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Reactions of Alkanes:
Radicals
Hydrocarbons
NATURAL GAS 90–95% methane (C1–C4)
5–10% ethane
small amounts of propane, butane,
and 2-methylpropane
1 2 3 4 5 6 7
Octane number: CH3CH2CH2CH2CH2CH2CH3
n-heptan :0
2,2,4-trimethylpentane: 100 CH3 CH3
CH3CCH
2 2CHCH 3
1 3 4 5
CH3
Reactivity
Strong C-H s bonds.
Unpolarized bonds due to equal
electronegativity of H and C.
Almost no charge.
h
CH3CH3 + Br2 CH3CH2Br + HBr
ethane
or ethylbromide
Mechanism of Halogenation
Halogenation starts with a homolytic bond
cleavage of the halogen-halogen bond
h
Br Br 2 Br
Br + H CH3 H Br + CH3
CH3 + Br Br Br CH3 + Br
Mechanism of Halogenation
Regeneration of the bromine radical in the
second propagation step allows a radical
chain reaction.
Br Br Br Br
Br CH3 Br CH3
H
Br CH2 + Br Br CH2 + HBr
Br
Br CH2 + Br Br Br CH2 + Br
Product Distribution
We replace only hydrogens.
When different carbons (primary, secondary,
tertiary) are present we can substitute a different
number of hydrogens.
Leads to different products. 2 2'
Cl
1'
1 3
Cl
2 2'
2 2' 1'
1
1' 3
1 3 2 2'
3 1'
1
Symmetry plane Cl
Product Distribution
Statistically we have a 6:4:2 ratio of various
positions in pentane, since 1,1’, and 2,2’
positions are identical.
2 2'
1'
1 3
CH3
Example 2
Percentage of Bromination for the following compound
CH3
b CH3
a
d
c
b CH3
a
d
c
b CH3
a
d
c
b CH3
a
d
c
Br
H
The carbon radical is sp2-hybridized.
The new bond to Br can be formed on either side.
H3CH2C
Br
Br Br
H CH3
+
H CH3 Br
H3CH2C H
Stereochemistry
CH3 H3 C Br Br CH3
Br2
+
Br Br
Br
CH3 CH3 CH3
Radical Inhibitors
HO
O O
HO
HO OH
Vitamin E
CH3 Ascorbic acid
HO
H3C O CH3
CH3
CH3 CH3 CH3 H3C