Mechanisms

Mechanisms
1) Free radical substitution – Alkane à halogenoalkane
Initiation:
Propagation:
Termination:
Overall:
2) Ozone depletion
• UV light breaks the C – Cl bond releasing chlorine radical

. .
CFCl3F à CCl2F + Cl
• This chlorine radical catalyses the decomposition of ozone with the chlorine radical coming
out unchanged (and available for more ozone decomposition).
. .
Cl + O3 à ClO + O2
. .
ClO + O3 à Cl + 2O2
Overall
2O3(g) à 3O2(g)
3) Nucleophilic substitution of halogenoalkanes
a) With aqueous hydroxide, OH- Hydrolysis – forming alcohols
• This reaction converts a halogenoalkane to an alcohol
Reagents: Aqueous sodium hydroxide
Conditions: Reflux
Hydrolysis: Splitting a molecule apart by using water molecules

b) With ethanolic potassium cyanide, KCN – forming nitriles
• This reaction converts a halogenoalkane to an alkyl nitrile

• This is a key reaction in chemical synthesis as the carbon chain length is increased
Reagents: Potassium cyanide dissolved in ethanol
Conditions: Reflux
c) With excess ethanolic ammonia, NH3 – forming amines
• This reaction converts a halogenoalkane to amines
Reagents: Excess ethanolic ammonia
Conditions: Reflux
The Mechanism
4) Elimination of halogenoalkanes
With ethanolic potassium hydroxide, reflux – forming alkenes
Reagents: KOH dissolved in ethanol
Conditions: Reflux
Substitution vs elimination
Substitution Elimination
Aqueous conditions – substitution Ethanolic conditions – Elimination
predominates predominates
OH- behaves as a nucleophile OH- behaves as a base (accepting a proton)
50 : 50 mixture of water : ethanol means substitution : elimination equally likely

5) Electrophilic addition mechanism of the alkenes:
The mechanism
a) Addition of halogens - Br2: Forming a dihalogenoalkane
Chemical test for C=C / unsaturation:
• Bromine water
• Orange to clear and colourless
b) Addition of hydrogen halides - HBr: Forming a halogenoalkane
c) Heating with H2O / H2SO4: Forming an alcohol (in 2 steps)
• However this happens in 2 stages with the sulphuric acid behaving as a catalyst:
• The sulphuric acid is used up in step 1 but regenerated in step 2

d) Hydration of alkenes with H2O / H3PO4 catalyst / 300oC / 60atm: Forming an alcohol
6) Addition to unsymmetrical alkenes: Markovnikov addition
1o as it has 1 alkyl group 2o as it has 2 alkyl group 3o as it has 3 alkyl group

attached attached attached
1o Primary carbocation 2o Secondary carbocation 3o Tertiary carbocation
1 alkyl group 2 alkyl groups 3 alkyl groups
Alkyl groups are slightly electron releasing
• As the number of alkyl groups increase there is an increase in the negative electrons
released to the positive charge
• This increases the stability of the carbocation
7) Dehydration of an alcohol – Elimination reaction
• The catalyst is concentrated sulphuric acid, H2SO4

• The reaction requires heat
Unsymmetrical alcohols
• Dehydration of unsymmetrical alcohols gives rise to 2 alkenes, position isomers
• The dehydration using ‘B’ would also give E/Z isomerism

8) Nucleophilic addition reactions of Aldehydes / Ketones
a) Reduction to alcohols
Conditions: NaBH4 - a source of hydride ions, H-
b) To form Hydroxynitriles
Conditions: KCN followed by dilute acid (HCl) – This produces HCN
CH3CHO(aq) + HCN(aq) à CH3CH(OH)CN(aq)
• CN- is the nucleophile and is attracted to the d+ carbon in the carbonyl group.
• In practise, KCN is added.

• This is because HCN is a weak acid (partially dissociates) giving a low [CN-]
• Can produce optical isomers
Nucleophilic addition – elimination reaction of the acyl chlorides
The mechanism:
1) With water:
2) With alcohol:
3) With ammonia:
4) With primary amines:

Nucleophilic addition – elimination reaction of the acid anhydrides
Summary – Carboxylic acid / derivative mechanisms

• The mechanism Is not required but they all follow the general mechanism:
Reactions of benzene – Electrophilic substitution
1) Nitration:
Reagents and conditions:
Concentrated nitric acid and concentrated sulphuric acid (catalyst) / Reflux at 55oC
Reaction:
a) Generation of the electrophile:
HNO3 + H2SO4 à NO2+ + HSO4- + H2 O
b) Electrophilic Substitution Steps
c) Regeneration of the catalyst
H+ + HSO4- à H2SO4
2) Fiedel – Crafts - Acylation:
Acyl chloride and AlCl3 (Halogen carrier / catalyst) / Heat under reflux
Reaction:
Carbocation is the electrophile

H+ + AlCl4- à AlCl3 + HCl
Extension – 3 and 4 are not in the specification.
3) Fiedel – Crafts - Alkylation:

Halogenoalkane, RCl and AlCl3 (Halogen carrier / catalyst) / Heat under reflux
Reaction:
Carbocation is the electrophile


4) Halogenation:
Halogen, Cl2 and AlCl3 (Halogen carrier / catalyst) / Heat under reflux
Reaction:
Chloronium is the electrophile


Nucleophilic substitution reactions involving amines:
1) With ammonia, NH3, to form 1o amines: Year 1, recap: The nucleophilic substitution
Reagents: Excess ethanolic ammonia
Conditions: Reflux
Ammonia 1o amine Quaternary

ammonium salt
o o
2) With 1 amines, RNH2, to form 2 amines, R2NH:
1o Amine 2o Amine Quaternary

ammonium salt
3) With 2o amines, R2NH, to form 3o amines, R3N:
2o Amine 3o Amine quaternary

ammonium salt
4) With 3 amines, R3N, to form quartenary ammonium salt, R4N+:
o
3o Amine Quaternary ammonium salt

Summary:
Ammonia 1o Amine 2o Amine 3o Amine 4o Amine

Mechanisms

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Mechanisms

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Mechanisms

1) Free radical substitution – Alkane à halogenoalkane

• UV light breaks the C – Cl bond releasing chlorine radical

a) With aqueous hydroxide, OH- Hydrolysis – forming alcohols

• This reaction converts a halogenoalkane to an alcohol

Reagents: Aqueous sodium hydroxide

Hydrolysis: Splitting a molecule apart by using water molecules

• This reaction converts a halogenoalkane to an alkyl nitrile

Reagents: Potassium cyanide dissolved in ethanol

c) With excess ethanolic ammonia, NH3 – forming amines

• This reaction converts a halogenoalkane to amines

Reagents: Excess ethanolic ammonia

With ethanolic potassium hydroxide, reflux – forming alkenes

Reagents: KOH dissolved in ethanol

OH- behaves as a nucleophile OH- behaves as a base (accepting a proton)

50 : 50 mixture of water : ethanol means substitution : elimination equally likely

a) Addition of halogens - Br2: Forming a dihalogenoalkane

Chemical test for C=C / unsaturation:

• The sulphuric acid is used up in step 1 but regenerated in step 2

1o as it has 1 alkyl group 2o as it has 2 alkyl group 3o as it has 3 alkyl group

• The catalyst is concentrated sulphuric acid, H2SO4

• Dehydration of unsymmetrical alcohols gives rise to 2 alkenes, position isomers

• The dehydration using ‘B’ would also give E/Z isomerism

Conditions: NaBH4 - a source of hydride ions, H-

Conditions: KCN followed by dilute acid (HCl) – This produces HCN

CH3CHO(aq) + HCN(aq) à CH3CH(OH)CN(aq)

• In practise, KCN is added.

4) With primary amines:

Summary – Carboxylic acid / derivative mechanisms

Reactions of benzene – Electrophilic substitution

HNO3 + H2SO4 à NO2+ + HSO4- + H2 O

b) Electrophilic Substitution Steps

c) Regeneration of the catalyst

Carbocation is the electrophile

c) Regeneration of the catalyst

H+ + AlCl4- à AlCl3 + HCl

Extension – 3 and 4 are not in the specification.

3) Fiedel – Crafts - Alkylation:

Reagents and conditions:

Carbocation is the electrophile

c) Regeneration of the catalyst

H+ + AlCl4- à AlCl3 + HCl

Reagents and conditions:

Chloronium is the electrophile

c) Regeneration of the catalyst

H+ + AlCl4- à AlCl3 + HCl

Ammonia 1o amine Quaternary

1o Amine 2o Amine Quaternary

2o Amine 3o Amine quaternary

3o Amine Quaternary ammonium salt

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