PROBLEMS ON ALKENE CHEMISTRY 2004 OCHeM.

com


1
1. Answer the following questions concerning the three alkenes shown below. Your answer should
use words and illustrations.
CH
3
O CH
3
C
A B C
1 2 3 4 5 6
F
F F
! -
! -
! -
O CH
3
! +


a) Which alkene would be most reactive with H
+
? Why?

B Resonance places a large amount of negative character on the double bond, making it a good
nucleophile.

b) Which alkene would be least reactive with H
+
? Why?

C Induction electron density from the double bond, making it a poor nucleophile.

c) Which alkene would be most reactive under conditions of catalytic hydrogenation? Why?

Since no charges are formed in catalytic hydrogenation, the electrostatic arguments used above
are less valid. One factor that may play a part is steric hindrance. Since the alkene must
approach the metal surface to react, any bulky groups that might prevent the alkene from
approaching the metal surface might slow down the reaction. B would be the least hindered
since the methyl group can be pointed away from the metal, while the other substituents always
have some part of it pointing towards the catalytic surface.

C
H
H
H
O
CH
3
C
F
F
F
metal surface


PROBLEMS ON ALKENE CHEMISTRY 2004 OCHeM.com


2
d) Will all three alkenes undergo Markovnikov addition of HBr? If not, which alkene or alkenes
wont and why?
In both A and B, the carbocation leading to Markovnikov product is more stable than that
leading to the anti-Markovnikov product. However, in C, the positive charge is even more
localized by induction, making it the less stable carbocation. The stability favors the carbocation
on the other carbon, leading to the correct product.

A B C
CH
3
O CH
3
C F
F F
! -
! -
! -
O CH
3
! +

PROBLEMS ON ALKENE CHEMISTRY 2004 OCHeM.com


3
2. Provide a mechanism for the following reaction. Then, predict the reaction energy diagram for the
entire reaction in the space provided. In your diagram, you must indicate the !H of the reaction,
label the activation energy (E
a
) of the rate-determining step, and clearly identify all intermediates
and products of the reaction.
Br
H Br
Br
H
H
H
H
+
A
B
C
D


A
H Br
B
Br
C
Br
D
!H
E
a
E
n
e
r
g
y
Rxn Coordinate


PROBLEMS ON ALKENE CHEMISTRY 2004 OCHeM.com


4
3. What starting materials & reagents are needed to produce the following compound?

Br
2
Br Br


4. Draw the major product of each of the following reactions. Be sure to include stereochemistry in
your answers where appropriate.

CH
3
CH
3
CH
3
CH
3
Br
2
H Cl
Cl
2
CH
3
CH
2
OH
CH
3
OH
CH
3
CH
3
Cl
H
CH
3
CH
3
Cl
H
CH
3
H
OH
CH
3
CH
2
O
Cl
CH
3
Br
Br
CH
3
H
OH
CH
3
CH
3
Cl
H
CH
3
CH
3
Cl
H
CH
3
Br
Br
CH
3
CH
2
O
Cl
d)
a)
b)
c)
1) Hg(OAc)
2
/ H
2
O
2) NaBH
4
1) BH
3
THF
2) H
2
O
2
, NaOH