UNIT 4

A2 ORGANIC CHEMISTRY
MECHANISMS AND
REAGENTS.

ALDEHYDES & KETONES

Identified by
Tollens reagent
Fehlings Solution
Aldehydes are oxidised to carboxylic acids. Therefore, the Tollens
and Fehlings must be reduced.
Tollens Reagent
Sodium hydroxide, aqueous silver nitrate this produces a precipitate.
Ammonia is then added to make aqueous [Ag(NH3)2]+
This is reduced to silver when an aldehyde is added.
Fehlings Solution
This is a blue solution containing Cu2+ ions. When aldehydes are
added and heated, these ions are reduced to cooper (I) oxide Cu 2O,
producing a brick-red ppt.
AQA A2 text
book, p64

ALCOHOLS FROM ALDEHYDES &

KETONES
ALDEHYDE

KETONE

Lithium
tetrahydridoaluminate LiAlH4

[H
]

Sodium tetrahydridoborate
NaBH4

PRIMARY
ALCOHOL
SECONDARY
ALCOHOL

5m
in

Mechanism
Nucleophilic addition
The reducing agents produce the H- ion (the nucleophile).
The carbonyl bond is polar, due to oxygen being more
electronegative.
First Step is the hydride ion being attracted to the + carbon.
Second step, the product of first step gains a proton.
AQA A2 text
book, p66

HYDROXYNITRILES FROM
ALDEHYDES & KETONES
ALDEHYDE
KETONE

HC
N

HYDROXYNITRILE

KCN/H2SO4

Mechanism
Similar to making alcohols!
Nucleophilic addition
The reducing agents produce the CN- ion (the nucleophile).
The carbonyl bond is polar, due to oxygen being more
electronegative.
First Step is the cyanide ion being attracted to the + carbon.
Second step, the product of first step gains a proton from the
solvent or hydrogen cyanide.
AQA A2 text

5m
in

book, p68

HYDROLYSIS OF THE NITRILE GROUP

The nitrile is hydrolysed in acidic conditions, producing a carboxylic
group.
H2O/ H+
HYDROXYNITRILE
CARBOXYLIC ACID
AMMONIUM

AQA A2 text
book, p69

ESTERS FROM CARBOXYLIC

ACIDS & ALCOHOLS
CARBOXYLIC ACID
ALCOHOLS

H2SO4 or HCl cat,

reflux

ESTER
WATER

No need for Mechanism

But you do need to be able to draw and name ester.
OH from carboxylic acid and H from OH in alcohol bond to
produce water.
First part of name comes from the alcohol, second from the
carboxylic acid.

AQA A2 text
book, p71

ESTER HYDROLYSIS
Acid Catalysed Hydrolysis
Reverse of esterification.
Dilute sulfuric acid or
hydrochloric acid.
Heat under reflux.
ESTER
WATER
Base-Catalysed Hydrolysis
Form a salt
Dilute strong base, sodium
hydroxide.
Heat under reflux.
This method is quicker than acid
ESTER
catalysed.
SODIUM
HYDROXIDE
AQA A2 text
book, p74

CARBOXYLIC ACID
ALCOHOLS
Heat with excess
dilute acid to
produce carboxylic
acid
SODIUM
CARBOXYLATE
ALCOHOLS

VEGETABLE OILS & ANIMAL FATS

Alkyl chain in Vegetable oils are unsaturated. Alkyl chain in Animal fats
are saturated.
TRIACYLGLYCEROLS or TRIGLYCERIDES (three esters) TRIESTERS
No need for Mechanism
Hydrolysed by heating with aqueous sodium hydroxide or potassium
hydroxide.
Produces glycerol (propane-1,2,3-triol) and sodium/potassium salt.
TRIACYGLYCEROL
SODIUM
HYDROXIDE
Three moles

AQA A2 text
book, p74-75

PROPANE-1,2,3TRIOL
SODIUM
CARBOXYLATE
Three moles
produced

BIODIESEL
No need for Mechanism
Base catalysed Transesterification.
Heating vegetable oil with methanol and sodium hydroxide.
Produces methyl esters with long chains and propane-1,2,3-triol.

TRIACYGLYCEROL
SODIUM
HYDROXIDE
METHANOL

PROPANE-1,2,3TRIOL
METHYL ESTER

Three moles
Three moles

AQA A2 text
book, p75

ACYL CHLORIDES
Mechanism
Nucleophilic Substitution reactions. (two steps addition +
elimination)
Greater + on carbon due to Cl and O bond.
1st Step (addition) nucleophile attacks carbon + . Pair of electrons
in C=O is transferred to oxygen.
2nd Step (elimination) lone pair of electrons on oxygen forms C=O,
chlorine is eliminated. Hydrogen attached to oxygen atom breaks.
alcohol
water
CARBOXYLIC ACID
ESTER
ACYL CHLORIDE
N-SUBSTITUTED
AMIDE
AQA A2 text
book, p76-81

Primary
amine

ammon
ia

Hydrogen chloride, HCl is the secondary

product.

5
AMIDEm
in

ACID ANHYDRIDE
Synthesis
Dehydrate a carboxylic acid (P4O10
cat)
Mechanism
Same as acyl chlorides.
Secondary product is a
carboxylic acid.
water
CARBOXYLIC ACID

alcohol

ACID ANYDRIDE
N-SUBSTITUTED
AMIDE
AQA A2 text
book, p76-81

Primary
amine

ammon
ia

ESTER

5
AMIDEm
in

Preferred in synthesis, cheaper, less violent reactions, no

fumes of HCl

NITRO COMPOUNDS FROM BENZENE

Mechanism
Generate the nitronium ion. Nitric acid and sulfuric acid.
Protonation of nitric acid, then protonated nitric acid breaks down.
Electrophilic substitution(addition then elimination).
Electrophile is attracted to the delocalized electron.
C-H bond breaks and restores the stable delocalized electron
structure.

BENZENE

UNSTABLE
POSITIVELY
CHARGED
INTERMEDIATE

5
min
NITROBENZE
NE

Temperature should be kept at 50oC. Further substitution occurs at 100oC

(1,3-dinitrobenzene).
AQA A2 text
book, p90-91

ICE DYES & DIAZONIUM SALTS

Ice Dyes
No need for mechanism but need to be able to draw compounds.
Sodium chloride and water is also formed.

PHENYLAMI
NE

Sodium nitrate(III),
HCl
Ice bath (chilled)

Coupling Reaction (azo dyes)

DIAZONIUM
SALT
WATER

SODIUM
CHLORIDE
No need for mechanism but you need to be able to draw compounds.
Diazonium salt reacts with phenylamine or other aromatic compounds to
produce azo dyes. HCl is also produced.

AQA A2 text
book, p92-93

TRINITROTOLUENE, TNT
No need for mechanism but need to be able to draw compounds.

METHYLBENZE
NE

AQA A2 text
book, p93

conc. HNO3
conc. H2SO4

2-METHYL-1,3,5TRINITROBENZENE

FIEDEL-CRAFTS ACYLATION
Mechanism
Generate the electrophile. Aluminium chloride and acyl chloride.
Electrophilic substitution(addition then elimination).
Electrophile is attracted to the delocalized electron.
C-H bond breaks and restores the stable delocalized electron
structure.
Aluminium chloride is regenerated whren [AlCl4]- reacts with H+.

BENZENE

AQA A2 text
book, p94

UNSTABLE
POSITIVELY
CHARGED
INTERMEDIATE

5
min
PHENYLETHANON
E
HYDROGEN
CHLORIDE

MAKING ALIPHATIC AMINES

From Haloalkanes
Excess ammonia reacting with primary
haloalkanes.
AMMONIA

nucleophil
e
NH3

base
NH3

AMMONIUM
SALT
HALIDE
ION

AMINE

HALOALKA
AMMONIUM
NE
HALIDE
Mechanism
If you can do this you can describe
Amine acting as a nucleophile
Amine acting as a base
How to make secondary, tertiary amines and quarternary
ammonium salts
From Nitrile
Amine can be made by reducing nitrile

5
min

NITRILE
AQA A2 text
book, p100-107

4[H
]

LiAlH4
H2/Ni

AMINE

MAKING AROMATIC AMINES

Reduction of aromatic nitro
compounds
NITROBENZE
NE

WATER

AMINE

6[H
]

NaOH
conc.HCl/Sn
or
conc.
HCl/Fe

AQA A2 text
book, p101

NH3+
INTERMEDIA
TE

ZWITTERIONS
Acting as a Base
Accepting protons.
NITROGEN IS
PROTONATED

AMINO ACID

H+

With Acid

HC
l

SALT

OH

NEGATIVE CHARGE ON
OXYGEN
SALT
WATE
R

Acting as an Acid
Donating protons.
AMINO ACID

With Base

AQA A2 text
book, p108-109

NaO
H

PROTEINS FROM AMINO ACIDS

Amino group reacting with carboxylic group of another amino acid.
PEPTIDE LINK
Each link produces one water molecule. Condensation reaction.
Can form ploymers (amino acids)
AMINO ACID
AMINO ACID

AQA A2 text
book, p110

DIPEPTIDE

WATER

AMINO ACIDS FROM PROTEINS

Hydrolysis of peptide link.

Heat
Water

AMINO ACID

6 moldm-3 HCl
for 24 hours

AMINO ACID

DIPEPTIDE

AQA A2 text
book, p112

ADDITION POLYMERS
Mechanism
Addition ploymerisation
Involves one functional groups.
Carbon, carbon double bond.
Need to be able to identify repeating units
Taught in AS Chemistry Unit 2.
ALKENE
Monomer

AQA A2 text
book, p114-115

AQA AS text
book, p218-219

POLY(ALKENE
)
Polymer

POLYESTERS
Mechanism
Condensation ploymerisation
Involves two functional groups.
Polyesters are formed from a dicarboxylic acid and a diol.
Carboxyl group forms an ester link with the hydroxy group.
Need to identify ester link.
Identify the repeating units.
DICARBOXYLI
C ACID

POLYESTER

DIOL

WATER

AQA A2 text
book, p116-117

POLYAMIDES
Mechanism
Condensation ploymerisation
Involves two functional groups.
Polyamide are formed from a dicarboxylic acid and a diamines.
Hydroxyl group from dicarboxylic acid reacts with hydrogen
attached to nitrogen of polyamide.
Forms an amide link.
Need to identify amide link.
Identify the repeating units.
DICARBOXYLI
C ACID

POLYAMIDE

DIAMINE

WATER

AQA A2 text
book, p118-119

Questions on Nylon often appear on exams.

BIODEGRADABLE POLYMERS
Esters and amides can be hydrolysed by water, acids, alkalis and
enzymes.
This is the same for polyesters and polyamides.
Break ester link or amide link!
DICARBOXYLIC
DIAMIN
r
Wate
ACID
E
NaOH
SODIUM SALT
POLYAMIDE
DIAMIN
OF
E
DICARBOXYLIC
ACID
DICARBOXYLIC
DIAMIN
ACID
ACID
E
With polyesters the secondary product is a diol.

You need to me able to identify repeating units.

AQA A2 text
book, p120-121

Now look at pages

124-133