1,2,4,5-Cyclohexanetetrol

1,2,4,5-Cyclohexanetetrol (also named cyclohexane-1,2,4,5-tetrol, 1,2,4,5-tetrahydroxycyclohexane, or para-cyclohexanetetrol) is an organic compound whose molecule can be described as a cyclohexane with four hydroxyl (OH) groups substituted for hydrogen atoms on two non-adjacent pairs of adjacent carbon atoms. Its formula can be written C
6H
12O
4, C
6H
8(OH)
4, or [–(CH(OH)–)2–CH
2–]2.

1,2,4,5-Cyclohexanetetrol

Generic structure of 1,2,4,5-cyclohexanetetrol.
Names
IUPAC name
cyclohexane-1,2,4,5-tetrol
Other names
1,2,4,5-tetrahydroxycyclohexane
1,2,4,5-cyclohexanetetrol
Identifiers
3D model (JSmol)
ChemSpider
Properties
Molar mass 148.16 g/mol
Density 1.6±0.1 g/cm3
Melting point 91.3 °C (196.3 °F; 364.4 K) estimated
Boiling point 297.1±40.0 estimated
very highly soluble in water
Hazards
Flash point 149.8±21.9 °C
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

There are 7 isomers with this same structural formula, which are among the 43 isomers of cyclohexanetetrol. They are all polyols, more specifically tetrols and cyclitols.[1] Some of them have biologically important roles in some organisms.

Isomers and nomenclature

There are 7 different isomers of this compound,[2] that differ in the orientation of the four hydroxyls relative to the mean plane of the ring. They can be denoted by the letter "α" or "β" after each carbon index ("2α","2β","4β", etc.), to indicate the corresponding side of the plane relative to the 1-hydroxyl; or by listing all the "α" indices, then a slash "/", then the "β" indices (or "0" if the second list is empty).[1]

The possible isomers are:

  • 1α,2α,4α,5α-, 1,2,4,5/0-, or all-cis, with all hydroxyls on the same side (achiral).
  • 1α,2α,4α,5β- or 1,2,4/5-, and its enantiomer.
  • 1α,2α,4β,5β- or 1,2/4,5- (achiral).
  • 1α,2β,4β,5α- or 1,4/2,5- (achiral).
  • 1α,2β,4α,5β- or 1,2/4,5-, and its enantiomer.

Synthesis

Methods which have been employed for the preparation of 1,2,4,5-cyclohexanetetrols include: reduction or hydrogenation of (1) tri-hydroxycyclohexanones, (2) hydroxylated aromatics, or (3) hydroxylated quinones; the (4) hydrogenolysis of dibromocyclohexanetetrols; the (5) hydration of diepoxycyclohexanes; and the hydroxylation of (6) cyclohexadienes or (7) cyclohexenediols.[2]

In 1998, Ahmet Maras and others reported the synthesis of racemic 1,4/2,5-cyclohexanetetrol (the chiral trans-trans para isomer) by hydroxyla-tion of 1,4-cyclohexadiene with stoichiometric amount of hydrogen peroxide (H
2O
2, 30% in 1-butanol), with selenium dioxide as catalyzer. The yield was 88%, with no trace of the 1,5/2,4 isomer. The racemic 1,4/2,5 isomer is soluble in ethanol, and yields colorless crystals with melting point 194–196 °C.[3] The (+) enantiomer is betitol, a natural product first identified in sugar beets.[4][5][6] The pure enantiomers crystallize as a monohydrate in the monoclinic C2 group (a = 10.675 Å, b = 7.3502 Å, c = 5.1968 Å, β = 103.877°)[7][8][9][10][11][12][13][14]

References
  1. CON and CBN IUPAC Commissions on Nomenclature (1968): "The Nomenclature of Cyclitols - Tentative Rules". European Journal of Biochemistry, volume 5, pages 1-12. doi:10.1111/j.1432-1033.1968.tb00328.x
  2. G. E. McCasland, Stanley Furuta, L. F. Johnson, and J. N. Shoolery (1963): Synthesis of the Five Diastereomeric 1,2,4,5-Cyclohexanetetrols. Nuclear Magnetic Resonance Configurational Proofs. Journal of Organic Chemistry, volume 28, issue 4, pages 894-900. doi:10.1021/jo01039a002
  3. Ahmet Maras, Mesut Erden, Hasan Seçen, and Yasar Sütbeyaz (1998): "One-pot synthesis from 1,4-cyclohexadiene of (±)-1,4/2,5-cyclohexanetetrol, a naturally occurring cyclitol derivative". Carbohydrate Research, volume 308, issues 3–4, April , Pages 435-437. doi:10.1016/S0008-6215(98)00073-1
  4. E.O. von Lippmann (1901), Chemische Berichte, volume 34, pages 1159-1162.
  5. J.D. Ramanathan, J.S. Craigie, J. McLachlan, D.G. Smith, and A.G. McInnes (1966): Tetrahedron Letters, volume 1966, pages 1527-1531.
  6. J. S. Craigie, J. McLachlan, and R. D. Tocher (1968): Canadian Journal of Botany, volume 46, pages 605-611.
  7. G. Mehta, S. Sen and S. Dey (2005). "(1S*,2S*,4S*,5S*)-Cyclohexane-1,2,4,5-tetrol monohydrate". Acta Crystallographica, volume C-61, pages o358-o360. doi:10.1107/S0108270105011066
  8. T. Posternak et al. (1955): Helvetica Chimica Acta, volume 38, pages 208-.
  9. R. Criegee and P. Becher (1957): Chemische Berichte, volume 90, pages 2516-.
  10. Nihat Akbulut and Metin Balci (1988): "A new and stereospecific synthesis of cyclitols: (1,2,4/3)-, (1,2/3,4)-, and (1,3/2,4)-cyclohexanetetrols". Journal of Organic Chemistry, volume 53, issue 14, pages 3338-3342. doi:10.1021/jo00249a039
  11. J. S. Craigie (1969): "Some Salinity-Induced Changes in Growth, Pigments, and Cyclohexanetetrol Content of Monochrysis lutheri". Journal of the Fisheries Research Board of Canada, volume 26, issue 11, pages 2959-2967. doi:10.1139/f69-282
  12. Th. Posternak and H. Friedli (1953): "Recherches dans la série des cyclitols XVI. Sur quelques cyclohexane‐tétrols‐1,2,3,4". Helvetica Chimica Acta, volume 36, issue 1, pages 251-259. doi:10.1002/hlca.19530360131
  13. Théodore Posternak and Dominique Reymond (1953): "Recherches dans la série des cyclitols XVII. Sur l'oxydation de divers cyclitols par Acetobacter suboxydans". Helvetica Chimica Acta, volume 36, issue 1, pages 260-268. doi:10.1002/hlca.19530360132
  14. T. Posternak and D. Reymond (1955): "Recherches dans la série des cyclitols XXI. Sur la configuration de cyclohexane‐tétrols et ‐triols optiquement actifs. Sur l'oxydation biochimique du cyclohexane‐tétrol‐1,4/2,3 (dihydro‐conduritol)". Helvetica Chimica Acta, volume 38, issue 1, pages 195-205. doi:10.1002/hlca.19550380123
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