WO2018160618A1 - Quinones robustes solubles dans l'eau à potentiel faible et élevé - Google Patents

Quinones robustes solubles dans l'eau à potentiel faible et élevé Download PDF

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WO2018160618A1
WO2018160618A1 PCT/US2018/020086 US2018020086W WO2018160618A1 WO 2018160618 A1 WO2018160618 A1 WO 2018160618A1 US 2018020086 W US2018020086 W US 2018020086W WO 2018160618 A1 WO2018160618 A1 WO 2018160618A1
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Prior art keywords
quinone
substituted
hydroquinone
moiety
sulfonate
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PCT/US2018/020086
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Shannon S. Stahl
James B. Gerken
Colin W. ANSON
Sung-Eun Suh
Alexiouis G. STAMOULIS
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Wisconsin Alumni Research Foundation
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Publication of WO2018160618A1 publication Critical patent/WO2018160618A1/fr
Priority to US16/150,405 priority Critical patent/US10597359B2/en
Priority to US16/822,189 priority patent/US11021441B2/en

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Definitions

  • the quinone/hydroquinone redox couple is used in many different technologies and has been extensively studied.
  • U.S. Patent Publication No.2015/0263371 which is incorporated by reference herein in its entirety, we disclosed using the quinone/hydroquinone redox couple as a charge transfer mediator to facilitate more efficient electrocatalytic oxygen reduction in electrochemical cells.
  • the available quinones are inadequate.
  • Hydroquinone can be sulfonated to yield useful compounds, such as the commercially available potassium hydroquinone monosulfonate. More vigorous sulfonation conditions give rise to the 2,5- and 2,6-disulfonated isomers. 1 These sulfonate salts have high water solubility compared to the parent hydroquinone, and the solubility of the acid is even higher (see Figure 1). Aerobic or electrochemical oxidation of these compounds produces the corresponding para-quinone. Sulfonation of catechol gives the 3,5-disulfonate, which can be oxidized to an ortho-quinone. These quinones have been proposed as redox-active species in flow batteries.
  • the disclosure encompasses a number of substituted 1,4- hydroquinones and substituted 1,4-quinones.
  • the substituted hydroquinones have the chemical formula:
  • R 1 , R 2 , R 3 and R 4 include a sulfonate or sulfonimide moiety
  • each R 1 , R 2 , R 3 and R 4 that does not include a sulfonate or sulfonimide moiety is independently an alkyl, a cycloalkyl, a thioether, a sulfoxide, a sulfone, a haloalkyl, a halogen, a nitrile, an imide, a phosphonate, a pyrazole, or combinations thereof; or (b) one, two, three, or all four of R 1 , R 2 , R 3 and R 4 include a phosphonate moiety, and each R 1 , R 2 , R 3 and R 4 that does not include a phosphonate moiety is independently an alkyl, a cycloalkyl, a thioether,
  • each R 1 , R 2 , R 3 and R 4 that includes a sulfonate moiety is (a) a sulfonate moiety directly bound to the hydroquinone or quinone ring, or (b) includes both a sulfonate moiety and a linking group that links the sulfonate moiety to the hydroquinone or quinone ring.
  • each R 1 , R 2 , R 3 and R 4 that includes a phosphonate moiety is (a) a phosphonate moiety directly bound to the hydroquinone or quinone ring, or (b) includes both a phosphonate moiety and a linking group that links the phosphonate moiety to the hydroquinone or quinone ring. [0013] In some embodiments, all four of R 1 , R 2 , R 3 and R 4 cannot be sulfonate directly bound to the hydroquinone or quinone ring.
  • all four of R 1 , R 2 , R 3 and R 4 cannot be phosphonate directly bound to the hydroquinone or quinone ring.
  • R 1 cannot be sulfonate directly bound to the hydroquinone or quinone ring.
  • R 1 and R 3 cannot both be sulfonate directly bound to the hydroquinone or quinone ring.
  • each linking group may include an ester, an amide, a sulfonamide, an imide, a sulfone, a sulfoxide, a thioether, a ketone, one or more alkyl chains, an aromatic ring, a pyrazole, or combinations thereof.
  • R 1 and R 2 , R 3 and R 4 , or both R 1 /R 2 and R 3 /R 4 each include a single linking group attached to the hydroquinone or quinone ring at the two designated positions.
  • one or more of the linking groups are selected from the imide - CONYCO-, where Y is -CH2CH2- or a benzene ring; the amide -CONHY, where Y is -CH 2 CH 2 - or a benzene ring; pyrazole; or dimethylpyrazole.
  • R 1 and R 2 , R 3 and R 4 , or both R 1 /R 2 and R 3 /R 4 each include a single sulfonimide attached to the hydroquinone or quinone ring at the two designated positions.
  • multiple substituted hydroquinone or quinone structures as described above are covalently linked together to form a substituted bicyclic, tricyclic or polycyclic hydroquinone or quinone.
  • hydroquinone or quinone includes 2, 3, 4, 5 or 6 covalently linked hydroquinone or quinone structures as described above.
  • the multiple substituted hydroquinone or quinone structures are covalently linked through one or more of the R 1 , R 2 , R 3 or R 4 that do not comprise a sulfonate moiety, sulfonimide moiety, or phosphonate moiety.
  • the multiple substituted hydroquinone or quinone structures are covalently linked through one or more alkyls.
  • one or more of the alkyls through which the multiple substituted hydroquinone or quinone structures are covalently linked are selected from -CH 2 - (methanediyl) or -CH(-) 2 (methanetriyl).
  • the -CH 2 - covalently links two different substituted hydroquinone or quinone structures, or the -CH(-)2 covalently links three different hydroquinone or quinone structures.
  • one or more of the R 1 , R 2 , R 3 or R 4 that include a sulfonate moiety, sulfonimide moiety, or phosphonate moiety are independently selected from the imide -CONRCO- attached at R 1 and R 2 or R 3 and R 4 , where R is
  • one or more of the R 1 , R 2 , R 3 or R 4 that do not include a sulfonate moiety, a sulfonimide moiety, or a phosphonate moiety are independently selected from -Cl, -CH3, -CH2-, -CF3, -CN, -CH(-)2 , and attached at R 1 and R 2 or R 3 and R 4 .
  • the -C H 2 - links two different substituted hydroquinone or quinone structures, or the -CH(-)2 links three different hydroquinone or quinone structures.
  • the substituted hydroquinone or quinone is more soluble in water than the corresponding unsubstituted hydroquinone or quinone, is stable in 1 M H2SO4, and has a reduction potential in the oxidized form that is equal to or greater than the reduction potential of the corresponding unsubstituted quinone (1,4-benzoquinone).
  • the substituted hydroquinone or quinone is one of the compounds shown in Figures 2-5 or a salt, acid form, reduced form, or oxidized form of any of these compounds.
  • the substituted hydroquinone is one of the following compounds, or a salt, acid form, reduced form, or oxidized form of any of these compounds:
  • t e sc osure encompasses a num er o su st tute 1,2- hydroquinones and substituted 1,2-quinones.
  • the substituted hydroquinones have the chemical formula:
  • R 1 , R 2 , R 3 and R 4 include a sulfonate or sulfonimide moiety
  • each R 1 , R 2 , R 3 and R 4 that does not include a sulfonate or sulfonimide moiety is independently an alkyl, a cycloalkyl, a thioether, a sulfoxide, a sulfone, a haloalkyl, a halogen, a nitrile, an imide, a phosphonate, a pyrazole, or combinations thereof; or (b) one, two, three, or all four of R 1 , R 2 , R 3 and R 4 include a phosphonate moiety, and each R 1 , R 2 , R 3 and R 4 that does not include a phosphonate moiety is independently an alkyl, a cycloalkyl, a thio
  • each R 1 , R 2 , R 3 and R 4 that includes a sulfonate moiety is (a) a sulfonate moiety directly bound to the hydroquinone or quinone ring, or (b) includes both a sulfonate moiety and a linking group that links the sulfonate moiety to the hydroquinone or quinone ring.
  • each R 1 , R 2 , R 3 and R 4 that includes a phosphonate moiety is (a) a phosphonate moiety directly bound to the hydroquinone or quinone ring, or (b) includes both a phosphonate moiety and a linking group that links the phosphonate moiety to the hydroquinone or quinone ring.
  • each linking group may include an ester, an amide, a sulfonamide, an imide, a sulfone, a sulfoxide, a thioether, a ketone, one or more alkyl chains, an aromatic ring, a pyrazole, or combinations thereof.
  • R 1 and R 2 , R 3 and R 4 , or both R 1 /R 2 and R 3 /R 4 each include a single linking group attached to the hydroquinone or quinone ring at the two designated positions.
  • one or more of the linking groups are selected from the imide - CONYCO-, where Y is -CH2CH2- or a benzene ring; the amide -CONHY, where Y is -CH 2 CH 2 - or a benzene ring; pyrazole; or dimethylpyrazole.
  • R 1 and R 2 , R 3 and R 4 , or both R 1 /R 2 and R 3 /R 4 each include a single sulfonimide attached to the hydroquinone or quinone ring at the two designated positions.
  • multiple substituted hydroquinone or quinone structures as described above are covalently linked together to form a substituted bicyclic, tricyclic or polycyclic hydroquinone or quinone.
  • hydroquinone or quinone includes 2, 3, 4, 5 or 6 covalently linked hydroquinone or quinone structures as described above.
  • the multiple substituted hydroquinone or quinone structures are covalently linked through one or more of the R 1 , R 2 , R 3 or R 4 that do not comprise a sulfonate moiety, sulfonimide moiety, or phosphonate moiety.
  • the multiple substituted hydroquinone or quinone structures are covalently linked through one or more alkyls.
  • one or more of the alkyls through which the multiple substituted hydroquinone or quinone structures are covalently linked are selected from -CH 2 - (methanediyl) or -CH(-) 2 (methanetriyl).
  • the -CH 2 - covalently links two different substituted hydroquinone or quinone structures, or the -CH(-)2 covalently links three different hydroquinone or quinone structures.
  • one or more of the R 1 , R 2 , R 3 or R 4 that include a sulfonate moiety, sulfonimide moiety, or phosphonate moiety are independently selected from the imide -CONRCO- attached at R 1 and R 2 or R 3 and R 4 , where R is
  • one or more of the R 1 , R 2 , R 3 or R 4 that do not include a sulfonate moiety, a sulfonimide moiety, or a phosphonate moiety are independently selected from -Cl, -CH3, -CH2-, -CF3, -CN, -CH(-)2, , and attached at R 1 and R 2 or R 3 and R 4 .
  • the -CH 2 - links two different substituted hydroquinone or quinone structures, or the -CH(-)2 links three different hydroquinone or quinone structures.
  • the substituted hydroquinone or quinone is more soluble in water than the corresponding unsubstituted hydroquinone or quinone, is stable in 1 M H2SO4, and has a reduction potential in the oxidized form that is equal to or greater than the reduction potential of the corresponding unsubstituted quinone (1,4-benzoquinone).
  • the substituted hydroquinone or quinone is one of the compounds shown in Figure 6 or a salt, acid form, reduced form, or oxidized form of any of these compounds.
  • the substituted hydroquinone is one of the following compounds, or a salt, acid form, reduced form, or oxidized form of any of these compounds:
  • the disclosure encompasses a number of substituted 9,10- anthrahydroquinones and substituted 9,10-anthraquinones.
  • the substituted anthraquinones have the chemical formula:
  • R 1 - R 8 includes both a sulfonate moiety and a linking group that links the sulfonate moiety to the anthraquinone ring and each R 1 - R 8 that does not include a sulfonate moiety is independently an alkyl, a cycloalkyl, a thioether, a hydroxy, an amino, or hydrogen, or combinations thereof; or (b) at least one of R 1 - R 8 includes both a phosphonate moiety and a linking group that links the phosphonate moiety to the anthraquinone ring and each R 1 - R 8 that does not include a phosphonate moiety is independently an alkyl, a cycloalkyl, a thioether, a hydroxy, an amino, or hydrogen, or combinations thereof.
  • each linking group may include an ether, an amine, a sulfonamide, an imide, a sulfone, a sulfoxide, a thioether, a ketone, one or more alkyl chains, or combinations thereof.
  • R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 , R 2 and R 3 , R 6 and R 7 , or multiple non-overlapping combinations of the above pairs each include a single linking group attached to the anthraquinone ring at the two designated positions.
  • the substituted anthraquinone is one of the following compounds, or a salt, acid form, reduced form, or oxidized form of any of these compounds:
  • te scosure encompasses a systemncu ng a liquid electrolyte solution in contact with an electrode, wherein the electrolyte solution includes a substituted hydroquinone,1,4-quinone, catechol, 1,2-quinone, anthraquinone or anthrahydroquinone as described above dissolved therein.
  • the electrolyte solution is an aqueous solution.
  • the electrolyte solution includes an organic solvent.
  • the electrolyte solution further includes oxygen.
  • the disclosure encompasses an electrochemical cell that includes the system described above in ionic communication with an anodic half-cell.
  • the disclosure encompasses an electrochemical cell that includes the system described above in ionic communication with a cathodic half-cell.
  • the cell is a fuel cell or a flow battery.
  • the disclosure encompasses a method of producing electricity.
  • the method includes the steps of contacting the anodic half-cell of the cell described above with a fuel, and contacting the system of the cell described above with oxygen, whereby the fuel is oxidized, oxygen is reduced, and electricity is produced.
  • the disclosure encompasses a substituted hydroquinone, 1,4- quinone, catechol, 1,2-quinone, anthraquinone, or anthrahydroquinone as described above for use as a redox mediator in a fuel cell or in a flow battery.
  • the disclosure encompasses a method of making a substituted hydroquinone, 1,4-quinone, catechol, 1,2-quinone, anthraquinone, or anthrahydroquinone as described above. Such methods are described in detail in the examples below.
  • Figure 1 illustrates a previously reported hydroquinone sulfonate synthesis, along with reported reactant, intermediate, and reactant solubilities in water.
  • Figure 2 shows the chemical structures of 28 exemplary substituted hydroquinones (compounds 1, 3, 6, 11a-d, 12a-d, 16-18, 21-30, 35a-d).
  • Figure 3 shows the chemical structure of an additional 21 exemplary substituted hydroquinones and quinones (compounds 36, 39-43, 44a-d, 45a-d, 46-47, 48a-d, 49).
  • Figure 4 shows the chemical structure of an additional 17 exemplary substituted hydroquinones and quinones containing thioether-linked sulfonates (compounds 52-54, 57- 70).
  • Figure 5 shows the aliphatic region of the 1H and the full 13C NMR of compound 52 and MESNA, mercaptoethanesulfonate, Na salt.
  • Figure 6 shows the chemical structure of an additional 11 exemplary substituted hydroquinones and quinones (compounds 73-77, 79, 85-86, 88, 90, 92).
  • Figure 7 shows the chemical structure of 12 exemplary substituted 1,2-hydroquinones and 1,2-quinones (compounds 93 - 104).
  • Figure 8 shows the chemical structure of 12 exemplary substituted 9,10- anthrahydroquinones and 9,10-anthraquinones (compounds 105 - 116).
  • Figure 9 shows the 1H and 13C NMR spectrum of compound 109.
  • Figure 10 shows the chemical structure of 12 exemplary substituted 9,10- anthrahydroquinones and 9,10-anthraquinones (compounds 117 - 128).
  • Figure 11 shows the chemical structure of 12 exemplary substituted 9,10- anthrahydroquinones and 9,10-anthraquinones (compounds 129 - 140).
  • the disclosed hydroquinones/quinones are disclosed hydroquinones/quinones and
  • anthraquinones/anthrahydroquinones are substituted with one or greater groups that each consist of or comprise a sulfonate moiety.
  • R is either the hydroquinone/quinone ring (i.e., the sulfonate is directly bound to the hydroquinone or quine ring) or a linking group that links the sulfonate moiety to the hydroquinone/1,4-quinone, catechol/1,2-quinone or anthraquinone/anthrahydroquinone ring.
  • Each linking group independently includes an ester, an amide, a sulfonamide, an imide, a sulfone, a sulfoxide, a thioether, a ketone, one or more alkyl chains, an aromatic ring, a pyrazole, or any combination thereof.
  • a non-limiting example of an aromatic ring that could be included in the linking group is a benzene ring.
  • Non-limiting examples of the one or more alkyl chains that could be included in the linking group include unbranched C1 or C2 alkyl chains, and unbranched, branched or cyclic C3, C4, C5, C6, C7, C8, C9 or C10 alkyl chains.
  • alkyl chains or aromatic rings may be included in the linking group, separated by one or more of the other listed groups. Furthermore, if one or more of the alkyl chains is branched, one or more of the groups that comprises a sulfonate moiety may include two or more sulfonate moieties.
  • the disclosed hydroquinones/1,4-quinones, catechol/1,2- quinone and anthraquinones/anthrahydroquinones are substituted with one or greater groups that each consist of or comprise a phosphonate moiety.
  • phosphonate or“phosphonate moiety” as used herein refers to a substituent having the general formula R-PO 3 2- , as well as the corresponding salts, acids (R- PO3H- and R-PO3H2), and esters.
  • R is either the hydroquinone/quinone ring (i.e., the phosphonate is directly bound to the hydroquinone or quinone ring) or a linking group that links the phosphonate moiety to the hydroquinone/1,4-quinone, catechol/1,2-quinone, or anthraquinone/anthrahydroquinone ring.
  • Each linking group independently includes an ester, an amide, a sulfonamide, an imide, a sulfone, a sulfoxide, a thioether, a ketone, one or more alkyl chains, an aromatic ring, a pyrazole, or any combination thereof.
  • An aromatic ring that could be included in the linking group is a benzene ring.
  • Non-limiting examples of the one or more alkyl chains that could be included in the linking group include unbranched C1 or C2 alkyl chains, and unbranched, branched or cyclic C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 or C 10 alkyl chains. Multiple alkyl chains or aromatic rings may be included in the linking group, separated by one or more of the other listed groups. Furthermore, if one or more of the alkyl chains is branched, one or more of the groups that comprises a phosphonate moiety may include two or more phosphonate moieties.
  • the disclosed hydroquinones/quinones are substituted with one, two, three or four groups that each consist of or comprise a sulfonimide moiety.
  • sulfonimide moiety refers to a substituent having the general formula R-SO2NHSO2-R’.
  • R and R’ can be the hydroquinone/quinone ring (i.e., the sulfonimide is directly bound in two places to the hydroquinone or quine ring(e.g., at R 1 /R 2 or at R 3 /R 4 ) or linking groups that links the sulfonimide moiety to the hydroquinone/quinone ring.
  • Each linking group independently includes an ester, an amide, a sulfonamide, an imide, a sulfone, a sulfoxide, a thioether, a ketone, one or more alkyl chains, an aromatic ring, a pyrazole, or any combination thereof.
  • An aromatic ring that could be included in the linking group is a benzene ring.
  • Non-limiting examples of the one or more alkyl chains that could be included in the linking group include unbranched C1 or C 2 alkyl chains, and unbranched, branched or cyclic C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 or C 10 alkyl chains. Multiple alkyl chains or aromatic rings may be included in the linking group, separated by one or more of the other listed groups.
  • each of the quinone/hydroquinone R 1 , R 2 , R 3 or R 4 that do not include a sulfonate moiety, phosphonate moiety, or sulfonimide moiety is an alkyl, a cycloalkyl, a thioether, a sulfoxide, a sulfone, a haloalkyl, a halogen, a nitrile, an imide, a pyrazole, or a combination of these.
  • Non-limiting examples of the alkyls that could be included include unbranched C 1 or C 2 alkyl chains, and unbranched, branched or cyclic C 3 , C4, C5, C6, C7, C8, C9 or C10 alkyl chains.
  • the disclosed compounds are capable of transferring protons and/or electrons by acid/base and/or oxidation/reduction reactions, have useful reduction potentials, are water soluble, and are stable under acid conditions. Accordingly, the disclosed compounds may be used as redox-active species in a variety of applications. In a non-limiting example, the disclosed compounds may be used to facilitate the reduction of oxygen in cathode half-cells, particularly in the context of emerging technologies such as in mediated fuel cells or organic mediator flow batteries.
  • hydroquinones/quinones as redox mediators to facilitate the reduction of oxygen in mediated fuel cells is described in, e.g., U.S. Patent Publication No.2015/0263371, which is incorporated by reference herein in its entirety.
  • a flow battery is a rechargeable fuel cell in which an electrolyte solution containing one or more dissolved redox-active mediators flows through the electrochemical cell.
  • Additional electrolyte is solution is stored externally, generally in tanks, and is usually pumped through the cell (or cells) of the battery, although gravity feed systems are also known. Flow batteries can be rapidly “recharged” by replacing the electrolyte liquid, while simultaneously recovering the spent material for processing and reuse.
  • a densely functionalized quinone, 34 has been prepared in only two steps from diethyl succinate. 30,31,32 Scheme 11 shows how this could produce the desired compounds 35a-d ( Figure 2). If the cyanide-catalyzed aminolysis to install polar functionality is unsuccessful, more conventional hydrolysis/coupling sequences could be used on the hydroquinone diester. 33,34
  • the bis-silyl enolate of succinic anhydride is capable of performing as a diene in Diels-Alder reactions, including with N-substituted maleimides to give 3,6- dihydroxyphthalimides. 38 With appropriately substituted succinic anhydrides and maleimides, this reaction would yield compounds 44a-d and 45a-d ( Figure 3).
  • An analogue to the carboximide group is the bis-sulfonimide group. 39
  • the more electron-withdrawing sulfonyl groups make the N-H bond more acidic.
  • benzene-1,2-bis-sulfonimide is as acidic as HCl.
  • quinones substituted with this group should be water-soluble anions.
  • Quinones can also act as Diels-Alder dienophiles, such as cyclohexadiene, and produce tricyclic products.
  • Thiols will readily add to quinones.
  • the resulting thioether linkage can be used to tether a solubilizing group, such as a sulfonate.
  • a solubilizing group such as a sulfonate.
  • Some examples of quinones containing thioether-linked sulfonates are given in Figure 4 and discussed here.
  • Reaction of 2-mercaptoethanesulfonate with chloranil (2) results in the substitution of chlorine by sulfur to eventually give the desired fully-substituted product, 50, in a mixture with a disulfide- linked byproduct, 51.
  • dichlorodicyanoquinone gives the disulfide exclusively (Scheme 15).
  • Thioethers can be readily oxidized by many methods to sulfoxides and sulfones. 43 Using one of these techniques on a thioether-quinone such as one of the ones shown above will produce a sulfoxide-quinone or sulfone-quinone. These quinones will have higher reduction potentials than the parent thioether and may have other properties that further enhance their usefulness.
  • an attached maleimide could be sulfonated, such as proposed to form structure 74, shown in Scheme 22.
  • 1,2-quinones have higher reduction potentials than the correspondingly substituted 1,4-quinones.
  • accessing these structures would be an efficient strategy to achieve quinones with increased redox potentials.
  • Similar sulfonate tethered by thioethers, as used in structure 52 or 54, should give access to higher potential, water-soluble, robust 1,2-hydroquinone structures.
  • Water-soluble anthraquinone structures have been utilized as the anodic mediator in aqueous flow batteries (see for instance U.S. Patent Application 2016/0043423). These structures typically include sulfonate substituents connected directly on the ring. Such compounds have been reported to undergo desulfonation, which leads to precipitation of the structures. 53 For this reason, alternate anthraquinone mediators without sulfonates directly connected to the ring are required. To address this concern, quinone 109 with sulfonate substituents attached to the ring via a thioether tether, was synthesized. Anthraquinones with pendant thioethers have been previously synthesized from the corresponding chlorinated anthraquinones, 54 but not with tethered sulfonates, which would provide increased water solubility, a desired trait.

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Abstract

L'invention concerne des hydroquinones substituées, des 1,4-quinones, des catéchols, des 1,2-quinones, des anthraquinones et des anthrahydroquinones. Les hydroquinones substituées et les catéchols répondent à la formule 1 tandis que les 1,4-quinones substituées ou les 1,2-quinones substituées ont la structure oxydée correspondante (1,4-benzoquinones et 1,2-benzoquinones). Un ou plusieurs des éléments parmi R1, R2, R33 et R4 comprennent une fraction sulfonate, une fraction sulfonimide ou une fraction phosphonate, et un élément quelconque parmi R1, R2, R3 et R4 ne comprenant pas l'une de ces fractions comprend un alkyle, un cycloalkyle, un thioéther, un sulfoxyde, une sulfone, un haloalkyle, un halogène, un nitrile, un imide, un pyrazole, ou des combinaisons associées. Les anthraquinones substituées répondent à la formule 1 tandis que les anthrahydroquinones substituées ont la structure réduite correspondante. Un ou plusieurs éléments parmi R1-R8 ont un sulfonate ou un phosphate attaché à l'anneau par un thioéther, une amine ou un éther comprenant au moins un groupe alkyle. Un élément quelconque parmi R1 à R8 qui ne contient pas l'une de ces fractions comprend un alkyle, un cycloalkyle, un thioéther, un sulfoxyde, une sulfone, un haloalkyle, un halogène, un hydroxyle, un alcoxyle, un éther, une amine, ou de l'hydrogène. Les hydroquinones substituées, les 1,4-quinones, les catéchols, les 1,2-quinones, les anthraquinones ou les anthrahydroquinones sont solubles dans l'eau, stables dans des solutions acides aqueuses et ont des potentiels de réduction utiles sous forme oxydée. Par conséquent, elles peuvent être utilisées comme médiateurs redox dans des technologies émergentes, telles que dans des piles à combustible à médiation ou des batteries à flux organique-médiateur.
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WO2021076847A1 (fr) * 2019-10-16 2021-04-22 American River Nutrition, Llc Compositions comprenant de la quinone et/ou du quinol et leurs procédés de préparation et d'utilisation
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EP3878837A1 (fr) 2020-03-11 2021-09-15 OM Pharma SA Dérivés d'hydroquinone 2,5- ou 2,6-disubstitutuées avec au moins un groupe carboxy, sulfo ou amido utiles comme médicaments
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