CHAPTER 6

CARBONYL COMPOUNDS
ALDEHYDES
KETONES
 LEARNING OUTCOMES
Classes: Aldehydes and ketones
Structure and physical properties :
boiling point and solubility
Preparation
- oxidation of alcohols
- ozonolysis of alkenes
- Friedel-Crafts acylation
Reactions
- nucleophilic addition (HCN, NaHSO3, water,
alcohols, Grignards reagents, ammonia)
- Reduction of carbonyl compounds
- Oxidation (Tollens, Fehlings & Schiffs reagents)
- Reaction with 2,4-dinitrophenylhydrazine
- Triiodomethane test
~Introduction to
aldehydes &
ketones~
 The carbonyl group (C=O) is found in aldehydes, ketones, and
many other organic functional groups.

The general formula for both aldehydes & ketones is CnH2nO

The carbon and oxygen in the carbonyl group are sp2-hybridized,

with bond angles of 120.

In ketones, two carbon groups are In aldehydes at least one

attached to the carbonyl carbon. hydrogen is attached to the
carbon.
Functional Groups Containing Carbonyls
~Nomenclature of
Aldehydes and
Ketones~
 Nomenclature of Aldehydes

1. Select the longest carbon chain containing the carbonyl

carbon.
2. The -e ending of the parent alkane name is replaced
by the suffix -al.

3. The carbonyl carbon is always numbered 1. (It is not

necessary to include the number in the name.)

4. Name the substituents attached to the chain in the usual

way.
 Nomenclature of Ketones
1. Select the longest carbon chain containing the carbonyl carbon.

2. The -e ending of the parent alkane name is replaced by the

suffix -one.

3. Number the chain starting with the end closest to the ketone
group (i.e., the carbonyl carbon should have the lowest possible
number).

4. Name the substituents attached to the chain in the usual way.

some important
aldehydes and
ketones
 physical
properties
aldehydes and
ketones
 The Polarity Of The Carbonyl Group

Carbonyl compounds are polar, containing a dipole

along the carbon-oxygen double bond.

This creates dipole-dipole interaction between carbonyl

compounds.
 Boiling point of carbonyl compounds
Since there is no hydrogen on the carbonyl oxygen, aldehydes and
ketones do not form hydrogen bonds with themselves.
Aldehydes and ketones therefore have boiling points that are in
between those of alcohols.

1. Alcohols form hydrogen bonds, and have high boiling points.

2. Hydrocarbons are nonpolar, and have low boiling points.
3. Aldehydes and ketones are polar, so they have higher boiling
points than hydrocarbons, but they are not as polar as
molecules which can hydrogen bond.
 Solubility of carbonyl compounds
Carbonyl compounds can hydrogen-bond to water through the
carbonyl oxygen.
Low-molecular weight aldehydes and ketones are water-soluble;
water solubility decreases as the size of the molecule increases.
Preparation of
aldehydes and
ketones
 Preparation of aldehydes
Oxidation of primary alcohol
Aldehydes can be prepared by the controlled oxidation of primary
alcohols using an acidified solution of potassium dichromate (VI) &
gentle warming.

The orange color of the dichromate (VI) ion, Cr2O72-, turns green
due to the formation of the chromium (III) ion, Cr3+
 Preparation of aldehydes
Oxidation of primary alcohol
The aldehyde is distilled out off as soon as it is formed to prevent
further oxidation to carboxylic acid. The temperature used is kept
below the boiling point of the alcohol and above that of aldehyde.

alcohol
aldehyde

heat
 Preparation of ketones
Oxidation of secondary alcohol

Refluxing a secondary alcohol with an acidified solution of

potassium dichromate (VI) or potassium manganate (VII).
 Preparation of ketones
Friedel-Crafts acylation of benzene

Friedel-Crafts acylation of benzene in the presence of anhydrous

aluminium chloride catalyst.
 Preparation of ketones
Ozonolysis of alkene
Chemical reaction of
aldehydes and
ketones
 Nucleophilic addition
The carbonyl group is highly polar. The carbonyl carbon is electron-
deficient that makes it susceptible to attack by electron-rich
nucleophiles, :Nu-
 Nucleophilic addition
1. Addition of hydrogen cyanide, HCN
 Nucleophilic addition
1. Addition of hydrogen cyanide, HCN
The cyanohydrin formed can be readily hydrolyzed to the
carboxylic acid by reacting it with dilute sulphuric acid.

The cyanohydrin can also be reduced to the amine by reacting it

with hydrogen gas over a nickel catalyst.
 Nucleophilic addition
2. Addition of sodium hydrogensulphate (IV)
When aldehyde or a ketone is shaken with a saturated solution of
aqueous sodium hydrogensulphate( IV), NaHSO3 colorless
crystals of carbonyl hydrogensulphate( IV) are formed.
 Nucleophilic addition
3. Addition of Grignard Reagents
This reaction can be used to prepare alcohols from carbonyl
compounds:
methanal produces 1 alcohols
aldehydes produce 2 alcohols
ketones produce 3 alcohols
 Nucleophilic addition
4. Addition of Amines

4. a) Addition of 1o Amines
Treatment of an aldehyde or ketone with a 1o amine affords imine.
 Nucleophilic addition
4. a) Addition of 1o Amines
 Nucleophilic addition
4. b) Addition of 2o Amines
Treatment of an aldehyde or ketone with 2o amine affords enamine.
Enamines have a nitrogen atom bonded to a double bond.
 Nucleophilic addition
5. Addition of water
Treatment of a carbonyl compound with H2O in the presence of an
acid or base catalyst adds the elements of H and OH across the
carbon-oxygen bond, forming a gem-diol or hydrate.
 Nucleophilic addition
5. Addition of alcohols acetal formation
Aldehydes and ketones react with two equivalents of alcohol to
form acetal. In an acetal, the carbonyl carbon from the aldehyde or
ketone is singly bonded to two OR (alkoxy) groups.
Reduction of carbonyl compounds
 Reduction of carbonyl compounds
The common reagents used for reducing aldehydes and ketones are:
1. LiAlH4, ether
2. NaBH4 dissolved in water or methanol
3. Na, ethanol at room temperature
4. H2, Nickel
Aldehydes are reduced to primary alcohols
 Reduction of carbonyl compounds
Ketones are reduced to secondary alcohols
Sample problem
 Example of Reduction in Organic Synthesis
Muscone, a strongly scented ketone isolated from musk, is an
ingredient in many perfumes.
Originally isolated from the male musk deer, muscone is now prepared
synthetically in the lab.
One step in the synthesis involves reducing a ketone to a 2o alcohol.
 Example of Reduction in Organic Synthesis
Sometimes chemists prepare molecules that do not occur in nature
because they have useful medicinal properties.

For example, fluoxetine (trade name: Prozac) is a prescription

antidepressant that does not occur in nature.

One step in a laboratory synthesis of fluoxetine involves reduction of a

ketone to a 2o alcohol.

Fluoxetine is widely used because it has excellent medicinal properties,

and because it is readily available by laboratory synthesis.
 Oxidation of carbonyl compounds
With acidified KMnO4 or K2Cr2O7

Aldehydes are readily oxidized on

heating with acidified KMnO4 or
K2Cr2O7 to produce carboxylic
acid.
 Oxidation of carbonyl compounds
With acidified KMnO4 or K2Cr2O7
Sample Problems
 Oxidation of carbonyl compounds
With Fehlings solution

Aliphatic aldehydes react with Fehlings solution to form a

reddish-brown precipitate of copper (I) oxide when heated.
Serve as a test to distinguish aldehyde from ketone.
RCHO + Cu(OH)2 + NaOH RCOONa + Cu2O + OH2

Ketones & aromatic aldehydes give

no reaction with Fehlings solution
 Oxidation of carbonyl compounds
With Tollens Reagent: silver mirror test

When Tollens reagent is heated with an aldehyde, the silver ion is

reduced to silver to form a silver mirror on the wall of the test tube.
RCHO + Ag2O + NH3 RCOONH4 + Ag + H2O

Ag(NH3)2OH
(Tollen's reagent)

Benzaldehyde, being less soluble than the

aliphatic aldehydes in Tollens reagent, reacts Ketones do not react
with Tollens reagent
more slowly.
 Oxidation of carbonyl compounds
With Tollens Reagent: silver mirror test
Sample Problems
 Reaction with 2,4-dinitrophenylhydrazine
Aldehydes & ketones react with a solution of 2,4-
dinitrophenylhydrazine in methanol to form yellow crystalline solids
or precipitate of 2,4-dinitrophenylhydrazones.

The 2,4-dinitrophenylhydrazones formed from the aliphatic alcohol

compounds are yellow whereas those from aryl compounds are orange.
The reaction - can be used to identify the presence of carbonyl groups
in organic compounds.
 The triiodomethane or Iodoform Reaction
Methyl carbonyl compounds, i.e those with the group, react
readily on warming with iodine in an alkaline solution to produce a
yellow precipitate of triiodomethane or iodoform, CHI3
 REMINDER
1. submit lab report 2
2. Submit assignment 2day
3. TEST 2 (alcohol & carbonyl)
next week rabu malam soalan
macam tutorial
- Boiling point & solubility
- Chemical test for alcohol
- Chemical rxn
THE END