In organic chemistry, a diene ( ); also diolefin, ) or alkadiene) is a covalent compound that contains two , usually among carbon atoms.
Classes
Dienes can be divided into three classes, depending on the relative location of the double bonds:
-
Cumulated dienes have the double bonds sharing a common atom. The result is more specifically called an allene.
-
Conjugated dienes have conjugated double bonds separated by one single bond. Conjugated dienes are more stable than other dienes because of resonance.
-
Unconjugated dienes have the double bonds separated by two or more single bonds. They are usually less stable than conjugated dienes. This can also be known as an isolated diene.
According to the Gold Book definition, a "diene" could include one or more which replace unsaturated carbon atoms, giving structures that could more specifically be called heterodienes.
Compounds that contain more than two double bonds are called . Polyenes and dienes share many properties.
Synthesis of dienes
On an industrial scale, butadiene is prepared by
thermal cracking of
. In a similarly non-selective process, dicyclopentadiene is obtained from
.
In the laboratory, more directed and more delicate processes are employed such as dehydrohalogenations and condensations. Myriad organic reaction 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 4-vinylcyclohexene are produced by dimerization of 1,3-butadiene.
Diene-containing are biosynthesis from acetyl CoA.
α,ω-Dienes have the formula (CH2)n(CH=CH2)2. They are prepared industrially by ethenolysis of cyclic dienes. For example, 1,5-hexadiene and 1,9-decadiene, useful crosslinking agents and synthetic intermediates, are produced from 1,5-cyclooctadiene and cyclooctene, respectively. The catalyst is derived from Re2O7 on alumina.
Reactivity and uses
Polymerization
The most heavily practiced reaction of alkenes, dienes included, is
polymerization. 1,3-Butadiene is a precursor to
Synthetic rubber used in tires, and
isoprene is the precursor to
natural rubber.
Chloroprene is related but it is a synthetic monomer.
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
(e.g., Danishefsky's diene).
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:
- :[Image:CODSCl2.png|450px|2,6-Dichloro-9-thiabicyclo[3.3.1nonane, synthesis and reactions]]
Metathesis reactions
Nonconjugated dienes are substrates for ring-closing metathesis reactions. These reactions require a metal
catalyst:
- :
Acidity
The position adjacent to a double bond is
because the resulting
allyl anion is stabilized by resonance. This effect becomes more pronounced as more alkenes are involved to create greater stability. For example, deprotonation at position 3 of a 1,4-diene or position 5 of a 1,3-diene give a
pentadienyl anion. An even greater effect is seen if the anion is aromatic, for example, deprotonation of
cyclopentadiene to give the cyclopentadienyl anion.
As ligands
Dienes are widely used chelating
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.
Chirality dienes have also been described.
Other diene complexes include (butadiene)iron tricarbonyl, cyclobutadieneiron tricarbonyl, and cyclooctadiene rhodium chloride dimer.
