Carbonyl Compounds (Aldehydes and Ketones)

 Aldehydes and ketones are called carbonyl compounds due to presence of carbonyl
group (>C=O).
 In aldehydes, the carbonyl carbon atom is attached to one hydrogen atom and one
alkyl group.
O
R C H
 In ketones, carbonyl carbon atom is attached to two alkyl groups.
O
R C R
 The carbonyl group is polar in nature due to electronegativity difference between
carbon and oxygen atoms.

>C δ+ = O δ-

 The carbonyl carbon atom is deficient of electrons and the reagent that attack on it
will always be nucleophile and the type of reaction that aldehyde and ketone undergo
is nucleophilic addition reaction.
 Ketones and aldehydes almost have similar chemical properties due to presence of
carbonyl group.
 Aldehydes are more reactive than ketones towards nucleophilic addition reaction.
 In aldehydes, due to presence of one alkyl group which has +I effect, the positive
charge on carbonyl carbon atom is reduced or neutralised.
 In ketones, due to presence of two alkyl groups which have more +I effect, further
decreases the positive charge or neutralise the positive charge on carbonyl carbon
atom.
 Reactivity: CH3COCH3 < CH3CHO < HCHO
Increasing order

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 Aldehydes
 Are carbonyl compounds which have –CHO (aldehyde) group as functional group.
 It is sp2 hybridised i.e. carbonyl carbon atom.

 General molecular formula: CnH2n+2CO / CnH2n+1CHO

Nomenclature
1) Common System.
 According to common system, names of aldehydes are derived from carboxylic acids
which they easily form on oxidation.
 Suffix ‘ic’ of carboxylic acid is replaced by ‘aldehyde’.
HCOOH HCHO
Formic acid Formaldehyde

2) IUPAC System.
 According to IUPAC system, aldehydes are derived from alkanes where ‘e’ is
replaced by ‘al’ (alkanal).
HCHO (Methanal), CH3CHO (Ethanal), CH3CH2CHO (Propanal)

Ketones
 Like aldehydes, ketones are also carbonyl compounds containing >C=O (ketone
group) as functional group.
 General molecular formula: CnH2nO

Types of Ketone
1) Simple Ketone.
 If two alkyl groups are same, ketones are called simple ketones.
Eg: O
CH3 C CH3

2) Mixed Ketone.

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  If two alkyl groups are different, ketones are called mixed ketones.
Eg: O
CH3 C C2H5

Nomenclature
1) Simple Ketone.

Simple Ketone Common Name (Dialkyl ketone) IUPAC Name (Alkanone)

O
CH3 C CH3 Dimethyl ketone 2-propanone

O
C2H5 C C2H5 Diethyl ketone 3-pentanone

2) Mixed Ketone.

Mixed Ketone Common Name IUPAC Name

Two alkyl groups are named

alphabetically (alkyl alkyl
ketone)

O
Ethyl methyl ketone 2-butanone
CH3 C C2H5

O
C2H5 C C3H7 Ethyl propyl ketone 3-hexanone

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 Preparation of Carbonyl Compounds

1) Formaldehyde from methanol and acetaldehyde from ethanol / Formaldehyde

and acetaldehyde from alcohol.
 When primary alcohols are oxidised in presence of oxidising agent (K 2Cr2O7 and
conc.H2SO4 or KMnO4 and conc.H2SO4), aldehydes are formed.
K2Cr2O7 / H2SO4
R – CH2OH + [O] R – CHO + H2O

K2Cr2O7 / H2SO4
H – CH2OH + [O] HCHO + H2O
Methanol Formaldehyde

K2Cr2O7 / H2SO4
C2H5OH CH3CHO + H2O
Ethanol Acetaldehyde

2) Benzaldehyde from toluene.

 Benzaldehyde is an aromatic aldehyde prepared by Etard reaction.
 Toluene is treated with chromyl chloride (CrO2Cl2) in carbon tetrachloride (CCl4) and
the product formed is decomposed with water to get Benzaldehyde.
CH3 CHO
CrO2Cl2 / CCl4
+ O2 + H2 O

3) Acetone from isopropyl alcohol.

 Ketones are produced by oxidation of secondary alcohols.
[O]
R – CHOH – R R – CO – R + H2O

K2Cr2O7 / H+
R – CH – R + [O] CH3 – CO – CH3 + H2O
OH
Isopropyl alcohol / Acetone / 2-propanone
2-propanol

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 Physical Properties of Carbonyl Compounds

Formaldehyde Actaldehyde Benzaldehyde Acetone

 Colourless  Colourless  Colourless,  Colourless,

gas with liquid with oily liquid pleasant
pungent pungent with smelling and
smell and smell boiling characteristic sweet taste
can be at 21 0C. smell of liquid boiling
condensed to  Slightly bitter at 56.5 0C.
liquid. soluble in almond.  Soluble in
 Highly water but  Heavier than water,
soluble in more soluble water and is alcohol and
water. in organic poisonous in ether.
 Its aqueous solvents like nature.  Highly
solution is ether, volatile and
used as alcohol, etc. inflammable.
antiseptic
and
disinfectant.

Chemical Properties of Aldehydes

1) Oxidation (Reaction due to H-atom of –CHO group).

a) By acidified K2Cr2O7.
 Aldehydes on oxidation give carboxylic acid.
[O]
– CHO – COOH
 When aldehydes are reacted with oxidising agent like K2Cr2O7 and H2SO4, carboxylic
acids are formed.
K2Cr2O7 / H2SO4
H – CHO + [O] HCOOH
Formaldehyde Formic acid

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 K2Cr2O7 / H2SO4
CH3CHO + [O] HCOOH
Acetaldehyde Acetic acid

CHO COOH
K2Cr2O7 / H2SO4
+ [O]

Benzaldehyde Benzoic acid

b) Oxidation by Tollen’s Reagent.

 Tollen’s reagent is an ammonical silver nitrate solution and is mild oxidising agent,
the oxidising agent is Ag2O.
 When aldehydes are heated with Tollen’s reagent a grey ppt. of silver mirror is
formed.

– CHO + Ag2O – COOH + Ag

Aldehyde Tollen’s reagent Carboylic acid Silver mirror

HCHO + Ag2O HCOOH + Ag

Formaldehyde

CH3CHO + Ag2O CH3COOH + Ag

Acetaldehyde

CHO COOH

+ Ag2O + Ag

Benzaldehyde

c) Oxidation by Fehling’s solution.

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  Fehling’s solution is alkaline solution of copper sulphate, the oxidising agent is cupric
oxide i.e. CuO.
 When aldehydes are heated with Fehling’s solution, red ppt. of cuprous oxide (Cu 2O)
is formed along with carboxylic acid.
– CHO + CuO – COOH + Cu2O
Aldehyde Fehling’s reagent Carboylic acid Red ppt.

HCHO + CuO HCOOH + Cu2O

Formaldehyde

CH3CHO + CuO CH3COOH + Cu2O

Acetaldehyde

 Benzaldehyde does not react with Fehling’s solution. This is the test to distinguish
between benzaldehyde and acetaldehyde or benzaldehyde and formaldehyde.

Note: Reaction of aldehyde with Tollen’s reagent and Fehling’s solution are used as chemical
test for the presence of aldehyde.

2) Reduction (Reaction due to –CHO group).

 When aldehydes are reduced with hydrogen in presence of suitable reagent (NaBH4
with catalyst Ni or Pt) alcohols are formed.
Ni / Pt
– CHO + H2 – CH2OH
NaBH4 / LiAlH4 Primary alcohol

Ni / Pt
H – CHO + H2 H – CH2OH
Formaldehyde NaBH4 / LiAlH4 Methyl alcohol

Ni / Pt
CH3 – CHO + H2 CH3 – CH2OH
Acetaldehyde NaBH4 / LiAlH4 Ethyl alcohol

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 CHO CH2OH
Ni / Pt
+ H2
NaBH4 / LiAlH4

Benzaldehyde Benzyl alcohol

3) Addition Reaction due to carbonyl group (>C=O).

 Nucleophilic addition reaction with HCN.
O δ- OH
– C δ+ – H + H+CN- –C–H
CN
Aldehyde Aldehyde cyanohydrine

O OH
H–C–H + HCN H–C–H
CN
Formaldehyde Formaldehyde cyanohydrine

O OH
CH3 – C – H + HCN CH3 – C – H
CN
Acetaldehyde Acetaldehyde cyanohydrine

OH
CHO H – C – CN

+ HCN

Benzaldehyde Benzaldehyde cyanohydrine

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 4) Cannizaro Reaction.
 Cannizaro reaction is a self oxidation and reduction reaction shown by aldehydes
which have no alpha hydrogen atom.
 Formaldehyde and benzaldehyde undergo Cannizaro reaction.
 In this reaction two molecules of aldehydes (same or different) with no α-hydrogen
atom are reacted with concentrated alkali (NaOH or KOH).
 One molecule of aldehyde is reduced to primary alcohol and the other molecule is
oxidised to carboxylic acid or sodium or potassium salt of carboxylic acid.

Conc. NaOH /
H – CHO + H – CHO CH3OH + HCOONa
KOH Methyl Sodium
[H] [O] alcohol formate

H – CH2OH H – COOH

CHO CHO CH2OH COONa

Conc. NaOH /
+ +
KOH
Benzyl Sodium
alcohol benzoate

Chemical Properties of Ketones

1) Reduction.
 Ketones can be reduced to alcohol either by catalytic hydrogenation in the presence of
catalysts (Ni, Pt, Pd, etc) or by using chemical reducing agents such as LiBH 4 or
NaBH4, ketone yields secondary alcohol.
LiAlH4 / NaBH4
CH3 – CO – CH3 + 2H CH3 – CHOH – CH3
Propanone Ni or Pt 2 – propanol

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 2) Nucleophilic Addition Reaction with HCN.
O base OH
CH3 – C – CH3 + HCN CH3 – C – CH3
CN
Acetone Acetone cyanohydrine

Note: Acetone does not give or does not reduce Tollen’s and Fehling’s tests or reagents.

Chemical Test to Distinguish Aldehydes and Acetones

Iodoform Test

 Like aldehydes, acetone also gives yellow ppt. of iodoform (CHI 3) on treatment with
iodine and sodium hydroxide.

Reagent HCHO CH3CHO CH3COCH3

 With  Gives deep  Gives deep  Gives wine

sodium blue colour red colour red colour
prusside solution, solution, solution.
and excess which which
NaOH. changes to changes to
red. green and
red.

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