High-solubility thioether quinones

Patent metadata

Field	Value
Publication number	US-10597359-B2
Application number	US-201816150405-A
Country	US
Kind code	B2
Filing date	Oct 3, 2018
Priority date	Feb 28, 2017
Publication date	Mar 24, 2020
Grant date	Mar 24, 2020

Abstract

Substituted hydroquinones and quinones and methods of synthesizing such compounds are disclosed herein. The substituted hydroquinones have the formula:

while the substituted quinones have the corresponding oxidized structure (1,4-benzoquinones). 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. 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

We 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 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. 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.

4. The substituted hydroquinone or benzoquinone of 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.

5. The substituted hydroquinone or benzoquinone of claim 4 , 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.

6. 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.

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

8. The substituted hydroquinone or benzoquinone of claim 1 , wherein the hydroquinone form is selected from the group consisting of:

wherein X is a hydrogen, an electron withdrawing group, or an alkyl; and

wherein X is a hydrogen, an electron withdrawing group, or an alkyl.

9. The substituted hydroquinone or benzoquinone of claim 8 , 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.

10. The substituted hydroquinone or benzoquinone of claim 1 , wherein the hydroquinone form is selected from the group consisting of:

wherein X is a hydrogen, an electron withdrawing group, or an alkyl; and

wherein X is a hydrogen, an electron withdrawing group, or an alkyl.

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. The substituted hydroquinone or benzoquinone of claim 10 , wherein X is methyl.

Assignees

• Wisconsin Alumni Res Found

Inventors

• Stahl Shannon S
• Gerken James B

Classifications

• C07C319/14

  of sulfides · CPC title

• H01M8/188

  by recharging of redox couples containing fluids; Redox flow type batteries · 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

• C07D231/18

  One oxygen or sulfur atom · CPC title