Chemistry

Diene
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This article is about organic chemicals. For the surname "Diene" used
in West Africa, see Serer people.

1,3-butadiene
In organic chemistry a diene ( /da.in/ DY -een) or diolefin (/da
olfn/ dy-OH -l-fin) is a hydrocarbon that contains two carbon
double bonds. Conjugated dienes are functional groups, with a general
formula of CnH2n-2. Dienes and alkynes are functional isomers. Dienes
occur occasionally in nature but are widely used in the polymer
industry.

Contents
[hide]

1 Classes

2 Synthesis of dienes

3 Reactivity and uses

o

3.1 Polymerization

3.2 Cycloadditions

3.3 Other addition reactions

3.4 Metathesis reactions

3.5 Acidity

3.6 As ligands

4 See also

5 External links

6 References

[edit] Classes
Dienes can be divided into three classes, depending on the relative
location of the double bonds:
1. Cumulated dienes have the double bonds sharing a common atom
as in a group of compounds called allenes.
2. Conjugated dienes have conjugated double bonds separated by
one single bond.
3. Unconjugated dienes have the double bonds separated by two or
more single bonds. They are usually less stable than isomeric
conjugated dienes. This can also be known as an isolated diene.
Compounds that contain more than two double bonds are called
polyenes. Polyenes and dienes, share many of their properties.

Some dienes: A: 1,2-Propadiene, also known as allene, is the simplest

cumulated diene. B: Isoprene, also known as 2-methyl-1,3-butadiene,
the precursor to natural rubber. C: 1,3-Butadiene, a precursor to
synthetic polymers. D: 1,5-Cyclooctadiene, an unconjugated diene
(notice that each double bond is two carbons away from the other). E:
Norbornadiene, a strained bicyclic and unconjugated diene. F:
Dicyclopentadiene. G: Linoleic acid, a fatty acid that is required in
the human diet.

[edit] Synthesis of dienes

On an industrial scale, butadiene is prepared by thermal cracking of
butanes. In a similarly non-selective process, dicyclopentadiene is
obtained from coal tars.

In the laboratory, more directed and more delicate processes are

employed such as dehydrohalogenations and condensations. Myriad
methods have been developed, such as the Whiting reaction. Families
of nonconjugated dienes are derived from the oligomerization and
dimerization of conjugated dienes. For example, 1,5-cyclooctadiene
and vinylcyclohexene are produced by dimerization of 1,3-butadiene.
Diene-containing fatty acids are biosynthesized from acetyl CoA.

[edit] Reactivity and uses

[edit] Polymerization
The most heavily practiced reaction of alkenes, dienes included, is
polymerization. Butadiene is a precursor to rubber used in tires, and
isoprene is the precursor to natural rubber. Chloroprene is a related
but synthetic monomer.

[edit] Cycloadditions
An important reaction for conjugated dienes is the Diels-Alder
reaction. Many specialized dienes have been developed to exploit this
reactivity for the synthesis of natural products, e.g. Danishefskys
diene.

[edit] Other addition reactions

Conjugated dienes add reagents such as bromine and hydrogen by both
1,2-addition and 1,4-addition pathways. Addition of polar reagents
can generate complex architectures:[1]

[edit] Metathesis reactions

Nonconjugated dienes are substrates for ring-closing metathesis
reactions. These reactions require metal catalyst:

[edit] Acidity
Conjugated and 1,4-dienes generally are somewhat acidic since
deprotonation of both classes gives pentadienyl anions. The
acidifying effect of the diene is very pronounced in cyclopentadiene.

[edit] As ligands
Dienes are widely used chelating ligands in organometallic chemistry.
In some cases they serve as placeholder ligands, being removed during
a catalytic cycle. For example, the cyclooctadiene ("cod") ligands in
bis(cyclooctadiene)nickel(0) are labile. In some cases, dienes are
spectator ligands, remaining coordinated throughout a catalytic cycle
and influencing the product distributions. Chiral dienes have also
been described.[2]