8/26/2019 Reactivity of Aldehydes & Ketones - Chemistry LibreTexts

REACTIVITY OF ALDEHYDES & KETONES

Aldehydes are typically more reactive than ketones due to the following factors.
1. Aldehydes are less hindered than ketones (a hydrogen atom is smaller than any other organic group).
2. The carbonyl carbon in aldehydes generally has more partial positive charge than in ketones due to the electron-donating nature of
alkyl groups. Aldehydes only have one e- donor group while ketones have two.

 Addition-Elimination Reactions  Addition of Alcohols to form Hemiacetals and

This page looks at the reaction of aldehydes and ketones with
2,4-dinitrophenylhydrazine (Brady's reagent) as a test for the
carbon-oxygen double bond. It also looks briefly at some
other similar reactions which are all known as addition-
elimination (or condensation) reactions.
Acetals
In this organic chemistry topic, we shall see how alcohols (R-
OH) add to carbonyl groups. Carbonyl groups are
characterized by a carbon-oxygen double bond. The two main
functional groups that consist of this carbon-oxygen double
bond are Aldehydes and Ketones.

 Addition of Secondary Amines to Form  Addition of Water to form Hydrates (Gem-

Enamines
Most aldehydes and ketones react with 2º-amines to give
products known as enamines. It should be noted that, like
acetal formation, these are acid-catalyzed reversible reactions
in which water is lost. Consequently, enamines are easily
converted back to their carbonyl precursors by acid-catalyzed
hydrolysis.
Diols)
It has been demonstrated that water, in the presence of an
acid or a base, adds rapidly to the carbonyl function of
aldehydes and ketones establishing a reversible equilibrium
with a hydrate (geminal-diol or gem-diol).

 Alpha-carbon Reactions  Carbonyl Group-Mechanisms of Addition

Many aldehydes and ketones undergo substitution reactions
at alpha carbons. These reactions are acid or base catalyzed,
but in the case of halogenation the reaction generates an acid
as one of the products, and is therefore autocatalytic. If the
alpha-carbon is a chiral center, as in the second example, the
products of halogenation and isotopic exchange are racemic.
The Carbonyl Group is a polar functional group that is made
up a carbon and oxygen double bonded together. There are
two simple classes of the carbonyl group: Aldehydes and
Ketones. Aldehydes have the carbon atom of the carbonyl
group is bound to a hydrogen and ketones have the carbon
atom of the carbonyl group is bound to two other carbons.
Since the carbonyl group is extremely polar across the carbon-
oxygen double bond, this makes it susceptible to addition
reactions like the ones that occur i

 Carbonyl Group Reactions  Clemmensen Reduction

The metal hydride reductions and organometallic additions The reaction of aldehydes and ketones with zinc amalgam
to aldehydes and ketones, described above, both decrease the (Zn/Hg alloy) in concentrated hydrochloric acid, which
carbonyl carbon's oxidation state, and may be classified as reduces the aldehyde or ketone to a hydrocarbon, is called
reductions. As noted, they proceed by attack of a strong Clemmensen reduction.
nucleophilic species at the electrophilic carbon. Other useful
reductions of carbonyl compounds, either to alcohols or to
hydrocarbons, may take place by different mechanisms.

 Conjugate Addition Reactions  Cyanohydrins

One of the largest and most diverse classes of reactions is
composed of nucleophilic additions to a carbonyl group.
Conjugation of a double bond to a carbonyl group transmits
the electrophilic character of the carbonyl carbon to the beta-
carbon of the double bond. These conjugated carbonyl are
called enones or α, β unsaturated carbonyls.
Cyanohydrins have the structural formula of R2C(OH)CN.
The “R” on the formula represents an alkyl, aryl, or
hydrogen. In order to form a cyanohydrin, a hydrogen
cyanide adds reversibly to the carbonyl group of an organic
compound thus forming a hydroxyalkanenitrile adducts
(commonly known and called as cyanohydrins).

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