1,2,3,4-Cyclohexanetetrol

Generic structure of 1,2,3,4-cyclohexenetetrol.
Names
Preferred IUPAC name
Cyclohexane-1,2,3,4-tetrol
Other names
Cyclohexaneerythritol
Identifiers
3D model (JSmol)
ChemSpider
  • InChI=1S/C6H12O4/c7-3-1-2-4(8)6(10)5(3)9/h3-10H,1-2H2
    Key: WESBWDZFWNIVRV-UHFFFAOYSA-N
  • C1CC(C(C(C1O)O)O)O
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

1,2,3,4-Cyclohexanetetrol (also named cyclohexane-1,2,3,4-tetrol, 1,2,3,4-tetrahydroxycyclohexane, or ortho-cyclohexanetetrol) is an organic compound whose molecule can be described as a cyclohexane with four hydroxyl (OH) groups substituted for hydrogen atoms on four consecutive carbon atoms. Its formula can be written C
6H
12O
4, C
6H
8(OH)
4, or (–CH(OH)–)4(–CH
2–)2.

There are 10 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.[2]

Isomers and nomenclature

There are 10 different isomers of this compound,[3] 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,3α,4α-, 1,2,3,4/0-, or all-cis, with all hydroxyls on the same side (achiral).
  • 1α,2α,3α,4β- or 1,2,3/4-, and its enantiomer.
  • 1α,2α,3β,4α- or 1,2,4/3-, and its enantiomer.[4]
  • 1α,2α,3β,4β- or 1,2/3,4-, and its enantiomer.[4]
  • 1α,2β,3α,4β- or 1,3/2,4-, and its enantiomer.[4]
  • 1α,2β,3β,4α- or 1,4/2,3- (achiral); dihydro-conduritol.

History

Synthesis of 1,2,3,4-cyclohexanetretrols was first reported in 1933 by Pierre Bedos and Adrien Ruyer, by hydrolysis of 1,2;3,4-diepoxy-cyclohexane. They separated the reaction products into two isomers, with melting points 210C (tetrabenzoate: 146C) and 187C (tetrabenzoate: 260C), respectively, in 1:2 ratio.[5]

In 1953, Théodore Posternak and H. Friedli obtained the achiral 1,4/2,3 isomer and racemic mixtures of the 1,2/3,4, 1,3/2,4, and 1,2,4/3 isomers. By biochemical oxydation, they removed the D- enantiomers of the last three, leaving the L- enantiomers.[6]

Posternak and Reymond observed in 1953 that the 1,3/2,4 isomer (D and L forms) is not attacked by a certain strain of A. suboxydans, whereas all the others were metabolized with consumption of 1 atom of oxygen (possibly by formation of a ketone-triol), except the 1,2/3,4 isomer (D and L) that consumed 2 atoms.[7]

In 1955, Posternak and Reymond studied the oxydation of the 1,4/2,3 isomer (dihydro-conduritol) by Acetobacter suboxydans, producing a trihydroxyketone. They also characterized the chiral isomers 1,3/2,4, 1,2,3/4,and 1,2,4/3.[8]

Synthesis

Methods which have been employed for the preparation of 1,2,3,4-cyclohexanetetrols include: reduction or hydrogenation of (1) cyclohexenetetrols, (2) tri-hydroxycyclohexanones, (3) pentahydroxycyclohexanones (inososes), (4) hydroxylated aromatics, or (5) hydroxylated quinones; the (6) hydrogenolysis of dibromocyclohexanetetrols; the (7) hydration of diepoxycyclohexanes; and the hydroxylation of (8) cyclohexadienes or (9) cyclohexenediols.[3]

In 2007, Peter Valente and others described the preparation of achiral 1,4/2,3-cyclohexanetetrol (toxocarol) from 2,3-dioxabicyclo[2.2.2]oct-5-ene, a cyclohexene with a peroxide bridge (–O–O–) replacing hydrogens in carbons 3 and 6. The previous route was reduction of the peroxide brige to yield 3α,6α-dihydroxy cyclohexene, followed by di-hydoxylation of the double bond; which yielded a mixture of the 1,4/2,3 and 1,2,3,4/0 isomers. The authors found that, by reversing the order of the two steps, they could obtain 1,4/2,3 in 80% yield.[9]

[10]

[11]

References

  1. 1 2 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. ↑ 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
  3. 1 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
  4. 1 2 3 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
  5. ↑ Pierre Bedos and Adrien Ruyer (1933): "Sur les oxydes et sur les polyalcools dérivés du cyclohexadiène-1.3.Comptes rendus hebdomadaires des séances de l'Académie des Sciences, volume 196, pages 625-627.
  6. ↑ 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
  7. ↑ 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
  8. ↑ 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
  9. ↑ Peter Valente,. Thomas D. Avery, Dennis K. Taylor, and Edward R. T. Tiekink (2008): "Synthesis and Chemistry of 2,3-Dioxabicyclo[2.2.2]octane-5,6-diols". Journal of Organic Chemistry, volume 74, issue 1, pages 274-282. doi:10.1021/jo8020506
  10. ↑ T. Posternak et al. (1955): Helvetica Chimica Acta, volume 38, pages 208-.
  11. ↑ R. Criegee and P. Becher (1957): Chemische Berichte, volume 90, pages 2516-.
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