Organic Chemistry/Dienes/Kinds of dienes

Organic chemistry > Dienes > Kinds of dienes

<< Dienes | Conjugation >>

Dienes have two or more carbon-carbon double bonds which may be either isolated (R'-C=C-R-C=C-R'), cumulated (R-C=C=C-R), or conjugated (R-C=C-C=C-R). Each state represents a different stability due to electron delocalization, and the conjugated form is generally favored in organic molecules.

Isolated Dienes
Isolated dienes typically show no "special" stability. Their two &pi;-bonds interact independent of one another and they compete as intermolecular reaction sites depending on steric, kinetic, and thermodynamic factors. Often, these types of dienes can be treated merely as larger, more complex alkenes, because the two bonds are said to have "communication" (proximal electron delocalization due to location).

Isolated dienes are not considered to be especially useful in common synthesis reactions, although intermediates may often take the form of an isolated diene.bb

Cumulated Dienes
Cumulated dienes are typically less stable than other alkenes. The main reason for the instability is the fact that this sort of diene is a probable transition state for an alkyne's triple bond to move down the carbon chain towards the most stable position. As you may recall, rotation does not occur around any &pi;-bond, which means that cumulated double bonds can lead to a less stable, higher energy compound being formed.

Typically, cumulated dienes are discussed only in advanced courses in organic chemistry, and so they will not be discussed in detail here. Beginning organic chemistry students should merely remember that cumulated dienes are 1) high energy and 2) most likely found as transition states.

Conjugated Dienes
Conjugated dienes are dienes which have at least two double bonds separated by a single carbon-carbon bond, and for this reason conjugated dienes are observed to have a special stability due to the overlap of electron orbitals. The areas of concentration of negative charge (electron density) overlap across the three bonds (two double bonds and one single bond) forming what behaves essentially as a single, continuous &pi;-bond across three carbon atoms. This delocalization of electron density stabilizes the molecule, resulting in the arrangement of lowest energy.

Atoms other than carbon which are capable of multiple bonds may also participate in conjugation. The heteroatoms most often associated with conjugation in dienes and other molecules are nitrogen and oxygen, but theoretically the majority of atoms in the Periodic Table of Elements could participate in conjugation chemistry. Most often, in organic molecules, heteroatoms participating in conjugation will be nitrogen atoms within a ring structure or a double-bonded oxygen attached to form a ketone or aldehyde.

Conjugation of double bonds is the largest part of what makes aromaticity relevant in organic chemistry, and conjugated double bonds have many other significant impacts on other types of dienes as well.

<< Dienes | Conjugation >>