High-Solubility Thioether Quinones

Patent metadata

Field	Value
Publication number	US-2019055193-A1
Application number	US-201816150405-A
Country	US
Kind code	A1
Filing date	Oct 3, 2018
Priority date	Feb 28, 2017
Publication date	Feb 21, 2019
Grant date	—

Abstract

The substituted hydroquinones and quinones are soluble in water, stable in aqueous acid solutions, and have a high reduction potential in the oxidized form. Accordingly, they can be used as redox mediators in emerging technologies, such as in mediated fuel cells or organic-mediator flow batteries.

First claim

1 . A substituted hydroquinone having the formula:

wherein one, two, three, or all four of R 1 , R 2 , R 3 and R 4 comprise a thioether moiety and a sulfonate moiety, and wherein each R 1 , R 2 , R 3 and R 4 that does not comprise a thioether and a sulfonate moiety sulfonate moiety is independently a hydrogen, an alkyl, or an electron withdrawing group; or
the oxidized form (the substituted 1,4-benzoquinone form) of said substituted hydroquinone.

2 . The substituted hydroquinone or benzoquinone of claim 1 , wherein each of the one, two, three, or four of R 1 , R 2 , R 3 and R 4 that comprise a thioether moiety and a sulfonate moiety independently has the chemical structure —S(CH 2 ) n SO 3 − , wherein n is 1, 2, 3 or 4.

3 . (canceled)

4 . The substituted hydroquinone or benzoquinone of claim 1 , wherein one of R 1 , R 2 , R 3 and R 4 comprises a thioether moiety and a sulfonate moiety, and wherein the R 1 , R 2 , R 3 and R 4 that do not comprise a thioether and a sulfonate moiety are independently a hydrogen, an electron withdrawing group, or an alkyl.

5 . The substituted hydroquinone or benzoquinone of any claim 1 , wherein three or all four of R 1 , R 2 , R 3 and R 4 comprise a thioether moiety and a sulfonate moiety.

6 . The substituted hydroquinone or benzoquinone of claim 5 , wherein three of R 1 , R 2 , R 3 and R 4 comprise a thioether moiety and a sulfonate moiety, and wherein the R 1 , R 2 , R 3 and R 4 that does not comprise a thioether and a sulfonate moiety is an electron withdrawing group or an alkyl.

7 . The substituted hydroquinone or benzoquinone of claim 1 , wherein the electron withdrawing group is selected from the group consisting of nitrile (cyanide), an amide, a ketone, —CF 3 , —SF 5 , an imide, an imidazole, a benzimidazole, an oxazole, a benzoxazole, a thiazole, a benzthiazole, and a pyrazole.

8 . The substituted hydroquinone or benzoquinone of claim 5 , wherein all four of R 1 , R 2 , R 3 and R 4 comprise a thioether moiety and a sulfonate moiety.

9 . (canceled)

10 . The substituted hydroquinone or benzoquinone of claim 9 , wherein the hydroquinone form is selected from the group consisting of:

and other salts, esters, and acids thereof;

and other salts, esters, and acids thereof;

wherein X is a hydrogen, an electron withdrawing group, or an alkyl, and other salt, esters and acids thereof; and

wherein X is a hydrogen, an electron withdrawing group, or an alkyl, and other salts, esters and acids thereof.

11 . The substituted hydroquinone or benzoquinone of claim 10 , wherein the electron withdrawing group is selected from the group consisting of nitrile (cyanide), an amide, a ketone, —CF 3 , —SF 5 , an imide, an imidazole, a benzimidazole, an oxazole, a benzoxazole, a thiazole, a benzthiazole, and a pyrazole.

12 . (canceled)

13 . The substituted hydroquinone or benzoquinone of claim 9 , wherein the hydroquinone form is selected from the group consisting of:

wherein X is a hydrogen, an electron withdrawing group, or an alkyl, and other salt, esters and acids thereof; and

wherein X is a hydrogen, an electron withdrawing group, or an alkyl, and other salts, esters and acids thereof.

14 . The substituted hydroquinone or benzoquinone of claim 13 , wherein the electron withdrawing group is selected from the group consisting of nitrile (cyanide), an amide, a ketone, —CF 3 , —SF 5 , an imide, an imidazole, a benzimidazole, an oxazole, a benzoxazole, a thiazole, a benzthiazole, and a pyrazole.

15 . The substituted hydroquinone or benzoquinone of claim 13 , wherein X is methyl.

16 . A method of installing one or more thioether sulfonate moieties onto one or more unsubstituted carbon atoms of a hydroquinone or 1,4-benzoquinone ring, the method comprising the steps of:
(a) contacting a first 1,4-benzoquinone having a first unsubstituted carbon atom on the benzoquinone ring with a first mercaptoalkylsulfonate, whereby a first hydroquinone adduct having the corresponding first thioether sulfonate moiety installed onto the first unsubstituted carbon atom is formed; and (b) oxidizing the first hydroquinone adduct by applying an electric current to it, whereby a second 1,4 benzoquinone having the first thioether sulfonate moiety installed onto the first unsubstituted carbon atom is formed.

17 . The method of claim 16 , further comprising the step of oxidizing a hydroquinone having one or more unsubstituted carbon atoms on the hydroquinone ring to form the first 1,4-benzoquinone.

18 . The method of claim 16 , wherein the second 1,4 benzoquinone has a second unsubstituted carbon atoms on the benzoquinone ring, and wherein the method further comprises the steps of:
(c) contacting the second 1,4-benzoquinone with a second mercaptoalkylsulfonate, whereby a second hydroquinone adduct having the corresponding second thioether sulfonate moiety installed onto the second unsubstituted carbon atom is formed; and (d) oxidizing the second hydroquinone adduct by applying an electric current to it, whereby a third 1,4 benzoquinone having the second thioether sulfonate moiety installed onto the second unsubstituted carbon atom is formed.

19 . The method of claim 18 , wherein the third 1,4 benzoquinone has a third unsubstituted carbon atoms on the benzoquinone ring, and wherein the method further comprises the steps of:
(e) contacting the third 1,4-benzoquinone with a third mercaptoalkylsulfonate, whereby a third hydroquinone adduct having the corresponding third thioether sulfonate moiety installed onto the third unsubstituted carbon atom is formed; and (f) oxidizing the third hydroquinone adduct by applying an electric current to it, whereby a fourth 1,4 benzoquinone having the third thioether sulfonate moiety installed onto the third unsubstituted carbon atom is formed.

20 . The method of claim 19 , wherein the fourth 1,4 benzoquinone has a fourth unsubstituted carbon atoms on the benzoquinone ring, and wherein the method further comprises the step of:
(g) contacting the fourth 1,4-benzoquinone with a fourth mercaptoalkylsulfonate, whereby a fourth hydroquinone adduct having the corresponding fourth thioether sulfonate moiety installed onto the fourth unsubstituted carbon atom is formed.

21 . The method of claim 16 , wherein the first 1,4-benzoquinone is a 1,4-benzoquinone having four unsubstituted carbon atoms on the benzoquinone ring.

22 . The method of claim 16 , wherein the first 1,4-benzoquinone is a 1,4-benzoquinone having three unsubstituted carbon atoms and a carbon atom substituted with an electron withdrawing group on the benzoquinone ring.

23 .- 25 . (canceled)

26 . The method of claim 16 , wherein the

Assignees

• Wisconsin Alumni Res Found

Inventors

• Stahl Shannon S
• Gerken James B

Classifications

• C07D231/18

  One oxygen or sulfur atom · CPC title

• C07C309/42 Primary

  having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings · CPC title

• C07D487/04

  Ortho-condensed systems · CPC title

• C07D209/48

  with oxygen atoms in positions 1 and 3, e.g. phthalimide · CPC title

• C07D285/14

  condensed with carbocyclic rings or ring systems · CPC title