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 In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen or carbon-carbon bonds. Due to carbon's ability to catenate (form chains with other carbon atoms), millions of organic compounds are known. The ...

whose molecule can be described as a

cyclohexane Cyclohexane is a cycloalkane with the molecular formula . Cyclohexane is non-polar. Cyclohexane is a colorless, flammable liquid with a distinctive detergent-like odor, reminiscent of cleaning products (in which it is sometimes used). Cyclohexan ...

with four

hydroxyl In chemistry, a hydroxy or hydroxyl group is a functional group with the chemical formula and composed of one oxygen atom covalently bonded to one hydrogen atom. In organic chemistry, alcohols and carboxylic acids contain one or more hydroxy ...

(OH)

groups A group is a number of persons or things that are located, gathered, or classed together. Groups of people * Cultural group, a group whose members share the same cultural identity * Ethnic group, a group whose members share the same ethnic iden ...

substituted for

hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...

atoms on four consecutive

carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...

atoms. Its

formula In science, a formula is a concise way of expressing information symbolically, as in a mathematical formula or a ''chemical formula''. The informal use of the term ''formula'' in science refers to the general construct of a relationship betwee ...

can be written , , or (––)₄(––)₂. There are 10

isomer In chemistry, isomers are molecules or polyatomic ions with identical molecular formulae – that is, same number of atoms of each element – but distinct arrangements of atoms in space. Isomerism is existence or possibility of isomers. Iso ...

s with this same

structural formula The structural formula of a chemical compound is a graphic representation of the molecular structure (determined by structural chemistry methods), showing how the atoms are possibly arranged in the real three-dimensional space. The chemical bondi ...

, which are among the 43 isomers of

cyclohexanetetrol A cyclohexanetetrol is a chemical compound consisting of a cyclohexane molecule with four hydroxyl groups (–OH) replacing four of the twelve hydrogen atoms. It is therefore a cyclitol (cyclic polyol). Its generic formula is or . Some cyclohexa ...

. They are all

polyol In organic chemistry, a polyol is an organic compound containing multiple hydroxyl groups (). The term "polyol" can have slightly different meanings depending on whether it is used in food science or polymer chemistry. Polyols containing two, thr ...

s, more specifically tetrols and

cyclitol In organic chemistry, a cyclitol is a cycloalkane containing at least three hydroxyl, each attached to a different ring carbon atom. The general formula for an unsubstituted cyclitol is or where 3 ≤ ''x'' ≤ ''n''. The name is also used for c ...

s. Some of them have biologically important roles in some organisms.

Isomers and nomenclature

There are 10 different

s of this compound, 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). 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. * 1α,2α,3β,4β- or 1,2/3,4-, and its enantiomer. * 1α,2β,3α,4β- or 1,3/2,4-, and its enantiomer. * 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. 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. 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. 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.

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. In 2007, Peter Valente and others described the preparation of achiral 1,4/2,3-cyclohexanetetrol ( toxocarol) from 2,3-dioxabicyclo .2.2ct-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.

References

CON and CBN IUPAC Commissions on Nomenclature (1968): "The Nomenclature of Cyclitols - Tentative Rules". ''European Journal of Biochemistry'', volume 5, pages 1-12. 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. 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. 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. 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. 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. T. Posternak et al. (1955): ''Helvetica Chimica Acta'', volume 38, pages 208-. 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. R. Criegee and P. Becher (1957): ''Chemische Berichte'', volume 90, pages 2516-. 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. Peter Valente,. Thomas D. Avery, Dennis K. Taylor, and Edward R. T. Tiekink (2008): "Synthesis and Chemistry of 2,3-Dioxabicyclo .2.2ctane-5,6-diols". ''Journal of Organic Chemistry'', volume 74, issue 1, pages 274-282. {{DEFAULTSORT:Cyclohexanetetrol, 1,2,3,4- Polyols Cyclohexanols