Chemistry IV Sem Carbonyl compounds-I

Session 1: Structure of carbonyl compound, synthesis of aldehydes

and ketones by oxidation of alcohol
Introduction
The carbon double bonded to an oxygen carbonyl group —is probably the —a most important
functional group found in organic compounds. Compounds containing carbonyl groups—
called carbonyl compounds— are abundant in nature. Many play important roles in biological
processes. Hormones, vitamins, amino acids, drugs, and flavourings are just
a few of the carbonyl compounds that affect us daily. An acyl group consists of a carbonyl
group attached to an alkyl group or to an aryl group.

The substituents attached to the acyl group strongly affect the reactivity of carbonyl
compounds. Carbonyl compounds can be divided into two classes. Class I carbonyl
compounds are those in which the acyl group is attached to an atom or a group that can
be replaced by another group. Carboxylic acids, acyl halides, acid anhydrides, esters,
and amides belong to this class. All of these compounds contain a group that can be replaced
by a nucleophile. Acyl halides, acid anhydrides, esters, and amides are all called carboxylic
acid derivatives because they differ from a carboxylic acid only in the nature of the group that
has replaced the OH group of the carboxylic acid.

1
Digital Learning-DCE Karnatak University
 Chemistry IV Sem Carbonyl compounds-I

Class II carbonyl compounds are those in which the acyl group is attached to a
group that cannot be readily replaced by another group. Aldehydes and ketones belong
to this class. The and alkyl or aryl or groups of aldehydes and ketones cannot be replaced by
a nucleophile.
The carbonyl carbon of the simplest aldehyde, formaldehyde, is bonded to two
hydrogens. The carbonyl carbon in all other aldehydes is bonded to a hydrogen and to
an alkyl (or an aryl) group. The carbonyl carbon of a ketone is bonded to two alkyl (or
aryl) groups. Aldehydes and ketones do not have a group that can be replaced by
another group, because hydride ions and carbanions and are too basic to be
displaced by nucleophiles under normal conditions.
Many compounds found in nature have aldehyde or ketone functional groups.
Aldehydes have pungent odors, whereas ketones tend to smell sweet. Vanillin and
cinnamaldehyde are examples of naturally occurring aldehydes. A whiff of vanilla
extract will allow you to appreciate the pungent odor of vanilla. The ketones carvone
and camphor are responsible for the characteristic sweet odors of spearmint leaves,
caraway seeds, and the camphor tree.

Nomenclature of Aldehydes
The systematic name of an aldehyde is obtained by replacing the terminal “e” from the
name of the parent hydrocarbon with “al.” For example, a one-carbon aldehyde is
methanal; a two-carbon aldehyde is ethanal. The position of the carbonyl carbon does
not have to be designated, because it is always at the end of the parent hydrocarbon
and therefore always has the 1-position.

2
Digital Learning-DCE Karnatak University
 Chemistry IV Sem Carbonyl compounds-I

Notice that the terminal “e” is not removed in hexanedial; the “e” is removed only to
avoid two successive vowels.
If the aldehyde group is attached to a ring, the aldehyde is named by adding
“carbaldehyde” to the name of the cyclic compound.
If a compound has two functional groups, the one with the lower priority is indicated
by its prefix. The prefix of an aldehyde oxygen that is part of the parent hydrocarbon is
“oxo.” The prefix of a one-carbon aldehyde group that is not part of the parent hydrocarbon
is “formyl.”

3
Digital Learning-DCE Karnatak University
 Chemistry IV Sem Carbonyl compounds-I

Ketones
The systematic name of a ketone is obtained by removing the “e” from the name of the
parent hydrocarbon and adding “one.” The chain is numbered in the direction that
gives the carbonyl carbon the smaller number. In the case of cyclic ketones, a number
is not necessary because the carbonyl carbon is assumed to be at the 1-position.
Frequently, derived names are used for ketones—the substituents attached to the
carbonyl group are cited in alphabetical order, followed by “ketone.”

4
Digital Learning-DCE Karnatak University
 Chemistry IV Sem Carbonyl compounds-I

Relative Reactivities of Carbonyl Compounds

We have seen that the carbonyl group is polar because oxygen, being more electronegative
than carbon, has a greater share of the electrons of the double bond (Section 17.5).
The partial positive charge on the carbonyl carbon causes carbonyl compounds to be
attacked by nucleophiles. The electron deficiency of the carbonyl carbon is indicated by
the blue areas in the electrostatic potential maps.

An aldehyde has a greater partial positive charge on its carbonyl carbon than does a
ketone because a hydrogen is electron withdrawing compared with an alkyl group. An
aldehyde, therefore, is less stable than a ketone, which makes it more
reactive toward nucleophilic attack.

Steric factors also contribute to the greater reactivity of an aldehyde. The carbonyl
carbon of an aldehyde is more accessible to the nucleophile than is the carbonyl carbon of
a ketone because the hydrogen attached to the carbonyl carbon of an aldehyde is
smaller than the alkyl group attached to the carbonyl carbon of a ketone. Steric factors
also become important in the tetrahedral transition state because the bond angles are
109.5°; therefore, the alkyl groups are closer to one another than they are in the carbonyl
compound, in which the bond angles are 120°. Ketones have greater steric
crowding in their transition states, so they have less stable transition states than aldehydes
have.
For the same reason, ketones with small alkyl groups bonded to the carbonyl carbon
are more reactive than ketones with large alkyl groups.

5
Digital Learning-DCE Karnatak University
 Chemistry IV Sem Carbonyl compounds-I

Structures of Carbonyl compounds

The carbonyl carbon in carbonyl compounds is hybridized. It uses its three orbitals to form
bonds to the carbonyl oxygen, the α-carbon, and a substituent (Y). The three atoms attached
to the carbonyl carbon are in the same plane, and their bond angles are each approximately
120°.

The carbonyl oxygen is also hybridized. One of its sp2 orbitals forms a bond
with the carbonyl carbon, and each of the other two orbitals contains a lone pair.
The remaining p orbital of the carbonyl oxygen overlaps with the remaining p orbital
of the carbonyl carbon to form a bond (Figure)

Synthesis of aldehydes and ketones by oxidation of alcohol

Oxidation of Primary Alcohols to Aldehydes
Primary alcohols can be oxidized to aldehydes and carboxylic acids

• The oxidation of aldehydes to carboxylic acids in aqueous solutions is easier than

oxidation of primary alcohols to aldehydes.

6
Digital Learning-DCE Karnatak University
 Chemistry IV Sem Carbonyl compounds-I

• It is, therefore, difficult to stop the oxidation of a primary alcohol at the aldehyde
stage unless specialized reagents are used.
An excellent reagent to use for converting a primary alcohol to an aldehyde is pyridinium
chlorochromate (abbreviated PCC), the compound formed when CrO3 is dissolved in
hydrochloric acid and then treated with pyridine:

• PCC, when dissolved in methylene chloride (CH2Cl2), will oxidize a primary alcohol
to an aldehyde and stop at that stage:

Oxidation of Secondary Alcohols to Ketones

Secondary alcohols can be oxidized to ketones. The reaction usually stops at the ketone stage
because further oxidation requires the breaking of a carbon–carbon bond:

Various oxidizing agents based on Cr(VI) have been used to oxidize secondary alcohols to
ketones. The most commonly used reagent is chromic acid (H2CrO4). Chromic acid is usually
prepared by adding Cr(VI) oxide (CrO3) or sodium dichromate (Na2Cr2O7) to aqueous sulfuric
acid, a mixture known as Jones reagent. Oxidations of secondary alcohols are generally
carried out by adding Jones reagent to a solution of the alcohol in acetone or acetic
acid. This procedure rarely affects double bonds present in the molecule. The balanced
equation is shown here:

7
Digital Learning-DCE Karnatak University
 Chemistry IV Sem Carbonyl compounds-I

As chromic acid oxidizes the alcohol to the ketone, chromium is reduced from the +6-
oxidation state (H2CrO4) to the +3-oxidation state (Cr3+). Chromic acid oxidations of secondary
alcohols generally give ketones in excellent yields if the temperature is controlled.
A specific example is the oxidation of cyclooctanol to cyclooctenone:

PCC will also oxidize a secondary alcohol to a ketone.

8
Digital Learning-DCE Karnatak University