organic reaction mechanisms

S.Narayana Iyer,M.Sc,M.Phil

Homolytic
Free Radical Substitution Free Radical Addition

Heterolytic
Electrophilic Addition Nucleophilic Substitution Electrophilic Substitution Nucleophilic Addition S N2 Nitration S N1 Br2 Alkylation Acylation

Free radical substitution

chlorination of methane i.e. homolytic breaking of covalent bonds Overall reaction equation CH4 + Cl2 Conditions ultra violet light excess methane to reduce further substitution CH3Cl + HCl

Free radical substitution mechanism

ultra-violet Cl H3C H3C H3C H3C Cl H Cl Cl Cl Cl H3C H3C H3C H3C Cl initiation step Cl Cl two propagation steps

H Cl

Cl

Cl CH3

termination step minor termination step

CH3

Further free radical substitutions

Overall reaction equations CH3Cl + Cl2 CH2Cl2 + HCl

CH2Cl2 + Cl2

CHCl3 + HCl

CHCl3 + Cl2 Conditions

CCl4 + HCl

ultra-violet light excess chlorine

Free radical addition

addition polymerisation of ethene i.e. homolytic breaking of covalent bonds Overall reaction equation n H2C=CH2 ethene Conditions free radical source (a species that generates free radicals that allow the polymerisation of ethene molecules) [ CH2CH2 ]n polyethene

Free radical addition mechanism

R H2C H2C R CH2 CH2 R H2C R H2C CH2R R CH2 H2C initiation step R CH2 CH2CH2R

chain propagation steps Addition of H2C=CH2 repeats the same way until: R(CH2)nCH2 H2C(CH2)mR R(CH2)nCH2 CH2(CH2)mR

termination step

polyethene

Electrophilic addition
bromine with propene CH3CH=CH2 + Br2
mechanism

CH3CHBrCH2Br 1,2-dibromopropane

hydrogen bromide with but-2-ene CH3CH=CHCH3+ HBr

mechanism

CH3CH2CHBrCH3 2-bromobutane

Electrophilic addition mechanism

bromine with propene H H H CH3 C + H C Br carbocation H H CH3 C Br 1,2-dibromopropane H C Br H
reaction equation

C C CH3 H + Br Br Br Br

Br

Electrophilic addition mechanism

hydrogen bromide with trans but-2-ene H CH3 H CH3 C + H C H reaction equation

C C CH3 H H +

carbocation CH3 H CH3 C Br H C H CH3

Br

Br

2-bromobutane

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 + Br2-methylpropan-2-ol

Nucleophilic substitution mechanism

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

Br

Br

SN2

reaction equation

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

in the slowest step)

Nucleophilic substitution mechanism

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

Br

CH3 2-methylpropan-2-ol
reaction equation

SN1

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

in the slowest step)

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

Nucleophilic substitution mechanism

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

SN2 S (substitution) N(nucleophilic) 2(species reacting

in the slowest step)
reaction equation

Nucleophilic substitution mechanism

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

Br

CH3 CN2,2-dimethyl propanenitrile

SN1

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

in the slowest step)
reaction equation

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

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 and re-forming the catalyst
reaction equation
+

NO2 H

O SO3H

NO2 H O SO3H

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 25oC and anhydrous AlBr3

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

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

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

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 H ethylbenzene Cl AlCl3

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

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

Acylation electrophilic substitution mechanism 2 2. Electrophilic attack on benzene + CH3C O O CH3C + H Cl 3. Forming the products and re-forming the catalyst CH3C O H Cl AlCl3 phenylethanone AlCl3

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

Nucleophilic Addition Mechanism hydrogen cyanide with propanone CH3COCH3 + HCN CH3C(OH)(CN)CH3 C N

NaCN (aq) is a source of cyanide ions 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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