Chemistry 303

Third Examination
December 3rd, 1996

Name_______________________________________________________
Lab TA______________________________________________________
This is an "open book" exam; you may use anything which is not alive.
There are 9 pages in this exam; please check to be sure you have a complete copy.
Dont worry--it is not that long. There is a lot of space for answers and working out. State your assumptions and
show your logic.
Use your arrows to show mechanism, with precision. Sloppy arrows will not be given full credit.

I._______/36
II._______/18
III.______/22
IV.______/25
total:_____________/100

Pledge_________________________________________________________________________________
1

I. ( 36 pts). Consider the interesting molecule, A. Its reactivity contrasts somewhat with the related
compound, B. As a warm up to analyzing reactions of A, please consider the structure and behavior of B.
You may add a sentence of explanation if you see ambiguities in the question.
R

H 2

S
Cl

Cl
4

5 B

A
A. (3 pts) For each of the carbons in B, indicate with a check if it is
a stereogenic center and, if so, whether it is R or S configuration.

C1
C2
C3
C4
C5
C6

___
___
___
___
___
___

R or S
R or S
R or S
R or S
R or S
R or S

Consider the following molecules as possible products from reactions of B.

H

OCH3
U

CH3O
V

OCH3
X

CH3O
Z

B. (2 pts) Which is the most likely product from the SN2 reaction of B with NaOCH3?
Circle single best answer
U V W

C. (2 pts) Which is the most likely product from the E2 reaction of B with NaOCH3?
Circle single best answer
U V W

D. (2 pts) Which is the most likely substitution product from B with AgNO3 in methyl alcohol solution?
Circle single best answer
U V W X Y Z
E. (2 pts) Which is the most likely elimination product from B with AgNO3 in methyl alcohol solution?
Circle single best answer
U V W X Y Z
F. (4 pts) Write a mechanism for the reaction in part D, above.

G. (3 pts). If you wished to increase the rate of the SN2 reaction of B with NaOCH3/CH3OH by adjusting
the nature of the leaving group, what would be a better choice of leaving group? Explain.

H. (6 pts) Obviously, the SN2 and E2 reactions of B give different products. Suppose we change the
nucleophile/base to NaOC(CH3)3 in tert-butyl alcohol solvent.
1. Write the product from the simple SN2 reaction:

2. Write the product from the simple E2 reaction:

3. How would the relative amount of SN2 product to E2 product differ for this reaction compared to the
reaction of B with NaOCH3/CH3OH? More SN2, More E2, or No Change? Explain in terms of mechanism.

______________________________________________________________________________________
Now consider the reactions of A. Reaction of A with NaOCH 3 in methyl alcohol solution gives the
same product (C) as reaction of A with AgNO3 in methyl alcohol solution.

Ag
R

S 1

CH3OH

Cl

NaOCH3, CH3OH

S
1

OCH3

J. (2 pts) What is the absolute configuration of the stereogenic center C1 in A?

R___

S___

K. (2 pts) What is the absolute configuration of the stereogenic center C1 in C?

R___

S___

Redrawn for convenience:

Ag
R

S 1

CH3OH

Cl

NaOCH3, CH3OH

S
1

OCH3

L. (8 pts) Write the most reasonable mechanism for the formation of C using Ag + consistent with the
observations, especially the fact that the product C is formed as one enantiomer with a particular
configuration..

___________________________________________________________________
II. (18 pts). Note the following pair of reactions. The first reaction should be familiar. The second
reaction is not one we have explicitly studied; it is a direct extension of things we talked about.
Br2, CH2Cl2 solvent
Ph
D

Br2,
irradiation

Br Br
Ph C C CH3
H H E

Br

Ph
F
(major)

no stereo relationships
implied

+
Br

Ph
G
(minor)

A. (2 pts) How many stereoisomers (enantiomers, diastereoisomers) of E are possible, in principle?

4

2__ 3___ 4___ 8___ cannot tell ___

B. (6 pts) Write the best mechanism for the formation of E (note that it is a mixture of only two
stereoisomers). Draw the stereoisomers in their most stable conformation using the Newman projection (you can
symbolize the phenyl group as Ph), and be sure your mechanism is consistent with the formation of those and
only those stereoisomers.
Br Br
Ph C C CH3
H H E

How are these stereoisomers related:

enantiomers? ____
diastereoisomers?____
(check all correct answers)
superimposable? ____
mirror images? ____
________________________________________________________________________________
C. (4 pts) Draw in Newman projection
one additional stereoisomer
(which is not a favored product
in the reaction)

How is this stereoisomer related to one or the other

of the isomers in part B, above (pick one for comparison)
a. enantiomers
____
b. diastereoisomer
____
c. non-superimposable ____
d. mirror images
____
(check all correct answers)

_________________________________________________________________________________
D. (6 pts) Write the best mechanism to account for the formation of F and G from D. Include a clear
function for the irradiation.
Ph

Br2,

irradiation

F
(major)

Br

Ph

+
Br

Ph
G
(minor)

III. (22 pts). Consider the reactions of two closely related reactants, G and J, in the presence of aqueous
base. The products H and K have different molecular formulas and form at somewhat different rates: K forms
faster under comparable conditions.
OH

Br

OH
slow reaction
NaOH, H2O

G, C13H25BrO

fast reaction
H, C13H26O2

Br

NaOH, H2O

IR: 3300 (s, broad)

2900 (s, several
peaks)
+ fingerprint

J, C13H25BrO

K, C13H24O
IR: 2900 (s,
several peaks)
+fingerprint

A. (7 pts) Draw the most stable conformer of G and of J,using the chair representation. Be sure your
drawing shows clearly which substituents are axial or equatorial; you need not draw in the hydrogens. Label each
substituent (not hydrogens) as (A) axial or (E) for equatorial. Which isomer is more stable, G or J? Explain
carefully.

B. (3 pts) How are G and J related? Circle all correct answers. stereoisomers
diastereoisomers
enantiomers
mirror images

____
____
____
____

C. (6 pts) What is the structure of product H? Write the best mechanism for its formation. What is the name
of this mechanism?

D. (6 pts) What is the structure of product K? Write the best mechanism for its formation. What is the name
of this mechanism?

IV. (25 pts).

A. Consider the following reaction. It occurs when M is dissolved in CH2Cl2, methyl alcohol is added,
and the mixture is heated gently.
Cl
H3C

+ CH3OH

CH2Cl2
solvent

OCH3
H3C

+ HCl

1. (6 pts) Write the best mechanism for the conversion of M to N . Include a representation of all
transition states and intermediates. Show any partial charges in the transition state(s). What is the name of this
mechanism?

2. (5 pts) Keeping in mind that the disappearance of M is independent of the concentration of methyl
alcohol, and depends only on the concentration of M, draw the appropriate reaction coordinate diagram, indicating
where your transition state(s) and intermediate(s) appear. Pay attention to the relative energy levels of reactant,
transition state(s), and intermediate(s). Label clearly the rate-determining transition state.

Extent of reaction

________________________________________________________________________________________
B . Consider the related substrate P under the same conditions.
Cl
CH3O

CH2Cl2

+ CH3OH

solvent

OCH3
CH3O

+ HCl

1. (4 pts) Would this reaction proceed faster, slower, or at the same rate as that from M? Write a mechanism
and explain in comparison with your mechanism for M.

2. (5 pts) Indicate clearly how the reaction coordinate diagram for this process compares with that for M.
Again, the rate is independent of the concentration of CH3OH, and is directly related to the concentration of P.

Extent of reaction

C. (5 pts) Now consider the reaction of T, under somewhat different conditions. The overall process
is similar, and it requires acid but only in catalytic amounts.
OCH3
CH3
CH3
T

+ EtOH

OEt
CH3

H+
CH2Cl2

CH3

EtOH = CH3CH2OH

Write the best mechanism for the conversion of T to X , making clear how the acid is required but is not
consumed.

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