AQA organic reaction mechanisms

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AS

Free Radical Substitution Electrophilic Addition Nucleophilic Substitution Elimination of HX from haloalkanes

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Elimination in alcohols (mechanism no longer required)

A2

Electrophilic Substitution Nucleophilic Addition

Friedel-Crafts Alkylation

Acylation

Nucleophilic Addition Elimination

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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

ultra-violet Cl2 Cl + Cl CH4 + Cl CH3 + Cl2 CH3 + Cl CH3 + CH3 initiation step CH3 + HCl CH3Cl + Cl CH3Cl CH3CH3 two propagation steps

termination step minor termination step

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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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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
mech

concentrated sulphuric acid with but-2-ene CH3CH=CHCH3+ HOSO3H

CH3CH2CH(OSO3H)CH3 2-butylhydrogensulphate
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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

H
CH3 C Br

H C Br
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Br 1,2-dibromopropane

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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Electrophilic addition mechanism

concentrated H2SO4 with cis but-2-ene

reaction equation

H
CH3 C H

C C CH3 CH3 H

carbocation C CH3 +

OSO3H
H CH3 C H

OSO3H -

CH3

2-butylhydrogensulphate

OSO3H
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Nucleophilic substitution
hydroxide ion with bromoethane CH3CH2Br + OH- (aqueous) cyanide ion with iodoethane CH3CH2I + CN- (ethanolic)
mechanism

CH3CH2OH + Brethanol
mechanism

CH3CH2CN + Ipropanenitrile
mechanism

ammonia with bromoethane

CH3CH2Br + 2 NH3

CH3CH2NH2 + NH4+Brethylamine
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Nucleophilic substitution mechanism

hydroxide ion with bromoethane

H + CH3 C

Br

H CH3 C OH

H
OH-

H
ethanol

Br

reaction equation

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Nucleophilic substitution mechanism

cyanide ion with iodoethane

H + CH3 C

Br

H CH3 C CN

H
CN-

H
propanenitrile

Br

reaction equation

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Nucleophilic substitution mechanism

ammonia with bromoethane H + CH3 C Br H CH3 C H + NH2 H NH3 H Br

H NH3

CH3 C
ethylamine H

NH2

NH4+Br Original slide prepared for the

reaction equation

Elimination of HX from haloalkanes

Elimination of HBr from 2-bromopropane
CH3CHBrCH3 + OHCH3CH=CH2 + H2O + Br(in ethanol) H CH3 C Br H H H C C

H propene H
Br -

C
H

CH3 OH acting as a base

OH

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Haloalkanes and hydroxide ions

nucleophilic substitution alcohol RCH3CH2OH + X-

+ OH- (aqueous) hydroxide acts as a nucleophile RCH2CH2X + OH- (ethanol) elimination hydroxide acts as a base RCH=CH2 + H2O + Xalkene

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Elimination of water from alcohols

Elimination of H2O from propan-1-ol CH3CH2CH2OH CH3CH=CH2 + H2O

Heat with concentrated H2SO4 or concentrated H3PO4

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Elimination mechanism water from propan-1-ol

H CH3 C H H + H OH

H
CH3 C

H H
C OH +

C
H H

H
C+

OH H C

H H protonated alcohol H OH

CH3 C

H
C

H + H

carbocation

CH3

propene

reaction equation

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Electrophilic Substitution
Nitration of benzene

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 + H2SO4 HSO4 + NO2 2. Electrophilic attack on benzene
+

H2 O

NO2 +
3. Forming the product and re-forming the catalyst (H+ reforms H2SO4 with HSO4-)

NO2 H
NO2

H+

reaction equation

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Friedel-Crafts alkylation
Where an H atom attached to an aromatic ring is replaced by a C atom
Alkylation of benzene C6H6 + RCl electrophilic substitution C6H5R + HCl

R = alkyl group Conditions / Reagents RCl (haloakane) 0 - 25oC and anhydrous AlCl3
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to prevent further substitution

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 + CH2CH3 CH2CH3 H +

3. Forming the product and re-forming the catalyst (H+ reforms AlCl3 and HCl with AlCl4-) CH2CH3 + ethylbenzene
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H+

Friedel-Crafts acylation
An H atom attached to an aromatic ring is replaced by a C atom where C is part of C=O
Acylation of benzene C6H6 + RCOCl electrophilic substitution 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

CH3 +

C
H

3. Forming the product

and re-forming the catalyst (H+ reforms AlCl3 and HCl with AlCl4-) CH3C

H+

phenylethanone
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Nucleophilic Addition
Reduction of carbonyls primary alcohol

RCHO
aldehyde

+ 2[H]

RCH2OH
RCH(OH)R

RCOR + 2[H]
ketone

secondary alcohol

Conditions / Reagents NaBH4 (aq) Room temperature and pressure

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Nucleophilic Addition Mechanism RCOR

+ 2[H]

RCH(OH)R

alcohol

reduction of propanone

NaBH4 is a source of hydride ions H

O H+ from H2SO4 (aq) O CH3 C CH3 H H+ OH CH3 C CH3 propan-2-ol
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+ CH3 C H

CH3

Nucleophilic Addition
addition of hydrogen cyanide to carbonyls to form hydroxynitriles RCOR
ketone

+ HCN

RC(OH)(CN)R RCH(OH)CN

RCHO + HCN
aldehyde

Conditions / Reagents
HCN (aq) supplies H+ and 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

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

+ CH3 C CN

OH CH3 C CH3 CN

CH3

2-hydroxy-2-methylpropanenitrile
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Nucleophilic Addition Elimination

4 main types of reaction mechanism to consider 1. acyl chloride + water carboxylic acid 2. acyl chloride + alcohol ester 3. acyl chloride + ammonia acid amide

4. acyl chloride + amine N-substituted amide

HCl is a secondary product in all of the above reactions.

Two of the 4 mechanisms are shown on the next few slides, but all 4 versions must be known for the exam. Mechanisms for acid anhydrides need not be learned (but equations should, giving a carboxylic Original slide prepared for the acid in place of HCl)

Nucleophilic Addition Elimination

Acylation of water to give carboxylic acids RCOCl + H2O RCOOH + HCl

carboxylic acid

RC
Conditions

O OH

room temperature and pressure

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Formation of ethanoic acid

ethanoyl chloride CH3COCl + H2 O CH3COOH + HCl ethanoic acid

O CH3 C OH

mechanism
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Nucleophilic Addition Elimination Mechanism + O CH3 C Cl OH H O C nucleophilic addition O CH3 C

OH

Cl H elimination O C + OH H Cl

CH3
OH

CH3

HCl
reaction equation
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Acylation of primary amines to N-alkyl amides RCOCl + RNH2 RCONHR + HCl N-alkylamide

RC
Conditions

O NHR O NHCH2CH2CH3
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room temperature and pressure

N-propylethanamide

CH3 C

Formation of N-propyl ethanamide from ethanoyl chloride CH3COCl + 1-aminopropane CH3CH2CH2NH2

CH3CONHCH2CH2CH3

HCl

N-propylethanamide
mechanism
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Nucleophilic Addition Elimination Mechanism nucleophilic O + addition CH3 C CH O C

Cl

NHCH2CH2CH3

NHCH2CH2CH3 H O C CH3

Cl H

elimination

O C + NHCH2CH2CH3 H Cl

CH3

NHCH2CH2CH3
HCl

reaction equation

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References
Steve Lewis for the Royal Society of Chemistry

Adapted by Mark Smith for Turton Chemistry Department

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