Reactions of aldehydes and ketones

Nucleophilic addition reactions

Instruction to students: Dr. Pramod P.S.
Please carefully go through each slides and
Asst. Professor
later prepare it’s note by referring any
standard textbooks. CPS, GMCT.

1
 Nucleophilic addition reactions of Aldehydes and
Ketones
A nucleophile is a chemical species that donates an electron pair to
form a chemical bond in relation to a reaction
a nucleophilic addition reaction is an addition reaction where a
chemical compound with an electron-deficient (or electrophilic double
or triple bond, a π bond), reacts with electron-rich reactant, termed
a nucleophile, with disappearance of the double bond and creation of
two new single, or σ bond

Dr. Pramod P.S.,CPS, GMCT

 Why do aldehydes and ketones undergo
nucleophilc addition reactions ?
In carbonyl compounds, the carbon-oxygen bond is polar.
Owing to the relatively higher electronegativity of the oxygen atom,
the electron density is higher near the oxygen atom.
This leads to the generation of a partial negative charge on the oxygen
atom and a partial positive charge on the carbon atom.
carbonyl carbon is electron-deficient.
carbonyl oxygen is electron-rich

Electron-deficient (acidic) carbonyl

Carbon of the carbonyl group is most
susceptible to attack by electron-rich,
nucleophilic reagents, that is, by bases!
e- deficient Carbonyl Carbon + e- rich Nucleophile Nucelophilic
addition reaction
Dr. Pramod P.S.,CPS, GMCT
 Mechanism of nucleophilc addition reactions

Carbonyl carbon demonstrates sp2 hybridization and together the

structure is coplanar.
Molecule is open to relatively unhindered attack
from above or below in a direction perpendicular
to the plane of the carbonyl group.
On the attack of the nucleophile, the hybridization
of the carbon atom changes from sp2 hybridization of
sp3 hybridization thereby forming tetrahedral alkoxide
intermediate complex.
This intermediate complex
will take a proton from
reaction medium to produce
an electrically neutral
compound.
Dr. Pramod P.S.,CPS, GMCT
 Mechanism of nucleophilc addition reactions

Here :Z is nucelophile (Nu-)

In the transition state, oxygen has started to acquire the electrons
and the negative charge that it will have in the product.
It is the tendency of oxygen to acquire electrons its ability to carry a
negative charge that is the real cause of the reactivity of the carbonyl
group toward nucleophiles.
Dr. Pramod P.S.,CPS, GMCT
 Why Aldehydes generally undergo nucleophilic
addition more readily than ketones?
Two explanations:
1. Steric effect: In aldehydes, the relatively
small hydrogen atom is attached to one side
of the carbonyl group, while a larger R
group is affixed to the other side.
In ketones, R groups are attached to both sides of the carbonyl group.
Thus, steric hindrance (crowding) is less in aldehydes than in ketones.
Hence nucelophile can easily attack aldehydes than ketones.
2.Electronic effects: aldehydes have only one R group to supply
electrons toward the partially positive carbonyl carbon.
Ketones have two electron‐supplying R groups attached to the carbonyl
carbon.
The greater amount of electrons being supplied to the carbonyl carbon,
the less the partial positive charge on this atom- lesser nucelophilic
addition. So ketones are relatively less reactive for Nucleophile attack
Dr. Pramod P.S.,CPS, GMCT
 Examples for nucleophilc addition reactions
1. Addition of Hydrogen cyanide
Cyanide addition to aldehydes & ketones gives cyanohydrin.
The reaction is usually carried out using NaCN or KCN & HCl.

Mechanism
Cyano group can
be converted into
other useful
functional groups
(-CO2H or -CH2NH2)

Dr. Pramod P.S.,CPS, GMCT

 Examples for nucleophilc addition reactions
2. Addition of Bisulphite

Sodium bisulfite adds to most aldehydes and to many ketones to form

bisulfite addition products:
Bisulfite addition products
are generally prepared for the
purpose of separating a
carbonyl compound from non-
Mechanism of Reaction carbonyl compounds.
Addition of acid or base destroys the bisulfite ion in equilibrium with
the addition product, and regenerates the carbonyl compound.
Dr. Pramod P.S.,CPS, GMCT
 Examples for nucleophilc addition reactions
3. Addition of water
The addition of water to an
aldehyde results in the formation of a
hydrate.

Mechanism of Reaction
Water, acting as a nucleophile, is
attracted to the partially positive
carbon of the carbonyl group,
generating an oxonium ion.

The oxonium ion liberates a

hydrogen ion that is picked up by
the oxygen anion in an acid‐base
reaction.

Dr. Pramod P.S.,CPS, GMCT

 Examples for nucleophilc addition reactions
4. Addition of Alcohol- Acetal and Hemiacetal formation
Reactions of aldehydes with alcohols produce
either hemiacetals (consisting of one —OH group and one —OR group
bonded to the same carbon) or acetals (consisting of two —OR groups
bonded to the same carbon), depending upon conditions.
Mixing the two reactants
together produces the
hemiacetal.

Mixing the two reactants

with hydrochloric acid
produces an acetal.

Dr. Pramod P.S.,CPS, GMCT

 Examples for nucleophilc addition reactions
4. Addition of Alcohol- Hemiacetal formation: Mechanism of reaction
An unshared electron pair on the alcohol's oxygen atom attacks the
carbonyl group.

The loss of a hydrogen ion to the oxygen anion stabilizes the oxonium
ion formed in Step 1.

Hemiacetal
Dr. Pramod P.S.,CPS, GMCT
THANK YOU
Instruction to students:
Prepare notes based on today’s class by
referring any standard textbooks. (include
mechanism of acetal formation )