Alkenes and Alkynes:

Addition Reactions
Table of content

1. Addition Reactions of alkenes

2. Addition of Unsymmetric Reagents to Unsymmetric

Alkenes; Markovnikov’s Rule

3. Hydroboration of Alkenes; Anti-Markovnikov’s Rule

4. Addition Reactions of Alkynes

1. Addition Reactions of alkenes

1. Addition of Halogens

2. Addition of water

3. Addition of acid

4. Addition of hydrogen
1. Addition of Halogens

Addition of X–X (X = Cl, Br, I) across

a C=C bond.

Br
Br2
C C C C
CCl4
Br
(vicinal
dibromide)
2. Addition of Water(Hydration)
• Addition of H–OH across a C=C
bond
• H+ is the electrophile
OH H
H2O
H2C CH2 H2C CH2
dilute H3O+
(e.g. dilute H2SO4, H3PO4)
3. Addition of Acid

• Addition of HCl, HBr, HI and H2SO4

across a C=C bond.
• H+ is the electrophile.

Br H
  Br
+ H Br
fast
3. Addition of Hydrogen

 Hydrogen adds to alkenes in the presence of an appropriate

catalyst. The process is called hydrogenation.
 The catalyst is usually a finely divided metal, such as nickel,
platinum, or palladium.
H2
H H
Pt, Pd or Ni
C C C C
solvent
heat and pressure

 Hydrogenation is an example of addition reactions on alkenes.

2. Addition of Unsymmetric Reagents
to Unsymmetric Alkenes: Markovnikov’s Rule
 For Symmetrical substrates
H H E Nu Nu E
E Nu same
C C H C C H as H C C H
H H H H H H

For Unsymmetrical substrates

H3C H E Nu Nu E
E Nu different
C C CH3 C C H from CH3 C C H
H H H H H H
Markovnikov’s
Rule
“ When an unsymmetric reagent adds to an unsymmetric
alkene, the electropositive part of the reagent bonds to the
carbon of the double bond that has the greater number of
hydrogen atoms attached to it.”.

  Nu
E Nu E

E = Electrophile it is always electropositive part and searches for negative charge

Nu = Nucleophile it is always electronegative part and searches for positive charge

 H H

☓
Br

(1o cation) fast Br

(minor)
H Br
slow
(r.d.s.)
H H
Br

(2o cation) fast

Br
(major)

Step 1
Step 2
 Example
s
Cl H
H Cl
(1) +
H Cl

(95 : 5)

H OH
H OH
(2) +

OH H
(98 : 2)
3. Hydroboration of Alkenes:
Anti-Markovnikov’s Rule
• Hydroboration involves addition of a hydrogen boron bond to
an alkene.
• The bond is polarized with the hydrogen δ- and the boron δ+.
Addition occurs so that the boron (the electrophile) adds to the
less-substituted carbon.

- +
R CH CH2 + H B R CH CH2 B

H
alkylboranes can be oxidized by hydrogen peroxide and
base to give alcohols.

Hydroboration oxidation reaction provides a route to

alcohols in the reverse of Markovnikov’s Rule
Markovnikov
OH
6 4 2 6 4
H3O , H2O
1 2 1
5 3 5 3

H
1-Hexene 2-Hexanol

Anti-Markovnikov
H
.
6 4 2 1. BH3 THF 6 4
OH
1 2
5 3 2. H2O2, HO 5 3 1

1-Hexene 1-Hexanol
(90%)
4. Addition Reactions of Alkynes.

1. Addition of Halogens

2. Addition of Hydrogen halides

3. Addition of Hydrogen
1. Addition of Halogens

X X
X2 (excess)
R C C H R C C H
CH2Cl2
(X = Cl, Br, I) X X

X H X X
X2 X2
R C C H C C R C C H
H X X X
(anti-addition)
 2. Addition of Hydrogen Halides.

X H
H X (excess)
R C C H R C C H
(X = Cl, Br, I)
X H

Br H Br H
HBr HBr
H3C C C H C C CH3 C C H
CH3 H Br H
gem-dibromide
 2. Addition of Hydrogen.
Full Hydrogenation into alkanes strong reducing conditions

H2 H H

Pt or Pd
H2

H H
Using these reaction
conditions, alkynes are usually
converted to alkanes and it is H H
diYcult to stop at the alkene
stage
 End of Lecture 6 
Thank You