Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

CHEMISTRY OF CARBONYL COMPOUNDS

Aldehydes and ketones contain a carbon oxygen double bond known as carbonyl group. The
general formula of carbonyl compounds is given as CnH2nO.

C O

Aldehydes and ketones are collectively called carbonyl compounds. Carbonyl compounds
containing carbonyl group also includes carboxylic acid and its derivatives. The term carbonyl for only
aldehydes and ketones is commonly used in the restricted sense. Aldehydes and ketones can be
regarded as the derivatives of formaldehydes.
O

H C H
Formaldehyde
-H
-H
+2R
+R
O O

R C H R C R
-2H

Aldehydes Ketones
-H

+2A
+R

O O

Ar C H Ar C Ar
Aromatic aldehydes Aromatic ketones
O

Functional group C H is called formyl group.

It is the characteristic functional group of aldehydes always occurs at the end of chain.
O

Functional group C is called Keto group.

It is the functional group of ketones, and it always occurs inside a chain.

Preparation of Aldehydes and Ketones: -

Aldehydes and ketones may be prepared by the following methods.
1. Oxidation of Alcohols: -
Aldehydes and ketones can be prepared by the controlled oxidation of primary and secondary
alcohols using acidified solutions of potassium dichromate or per-magnate primary alcohols gives
aldehydes and secondary alcohols give ketones.
Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

O
+
K2Cr2O7 / H
CH3CH2OH + O H3C C H + H2O
OH O
+
K2Cr2O7 / H
H3C C CH3 + O H3C C CH3 + H2O
H
2. Dehydrogenation of Alcohols: -
Aldehydes and ketones can be prepared by catalytic dehydrogenation of alcohols. Primary
alcohols give aldehyde while secondary alcohols give ketones when pass over a copper catalyst at
300oC.
O

Cu
CH3CH2OH H3 C C H + H2
300o
OH O

Cu
H3C C CH3 H3C C CH3 + H2
H 300o
3. Ozonolysis of Alkenes: -
Aldehydes and ketones can be prepared by ozonolysis of alkenes, alkenes are treated with
ozone and ozonides produced are decomposed by Zn + H2O to form aldehydes and ketones.
O O
H2 O3 H2
H3C C C C CH3 H3C C H + H3C C C H
H H Zn + H2O

4. Hydration of Alkynes: -
Hydration of alkynes yields aldehydes water adds to acetylene in the presence of mercuric
Sulphates and Sulphuric acid to form unstable enol intermediate. This intermediate rearrange to give
ethanol and hydration of alkyne other than acetylene gives ketones.
H OH H O

HgSO4
HC CH + H OH HC CH H2C C H
H+

OH O

HgSO4
H3C C CH + H OH H3C C CH2 H3C C CH3
H+

5. Hydrolysis of Gem-Dihalides: -
The hydrolysis of gem dihalides where halogen atoms are attached to terminal carbon gives
and non-terminal gem dihalides give ketones when treated with alkaline aqoues solution.
Cl OH O
H2O H2O
H3C C Cl H3C C OH H3C C H
H NaOH H
OH O
H H2O H2O
H3C C CH2 H3C C CH3 H3C C CH3
NaOH
Cl Cl OH
6. Pyrolysis of Calcium Salts of Acids: -
Only symmetrical ketones may be prepared by heating calcium slats of acids at 400oC.
Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

O
O
H3C C O
Ca2+ Heat
H3C C CH3 + CaCO3
H3C C O

7. Catalytic Decomposition of acids: -

Symmetrical ketones can also by prepared by passing the vapors of a suitable carboxylic acid
over heated MnO.
O O

MnO
H3C C OH + HO C CH3 H3C C CH3 + H2O + CO2
300o
O

8. Reduction of acid Chlorides: -

Aldehydes can be prepared by the hydrogenation of acid chlorides in the presence of palladium
supported over barium Sulphate.
O O

Pd / BaSO4
H3C C Cl + H2 H3C C H + HCl

9. Oxo-Process: -
In this process alkene are treated with carbon monoxide and hydrogen in the presence of cobalt
carbonyl catalyst at high temperature and pressure only aldehydes are prepared by this method.
H O
[Co(CO)4] H2
R C CH2 + CO + H2 R C C C H + HCl
H H

10. Wacker Process: -

Aldehydes and ketones can be prepared by the treatment of alkene with an acidified aq solution
of PdCl2 and CuCl2.
O
CuCl2
H2C CH2 + PdCl2 + H2O H3C C H + Pd + 2HCl

CuCl2
H3C C CH2 + PdCl2 + H2O H3C C CH3 + Pd + 2HCl
H

O
11. Friedel Craft acylation: -
Aromatic ketones are prepared by Friedel Craft acylation by treating with acid halides in the
presence of a Lewis acid.
O
AlCl3 C R
+ R C Cl + HCl
O

Physical Properties: -
1. Aldehydes are more reactive than ketones due to hydrogen atom.
2. Formaldehyde is a gas while other aldehydes and ketones are colorless liquids.
3. Aldehydes have unpleasant, pungent smell while ketones have pleasant and sweet odour.
4. Density of both are less than water.
Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

5. Lower aldehydes and ketones are soluble in water.

6. Aldehydes and ketones are polar compounds. They have high boiling points but less than
corresponding alcohols due to lack of hydrogen bonding.
7. Carbonyl groups give IR spectrum bond due to C = O stretching in 1665 -1789 cm-1 regions.
8. The carbonyl compounds are soluble in organic solvent while acetone itself acts as a solvent.
Nature of Carbonyl Group: -
The carbonyl group has a σ sigma bond and a π (Pi) bond. Oxygen being more electronegative
making C = O bond polarized so that oxygen become negatively charged and carbon positively
charged. The polar C = O bond makes the carbonyl carbon electrophile and oxygen atom as
nucleophile.
O O

C C

Electrophilic carbon reacts with bases and nucleophilic oxygen reacts with acids and
electrophiles. It is the polarity of the carbonyl group that controls the reactivity of molecules of
aldehydes and ketones.
Thus, carbonyl group undergoes both electrophilic and nucleophilic reactions. Therefore,
nucleophilic react with aldehydes and ketones at the carbon center and electrophilic react at the
oxygen center.
Chemical Properties of Carbonyl Compounds: -
The carbonyl compounds undergo nucleophilic addition reaction. In these reactions the
negative part of the reagent combines with the electrophilic carbon of the carbonyl group whereas
the positive art which is usually hydrogen goes to the oxygen atom.

+ −
C O + H Nu Nu C OH

The nucleophilic addition reactions of carbonyl groups are catalyzed by acids and bases. A base
catalyst increases the nucleophilic character of the reagent while an acid catalyst promotes the
nucleophilic attack by increasing the positive character of the carbonyl carbon atom.
1. Addition of Water: -
Aldehydes and ketones add a molecule of water yields their hydrates.
OH
C O + H2O C
OH
Hydrate ( a gem diol)

2. Addition of Alcohols: -
Alcohols also add to carbonyl double bond of aldehydes and ketones to give addition product
called hemiacetals and hemiketals respectively.
OCH3
R R
C O + CH3OH C
H OH
H
Hemiacetal
 Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

R R OCH3
C O + CH3OH C
R R OH
Hemiketal
3. Addition of Hydrogen Cyanide: -
Addition of hydrogen cyanide to carbonyl compounds give cyan-alcohols known as
cyanohydrins.
H3C H3C CN
C O + HCN C
H3C H3C OH

Acetone cyano hydrine

4. Addition of Grignard Reagents: -

The addition of Grignard reagent gives a variety of alcohols productions.
OMgX OH
H+
C O + RMgX C C + MgX(OH)
R H2O R
Depending on the nature of groups attached to carbonyl carbon give primary secondary and
tertiary alcohols.
5. Addition of Ammonia: -
Aldehydes (except Formaldehyde) react with ammonia to form solid aldehyde ammonias.
OH
H3C
C O + NH3 H3C C NH2
H
H
6. Aldol Condensation: -
Aldehydes containing α-hydrogens undergo addition in the presence of a base to form product
called Aldols. The reactions are called Aldol condensation.
ALDOL =ALD = Aldehyde, OL = Alcohol

O H O OH O
OH - H2
H3C C H + H2C C H H3C C C C H
H
3-Hydroxybutanal (aldol)
Mechanism: -
i. Enolate ion formation.
H O O
OH -
H2C C H H2C C H + H2O

ii. Enolate ion attacks the carbonyl carbon.

O O O O
H2
H3C C H + H2C C H H3C C C C H
H

iii. Acceptance of proton from base.

Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

HO H

O O OH O
H2 H2
H3C C C C H H3C C C C H + OH -
H H
3-Hydroxybutanal (aldol)

Ketones are also possible when α-hydrogen is available.

O H O OH O
Ba(OH)2 H2
H3C C CH3 + H2C C CH3 H3C C C C CH3

CH3
4-Methyl-4-Hydroxypent-2-0ne (ketol)
7. Chlorination: -
Chlorine will successively replace the α-hydrogens in aldehydes and ketones.
O O

H3C C H + 3Cl2 Cl3C C H + 3HCl

8. Reduction to Alcohols: -
Aldehyde and ketones can be reduced to alcohols by treatment with hydrogen and Ni catalyst.
O OH

R C H + H2 Ni
R C H
H

O OH

H2 Ni
R C R + R C R
H
9. Wolf Kishner Reduction: -
The wolf -Kishner reduction is a reaction used in organic chemistry to convert carbonyl
compounds to alkanes. This involve the use of a basic solution of hydrazine as reducing agent.
Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

NH2 NH-
O N N
NH2NH2 OH-
R C R R C R R C R
-H2O -H2O

NH- NH NH

N N N
H+
R C R R C R R C R
H
NH

N
-N2 H2
R C R R C R
H

10. Tollens Reagent: -

It is an ammoniacal solution of silver oxide and is used to indicate the presence of aldehyde
group in a molecule. it is also known as silver mirror test.
O O

R C H + 2Ag(NH3)2OH R C ONH4+ + 2Ag + H2O + 3NH3

11. Fehling’s Solution: -
It is an alkaline solution of cupric ion complexed with sodium potassium tartrate ion. It is used
to indicate the presence of aldehydic functional group.
O O

R C H + 2Cu(OH)2 + NaOH R C ONa + Cu2O + 3H2O

Red

12. Cannizzaro Reaction: -

Aldehydes lacking α-hydrogen when heated with concentrated NaOH undergo a disproportion
reaction one half of the aldehyde molecule are oxidized to carboxylic acid and one half one reduced
to an alcohol this reaction is known as Cannizzaro reaction.
O O

H C H + NaOH Heat
H C ONa + CH3OH

Mechanism: -
Two steps are involved.
Step 1. Attack of the OH- on the carbonyl group.
O O

H C H + OH H C H

OH
Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

Step 2. Hydride Transfer.

O O O O

H C H + H C H H C + CH3O H C + CH3OH

OH OH O

13. Reduction to Pinacols: -

Ketones when reduced in neutral or alkaline medium form Pinacols.
O CH3 CH3

Mg / Hg
2 H3 C C CH3 + 2H H3C C C CH3
H2O

OH OH
2,3-Dmethylbutan-1,2-diol ( Pinacol)