Chemistry 2302

Exam 3
April 27, 2016

Prof. Douglas

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General Instructions & Tips:
1) Use pen, cross out anything you dont want us to grade.
2) Electronic Devices of any kind are not allowed: turn off and stow.
3) Carefully read all instructions for questions. Do not assume that the instructions are
identical to the practice exam or old exams.
4) Model kits, calculators, and stencils are not allowed.
5) Maximize partial credit by first attempting questions you feel you can answer correctly, rather
than tackling problems in sequence.
6) Clear drawings make it easy to assign full/partial credit.
7) There is at least one problem on each page except this one: dont miss any!

Last Name: _____________________

(1 bonus point)

First Name: _____________________

Student ID #__________________

Point Tally:
Bonus Point

/1

Problem 1.
/24
Acids & Bases
Problem 2.
/23
Amines
Problem 3.
/22
Carbonyl rxns & mech part 1

Problem 5.
/22
Carbonyl rxns & mech part 2
Problem 6.
/10
Multistep Synthesis

Total:

/100

Problem 1, Acid & base strength:

Part 1: (12 pts, 2 each) In the space indicated, draw the conjugate base of each molecule in the
chart above. In cases where the molecule has more than one acidic carbon, draw the conjugate
base resulting from thermodynamic deprotonation.
Part 2: (12 pts, 2 each) For each boxed pair, circle the molecule that is the stronger acid.
O
N

OH

t-Bu

NH

O
NH 2

H2
N

O
OMe

N
H2

N
H

Draw conjugate bases below.

N
H

Problem 2, Amines: Multiple Choice & Short Answer, (22 points, values indicated below)
Answer the following questions about benzphetamine, a habit-forming diet pill that is listed as a
controlled substance in the USA.
Me
N

Didrex

Me

A) How many stereogenic centers are in Didrex? Circle your choice below. (1 points)
a) zero, b) one, c) two, d) three, e) more than three
B) Draw the structures of two different amides that would form Didrex after reduction with
LiAlH4, followed by work up with water. (4 points, 2 points each)

C) What two alkene products are formed by Hofmann Elimination of Didrex? (treatment with
excess MeI, then Ag2O, then heat). (2 points each) Indicate the major product. (2 points) (6
points total)

D) What carbonyl compound and amine can be used to make Didrex by reductive amination?
Draw two of the possible three carbonyl/amine pairs. (2 points for each structure, 2 points for
indicating correct pairs of carbonyl/amine, 12 points total)

Bonus point: Circle the minimum portion of the Didrex molecule that is most responsible for its
psychoactive properties.

Problem 3, Carbonyl compounds & mechanisms: Multiple Choice & Short Answer, (22
points, values indicated below)
A) (3 points) The di-ketone shown is called the Wieland-Miescher ketone. Draw the starting
material that would be needed to form alpha-beta unsaturated ketone portion of this compound
by an intramolecular aldol cyclization.
H 3C

O
Wieland-Miescher ketone

B) (6 points, 3 points each) Draw the structures of the two carbonyl compounds needed to
prepare your compound in part A via a Michael Reaction.

C) (10 points) Draw a mechanism for the Micheal Reaction of your compounds in part B. Use
NaOH as the base catalyst. (4 points for correct arrows, 4 points for correct intermediates with
correct formal charges, 2 points for correct sequence of events)

D) (3 points) The two steps above could be run in one base-catalyzed process. That particular
combination is a tandem reaction called the _______________.
a) Robinson Annulation
b) Acetoacetate Synthesis
c) Gabriel Reaction

d) Malonic Ester Synthesis

e) Curtius Rearrangement

Problem 4, Carbonyl compounds & mechanisms part 2: Multiple Choice & Short Answer,
(22 points, values indicated below)
A) (9 points, 3 points each) Draw the structures of compounds AC in the following synthesis
of ibuprofen from 2-(4-isobutylphenyl)acetic acid. Be sure to label your structures A, B, & C.
CH 3

CO2H
[1] SOCl2

CH 3

NaOEt

H 3C

[2] EtOH
pyridine
EtO

[1] NaOEt
[2] CH 3I

H 3O+
heat

OH

CH 3
O

H 3C
ibuprofen

OEt

B) (6 points) What do you expect when acetone (2-propanone, shown on the right)

CH 3
reacts with acetic acid and Br2? H 3C
a) an aldol reaction
propan-2-one
b) 1-bromo-2-propanone
c) 2-bromoethanoic acid
d) bromoform (CHBr3)
e) none of the above

reacts with excess NaOH and I2?

a) an aldol polymer will form
b) 1-iodo-2-propanone
c) hexa-iodo-acetone (2 CI3 groups)
d) iodoform (CHI3)
e) none of the above

C) (4 points) Draw a three step synthesis of the cyclic ketone below that uses the starting
materials shown. Your synthesis should include a Dieckmann Reaction and an Acetoacetic Ester
Decarboxylation. Show intermediates and reagents (or reaction conditions) for full credit.
Br

O
OMe

MeO
O

D) (3 points) Draw the expected product. You may ignore stereochemistry.

O
[1] LDA, 78C
CH 3

[2] CH 3CH2I

Problem 5 (10 points, 5 each)

Propose multistep synthesis routes to the compounds shown using the starting materials shown
and any other reagents/reactants you need. To maximize partial credit, be sure to draw out the
products of each reaction you propose. No partial credit will be awarded for reactive
intermediates/mechanisms (such as carbocations).
Note: Full credit will be provided if your conditions provide selectivity for the desired product if
mixtures can result.
a. Choose Only One!
O

O
CH 3

t-Bu NH 2

OR

t-Bu

CH 3
O

CH 3I
H 3C

OEt

CH 3

b. Choose Only One!

Br

Br

OH

Br

OR

O
H 3C

O
H 3C

CH 3

CH 3
CH 3