Chemistry 303

fall 1995
THIRD EXAMINATION
7:30 pm, December 5th, 1995
Duration: 2 hr
Name________________________________________________
Lab TA.______________________________________________
(if you do not know his/her name, give time of lab section)
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
Write only in the space provided with each question.
Writing the "mechanism" means showing the electron flow with the arrow formalism relating all intermediates.
It does not mean drawing the transition states, unless such is specifically called for.

Score:
1._______/20
2._______/20
3._______/15
4._______/17
5________/12
6._______/16
total: _____/100
There are 9 pages in this exam; please check now to be sure you have a complete set.
Please be aware that a small number of students will be taking the exam at different times up until the afternoon
on Wednesday. It would be well not to discuss the exam until after that time.

Pledge:_________________________________________________________________________
1

1. (20 pts). Consider substitution reacitons on the structurally related compounds, U and V.

OMe

Ag+
MeOH

OMe

Ag+
MeOH

O
X

Br

Na+ -SMe
MeOH

Br

Na+ -SMe
MeOH

U
O
V

SMe

SMe

A. (5 pts) Write the most likely mechanism for the formation of Z, including a representation of the
transition state for the rate-determining step, showing all partial charges and partial bonds. Be sure
to distinguish between transition states and intermediates (if any). On the chart below, draw a free
energy diagram representing the progress of the reaction. Show clearly the activation energy for the
rate-determining step.

reaction progress
B. (4 pts) Use your mechanism and transition state picture for (A) above to explain why U and V both
react much faster than ethyl bromide under these conditions.

C. (6 pts) Write the most likely mechanism for the formation of W, including a representation of the
transition state for the rate-determining step, showing all partial charges and partial bonds. Be sure
to distinguish between transition states and intermediates (if any). On the chart below, draw a free
energy diagram representing the progress of the reaction. Show the activation energy for the ratedetermining step.

reaction progress
D . (5 pts) Specify whether the formation of X or of W is slower, and explain carefully using the free
energy diagram.

2. (20 pts) Consider the following substitution reaction:

H3C
H

Cl

OH
H 2O

CH3
H C OH
Ph
N

no stereochemistry intended

M [] +22o
The pure enantiomers of N show [] = +16 o, and [] = -16o.
A. (2 pts) What is the absolute configuration of M ?

or

(circle best answer)

B . (5 pts) Nothing is perfect. Using 0.1 M NaOH in water, the product N is isolated by simple
chromatography and shown to have [] +12o.
Write the mechanism(s) for the formation of N , including a careful drawing of the stereoisomer likely
to predominate under these conditions. Specify the configuration for this isomer as R or S

C. (3 pts) Why does the product show [

less than that for a pure enantiomer of N ?

2. Continued:

Re-drawn:
H3C
H

Cl

CH3
H C OH
Ph
N

OH
H 2O

no stereochemistry intended

M [] +22o
D. (5 pts) Using 0.001 M NaOH in water with M, the reaction proceeds slower and, after purification by
chromatography, the product N has [] = +4 o.
Explain carefully the most likely reason for the change in rate and rotation for the product.

E. (5 pts)

Suppose the water is replaced by DMSO as solvent,

with 0.1 M NaOH again.

O
Me

DMSO
Me

i. Please analyze the effect of the new solvent on the reaction rate compared to that for part (B)
above?

ii. Would you expect [ ] to increase or decrease compared to that in part (B) above? Explain.

3. (15 pts) Consider the following reactions:

Cl

H2O
heat

[X]
C5H10O

[Y]
C5H10O

[Z]
C5H8

Selectred Spectral data possibly useful in confirming the structures. You need not interpret the spectral data,
but if you do not know the structure, interpretation can get partial credit.
[X ] 1H NMR: 1.82 (s, 3H), 1.94 (s, 3H); 2.52 (br s, lH), 4.5 (d, J=7, 2H), 5.3 (t, J=7, 1H)
UV: no absorption above 200 nm
[Y] 1H NMR: 1.42 (s, 6H), 2.43 (br s, 1H); overlapping multiplets 5-6 ppm, 3H
UV: no absorption above 200 nm
[Z] 1H NMR: 1.85 (s, 3H), overlapping multiplets 5-6 ppm, 5H
UV: max 224 nm ( 18,000)
A (10 pts) Write structures for X and for Yconsistent with the spectral data and a mechanism for
their formation under these conditions. What is the name of this mechanism? Would you expect X or Y
to be favored?

B (5 pts) Write a structure for Z consistent with the spectral data and a mechanism for its formation
under these conditions. What is the name of this mechanism?

4. (17 pts) The reaction of 1-methylcyclohexene with a mixture of bromine and water gives a single product,
A. The product can undergo reaction with NaH in ether solution to give a new molecule, B by loss of the
elements of HBr.
CH3
CH3
O
Br2, H2O
NaH
B
A
ether
C7H13BrO
A (6 pts) The following structures have the correct molecular formula for A. Pick the one which is
most likely for A and draw the mechanism which explains its selective formation. Draw all
intermediates and be sure your mechanism reveals the regio- and stereo-selectivity.

OH

Br

HO

Me

B. ( 2 pts) The following structure

H
is identical to which of
HO
the chair drawings?

Br

OH
Br

Me

OH

Me
Br

Br

HO

Me

Me

Br

(circle correct answer)

Me

C. (2 pts) In structure ( ), what is the absolute configuration of the carbon bearing the OH group? R S
(circle)
D. (2 pts) Which is the least stable molecule?
(circle single best answer)
Explain in one sentence:
E. (5 pts) Draw the alternate (less stable) chair arrangment for A. Which chair form of A is the best precursor
of B? Show by writing a mechanism for formation of B from A.

5. (12 pts) Compound B can be converted into two new isomers, under the following conditions:
CH3
O
B

OH
CH3 +

a. Li NMe2
b. neutralize
C

CH2

OH

D OH

CH3
not observed

A. (2 pts) Is the LiNMe2 behaving as a strong base or nucleophile in this process?

B. (6 pts) Write a mechanism for the formation of C ; Name this mechanism.
[It may be helpful to draw a chair representation of B at the outset]

C. (4 pts) Explain carefully why E is relatively disfavored following a similar mechanism.

6. (16 pts). There is a wonderful leaving group: N2! It can be arranged by treating an amino group with
HONO (nitrous acid) to form a diazonium ion, which then ionizes with loss of N2 or can be nudged
out by an electron pair.
H 2O

R-NH2 + HONO

R N N
diazonium ion

N2

The nudging can be internal, as reflected in the following examples. The interesting point here is that the
product structure depends on the stereo-arrangement of the groups on the cyclohexane ring.

N2+

N2+

H
O

OH

B.

H
OH
H

H
O

H
H

N2+
OH

C.
H

Write mechanisms for each case, A-C. The key idea in each example is "what nudges out the N2+ ?" Be sure
your description makes clear why the particular product is favored in each case.Write clearly.