NAME________________________________

LAST FIRST


CHEMISTRY 202.001

Fall 2012
October 2, 2012

HOUR EXAMINATION I

75 MINUTES

This examination packet consists of a total of eleven (11) pages. In addition to the cover page, there are
eight pages with questions (I VI) on pages 2 - 9. Page 10 is a blank page for Scratch Paper and page 11
is a periodic table. This is a closed note-closed book exercise. Please be sure that you have a complete
examination and that you endorse the statement of the Duke Community Standard as presented below.


Please put your name at the top of this page and page 2 and your initials at the tops of pages 3-9.


PLACE THE INITIAL OF YOUR LAST NAME IN THE BOX BELOW










Initial of LAST Name

_____________________________________________________________________________________

Your signature below indicates that you have taken this examination in accord with the provisions of the
Duke Community Standard.

I will not lie, cheat, or steal in my academic endeavors;
I will conduct myself honorably in all my endeavors; and
I will act if the Standard is compromised.



Signed___________________________________________
Name/Initials__________________________________

2
CHEMISTRY 202.001
Fall 2012
October 2, 2012

HOUR EXAMINATION I

Question Points Score

I 30

II 63

III 25

IV 25

V 25

VI 32

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TOTAL 200
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Exam Begins Here

I. (30 points). In the answer area below, darken the space of the most appropriate response to each of the
following multiple choice questions.

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ANSWERS TO QUESTION I

a b c d e a b c d e

1. // // // // // 4 // // // // //

2. // // // // // 5. // // // // //

3. // // // // //


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3
1. What were the starting material pairs used to prepare the following Diels-Alder adduct?
CH
3
CH
3
CO
2
H
+
CH
3
CH
3
CO
2
H
CH
3
CO
2
H
+
CH
3
CO
2
H
+
CH
3
CH
3
CH
3
+
CH
3
CO
2
H
CH
3
A B C
D

a. A
b. B
c. C
d. D
e. That compound is NOT a Diels-Alder adduct.

2. Arrange the following compounds in order of increasing acidity.
H
NH
3
H
2
O
A B C D E
H

a. A>E>B>D>C
b. A>B>C>D>E
c. E>A>C>D>B
d. A>C>E>D>B
e. E>D>B>A>C

3. Assuming that each of the following structures is planar, which of the ions below would be likely to be
aromatic?
O
H
H
H
A B C

a. A
b. B
c. C
d. B & C
e. A & B
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4
4. An example of a meta-directing group that is also an activator is?

a. CHO
b. I
c. -NMe
3
+

d. NO
2

e. there are no meta-directing activators.

5. Which of the following compounds would you not expect from the reaction shown below?

Br
1. Mg/ether
2.
O
3. H
3
O
+
?
CH
3
Ph
Ph
OH OH OH
A B
C
D E


a. A
b. B
c. C
d. D
e. E

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5
II. (63 points). Draw the structure of the major organic product(s) of each of the following reactions.
Indicate stereochemistry if it is an issue. If no reaction would occur write NR. Reaction mechanisms
are not necessary.

H
3
C CH
3
NBS/CCl
4
/50
o
CH
3
CH
3
OH
H
2
SO
4
CH
3
CH
3
HBr (1 equiv.)
(thermodynamic product)
warm
O
2
N NO
2
Cl
iPrNH
2
warm
O
H
1. CH
3
CH
2
MgBr
2. CH
3
CH
2
Br
3. Na/NH
3
+
CO
2
CH
3
CO
2
CH
3
warm
CH
3
O
H
3
CO
SO
3
/H
2
SO
4
Cl
CH
3
NaOCH
3
300
o
1.
2.
3.
4.
5.
6.
7.
8.
9.
O
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6
III. (25 points). It has been found that the reaction of the cyclopentadiene derivative A with maleic
anhydride B at 15
o
leads to two products, C and D, with a very strong preference for C. On the other
hand, when the reaction is conducted at 60
o
for longer periods of time, or if C is heated under the higher
temperature conditions, product D dominates. The mass spectra for C and D each show a molecular ion
at 204 amu. What are the structures of C and D? Use an appropriate energy diagram to explain why C is
favored at low temperatures and D at high.

+
C + D
(dominates at 15
o
) (dominates at 60
o
)
CH
3
CH
3
A B
O
O
O


A. (12) What are the structures of C and D?

C
D


B. (13) Use an appropriate energy diagram to explain why C is favored at low temperatures and D at high.

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7
IV. (25 points). Show how you would carry out the following transformation starting from toluene. In
addition you may use any other organic compound containing three carbons or less that does not contain
deuterium (D) as well as any inorganic reagents you might need. Reaction mechanisms are not necessary.

CH
3
?
CH
3
D D
D
H


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8
V. (25 points). When o-chloroanisole was monochlorinated under standard EAS reaction conditions
(Cl
2
/FeCl
3
), two C
7
H
6
Cl
2
O products, A and B, were obtained. In the
1
H NMR spectra, both products
exhibited a three proton singlet around ! ~3.7 (-OCH
3
). In addition, the aromatic region of A showed a
singlet and two doublets (J = 8.5 Hz) while the aromatic region of B showed one doublet and one triplet (J
= 8.5 Hz) in a 2/1 ratio. (note: anisole is methoxy benzene.)

A. (12) What are the structures of A and B?
A B


B. (13) Provide a detailed reaction mechanism for the formation of either A or B.

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9
VI. (32 points).
A. (16) Treatment of ketone A (C
13
H
6
Cl
2
O) with sodium methoxide at 60
o
leads to product B in which one
of the chlorine atoms has been replaced by CH
3
O. What is the structure of B? Provide a mechanism for
its formation.
O
Cl
Cl
NaOCH
3
/CH
3
OH
60
o
A
B (C
14
H
9
ClO
2
)
















B. (16) Which of the two cyclic amines (A) or (B) would you expect to be more basic? Explain?
N
N
A B
CH
3
CH
3