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Chapter 15
Smith
1
Introduction
• A radical is a chemical species with
a single unpaired electron in an
orbital.
• Two radicals arise when a bond is cleaved
homolytically.
4
Step 1. Initiation Reaction: Formation of chlorine radical
heat
Cl Cl 2 Cl
H H
H C H + Cl H C + H Cl
H H
5
Two Radicals May React with
Each Other
Step 3. Termination: Radical reacts with radical
Cl + Cl Cl Cl
O O + Cl O O Cl
Oxygen is a radical inhibitor, it reacts with a radical such as
Cl thereby keeping it from reacting with another species.
heat CH3Br
CH4 + Br2 + HBr
hν
+ Cl2 Cl + HCl
All Hydrogens are alike, replacement of any one gives the same product.
7
Show the monohalogenation products
for the following reaction.
Cl2
heat or UV light
Cl Cl
Cl + +
+ Cl
Cl
Five different H atoms produce five unique products.
9
How do halogenation reactions
occur?
• Three essential steps :
• 1. Radical Initiation (heat or UV light)
• 2. Radical Propagation (two steps)
• 3. Radical Termination (three ways)
10
Radical Initiation
• Halogen + heat or UV light radical
∆
Br2 or Br
hν
Br = Br
Initiation: Two radicals are formed by homolysis of a σ bond, starting the rxn.
11
Radical Propagation
homolytic clevage
H of blue bond
(a) Br + H + H Br
C
H sp H sp C H
2
H
3
H
homolytic clevage
H of pink bond
Br
(b) C H Br
H C H
+ Br Br +
H
H
Br
(b) H C H Br H C H
+
H H
H H
(c) H H C H C C
C H + H H
H H H H
o
CH3
∆H overall
BrCH3
Reaction coordinate
H H H CH3 CH3
H C H H C C H H3C C H H3C C H
H H H H CH3
methyl H's primary H's secondary H's tertiary H's
16
Bromination vs Chlorination
• Bromination is slower and more
selective than chlorination.
• Selectivity is in the order IIIo > IIo
> Io, the order of radical stability.
• The selectivity of bromination can be
explained by Hammond’s postulate,
because alkyl radical formation in
bromination is endothermic and in
chlorination is exothermic.
17
Halogenation in Synthesis
• Convert alkanes (usually symmetrical) into
alkyl halides, from which alcohols, ethers
and alkenes can be formed in one step.
Br2
Br
heat
HO- (SN2) OH
Br RO-
OR
-
t-BuO (E2)
18
Make trans-1,2-dibromocyclohexane
from cyclohexene
Classroom Activity
19
Stereochemistry of Halogenation
Starting Result
material
a. Achiral Product is achiral or a racemic mixture
(not chiral)
b.1.Chiral w/rxn Configuration at * (stereogenic center) is
away from * retained
* hν Br Cl
+ Br2 * + * + * + *
Cl Cl Br * Cl * Cl
(R)-2-chlorobutane reaction at * gives a Br Br
creation of a new * gives
racemic mixure of enantiomers
a pair of diastereomers
Halogenation at Io carbon away from * retains the R configuration.
21
Problems
• Work problems 15.1 through 15.18 in
Smith.
22