CHEM

221

Bruice Chapter 4

4.37 a)

b)

Answers to problems in the coursepack

c)

d)

nucleophile

electophile
CH3CHCH3

CH3CH=CH2
nucleophile

4.38a)

H-Br
electophile

b)

4.39 a)

c)

h)

i)

d)

f)

j)

k)

g)

m)

4.41 a)

CHEM 221

Bruice Chapter 4

Answers to problems in the coursepack

B is a tetrasubstituted alkene, A is a trisubstituted alkene and C is a disubstituted alkene. The more

substituted the alkene is the more stable it is. Hence 2,3-dimethyl(B) is the most stable, 3,4-dimethyl
(A) is the second most stable and 4,5-dimethyl (C) is the least stable.
b) B it is the most stable, the lowest in energy and it will give the smallest amount of energy upon
hydrogenation. Since the reaction is exothermic, it will be negative and the highest value. It will be the
least negative of the three.
c)C it is the least stable, the highest in energy and it will give the largest amount of energy upon
hydrogenation. Since the reaction is exothermic, it will be negative and the smallest value. It will be the
most negative of the three.

H+
H2O
1)Hg(OAc)2
2) NaBH4

1) BH3 THF
2) NaOH, H2O2

4.42

CHEM 221

Bruice Chapter 4

Answers to problems in the coursepack

4.43

The first step involves protonation of the double bond. It can produce two carbocation A, with 1
electrondonating group i.e. primary and B, with two electrondonating groups i.e. secondary.
Electrondonating groups stabilize the electrondeficient carbocation by donating electrons. B is more
stable than A because it has more electrondonating groups. It is the major intermediate formed in the
first step. Whence B is formed it could react with the bromide ion to form 2-bromo-3-methylbutane. B
could also rearrange to form C. The migration of a hydride H- forms a new carbocation C which is
tertiary i.e. it has three electrondonating groups. It is more stable than B and can further react with Br-
to give 2-bromo-2-methylbutane.
4.44 a) See structures in 3.37 L is the most stable because it is the most substituted. It is the only one
that has four alkyl substituents. Each alkyl groups increases the number of C-sp2-Csp3 bonds which are

most stable thanCsp3-sp3 bonds.

b)Among all possibilities, A is the only that has only one alkyl group on the double bond. With the

A
fewest number of alkyl groups, it is the least stable alkene.

CHEM 221

Bruice Chapter 4

Answers to problems in the coursepack

4.46

1)BH3THF
2) NaOH, H2O2

H2

Br2
THF

Pd/C
HBr

H+
H2O

Br2
H2O

4.47a)

d)

e)

f)

h)

CHEM 221

Bruice Chapter 4

Answers to problems in the coursepack

H2
HCl

Pd/C
4.48 a)

THF c)

b)

1)BH3THF
2) NaOH, H2O2

Br2
H2O e)

d)

H+
H2O

4.49

4.50 a)first one is tertiary, second one is secondary; first one is more stable. B)second one is more stable

because the chlorine can stabilize the carbocation by forming a chlorinium ion
c)first
one is a trisubtituted alkene and the second one is disusbtituted. First one is more stable. d) Same
argument as c) , but second compound is more stable.
4.57 a) There are five alkenes.

H2
Pt
A

CHEM 221

Bruice Chapter 4

Answers to problems in the coursepack

b)B is the most stable because it is the most substituted alkene with three alkyl groups. All other ones
have two alkyl groups.
4.58 a)

b)The initially formed carbocation is B. A is not formed because it is primary, 1EDG. B is tertiary with 3
EDG and is more stable than A.
c) The first rearranged carbocation, C, is secondary. The second rearranged carbocation, D, is tertiary.
d) The first rearrangement from B to C produces a secondary carbocation(C), less stable than a tertiary
carbocation(B). Ring strain should also be considered. C is a five-membered ring whereas B is a four-
membered ring. C, although it is secondary is more stable than B because it has less ring strain. This is
the driving force for the first rearrangement.
The second rearrangement from C to D is standard. The rearranged carbocation is tertiary i.e. more
stable than C (secondary). Both are five-membered rings. Ring strain is not an issue.

CHEM 221

Bruice Chapter 4

Answers to problems in the coursepack

4.60

For this problem, the rearrangement from B to C is also favored due to ring strain relief. Six-membered
ring has less ring strain than five-membered ring. The rearrangement is also favored due to the fact that
C is tertiary whereas B is secondary.