Addition Reactions of Carbon-Carbon

Pi Bonds Part 2
Part 1 Summary
1
o
carbocation
Disfavored pathway
3
o
carbocation
Favored pathway
Minor product
Major product
Higher
!G

Lower
!G

Alkene + HBr
Alkene Alkyne
Both have pi bonds
Both are nucleophiles
Both undergo electrophilic addition
Part 1 Summary
Similar for alkyne + HBr:
Markovnikov's Rule: In the addition of a protic acid HX to an alkene, the acid hydrogen
(H) becomes attached to the carbon with fewer alkyl substituents, and the halide (X)
group becomes attached to the carbon with more alkyl substituents.
Similar for alkene + H
3
O
+
:
Alkyne Hydration
Observation:
Alkene has one pi bond.
Alkene adds one molecule of H
2
O.
Addition obeys Markovnikov's rule.
Questions: Alkyne has two pi bonds.
Explore via mechanism...
Does alkyne add H
2
O?
Does this addition follow Markovnikov's rule?
Does alkyne add two molecules H
2
O?
? ?
Alkyne Hydration - Mechanism
Our standard "pi bond plus H-X" mechanism...
"
+
"
-
An enol (alkene alcohol)
Not the observed product
Actual product =
Explanation: What's going on in the reaction?
Molecules in a reaction do not all do the same thing simultaneously
Alkyne Hydration - Mechanism
Molecules in a reaction do not all do the same thing simultaneously
Can product continue to react?
Pi bond + H
3
O
+
...
versus
Actual product
Alkyne Hydration
Overall reaction:
Complete mechanism:
Markovnikov addition of H
2
O
Alkyne Hydration - FAQs
FAQ: Why not stop at enol?
Enol form $ Tautomers % Keto form
Tautomerization
FAQ: Why does second carbocation not capture water?