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Exam 3
April 27, 2016
Prof. Douglas
[ ]
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!
(1 bonus point)
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
OH
t-Bu
NH
O
NH 2
H2
N
O
OMe
N
H2
N
H
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
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
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
[2] CH 3CH2I
O
CH 3
t-Bu NH 2
OR
t-Bu
CH 3
O
CH 3I
H 3C
OEt
CH 3
Br
OH
Br
OR
O
H 3C
O
H 3C
CH 3
CH 3
CH 3