ALKADIENES

- compounds that contain two C=C bonds.

Nomenclature:
IUPAC system:
- use the suffix -diene to denote the
presence of two C=C bonds.
- The first C=C bond is always part of the
parent chain and takes precedence over
other substituents it is assigned the
lowest possible number.
Three Types Of Alkadienes:
Cumulenes or cumulated dienes
- dienes that have C=C bonds on adjacent carbons
(1,2-dienes).
- not an important class of compounds; generally
difficult to prepare.
- isomerize to more stable dienes.
Isolated dienes
- have C=C bonds that are separated by two or
more C-C bonds.
- The double bonds in these compounds react
independently of each other they undergo
reactions typical of alkenes but two moles of
the reagent are required to produce a
saturated product.
Conjugated dienes
- also known as 1,3-dienes
- are dienes in which the C=C are separated by
only 1 C-C bond.
- most commercially important conjugated
dienes: butadiene and 2-methyl-1,3-butadiene
or isoprene
 Consider butadiene:

Conjugated dienes are significantly more stable than

isolated and cumulated dienes because of two reasons:
(a) delocalization of p electrons to give some double
bond character to the C2-C3 bond
(b) the overlap of Csp2-Csp2 orbitals to form the C-C s
bonds. Thus, conjugated dienes are stabilized by
resonance.
REACTIONS OF ALKADIENES
1. Electrophilic addition
- Isolated dienes react like ordinary alkenes, i.e.
One mole of reagent is consumed per C=C bond
no change in the position of the remaining C=C
bond.

example:
 - Conjugated Dienes: the reaction of one mole of
reagent per mole of diene always produces two
products.
example:
2. Free Radical Addition of Conjugated Dienes
example:

reaction mechanism:
(3), (4), (3), (4) ...... then termination
3. Polymerization essentially 1,4-addition
4. Ozonolysis
- All C=C bonds are attacked by ozone at
the same time ozonolysis is a useful tool for
structure elucidation. From the fragments
obtained, the positions of the C=C bonds in the
original diene molecule can be inferred.
- example:
Analysis of Alkadienes:

- similar to that of alkenes; the useful test

tube reactions are the bromine test and the Baeyer
Reaction.