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Edexcel organic reaction mechanisms

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Homolytic
Free Radical Substitution

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Free Radical Addition

Heterolytic
Electrophilic Addition Nucleophilic Substitution Electrophilic Substitution Nucleophilic Addition
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S N2

S N1

Nitration

Br2

Alkylation

Acylation

Free radical substitution


chlorination of methane

i.e. homolytic breaking of covalent bonds


Overall reaction equation

CH4 + Cl2
Conditions

CH3Cl + HCl

ultra violet light excess methane to reduce further substitution

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Free radical substitution mechanism


Cl H3C H3C H3C Cl H Cl Cl ultra-violet Cl H3C Cl H

initiation step
Cl Cl

Cl Cl

H3C
H3C H3C

Cl
Cl CH3

two propagation steps

termination step minor termination step


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H3C

CH3

Further free radical substitutions


Overall reaction equations CH3Cl + Cl2
CH2Cl2 + Cl2 CHCl3 + Cl2 Conditions

CH2Cl2 + HCl
CHCl3 + HCl CCl4 + HCl

ultra-violet light excess chlorine


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Free radical addition


addition polymerisation of ethene

i.e. homolytic breaking of covalent bonds


Overall reaction equation

n H2C=CH2 ethene
Conditions

[ CH2CH2 ]n polyethene

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


R
H2C H2C

R
CH2 R H2C

R
H2C CH2R

R CH2

initiation step R CH2 CH2CH2R

CH2

H2C

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
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polyethene

Electrophilic addition
bromine with propene
CH3CH=CH2 + Br2
mechanism

CH3CHBrCH2Br 1,2-dibromopropane
mechanism

hydrogen bromide with but-2-ene


CH3CH=CHCH3+ HBr

CH3CH2CHBrCH3 2-bromobutane

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Electrophilic addition mechanism


bromine with propene H H
reaction equation

C C CH3 H

H
CH3 C +

H
C Br

carbocation
H

+ Br Br Br Br

Br

H
CH3 C

H C Br H

Br 1,2-dibromopropane

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Electrophilic addition mechanism


hydrogen bromide with trans but-2-ene

CH3

reaction equation

C C CH3 H H +

H
CH3 C +

H
C H

carbocation
CH3 H CH3 C Br H

Br

Br

C
H

CH3

2-bromobutane
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Nucleophilic substitution
hydroxide ion with bromoethane CH3CH2Br + OH- (aqueous)
mechanism

CH3CH2OH + Brethanol

hydroxide ion with 2-bromo,2-methylpropane


mechanism

(CH3)3CBr + OH- (aqueous)

(CH3)3COH + Br-

2-methylpropan-2-ol

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Nucleophilic substitution mechanism


hydroxide ion with bromoethane H + CH3 C H Br H CH3 C H OH (SN2)

Br

OH-

S N2

ethanol
reaction equation

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

in the slowest step)


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Nucleophilic substitution mechanism


OH- ion with 2-bromo,2-methylpropane CH3 + CH3 C Br CH3 CH3 C+ Br (SN1) CH3

CH3 C
OH

Br

CH3

CH3

CH3

S N1

OH-

2-methylpropan-2-ol
reaction equation

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

in the slowest step)


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Nucleophilic substitution
cyanide ion with iodoethane CH3CH2I (ethanol) + CN-(aq)
mechanism

CH3CH2CN + Ipropanenitrile

cyanide ion with 2-bromo,2-methylpropane


mechanism

(CH3)3CBr (ethanol) + CN- (aqueous) (CH3)3CCN + Br2,2-dimethylpropanenitrile


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Nucleophilic substitution mechanism


cyanide ion with iodoethane (SN2) H + CH3 C H CH3 C CN I

H
CN-

H
propanenitrile

S N2
in the slowest step)
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S (substitution) N(nucleophilic) 2(species reacting


reaction equation

Nucleophilic substitution mechanism


CN- ion with 2-bromo,2-methylpropane
CH3 + CH3 C Br CH3 CH3 C+ Br

(SN1)
CH3

CH3 C
CN

Br

CH3

CH3

S N1

CH3

CN-

2,2-dimethyl propanenitrile

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


reaction equation

in the slowest step)


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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

+ H2 O

Conditions / Reagents concentrated HNO3 and concentrated H2SO4

50oC

mechanism

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electrophilic substitution mechanism (nitration) 1. Formation of NO2 the nitronium ion


+

HNO3 + 2H2SO4

NO2

+ 2HSO4- + H3O+

2. Electrophilic attack on benzene

NO2 +
3. Forming the product

NO2 H

O SO3H

NO2 H O SO3H
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and re-forming the catalyst


reaction equation

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
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Electrophilic substitution mechanism 1. Formation of the electrophile Br Br AlBr3

+ Br

Br

AlBr3

2. Electrophilic attack on benzene + Br Br H +

Br

AlBr3

3. Forming the products and re-forming the catalyst

Br

Br

bromobenzene

AlBr3
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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
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Alkylation example With chloroethane C6H6 + CH3CH2Cl overall reaction equation C6H5CH2CH3 + HCl

Three steps in electrophilic substitution mechanism 1. Formation of the electrophile (a carbocation) AlCl3 + CH3CH2 Cl AlCl3

CH3CH2

Cl

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Alkylation electrophilic substitution mechanism 2

2. Electrophilic attack on benzene + CH3CH2 CH3CH2 H +


3. Forming the product and re-forming the catalyst

Cl

AlCl3

CH3CH2 H Cl

AlCl3

ethylbenzene
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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

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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 Cl AlCl3 + CH3C O Cl

AlCl3

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Acylation electrophilic substitution mechanism 2 2. Electrophilic attack on benzene

+ CH3C O

CH3C
+ H Cl AlCl3

3. Forming the products


and re-forming the catalyst CH3C

Cl
AlCl3

phenylethanone
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Nucleophilic Addition
addition of hydrogen cyanide to carbonyls to form hydroxynitriles RCOR + HCN RC(OH)(CN)R RCH(OH)CN

RCHO + HCN

Conditions / Reagents
NaCN (aq) and H2SO4(aq) supplies H+ supplies the CN- nucleophile Room temperature and pressure
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Nucleophilic Addition Mechanism hydrogen cyanide with propanone CH3COCH3 + HCN CH3C(OH)(CN)CH3 C N

NaCN (aq) is a source of cyanide ions O H+ from H2SO4 (aq) H+ O CH3 C CH3 CN

+ CH3 C CN

O CH3 C CH3

H CN

CH3

2-hydroxy-2-methylpropanenitrile
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References
Steve Lewis for the Royal Society of Chemistry

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