Chapter 5.

Alkenes and Alkynes II:

Reactions
Elimination Reactions
Addition Reactions
 Addition of Halogens
X
C C + X2 C C
X
 Examples
Br
Br2
CH3CH2CH CH2 CH3CH2CHCH2Br

Cl
Cl2
CH3CH CHCH2CH3 CH3CHCHCH2CH3
Cl
Mechanism
 Halohydrin Formation
OH
C C + X2 H O C C
2
X

OH
Br2
CH3CH CHCH3 CH3CHCHCH3
H2O
Br
 Mechanism
Br Br
Br
CH3CH CHCH3 CH3CH CHCH3

OH2

Br Br
CH3CHCHCH3 CH3CHCHCH3
OH OH
H
Orientation of the OH toward the more stable
cabocation (follows Markovnikov addition)
Hydrogenation

Addition of Hydrogen
 Reduction of Alkenes
• Addition of H-H across C=C
• Reduction in general is addition of H2 or its equivalent
• Requires Pt, Pd, or Ni as powders on carbon and H2
• Hydrogen is first adsorbed on catalyst
• Reaction is heterogeneous

M
C C + H2 C C
H H
M = Pt, Pd, or Ni
 H2
CH3CH2CH CH2 CH3CH2CH2CH3
Ni

CH3 H H2
C C CH3CH2CH2CH3
Ni
H CH3

CH3 CH3 H2
C C CH3CH2CH2CH3
Pt
H H
Mechanism
 Addition of Water to Alkenes

• Acid-Catalyzed Hydration
• Oxymercuration-Demercuration
• Hydroboration-Oxydation
Acid-Catalyzed Hydration

OH
C C + H2O H
C C
H
 Mechanism
H OH2

CH2 CH2 CH2 CH3

H
OH
CH2CH3 CH3CH2OH
Mechanism
 Markovnikov Addition

H
CH3CH CH2 H2O CH3CHCH3
OH
Oxymercuration-Demercuration
Use mercuric acetate in THF followed by sodium
borohydride
Markovnikov orientation
via mercurinium ion
Mechanism
 Hydroboration-Oxidation
OH H
.
1. BH3 THF
C C C C
2. H2O2

•Herbert Brown invented hydroboration (received the

1979 Nobel Chemistry Prize.)

•Borane (BH3) is electron deficient is a Lewis acid

•Borane adds to an alkene to give an organoborane

Hydroboration-Oxidation
 BH3 Is a Lewis Acid
• Six electrons in outer shell
• Coordinates to oxygen electron pairs in ethers
 Hydroboration-Oxidation Forms an
Alcohol from an Alkene
• Addition of H-BH2 (from BH3-THF complex) to three alkenes
gives a trialkylborane
• Oxidation with alkaline hydrogen peroxide in water produces
the alcohol derived from the alkene
 Orientation in Hydration via
Hydroboration
• Regiochemistry is opposite to Markovnikov
orientation (Anti-Markovnikov)
– OH is added to carbon with most H’s

• H and OH add with syn stereochemistry, to

the same face of the alkene (opposite of anti
addition)
 Anti-Markovnikov Addition

H3C CH3
.
1. BH3 THF
C CH2 CH3 CH CH2
2. H2O2
H3C OH
Syn Addition
 Mechanism of Hydroboration
• Borane is a Lewis acid
• Alkene is Lewis base
• Transition state involves
anionic development on
B
• The components of BH3
are across C=C