Organic Chemistry I
4.3 Addition Reactions
2/27/2025 8:02 PM 1
ü Addition reactions occur in compounds having electrons in:
– carbon–carbon double (alkenes) or
– triple bonds (alkynes) or
– carbon–oxygen double bonds (aldehydes and ketones).
ü In an addition reaction, the product contains all of the
elements of the two reacting species.
+ - Addition
C C + C C
E Nu
Nu E
Alkene Reagent
Product
Mechanism and Reactivity
ü The two electrophilic addition mechanisms are designated
as the AdE2 and AdE3 mechanisms.
ü The AdE2 is bimolecular, or the reaction has two reagents
involved in the rate-determining step.
ü The AdE3 is trimolecular, or a reaction with three reagents
involved in the rate-determining step.
ü The AdE2 mechanism corresponds closely to the E1
mechanism, and the AdE3 mechanism corresponds closely
to the E2 mechanism.
The AdE2 Reaction Mechanism
• Step 1: Pi electrons attack the electrophile.
• Step 2: Nucleophile attacks the carbocation.
ü In the first step the electrophilic portion of the reagent adds to the
substrate to form a carbocation.
ü In the second step the nucleophile adds to the carbocation
intermediate to complete the addition reaction.
The AdE3 Mechanism
ü The AdE3 mechanism requires a simultaneous collision of three
reactive species.
ü These species include the substrate molecule containing the
double bond, the electrophile, and the nucleophile.
ü In an AdE3 mechanism the electrophile and the nucleophile come
from two separate molecules.
ü The addition of an unsymmetrical reagent to an unsymmetrical
alkene or alkyne can, in principle, take place in either of two
directions.
ü The electrophilic portion of the reagent could add to either of the
carbons involved in the double bond.
ü Then the remaining nucleophilic portion could add to the other
carbon.
Types of Addition Reactions
Markovnikove’s Rule
ü addition of unsym-metrical reagents, e.g. HX, H2O or ROH, to an
unsymmetrical alkene proceeds in a way that the hydrogen atom
adds to the carbon that already has the most hydrogen atoms.
ü The reaction is regioselective, a regioselective reaction is a
reaction that can potentially yield two or more constitutional
isomers, but actually produces only one isomer.
ü The modern Markovnikov rule states that, in the ionic addition of
an unsymmetrical reagent to a double bond, the positive portion
of the adding reagent adds to a carbon atom of the double bond to
yield the more stable carbocation as an intermediate.
Anti-Markovnikove (Radical) Addition
It is possible to obtain anti-Markovnikov products when HBr is added
to alkenes in the presence of free radical initiators, e.g. hydrogen
peroxide (HOOH) or alkyl peroxide (ROOR).
Michael Addition
When HX adds to a double bond conjugated with a carbonyl
group, the X ends up on the beta carbon.
Mechanism
Examples of Addition Reactions
1. Addition of Hydrogen to Alkenes and Alkynes
üPreparation of Alkanes
ü Addition of hydrogen atoms in the presence of a metal
catalyst (Pd-C, Pt-C, Reny Ni …) to double or triple
bonds is known as hydrogenation or catalytic
hydrogenation.
2. Addition of Water to Alkenes
ü Preparation of Alcohols
ü Addition of water is known as a hydration reaction
ü The hydration reaction occurs when alkenes are treated
with aqueous acids, most commonly H2SO4, to form
alcohols.
3. Oxymercuration–Reduction of Alkenes
Preparation of Alcohols
Mechanism
4. Hydroboration–Oxidation of Alkenes
ü Preparation of Alcohols
ü Addition of water to alkenes by hydroboration–oxidation gives
alcohols via anti-Markovnikov addition.
Mechanism
5. Addition of Sulphuric Acid to Alkenes
Preparation of Alcohols
6. Addition of Halides to Alkenes
Preparation of Alkyl dihalides
Other Reactions of Double Bonds
1. Ozonization
A most widely used method for the oxidative cleavage
of double bonds is ozonolysis.
Mechanism
2. Diels-Alder Reaction
ü the Diels–Alder reaction is a [4+2] cycloaddition of a
conjugated diene and a dienophile (an alkene or alkyne).
ü an electrocyclic reaction that involves the 4 π-electrons
of the diene and 2 π-electrons of the dienophile.
ü The driving force of the reaction is the formation of new
σ-bonds, which are energetically more stable than the
π-bonds.
Examples
O O
H
1
Benzene
O O
Heat
4
O H O
1,3-butadiene maleic anhydride Tetrahydrophthalic anhydride
A conjugated diene A dienophile 95
O
O
Heat OMe
+ OMe
Methyl acetylenecarboxylate
Methyl cis-3,6-dimethyl-
1,4-Dimethyl-1,3-butadiene 1,4-cyclohexadiene-1-carboxylate
3. Glycol Formation
ü A dihydroxylation reaction adds two OH groups to a double bond
to form a diol.
ü The reaction of an alkene with cold alkaline potassium
permanganate (KMnO4) or with osmium tetroxide (OsO4) in an
aqueous hydrogen peroxide solution
Examples
4. Addition Polymerization
A high-molecular-weight material comprising a large number of
monomer subunits is called a polymer.
Mechanism
