3.3.

8 Aldehydes and Ketones

3.3.5 reminder:

Primary and secondary alcohols can be oxidised using ____________________________

___________________________________ _________________________________ . The colour change is
from ___________________ to _______________ .

Product if heated under distillation with Product if heated under reflux with
Alcohol
H2SO4/K2Cr2O7 H2SO4/K2Cr2O7

Primary

Secondary

Tertiary
Carbonyl compounds have the functional group _______.

These include ______________________________ and _________________________________ .

Naming carbonyl compounds

Aldehydes

End in –al. No number required.

1) Name these two:

Ketones
 End in -#-one.

2) What would be the smallest ketone? Draw and name.

3) Name these two:

Reactions that both aldehydes and ketones do

1) With KCN (potassium cyanide)*

Type of reaction: _____________________________________ ________________________________

Conditions: Add carbonyl compound to acidified potassium cyanide (H+/KCN(aq)). This has the effect of
“adding HCN”.

KCN contains the CN- ion. Draw a dot and cross diagram of a CN- ion.

HC
Ketone / aldehyde +  Hydroxynitrile1
N

+ 

Propanone

Mechanism:
Hazards of KCN:

1
hydroxynitriles are easily converted into amines or carboxylic acids - except they have an extra carbon!
Enantiomers

Aldehydes and unsymmetrical ketones form enantiomers when reacting with H +/KCN

HC
Ketone / aldehyde +  Hydroxynitrile1
N

+ 

butanone

In the reaction above, label the chiral carbon in the product with a *.

Draw the two enantiomers formed.

Explain why this reaction forms a racemic mixture.

2) With NaBH4 (sodium borohydride)*

Type of reaction: ______________________________________ AND

_____________________________ _______________________________________

Conditions: Add carbonyl compound to NaBH4 in alkaline solution

Ketone / aldehyde + 2[H]  Alcohol

+ 

Ethanal

+ 

Propanone

Mechanism:
 B

Reactions that only aldehydes do

Aldehydes can do more reactions than ketones because they can be ______________________________ .

1) With potassium dichromate(VI) and sulphuric acid (H2SO4 / K2Cr2O7)

Type of reaction: ________________________________________

Conditions: Add carbonyl compound to H2SO4 / K2Cr2O7 and heat under reflux

Aldehyde + [O]  Carboxylic acid

+ 

Ethanal

Can be used as a TEST for ______________________. If the group is present, a colour change from
_________________ to __________________ is seen. (Ketones will remain ______________ )

2) With Tollens’ reagent (silver nitrate in aqueous ammonia – also known as ammoniacal silver nitrate) +
heat in water bath
Type of reaction: ________________________________________

TEST for __________, so reacts with ________________________________

If the group is present, a ________________________________________________________ is seen.

Ketones will ______________________________________________________________________

because:
3) With Fehling’s solution (based on copper(II) sulfate) + heat in water bath
Type of reaction: ________________________________________

TEST for __________, so reacts with ________________________________

If the group is present, a ________________________________________________________ is seen.

Ketones will ______________________________________________________________________

because:

B
 3.3.9 Carboxylic acids and esters
Carboxylic acids

Carboxylic acids have the functional group ___________.

Naming carboxylic acids

End in –oic acid

1) Name:

Forming carboxylic acids

1) Oxidation of primary alcohols

2) Hydrolysis of an ester
3) Hydrolysis of an amide

Reactions of carboxylic acids

1) With carbonates (base) – makes CO2! TEST

Carboxylic acid + Na2CO3  Carboxylate + H2O + CO2

+  + +

Ethanoic acid

Why can they react?

Can be used as a TEST for ______________________. If the group is present, __________________ is

observed.

What’s a carboxylate?
Uses of carboxylic acids / carboxylates



2) With an alcohol and sulphuric acid catalyst

Type of reaction: ___________________________________ / ________________________________

Conditions: Mix carboxylic acid with alcohol and concentrated H2SO4. Warm.

Carboxylic acid + Alcohol  Ester + H2O

+  +

Propanoic acid Butan-1-ol

+  +

Butanoic acid Ethanol

 Esters
Esters have the functional group ___________________ .

Naming esters

Uses of esters






Forming esters:

1) With a carboxylic acid and alcohol (sulphuric acid catalyst)

Carboxylic acid + Alcohol  Ester + H2O

+  +

Ethanoic acid Ethanol

2) With an acid anhydride and alcohol

Carboxylic
Acid anhydride + Alcohol  Ester +
acid

+  +

Ethanoic anhydride Propan-1-ol

3) With an acyl chloride and alcohol

 Acyl chloride + Alcohol  Ester + HCl

+  +

Ethanoyl chloride Ethanol

Reactions of esters – only one, hydrolysis – but two different methods

You can split the ester linkage with acid or base.

Acid

Conditions: Mix ester with dilute sulphuric acid or hydrochloric acid and heat under reflux.

Equation:

NB: annoying as reversible!

Base

Conditions: Mix ester with dilute sodium hydroxide and heat under reflux.

Equation:

NB: not reversible! And easily converted into the acid by ___________________________________!

Base hydrolysis is used to make soap from animal fats or vegetable oils.
 Animal fats and vegetable oils are esters of propane-1,2,3-triol (glycerol):

+ ethanoic acid 

(In real vegetable oils and animal fats, the carboxylic acid part is usually very long).

When these esters are hydrolysed in alkaline conditions, it makes:

Biodiesel

Biodiesel is a mixture of methyl esters of long-chain carboxylic acids. It is made by reacting vegetable oils
with methanol with a catalyst.

1. Break down the existing esters in vegetable oils

2. Make a new “methyl” ester using methanol
 Polyesters

If you have a diol and a dicarboxylic acid you can make a polyester!

Type of polymerisation: ____________________________

Example: What do you make from ethane-1,2-diol and propanedioic acid?

Draw the monomers.

Draw the repeating unit.

e.g. Terylene – used for making clothes – “polyester”

What are the monomers?

Intermolecular forces in polyesters

Polyesters can be hydrolysed by acid or alkali

C
 3.3.9.2 Acyl chlorides

Acyl chlorides have the functional group ___________________ . Their names end in –oyl chloride. They
are like carboxylic acids but they are very reactive.

Reactions of acyl chlorides:

1) With alcohols *
Acyl chloride + Alcohol  Ester + HCl

+  +

Propanoyl chloride Ethanol

NB this will also react with phenol as the alcohol. Phenol won’t form an ester with a carboxylic acid,
which shows how much more reactive an acyl chloride is.

2) With water *
Acyl chloride + Water  Carboxylic acid + HCl

+  +

Butanoyl chloride

3) With NH3 (ammonia) *

Acyl chloride + NH3  Amide + HCl

+  +

Propanoyl chloride
4) With amines *
Acyl chloride + Amine  Amide + HCl

+  +

Propanoyl chloride Ethylamine

Mechanism

Name of mechanism: ________________________________________________________

 3.3.9.2 Acid anhydrides

Acid anhydrides have the functional group

Reactions of acid anhydrides: (NB same as acyl chlorides)

1) With alcohols
Carboxylic
Acid anhydride + Alcohol  Ester +
acid

+  +

Ethanoic anhydride Ethanol

2) With water
Acid anhydride + Water  Carboxylic acid

+ 

Ethanoic anhydride

3) With NH3 (ammonia)

Carboxylic
Acid anhydride + Ammonia  Amide +
acid

+  +

Ethanoic anhydride
4) With amines
Carboxylic
Acid anhydride + Amine  Amide +
acid

+  +

Ethanoic anhydride Methylamine

Making aspirin

What other product is made?

You can make aspirin using an acyl chloride (ethanoyl chloride) instead of an acid anhydride (ethanoic
anhydride). Why is the anhydride generally a better route?


Preparation and purification of an organic liquid
Purification of an organic solid
Filtration under reduced pressure

Recrystallisation

Method Reason

Add a minimum amount of hot

solvent to get the solid to
dissolve.

Filter the hot mixture.

Allow to cool (slowly). Crystals

form.

Filter the cold mixture.

Wash the crystals with a tiny

volume of cold solvent.
Leave crystals to dry (e.g. in a
dessicator).

Melting point measurement