Homolytic
Free Radical Substitution
Heterolytic
Electrophilic Addition Nucleophilic Substitution Electrophilic Substitution Nucleophilic Addition
Original slide prepared for the
S N2
S N1
Nitration
Br2
Alkylation
Acylation
CH4 + Cl2
Conditions
CH3Cl + HCl
initiation step
Cl Cl
Cl Cl
H3C
H3C H3C
Cl
Cl CH3
H3C
CH3
CH2Cl2 + HCl
CHCl3 + HCl CCl4 + HCl
n H2C=CH2 ethene
Conditions
[ CH2CH2 ]n polyethene
free radical source (a species that generates free radicals that allow the polymerisation of ethene molecules)
Original slide prepared for the
R
CH2 R H2C
R
H2C CH2R
R CH2
CH2
H2C
termination step
R(CH2)nCH2
CH2(CH2)mR
Original slide prepared for the
polyethene
Electrophilic addition
bromine with propene
CH3CH=CH2 + Br2
mechanism
CH3CHBrCH2Br 1,2-dibromopropane
mechanism
CH3CH2CHBrCH3 2-bromobutane
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
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
Original slide prepared for the
Nucleophilic substitution
hydroxide ion with bromoethane CH3CH2Br + OH- (aqueous)
mechanism
CH3CH2OH + Brethanol
(CH3)3COH + Br-
2-methylpropan-2-ol
Br
OH-
S N2
ethanol
reaction equation
CH3 C
OH
Br
CH3
CH3
CH3
S N1
OH-
2-methylpropan-2-ol
reaction equation
Nucleophilic substitution
cyanide ion with iodoethane CH3CH2I (ethanol) + CN-(aq)
mechanism
CH3CH2CN + Ipropanenitrile
H
CN-
H
propanenitrile
S N2
in the slowest step)
Original slide prepared for the
(SN1)
CH3
CH3 C
CN
Br
CH3
CH3
S N1
CH3
CN-
2,2-dimethyl propanenitrile
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
50oC
mechanism
HNO3 + 2H2SO4
NO2
+ 2HSO4- + H3O+
NO2 +
3. Forming the product
NO2 H
O SO3H
NO2 H O SO3H
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
25oC
Original slide prepared for the
+ Br
Br
AlBr3
Br
AlBr3
Br
Br
bromobenzene
AlBr3
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 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
Cl
AlCl3
CH3CH2 H Cl
AlCl3
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
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
+ CH3C O
CH3C
+ H Cl AlCl3
Cl
AlCl3
phenylethanone
Original slide prepared for the
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
Original slide prepared for the
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
Original slide prepared for the
Advice
To get back to the mechanism links page from anywhere in the presentation, click the button at the top right corner of the screen.
This version provides the organic mechanisms specified (2002/3) by the Edexcel exam board. Each stage of a reaction equation, its conditions and mechanism are revealed in turn on a mouse click or keyboard stroke. Note that there is another version available where each reaction and mechanism play automatically after an initiating click or key stroke. The number of ways of navigating through this presentation may depend on the version of PowerPoint being used and how it is configured. Some possible ways of advancing: left mouse click or return key or right arrow key or up arrow key. Some possible ways of reversing: backspace key or left arrow key or down arrow key.
References
Steve Lewis for the Royal Society of Chemistry