ORGANIC CHEMISTRY MECHANISM SUMMARY

FREE RADICAL SUBSTITUTION (FRS)

Exemplified by the substitution of methane by chlorine
Step 1: Initiation Step 2: Propagation Step 3: Termination
Cl—Cl  uv  Cl• + Cl• a) Cl• + CH4  CH3• + HCl a) Cl• + Cl•  Cl2
b) CH3• + Cl2  CH3Cl + Cl• b) CH3• + Cl•  CH3Cl
Then (a), (b), (a), (b)… c) CH3• + CH3•  CH3CH3

ELECTROPHILIC ADDITION
Exemplified by the addition of HBr to an alkene
H H
H H

s lo w
Step 1
C C + H Br

H C
+
C + Br
-

H H H H
carbocation
intermediate
H H H H
-
Step 2 H C
+
C + :Br fa s t H C C H
H Br
H H

ELECTROPHILIC AROMATIC SUBSTITUTION

Exemplified by the addition of NO2 to benzene
Step 1
Generation
HNO3 + 2H2SO4 → NO2+ + H3O+ + 2HSO4-
of
electrophile
H NO2

Step 2 s lo w
Electrophilic
NO2
+
+ +
attack
benzoniu
m ion
NO2
H NO2
Step 3
Loss of fa s t
proton HSO4
-
+ + + H2SO 4

NUCLEOPHILIC SUBSTITUTION – S 2 – ONE STEP

N

‡ R3
R3 R3
-    -
Nu : C X Nu C X Nu C + X

R1 R1 R2 R1
R2 R2
pentavalent transition state

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NUCLEOPHILIC SUBSTITUTION – S 1 – TWO STEP
N

-
R3 Nu : R3 R3 R3
s lo w fa s t
+
+
X C  C Nu C C Nu

-
R1 R2 R1 R2 : Nu R 1 R2 R2 R1
carbocation intermediate two products
(planar) racemic mixture

NUCLEOPHILIC ADDITION
Exemplified by the addition of CN- to ethanal

Step 1
Generatio
n of KCN → K+ + CN-
nucleophi
le
CN
H3C
Step 2  -
- s lo w
Nucleophi
lic attack
 C O + :CN H3C C O

H
H
CN CN
- fa s t -
Step 3
Protonati
H3C C O + H C N H3C C OH + CN
on
H H
Cyanohydrin

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