Chemistry 152

Organic Chemistry
Exam I
June 1, 2011

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Answer questions in the spaces provided
This exam is worth 150 points
The exam period is 75 minutes. YOU MUST TURN IN YOUR EXAM WITHIN THE ALLOTED TIME
TO RECEIVE FULL CREDIT.

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 POINTS

Problem 1 __________

Problem 2 __________

Problem 3 __________

Problem 4 __________

Problem 5 __________

Problem 6 __________

Problem 7 __________

Problem 8 __________

Problem 9 __________

Total __________

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1) (20 points). Draw the initially formed enol and subsequently formed carbonyl containing product in

each of the following transformations.

H H
1) B
2

2) H2O2/OH

enol

carbonyl compound

H
H2O
Hg(II) (cat), H3O+ (cat)

enol

carbonyl compound

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2) (20 points). Reaction of benzoyl chloride with bromobenzene and aluminum trichloride (1 equiv)
forms two major products A and B. Show the structure of A and B and provide an arrow-pushing
mechanism for the formation of either of these products.

Br Cl

A and B
AlCl3

2) (15 points). Acid-catalyzed dehydration of 1-tert-butyl-2-methylcyclohexanol (A) forms a mixture of

1-tert-butyl-2-methylcyclohexene (B) and 1-tert-butyl-6-methylcyclohexene (C) via the carbocationic
intermediate D. When analyzed early in the reaction, C represents the major product, whereas at
longer times B represents the major product. Provide an energy coordinate diagram consistent with
these observations.

t-Bu OH t-Bu t-Bu t-Bu

CH3 H2SO4 CH3 CH3 CH3
+

A B C D

2) (12 points) Draw all the products formed in the reaction of 3-methylenecyclohexene with hydrogen
bromide. Circle the compound(s) corresponding to "kinetic" products.

HBr

3) (10 points). Show the most stable carbocation generated from addition of HBr to
cyclohexylacetylene. Assign the hydbridization and geometry of the electron-dficient carbon atom.

4
H
HBr

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3) (20 points) Pyridine is moderately basic and is protonated at nitrogen. Pyrrole is ~10 9 times less
basic than is pyridine and undergoes protonation at C2 rather than at nitrogen. Why is pyrrole so
much less basic than is pyridine and why does pyrrole protonate at C2 rather than at nitrogen or C3?

H
N N
H+

pyridine pKa = 5.2

H H H H
N H H+ N H+ N
H

pKa 4 pyrrole

or

3) (15 points). The carbonyl oxygen atom of 4-pyrone is many orders of magnitude more basic than is
the ether (ring) oxygen atom. Explain with structures, arrows, and as few words as you can get by
with.

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4) (20 points) Cyclooctatetraene (COT) dianion was first synthesized in 1960 by treatment of COT
with potassium metal and is planar and unusually stable (for a dianion), but not all are convinced that
COT dianion is aromatic. Evaluate the aromaticity of the COT dianion based on (1) Huckel's rule and
(2) molecular orbital arguments and identify the potential source of confusion.

2
2K
2 K+

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5) (15 points) Draw all diastereomers formed in each of the following Diels-Alder reactions, indicate
the predominant product, and indicate the endo and exo isomers (you need show only one
enantiomer of a chiral compound)

OMe Me
+
MeO Me

MeO O
+
MeO

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x) The dimethylamino group of N,N-dimethylaniline is typically a highly activating, o,p-directing group
for electrophilic aromatic substitution. However, nitration of N,N-dimethylaniline is actually much
slower than is the nitration of benzene and forms predominantly N,N-dimethyl-3-nitroaniline upon
basic work-up. Explain the anomalous behavior observed in the nitration of N,N-dimethylaniline. The
pKa of sulfuric acid is 3. The pKa of the conjugate acid of aniline is 4.6.

NMe2 NMe2
1) H2SO4/HNO3
2) H2O/OH
NO2

7) (15 points). Account for the following relative rates of the reaction of 2,3-dimethylbutadiene, 1,3-
butadiene, and 2,3-di-tert-butylbutadiene with dieneophiles in the Diels-Alder reaction (Name here).

Me t-Bu
> >>

Me t-Bu

increasing rate

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1) (15 points) Arrange the following benzene derivatives in order of increasing rate of reaction with
HNO3/H2SO4; slowest = 1, fastest = 6.

CH3 OCH3 NO2 Cl

1) (10 points) How would the following three compounds (A - C) be distinguished by UV-Vis
spectroscopy?

A B C

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