Monohalogenation

Examples:

Examples:

Examples:

Conclusions:
1.Reaction rates reflect the ease of hydrogen abstraction

Ease of hydrogen abstraction:

3o > 2o > 1o > CH4

Conclusions:
2. Reaction rates parallel the stabilities of the alkyl free
radicals formed in the chain propagation steps.

Stability of FREE RADICALS:

3o > 2o > 1o > .CH3
Ease of formation of FREE RADICALS:
3o > 2o > 1o > .CH3

Hyperconjugation - theoretical basis for stability trends

of free radicals

Conclusions:
3. Reaction rates are also affected by the type of halogen.
Cl more reactive; less selective; no isomer greatly
predominates
Br less reactive; more selective; predominant product
comes from the MOST STABLE free radical

Relative Reactivity:
F2 >> Cl2 > Br2 >> I2

***Remember***
The more stable the free radical, the more easily it is formed!

Relative proportion of products =

reactivity factor (r) x probability factor (p)
Where the reactivity factors are as follows:
p.4-3

Reactivity factors:
30
X = Cl
5.0
X = Br
1600

20
3.8
82

10
1.0
1.0

monohalogenation ==
%%monohalogenation

Relative rate x No. of equivalent H

X 100
(Relative rate x No. of equiv. H)

Y=?%
monohalogenation ==
%%monohalogenation

(1.0) (9)

(5.0) (1)

X=?%

Relative rate x No. of equivalent H

X 100
(Relative rate x No. of equiv. H)
%
9
9/14 x 100 = 64.29 % A
5
5/14 x 100 = 35.71 % B
14

4. Ring Opening Reactions of Small Cycloalkanes

*small rings (i.e., cyclopropane and cyclobutane) may
be prone to ring opening reactions due to angle strain.

Examples of such reactions are (p.4-3):