CHAPTER 9:

ELECTROPHILIC
ADDITION REACTION
 Learning objectives
• Recognize and explain the electrophilic
addition mechanism of alkenes and alkynes
• Explain the Markovnikov regiochemistry
• Predict carbocation stability and
rearrangement products
• Illustratethe different reactions and
mechanisms using examples

2
 Alkene
• Compounds with C=C
• General formula C H n 2n

• Also known as olefins

• Example: Ethylene (ethene) – plant hormone for
fruit ripening

H H

C C

H H 3
Electrophilic Addition of Hydrogen
Halides to Alkenes
General equation for electrophilic addition

 When EY is a hydrogen halide

4
 Electrophilic Addition Reaction

• Alkene behave as nucleophile in polar reaction

• Double bond is electron rich. Donate electron
• Example: Addition of HBr to (CH ) CH =CH 3 2 2 2

H3C H H3C H H3C H

C C C C H H3C C C H
H3C H H3C H Br H
H
Br
Br

5
• Electrophilic addition of hydrogen halides to
alkenes proceeds by rate-determining formation
of a carbocation intermediate

6
7
 Regioselectivity of
Hydrogen Halide Addition :
Markovnikov’s Rule

8
• When double bond has the same degree of
substitution, a mixture of products will be
formed.

CH3CH2CH CHCH3

ether Br H
CH3CH2CH CHCH3 + HBr +
CH3CH2CH CHCH3
H Br

9
 Markovnikov rule
In addition of HX to an alkene, the hydrogen attaches to the
carbon with fewer alkyl substituents and the X attaches to
the carbon with more alkyl substituents.

H3C H3C
HC CH2 + HCl CH CH2
Cl H
propene 2-chloropropane

via the most substituted carbocation i.e. the most stable

10
Mechanistic Basis for Markovnikov's Rule:

H H R R

C C C C
H H R H R H R R
methyl primary (1o) secondary (2o) tertiary (3o)

less most
stable stable
stability increases
11
Examples:

12
13
 Carbocation Rearrangements
in Hydrogen Halide Addition to Alkenes

14
 1) Hydride shift
• Rearrangement of carbocation to form a more stable
carbocation
• Example:
H H
hydride
H3C H H shift H
H3C H3C
C C C H C H
H3C C C C
H H3C C H H3C C H
H H Cl H H
H

A 2o carbocation A 3o carbocation

Cl- Cl-

H Cl
H H3C H
H3C
C H C H
C C
H3C C H3C C H
H
Cl H H
H

approx. 50% approx. 50%

15
 2) Methide shift

• Shift of an alkyl group can also occur.

• Example:

CH3 CH3
methyl
H3C H H shift H
H3C H3C
C C C H C H
H3C C C C
H H3C C H H3C C H
H H Cl H3C H
H

A 2o carbocation A 3o carbocation

Cl- Cl-

CH3 Cl
H H3C H
H3C
C H C H
C C
H3C C H3C C H
H
Cl H3C H
H

16
 Reactions of alkene
1) Addition of halogens
• Br2 and Cl2 adds readily to form 1,2 –dihalides, F2 is too reactive, I2 do not react
with most alkenes

• anti-stereochemistry, involving a halonium ion R2X+ intermediate which blocks

attack of the X- on the same side

Br Br Br
Br Br
C C C C C C C C

Br
+ Br-

+ Br-
H Br
H H trans-1,2-dibromo
H H cyclopentane
Br Br H
Br Br

17
 2) Formation of halohydrin
• Alkenes add HO-X (X=Br,or Cl) when they react with halogen in the
presence of water
• Anti-stereochemistry water competes with the X- ion as
nucleophile and intercepts it to react with the halonium ion
intermediate to form a halohydrin
Br
Br Br Br Br
C C
C C C C C C
OH
H
+ H 2O
H2O

Br
C C

OH
Reaction carried out in solvent such as DMSO (wet ie with water) using NBS
(N-bromosuccinimide) as source of Br2

18
 3) Hydration
i) Acid catalyzed hydration
• Water adds to alkene to give alcohols in the presence of strong
acid catalyst.
• Reaction important industrially but reaction conditions are too
severe for most molecules.
H2O H
H A - H
H3C H + A O H
CH3 H
C C C C H CH3 C C H
CH3 H H3C H CH3 H

CH3 H
CH3 C C H
OH H
2-methyl-2-propanol
19
 ii) Oxymercuration
• Markovnikov product
• Product form by addition of Hg(OAc) followed by reduction with
NaBH4 via mercurinium ion

i) Hg(OAc)2, H2O/THF CH3

CH3
ii) NaBH4 OH

1-methylcyclopentanol

Mechanism:
OAc
Hg HgOAc HgOAc
H
HgOAc
CH3 CH3 NaBH
CH3 H2O 4 CH
3
CH3 OH
O H
OH
H
mercurinium ion H 2O

20
iii) Hydroboration
• Addition B-H bond of borane, BH3, to yield organoborane
RBH2 intermediate. C-B bond form on the least substituted
carbon. Considering the steric effect.
• Oxidation of alkylborane with H2O2 gives alcohol
• Anti-Markovnikov product
H
H
H B H H BH2
H B H
+ C C
C C
C C
alkylborane

21
Hydroboration (cont.)

• In THF, borane-THF complex form:

H H
H B O H B O
H H

• Rapid borane addition to the double bond, occurring 3

times to yield a trialkylborane which is then oxidized to
the alcohol with H2O2
OH

THF H2O2
3 + BH3 3 + B(OH)3
B OH-, H2O

22
Hydroboration (cont.)

• In the addition to unsymmetrically substituted alkene,

boron adds to the less substituted carbon. Less steric
crowding in the transition state.
H2O2, OH-
+
H CH3
H H2B CH3 CH3
H B HO
H (less steric crowding)

CH3 does not

happen
+
not formed
H CH3
H B H H2B CH3

H
(more steric crowding)

23
 Example:

CH2CH3 CH2CH3
H
CH3CH2
1. Hg(OAc)2, H2O 1. BH3, THF HO
2. NaBH4 2. H2O2, OH-
HO H
H H
anti-Markovnikov addition Markovnikov addition

Something is
wrong
somewhere.. But
what is it?

24
 Alkoxymercuration-Demercuration:
preparation of ether
• Use mercuric acetate with an alcohol to add RO-H to a
double bond and form the Markovnikov product.

H
1) Hg(OAc)2, CH3OH
CH3CH2CH CH2 CH3CH2CH CH2
2) NaBH4
OCH3

Hg(OAc)2 NaBH4
CH3CH2CH CH2 CH3CH2CH CH2 CH3CH2CH CH2

OCH3 HgOAc OCH3 H

25
ALKYNE
C C
 Alkyne
• Compound containing triple bond
• sp carbon, linear geometry
• Name ending –yne
• If a compound has both a double and triple bond, double bond is
given a lower number.

HC CCH2CH2CH CH2
hex-1-en-5-yne

27
 Reaction of alkynes

1) Addition of HX – follow Markovnikov regiochemistry

If HBr is in excess, second HBr can add to give dihaloalkane

Br H Br H
HBr HBr
CH3CH2CH2CH2C CH C C Br C C H
CH3CH2CH2CH2C H CH3CH2CH2CH2C H

2) Addition of Br2 and Cl2 – trans stereochemistry

Br H Br Br
Br2 Br2
CH3CH2C CH C C CH2CH3C C CH
CH2Cl2
CH3CH2C Br Br Br

Mechanism similar but not identical to addition of alkene.

Vinylic carbocation form less readily than alkyl 28
 3) Hydration
i) Hg2+ catalyzed hydration (direct addition of water)

Mercury(II) sulfate as Lewis acid catalyst. Follow Markovnikov

regiochemistry (OH added to highly substituted carbon, H to less
substituted)
H2O, H2SO4 HO H
CH3CH2CH2CH2C CH
HgSO4 C C
CH3CH2CH2CH2C H

keto-enol
tautomerism

CH3CH2CH2CH2C CH3
Tautomer = constitutional isomer that interconverts rapidly
29
 Alkyne hydration
a) Internal alkyne (unsymmetrical) (gave 2 ketones)
H3O+ O O
R C C R' +
HgSO4
R CH2R' RH2C R'
mixture

b) Terminal alkyne (only one methyl ketone formed)

H3O+ O
R C C H
HgSO4
R CH3

A methyl ketone

30
 ii) Hydroboration
Product is ketone or aldehyde (anti-Markovnikov product)
H BH2 OH
BH3 H2O2 H
3 H3CH2CC CCH2CH3
C C
THF C C
H3CH2C CH2CH3 H2O, NaOH H3CH2C CH2CH3

keto-enol
tautemerism

3
H3CH2CH2C CH2CH3

H BH2 O
BH3 H2O2
H3CH2CC CH C C
THF H2O, NaOH
H3CH2C H H3CH2CH2C H

31