TH E

CHE MI STR Y
OF
ALD EHY DE S
AN D KET ON ES
A guide for A level students

KNOCKHARDY PUBLISHING
 KNOCKHARDY PUBLISHING

ALDEHYDES & KETONES

INTRODUCTION
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ALDEHYDES & KETONES
CONTENTS
• Prior knowledge
• Bonding in carbonyl compounds
• Structural differences
• Nomenclature
• Preparation
• Identification
• Oxidation
• Nucleophilic addition
• Reduction
• 2,4-dinitrophenylhydrazine
 ALDEHYDES & KETONES
Before you start it would be helpful to…

• know the functional groups found in organic chemistry

• know the arrangement of bonds around carbon atoms
• recall and explain the polarity of covalent bonds
 CARBONYL COMPOUNDS - BONDING

Bonding the carbon is sp2 hybridised and three sigma (s) bonds are planar

PLANAR
WITH
BOND
ANGLES
OF 120°
 CARBONYL COMPOUNDS - BONDING

Bonding the carbon is sp2 hybridised and three sigma (s) bonds are planar
the unhybridised 2p orbital of carbon is at 90° to these

P ORBITAL

PLANAR
WITH
BOND
ANGLES
OF 120°
 CARBONYL COMPOUNDS - BONDING

Bonding the carbon is sp2 hybridised and three sigma (s) bonds are planar
the unhybridised 2p orbital of carbon is at 90° to these
it overlaps with a 2p orbital of oxygen to form a pi (π) bond

P ORBITAL

PLANAR
WITH
BOND
ANGLES
OF 120°
 CARBONYL COMPOUNDS - BONDING

Bonding the carbon is sp2 hybridised and three sigma (s) bonds are planar
the unhybridised 2p orbital of carbon is at 90° to these
it overlaps with a 2p orbital of oxygen to form a pi (π) bond

P ORBITAL

ORBITAL
PLANAR OVERLAP
WITH
BOND
ANGLES
OF 120°
 CARBONYL COMPOUNDS - BONDING

Bonding the carbon is sp2 hybridised and three sigma (s) bonds are planar
the unhybridised 2p orbital of carbon is at 90° to these
it overlaps with a 2p orbital of oxygen to form a pi (π) bond

P ORBITAL

ORBITAL
PLANAR OVERLAP
WITH NEW
BOND ORBITAL
ANGLES
OF 120°
 CARBONYL COMPOUNDS - BONDING

Bonding the carbon is sp2 hybridised and three sigma (s) bonds are planar
the unhybridised 2p orbital of carbon is at 90° to these
it overlaps with a 2p orbital of oxygen to form a pi (π) bond

P ORBITAL

ORBITAL
PLANAR OVERLAP
WITH NEW
BOND ORBITAL
ANGLES
OF 120°

as oxygen is more electronegative than carbon the bond is polar

 CARBONYL COMPOUNDS - STRUCTURE

Structure carbonyl groups consists of

a carbon-oxygen double bond

the bond is polar due to the

difference in electronegativity

Difference ALDEHYDES - at least one H attached to the carbonyl group

H CH3
C=O C=O
H H
 CARBONYL COMPOUNDS - STRUCTURE

Structure carbonyl groups consists of

a carbon-oxygen double bond

the bond is polar due to the

difference in electronegativity

Difference ALDEHYDES - at least one H attached to the carbonyl group

H CH3
C=O C=O
H H
KETONES - two carbons attached to the carbonyl group

CH3 C2H5
C=O C=O
CH3 CH3
 CARBONYL COMPOUNDS - FORMULAE

Molecular C3H6O

Structural C2H5CHO CH3COCH3

C2H5 CH3
C=O C=O
H CH3

Displayed H H H H O H

H C C C O H C C C H

H H H H

Skeletal
O O
 CARBONYL COMPOUNDS - NOMENCLATURE

Aldehydes C2H5CHO propanal

Ketones CH3COCH3 propanone

CH3CH2COCH3 butanone

CH3COCH2CH2CH3 pentan-2-one

CH3CH2COCH2CH3 pentan-3-one

C6H5COCH3 phenylethanone
 CARBONYL COMPOUNDS - FORMATION

ALDEHYDES

Oxidation of
primary (1°) alcohols RCH2OH + [O] ——> RCHO + H2O

beware of further oxidation RCHO + [O] ——> RCOOH

Reduction of
carboxylic acids RCOOH + [H] ——> RCHO + H2O

KETONES

Oxidation of
secondary (2°) alcohols RCHOHR + [O] ——> RCOR + H2O
 CARBONYL COMPOUNDS - IDENTIFICATION

Method 1 strong peak around 1400-1600 cm-1 in the infra red spectrum

Method 2 formation of an orange precipitate with 2,4-dinitrophenylhydrazine

Although these methods identify a carbonyl group, they cannot tell the difference
between an aldehyde or a ketone. To narrow it down you must do a second test.
 CARBONYL COMPOUNDS - IDENTIFICATION

Differentiation to distinguish aldehydes from ketones, use a mild oxidising agent

Tollen’s
Reagent ammoniacal silver nitrate
mild oxidising agent which will oxidise aldehydes but not ketones
contains the diammine silver(I) ion - [Ag(NH3)2 ]+
the silver(I) ion is reduced to silver Ag+(aq) + e¯ ——> Ag(s)
the test is known as THE SILVER MIRROR TEST
 CARBONYL COMPOUNDS - IDENTIFICATION

Differentiation to distinguish aldehydes from ketones, use a mild oxidising agent

Tollen’s
Reagent ammoniacal silver nitrate
mild oxidising agent which will oxidise aldehydes but not ketones
contains the diammine silver(I) ion - [Ag(NH3)2 ]+
the silver(I) ion is reduced to silver Ag+(aq) + e¯ ——> Ag(s)
the test is known as THE SILVER MIRROR TEST

Fehling’s
Solution contains a copper(II) complex ion giving a blue solution
on warming, it will oxidise aliphatic (but not aromatic) aldehydes
the copper(II) is reduced to copper(I)
a red precipitate of copper(I) oxide, Cu2O, is formed

The silver mirror test is the better alternative as it works with all aldehydes

Ketones do not react with Tollen’s Reagent or Fehling’s Solution

 CARBONYL COMPOUNDS - CHEMICAL PROPERTIES

OXIDATION

• provides a way of differentiating between aldehydes and ketones

• mild oxidising agents are best
• aldehydes are easier to oxidise
• powerful oxidising agents oxidise ketones to a mixture of carboxylic acids

ALDEHYDES easily oxidised to acids

RCHO(l) + [O] ——> RCOOH(l)

CH3CHO(l) + [O] ——> CH3COOH(l)

KETONES oxidised under vigorous conditions to acids with fewer carbons

C2H5COCH2CH3(l) + 3 [O] ——> C2H5COOH(l) + CH3COOH(l)

 CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

Mechanism occurs with both aldehydes and ketones

involves addition to the C=O double bond

unlike alkenes, they are attacked by nucleophiles

attack is at the positive carbon centre due to the

difference in electronegativities

alkenes are non-polar and are attacked by electrophiles

undergoing electrophilic addition

Group Bond Polarity Attacking species Result

ALKENES C=C NON-POLAR ELECTROPHILES ADDITION

CARBONYLS C=O POLAR NUCLEOPHILES ADDITION
 CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

Reagent hydrogen cyanide - HCN (in the presence of KCN)

Conditions reflux in alkaline solution

Nucleophile cyanide ion CN¯

Product(s) hydroxynitrile (cyanohydrin)

Equation CH3CHO + HCN ——> CH3CH(OH)CN

2-hydroxypropanenitrile

Notes HCN is a weak acid and has difficulty dissociating into ions

HCN H+ + CN¯

the reaction is catalysed by alkali which helps

produce more of the nucleophilic CN¯
 CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

Mechanism Nucleophilic addition

STEP 1

Step 1 CN¯ acts as a nucleophile and attacks the slightly positive C

One of the C=O bonds breaks; a pair of electrons goes onto the O
 CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

Mechanism Nucleophilic addition

STEP 1 STEP 2

Step 1 CN¯ acts as a nucleophile and attacks the slightly positive C

One of the C=O bonds breaks; a pair of electrons goes onto the O

Step 2 A pair of electrons is used to form a bond with H+

Overall, there has been addition of HCN
 CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

Mechanism Nucleophilic addition

STEP 1 STEP 2

Step 1 CN¯ acts as a nucleophile and attacks the slightly positive C

One of the C=O bonds breaks; a pair of electrons goes onto the O

Step 2 A pair of electrons is used to form a bond with H+

Overall, there has been addition of HCN
 CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

Mechanism Nucleophilic addition

STEP 1 STEP 2

Step 1 CN¯ acts as a nucleophile and attacks the slightly positive C

One of the C=O bonds breaks; a pair of electrons goes onto the O

Step 2 A pair of electrons is used to form a bond with H+

Overall, there has been addition of HCN
CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

ANIMATED MECHANISM
 CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION
Watch out for the possibility of optical isomerism in hydroxynitriles

CN¯ attacks from above

CN¯ attacks from below

 CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION
Watch out for the possibility of optical isomerism in hydroxynitriles

CN¯ attacks
from above

CN¯ attacks
from below
CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

ANIMATED MECHANISM
 CARBONYL COMPOUNDS - REDUCTION WITH NaBH4

Reagent sodium tetrahydridoborate(III) (sodium borohydride), NaBH4

Conditions aqueous or alcoholic solution

Mechanism Nucleophilic addition (also reduction as it is addition of H¯)

Nucleophile H¯ (hydride ion)

Product(s) Alcohols Aldehydes are REDUCED to primary (1°) alcohols.

Ketones are REDUCED to secondary (2°) alcohols.

Equation(s) CH3CHO + 2[H] ——> CH3CH2OH

CH3COCH3 + 2[H] ——> CH3CHOHCH3

Notes The water provides a proton

Question NaBH4 doesn’t reduce C=C bonds. WHY?

CH2 = CHCHO + 2[H] ———> CH2 = CHCH2OH
 CARBONYL COMPOUNDS - REDUCTION WITH HYDROGEN

Reagent hydrogen

Conditions catalyst - nickel or platinum

Reaction type Hydrogenation, reduction

Product(s) Alcohols Aldehydes are REDUCED to primary (1°) alcohols.

Ketones are REDUCED to secondary (2°) alcohols.

Equation(s) CH3CHO + H2 ——> CH3CH2OH

CH3COCH3 + H2 ——> CH3CHOHCH3

Note Hydrogen also reduces C=C bonds

CH2 = CHCHO + 2H2 ——> CH3CH2CH2OH

 CARBONYL COMPOUNDS - REDUCTION

Introduction Functional groups containing multiple bonds can be reduced

C=C is reduced to CH-CH
C=O is reduced to CH-OH
C≡N is reduced to CH-NH2

Hydrogen H• H2
H+ (electrophile) H¯ (nucleophile)

Reactions Hydrogen reduces C=C and C=O bonds

CH2 = CHCHO + 4[H] ——> CH3CH2CH2OH

Hydride ion H¯ reduces C=O bonds

CH2 = CHCHO + 2[H] ——> CH2=CHCH2OH

Explanation C=O is polar so is attacked by the nucleophilic H¯

C=C is non-polar so is not attacked by the nucleophilic H¯
 CARBONYL COMPOUNDS - REDUCTION

Example What are the products when Compound X is reduced?

COMPOUND X H2

NaBH4
 CARBONYL COMPOUNDS - REDUCTION

Example What are the products when Compound X is reduced?

COMPOUND X H2

NaBH4

C=O is polar so is attacked by the nucleophilic H¯

C=C is non-polar so is not attacked by the nucleophilic H¯
 2,4-DINITROPHENYLHYDRAZINE

Structure

C6H3(NO2)2NHNH2

Use reacts with carbonyl compounds (aldehydes and ketones)

used as a simple test for aldehydes and ketones
makes orange crystalline derivatives - 2,4-dinitrophenylhydrazones
derivatives have sharp, well-defined melting points
also used to characterise (identify) carbonyl compounds.

Identification / characterisation
A simple way of characterising a compound (finding out what it is) is to
measure the melting point of a solid or the boiling point of a liquid.
 2,4-DINITROPHENYLHYDRAZINE C6H3(NO2)2NHNH2

The following structural isomers have similar boiling points because of similar
van der Waals forces and dipole-dipole interactions. They would be impossible
to identify with any precision using boiling point determination.
CHO CHO CHO
Cl

Cl
Cl
Boiling point 213°C 214°C 214°C

Melting point of
2,4-dnph derivative 209°C 248°C 265°C

By forming the 2,4-dinitrophenylhydrazone derivative and taking its melting point,

it will be easier to identify the unknown original carbonyl compound.
 REVISION CHECK
What should you be able to do?

Recall the structure of and bonding in the carbonyl group

Explain the difference in structure between aldehydes and ketones
Recall the different response to oxidation of aldehydes and ketones
Recall and understand the mechanism of nucleophilic addition
Recall the products from the reduction of carbonyl compounds

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 TH E
CHE MI STR Y
OF
ALD EHY DE S
AN D KET ON ES
THE END

© 2003 JONATHAN HOPTON & KNOCKHARDY PUBLISHING