Unit 3 Addition Reactions
Contents-
A) Reactions of Carbon - Carbon Double Bond
A .
B) Reactions of Carbon - Carbon Triple Bond
C) Reactions of Carbon - Oxygen Double Bond
V.
L E
B A
A R
r.
D
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Addition Reactions :- Reaction in which two or more reactants combine to form a
.
product without loss of any atom present in the reactant.
Sp Hybridization Sp2 Hybridization Sp3 Hybridization
Triple bond Double bond
. A
Single bond
V
1σ 2π bonds 1σ 1π bonds All σ bonds
L E
For example
B A
H H
A R CCl4
H H
.
C C + Br Br H C C H
H
D r H
An addition reaction Br Br
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A) Reactions of Carbon - Carbon Double Bond
Examples of Addition Reactions
A .
V.
L E
B A
A R
r.
D
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A .
V.
L E
B A
A R
r.
D
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Mechanism of Electrophilic Addition to C = C Bond
Consider general reaction -
A .
V.
Two steps are involved.
Step 1- Slow step.
L E
B A
Involves addition of electrophilic reagent to the double bond.
Electrophile – Can be neutral or positively charged species.
R
π electrons of the alkene double bond attack the electron deficient H+ (of the reagent),
A
forming the C – H bond.
.
Due to this, the other double bonded C atom becomes electron deficient – carbocation.
D r
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Step 2 –Fast step.
Involves the attack of the conjugate base of the acidic reagent to the carbocation to form the product.
A .
V.
E
Evidence for this mechanism
A L
R B
• Rate of reaction depends on concentration of both – alkene and reagent H – X.
• Reaction requires acidic reagent. Orientation of addition and reactivity of the alkene is
. A
consistent with the mechanism.
r
• In some cases rearrangement is possible.
D
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Hydrohalogenation : - Orientation and Reactivty
Markovnikoff’s Rule – Negative part of the reagent adds to that double bonded carbon atom
which has less number of hydrogen atoms.
For example
A .
V.
L E
B A
A R
r.
D
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Stability of Carbocation
.
Rate of addition of a hydrogen ion to a double bond depends on the stability of the of the
A
carbocation.
.
This factor gives information about i) orientation of addition to a alkene ii) relative
V
reactivities of different alkenes.
L E
B A
A R
r.
D
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Anti – Markovnikoff’s Addition – Peroxide Effect
When HBr adds to an unsymmetrical alkene in presence of peroxide , light or other free radicals,
of hydrogen atoms.
A .
the negative part of the reagent adds to that double bonded carbon atom which has more number
V.
Peroxide is used as radical initiator which initiates free radical reaction.
Due to this radical initiator, the hydrogen and the bromine add to the double bond homolytically.
E
Intermediate is free radical ( not carbocation).
L
Mechanism involves three steps in free radical reaction- initiation, propagation and termination.
B A
A R
r.
D
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A .
Step 1 – Decomposition of peroxide gives free radicals.
V.
Step 2 – This free radical abstracts hydrogen radical from HBr to form bromine
radical.
L E
Step 3 – This bromine radical attaches to one of the doubly bonded carbon atom.
A
Other C is left with an odd electron and alkene is converted to a free radical.
B
Step 4 – This C radical abstract hydrogen radical from HBr and converted to
R
product.
r. A
D
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Free radical reactions are governed by two factors.
1) Stability of the radical -
A .
V.
L E
A
Bromine radical adds to the terminal C atom to form more stable secondary radical (rather
B
to the internal C atom than the primary free radical).
R
2) Steric factor – Addition of free radical to the terminal C which is less hindered, leads
to the less crowded transition state and therefore more stable.
. A
HCl and HI do not show peroxide effect as chloride radical is more reactive and iodide
r
radical formation is too sluggish. Both add according to Markovnikoff’s rule.
D
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Rearrangement - Support for formation of carbocation
A .
V. +
L E
B A
R
1,2 shift of the methyl group convert the initially formed secondary carbocation into a
A
more stable tertiary carbocation.
r.
D
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Addition of Halogens : Halogenation
After addition vicinal dihalogen compounds are formed.
.
Bromine and chlorine – In presence of CCl 4 adds to double bonds to give vicinal dibromo and
A
dichloro derivatives.
.
Iodine – No reaction with alkenes.
V
Mechanism – Cyclic intermediate halonium ion is formed.
L E
B A
A R
First step – slow step. π electrons attack the bromine molecule to form cyclic bromonium ion.
Second step – Bromide anion attacks the C atom from the back side to open the ring and form
r.
the dibromo compound.
Reaction is stereospecific and gives anti addition product.
D
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Evidences for the mechanism –
1) Rate of bromination reaction depends on concentration of alkenes and bromine. Therefore it is a
bimolecular electrophilic addition reaction.
A .
2) Effect of structure alkene on rate reaction rate –
V.
Electron donating groups – Activate the alkene and increases the rate of the reaction. Alkyl groups
E
are activating groups, more substituted alkenes react fast with halogens.
A L
Electron withdrawing groups – Deactivate the alkene and decreases the rate of the reaction.
R B
3) Effect of Nucleophile – Evidence for the halonium ion intermediate –
If reaction is carried out in presence of nucleophile like Cl-, NO3- and H2O etc, then in addition to
A
the formation of dibromo product, bromo – chloro or bromo – nitro or bromo alcohol product is
r.
also formed.
D
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A .
V.
L E
4) Stereochemistry – Two bromines add in opposite direction. Two bromines are anti to each
other.
B A
R
Trans Meso product
Cis racemic product
r. A
D
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Addition of Hypohalous acids HOX
A .
Addition of halogens in presence of water gives compounds with halogen and hydroxyl group
on the adjacent carbon atoms.
Two steps
V.
E
First step – Halogen adds to form halonium ion.
L
Second step – Attack of OH - at more substituted carbon atom to givehalohydrin.
A
OH - adds to the more substituted carbon atom.
Halogen adds to the less substituted carbon atom.
B
Addition according to the Markovnikoff’s rule.
R
r. A
D
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A .
V.
L E
B A
A R
r.
D
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Oxymercuration - Demercuration
A .
V.
Alkenes react with mercuric acetate in presence of water to give organo –
mercury compound, which on reduction give alcohol.
adds to the more substituted C atom.
L E
Oxymercuration step - Mercury adds to the less substituted C atom while OH
A
Demercuration step – second step C – Hg bond reduced to C – H bond.
B
Mechanism -
A R
r.
Formation of cyclic mercurinium ion. OH- attacks the C atom from the back side so
that the mercurinium opens to less hindered side of the double bond. This step is
D
stereo specific.
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Example -
A .
V.
L E
B A
A R
r.
D
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Hydroxylation : Formation of 1,2 Diol
Addition of two hydroxyl groups across the double bond of an alkene giving 1,2 diol
.
(Glycol) is known as hydroxylation.
A
Reagent – OsO4, alkaline KMnO4, per acid.
V.
L E
1) Hydroxylation by OsO4 - Osmium tetroxide adds to carbon carbon double bond of alkene to
form cyclic osmic ester. Os – O bonds are then cleaved by water to give 1, 2 diol.
A
Syn addition ( addition is from same side), therefore product is cis diol.
B
A R
r.
D
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2) Hydroxylation by alkaline KMnO 4
A .
V.
L E
Formation of cyclic permangnate ester in syn fashion.
diol.
B A
This cyclic permangnate ester undergoes hydrolytic cleavage of Mn – O bonds to give cis 1,2
R
Disadvantage – As KMnO4 is strong oxidizing agent, it can firther oxidize 1,2 diol into two
A
molecules of acid.
r.
D
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3) Hydroxylation by Per acid
Per acid oxidizes alkene by addition of oxygen across the double bond to form an
.
epoxide.
A
Epoxide is attaked by the nucleophile OH- ion from the opposite side to that of the oxygen
.
bridge to give trans 1,2 diol.
V
Anti addition
L E
B A
A R
r.
D
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Hydroboration – Oxidation :- Formation of Alcohols
Diborane in presence of solvent ether adds to carbon carbon double bond to form trialkyl
.
borane at room temperature, which on further oxidation with alkaline peroxide gives alcohol.
. A
V
L E
B A
R
Boron adds to the less substituted C atom of the double bond .
A
H adds to the more substituted C atom of the double bond .
r.
C- B bond then oxidized to C – O bond to give the alcohol.
Overall reaction – Addition of water molecule across the double bonded C atoms (similar to
D
hydration reaction).
But in this case addition is anti Markovnikoff
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Example of Hydroboration – Oxidation
A .
V.
L E
B A
A R
r.
D
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Hydrogenation
Conversion of C = C bond into a C – C bond.
.
Exothermic reaction.
Quantity of heat evolved when one mole of an unsaturated compound is hydrogenated is called heat of
hydrogenation (∆ H ) .
. A
V
For each double bond in alkene ∆ H is about 30 Kcal/mol.
Effect of catalyst on the progress of the reaction -
E
Uncatalyzed reaction- Very high activation energy.
L
Catalyzed reaction- Lower the activation energy. Reaction
proceed rapidly at room temperature. Eg – Ni, Pd, Pt, Ru, Rh
B A Reactants first adsorbed on the catalyst surface.
Surface of the catalyst breaks π bond of alkene before the
A R reaction with hydrogen.
As one face of the alkene is blocked, the addition of
r. hydrogen takes place from one side (syn addition).
After the formation of the product, it (product) leaves the
D
surface of the catalyst.
Now catalyst is free to adsorb new alkene and hydrogen molecule.
Cis alkenes hydrogenated more rapidly than trans.
Rate of reaction decreases with increasing substituents in the alkene.
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Examples of Hydrogenation Reaction
A .
V.
L E
B A
A R
r.
D
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Ozonolysis : Formation of Aldehydes and Ketones
It is a cleavage reaction in which the C=C bond is completely cleaved into smaller molecules.
A .
V.
L E
B A
A R
.
Two step reaction
r
First step – Addition of ozone to the double bond to form an ozonide.
Second step – Hydrolysis of ozonide to give cleavage product.
D
Ozonides are not isolated as they are explosives. Therefore are treated with water in
presence of reducing agent Zn metal.
This is to avoid the formation of H2O2 which would otherwise further oxidize the
resultant aldehydes and ketones.
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Ozonolysis is an important technique to identify the original alkene by knowing the
degraded products.
.
For example
. A
V
L E
After ozonolysis if the degraded products are acetone and propanaldehyde then we
pentene.
B A
can work back to the structure of the original alkene that is 2 – methyl – 2 –
A R
r.
D
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B) Reactions of Carbon - Carbon Triple Bond
1) Addition of Hydrogen
A .
.
2) Addition of Halogen
3) Addition of Halogen Acids
V
4) Addition of Water
5) Formation of Metal Acetylides
L E
B A
A R
r.
D
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1) Addition of Hydrogen
Addition of Hydrogen to alkyne gives an alkene . Stereoselective reaction.
Non terminated alkyne ---
A .
Gives trans alkene when reduction of alkyne is carried out with Na or Li in liquid ammonia.
catalyst.
V.
Gives cis alkene when reduction of alkyne is carried out with Pd catalyst called as Lindlar’s
L E
2 – butyne on reduction
B A
R
with Na in liquid ammonia gives trans -2- butene.
With Lindlar’s catalyst gives cis -2- butene.
r. A
D
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Terminal alkyne ---
For example 1-butyne gives only 1- butene.
A .
V.
L E
Complete reduction – Alkyne undergo complete reduction by addition of two moles of hydrogen in
A
the presence of catalysts like Pt, Ni or Pd to give alkane.
R B
r. A
D
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2) Addition of Halogen
.
Electrophilic addition of halogens to alkynes is slower than alkenes.
A
Because in case of alkynes, formation of cyclic halonium ion is difficult.
One mole of halogen gives vicinal dihalo alkene.
Second mole of halogen gives vicinal tetra halo alkene.
V.
L E
B A
A R
r.
D
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3) Addition of Halogen Acids
Mechanism - Involves formation of vinylic carbocation.
For example
(Incase of alkenes formation of carbocation takes place).
A .
V.
Unsymmetrical alkynes –
L E
Addition according to the Markovnikoff’s rule. Final product is gem – dihalide.
For example
B A
A R
r.
D
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4) Addition of Water
Alkynes can be hydrated in presence of acid.
.
For simple alkynes , a molecule of water adds in presence of HgSO 4.
A
Reaction involves formation of carbocation.
.
Markovnikoff’s rule
V
L E
B A
A R
r.
D
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5) Formation of Metal Acetylides
Triply bonded C atom is more electronegative than a doubly or singly bonded C atom.
.
Therefore triply bonded compound shows appreciable acidity.
A
Metals like Na, Li, Mg reacts with acetylene to liberate hydrogen gas and form metal
.
acetylides.
V
When acetylene reacts with lithium amide, it gives ammonia and lithium acetylide.
Weaker acid, H – NH2 is displaced from its salt by a stronger acid acetylene.
L E
B A
Similarly acetylene is stronger acid than alkane .
R
When a terminal alkyne is treaeted with alkyl lithium or alkyl magnesium bromide, the alkyne is
A
displaced from it’s salt and the metal acetylide is obtained.
r.
D
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When lithium acetylide reacts with water, hydroxide ion is formed and acetylene is liberated.
.
Thus acetylene is weaker acid than water.
. A
V
E
Relative acidities are in the following order
A L
R B
r. A
D
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