Chapter 3
Dienes
3.1 Introduction
Dienes are simply alkenes that contain two carbon-carbon
double bonds. They therefore have essentially the same properties
as the alkenes we have already studied. For certain of the dienes,
these alkene properties are modified in important ways; we shall
focus our attention on these modifications.
Dienes are named by the IUPAC system in the same way as
alkenes, except that the ending –diene is used, with two numbers
to indicate the position of the two double bonds. This system is
easily extended to compounds containing any number of double
bonds.
CH2=CH-CH=CH2 CH2=CH-CH2-CH=CH2
1,3-Butadiene 1,4-Pentadiene
CH2=CH-CH=CH-CH=CH2
1,3,5-Hexatriene
Dienes are divided into two important classes according to
the arrangement of the double bonds. Double bonds that alternate
with single bonds are said to be conjugated; double bonds that are
separated by more than one single bond are said to be isolated.
1
A third class of dienes, of increasing interest to organic
chemists, contains cumulated double bonds; these compounds are
known as allenes;
3.2 Preparation and Properties of Dienes
Dienes are usually prepared by adaptations of the methods
used to make simple alkenes. For example, the most important
diene, 1,3-butadiene (used to make synthetic rubber), has been
made by cracking process, or by dehydration of an alcohol
containing two –OH groups:
2
The chemical properties of a diene depend upon the
arrangement of its double bonds. Isolated double bonds exert little
effect on each other, and hence each reacts as though it were the
only double bond in the molecule. Except for the consumption of
larger amounts of reagents, then, the chemical properties of the
non-conjugated dienes are identical with those of the simple
alkenes.
Conjugated dienes differ from simple alkenes in three ways:
(a) they are more stable, (b) they undergo 1,4-addition, and (c)
toward free radical addition, they are more reactive.
3.3-(Reaction) Electrophilic Addition to Conjugated dienes, 1,4-
Addition
When 1,4-Pentadiene is treated with bromine under conditions
that favor formation of the dihalide ,there is obtained the expected
product, 4,5-dibromo-1-pentene. Addition of more bromine yield
the 1,2,4,5-tetrabromopentane.
3
This is typical of the behavior of dienes containing isolated
double bonds: the double bonds react independently, as though
they were in different molecules.
When 1,3-butadiene is treated with bromine under
similar conditions, there is obtained not only the expected 3,4-
dibromo-1- butene, but also 1,4-dibromo-2-butene. Treatment
with HCl yields not only 3-chloro-1-butene, but also 1-chloro-
2-butene. Hydrogenation yields not only 1-butene but also 2-
butene.
Study of many conjugated dienes and many reagents shows
that such behavior is typical: in addition to conjugated dienes,
a reagent may attach itself not only to a pair of adjacent
carbons (1,2-addition), but also to the carbons at the two
ends of the
4
conjugated system (1,4-addition). Very often the 1,4-
addition product is the major one.
5
3.4 Analysis of Dienes:
Dienes respond to characterization tests in the same way as
alkenes, they decolorize bromine in carbon tetrachloride without
evolution of hydrogen bromide, and they decolorize cold, neutral,
dilute permanganate; they are not oxidized by chromic anhydride.
They are, however, more unsaturated than alkenes.
Ozonolysis of dienes yields aldehydes and ketones, including
double-ended ones containing two C=O groups per molecule. For
example: