Chemistry 303b

fall, 1999

THIRD EXAMINATION
7:30 PM, DECEMBER 16TH, 1999
Duration: 2.5 hr
TEACHING KEY
[This is not intended as an example of how I would have answered the questions nor precisely the answers on
which the grading was based. It is designed to give you some more understanding as to how to approach such
problems as well as giving the answers.]
This is an "open book" examination; you may use anything which is not alive.
Note: if you do not know the complete or specific answer, give a partial or general answer-Write only in the space provided for each question.

WRITE SOMETHING
Score:
1___________/18
2___________/15
3___________/15
4___________/12
5___________/12
6___________/16
7___________/12
Total:

/100

There are 9 pages in this exam.

Please check now to be sure you have a complete set.

If you are using a resonance argument in your answer, draw the relevant resonance structures.
If you are asked to analyze a structure and you have no idea what it is, do a general analysis of the data and
propose partial structures.
Write mechanisms completely and carefully. We sometimes skip steps in lecture; don't do it
on the exam.
Please be aware that a small number of students will be taking the exam at different times up until the evening on
Friday. It would be well not to discuss the exam until after that time.
See you tomorrow morning...
PLEDGE:_________________________________________________________________
I. (18 pts) Consider the following pairs of reactions, carried out under identical conditions. One of the
reactions is much faster than the other for each pair.

A. (6 pts) Predict which reaction is the faster, draw the mechanism carefully with a clear representation of the
transition state, and explain why the other reaction is much slower.
Br
Br

THF

+ NaSMe

THF

+ NaSMe

SMe
THF =
O
(common solvent)

SMe

B. (6 pts) Predict which of the following E2 reactions will be faster; draw a careful representation of the
transition state and use this picture as part of your answer. Draw the major product of the faster reaction, taking
care to specify whether the major product is E or Z (or not relevant).
NC

Br

Et3 N:
E2
Et3 N:

Br

E2

C. (6 pts) Consider the following substitution reactions. Pick the one which is fastest and write the mechanism,
including a careful drawing of the product(s) for that reaction. Explain why it is faster.
AgNO3
Br

MeOH

AgNO3
Br

MeOH

_________________________________________________________________________________________3
II. (15 pts) Considering molecules with 5 carbons or fewer, any number of H, zero or one oxygen, zero or
one bromine and no double bonds, design a structure which is:
A. (5 pts) Most reactive in the SN1 reaction using AgNO3 in MeOH. [draw the molecule and the products]
Explain your choice.

B. (5 pts) Most reactive in an SN2 process with EtNH2. Explain your choice with a mechanism and draw the
product.

C. (5 pts) With one double bond, most reactive in the addition of HOBr. Explain with a mechanism and draw the
exact product from your reaction.

III. (15 pts). Consider the reactions of the following alkenes with HBr (no radical processes).
a. HBr

H
?

a. HBr
N

Br
P

A. (5 pts) Write the structure of the major product expected from M; explain your choice. Note that the same
reaction with N gives the major isomer P, shown. What does this tell you about the relative effects of two alkyl
groups vs one phenyl group in the regioselectivity of electrophilic addition of HBr?

B. (5 pts) The lectures (and text) have a simple rationale to explain why hydroboration/oxidation gives overall 5
"anti-Markovnikoff" addition of H-OH to a double bond. What would this predict for the major product from the
reaction of M under the conditions shown? Show the intermediate from the first addition of BH3. What is the
basis of this regioselectivity?
a. BH3
b. H2O2/HO

?
-

C. (5 pts) Another textbook, however, completely ignores this picture and suggests an alternative reason to
explain the regioselectivity in hydroboration, including the example in part B. Their evidence is, e.g., the reaction
of N which gives the major product Q. What is the best explanation for this regioselectivity?
H
a. BH3

OH

b. H2O2/HON

IV. (12 pts) Bromobenzene is very slow (essentially inert) under typical reaction conditions for the usual
SN1, SN2, E1, and E2 with 2-bromobutane. These mechanisms are sensitive to one or more of the following
general agents: nucleophile/base (weak, moderate, strong), basic or acidic conditions, Ag+ . The solvent type is
also a factor (polar, non-polar, protic, aprotic)
A. (6 pts) Consider S N 2 . Propose reaction conditions (solvent type, other agents?) which should give a fast
SN2 reaction of 2-bromobutane with sodium ethoxide, and write the mechanism carefully; explain your choice.
Then explain why bromobenzene does not react in the same way under these conditions.
NaOEt
Br

S N2

B . (6 pts) Consider S N 1: Propose reaction conditions which should give a fast SN1 reaction with
2-bromobutane (propose the best nucleophile type and a specific example; other agents; solvent type) and write
the mechanism carefully; explain. Then explain why bromobenzene does not react in the same way under these
conditions.
S N1
Br

V. (12 pts). Consider the reduction of acetaldehyde by NADH.

O

NH2

NH2
N
R

NADH

O
H 3C
H

H2O

N
R

NAD
(business end only)

+ CH3CH 2OH

N
R

mutant NADH

A. (6 pts) Write a careful stepwise mechanism for the reduction of acetaldehyde into ethyl alcohol with NADH,
the reduced form of the cofactor NAD.

B . (6 pts) The side chain indicated by an arrow in NADH has no apparent role in the process, but Nature would
certainly not waste energy putting in such a group for no reason. Obviously, it can have some hydrogen bonding
possibilities for molecular association, but it might also have an effect on the intrinsic reactivity of NADH.
Compare NADH with "mutant" NADH: which is more reactive in this reduction process? Explain carefully.

VI. (16 pts). We have several examples where the rate-determining step in a process can proceed in one step
(concerted) or in two steps with a reactive intermediate (stepwise). The issue of concerted vs stepwise can be
important when analyzing competing reactions on the same general pathway.
Zinc chloride is a moderately strong Lewis acid. It reacts with the epoxide S to give the products T and U
which are compared by spectroscopy. Note that the process strongly favors the formation of T.
H

OH
O
H

ZnCl2 (catalyst)

OH
+

CH2Cl2 (solvent)
S

T
major

U
minor

A. (5 pts) Imagine spectroscopy to distinguish the structures of T and U (assuming you do not have authentic
samples of each)
Can they be distinguished by:
(if yes, explain with a single key difference)
UV____________________________________________________________________________
IR ____________________________________________________________________________
mass spec_______________________________________________________________________

1H

NMR________________________________________________________________________

13C

NMR________________________________________________________________________

B. (5 pts) Write a reasonable mechanism to rationalize the formation of U . First, draw both chair forms of the
reactant, S . Draw the chair form of cyclohexane for all intermediates. Indicate which is the rate-determining
step. Show the catalytic role of ZnCl2 (no net consumption).

C. (6 pts). Write the best mechanism for the formation of T. Draw the chair form of cyclohexane for
the reactant and all intermediates. Indicate clearly which is the rate-determining step. Discuss how your
mechanism is consistent with the preferred formation of T instead of U .

_______________________________________________________________________________________
VII. (12 pts). Consider the following conversion. Write a pathway through reasonable mechanisms and
intermediates which best rationalizes this process. Shorter pathway via more stable intermediates will get more
credit.

OH
H2SO 4
H2O

OH

Ha
Ha

Hint: If H a is a deuterium, one can trace the process and see that
it ends up as H a in the product.