Chemistry 303

fall 1994
THIRD EXAMINATION
8:00 am, December 9th, 1994
Duration: 2 hr
Name________________________________________________
Lab TA.______________________________________________

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 SOMETHING
NOTE: write your mechanisms CAREFULLY. A good answer will require precision in the use of the
arrows.
Grade:
1._______/20
2._______/40
3._______/10
4._______/30
total: _____/100
There are 8 pages in this exam; please check now to be sure you have a complete set.

Pledge:_________________________________________________________________________________
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I. (20 pts) Choose that reaction of each of the following pairs which proceeds fastest and write the major
product(s) for that reaction. Assume identical conditions where not specified. Write a one-sentence
explanation for your choice, and name the mechanism you have chosen.
A.

1.

+ NaOH

Br
Br

2.

+ NaOH

_______________________________________________________________________________________

B.

1.

(CH3 )3 N:

CH 3 CH2 I

2.

(CH3 )3 N:

CH 3 CH2 I

CH3 OH

hexane

_______________________________________________________________________________________
C.

1.

2.

N:

..

(CH3 )2 NH

CH3 CH2 I

CH3 CH2 I

CH3 OH

CH3 OH

_______________________________________________________________________________________
D. 1. n-butyl methyl ether + HI
Write a mechanism
for your choice.
2. n-butyl ethyl ether

+ HI

_______________________________________________________________________________________
E.
O +

MgBr

O +

MgBr

ether

ether

II. (40 pts) Consider the following rate and product data: reaction (B) is much faster than (A) under the same
conditions. Reaction (A) gives only one product (C) while reaction (B) gives a mixture C + D, favoring D.

(A)

Cl
A

(B)

ether

C, C 7 H12

CH3

Cl
B

K+ -OC(CH3 )3

K+ -OC(CH3 )3
ether

C + D, both C 7 H12

D is the major product

CH3

Note also that reaction of either A or B with silver nitrate in ethanol gives a mixture of C + D and substitution
products (same mixture from either reactant):

(C)

Cl
A

CH3

AgNO3
EtOH

mixture of C+ D
and substitution
products

AgNO3
EtOH

Cl
CH3 B

__________________________________________________________________________________
1. (4 pts) Draw the more stable chair form of each of the starting materials, A and B . Which is of higher
energy (less stable)? Discuss any ambiguity. Indicate on one of your structures whether the CH3 group and
the Cl are axial or equatorial.

2. (4 pts) Suggest structures for C and D. Point out two features from each NMR spectrum which clearly
differentiate the structures. NMR spectra data (next page):
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C: 0.9 ppm, doublet with J = 7Hz area 3H; series of multiplets between 1.2-2.2 ppm, area 7H;
5.6 ppm, multiplet, area 1H; 5.7 ppm, multiplet, area 1H.
D: 1.5 ppm, multiplet, area 4H; 1.7 ppm, singlet, area 3H; 1.9 ppm, multiplet, area 4H;
5.4 ppm, broadened singlet, area 1H.

3. (5 pts) Using the usual arrow formalism, write a mechanism for reaction (A).

4. (5 pts) Write a mechanism for reaction (B) which shows clearly the formation of both products.

5. (10 pts) Using the usual reaction coordinate diagrams, compare reaction (A) and reaction (B). Indicate the
position of the reactant, product(s), transition state(s), and intermediates (if any). Take care to show the
relative energies which justify the difference in rate [reaction (B) is faster than ( A)].

6. (2 pts) Explain why product D is preferred over C in reaction (B).

7. (6 pts) Write a mechanism for substrate A in reaction (C). In addition to C and D, three different
substitution products are likely. Write them and indicate how each forms in your mechanism.

8. (4 pts) Using your mechanism, predict whether A or B will be more reactive with silver nitrate in ethanol.
Explain briefly.

______________________________________________________________________________________
III. (10 pts) Consider the reaction of X under the conditions specified.
CH 3
H

N:
X

CH 3

a. CH3 I
b. water, heat

HO
CH3

N(CH3)2
Y

What is the configuration of the

stereogenic carbon in X ?
R or S

Write the usual stepwise mechanism for the reaction. Show all intermediates. Is the product Y most likely to
be optically active (primarily one enantiomer)? If so, is it the result of inversion or retention? Be sure your
mechanism is consistent with the result.

IV. (30 pts). In an early mechanistic study, the following data were collected on compound E. Reaction of E
with thionyl chloride (SOCl2) produces compound F as the organic product. Treatment of F with sodium
hydroxide gives G. Oxidation with CrO3 of either E or G leads to H. Reaction of E with ZnCl2/HCl gives a
product, J, with the same NMR spectrum as F but zero molecular rotation. A startling mechanistic conclusion
(since proven wrong) was deduced from these reactions and the molecular rotation data given below.
[J] []D 0o
ZnCl2
HCl

CH3

H
OH

SOCl2

E
CrO3

[F]
[]D +43o

[]D +10o

NaOH

[G]
[]D -10o

CrO3

[H] []D 0o

[H] []D 0o
_________________________________________________________________________________________________________

A. (3 pts) What is the absolute configuration of E in the R/S system? R

(circle best)

B. (9 pts) Draw structures for F, G, and H. Assign absolute configuration (R/S) to F and G.

C. (3 pts) Why is H optically inactive?

D. (3 pts) Why is J optically inactive?

E. (6 pts) Propose a mechanism for the conversion of E to F with thionyl chloride which is consistent with
the relative configurations implicated by the data above.

F. (6 pts) The mechanistic conclusion brings into question the reliability of the experimental data, especially
the rotation value for G. Suggest a mechanism more in line with general theory for this sort of reaction and
indicate how it would require different rotation data.

THAT'S IT!

See you TUESDAY (or, for sure, after the holidays).

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