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Chemistry 303

fall, 2001

THIRD EXAMINATION
7:30 pm December 3rd
Duration: 2.5 hr
Name____________________________________________________________
Lab TA__________________________________________________________
(if you do not know his/her name, give day of lab section. NOT Hooley)
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___________/21
2___________/21
3___________/34
4___________/08
5___________/16

Total:

/100

There are 10 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.
Please be aware that a small number of students will be taking the exam at different times up until late afternoon on
Tuesday. It would be well not to discuss the exam until after that time.
NOTE: You will be asked to write mechanisms and use the arrow formalism. Please use it
precisely, carefully, and correctly. Show charges carefully. Distinguish between an
intermediate and a transition state. A "good" mechanism is short and proceeds through lower
energy intermediates/transition states.
NOTE: you may buy structures A, B, or C (Problem I) at a price of 4 pts each.
you may also buy structure T (Problem III) at a price of 10 pts.
Just ask the proctor.

PLEDGE:_________________________________________________________________

I. (21 pts) Consider the following reaction of X, and the products indicated.

Cl
X

A C 6H10 major product


B C6H10 minor product
C C7H14O minor product

Na :OMe
ether

CH3

Note: you may purchase the structures of


A, B, or C at a cost of 4 pts each

A. (1 pt) What is the most likely mechanism for the formation of A, the major product?
SN2

SN1

E2

E1 none of these

(circle single best answer)

B. (1 pt) What is the configuration at the carbon bearing the methyl group in X ?

cannot tell

C. (1 pt) What is the configuration at the carbon bearing the Cl substituent in X ?

cannot tell

D. (1 pts) Draw carefully the enantiomer of X .

E. (1 pts) Draw carefully one diastereoisomer of X .

F. (4 pts) Using the arrow formalism carefully, write the mechanism for the process giving A, showing clearly
the structure of the major product.

G. (2 pts) Draw a careful representation for the transition state for this process, showing clearly all partial
bonds and partial charges.

H. (3 pts) There is an isomer of A which could be formed by the same mechanism, shown as B.
Please draw here the structure of B and indicate why it is less preferred than the major product.

I. (3 pts) There is also another minor product, C, obtained as a single enantiomer. What is the structure of
C? Write the mechanism for its formation.

J. (4 pts) The first two products, A and B, are obviously isomers.


1. (1 pt) Can you use Mass Spectrometry to differentiate them?
Explain, if necessary.

methyl

yes

no

2. (3 pts) 1H NMR will certainly be helpful. Each isomer contains a methyl group. Please explain how
the chemical shift and pattern of peaks for the methyl group in A will differ from that for the
group in B.

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II. (21 pts) Consider each of the following pairs of reactions.
Please decide which reaction is faster for each pair and write the product(s) for that reaction. Give the single
most important reason why you think that one is faster. You probably have to draw the mechanism to make your
point. Give the name of the mechanism. If you have trouble deciding which mechanism is operating, specify a
reasonable mechanism, and then indicate which example would be faster by that mechanism. For each of the
faster reactions, indicate clearly which is the nucleophile and which is the electrophile.
Br
A.

HO

NaH

C4H 8O

1.

HO
2.

NaH

C3H 6O

Br

________________________________________________________________________________________
B.

Br2, H2O
1.

CH2 Cl2 solvent

CF3
2.

Br2, H2O
CH2 Cl2 solvent

_________________________________________________________________________________________
C.
Br

CH3 OH
substitution product

Br

(CH3)2 NH

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III. (34 pts) An Orgo student planned a synthesis of W from U , and figured that one of our
standard substitution mechanisms would be perfect. He simply heated U in acetic acid and expected W would
form in a fast, favorable reaction. The reaction was fast but, unfortunately, W was only a minor product. The
main product was an isomer, T. Another minor product, S , was also observed. Dr. Gingrich appeared and
asked cryptically "Aren't you forgetting that the rate-determining step is not necessarily the product-determining
step?" and then went off to have a cigarette. Note: you may buy the structure of T at any time for 10 pts
penalty.
Spectral data for T: IR: 1743(s), 1676(m)
CH3 CO2H
I
U

heat

O
W
(minor)

+ T + S
(major) (minor)

1H

NMR(CDCl3): 1.71(s,3H); 1.77(s,3H),


2.05(s,3H), 4.57(d, J=6Hz, 2H), 5.34(t,
J=6Hz, 1H) ppm
13C NMR(CDCl ): 18.0, 21.0, 25.8, 61.4,
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118.6, 139.0, 171.0 ppm

A. (6 pts) Draw the mechanism which leads to W . Show any intermediates. What is the general name of this
mechanism? Why was this reaction expected to have a particularly favorable rate-determining step?

B. (5 pts) Draw the structure for T and correlate it with the 1H NMR data. That is, make clear which H (or set
of equivalent H) give rise to which of the 5 peaks. Make clear which H are coupled to which other H.
Indicate any ambiguous assignments.

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continued....
III, cont. C. (5 pts). Write the best mechanism for the formation of T, showing all intermediates.
Explain why this is the major product, in preference to W .

D. (6 pts) The only spectral data collected for S were the mass spectum [m/z 69(5.6%), 68(100%)]
and the UV spectrum [ max 223, 21,500]
1. Write the structure for S .

2. Explain how this structure is consistent with the UV spectrum.

3. Write a mechanism for the formation of S . What is the name of this mechanism?

E. (4 pts). Compared to the rate of formation of W, is the rate of formation of T: higher


?
circle single best answer and explain your choice briefly.

lower

same

Prob III, cont.


F. (8 pts). Now draw carefully two reaction coordinate diagrams, one for the conversion of U to W ,
and a second one for the conversion of U to T. On the diagrams, take care to make the energy levels qualitatively
correct between the two so that the energy of transition states and intermediates can be compared between the two;
the reactants start at the same energy.
Draw structures of intermediates but not transition states.
Use these diagrams to explain what Henry meant by "the rate-determining step is not necessarily the
product-determining step."
Identify the activation energies in the product-determining step for formation of W and for T. Your
diagram should make clear their relative magnitude.

G
U

extent of reaction

G
U

extent of reaction

IV. (8 pts). Consider the following conversion of M to N .


H

Br

Na :CN

CN

O
N

(no stereochemistry implied)

A. (1 pts) Identify clearly the stereogenic centers in M with a circle.


B. (7 pts) The conversion of M to N is a multi-step process and leads to a single enantiomer of N .
Draw the best mechanism here, showing all intermediates (but not transition states).
Label each step as SN2, S N1, E2, or E1 where relevant.
Draw clearly the exact structure (stereochemistry) of the product N .
H Br
H
O
M

:CN

V. (16 pts) The following substitution reaction was studied in an effort to prepare one
enantiomer of E. The desired pure enantiomer of E has a molecular rotation []D = +68 o.
H
I

CN

CH3
D
[]D = +45o

CH3 -NH2
in a solvent

H H
H
NC
N
CH3
H 3C
E
[]D = see conditions

A. (4 pts) When the reaction was run in hexane (100 mL) as a solvent the rate was very low, and the product had
[]D = +68 o. Draw carefully the primary mechanism which must be operating in hexane solution. Show the
structure of the main enantiomer of E that is formed. Name the mechanism.

B. (5 pts) When the reaction was run in DMSO as solvent (100 mL) with everything else the same, the rate was
much higher but the product had []D = +18 o. Use a mechanistic analysis with words and pictures to explain
why the change in solvent to DMSO resulted in a higher rate and a lower molecular rotation for the product.
The spectral data in all cases were completely consistent with the general structure E.

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C. (4 pts) In an effort to increase the [] value, the reaction was tried again in DMSO, but this time
with ten times less solvent (e.g., with 10 mL instead of 100 mL). Everything else was the same.
Rewardingly,
the []Dwas now higher, at +51 o. Please explain in terms of your mechanism analysis in part B.

D. (3 pts) When the methylamine was replaced as nucleophile by aniline (Ph-NH2), reaction with D in DMSO
gave a product (F) for which []D = 0o. Explain why this nucleophile gives a product with []D = 0o.
H H
H
N

NC
F

_________________________________________________________________________________________

End Exam 3

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