Cyclohexane

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Cyclohexane
Cyclohexane 3D structure of a cyclohexane molecule
Skeletal formula of cyclohexane in its chair conformation Ball-and-stick model of cyclohexane in its chair conformation
Identifiers
CAS number 110-82-7 YesY
PubChem 8078
ChemSpider 7787 YesY
UNII 48K5MKG32S YesY
DrugBank DB03561
KEGG C11249 YesY
ChEBI CHEBI:29005 YesY
ChEMBL CHEMBL15980 YesY
Jmol-3D images Image 1
Properties
Molecular formula C6H12
Molar mass 84.16 g/mol
Appearance colorless liquid
Odor sweet, gasoline-like
Density 0.7781 g/mL, liquid
Melting point 6.47 °C (43.65 °F; 279.62 K)
Boiling point 80.74 °C (177.33 °F; 353.89 K)
Solubility in water Immiscible
Solubility soluble in ether, alcohol, acetone
miscible with olive oil
Refractive index (nD) 1.42662
Viscosity 1.02 cP at 17 °C
Thermochemistry
Std enthalpy of
formation
ΔfHo298
-156 kJ/mol
Std enthalpy of
combustion
ΔcHo298
-3920 kJ/mol
Hazards
MSDS External MSDS
EU classification Flammable ('F)
Harmful ('
)
Dangerous for
the environment (N)
Severe eye irritant, may cause corneal clouding
R-phrases R11, R38, R65, R67, R50/53
S-phrases (S2), S9, S16, S25, S33, S60, S61, S62
NFPA 704
Flammability code 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g., gasoline) Health code 1: Exposure would cause irritation but only minor residual injury. E.g., turpentine Reactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g., liquid nitrogen Special hazards (white): no codeNFPA 704 four-colored diamond
Flash point −20 °C (−4 °F; 253 K)
Related compounds
Related cycloalkanes Cyclopentane
Cycloheptane
Related compounds Cyclohexene
Benzene
Supplementary data page
Structure and
properties
n, εr, etc.
Thermodynamic
data
Phase behaviour
Solid, liquid, gas
Spectral data UV, IR, NMR, MS
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 YesY (verify) (what is: YesY/N?)
Infobox references

Cyclohexane is a cycloalkane with the molecular formula (CH2)6. Cyclohexane is mainly used for the industrial production of adipic acid and caprolactam, which are precursors to nylon. Cyclohexane is a colourless, flammable liquid with a distinctive detergent-like odor, reminiscent of cleaning products (in which it is sometimes used).[1]

Production and reactions[edit]

On an industrial scale, cyclohexane is produced by hydrogenation of benzene.[2] Producers of cyclohexane accounts for approximately 11.4% of global demand for benzene.[3] The reaction is highly exothermic, with ΔH(500 K)� = 216.37 kJ/mol). Dehydrogenation commenced noticeably above 300 °C, reflecting the favorable entropy for dehydrogenation.[1]

Historical methods[edit]

Unlike benzene, cyclohexane is not easily obtained from natural resources such as coal. For this reason, early investigators synthesized their cyclohexane samples.[4] In 1867 Marcellin Berthelot reduced benzene with hydroiodic acid at elevated temperatures.[5] He incorrectly identified the reaction product as n-hexane not only because of the convenient match in boiling point (69 °C), but also because he did not believe benzene was a cyclic molecule (in contrast to his contemporary August Kekulé) but rather some sort of association of acetylene. In 1870 one of his sceptics, Adolf von Baeyer repeated the reaction[6] and pronounced the same reaction product hexahydrobenzene and in 1890 Vladimir Markovnikov believed he was able to distill the same compound from Caucasus petroleum, calling his concoction hexanaphtene. In 1894 Baeyer synthesized cyclohexane starting with a Dieckmann condensation of pimelic acid followed by multiple reductions:

1894 cyclohexane synthesis Baeyer

In the same year E. Haworth and W.H. Perkin Jr. (1860–1929) prepared it via a Wurtz reaction of 1,6-dibromohexane.

1894 cyclohexane synthesis Perkin / haworth

Surprisingly their cyclohexanes boiled higher by 10°C than either hexahydrobenzene or hexanaphtene but this riddle was solved in 1895 by Markovnikov, N.M. Kishner, and Nikolay Zelinsky when they reassigned "hexahydrobenzene" and "hexanaphtene" as methylcyclopentane, the result of an unexpected rearrangement reaction.

reduction of benzene to methylcyclopentane

Reactions[edit]

Cyclohexane is rather unreactive, being a non-polar, hydrophobic hydrocarbon. It reacts with superacids, such as HF + SbF5, which will lead to cracking. Substituted cyclohexanes, however, may be reactive under a variety of conditions, many of which are important in organic chemistry.

Uses[edit]

Commercially most of cyclohexane produced is converted into cyclohexanonecyclohexanol mixture (or "KA oil") by catalytic oxidation. KA oil is then used as a raw material for adipic acid and caprolactam.[1]

Laboratory uses[edit]

Cyclohexane is sometimes used as a repelent organic solvent.

Cyclohexane is also used for calibration of differential scanning calorimetry (DSC) instruments, because of a convenient crystal-crystal transition at −87.1 °C.[7]

Heat treating equipment manufacturer Surface Combustion uses cyclohexane as a gas in their high purity vacuum carburizing furnaces.

Conformation[edit]

The 6-vertexed ring does not conform to the shape of a perfect hexagon. The conformation of a flat 2D planar hexagon has considerable angle strain because its bonds are not 109.5 degrees; the torsional strain would also be considerable because all of the bonds would be eclipsed bonds. Therefore, to reduce torsional strain, cyclohexane adopts a three-dimensional structure known as the chair conformation.There are also two other intermediate conformers; half chair, which is the most unstable conformer, and twist boat, which is more stable than the boat conformer. This was first proposed as early as 1890 by Hermann Sachse, but only gained widespread acceptance much later. The new conformation puts the carbons at an angle of 109.5°. Half of the hydrogens are in the plane of the ring (equatorial) while the other half are perpendicular to the plane (axial). This conformation allows for the most stable structure of cyclohexane. Another conformation of cyclohexane exists, known as boat conformation, but it interconverts to the slightly more stable chair formation. If cyclohexane is mono-substituted with a large substituent, then the substituent will most likely be found attached in an equatorial position, as this is the slightly more stable conformation.

Cyclohexane has the lowest angle and torsional strain of all the cycloalkanes, as a result cyclohexane has been deemed a 0 in total ring strain, a combination of angle and torsional strain. This also makes cyclohexane the most stable of the cycloalkanes and therefore will produce the least amount of heat (per CH2 unit) when burned compared to the other cycloalkanes.

A cyclohexane molecule in chair conformation. Hydrogen atoms in axial positions are shown in red, while those in equatorial positions are in blue.


Solid phases[edit]

Cyclohexane has two crystalline phases. The high-temperature phase I, stable between 186 K and the melting point 280 K, is a plastic crystal, which means the molecules retain some rotational degree of freedom. The low-temperature (below 186 K) phase II is ordered. Two other low-temperature (metastable) phases III and IV have been obtained by application of moderate pressures above 30 MPa, where phase IV appears exclusively in deuterated cyclohexane (note that application of pressure increases the values of all transition temperatures).[8]

Cyclohexane phases[8]
No Symmetry Space group a (Å) b (Å) c (Å) Z T (K) P (MPa)
I Cubic Fm3m 8.61 4 195 0.1
II Monoclinic C2/c 11.23 6.44 8.20 4 115 0.1
III Orthorhombic Pmnn 6.54 7.95 5.29 2 235 30
IV Monoclinic P12(1)/n1 6.50 7.64 5.51 4 160 37

Here Z is the number structure units per unit cell; the unit cell constants a, b and c were measured at the given temperature T and pressure P.

See also[edit]

References[edit]

  1. ^ a b c M. Larry Campbell. "Cyclohexane" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2012. doi:10.1002/14356007.a08_209.pub2
  2. ^ Fred Fan Zhang, Thomas van Rijnman, Ji Soo Kim, Allen Cheng "On Present Methods of Hydrogenation of Aromatic Compounds, 1945 to Present Day" Lunds Tekniska Högskola 2008
  3. ^ Market Study Benzene, Ceresana, July 2011 [1]
  4. ^ Warnhoff, E. W. (1996). "The Curiously Intertwined Histories of Benzene and Cyclohexane". J. Chem. Ed. 73 (6): 494. doi:10.1021/ed073p494. 
  5. ^ See:
    • Bertholet (1867) "Nouvelles applications des méthodes de réduction en chimie organique" (New applications of reduction methods in organic chemistry), Bulletin de la Société chimique de Paris, series 2, 7 : 53-65.
    • Bertholet (1868) "Méthode universelle pour réduire et saturer d'hydrog'ene les composés organiques" (Universelle method for reducing and saturating with hydrogen organic compounds), Bulletin de la Société chimique de Paris, series 2, 9 : 8-31. From page 17: "En effet, la benzine, chauffée à 280° pendant 24 heures avec 80 fois son poids d'une solution aqueuse saturée à froid d'acide iodhydrique, se change à peu près entièrement en hydrure d'hexylène, C12H14, en fixant 4 fois son volume d'hydrog'ene: C12H6 + 4H2 = C12H14 … Le neuveau carbure formé par la bezine est un corps unique et défini: il bout à 69°, et offre toutes les propriétés et la composition de l'hydrure d'hexylène extrait des pétroles." (In effect, benzene, heated to 280° for 24 hours with 80 times its weight of an aqueous solution of cold saturated hydroiodic acid, is changed almost entirely into hydride of hexylene, C12H14, [Note: this formula for hexane (C6H14) is wrong because chemists at that time used the incorrect atomic mass for carbon.] by fixing [i.e., combining with] 4 times its volume of hydrogen: C12H6 + 4H2 = C12H14 … The new carbon compound formed by benzene is a unique and well-defined substance: it boils at 69° and presents all the properties and the composition of hydride of hexylene extracted from oil.)
  6. ^ Adolf Baeyer (1870) "Ueber die Reduction aromatischer Kohlenwasserstoffe durch Jodphosphonium" (On the reduction of aromatic hydrocarbons by phosphonium iodide [H4IP]), Annalen der Chemie und Pharmacie, 155 : 266-281. From page 279: "Bei der Reduction mit Natriumamalgam oder Jodphosphonium addiren sich im höchsten Falle sechs Atome Wasserstoff, und es entstehen Abkömmlinge, die sich von einem Kohlenwasserstoff C6H12 ableiten. Dieser Kohlenwasserstoff ist aller Wahrscheinlichkeit nach ein geschlossener Ring, da seine Derivate, das Hexahydromesitylen und Hexahydromellithsäure, mit Leichtigkeit wieder in Benzolabkömmlinge übergeführt werden können." (During the reduction [of benzene] with sodium amalgam or phosphonium iodide, six atoms of hydrogen are added in the extreme case, and there arise derivatives, which derive from a hydrocarbon C6H12. This hydrocarbon is in all probability a closed ring, since its derivatives — hexahydromesitylene [1,3,5 - trimethyl cyclohexane] and hexahydromellithic acid [cyclohexane-1,2,3,4,5,6-hexacarboxylic acid] — can be converted with ease again into benzene derivatives.)
  7. ^ Price, D. M. (1995). "Temperature Calibration of Differential Scanning Calorimeters". Journal of Thermal Analysis 45 (6): 1285–1296. doi:10.1007/BF02547423. 
  8. ^ a b Mayer, J.; Urban, S.; Habrylo, S.; Holderna, K.; Natkaniec, I.; Würflinger, A.; Zajac, W. (1991). "Neutron Scattering Studies of C6H12 and C6D12 Cyclohexane under High Pressure". Physica status solidi (b) 166 (2): 381. doi:10.1002/pssb.2221660207. 

External links[edit]