Edexcel organic reaction mechanisms

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Homolytic
Free Radical Substitution

Free Radical Addition

Heterolytic
Electrophilic Addition

Nucleophilic Substitution SN 2 SN1

Electrophilic Substitution Nitration Br2 Alkylation Acylation

Nucleophilic Addition

Original slide
prepared for the
Free radical substitution
chlorination of methane
i.e. homolytic breaking of covalent bonds

Overall reaction equation

CH4 + Cl2 CH3Cl + HCl

Conditions

ultra violet light

excess methane to reduce further substitution

Original slide
prepared for the
Free radical substitution mechanism
ultra-violet
Cl Cl Cl Cl initiation step

H3C H Cl H3C H Cl two

propagation
H3C Cl Cl H3C Cl Cl steps

H3C Cl H3C Cl termination step

minor
H3C CH3 H3C CH3
termination step
Original slide
prepared for the
Further free radical substitutions

Overall reaction equations

CH3Cl + Cl2 CH2Cl2 + HCl

CH2Cl2 + Cl2 CHCl3 + HCl

CHCl3 + Cl2 CCl4 + HCl

Conditions ultra-violet light

excess chlorine
Original slide
prepared for the
Free radical addition
addition polymerisation of ethene
i.e. homolytic breaking of covalent bonds

Overall reaction equation

n H2C=CH2 [ CH2CH2 ]n
ethene polyethene

Conditions
free radical source
(a species that generates free radicals
that allow the polymerisation of ethene molecules)

Original slide
prepared for the
Free radical addition mechanism
R R R R initiation step

H2C CH2 R H2C CH2 R

H2C CH2 H2C CH2R H2C CH2 CH2CH2R

chain propagation steps
Addition of H2C=CH2 repeats the same way until:

R(CH2)nCH2 H2C(CH2)mR

termination step R(CH2)nCH2 CH2(CH2)mR

polyethene
Original slide
prepared for the
Electrophilic addition
bromine with propene mechanism

CH3CH=CH2 + Br2 CH3CHBrCH2Br

1,2-dibromopropane

hydrogen bromide with but-2-ene mechanism

CH3CH=CHCH3 + HBr CH3CH2CHBrCH3

2-bromobutane

Original slide
prepared for the
Electrophilic addition mechanism
bromine with propene reaction equation

H H
C C
H H carbocation
CH3 H
CH3 C C H
+ +
Br
Br
H H
Br
- Br-
Br CH3 C C H

Br Br Br
1,2-dibromopropane
Original slide
prepared for the
Electrophilic addition mechanism
hydrogen bromide with trans but-2-ene
reaction equation
H CH3
C C
H H carbocation
CH3 H
CH3 C C CH3
+ +
H
H
H H
Br-
Br
-
CH3 C C CH3

Br H
2-bromobutane
Original slide
prepared for the
Nucleophilic substitution

hydroxide ion with bromoethane mechanism

CH3CH2Br + OH- (aqueous) CH3CH2OH + Br-

ethanol

hydroxide ion with 2-bromo,2-methylpropane

mechanism

(CH3)3CBr + OH- (aqueous) (CH3)3COH + Br-

2-methylpropan-2-ol

Original slide
prepared for the
Nucleophilic substitution mechanism
hydroxide ion with bromoethane (SN2)

H H
+ -
CH3 C Br CH3 C OH
H Br
-
H
OH- ethanol
SN2
reaction equation

S (substitution) N(nucleophilic) 2(species reacting

in the slowest step)
Original slide
prepared for the
Nucleophilic substitution mechanism
OH- ion with 2-bromo,2-methylpropane (SN1)

Br
- -
Br
CH3 CH3 CH3
+ -
CH3 C Br CH3 C+ CH3 C OH

CH3 CH3 CH3

OH-
2-methylpropan-2-ol
SN1 reaction equation

S (substitution) N(nucleophilic) 1(species reacting

in the slowest step)
Original slide
prepared for the
Nucleophilic substitution

cyanide ion with iodoethane mechanism

CH3CH2I (ethanol) + CN-(aq) CH3CH2CN + I-

propanenitrile

cyanide ion with 2-bromo,2-methylpropane

mechanism
(CH3)3CBr (ethanol) + CN- (aqueous)
(CH3)3CCN + Br-
2,2-dimethylpropanenitrile

Original slide
prepared for the
Nucleophilic substitution mechanism
cyanide ion with iodoethane (SN2)

H H
+ -
CH3 C I CH3 C CN
H I
-
H
CN- propanenitrile
SN2

S (substitution) N(nucleophilic) 2(species reacting

in the slowest step)
reaction equation
Original slide
prepared for the
Nucleophilic substitution mechanism
CN- ion with 2-bromo,2-methylpropane (SN1)
-
Br -
Br
CH3 CH3 CH3
+ -
CH3 C Br CH3 C+ CH3 C CN

CH3 CH3 CH3

SN1
CN- 2,2-dimethyl
propanenitrile

S (substitution) N(nucleophilic) 1(species reacting

in the slowest step)
reaction equation
Original slide
prepared for the
Electrophilic Substitution
Nitration of benzene

Where an H atom attached to an aromatic ring

is replaced by an NO2 group of atoms

C6H6 + HNO3 C6H5NO2 + H2O

Conditions / Reagents
concentrated HNO3 and concentrated H2SO4
50oC

mechanism
Original slide
prepared for the
electrophilic substitution mechanism (nitration)

+
1. Formation of NO2 the nitronium ion
+
HNO3 + 2H2SO4 NO 2 + 2HSO4- + H3O+

2. Electrophilic attack on benzene

+
NO2 NO2
-
H O SO3H
+
NO2
3. Forming the product
and re-forming the catalyst H O SO3H

reaction equation Original slide

prepared for the
Bromination of benzene
Where an H atom attached to an aromatic ring
is replaced by a Br atom

electrophilic substitution

C6H6 + Br2 C6H5Br + HBr

R = alkyl group

Conditions / Reagents
Br2 and anhydrous AlBr3
25oC

Original slide
prepared for the
Electrophilic substitution mechanism

1. Formation of the electrophile

+ -
Br Br AlBr3 Br Br AlBr3

2. Electrophilic attack on benzene

+ Br -
Br
H Br AlBr3
+

Br
3. Forming the products H Br

and re-forming the catalyst

AlBr3
bromobenzene
Original slide
prepared for the
Alkylation of benzene
Where an H atom attached to an aromatic ring
is replaced by a C atom

electrophilic substitution

C6H6 + RCl C6H5R + HCl

R = alkyl group

Conditions / Reagents
RCl (haloakane) and anhydrous AlCl3
0 - 25oC to prevent further substitution
Original slide
prepared for the
Alkylation example

With chloroethane overall reaction equation

C6H6 + CH3CH2Cl C6H5CH2CH3 + HCl

Three steps in electrophilic substitution mechanism

1. Formation of the electrophile (a carbocation)

-
AlCl3 + Cl AlCl3
CH3CH2 Cl CH3CH2

Original slide
prepared for the
Alkylation electrophilic substitution mechanism 2

2. Electrophilic attack on benzene

+
CH3CH2 CH3CH2
H
+ -
Cl AlCl3

3. Forming the product

and re-forming the catalyst CH3CH2

AlCl3

H Cl
ethylbenzene
Original slide
prepared for the
 Acylation of benzene
An H atom attached to an aromatic ring
is replaced by a C atom where C is part of C=O

electrophilic substitution

C6H6 + RCOCl C6H5COR + HCl

Conditions / Reagents
RCOCl (acyl chloride) and anhydrous AlCl3
50 oC

Original slide
prepared for the
 Acylation example

With ethanoyl chloride overall reaction equation

C6H6 + CH3COCl C6H5COCH3 + HCl

Three steps in electrophilic substitution mechanism

1. Formation of the electrophile (an acylium ion)

O +
CH3C O
CH3C -
Cl AlCl3 Cl AlCl3

Original slide
prepared for the
Acylation electrophilic substitution mechanism 2

2. Electrophilic attack on benzene

+ O
CH3C O CH3C
H
+ -
Cl AlCl3

3. Forming the products

O
CH3C H Cl
and re-forming the catalyst
AlCl3
phenylethanone
Original slide
prepared for the
Nucleophilic Addition
addition of hydrogen cyanide to carbonyls
to form hydroxynitriles

RCOR + HCN RC(OH)(CN)R

RCHO + HCN RCH(OH)CN

Conditions / Reagents
NaCN (aq) and H2SO4(aq) supplies H+
supplies the CN- nucleophile
Room temperature and pressure

Original slide
prepared for the
Nucleophilic Addition Mechanism

hydrogen cyanide with propanone

CH3COCH3 + HCN CH3C(OH)(CN)CH3

NaCN (aq) is a source of cyanide ions C N

- H+ from H2SO4 (aq)

O H +
+ O O H
CH3 C
CH3 CH3 C CN CH3 C CN

CN CH3 CH3
2-hydroxy-2-methylpropanenitrile

Original slide
prepared for the
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 References
Steve Lewis for the Royal Society of Chemistry

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prepared for the