N Goalby chemrevise.

org Mechanism Summary for A-level AQA Chemistry

Electrophilic Addition of Alkenes with Bromine Electrophilic Addition of Alkenes with hydrogen
bromide
H H H H H H H H
H H
+
C C H C C H H C C H H3C C C CH3 +
H3C C C CH3
H H Br +
Br δ+ Br Br Hδ H
-
Br δ
:Br -
:Br -
Br
δ-
H H
Electrophilic Addition of Alkenes with sulphuric acid H3C C C CH3
H H H H Br H
+
H3C C C H H3C C C H
Elimination of Halogenoalkanes with ethanolic
δ+ H
hydroxide ions
H -:OSO
2OH H H H H
OSO 2OH
δ- H CH3 C C H CH3 C C H
H
+ Br - + H2O
H3C C C H Br H
H :OH-
OSO 2OH

Acid catalysed elimination mechanism: alcohols  alkenes

H
H H H H H
H3C C CH3 H3C C CH3 +
H C C CH3 H C C CH3
The H+ comes
O H +
from the O H H H+
:

H conc H2SO4 or
+
conc H3PO4 H

Acid catalysed addition mechanism for hydration of ethene

H H H H H H
H H
+ H
H C C H H C C H C C H
C C
H +
H H H H O H H O H+
O
H+ The comes from
H+ H H
the conc H3PO4 H

Nucleophilic Substitution of Free Radical Substitution of Alkanes with Bromine

Halogenoalkanes with aqueous hydroxide
ions. H H STEP ONE Initiation
δ+ δ- Essential condition: UV light
H3C C Br H3C C OH + :Br -
Br2  2Br
.
-HO:
H H
STEP TWO Propagation
.
CH3CH3 + Br  HBr + CH3CH2
.
Nucleophilic Substitution of Halogenoalkanes
with cyanide ions. .
CH3CH2 + Br2  CH3CH2Br + Br
.
H H
δ+ δ- STEP THREE Termination
H3C C Br H3C C CN + :Br - .
CH3CH2 + Br  CH3CH2Br
.
-NC:
H H .
CH3CH2 + CH3CH2  CH3CH2CH2CH3
.
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Nucleophilic Substitution reactions of ammonia/amines

Reaction 1 with ammonia forming primary amine

H H
+
H3C C Br H3C C NH3 Br -
H
H
3HN:

H H
+
H3C C NH2 H3C C NH2 + NH4Br
:NH3
H H H

Reaction 2 forming secondary amine

The amine formed in the first reaction has a lone pair of electrons on the
nitrogen and will react further with the haloalkane.
H
+
C Br H3C CH2 NH2 CH2 CH3
H3C Br -
H
:

CH3CH2NH2
+
H3C CH2 NH CH2 CH3 H3C CH2 NH CH2 CH3 + NH4Br
:NH3
H Diethylamine

Reaction 3 forming a tertiary amine

H CH3
CH2
H3C C Br +
H3C CH2 NH CH2 CH3
H
:

H3C CH2 NH CH2 CH3

CH3
CH2 CH3
+ CH2
H3C CH2 N CH2 CH3
:NH3 H3C CH2 N CH2 CH3
H triethylamine

Reaction 4 forming a quaternary ammonium salt

H

H3C C Br CH3
CH2
H +
H3C CH2 N CH2 CH3
:

H3C CH2 N CH2 CH3 CH2

CH2 CH3
CH3
Tetraethylammonium ion
 N Goalby chemrevise.org Mechanism Summary for A-Level AQA Chemistry

Nucleophilic Addition Mechanism Nucleophilic Addition Mechanism

H+ from water or weak acid
O
δ-
O:
- H+ δ-
H+ from sulphuric acid

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

Nucleophilic Addition –Elimination Mechanism Nucleophilic Addition –Elimination Mechanism

O δ- :O- δ- :O
-
O
CH3 C δ+ + +
H3C C OH CH3 C δ+
H3C C OCH2CH3
Cl Cl
:OH Cl H
Cl H
: OCH CH
O 2 3
H O
CH3 C H
C
OH H3C OCH2CH3

Nucleophilic Addition –Elimination Mechanism Nucleophilic Addition –Elimination Mechanism

δ- : O- δ-
O : O-
O
+ CH3 Cδ+ +
CH3 C δ+ H3C C NH2 H3C C NHCH2CH3
Cl
Cl Cl H :NHCH CH Cl H
: NH3 2 3
O O
H
C C
H3C NH2 H3C NHCH2CH3

Electrophilic Substitution Electrophilic Substitution

Equation for Formation of electrophile Equation for Formation of the electrophile.
HNO3 + 2H2SO4  NO2+ + 2HSO4- + H3O+ AlCl3 + CH3COCl  CH3CO+ AlCl4-

NO 2 O O
NO2+
+ C CH3
H C CH3
+
H
+

NO 2 O
C
+ H+ CH3

H+ + HSO4-  H2SO4 H+ + AlCl4-  AlCl3 + HCl

 KOH aqueous
Reaction Summary for A-level AQA Chemistry heat under reflux
Nu Sub
dihalogenoalkane diol
poly(alkene)
high pressure
catalyst Br2, Cl2 room temp
EAdd
alkane
alkene
HBr, HCl room temp
EAdd Br2, Cl2
Step 1 H2SO4 UV light
EAdd Fr Sub
conc. H2SO4 or
Step 2 H2O warm
conc. H3PO4
hydrolysis Elimination, KOH alcoholic
dehydration KOH aqueous heat under reflux
heat under reflux Elimination
NuSub
halogenoalkane
alcohol
NaBH4
NaBH4 Alcoholic NH3
Red Nu Add KCN in ethanol/
Red Nu Add heat under
water mixture heat pressure
under reflux NuSub
NuSub
If secondary
If primary Na2Cr2O7/H+ LiAlH4 in ether
Na2Cr2O7/H+ heat nitrile reduction 1o amine
heat and distill oxidation
partial ox Carboxylic acid + halogenoalkane
H2SO4 NuSub
heat

aldehyde ketone esterification

2o amine Acyl chloride
room temp
3o amine Nu add/elim
NaCN + H2SO4 Quaternary salt
Nu Add

(If primary) Na2Cr2O7/H+ Esters and amides secondary

heat under reflux + excess hydroxynitrile can be hydrolysed
by NaOH and acids amide
oxidising agent
Oxidation

Alcohol + H2SO4 ester 1o amine

carboxylic acid heat room temp
esterification Nu add/elim

Alcohol
room temp Primary
H2O room temp Nu add/elim
Nu add/elim amide
Acyl chloride/ NH3 room temp
Nu add/elim
acid anhydride

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 Aromatic synthetic routes

NO2
conc nitric acid + NH2
NH CH3
conc sulphuric acid Sn and HCl CH3Cl
reduction Nu sub
Electrophilic
substitution

CH3COCl
acyl chloride in the presence Nucleophilic add-el
of anhydrous aluminium
chloride catalyst
Electrophilic substitution O
NH C CH3
O H
C O
CH3
NaCN + H2SO4 C CN
Nu Add
CH3

NaBH4
Red Nu Add
H LiAlH4
reduction
O
OH
CH
CH3 C CH2 NH2

CH3

CH3CO2H + H2SO4
heat
esterification

O
H3C CH O C CH3

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