1

Chemistry 303
fall 2005
FINAL EXAMINATION
1:30 pm, January 24th, 2006
Duration: 3 hr
There will be an additional 30 min added before the exams are collected, for the course evaluations by those of
you who did not fill out one before.

KEY_______________________________

Name_________________

Lab TA______________________________________________ [do not write Julia nor Brow]

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-NOTE: write your mechanisms CAREFULLY. A good answer will require precision in the use of the arrows
and description of spectral information. READ each question completely and carefully before answering. As
usual, a resonance argument requires resonance structures carefully drawn.
Please be aware that a small number of students will be taking the exam tomorrow. It would be well not to
discuss the exam until after that time.
There are 14 pages in this exam. Please check to be sure you have a complete set.
Write only in the space provided for each question.
Score:
p2______/20
p8_______/12

p3_______/20
p9_______/12

p4_______/23
p10_______/15

p5_______/20

p6______/17

p7_______/14

p11______/21 p13____ /17

p14_______/09

Total: _________/200

PLEDGE:_________________________________________________________________

I. (20 pts). For each of the following pairs of reactions,

a. predict which will occur faster,
b. write the most likely organic product for the faster reaction,
c. write the mechanism (not transition states) for the faster reaction, and
d. give the single most important reason for the difference (explain in detail). Explain any ambiguity.
A.

Br
+

THF
solvent

N:
H

OMe

Br

Better cation;
better TS,
faster reaction

THF

N:

OMe

solvent

New resonance structure;

added bond makes it a "good"
structure

OMe
H
faster

:N

E1
+

H N

OMe

OMe

This process could be SN1, E1, or E2. E2 is disfavored by the fact that the base is weak. The SN1/E1 are strongly
favored by the ease of ionization of a tertiary benzylic halide. Then the overall rate would be the first ionization step,
and the nature of the base is irrelevant.
In the absence of a good nucleophile, the second step (product determining) would likely be E1, leading to the
alkene.
The second reaction has the weaker base (lone pair held tightly in sp2 orbital), but that is irrelevant to the RDS and
therefore the overall rate.

____________________________________________________________________________
H+
B.

H
:OH2

H2SO4 (catalytic)
H2O

H
H

O
H

faster

H2SO4 (catalytic)
H2O
b

H
O
H

H+

This is electrophilic addition of a proton to an alkene. The RDS is the first step, formation of the cation.
The first reaction leads to cation (a), a tertiary cation. The second reaction leads to a secondary cation (b),
less stable. Therefore, since the TS for such reactions parallels the stability of the intermediate cation, the
first reaction TS will be more stable and this reaction will be faster.