Mechanism Summary for AS AQA Chemistry

Nucleophilic Substitution of Haloalkanes Nucleophilic Substitution of Haloalkanes

with aqueous hydroxide ions. with cyanide ions.
H H H H
δ+ δ- δ+ δ-
H3C C Br H3C C OH + :Br - H3C C Br H3C C CN + :Br -

-HO: -NC:
H H H
H

Nucleophilic Substitution of Haloalkanes with ammonia

H H Elimination of Haloalkanes with ethanolic
H :Br -
hydroxide ions
δ+ δ- +
CH3 CH2 C Br CH3 CH2 C N H H H H H
3HN:
H H CH3 C C H CH3 C C H
H
:NH3
+ Br - + H2O
Br H
H
:OH-
CH3 CH2 C NH2 + NH Br
4
H

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 δ+
Br δ+ Br Br H H
:Br - δ- :Br -
Br
Br
δ-
H H

Electrophilic Addition of Alkenes with sulphuric acid H3C C C CH3

H H H Br H
H
+
H3C C C H H3C C C H

δ+ H Free Radical Substitution of Alkanes with Bromine

H -:OSO
2OH
OSO 2OH STEP ONE Initiation
δ- H Essential condition: UV light
H
Br2
2Br
.
H3C C C H
H STEP TWO Propagation
OSO 2OH . .
CH3CH3 + Br
HBr + CH3CH2
.
CH3CH2 + Br2
CH3CH2Br + Br
.

STEP THREE Termination

.
CH3CH2 + Br
CH3CH2Br
.
.
CH3CH2 + CH3CH2
CH3CH2CH2CH3
.

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 Mechanism Summary for A2 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 2CH3 Cl H
: NH3 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

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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
+
H3C CH2 NH2 CH2 CH3
H3C C Br 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

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 KOH aqueous
heat under reflux
Nu Sub
dihaloalkane diol
poly(alkene)
high pressure
catalyst Br2, Cl2 room temp
EAdd
alkane
alkene
Br2, Cl2
Step 1 H2SO4 UV light
EAdd Fr Sub
conc. H2SO4 or
Step 2 H2O warm
conc. H3PO4
hydrolysis Elimination,
dehydration
KOH aqueous
heat under reflux
NuSub
alcohol haloalkane
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 haloalkane
Caboxylic acid + NuSub
H2SO4
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+
heat under reflux + excess Esters and secondary
oxidising agent hydroxynitrile amides can be
amide
Oxidation hydrolysed by
NaOH and acids

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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