6.1.

2 Carbonyl Compounds
Carbonyls are compounds with a C=O bond.
Carbonyls: Aldehydes and Ketones 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

Solubility in water
CH3
The smaller carbonyls are soluble Pure carbonyls cannot hydrogen bond, but
in water because they can form O H O C bond instead by permanent dipole forces.
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 sulfuric 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 Tollen’s
Observation: the orange dichromate ion reagent. This are used as a test for the
(Cr2O72-) reduces to the green Cr 3+ ion presence of aldehyde groups

Tollens’ Reagent
Reagent: Tollens’ 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 Tollens’ reagent into a
carboxylic acid. 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.

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

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Reduction of carbonyls
Reducing agents such as NaBH4 (sodium tetrahydridoborate)
Reagents: NaBH4 In aqueous ethanol or LiAlH4 (lithium tetrahydridoaluminate) will reduce carbonyls
Conditions: Room temperature and pressure to alcohols.

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

Nucleophilic Addition Mechanism

δ- O
O NaBH4 contain a source of
O - H H O H nucleophilic hydride ions
δ+ - (H-) which are attracted to
C
H3C C CH3 H3C C CH3 +OH the positive carbon in the
H3C CH3 C=O bond.
H H
H-

Catalytic Hydrogenation
Carbonyls can also be reduced using catalytic hydrogenation Example Equations
Reagent: hydrogen and nickel catalyst CH3CHO + H2  CH3CH2OH
Conditions: high pressure CH3COCH3 + H2  CH3CH(OH)CH3

Addition of hydrogen cyanide to carbonyls to form hydroxynitriles

R
Reaction: carbonyl  hydroxynitrile The NaCN supplies the
Reagent: sodium cyanide (NaCN) and dilute sulfuric nucleophilic CN- ions. The NC C OH
acid. H2SO4 acid supplies H+ ions
Conditions: Room temperature and pressure needed in second step of the
H
Mechanism: nucleophilic addition mechanism hydroxynitrile

CH3 When naming hydroxy

CH3COCH3+ HCN  CH3C(OH)(CN)CH3
nitriles the CN becomes
NC C OH part of the main chain
2-hydroxy-2-methylpropanenitrile
CH3
We could use HCN for this reaction but it
CH3CHO + HCN  CH3CH(OH)CN CH3 is a toxic gas that is difficult to contain.
The KCN/NaCN are still, however, toxic,
2-hydroxypropanenitrile NC C OH
because of the cyanide ion.
H

Nucleophilic Addition Mechanism

H+ from sulfuric acid
δ-
O
O:
- H+ O H
δ+ H3C C CH3
C H3C C CH3
H3C CH3
CN CN
:CN-

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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

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

OH orange precipitate

Tollens’ Reagent
Reagent: Tollens’ 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
Tollens’ reagent into a carboxylic acid. 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.

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

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