1

Chemistry 303
fall, 2000
THIRD EXAMINATION
7:30 PM, DECEMBER 4TH, 2000
Duration: 2.5 hr
Name____________________________________________________________
Lab TA__________________________________________________________
(if you do not know his/her name, give day of lab section. NOT Hooley nor Chlenov)
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 for each question.
Score:
1___________/17
2___________/14
3___________/16
4___________/23
5___________/20
6___________/10
Total:

/100

There are 10 pages in this exam, followed by two pages of spectra. Please check now to be sure you have a
complete set. You may detach the spectra pages and leave them separate from the exam.
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

2
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.

PLEDGE:_________________________________________________________________
I. (17 pts) Consider the following reaction. The specific rotation of A is [!]D = +26o. After the reaction
with NaOEt is complete, the rotation of the product mixture and the 1H NMR spectrum can be measured.
Me H

Me H
Cl
+ NaOEt

H Me
OEt

OEt

and/or

(THF, solvent)
A

A. (5 pts) In a perfect SN2 process, what would be the specific rotation of the product(s)?
(circle)
+26o
-26o
0o
+13o
cannot tell
Explain your choice by writing the mechanism of this reaction, using the usual arrow formalism and
showing any intermediates and the major product(s). You need not show transition states.

B. (4 pts) In another experiment, the NaOEt/THF mixture was replaced with Ag(NO3)/EtOH (solvent). After
reaction was complete, the 1H NMR spectrum was the same as that from (A), but the rotation was
measured to be 0o. Explain carefully in terms of a mechanism which shows clearly the role of the
Ag(NO3). Explain why the rotation is 0o and yet the 1H NMR spectrum is unchanged.

continued
C. In another experiment, with Ag(NO3) and CH2Cl2 as solvent, the product(s) again showed a rotation
of 0o, but the NMR spectra were different from that expected for A/B [See Spectra, p 11]
1. (3 pts) Draw the structure of the product which is likely to form under these conditions and
consistent with this 1H NMR spectrum. Point out one key aspect of the 1H NMR spectrum which is
inconsistent with the structures A and B, and consistent with your structure.

2. (1 pts) Explain carefully why the rotation is 0o for the product.

3. (4 pts) Show the mechanism by which it forms. What is the name of this mechanism? Explain why
this product is favored with these reaction conditions compared to those in part (B).

II. (14 pts). The reaction below represents a series of three experiments where the three versions of G,
differing in the substitutents X, underwent conventional hydroboration. In each case, hydroboration of the
reactants shown below leads to two boron compounds, C and D. Since there is excess BH3, each boron
reacted only once. The usual oxidation in base provides the alcohols, E and F. The ratio of E and F in the
product mixture varied depending on X, as shown in the Table.
{C}

H
X

NaOH
+ excess BH3

H2O2

X
E

and

H
{D}

H2O2
NaOH

CH2 CH2OH

OH
X
F

. X
E
F .
H
81% 19%
OCH3
93%
7%
CF3
66% 34%
________________________________
A. (8 pts) Draw the product C for the case
where X = H, and the mechanism by which
it forms including a nice picture for the
transition state of the rate-determining step.
Explain why C/E is favored.

CH3

B. (6 pts) Using your mechanism, explain why the process tends to give more C/E when X=OMe
and less C/E when X=CF3.

III. (16 pts). The molecule H is an interesting substrate for substitution chemistry. Write mechanisms to
rationalize each of the following processes, and name the mechanism as well (e.g., SN2, SN1, E2, E1).
If you choose E1, explain why not E2 (and vice versa). If you choose SN1, explain why not SN2 (and vice
versa)
OMe

A. (5 pts)
Cl

OMe
H

NaOMe

OMe

ether solution

OMe

__________________________________________________________________________________
OMe

B. (5 pts)

OMe

NaSMe

Cl

OMe
H

ether solution

MeS

OMe

Explain why this product is preferred

instead of the product in part (A).

__________________________________________________________________________________

6
C. (6 pts)
Cl
H

OMe

EtOH
(solvent)

OMe

catalytic
amount of
H2SO 4

OEt
Cl

OEt

Your mechanism should show the role of the acid, as a catalyst.

[Hint: this is a multi-step repetitive process, where the proton
does its job over and over]
Explain why substitution for -OMe is favored in this case,
while substitution for Cl is favored in part (B).

IV. (23 pts). Consider the reaction of the cyclopropyl alkene K with HBr in ether solution to give mainly one
addition product, J. Based on our general mechanisms, J could be one of 4 isomeric products, a-d.
However, only one is favored for this particular substrate and conditions. The NMR spectra for the favored
product, J, are included on page 12 (Spectra sheet).
Br

H-Br
ether

Br
a

Br

Br
b

__________________________________________
A. (4 pts) Write the best mechanism for the formation of a under these conditions.

B. (4 pts) Write the best mechanism for the formation of b under these conditions.

C. (4 pts) Write the best mechanism for the formation of c under these conditions.

continued
D. (4 pts) Write the best mechanism for the formation of d under these conditions.

E. (4 pts) Considering the 1H NMR spectrum for J shown on the Data Sheets, which of the structures a-d best
fits the 1H NMR spectrum? Re-draw the structure here, and label each group of equivalent protons with
their chemical shift (obtained from the spectrum) and pattern (singlet, doublet, etc., or multiplet). Indicate
clearly which protons are coupled with which others to give the observed patterns.

F. (3 pts) Explain briefly the major factor which makes your choice for J the more favorable product under
these reaction conditions.

V. (20 pts) Consider the following reaction between an alkoxide salt and an ammonium salt.
CH3
O Na

CH3CH2 N CH2 CH3 Cl

S N2
solvent

solvents:
Product
O
THF

OH
isopropyl alcohol

A. (6 pts) What are the most likely products from the SN2 process? Write a mechanism showing this process.
Suggest an alternative SN2 product from these reactants, and explain why it is not preferred.

B. (4 pts) Consider the two solvents shown, THF and isopropyl alcohol. In which solvent would the reaction
proceed at the higher rate? Explain in terms of mechanism.

Continued...
C. (5 pts) Note that the related compound U reacts rapidly to give two products, C9H10O and C3H9N.
Write a mechanism for this process, showing the products. What is the name of this mechanism?
fast
O
U

C9H 10O + C3H 9N

10

D. (5 pts) Note that the related compound W is essentially inert in the following reaction under the same
conditions. Explain the low reactivity of W, considering a mechanism parallel to that in part (C). Consider
the relevant transition state.
Very slow reaction
O

VI. (10 pts). The following conversion involves several steps by examples of our general mechanisms.
A. (6 pts) Please write a careful mechanism, showing all intermediates. Specify which is likely to be the
rate-determining-step and justify your choice.You need not show transition states.
O CH 2CH3

NH
Cl

acetone (solvent)
heat

N
H

H
+ CH3CH 2-Cl

11

B. (4 pts) The same conversion occurs at much lower temperature (faster) if excess NaI is added to the
mixture. Explain the accelerating effect of NaI in terms of mechanism.
O CH 2CH3
O

NH
Cl

NaI
acetone (solvent)

O
O

room temperature
H

H
+ CH3CH 2-I + NaCl