Exam I Chem 206.

03 February 22, 2018 Key

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Name_______________________________ 2 10
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JHED ID_____________________________ 5 20
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I agree to complete this exam without 7 6
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unauthorized assistance from any person, 9 10
materials, or device.

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Signature and Date
total 100

Exam policy
1) No electronic devices of any kind, such as calculators, cell phones, or advanced
digital watches are allowed. Possession of such devices during the exam is grounds
for awarding a zero on the exam.
2) Molecular models are allowed, but no instruction pages are permitted.
3) Relevant tables, including the periodic table, are attached at the end of this exam.
4) Numerical values given in one question apply only to that question, and should not
be used in other questions, unless there is a specific instruction to do so. If
necessary, the values from the provided tables should be used, even if they differ
from values that you may remember from different sources.
5) When listing reagents, a backslash (/) is used between reagents that are employed
simultaneously and a semicolon (;) is used between reagents that are employed in a
stepwise fashion.
6) Use the boxes provided for your answer if they are present. Answers
that are not written in the boxes will not be considered for grading.
7) Be neat and clear. Make sure we know which answer is to be graded.
8) Some questions will have points deducted for incorrect responses. Longer
synthetic routes receive fewer points than shorter, more direct
answers.
9) Keep your answers brief.

Notes: I. The stereochemistry in structural drawings and reaction schemes is not shown unless
explicitly indicated with wedge-bond designations. For example:

Br Br

Cl Cl
Stereochemistry not shown Stereochemistry shown
II. Abbreviations used: Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, Pe = pentyl, Ph = phenyl, (i.e.,
benzene as a substituent), AcO = acetate (H3CCOO).
III. When listing reagents, a slash (/) is used between reagents that are employed simultaneously, and a
semicolon (;) is used between reagents that are employed in a stepwise fashion.

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1. (28 pts) Provide the missing starting material, major organic product(s),
conditions, or reagent(s) for the following transformations. Assume acid workup
in the missing reagent steps.

Cl
Cl2/AlCl3 +
A. Cl

Br
NBS
B.
ROOR/

NH2
H 1) trace H+ NHCH2 CH2 CH3
C. + 2) NaBH3 CN
O 3) H3 O
+

O OH
D. 1. NaBH4 (LAH)
2. H2O (H3O+)

NO2 NO2

E. HNO3
H2 SO4
NO2

O OH
1. PhMgBr
F. H Ph Ph
2. H3 O+

O
O
Cl
G.
AlCl3

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2. (10 pts) Draw the mechanism (using appropriate mechanistic arrows) for the
production of product. Show both deprotonation and protonation steps. Lone
pairs are not indicated.

3. (8 pts) Provide the missing reagents for the following transformation:

(acid quench is not required for full credit)

4. (4 pts) Provide the product of the following transformation:

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5. (20 pts) Provide the reagents (including organic substrates) in the following
synthetic schemes. You may use any monofunctional organic molecules, triphenyl
phosphine, any carbonyl containing dienophile, or diene containing 6 or fewer carbons
and any inorganic reagents that you need. NOTE: the number of steps are NOT
indicated and it is for you to determine. All transformations require more than one
step.

1. NaBH4 ; H+
2. TsCl/pyr or equiv. H
H
A. 3. KCN
CN
O

1. CH3 MgBr; H+
H 2. TsCl/pyr or equiv.
B. 3. KCN
O CN

1. Ph3 P=CH2
H 2. BH3 -THF
3. H2 O2 /HO -/H2 O OH
C.
O
or: CH3MgBr; H+ then dehydration; step 2, 3

1. NH2 Et trace H+ H
2. NaBH3 CN N
H +
D. 3. H3 O
O
OH
1. PhMgBr
H
+
2. H2 O/H
E.
O

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6. A. (6 pts) Draw all of the mono-chlorinated constitutional isomers that form in
the substitution reaction below:

B. (4 pts) How many mono-chlorinated isomers, including stereoisomers, are possible

7. (6 pts) Provide the missing reagents and the missing intermediate product for the
following transformation:

8. (4 pts) In the Wittig reaction we must decide which part of the alkene product
came from the carbonyl reagent and which is coming from the ylide. For the following
pairs of molecules, indicate which would be the better set of reagents for the Wittig
reaction and briefly state why: A is better because of the SN2 rxn with Ph3P:

A. Br
+

Br
O
+
B.

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9. (10 pts) Provide a synthesis for the following molecules using the indicated
starting material. You may use any monofunctional organic molecules, any
carbonyl containing dienophile, or diene containing 6 or fewer carbons, triphenyl
phosphine, or any inorganic reagents that you need. The number of arrows does
NOT necessarily correspond to the number of steps.

OH

NBS/h H

O
Br Mg MgBr
Et2O

O
H O

O
Ph3P=CH2
1. CH3Br + Ph3P
H 2. BuLi

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End of the Exam