CHAPTER 10

ALDEHYDE AND KETONE

Learning outcomes
Learning outcomes:

a. Write the general formula of aldehydes and ketones.

b. Draw the structures and name the carbonyl compounds for

aldehyde and ketone (Parent Chain <C10) according to the IUPAC
nomenclature.
c. Describe constitutional isomerism in carbonyl compound.

d. State the physical properties of aliphatic and aromatic aldehyde and

ketone.
e. Describe the preparation of carbonyl compounds through:-
i) oxidation of alcohol
ii) ozonolysis of alkenes
iii) Freidel-Crafts acylation of arenes

f. Describe the reactions of carbonyl compounds with reference to:-

i) addition of aqueous HCN and its mechanism
ii) reduction to alcohol using LiAlH 4 followed by H3O+ or NaBH4
followed by H3O+ or H2/catalyst (Pt/Pd/Ni)
iii) condensation with NH3 derivatives such as hydroxylamine,
hydrazine and phenylhydrazine
iv) oxidation with KMnO4/H3O+ or Cr2O72-/H3O+

g. Describe the chemical test of aldehyde and ketone

i) Tollen’s reagent
ii) Fehling’s reagent
iii) Schiff’s reagent
iv) Iodoform test
Overview
Aldehyde
Ketones
 Introduction
 Aldehydes and ketones are a group of compounds
containing the carbonyl group (-C=O).

 Aldehydes (RCHO) and ketones (RCOR’)

can be characterised by the presence of an acyl group
(RC=O) bonded either to H (aldehydes) or
another C (ketones).

Aldehyde Ketone

6
 Aldehyde Nomenclature
Find longest carbon chain that contains the aldehyde
group.
Change ending of base hydrocarbon name drop –e,
change to –al.
All other branches and groups are named using standard
IUPAC system
O
5
H3C H 3 1
6 4 2
butanal 3-methylhexanal
(Butyraldehyde)
O O

H H
hexanedial
Pentanedial 7
(Glutaraldehyde)
If -CHO is attached to a ring, use the suffix
-carbaldehyde
 Aldehyde Common Names
Table 10.1
Structure IUPAC name Common name
O

H H Methanal Formaldehyde

H3C H Ethanal Acetaldehyde

O
H3C
H Propanal Propionaldehyde

H3C H Butanal Butyraldehyde

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Table of Functional Group Priorities for
Nomenclature
Class Suffix Name Prefix Name

Carboxylic acid
-oic acid Carboxy
Ester
-oate Alkoxycarbonyl
Amide
-amide Amido
Nitrile
-nitrile Cyano
Aldehyde
-al Formyl (-CH=O)
Ketone
-one Oxo (=O)
Alcohol
-ol Hydroxy
Increasing Amine
priority -amine Amino
Alkene
-ene Alkenyl
Alkyne
-yne Alkynyl
Alkane
-ane Alkyl
Ether
- Alkoxy
Alkyl halide
- Halo
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 CH3 O O O

H
H3C H
3-methylhexanal 3-cyclobutyl-3-oxopropanal

H
OH O Cl O

H3C H
3-hydroxybutanal
(2Z)-3-chloro-3-phenylprop-2-enal
 Ketones Nomenclature
• Replace -e with -one. Indicate the position of the
carbonyl with a number.
• Number the chain so that carbonyl carbon has the
lowest number.
• For cyclic ketones, carbonyl carbon is assigned the
number 1.

O
O 1
3 4
CH3 C CH CH3
1 2 3
CH3 Br

3-methyl-2-butanone 3-bromocyclohexanone

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 Ketone nomenclature
Structure IUPAC name Common name

O
propanone
H3C C
Acetone
CH3
Table Dimethyl Ketone

10.3 O
butan-2-one
C
H3C CH2 Methyl Ethyl Ketone
(MEK)
CH3

O
C CH2 pentan-2-one n-propyl methyl
H3C CH2 CH3 ketone

O
H3C C CH3 pentan-3-one Diethyl ketone
CH2 CH2

1-phenylpropan-1-one
CH2
CH3 Propiophenone

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 Structural Isomerism
 Constitutional Isomerism
Aldehyde H3C H
O
C4H8O
H3C H
H3C O
butanal 2-methylpropanal
Ketone

C5H10O
CH3
O O
O
H3C CH3 CH3
H3C CH3
pentan-3-one CH3
pentan-2-one
3-methylbutan-2-one
 Physical properties
 Moderately polar
due to C=O group

 Boiling points
Lower than alcohols and higher than alkanes

 Solubility
Low MW species are soluble in water,
C=O can form H-bonds with H2O;
deceases as the R chain gets longer

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 Carbonyl structure

• Carbon is sp2 hybridized.

• C=O bond is shorter, stronger & more polar than
C=C bond in alkenes.
• Planar geometry & 120o bond angles.

Table 10.4

16
 Carbonyl group is a dipole & polar

• C=O cannot form H-bond with each other.

• But C=O can form H-bonds with H2O;
• lower aldehydes & ketones have appreciable H2O
solubility

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 Preparation

1. Oxidation of alcohol
2. Ozonolysis of alkenes
3. Freidel-Crafts acylation (from
arenes)

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 1. Oxidation of alcohols
 Primary alcohol (1º) can be oxidised to aldehyde by using
pyridium chlorochromate (PCC) in anyhydrous media such as
dichloromethane, CH2Cl2.
General Equation :-
OH O
PCC
R H R H
CH 2Cl 2
H

1° Alcohol Aldehyde

Example:-

OH O
PCC
H H
H CH 2Cl 2
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propanol propanal
 1. Oxidation of alcohols
 Secondary alcohol (2°) can be oxidised to ketones using oxidation
agent such as KMnO4 , K2Cr2O7 (as strong agents) in acidic and
heat.

General Equation :-
O
OH H 30 +
C + H 2O
R C R + KM nO 4 R R
H

2° Alcohol Ketone

Example:-

OH O
H 30 +
H3C C CH3 C + H 2O
+ K M nO 4 H3C CH3
H

propan-2-ol propan-2-one
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 1. Oxidation of alcohols

• Tertiary alcohols are resistant to oxidation.

Example:-

OH
H3C C CH3 PCC
NO R EA CTIO N
CH3 C H 2C l2
2-methylpropan-2-ol

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 2. Ozonolysis of alkenes
 Ozonolysis is an example of oxidative cleavage where an oxidation reaction
cleaves the reactant into pieces (the number of C-O bond increases).
 example, when an alkene is treated with ozone (O3), Hydrolysis of the ozonide
intermediate in the presence of Zn, permits aldehyde products to be isolated
without further oxidation.
General Equation :-

H R' 1) O 3 H R'

2) H 2 0, Zn
O + O
R R'' R R''

Example :-

H 1) O 3 H

2) H 2 0, Z n
O + O

ethanal
3-methylpent-2-ene butan-2-one
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 3. Freidel-Crafts acylation of arenes
 The reaction is carried out by treating the aromatic compound
(benzene) with a carboxylic acid chloride (RCOCl) in the presence of
aluminium trichloride (AlCl3), an acyl group (R-C=O) is introduced
onto the benzene ring.
General Equation :-

Cl
AlCl 3
+ R + H Cl
O R
O

Example :-
Cl
AlCl 3
+ + H Cl
O
O
benzene acetyl chloride
1-phenylethan-1-one
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 Reaction

1. Addition of hydrogen cyanide, HCN

2. Reduction to alcohol
3. Condensation with ammonia
derivatives
4. Oxidation
1. Addition of hydrogen cyanide, HCN

• Aldehyde & ketone react with HCN to form cyanohydrin.

• Cyano group can later be hydrolyzed or reduced.

O OH
H3C CH2 C CH3 + HCN H3C CH2 C CN
CH3

How about the mechanism??

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 • Dissociation of aqueous hydrogen cyanide

HCN CN- + H+

• Attack of the nucleophile, CN- on the electron-deficient carbonyl carbon atom.

H H CN
C O + CN - C -
slow
O
H3C H3C

 Abstraction of a H+ ion forms HCN to complete the reaction

H CN H CN

C + H+ C
- fast
O OH
H3C H3C
2. Reduction to alcohol

Aldehydes are reduced to give primary alcohol.

Ketones are reduced to give secondary alcohol.

Using

a) Lithium aluminium hydride (LiAlH4), followed by H30+

b) sodium borohydride (NaBH4), followed by H30+
c) catalytic hydrogenation (Ni/Pt)

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 2. Reduction to alcohol
General Equation :-
O OH
R C H 1) LiA lH 4 R C H
H
2) H 3 O +
Aldehyde Primary Alcohol

O OH
1) LiAlH 4
R C R R C R
2) H 3 0 + H

ketone secondary alcohol

Example :-

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 3. Condensation with ammonia derivatives
General Equation :-
H R
O + H2N X N X + H 2O
R R
Aldehyde imine

R R
O + H2N X N X + H 2O
R R

Ketone imine

Example :-
 4. Oxidation
Aldehyde

General Equation :-

Example :-
 4. Oxidation

Ketone

Example :-
 10.6 Identification Test
Tollen’s Reagent
 Tollen’s test can be used to distinguish aldehyde and ketone.
Aldehyde causes formation of a silver mirror (oxidation of
aldehyde and reduction of the Ag+).
 Ketones generally do not react with the Tollen’s reagent.

O OH- O
+ -
R H
+ Ag(NH3)2 R O + Ag
Aldehyde  Silv er
m irror

+
O Ag(NH 3)2
R R' NO REACTIO N
H2O
K etone

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 Fehling’s Reagent

 Aldehyde causes formation of a red precipitate of

Cu2O but no reaction for ketone.

 Fehling’s reagent is made up of CuSO4 in NaOH and

sodium tartrate which form copper tartrate
complex.
O O
-
+ 2 Cu2+ + 4 OH + +
R H Cu2O H2O
R OH
Copper (I) oxide
(Brick red precipitate
Schiff’s Reagent

 Aldehydes (with the exception of a few aromatic aldehyde) react with

decolorized Schiff’s reagent to give a pink-purple solution.

 Ketones (with the exception of propanone), do not react with Schiff’s

reagent.

 Schiff's reagent is made from pararosanilin treated with sulphurous

acid.
OH
R H
NH2 HN SO 2

2 R -C H O +
H2N SO 3H H2N

NH2 HN SO 2H
Decolorized Schiff’s reagent pink-purple colour complex
 Iodoform test (Detecting methyl ketone)
 Iodoform reaction of methyl ketone (-CH3) can be used to
identify the presence of a CH3C=O group in aldehyde and
ketone.
 Treatment with iodine (I2) and sodium hydroxide (NaOH) causes
formation of iodoform (CHI3).
 Iodoform is an easy to recognise where it can be observed as a
yellow precipitate.
 Ketones that have a methyl group next to the carbonyl
undergo a special reaction.

O I2 O
- +
CH3 O + Na + CHI 3
R NaOH R
Yellow precipitate
 Summary

Aldehyde Ketone
OH OH
HCN HCN
R C CN
R C CN
H
CH3
OH
1) LiAlH4 OH
1) LiAlH4
2) H3O+ R C H
H 2) H3O+ R C H
OH CH3
1) NaBH4 O
O 2) H3O+ R C H OH
C CH3 1) NaBH4
C H H
R 2) H3O+ R C H
R
Ni/Pt OH
aldehyde ketone CH3
R C H
OH
H Ni/Pt
R C H
H2N CH3 R N
C CH3 + H2 O
CH3
H
R N
KMnO 4 O H2N CH3 C CH3 + H2 O
H3O+ C OH
CH3
R
The End-