18.

Carbonyls: Aldehydes and Ketones

Carbonyls are compounds with a C=O bond.
They can be either aldehydes or ketones

H O H O H If the C=O is in the middle of

If the C=O is on the end of the
H. C C chain with an H attached it is an H C C C H the chain it is a ketone
The name will end in -one
aldehyde. H H
H H The name will end in –al
CH3COCH3 propanone
CH3CHO ethanal

Intermolecular forces in Carbonyls Solubility in water

Pure carbonyls cannot hydrogen bond, but CH3
bond instead by permanent dipole forces. The smaller carbonyls are soluble
δ- δ+ δ-
in water because they can form O H O C
hydrogen bonds with water.
H CH3
δ-
Reactions of carbonyls O
In comparison to the C=C bond in
The C=O bond is polarised because alkenes, the C=O is stronger and does
O is more electronegative than δ+ not undergo addition reactions easily.
C
carbon. The positive carbon atom
attracts nucleophiles. H3C CH3
This is in contrast to the electrophiles
that are attracted to the C=C .
nucleophile
Oxidation Reactions

Potassium dichromate K2Cr2O7 is Key point: Aldehydes

Primary alcohol  aldehydes  carboxylic acid
an oxidising agent that causes can be oxidised to
alcohols and aldehydes to Secondary alcohol  ketones carboxylic acids, but
oxidise. Tertiary alcohols do not oxidise ketones cannot be
oxidised.
Oxidation of Aldehydes

Reaction: aldehyde  carboxylic acid H H O H H O

Reagent: potassium dichromate (VI) solution and H C C C + [O]  H C C C
dilute sulphuric acid.
Conditions: heat under reflux H H H H H O H

Full Equation for oxidation RCHO + [O]  RCO2H

3CH3CHO + Cr2O72- + 8H+  3 CH3CO2H + 4H2O + 2Cr3+
Aldehydes can also be oxidised using Fehling’s
Observation: the orange dichromate ion solution or Tollen’s Reagent. These are used
(Cr2O72-) reduces to the green Cr 3+ ion as tests for the presence of aldehyde groups

Tollen’s Reagent
Reagent: Tollen’s Reagent formed by mixing
aqueous ammonia and silver nitrate. The
active substance is the complex ion of
[Ag(NH3)2]+ .
Conditions: heat gently
Reaction: aldehydes only are oxidised by
Tollen’s reagent into a carboxylic acid and
the silver(I) ions are reduced to silver atoms
Observation: with aldehydes, a silver mirror forms
coating the inside of the test tube. Ketones
result in no change.
Fehling’s solution
Reagent: Fehling’s Solution containing blue Cu 2+ ions.
Conditions: heat gently
Reaction: aldehydes only are oxidised by Fehling’s
Solution into a carboxylic acid and the copper ions
are reduced to copper(I) oxide . .
Observation: Aldehydes :Blue Cu 2+ ions in solution
change to a red precipitate of Cu 2O. Ketones do
not react.
CH3CHO + 2Cu2+ + 2H2O  CH3COOH + Cu2O + 4H+

CH3CHO + 2Ag+ + H2O  CH3COOH + 2Ag + 2H+

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Reduction of carbonyls Reducing agents such as NaBH4 (sodium tetrahydridoborate)
Reagents: LiAlH4 In dry ether or LiAlH4 (lithium tetrahydridoaluminate) will reduce carbonyls
Conditions: Room temperature and pressure to alcohols.
Type of reaction: Reduction
Role of reagent: Reducing agent

Aldehydes will be reduced to primary alcohols Ketones will be reduced to secondary alcohols.
H H O H H H H O H H H H

H C C C + 2[H] H C C C O H H C C C H + 2[H]  H C C C H

H H H H H H H O H
H H
propanal Propan-1-ol propanone H
Propan-2-ol

Addition of hydrogen cyanide to carbonyls to form hydroxynitriles

R
Reaction: carbonyl  hydroxynitrile
When naming hydroxy
Reagent: HCN in presence of KCN NC C OH
nitriles the CN becomes
Conditions: Room temperature and pressure
part of the main chain
Mechanism: nucleophilic addition
H
hydroxynitrile
CH3COCH3+ HCN  CH3C(OH)(CN)CH3 CH3
NC C OH
2-hydroxy-2-methylpropanenitrile The extra KCN increases the
CH3 concentration of the CN- ion
CH3
CH3CHO + HCN  CH3CH(OH)CN nucleophile needed for the
NC C OH first step of the mechanism
2-hydroxypropanenitrile H

Nucleophilic Addition Mechanism

δ-
O
O:
- -
H CN O H
δ+ H3C C CH3
C H3C C CH3
H3C CH3
CN CN
:CN-

Reaction of carbonyls with iodine in presence of alkali

Reagents: Iodine and sodium hydroxide Only carbonyls with a methyl group next to O
Conditions: warm very gently the C=O bond will do this reaction. Ethanal
is the only aldehyde that reacts. More H3C C H
The product CHI3 is a yellow crystalline commonly is methyl ketones.
precipitate with an antiseptic smell

This reaction is called the Iodoform test

CH3COCH3 + 3I2 + 4NaOH → CHI3 + CH3COONa + 3NaI +3H2O

CH3COCH2CH3+ 3I2 + 4NaOH → CHI3 + CH3CH2COONa + 3NaI +3H2O

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Reaction with 2,4-dinitro phenylhydrazine
2,4-DNP reacts with both aldehydes and ketones. The Use 2,4-DNP to identify if the compound is a
product is an orange precipitate, It can be used as a test carbonyl. Then to differentiate an aldehyde
for a carbonyl group in a compound. from a ketone use Tollen’s reagent.

The melting point of the crystal formed can be used to help identify which carbonyl was used. Take the melting
point of orange crystals product from 2,4-DNP. Compare melting point with known values in database

H O 2N You don’t need to

learn these equations

H3C C
..
H2N NH NO2
for the exam

+
O 2,4-DNP
addition

O 2N H O 2N
H
elimination of
water
H3C C NH NH NO2 H3C C N NH NO2

orange precipitate
OH

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