Organic Chemistry

We can say that adds preferentially to C-1 because C-1 is bonded to two hydro-
gens, whereas C-2 is bonded to only one hydrogen. Or we can say that adds to C-1
because that results in the formation of a secondary carbocation, which is more stable
than the primary carbocation that would be formed if added to C-2.

PROBLEM 4

What would be the major product obtained from the addition of HBr to each of the follow-

ing compounds?

a. c. e.

b. d. f.

PROBLEM-SOLVING STRATEGY

a. What alkene should be used to synthesize 3-bromohexane?

The best way to answer this kind of question is to begin by listing all the alkenes that

could be used. Because you want to synthesize an alkyl halide that has a bromo sub-

stituent at the C-3 position, the alkene should have an carbon at that position. Two

alkenes fit the description: 2-hexene and 3-hexene.

Because there are two possibilities, we next need to determine whether there is any ad-

vantage to using one over the other. The addition of to 2-hexene can form two dif-

ferent carbocations. Because they are both secondary carbocations, they have the same

stability; therefore, approximately equal amounts of each will be formed. As a result,

half of the product will be 3-bromohexane and half will be 2-bromohexane.

The addition of to either of the carbons of 3-hexene, on the other hand, forms

the same carbocation because the alkene is symmetrical. Therefore, all of the product

will be the desired 3-bromohexane.

H+ sp^2

H+

2-hexene

CH 3 CH CHCH 2 CH 2 CH 3

3-hexene

CH 3 CH 2 CH CHCH 2 CH 3

sp^2

3-bromohexane

? HBr CH 3 CH 2 CHCH 2 CH 2 CH 3

Br

+

CH 2 CCH 2 CH 2 CH 3 CH 3 CH“CHCH 3

CH 3

CH 3 CH CCH 3

CH 3

CH 3 CH 2 CH“CH 2 CH 3 CH 2

H+

H+

H+

Section 4.4 Regioselectivity of Electrophilic Addition Reactions 149

Vladimir Vasilevich Markovnikov

(1837–1904)was born in Russia, the

son of an army officer. He was a pro-

fessor of chemistry at Kazan, Odessa,

and Moscow Universities. By synthe-

sizing rings containing four carbons

and seven carbons, he disproved the

notion that carbon could form only

five- and six-membered rings.

CH 3 CH CHCH 2 CH 2 CH 3

3-bromohexane

CH 3 CH 2 CHCH 2 CH 2 CH 3 CH 3 CH 2 CHCH 2 CH 2 CH 3

Br

Br−

2-bromohexane

CH 3 CHCH 2 CH 2 CH 2 CH 3 CH 3 CHCH 2 CH 2 CH 2 CH 3

Br

2-hexene

Br−

+

+

HBr

HBr

secondary

carbocation

secondary

carbocation

3-bromohexane

CH 3 CH 2 CH CHCH 2 CH 3 CH 3 CH 2 CHCH 2 CH 2 CH 3 CH 3 CH 2 CHCH 2 CH 2 CH 3

Br

3-hexene

HBr Br−

+

only one

carbocation

is formed