

Br Br

R COOH COOH

RCl / AlCl3 Oxidation HNO3

H2SO4 NO2
Examples:
CrO3
H2CrO4 Reduction
Na2Cr2O7
Example:
Sn / HCl
COOH

NH2

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QUESTION C3 (3
marks)
Analyze the following sequence of organic reactions and determine the structure of the final
product. Draw the correct structure of the final product in the appropriate box provided. To
avoid duplication, in cases where ortho/para directing has resulted in two isomeric compounds,
complete the sequence using only the para-isomer. Be certain to consider the regiochemistry
and stereochemistry where applicable.

(a)
+
CH3Cl HNO3 KMnO4, NaOH H3O COOH
A
AlCl3 H2SO4

NO2

COMPOUND A

(b)
O

HNO3 CH3CCl HNO3 +

Fe KOH NaNO2, H3O CuCN
B
H2SO4 HCl H 2O - 5oC

CN

NO2

COMPOUND B

(c)

NO2 O O

CH3CCl CH3CH2CCl +
Sn KOH NaNO2, H3O CuCN
C
HCl AlCl3 H2O - 5oC

CN

CCH2CH3
12
O

COMPOUND C
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