Aldehydes and ketones are two important classes of compounds that contain

carbonyl group, C=O, as their functional group.

In all other aldehydes, the carbonyl carbon atom is bonded to one hydrogen
atom and either an alkyl or an aryl group. In ketones the carbonyl carbon atom is
bonded to two carbon atoms, which can be any combination of aryl and alkyl groups.

Many aldehydes and ketones are important to the normal function of the human
body. For example, the aldehyde, 11-trans-retinal, plays an important role in our
ability to see, while the steroid hormone progesterone, a ketone, is secreted in women
at the time of ovulation.
Naming Aldehydes and Ketones
Aldehydes are named according to the IUPAC system by identifying the longest
continuous chain of carbon atoms that contains the — CHO group. This establishes
parent alkane name. The terminal -e of the parent alkane name is then replaced by -al
to signify the presence of an aldehyde group. The carbon atom of the -CHO group is
always assigned number 1. The suffix -dial is used to indicate the presence of two —
CHO groups, -trial for three, and so forth. The following examples illustrate these
rules.

We shall use the common names formaldehyde, acetaldehyde, and benzaldehyde

because they are used far more frequently than their systematic names.
Low molecular weight substituted aldehydes are sometimes named by
designationg the positions of their substituents with Greek letters. The position next
to the carbonyl group is designated α in these common names.

Ketones are named according to the IUPAC system by identifying the longest
continuous chain of carbon atoms that contains the carbonyl group. This establishes
the parent alkane name. The terminal -e of the parent alkane name is then placed by -
one to identify the compound as a ketone. The carbonyl carbon atom is assigned the
lowest possible number in the chain, regardless of the presence of alkyl groups,
halogen atoms, hydroxy groups, or carbon-carbon double or triple bonds.
The suffix -dione is used to indicate a ketone that contains two carbonyl groups,
-trione for three, and so forth. As with aldehydes, the final -e of the name
 Carbonil group is a planar group, whose bond angles around the carbonyl carbon
atom are close to 120°. The average carbon-oxygen double bond length is 121 pm,
which is much shorter than the typical carbon-carbon double bond length in alkenes.

The electron structure of the carbonyl group.

The localized valence bond orbital model of the electron structure of
formaldehyde is shown in Figure. The correct geometry is obtained by using an sp2
hybrid carbon atom for the carbon atom of the carbonyl group. The σ bonds to the
two hydrogen atoms and a single σ bond to oxygen are formed by end-on overlap of
the three sp2 hybrid orbitals of the carbonyl carbon atom. Sideways overlap of the
remaining p atomic orbital of the sp2 hybrid carbon with a p orbital of oxygen forms
the π bond.
Oxygen is more electronegative than carbon, so the resonance structure
containing a negative charge on the oxygen atom and a positive charge on the
carbonyl carbon atom.

The electron distribution in the carbon-oxygen double bond is not symmetrical.

It is us that the oxygen atom has an excess of electron density while the carbon ton is
electron deficient. The oxygen atom is electron rich and the carbonyl carbon atom
and the two hydrogen atoms are electron deficient, which makes formaldehyde a
polar molecule.

Basicity of Aldehydes and Ketones

The electronegativity difference between carbon and oxygen of the carbonyl
group results in a partial positive charge on the carbonyl carbon atom and a partial
negative charge on the carbonyl oxygen atom. As a result, the oxygen atom is
nucleophilic and the site of reactions with acids and electrophiles, while the carbonyl
carbon atom is electrophilic and the site of reactions with bases and nucleophiles.
 Summary of Mechanisms of Nucleophilic Addition Reactions of Aldehydes
and Ketones
The mechanisms of all nucleophilic addition reactions of aldehydes and ketones
share a common step. This common is the addition of a nucleophile to the carbonyl
carbon atom to form a tetrahedral intermediate. In neutral or basic solutions, this is
the first step of the mechanism.
The common first step in the neutral or basic solutions is nucleophilic
addition to the carbonyl carbon atom to form a tetrahedral intermediate.
In acid solution, protonation of the carbonyl oxygen atom is the first step,
followed by addition of the nucleophile to the carbonyl carbon atom of the conjugate
acid.
In acid solutions, nucleophilic addition to the conjugate acid of aldehyde or
ketone is usually the second step.

The product of nucleophilic addition reactions of aldehydes and ketones depends

on what happens to the tetrahedral intermediate.

Nucleophilic Addition reactions of Aldehydes and Ketones

1. Reduction

2. HCN

3. H2O
4. Alcohols

5. Primary amines.

Oxidation reactions
1.

2.

Nucleophilic Substitution Reactions of Aldehydes and Ketones

1. Halogenation

2. Aldol condensation