1

C H CH
Addition to Carbon-Carbon Pi Bonds
C H
2
CH
2
H
2
O
catalyst
C H
3
OH
Need a catalyst
This is one way ethanol is manufactured
How does this reaction proceed?
Pi Bonds
Alkene Alkyne
Two election clouds Many mechanisms that apply
alkenes also apply to alkynes.
Generic Addition Mechanism
R
R R
R
electrophile
RDS
C
+
elec
R
R R
R
nucleophile
elec
R R R
nuc R
Carbocation Intermediate:
Which fate?
Rearrangement nothing better than tertiary
Lose proton no protons to lose
Capture nucleophile!
H
H H
H
2
C
+
C H
3
C H
3
H
Br
-
CH
3
C H
3
C H
3
Br
CH
4
CH
2
+
C H
3
C H
3
Br
-
C H
3
C H
3
Br
CH
2
H X
X H
Addition of HX to a Pi Bond
X = Cl, Br, I
CH
2
C H
3
C H
3
H Br
C
+
C H
3
C H
3
H
or
CH
2
+
C H
3
C H
3
Tertiary Primary - less stable carbocation
3 is more stable carbocation:
Which fate?
Rearrangement wont stabilize charge
Lose proton reaction will go backwards
Capture nucleophile Br
-
!
Major Product
Formed from tertiary carbocation intermediate
Minor Product
Formed from primary carbocation intermediate
This noted addition of Br to the more substituted end of the alkene was discovered by Markovnikov
Markovnikovs Rule:
When a hydrogen halide adds to an alkene, the hydrogen is added to the carbon bearing the most
hydrogen substituents (least substituted carbon), and the halide is added to the end of the alkene with the
least number of hydrogens.
H goes to the least substituted carbon
X goes to the more substituted carbon
3
C H
2
C
+
CH
3
Br
-
C H
2
CH
3
Br
H Br
C H
3
C
+
CH
3
Br
C
+
CH
3
Br H
H
C H
3
CH
3
Br
+
Br -
C H
3
CH
3
Br
Br
Addition of HBr to a Triple Bond
CH
3
H
H Br
C
+
CH
3
H
C H
2
C
+
CH
3
+
1 - Minor Product 2 - Major Product
Major Product:
C H
2
C
+
CH
3
Carbocation fate?
Lose a proton unproductive, would move reaction backwards
Rearrangement Vinyl carbocations CANNOT rearrange!
C H
2
C
+
H
C H
2
C
+
H
H
H
X
x
Capture a nucleophile!
1 without resonance
2 with resonance! FINAL PRODUCT
One contributor with
complete octets!
4
Addition of H
2
O
C H
2
CH
2 +
H OH
C H
3
OH
Ethylene
Example:
H OH
C
+
H
+
O H
-
No!
OH is not a leaving group
unless you have a very good
acid
Mechanism:
H OH
2
+
C
+
+
O H
2
Carbocation Intermediate:
Rearrangement is unproductive
Lose proton reaction goes backwards
Capture nucleophile: H
2
O
C
+
O H
2
O
+
H
H
O H
2
O H
+
O H
3
+
This reaction is reversible
It is in EQUILIBRIUM!
+
O H
2
O H
Favors alkene just a little
How do you control the direction of equilibrium? Think of la Chateliers Principle: increase the
concentration on one side (reactants or products) to shift the equilibrium to the other side.
5
Ph
CH
2
H
H
3
O
+
Ph
CH
3
H O H
Ph
CH
H
3
O
+
Ph
CH
2
OH
Addition of H
2
O
OH
H
2
SO
4
(aq)
H
3
O
+
Ph =Phenyl =C
6
H
5
Ph
H OH
2
+
Ph
C
+
H
C
+
Ph
O H
2
O
+
Ph
H
H
O H
2
Carbocation intermediate:
Resonance, but no extra stability
Rearrange to 3 with resonance
O H
Ph
+
O H
3
+
Alkynes and H
3
O
+
Alkene and H
3
O
+
Alkyne and H
3
O
+
Enol
6
Ph C
+
CH
3
OH
Ph
C
+
OH
H
H
Ph
CH
3
O
+
H
OH
2
Ph
CH
3
O
+
O H
3
+
Ph C
+
CH
3
OH
OH
2
Ph
CH
3
OH O H
2
+
Mechanism:
Ph
CH
H OH
2
+
Ph C
+
CH
2
Ph
CH
2
O
+
H
H
OH
2
OH
2
Ph
CH
2
OH
H OH
2
+
Or ?
2 with resonance 1 without resonance
Resonance contributor Major Product
with complete octets
The intermediate labeled 1 without resonance can proceed to deprotonation and formation of an
enol. The keto product is favored greatly.
Ph
OH
H
H
Ph
CH
3
O
Enol Keto
These products are tautomers, which are created through
tautomerization, a process where a hydrogen atom migrates to
another carbon and a double bond shifts to an adjacent bond.
Why not?
This product will go backwards
to the happiest stage (keto form)
7
Br Br
Br
Br
Miscellaneous Additions
a) Catalytic Hydrogenation
H
2
Pt
H
H
- Syn-addition: new things are added on the same face
- Markovnikovs rule does not apply
- No nucleophile or electrophile
- Catalyst is a transition metal
- Think of it as removing the pi bond
b) Addition of Br
2

+

-
- Anti-addition
- Markovnikovs rule does not apply
- Electrophile = Br
2
(induced
+
/
-
when Br
2
approaches the pi bond)
- Nucleophile = alkene
c) Hydroboration-Oxidation
1. BH
3
2. H
2
O
2
, HO
-
H
OH
- Syn-addition
- Anti-Markovnikov
- Electrophile = BH
3
(Borane, because of the open octet)
- Nucleophile = alkene
- Addition of water on the alkene converts it into an alcohol
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d) Ozonolysis
1. O
3
2. (CH
3
)
2
S
O
+
O
H
H
- Syn-addition
- No nucleophile or electrophile
- Ozone (O
3
) reacts with an alkene and forms carbonyls
o Imagine the pi bond splitting in half and each end bonding to oxygen