Cycloalkane

Ball-and-stick model of cyclobutane

Cycloalkanes (also called naphthenes - not to be confused with naphthalene) are types of alkanes that have one or more rings of carbon atoms in the chemical structure of their molecules. Alkanes are types of organic hydrocarbon compounds that have only single chemical bonds in their chemical structure. Cycloalkanes consist of only carbon (C) and hydrogen (H) atoms and are saturated because there are no multiple C-C bonds to hydrogenate (add more hydrogen to). A general chemical formula for cycloalkanes would be C_nH_2(n+1-g) where n = number of C atoms and g = number of rings in the molecule. Cycloalkanes with a single ring are named analogously to their normal alkane counterpart of the same carbon count: cyclopropane, cyclobutane, cyclopentane, cyclohexane, etc. The larger cycloalkanes, with greater than 20 carbon atoms are typically called cycloparaffins.

Cycloalkanes are classified into small, common, medium, and large cycloalkanes, where cyclopropane and cyclobutane are the small ones, cyclopentane, cyclohexane, cycloheptane are the common ones, cyclooctane through cyclotridecane are the medium ones, and the rest are the larger ones.

Nomenclature

See also: IUPAC nomenclature

Bicyclo[2.2.1]heptane (also known as norbornane)

The naming of polycyclic alkanes such as bicyclic alkanes and spiro alkanes is more complex, with the base name indicating the number of carbons in the ring system, a prefix indicating the number of rings (e.g., "bicyclo"), and a numeric prefix before that indicating the number of carbons in each part of each ring, exclusive of vertices. For instance, a bicyclooctane that consists of a six-member ring and a four-member ring, which share two adjacent carbon atoms that form a shared edge, is [4.2.0]-bicyclooctane. That part of the six-member ring, exclusive of the shared edge has 4 carbons. That part of the four-member ring, exclusive of the shared edge, has 2 carbons. The edge itself, exclusive of the two vertices that define it, has 0 carbons.

There is more than one convention (method or nomenclature) for the naming of compounds, which can be confusing for those who are just learning, and inconvenient for those who are well rehearsed in the older ways. For beginners it is best to learn IUPAC nomenclature from a source that is up to date, because this system is constantly being revised. In the above example [4.2.0]-bicyclooctane would be written bicyclo[4.2.0]octane to fit the conventions for IUPAC naming. It has then got room for an additional numerical prefix if there is the need to include details of other attachments to the molecule such as chlorine or a methyl group. Another convention for the naming of compounds is the common name, which is a shorter name and it gives less information about the compound. An example of a common name is terpineol, the name of which can tell us only that it is an alcohol (because the suffix 'ol' is in the name) and it should then have a hydroxide (OH) group attached to it.

An example of the IUPAC method is given in the image to the right. In this example the base name is listed first, which indicates the total number of carbons in both rings including the carbons making up the shared edge (e.g., heptane, which means hept or 7 carbons, and ane, which indicates only single bonding between carbons). Then in front of the base name is the numerical prefix, which lists the number of carbons in each ring, excluding the carbons that are shared by each ring, plus the number of carbons on the bridge between the rings. In this case there are two rings with two carbons each and a single bridge with one carbon, excluding the carbons shared by it and the other two rings. There is a total of three numbers and they are listed in descending order separated by dots, thus: [2.2.1].

Before the numerical prefix is another prefix indicating the number of rings (e.g., "bicyclo"). Thus, the name is bicyclo[2.2.1]heptane.

The group of cycloalkanes are also known as naphthenes, as they are compounds of petroleum or naphtha.

Properties

Cycloalkanes are similar to alkanes in their general physical properties, but they have higher boiling points, melting points, and densities than alkanes. This is due to stronger London forces because the ring shape allows for a larger area of contact. Containing only C-C and C-H bonds, unreactivity of cycloalkanes with little or no ring strain (see below) are comparable to non-cyclic alkanes.

Ring strain

The carbon atoms in cycloalkanes are sp³ hybridized and are therefore a deviation from the ideal tetrahedral bond angles of 109°28'. This causes an increase in potential energy and an overall destabilizing effect. Eclipsing of hydrogen atoms is an important destabilizing effect, as well. The strain energy of a cycloalkane is the theoretical increase in energy caused by the compound's geometry, and is calculated by comparing the experimental standard enthalpy change of combustion of the cycloalkane with the value calculated using average bond energies.

Ring strain is highest for cyclopropane, in which the carbon atoms form a triangle and therefore have 60 degree C-C-C bond angles. There are also three pairs of eclipsed hydrogens. The ring strain is calculated to be around 120 kJ/mol.

Cyclobutane has the carbon atoms in a puckered square with approximately 90-degree bond angles; "puckering" reduces the eclipsing interactions between hydrogen atoms. Its ring strain is therefore slightly less, at around 110 kJ/mol.

For a theoretical planar cyclopentane the C-C-C bond angles would be 108 degrees, very close to the measure of the tetrahedral angle. Actual cyclopentane molecules are puckered, but this changes only the bond angles slightly so that angle strain is relatively small. The eclipsing interactions are also reduced, leaving a ring strain of about 25 kJ/mol.

In cyclohexane the ring strain and eclipsing interactions are negligible because the puckering of the ring allows ideal tetrahedral bond angles to be achieved. As well, in the most stable chair form of cyclohexane, axial hydrogens on adjacent carbon atoms are pointed in opposite directions, virtually eliminating eclipsing strain.

After cyclohexane, the molecules are unable to take a structure with no ring strain, resulting in an increase in strain energy, which peaks at 9 carbons (around 50 kJ/mol). After that, strain energy slowly decreases until 12 carbon atoms, where it drops significantly; at 14, another significant drop occurs and the strain is on a level comparable with 10 kJ/mol. After 14 carbon atoms, sources disagree on what happens to ring strain, some indicating that it increases steadily, others saying that it disappears entirely. However, bond angle strain and eclipsing strain are an issue only for smaller rings.

Reactions

The simple and the bigger cycloalkanes are very stable, like alkanes, and their reactions, for example, radical chain reactions, are like alkanes.

The small cycloalkanes - in particular, cyclopropane - have a lower stability due to Baeyer strain and ring strain. They react similarly to alkenes, though they do not react in electrophilic addition, but in nucleophilic aliphatic substitution. These reactions are ring-opening reactions or ring-cleavage reactions of alkyl cycloalkanes. Cycloalkanes can be formed in a Diels-Alder reaction followed by a catalytic hydrogenation.

See also

• Cycloalkene

References

• IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version:  (1995) "Cycloalkanes".
• Organic Chemistry IUPAC Nomenclature. Rule A-23. Hydrogenated Compounds from Fused Polycyclic Hydrocarbons http://www.acdlabs.com/iupac/nomenclature/79/r79_73.htm
• Organic Chemistry IUPAC Nomenclature.Rule A-31. Bridged Hydrocarbons: Bicyclic Systems. http://www.acdlabs.com/iupac/nomenclature/79/r79_163.htm
• Organic Chemistry IUPAC Nomenclature.Rules A-41, A-42: Spiro Hydrocarbons http://www.acdlabs.com/iupac/nomenclature/79/r79_196.htm
• Organic Chemistry IUPAC Nomenclature.Rules A-51, A-52, A-53, A-54:Hydrocarbon Ring Assemblies http://www.acdlabs.com/iupac/nomenclature/79/r79_158.htm

External links

• "Cycloalkanes" at the online Encyclopædia Britannica
• "Cycloalkanes" by the Chemistry staff at Westminster College