Chapter 9

Reactions of Alkanes:
Radicals
 Hydrocarbons
NATURAL GAS 90–95% methane (C1–C4)
5–10% ethane
small amounts of propane, butane,
and 2-methylpropane

PETROLEUM Thick viscous mixture of hundreds of

hydrocarbons (mostly C5–C20).
Formed from the decomposition of
ancient marine plants and animals.

COAL Mixture of carbon and solid, high

molecular weight hydrocarbons (>C20).

COAL TAR Many aromatic and heteroaromatic

compounds.
Hydrocarbons
 Hydrocarbons

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.

butane chloropropane 1-butene butanal

 Reactivity

Neither nucleophiles nor electrophiles have

a good point to attack.
Old name paraffins from latin
“parum affinis” = little affinity.
Very stable, unreactive.
Chlorination and Bromination
h
CH4 + Cl2 CH3Cl + HCl
methane methylchloride

Halogenations using chlorine gas or bromine using

high temperature or UV radiation lead to a reaction

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

This step is also called the initiation step

single barb means only one
electron moved
 Mechanism of Halogenation
The highly reactive radical reacts with the
alkane in a propagation step

Br + H CH3 H Br + CH3

This generates a new radical, a carbon radical,

that continues to react with another bromine
molecule

CH3 + Br Br Br CH3 + Br
 Mechanism of Halogenation
Regeneration of the bromine radical in the
second propagation step allows a radical
chain reaction.

New radicals are generated until all halogen

or all alkane is consumed.
 Mechanism of Halogenation
Reaction comes to an end by the
combination of two radical species
(terminations steps).

Br Br Br Br

Br CH3 Br CH3

H3C CH3 H3C CH3

 Halogenation
Overall, hydrogens are replaced by halogens

Radical substitution reaction

Monosubstitution requires a large excess of

alkane so that probability to find another
alkane is much larger than an already
substituted haloalkane.
 Halogenation
Reaction of a halogen radical with a
haloalkane leads to dihalogenated products.

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

Experimentally, however, we obtain a larger amount

of 2-chloropentane (53%, calc.: 33%) and 3-
chloropentane (26.5%, calc.: 17%).
1-Chloropentane, on the other hand, is produced in
much lower amount, 20.5%, than the expected 50%.
 Product Distribution
Reactivity of carbons is determined by the
number of hydrogens, or better to say the
number of stabilizing substituents.
Similar to cationic centers, we find:
R H H H
> > >
R R R R R H H H

 Tertiary radicals are more stable than

secondary radicals, which in turn are more
stable than primary radicals.
 Halogenation Reactivity
Product ratios are different for Bromination
and Chlorination
Apparently bromine is more selective
Bromine is also overall less reactive
For chlorination we find:
• 1:3.8:5 primary:secondary:tertiary
For bromination we find:
• 1:82:1600 primary:secondary:tertiary
 Example
Determine the percentages for monochlorination products
of the following compound:
CH3
H3C
CH CH3
CH
CH2
H3C
 Example
Determine the percentages for monochlorination products
of the following compound:
CH3
H3C
CH CH3
CH
CH2
H3C

First, determine equal positions in the molecule

 Example
Determine the percentages for monochlorination products
of the following compound:
a b CH3
H3C c
CH CH3
CH e
f CH2
H3Ca d

First, determine equal positions in the molecule

 Example
Determine the percentages for monochlorination products
of the following compound:
a b CH3
H3C c
CH CH3
CH e
f CH2
H3Ca d

First, determine equal positions in the molecule.

Second, multiply reactivity with statistical factor
(number of hydrogens).
 Example
Determine the percentages for monochlorination products
of the following compound:
a b CH3
H3C c
CH CH3
CH e
f CH2
H3Ca d

First, determine equal positions in the molecule.

Second, multiply reactivity with statistical factor.
A: 6*1=6 D: 2*3.8=7.6
B: 3*1=3 E: 1*5.0=5.0
C: 3*1= 3 F: 1*5.0=5.0
 Example
Determine the percentages for monochlorination products
of the following compound:
a b CH3
H3C c
CH CH3
CH e
f CH2
H3Ca d

First, determine equal positions in the molecule.

Second, multiply reactivity with statistical factor.
A: 6*1=6 D: 2*3.8=7.6
B: 3*1=3 E: 1*5.0=5.0
C: 3*1= 3 F: 1*5.0=5.0
Third, add all numbers up and determine percentages.
 Example
Determine the percentages for monochlorination products
of the following compound:
a b CH3
H3C c
CH CH3
CH e
f CH2
H3Ca d

First, determine equal positions in the molecule.

Second, multiply reactivity with statistical factor.
A: 6*1=6 D: 2*3.8=7.6
B: 3*1=3 E: 1*5.0=5.0
C: 3*1= 3 F: 1*5.0=5.0
Third, add all numbers up and determine percentages.
Total: 29.6; A: 6/29.6=20.3% B,C: 3/29.6=10.1% each
D: 7.6/29.6=25.7% E,F: 5/29.6=16.9% each
 Example 2
Percentage of bromination for the following compound

CH3
 Example 2
Percentage of Bromination for the following compound

CH3

First, determine equal positions in the molecule

 Example 2
Percentage of Bromination for the following compound

b CH3
a
d
c

First, determine equal positions in the molecule

Second, multiply reactivity with statistical factor.
 Example 2
Percentage of Bromination for the following compound

b CH3
a
d
c

First, determine equal positions in the molecule

Second, multiply reactivity with statistical factor.
A: 3*1 =3 B: 1*1600 = 1600
C: 4*82 = 328 D: 4*82 = 328
 Example 2
Percentage of Bromination for the following compound

b CH3
a
d
c

First, determine equal positions in the molecule

Second, multiply reactivity with statistical factor.
A: 3*1 =3 B: 1*1600 = 1600
C: 4*82 = 328 D: 4*82 = 328
Third, add all numbers up and determine percentages.
 Example 2
Percentage of Bromination for the following compound

b CH3
a
d
c

First, determine equal positions in the molecule

Second, multiply reactivity with statistical factor.
A: 3*1 =3 B: 1*1600 = 1600
C: 4*82 = 328 D: 4*82 = 328
Third, add all numbers up and determine percentages.
Total = 2259; A: 3/2259= 0.1% B: 70.8%
C, D: 328/2259 = 14.5%
 Stereochemistry
Br2 , UV-light
Br

Br

Monobromination of butane gives two products:

1-bromobutane and 2-bromobutane.
2-bromobutane we obtain as a racemic mixture.
 Stereochemistry
In the first step we generate a carbon radical.

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

In case the reaction takes place at a stereocenter,

stereochemical information is lost and a diastereomeric
mixture will be obtained.

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