Cycloalkane
Inorganic chemistry,thecycloalkanes(also callednaphthenes,but distinct fromnaphthalene) are themonocyclicsaturatedhydrocarbons.[1]In other words, a cycloalkane consists only ofhydrogenandcarbonatoms arranged in a structure containing a single ring (possibly withside chains), and all of the carbon-carbon bonds aresingle.The larger cycloalkanes, with more than 20 carbon atoms are typically calledcycloparaffins.All cycloalkanes are isomers ofalkenes.[2]
The cycloalkanes without side chains (also known asmonocycloalkanes) are classified as small (cyclopropaneandcyclobutane), common (cyclopentane,cyclohexane,andcycloheptane), medium (cyclooctanethroughcyclotridecane), and large (all the rest).
Besides this standard definition bythe International Union of Pure and Applied Chemistry(IUPAC), in some authors' usage the termcycloalkaneincludes also those saturated hydrocarbons that are polycyclic.[2] In any case, the general form of thechemical formulafor cycloalkanes is CnH2(n+1−r),wherenis the number of carbon atoms andris the number of rings. The simpler form for cycloalkanes with only one ring is CnH2n.
Nomenclature
[edit]
Unsubstituted cycloalkanes that contain a single ring in their molecular structure are typically named by adding the prefix "cyclo" to the name of the corresponding linearalkanewith the same number ofcarbonatoms in its chain as the cycloalkane has in its ring. For example, the name ofcyclopropane(C3H6) containing a three-membered ring is derived frompropane(C3H8) - analkanehaving threecarbonatoms in the main chain.
The naming of polycyclic alkanes such asbicyclicalkanes andspiroalkanes is more complex, with the base name indicating the number of carbons in the ring system, a prefix indicating the number of rings ( "bicyclo- "or"spiro- "), and a numeric prefix before that indicating the number of carbons in each part of each ring, exclusive of junctions. For instance, a bicyclooctane that consists of a six-membered ring and a four-membered ring, which share two adjacent carbon atoms that form a shared edge, is [4.2.0]-bicyclooctane. That part of the six-membered ring, exclusive of the shared edge has 4 carbons. That part of the four-membered 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 froma source that is up to date,[3]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 then has 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 thecommon name,which is a shorter name and it gives less information about the compound. An example of a common name isterpineol,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 ahydroxyl group(–OH) attached to it.
The IUPAC naming system for organic compounds can be demonstrated using the example provided in the adjacent image. The base name of the compound, indicating the total number of carbons in both rings (including the shared edge), is listed first. For instance, "heptane" denotes "hepta-", which refers to the seven carbons, and "-ane", indicating single bonding between carbons. Next, the numerical prefix is added in front of the base name, representing the number of carbons in each ring (excluding the shared carbons) and the number of carbons present in the bridge between the rings. In this example, there are two rings with two carbons each and a single bridge with one carbon, excluding the carbons shared by both the rings. The prefix consists of three numbers that are arranged in descending order, separated by dots: [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.
Cycloalkanes as a group are also known asnaphthenes,a term mainly used in thepetroleumindustry.[4]
Properties
[edit]Table of cycloalkanes
[edit]| Alkane | Formula | Boiling point [°C] | Melting point [°C] | Liquid density [g·cm−3] (at 20 °C) |
|---|---|---|---|---|
| Cyclopropane | C3H6 | −33 | −128 | |
| Cyclobutane | C4H8 | 12.5 | −91 | 0.720 |
| Cyclopentane | C5H10 | 49.2 | −93.9 | 0.751 |
| Cyclohexane | C6H12 | 80.7 | 6.5 | 0.778 |
| Cycloheptane | C7H14 | 118.4 | −12 | 0.811 |
| Cyclooctane | C8H16 | 149 | 14.6 | 0.834 |
| Cyclononane | C9H18 | 169 | 10-11 | 0.8534 |
| Cyclodecane | C10H20 | 201 | 9-10 | 0.871 |
Cycloalkanes are similar to alkanes in their general physical properties, but they have higherboiling points,melting points,anddensitiesthan alkanes. This is due to strongerLondon forcesbecause the ring shape allows for a larger area of contact. Containing only C–C and C–H bonds, unreactivity of cycloalkanes with little or noring strain(see below) are comparable to non-cyclic alkanes.
Conformations and ring strain
[edit]In cycloalkanes, the carbon atoms aresp3hybridized,which would imply an idealtetrahedral bond angleof 109° 28′ whenever possible. Owing to evident geometrical reasons, rings with 3, 4, and (to a small extent) also 5 atoms can only afford narrower angles; the consequent deviation from the ideal tetrahedral bond angles causes an increase in potential energy and an overall destabilizing effect. Eclipsing of hydrogen atoms is an important destabilizing effect, as well. Thestrain energyof a cycloalkane is the increase in energy caused by the compound's geometry, and is calculated by comparing the experimentalstandard enthalpy change of combustionof the cycloalkane with the value calculated using average bond energies. Molecular mechanics calculations are well suited to identify the many conformations occurring particularly in medium rings.[5]: 16–23
Ring strain is highest forcyclopropane,in which the carbon atoms form a triangle and therefore have 60 °C–C–C bond angles. There are also three pairs of eclipsed hydrogens. The ring strain is calculated to be around 120 kJ mol−1.
Cyclobutanehas the carbon atoms in a puckered square with approximately 90° bond angles; "puckering" reduces the eclipsing interactions between hydrogen atoms. Its ring strain is therefore slightly less, at around 110 kJ mol−1.
For a theoretical planarcyclopentanethe C–C–C bond angles would be 108°, 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−1.[6]
Incyclohexanethe ring strain and eclipsing interactions are negligible because the puckering of the ring allows ideal tetrahedral bond angles to be achieved. In the most stablechair formof cyclohexane, axial hydrogens on adjacent carbon atoms are pointed in opposite directions, virtually eliminating eclipsing strain. In medium-sized rings (7 to 13 carbon atoms) conformations in which the angle strain is minimised createtransannular strainorPitzer strain.At these ring sizes, one or more of these sources of strain must be present, resulting in an increase in strain energy, which peaks at 9 carbons (around 50 kJ mol−1). 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−1.At larger ring sizes there is little or no strain since there are many accessible conformations corresponding to a diamond lattice.[5]
Ring strain can be considerably higher inbicyclic systems.For example,bicyclobutane,C4H6,is noted for being one of the most strained compounds that is isolatable on a large scale; its strain energy is estimated at 267 kJ mol−1.[7][8]
Reactions
[edit]Cycloalkanes, referred to as naphthenes, are a major substrate for the catalytic reforming process.[9]In the presence of a catalyst and at temperatures of about 495 to 525 °C, naphthenes undergodehydrogenationto give aromatic derivatives:
The process provides a way to produce high octane gasoline.
In another major industrial process, cyclohexanol is produced by theoxidationofcyclohexanein air, typically using cobaltcatalysts:[10]
- 2 C6H12+ O2→ 2 C6H11OH
This process coformscyclohexanone,and this mixture ( "KA oil" for ketone-alcohol oil) is the main feedstock for the production ofadipic acid,used to makenylon.
The small cycloalkanes – in particular, cyclopropane – have a lower stability due toBaeyer strainandring strain.They react similarly toalkenes,though they do not react inelectrophilic addition,but innucleophilic aliphatic substitution.These reactions are ring-opening reactions or ring-cleavage reactions ofalkyl cycloalkanes.
Preparation
[edit]Many simple cycloalkanes are obtained from petroleum. They can be produced byhydrogenationof unsaturated, even aromatic precursors.
Numerous methods exist for preparing cycloalkanes by ring-closing reactions of difunctional precursors. For example, diesters are cyclized in theDieckmann condensation:
The Dieckmann condensation
Theacyloin condensationcan be deployed similarly.
For larger rings (macrocyclizations) more elaborate methods are required since intramolecular ring closure competes with intermolecular reactions.
TheDiels-Alder reaction,a [4+2] cycloaddition, provides a route to cyclohexenes:
The corresponding [2+2] cycloaddition reactions, which usually require photochemical activation, result in cyclobutanes.
See also
[edit]References
[edit]- ^IUPAC,Compendium of Chemical Terminology,2nd ed. (the "Gold Book" ) (1997). Online corrected version: (2014) "Cycloalkane".doi:10.1351/goldbook.C01497
- ^ab"Alkanes & Cycloalkanes".www2.chemistry.msu.edu.Retrieved2022-02-20.
- ^"Blue Book".iupac.qmul.ac.uk.Retrieved2023-04-01.
- ^Fahim, MA, et al. (2010).Fundamentals of Petroleum Refining.p. 14.doi:10.1016/C2009-0-16348-1.ISBN978-0-444-52785-1.
- ^abDragojlovic, Veljko (2015)."Conformational analysis of cycloalkanes"(PDF).Chemtexts.1(3).doi:10.1007/s40828-015-0014-0.S2CID94348487.
- ^McMurry, John (2000).Organic chemistry(5th ed.). Pacific Grove, CA: Brooks/Cole. p. 126.ISBN0534373674.
- ^Wiberg, K. B.(1968)."Small Ring Bicyclo[n.m.0]alkanes ".In Hart, H.; Karabatsos, G. J. (eds.).Advances in Alicyclic Chemistry.Vol. 2.Academic Press.pp. 185–254.ISBN9781483224213.
- ^Wiberg, K. B.;Lampman, G. M.; Ciula, R. P.; Connor, D. S.; Schertler, P.; Lavanish, J. (1965). "Bicyclo[1.1.0]butane".Tetrahedron.21(10): 2749–2769.doi:10.1016/S0040-4020(01)98361-9.
- ^Irion, Walther W.; Neuwirth, Otto S. (2000). "Oil Refining".Ullmann's Encyclopedia of Industrial Chemistry.doi:10.1002/14356007.a18_051.ISBN3-527-30673-0.
- ^Michael Tuttle Musser "Cyclohexanol and Cyclohexanone" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005.
- IUPAC,Compendium of Chemical Terminology,2nd ed. (the "Gold Book" ) (1997). Online corrected version: (1995) "Cycloalkanes".doi:10.1351/goldbook.C01497
- Organic Chemistry IUPAC Nomenclature. Rule A-23. Hydrogenated Compounds from Fused Polycyclic Hydrocarbonshttp:// acdlabs /iupac/nomenclature/79/r79_73.htm
- Organic Chemistry IUPAC Nomenclature.Rule A-31. Bridged Hydrocarbons: Bicyclic Systems.http:// acdlabs /iupac/nomenclature/79/r79_163.htm
- Organic Chemistry IUPAC Nomenclature.Rules A-41, A-42: Spiro Hydrocarbonshttp:// acdlabs /iupac/nomenclature/79/r79_196.htm
- Organic Chemistry IUPAC Nomenclature.Rules A-51, A-52, A-53, A-54:Hydrocarbon Ring Assemblieshttp:// acdlabs /iupac/nomenclature/79/r79_158.htm
External links
[edit]- "Cycloalkanes"at the onlineEncyclopædia Britannica
