REDOX-ACTIVE COMPOUNDS AND USES THEREOF

Abstract

The present invention relates to novel lignin-derived compounds and compositions comprising the same and their use as redox flow battery electrolytes. The invention further provides a method for preparing said compounds and compositions as well as a redox flow battery comprising said compounds and compositions. Additionally, an assembly for carrying out the inventive method is provided.

Claims

1-34. (canceled)

35. A compound characterized by any one of General Formulas (1)-(6): ##STR00094## ##STR00095## wherein, each R.sup.1-R.sup.8 in General Formula (1), each R.sup.1-R.sup.10 in General Formula (2), each R.sup.1-R.sup.4 in General Formula (3), each R.sup.1-R.sup.6 in General Formula (4), each R.sup.1-R.sup.6 in General Formula (5), and each R.sup.1-R.sup.8 in General Formula (6) is independently selected from —H, -Alkyl, -AlkylG.sup.a, -Aryl, —SO.sub.3H, —SO.sub.3.sup.−, —PO.sub.3H.sub.2, —OH, —OG.sup.a, —SH, -Amine, —NH.sub.2, —CHO, —COOH, —COOG.sup.a, —CN, —CONH.sub.2, —CONHG.sup.a, —CONG.sup.a.sub.2, -Heteroaryl, -Heterocycyl, NOG.sup.a, —N.sup.+OG.sup.a, —F, —C, and —Br, or are joined together to form a saturated or an unsaturated carbocycle, wherein the saturated or the unsaturated carbocycle is —H, -Alkyl, -AlkylG.sup.a, —SO.sub.3H/—SO.sub.3.sup.−, OG.sup.a, or —COOH; wherein each G.sup.a is independently selected from —H, -Alkyl, -AlkylG.sup.b, -Aryl, —SO.sub.3H, —SO.sub.3.sup.−, —PO.sub.3H.sub.2, —OH, —OAlkyl, —OOH, —OOAlkyl, —SH, —SAlkyl, —NH.sub.2, —NHAlkyl, —NAlkyl.sub.2, —NAlkyl.sub.3.sup.+, —NHG.sup.b, —NG.sup.b.sub.2, —NG.sup.b.sub.3.sup.+, —CHO, —COOH, —COOAlkyl, —CN, —CONH.sub.2, —CONHAlkyl, —CONAlkyl.sub.2, -Heteroaryl, -Heterocycyl, —NOG.sup.b, —N.sup.+OAlkyl, —F, —Cl, and —Br; wherein each G.sup.b is independently selected from —H, -Alkyl, -Aryl, —SO.sub.3H, —SO.sub.3.sup.−, —PO.sub.3H.sub.2, —OH, —OAlkyl, —OOH, —OOAlkyl, —SH, -SAlkyl, —NH.sub.2, —NHAlkyl, —NAlkyl.sub.2, —NAlkyl.sub.3.sup.+, —CHO, —COOH, —COOAlkyl, —CN, —CONH.sub.2, —CONHAlkyl, —CONAlkyl.sub.2, -Heteroaryl, -Heterocycyl, —N.sup.+OAlkyl, —F, —Cl, and Br.

36. The compound of claim 1, wherein 1-5; 2-5; 1, 3, or 4; or 3-4 of R.sup.1-R.sup.8 in General Formula (1), R.sup.1-R.sup.10 in General Formula (2), R.sup.1-R.sup.4 in General Formula (3), R.sup.1-R.sup.6 in General Formula (4), R.sup.1-R.sup.6 in General Formula (5), and R.sup.1-R.sup.8 in General Formula (6) are independently selected from Alkyl, -AlkylG.sup.a, -Aryl, —SO.sub.3H, —SO.sub.3.sup.−, —PO.sub.3H.sub.2, —OH, —OG.sup.a, —SH, -Amine, —NH.sub.2, —CHO, —COOH, —COOG.sup.a, —CN, —CONH.sub.2, —CONHG.sup.a, —CONG.sup.a.sub.2, -Heteroaryl, -Heterocycyl, NOG.sup.a, —N.sup.+OG.sup.a, —F, —Cl, and —Br, or are joined together to form a saturated or an unsaturated carbocycle, wherein the saturated or the unsaturated carbocycle is -Alkyl, -AlkylG.sup.a, —SO.sub.3H/—SO.sub.3.sup.−, —OG.sup.a, or —COOH; wherein each G.sup.a is independently selected from —H, -Alkyl, -AlkylG.sup.b, -Aryl, —SO.sub.3H, —SO.sub.3.sup.−, —PO.sub.3H.sub.2, —OH, —OAlkyl, —OOH, —OOAlkyl, —SH, —SAlkyl, —NH.sub.2, —NHAlkyl, —NAlkyl.sub.2, —NAlkyl.sub.2.sup.+, —NHG.sup.b, —NG.sup.b.sub.2, —NG.sup.b.sub.3.sup.+, —CHO, —COOH, —COOAlkyl, —CN, —CONH.sub.2, —CONHAlkyl, —CONAlkyl.sub.2, -Heteroaryl, Heterocycyl, —NOG.sup.b, —N.sup.+OAlkyl, —F, —Cl, and —Br; wherein each G.sup.b is independently selected from —H, -Alkyl, -Aryl, —SO.sub.3H, —SO.sub.3.sup.−, —PO.sub.3H.sub.2, —OH, —OAlkyl, —OOH, —OOAlkyl, —SH, -SAlkyl, —NH.sub.2, —NHAlkyl, —NAlkyl.sub.2, —NAlkyl.sub.3.sup.+, —CHO, —COOH, —COOAlkyl, —CN, —CONH.sub.2, —CONHAlkyl, —CONAlkyl.sub.2, -Heteroaryl, -Heterocycyl, —N.sup.+OAlkyl, —F, —Cl, and —Br.

37. A composition, comprising at least one or at least two compounds of claim 35.

38. The composition of claim 37, wherein the composition is an aqueous composition.

39. The composition of claim 37, wherein the composition comprises: (a) at least one compound according to Formula (1), preferably at least one compound of Formula (1) (b) (reduced state) and at least one corresponding compound of Formula (1) (a) (oxidized state); (b) at least one compound according to Formula (2), preferably at least one compound of Formula (2)(b) (reduced state) and at least one corresponding compound of Formula (2(a) (oxidized state); (c) at least one compound according to Formula (3), preferably at least one compound of Formula (3)(b) (reduced state) and at least one corresponding compound of Formula (3) (a) (oxidized state); (d) at least one compound according to Formula (4), preferably at least one compound of Formula (4) (b) (reduced state) and at least one corresponding compound of Formula (4) (a) (oxidized state); (e) at least one compound according to Formula (5), preferably at least one compound of Formula (5) (b) (reduced state) and at least one corresponding compound of Formula (5) (a) (oxidized state); and/or (f) at least one compound according to Formula (6), preferably at least one compound of Formula (6) (b) (reduced state) and at least one corresponding compound of Formula (6) (a) (oxidized state).

40. The composition of claim 39, wherein the composition comprises: (a) at least one compound of Formula (1) (b) (reduced state) and at least one corresponding compound of Formula (1) (a) (oxidized state); (b) at least one compound of Formula (2)(b) (reduced state) and at least one corresponding compound of Formula (2(a) (oxidized state); (c) at least one compound of Formula (3)(b) (reduced state) and at least one corresponding compound of Formula (3) (a) (oxidized state); (d) at least one compound of Formula (4) (b) (reduced state) and at least one corresponding compound of Formula (4) (a) (oxidized state); (e) at least one compound of Formula (5) (b) (reduced state) and at least one corresponding compound of Formula (5) (a) (oxidized state); and/or (f) at least one compound of Formula (6) (b) (reduced state) and at least one corresponding compound of Formula (6) (a) (oxidized state).

41. A method for preparing the compound of claim 1 or a composition comprising at least one of the compound of claim 1, comprising the steps of: (a) providing a starting material; (b) subjecting the starting material to a process suitable to obtain at least one low molecular weight precursor compound; (c) isolating and/or modifying at least one low molecular weight precursor compound; thereby obtaining at least one low molecular weight aromatic precursor compound; (d) subjecting the at least one low molecular weight precursor compound to a condensation reaction, ring expansion or 3-ring formation reaction, thereby obtaining a condensation product, an aromatic or aliphatic multi-ring system; and/or (e) subjecting the condensation product to a modification reaction, preferably wherein one or more substituents are introduced into the condensation product, or to a transformation reaction of an aliphatic compound into a multi-ring aromatic system, to obtain at least one substituted low molecular weight aromatic compound or a composition comprising the same; wherein the starting material is lignocellulosic material, crude oil, coal, or pure organic substances.

42. The method of claim 41, wherein the starting material is lignocellulosic material and the method comprises the followings steps: (1) subjecting lignocellulosic material to a pulping process; thereby obtaining modified lignin-derived components; (2) isolating the modified lignin-derived components; (3) subjecting the modified lignin-derived components to a chemical decomposition step; thereby obtaining decomposition products comprising or consisting of at least one low molecular weight precursor compound; (4) isolating at least one low molecular weight precursor compound; thereby obtaining at least one low molecular weight precursor compound or aromatic precursor compound; (4′) modifying the low molecular weight aromatic precursor compound, thereby obtaining at least one low molecular weight compound or at least one low molecular weight aromatic compound; (5) subjecting the at least one low molecular weight aromatic precursor compound or the at least one low molecular weight precursor compound to a condensation reaction, ring expansion or 3-ring formation reaction to obtain at least one condensation product; and (6) subjecting the at least one condensation product to a modification reaction, preferably wherein one or more substituents are introduced into the at least one precursor compound or condensation product, or to a transformation reaction of an aliphatic compound into a multi-ring aromatic system; thereby obtaining at least one substituted low molecular weight aromatic compound or a composition comprising the same.

43. The method of claim 42, wherein step (1) comprises the sub-steps of: (1.1) providing a lignocellulosic material; (1.2) subjecting the lignocellulosic material to (a) a Kraft process or (b) a sulfite process; and (1.3) separating the pulp from the process stream obtainable from the pulping process in sub-step (1.2).

44. The method of claim 42, wherein step (3) comprises: (a) oxidative cracking of the modified lignin-derived components in the presence of a heterogeneous or homogeneous catalyst, comprising a metal ion or a metalloid component; or (b) reductive cracking of the modified lignin-derived components in the presence of a heterogeneous or homogeneous catalyst, comprising a metal ion or metalloid component; or (c) subjecting the modified lignin-derived components to electro-oxidation in alkaline or acidic solution; or (d) non redox cracking of the modified lignin-derived components in the presence of a heterogeneous or homogeneous catalyst, comprising a metal ion or a metalloid component.

45. The method of claim 42, wherein the precursor compound(s) comprise at least one aromatic ring.

46. The method of claim 45, wherein the aromatic ring(s) is/are substituted in at least one position by a functional group, wherein at least one of these functional groups is alkoxy or hydroxyl.

47. The method of claim 45, wherein the at least one precursor compound is characterized by Formula I a: ##STR00096## wherein each of R.sup.1-R.sup.5 is independently selected from hydrogen; hydroxy; carboxy; amino; linear or branched substituted C.sub.1-6 alkyl; linear or branched, substituted, C.sub.1-6 alkenyl; linear or branched substituted C.sub.1-6 alcohol; linear or branched, substituted, C.sub.1-6 aminoalkyl; linear or branched substituted C.sub.1-6 carboxyalkyl; linear or branched substituted C.sub.1-6 alkoxy or C.sub.1-6 carboxyalkoxy; linear or branched substituted C.sub.1-6 aldehyde; carboxylic acids; substituted aryl; esters; oxo; or carbonyl, wherein at least one of R.sup.1, R.sup.3 or R.sup.5 is hydroxy or linear or branched substituted C.sub.1-6 alkoxy or C.sub.1-6 carboxyalkoxy; and wherein R.sup.6 is selected from the group consisting of hydrogen; hydroxy; linear or branched substituted C.sub.1-6 carboxyl; linear or branched C.sub.1-6 aldehyde; and linear or branched substituted C.sub.1-6 alcohol; or by Formula I b: ##STR00097## wherein each of R.sup.1-R.sup.9 is independently selected from hydrogen; hydroxy; carboxy; amino; linear or branched substituted C.sub.1-6 alkyl; linear or branched, substituted, C.sub.1-6 alkenyl; linear or branched substituted C.sub.1-6 alcohol; linear or branched substituted C.sub.1-6 aminoalkyl; linear or branched substituted C.sub.1-6 carboxyalkyl; linear or branched substituted C.sub.1-6 alkoxy or C.sub.1-6 carboxyalkoxy; linear or branched substituted C.sub.1-6 aldehyde; carboxylic acids; substituted aryl; esters; oxo or carbonyl; wherein R.sup.5 is hydroxy or linear or branched substituted C.sub.1-6 alkoxy; and R.sup.10 is selected from the group consisting of hydrogen; hydroxy; linear or branched substituted C.sub.1-6 carboxyl; linear or branched substituted C.sub.1-6 aldehyde; and linear or branched C.sub.1-6 alcohol.

48. The method according to claim 47, wherein the at least one precursor compound is selected from the group consisting of phenolic derivatives of biphenyl, benzylalcohol, benzaldehydes and benzoic acid, preferably derivatives of p-hydroxy benzylalcohol, p-hydroxy benzaldehydes and p-hydroxy benzoic acid or esters thereof, or, more preferably, vanillin, guaiacol, eugenol, syringol, phenol, syringaldehyde, vanillic acid and esters thereof, syringic acid and esters thereof and/or a derivative of any of the above, and/or a combination of the above.

49. The method of claim 42, wherein step (4) comprises the sub-steps of: (4.1) isolating the at least one precursor compound; (4.2) oxidizing the at least one precursor compound; and/or (4.3) purifying the at least one precursor compound.

50. The method according to claim 49, wherein oxidation step (4.2) comprises oxidizing the at least one precursor compound in the presence of (i) an oxidizing agent selected from the group consisting of H.sub.2O.sub.2, O.sub.2, and air, and (ii) a homogeneous or heterogeneous catalyst, comprising a metal ion or a metalloid component.

51. The method of claim 49, wherein the at least one precursor compound is a quinone or hydroquinone or phenazine precursor compound of any one of General Formulas I a, II a, II b, or III a-d: ##STR00098## ##STR00099## wherein each of R.sup.1-R.sup.5 in General Formula a, each of R.sup.1-R.sup.9 in General Formula II b, each of R.sup.1-R.sup.4 in General Formula III a, each of R.sup.2-R.sup.5 in General Formula III b, each of R.sup.1-R.sup.4 in General Formula III c, and each of R.sup.1-R.sup.9 in General Formula III d, is independently selected from hydrogen; hydroxy; amino; carboxy; linear or branched substituted C.sub.1-6 alkyl; linear or branched substituted C.sub.1-6 alkenyl; linear or branched substituted C.sub.1-6 alcohol; linear or branched substituted C.sub.1-6 aminoalkyl; linear or branched substituted C.sub.1-6 carboxyalkyl; linear or branched substituted C.sub.1-6 alkoxy or C.sub.1-6 carboxyalkoxy; linear or branched substituted C.sub.1-6 aldehyde; carboxylic acids; amino; esters; oxo or carbonyl; or wherein each of R.sup.1-R.sup.6 in General Formula I a is independently selected from hydrogen; hydroxy; carboxy; amino; linear or branched substituted C.sub.1-6 alkyl; linear or branched substituted C.sub.1-6 alkenyl; linear or branched substituted C.sub.1-6 alcohol; linear or branched substituted C.sub.1-6 aminoalkyl; linear or branched substituted C.sub.1-6 carboxyalkyl; linear or branched substituted C.sub.1-6 alkoxy or C.sub.1-6 carboxyalkoxy; linear or branched substituted C.sub.1-6 aldehyde; carboxylic acids; substituted aryl; esters; oxo; or carbonyl, wherein at least one of R.sup.1, R.sup.3 or R.sup.5 is hydroxy, amino or linear or branched substituted C.sub.1-6 alkoxy or C.sub.1-6 carboxyalkoxy; and wherein R.sup.6 is selected from the group consisting of hydrogen; hydroxy; linear or branched substituted C.sub.1-6 carboxyl; linear or branched C.sub.1-6 aldehyde; and linear or branched substituted C.sub.1-6 alcohol.

52. The method of claim 51, wherein in General Formula II a, R.sup.1-R.sup.3 is hydroxyl or at least one of R.sup.1-R.sup.3 is selected from the group consisting of hydroxyl, OMe, amino, carboxy, and CHO.

53. The method of claim 51, wherein in General Formula II b, R.sup.5 is hydroxyl.

54. The method of claim 51, wherein the at least one precursor compound is selected from the group consisting of phenolic derivatives of biphenyl, benzylalcohol, benzaldehydes and benzoic acid, derivatives of p-hydroxy benzylalcohol, p-hydroxy benzaldehydes and p-hydroxy benzoic acid or esters thereof, vanillin, guaiacol, eugenol, syringol, phenol, syringaldehyde, vanillic acid and esters thereof, syringic acid and esters thereof and/or a derivative of any of the above, and/or a combination of the above.

55. The method of claim 42, wherein the purification step (4.3) comprises an extraction method.

56. The method of claim 55, wherein the extraction method is solid phase extraction or fluid-fluid phase extraction method.

57. The method of claim 42, wherein the at least one quinone or hydroquinone precursor compound is further subjected to a transformation step (4.4), thereby obtaining an o-phenylenediamine precursor compound.

58. The method of claim 42, further comprising subjecting the at least one quinone or hydroquinone precursor compound to a condensation step (5), and a further purification step to obtain at least one condensation product.

59. The method according to claim 58, wherein the condensation step (5) comprises subjecting a quinone or hydroquinone precursor compound, obtained from step (4.1), (4.2) or (4.3), to a condensation reaction with an o-phenylenediamine precursor compound, obtained from step (4.4), to obtain at least one compound according to General Formula (1)-(6) of claim 1.

60. The method of claim 41, further comprising step (f) of modifying the at least one condensation product.

61. The method according to claim 60, wherein step (f) comprises introducing one or more substituents into the at least one condensation product, at a position of the aryl structure other than those characterized by an oxo or hydroxyl group, wherein the substituents are directly bound to the aryl structure or bound via an alkyl linker to the aryl structure, via a methyl linker.

62. The method according to claim 61, wherein the at least one substituent is each independently selected from Alkyl, -AlkylG.sup.a, -Aryl, —SO.sub.3H, —SO.sub.3.sup.−, —PO.sub.3H.sub.2, —OH, —OG.sup.a, —SH, -Amine, NH.sub.2; CHO, —COOH, —COOG.sup.a, —CN, —CONH.sub.2, —CONHG.sup.a, —CONG.sup.a.sub.2, -Heteroaryl, Heterocycyl, NOG.sup.a, —N.sup.+OG.sup.a, —F, —C, and —Br, or are joined together to form a saturated or unsaturated carbocycle, more preferably from -Alkyl, -AlkylG.sup.a, SO.sub.3H/—SO.sub.3.sup.−, —OG.sup.a, and —COOH; wherein each G.sup.a is independently selected from —H, -Alkyl, -AlkylG.sup.b, -Aryl, —SO.sub.3H, —SO.sub.3.sup.−, —PO.sub.3H.sub.2, —OH, —OAlkyl, —OOH, —OOAlkyl, —SH, —SAlkyl, —NH.sub.2, —NHAlkyl, —NAlkyl.sub.2, —NAlkyl.sub.3.sup.+, —NHG.sup.b, —NG.sup.b.sub.2, —NG.sup.b.sub.3.sup.+, —CHO, —COOH, —COOAlkyl, —CN, —CONH.sub.2, —CONHAlkyl, —CONAlkyl.sub.2, -Heteroaryl, Heterocycyl, —NOG.sup.b, —N.sup.+OAlkyl, —F, —Cl, and —Br; wherein each G.sup.b is independently selected from —H, -Alkyl, -Aryl, —SO.sub.3H, —SO.sub.3.sup.−, —PO.sub.3H.sub.2, —OH, —OAlkyl, —OOH, —OOAlkyl, —SH, -SAlkyl, —NH.sub.2, —NHAlkyl, —NAlkyl.sub.2, —NAlkyl.sub.3, —CHO, —COOH, —COOAlkyl, —CN, —CONH.sub.2, —CONHAlkyl, —CONAlkyl.sub.2, -Heteroaryl, Heterocycyl, —N.sup.+OAlkyl, —F, —Cl, and Br.

63. The method of claim 42, further comprising by its steps (5) or (6) a reaction selected from the group consisting of the following reactions: condensation of a substituted or unsubstituted 2-nitrophenol and a substituted or unsubstituted 2-aminophenol compound, a dimerization of substituted or unsubstituted 3,4-diamino-5-methoxybenzoic acid, a cyclization reaction of substituted or unsubstituted 4,4′-azanediylbis(3-methoxy-5-nitrobezoic acid), a dimerization of substituted or unsubstituted 2-aminocyclohexanones, a condensation substituted or unsubstituted 2,5-dihydroxybenzoquinone or substituted or unsubstituted 2-hydroxycyclohexa-2,5-diene-1,4-dione and substituted or unsubstituted 3,4-diaminobenzene-1-sulfonic acid, a dimerization of substituted or unsubstituted 4-nitrosophenols, a dimerization of substituted or unsubstituted methoxycyclohexanol, a dimerization of substituted or unsubstituted 3,4-dihydroxycyclohexane-1-carboxylic acid in the presence of ammonia, reaction of 3,4-dioxocyclohexa-1,5-diene-1-carboxylic acid with 3,4-diaminobenzoic acid, a condensation of substituted or unsubstituted 2-aminocyclobezoquinone with substituted or unsubstituted 3,4-diaminobezene-1-sulfonic acid, a condensation reaction of substituted or unsubstituted 2-methoxybenzoquinone with an amine, 2-(methylamino)ethan-1-ol and subsequent reaction with substituted or unsubstituted 2-amino-5-methoxycyclohexa-2,5-diene-1,4-dione or subsequent reaction with substituted or unsubstituted 3,4-diaminobezene-1-sulfonic acid, a dimerization of substituted or unsubstituted 2-aminobenzoquinones or 2-amino-6-methoxycyclohexa-2,5-diene-1,4-dione, a cyclization reaction of substituted or unsubstituted benzofuroxane, by reacting 7-methoxy-3-oxo-2,1,3λ.sup.5-benzoxadiazole-5-carboxylate with 2-methoxyhydroquinone or by reacting substituted or unsubstituted benzofuroxan with substituted or unsubstituted 2-methoxy-hydroquinone or by reacting benzofuroxane with substituted or unsubstituted 3,4-dihydroxybenzoic acid or by reacting 3-oxo-2,1,3λ.sup.5-benzoxadiazole-5-sulfonic acid with 2-methoxy-hydroquinone, reaction of substituted or unsubstituted 2-hydroxy-5-methoxycyclohexa-2,5-diene-1,4-dione and substituted or unsubstituted 3,4-diaminobenzene-1-sulfonic acid, treatment of substituted or unsubstituted vanillic acid under pressure with ammonia to yield substituted or unsubstituted 4,4′-azanediylbis(3-methoxybenzoic acid), reaction of substituted or unsubstituted 3,4-diaminobenzoic acid or substituted or unsubstituted 3,4-diamino-5-methoxy-benzoic acid with 2,5-dihydroxybenzoquinone, treatment of substituted or unsubstituted vanillic acid with sodium nitrite in the presence of acid, reaction of substituted or unsubstituted 3-(hydroxyimino)-5-methoxy-4-oxocyclohexa-1,5-diene-1-carboxylic acid with substituted or unsubstituted 3,4-diaminobenzene-1-sulfonic acid, dimerization of substituted or unsubstituted 3-amino-5-methoxy-4-oxocyclohexane-1-carboxylicacid, reaction of substituted or unsubstituted 3-amino-4-hydroxy-5-methoxybenzoic acid with substituted or unsubstituted 2,5-dihydroxybenzoquinone, reaction of substituted or unsubstituted 2-hydroxy-6-methoxy-3-oxo-3H-phenoxazine-8-carboxylic acid or 2-amino-4,6-dimethoxy-3-oxo-3H-phenoxazine-8-carboxylic acid or 1-methoxy-3H-phenoxazin-3-one with ammonia or a primary amine, dimerization of substituted or unsubstituted 5-aminovanillic acid, dimerization of substituted or unsubstituted Methyl 3-amino-4-hydroxy-5-methoxycyclohexane-1-carboxylate, dimerization of a substituted or unsubstituted 2-aminocyclohexanols, dimerization of a substituted or unsubstituted 2-aminocyclohexanones, and dimerization of substituted or unsubstituted Methyl 3-amino-5-methoxy-4-oxocyclohexane-1-carboxylate.

64. The method of claim 42, further comprising a step of isolating the at least one substituted compound or composition comprising the at least one compound.

65. The method of claim 42, further comprising after step (5)-(6) a step (7) of providing the obtained compound(s) or a composition as a redox flow battery electrolyte.

66. A compound or a composition comprising the compound, obtainable by a method of claim 42.

67. The compound or the composition of claim 66, wherein the compound is of any one of the Formulas (1)-(6).

68. A redox flow battery electrolyte solution, comprising the compound or the composition of claim 1 dissolved or suspended in a suitable solvent.

69. The redox flow battery electrolyte solution, wherein the solvent is water

70. A method of using the compound or the composition of claim 1 as a redox flow battery electrolyte.

71. A redox flow battery, comprising the substituted low molecular weight aromatic compound or the composition of claim 1.

72. The redox flow battery of claim 71, wherein the redox flow battery comprises a first electrolyte solution comprising a first redox active electrolyte; a first electrode in contact with the first electrolyte solution; a second electrolyte solution, comprising a second redox active electrolyte; a second electrode in contact with the second electrolyte solution; wherein one or both of the first and the second redox active electrolytes comprise at least one substituted low molecular weight aromatic compound or composition of claim 1.

Description

DESCRIPTION OF THE FIGURES

[0671] FIG. 1 shows synthesis steps of alloxazine-based electrolytes from benzoquinones.

[0672] FIG. 2 shows synthesis steps of alloxazine-based electrolytes from 2-hydroxyphenols or 2-methoxyphenols.

[0673] FIG. 3 shows electrochemical data for selected posolytes and negolytes, the negolytes being phenazin derivatives and the posolytes anorganic redox-active compounds based on.

EXAMPLES

[0674] The examples shown in the following are merely illustrative and shall describe the present invention in a further way. These examples shall not be construed to limit the present invention thereto. The following preparations and examples are given to enable those skilled in the art to more clearly understand and to practice the present invention. The present invention, however, is not limited in scope by the exemplified embodiments, which are intended as illustrations of single aspects of the invention only, and methods, which are functionally equivalent are within the scope of the invention. Indeed, various modifications of the invention in addition to those described herein will become readily apparent to those skilled in the art from the foregoing description, accompanying figures and the examples below. All such modifications fall within the scope of the appended claims.

Example 1: Synthesis of 7,8-Dihydroxyphenazine-2-Sulfonic Acid

[0675] 2,5-Dihydroxy-1,4-benzoquinone (8.1 g, 57.4 mmol) was added to 150 mL boiling water, then 3,4-diaminobenezenesulfonic acid (10.8 g, 57.4 mmol) was added within a few minutes. The brown suspension was stirred at 95° C. for 18 h, cooled to room temperature and 150 mL acetone were added to the reaction mixture. After filtration the product was obtained as a brown solid (14.1 g, 84%).

Example 2: Synthesis of 7,8-Dihydroxyphenazine-2-Carboxylic Acid

[0676] 2,5-Dihydroxy-1,4-benzoquinone (2.8 g, 20 mmol) was added to 100 mL boiling water, then 3,4-diaminobenzoic acid (3.1 g, 20 mmol) acid was added within a few minutes. The brown suspension was stirred at 95° C. for 18 h, cooled to room temperature and 150 mL acetone was added to the reaction mixture. After filtration the product was obtained in a quantitative yield.

Example 3: Synthesis of 2,3-Dihydroxyphenazine

[0677] 2,5-Dihydroxy-1,4-benzoquinone (4.0 g, 28.5 mmol) was added to 100 mL boiling water, then 1,2-phenylenediamine (3.1 g, 28.5 mmol) was added within a few minutes. The brown suspension was stirred at 80° C. for 18 h, cooled to room temperature and 130 mL acetone were added to the reaction mixture. After filtration the product was obtained in a quantitative yield.

Example 4: Synthesis of Phenazine and 2,3-Dihydroxyphenazine

[0678] 1,2-Dihydoxybenzene (0.3 g, 2.8 mmol) and 1,2-phenylenediamine (0.3 g, 2.8 mmol) were heated in a microwave vial to 210° C. for 15 minutes. The melt solidified, was cooled to room temperature and washed several times with water. The insoluble product (0.2 g) contained phenazine and 2,3-dihydroxyphenazine according to HPLC and absorption spectroscopy. Washing the product mixture with 2 M aqueous sodium hydroxide yielded the desired phenazine.

Example 5

[0679] ##STR00059##

[0680] A method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a dimerization of 2-amino cyclohexanones. In some embodiments, vanillic acid is nitrated (reaction 1.1) with but not limited to nitric acid in combination with or without nitrous acid under cooling at least at 0° C., at least 10° C., at least 20° C. under room temperature, or under heating at least at 30° C., at least 40° C., at least 50° C., at least 60° C., at least 70° C., at least 80° C., at least 90° C., at least 100° C., at least 110° C., at least 120° C., at least 130° C., at least 140° C., at least 150° C. Then, 4-hydroxy-3-methoxy-5-nitrobenzoic acid is reacted with an alcohol such as but not limited to methanol (reaction 1.2) in some embodiments, in the presence of a catalyst, such as but not limited to H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, CH.sub.3COOH between 20-150° C., preferably between 20-100° C. most preferably between 30-70° C., to give methyl 4-hydroxy-3-methoxy-5-nitrobenzoate.

[0681] Methyl 4-hydroxy-3-methoxy-5-nitrobenzoate is reduced to methyl 3-amino-4-hydroxy-5-methoxybenzoate (reaction 1.3) by treatment with an reducing agent such as SnCl.sub.2 in water/methanol mixture, or with iron in ammonium chloride solution, or with iron in acetic acid/ethanol mixture, or with zinc in ammonium chloride solution, or by hydrogenation with a catalyst such as but not limited to Pd, Pt, Ni, Rh or Ru between 20-150° C., preferably between 20-100° C. Methyl 3-amino-4-hydroxy-5-methoxybenzoate is hydrogenated to methyl 3-amino-5-methoxy-4-oxocyclohexane-1-carboxylate (reaction 1.4) using doped catalyst such as but not limited to Pd, Pt, Ni, Co, Rh or Ru under 10-200 bar H.sub.2, preferably 10-100 bar H.sub.2 pressure between 50-250° C., preferably between 80-200° C. In some embodiments, reaction 1.3 and 1.4 are combined to a single hydrogenation reaction. Methyl 3-amino-5-methoxy-4-oxocyclohexane-1-carboxylate is then dimerized to dimethyl 4,9-dimethoxy-1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylate (reaction 1.5) by treatment optionally in the presence of a catalyst such as but not limited to trifluoroacetic acid, H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, acetic acid, p-toluenesulfonic acid between 0-100° C., preferably 0-50° C., more preferably between 10-30° C. In some embodiments, the reaction 1.5 is spontaneously.

[0682] Dimethyl 4,9-dimethoxy-1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylate is converted to 4,9-dimethoxyphenazine-2,7-dicarboxylic acid (reaction 1.6) by treatment with a catalyst such as but not limited to palladium on carbon between 50-300° C., preferably 100-200° C. Finally, dimethyl 4,9-dimethoxyphenazine-2,7-dicarboxylate is hydrolyzed to 4,9-dimethoxyphenazine-2,7-dicarboxylic acid (reaction 1.7) by treatment with aqueous alkaline solution at 20-120° C., preferably 20-90° C.

Example 6

[0683] ##STR00060##

[0684] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a dimerization of 2-amino cyclohexanones. In some embodiments, vanillic acid is reacted with an alcohol such as but not limited to methanol (reaction 2.1) in some in the presence of a catalyst, such as but not limited to H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, CH.sub.3COOH between 20-150° C., preferably between 20-100° C. most preferably between 30-70° C. to give methyl 4-hydroxy-3-methoxybenzoate. Methyl 4-hydroxy-3-methoxybenzoate is nitrated (reaction 2.2) with but not limited to nitric acid in combination with or without nitrous acid under cooling at least at 0° C., at least 10° C., at least 20° C. under room temperature, or under heating at least at 30° C., at least 40° C., at least 50° C., at least 60° C., at least 70° C., at least 80° C., at least 90° C., at least 100° C., at least 110° C., at least 120° C., at least 130° C., at least 140° C., at least 150° C.

[0685] Then, methyl 4-hydroxy-3-methoxy-5-nitrobenzoate is hydrogenated to methyl 3-amino-5-methoxy-4-oxocyclohexane-1-carboxylate (reaction 2.3) using doped catalyst such as but not limited to Pd, Pt, Ni, Rh or Ru under 10-200 bar H.sub.2, preferably 10-100 bar H.sub.2 pressure between 50-250° C., preferably between 80-200° C. Methyl 3-amino-5-methoxy-4-oxocyclohexane-1-carboxylate is then dimerized to dimethyl 4,9-dimethoxy-1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylate (reaction 2.4) by treatment optionally in the presence of a catalyst such as but not limited to trifluoroacetic acid, H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, acetic acid, p-toluenesulfonic acid between 0-100° C., preferably 0-50° C., most preferably between 10-30° C. In some embodiments, the reaction 1.5 is spontaneously. Dimethyl 4,9-dimethoxy-1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylate is converted to 4,9-dimethoxyphenazine-2,7-dicarboxylic acid (reaction 2.5) by treatment with a catalyst such as but not limited to palladium on carbon between 50-300° C., preferably 100-200° C. Finally, dimethyl 4,9-dimethoxyphenazine-2,7-dicarboxylate is hydrolyzed to 4,9-dimethoxyphenazine-2,7-dicarboxylic acid (reaction 2.6) by treatment with aqueous alkaline solution at 20-120° C., preferably 20-90° C.

Example 7

[0686] ##STR00061##

[0687] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a dimerization of 2-amino cyclohexanol. In some embodiments, vanillic acid is reacted with an alcohol such as but not limited to methanol (reaction 3.1) in some embodiments, in the presence of a catalyst, such as but not limited to H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, CH.sub.3COOH between 20-150° C., preferably between 20-100° C. most preferably between 30-70° C. to give methyl 4-hydroxy-3-methoxybenzoate. Methyl 4-hydroxy-3-methoxybenzoate is nitrated (reaction 3.2) with but not limited to nitric acid in combination with or without nitrous acid under cooling at least at 0° C., at least 10° C., at least 20° C. under room temperature, or under heating at least at 30° C., at least 40° C., at least 50° C., at least 60° C., at least 70° C., at least 80° C., at least 90° C., at least 100° C., at least 110° C., at least 120° C., at least 130° C., at least 140° C., at least 150° C. Then methyl 4-hydroxy-3-methoxy-5-nitrobenzoate is hydrogenated to methyl 3-amino-4-hydroxy-5-methoxycyclohexane-1-carboxylate (reaction 3.3) using a transition metal catalyst such as but not limited to Pd, Pt, Ni, Rh or Ru under 10-200 bar H.sub.2, preferably 10-100 bar H.sub.2 pressure between 50-250° C., preferably between 80-200° C. Methyl 3-amino-4-hydroxy-5-methoxycyclohexane-1-carboxylate is then dimerized to dimethyl 4,9-dimethoxy-1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylate (reaction 3.4) in the presence of an oxidation agent such as but not limited to O.sub.2, H.sub.2O.sub.2, sodium hypochlorite, cerium ammonium nitrate or potassium permanganate and optionally an catalyst.

[0688] Dimethyl 4,9-dimethoxy-1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylate is converted to 4,9-dimethoxyphenazine-2,7-dicarboxylic acid (reaction 3.5) by treatment with a catalyst such as but not limited to palladium on carbon between 50-300° C., preferably 100-200° C. Finally, dimethyl 4,9-dimethoxyphenazine-2,7-dicarboxylate is hydrolyzed to 4,9-dimethoxyphenazine-2,7-dicarboxylic acid (reaction 3.6) by treatment with aqueous alkaline solution at 20-120° C., preferably 20-90° C.

Example 8

[0689] ##STR00062##

[0690] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: transformation of a phenoxazine to a phenazine. In some embodiments, 3-amino-4-hydroxy-5-methoxybenzoic acid is reacted with 2,5-dihydroxybenzoquinone (reaction 4.1) in a solvent such as but not limited to water, methanol, ethanol, acetonitrile or DMF under cooling at least at 0° C., at least 10° C., at least 20° C. under room temperature, or under heating at least at 30° C., at least 50° C., at least 80° C., at least 100° C., at least 120° C., at least 150° C. to give 2-hydroxy-6-methoxy-3-oxo-3H-phenoxazine-8-carboxylic acid. 2-hydroxy-6-methoxy-3-oxo-3H-phenoxazine-8-carboxylic acid is then reacted with ammonia (R═H) or primary amine (reaction 4.2) between 20-250° C., preferably between 50-200° C. and at 0-150 bar preferably 0-100 bar.

##STR00063##

[0691] In some embodiments, 5-Aminovanillic acid is dimerized to 2-amino-4,6-dimethoxy-3-oxo-3H-phenoxazine-8-carboxylic (reaction 4.3) in the presence of an oxidant, such as but not limited to 02, H.sub.2O.sub.2, sodium hypochlorite, cerium ammonium nitrate, potassium permanganate or manganese dioxide and optionally a catalyst such as but not limited to potassium iodide, sodium tungstate, CuAlO(OH), or cupper chloride between 20-200° C. preferably 20-120° C. Subsequently 2-amino-4,6-dimethoxy-3-oxo-3H-phenoxazine-8-carboxylic acid is reacted with ammonia (R═H) or primary amine (reaction 4.4) between 20-250° C., preferably between 50-200° C. and at 0-150 bar preferably 0-100 bar.

##STR00064##

[0692] In some embodiments, 2-aminophenol acid is reacted with 2,6-dimethoxybenzoquinone (reaction 4.5) in the presence of a catalyst such as, but not limited to sulfuric acid, hydrochloric acid, phosphoric acid or organic acids such as acetic acid. At temperatures between 0-200° C. preferably between 20 to 120° C. Subsequently 1-methoxy-3H-phenoxazin-3-one was reacted with ammonia (R═H) or primary amine (reaction 4.6) between 20-250° C., preferably between 50-200° C. and at 0-150 bar preferably 0-100 bar.

Example 9

[0693] ##STR00065##

[0694] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a treatment of monomers with sodium nitrite. In some embodiments, vanillic acid is treated with sodium nitrite (reaction 5.1) in presence of acid such as but not limited to sulfuric acid, hydrochloric acid, phosphoric acid or organic acids such as acetic acid in water or an alcohol to yield 3-(hydroxyimino)-5-methoxy-4-oxocyclohexa-1,5-diene-1-carboxylic acid. 3-(hydroxyimino)-5-methoxy-4-oxocyclohexa-1,5-diene-1-carboxylic acid is then reacted with 3,4-diaminobenzene-1-sulfonic acid (reaction 5.2) between 0-200° C., preferably between 20-140° C. to give 4-methoxy-7-sulfophenazine-2-carboxylic acid.

##STR00066##

[0695] In some embodiments, 3-(hydroxyimino)-5-methoxy-4-oxocyclohexa-1,5-diene-1-carboxylic acid is hydrogenated to 3-amino-5-methoxy-4-oxocyclohexane-1-carboxylic acid (reaction 5.3) using doped catalyst such as but not limited to Pd, Pt, Ni, Rh or Ru under 10-200 bar H.sub.2, preferably 10-100 bar H.sub.2 pressure between 50-250° C., preferably between 80-200° C. 3-amino-5-methoxy-4-oxocyclohexane-1-carboxylic acid is then dimerized to 4,9-dimethoxy-1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylic acid (reaction 5.4) by treatment optionally in the presence of a catalyst such as but not limited to trifluoroacetic acid, H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, acetic acid, p-toluenesulfonic acid between 0-100° C., preferably 0-50° C., most preferably between 10-30° C. In some embodiments, the reaction 1.5 is spontaneous. 4,9-dimethoxy-1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylic is converted to 4,9-dimethoxyphenazine-2,7-dicarboxylic acid (reaction 5.5) by treatment with a catalyst such as but not limited to palladium on carbon between 50-300° C., preferably 100-200° C.

Example 10

[0696] ##STR00067##

[0697] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a treatment of monomers with ammonia under pressure. In some embodiments, vanillic acid is treated with ammonia (reaction 6.1) at 10-300 bar, preferably at 10-200 bar, more preferably at 10-50 bar, optionally in the presence of catalyst such as but not limited to Mo, W, Ir, RU, Pd, Pt, aluminum oxide, H-151 alumina, palladium on carbon, zeolite, copper (1) oxide at 30-400° C., preferably at 50-200° C. to give 3,4-diaminobenzoic acid. Then 3,4-diaminobenzoic acid is reacted with 2,5-dihydroxybenzoquinone (reaction 6.2) at 20-200° C., preferably at 40-120° C. to give 7,8-dihydroxyphenazine-2-carboxylic acid.

##STR00068##

[0698] In some embodiments, vanillic acid is treated with ammonia (reaction 6.3) at 10-300 bar, preferably at 10-200 bar, more preferably at 10-50 bar, optionally in the presence of catalyst such as but not limited to Mo, W, Ir, Ru, Pd, Pt, aluminum oxide, H-151 alumina, palladium on carbon, zeolite, copper (I) oxide at 30-400° C., preferably at 40-300° C., most preferably at 50-200° C. to give 3,4-diaminobenzoic acid. Then, 4-amino-3-methoxybenzoic acid is nitrated (reaction 6.4) with but not limited to nitric acid in combination with or without nitrous acid under cooling at least at 0° C., at least 10° C., at least 20° C. under room temperature, or under heating at least at 30° C., at least 50° C., at least 70° C., at least 100° C., at least 120° C., at least 150° C. to give 4-amino-3-methoxy-5-nitrobenzoic acid. 4-amino-3-methoxy-5-nitrobenzoic acid is reduced to 3,4-diamino-5-methoxybenzoic acid (reaction 6.5) by treatment with an reducing agent such as SnCl.sub.2 in water/methanol mixture, or with iron in ammonium chloride solution, or with iron in acetic acid/ethanol mixture, or with zinc in ammonium chloride solution, or by hydrogenation with a catalyst such as but not limited to Pd, Pt, Ni, Rh or Ru between 20-150° C., preferably between 20-100° C. 3,4-diamino-5-methoxybenzoic acid is reacted with 2,5-dihydroxybenzoquinone (reaction 6.6) at 20-200° C., preferably at 40-120° C. to give 7,8-dihydroxy-4-methoxyphenazine-2-carboxylic acid.

Example 11

[0699] ##STR00069##

[0700] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a treatment of monomers with ammonia under pressure. In some embodiments, vanillic acid is treated with ammonia (reaction 7.1) at 10-300 bar, preferably at 10-200 bar, more preferably at 10-100 bar, optionally in the presence of catalyst such as but not limited to Mo, W, Ir, Ru, Pd, Pt, aluminum oxide, H-151 alumina, palladium on carbon, zeolite, copper (1) oxide at 30-400° C., preferably at 50-300° C. to give 4,4′-azanediylbis(3-methoxybenzoic acid). 4,4′-azanediylbis(3-methoxybenzoic acid) is then nitrated (reaction 7.2) with but not limited to nitric acid in combination with or without nitrous acid under cooling at least at 0° C., at least 10° C., at least 20° C. under room temperature, or under heating at least at 30° C., at least 50° C., at least 70° C., at least 100° C., at least 120° C., at least 150° C. to give 4-(4-carboxy-2-methoxyanilino)-3-methoxy-5-nitrobenzoic acid. 4-(4-carboxy-2-methoxyanilino)-3-methoxy-5-nitrobenzoic acid is reduced to 3-amino-4-(4-carboxy-2-methoxyanilino)-5-methoxybenzoic acid (reaction 7.3) by treatment with an reducing agent such as SnCl.sub.2 in water/methanol mixture, or with iron in ammonium chloride solution, or with iron in acetic acid/ethanol mixture, or with zinc in ammonium chloride solution, or by hydrogenation with a catalyst such as but not limited to Pd, Pt, Ni, Rh or Ru between 20-150° C., preferably between 20-100° C. 3-amino-4-(4-carboxy-2-methoxyanilino)-5-methoxybenzoic acid is cyclized to 4-methoxyphenazine-2,7-dicarboxylic (reaction 7.4) acid in the presence of an oxidation reagent such as, but not limited to oxygen, hydrogen peroxide, PhI(OAc).sub.2, sodium periodate, sodium hypochlorite, cerium ammonium nitrate, MnO.sub.2, KMnO.sub.4, optionally with a catalyst at 20-150° C., preferably 20-100° C.

Example 12

[0701] ##STR00070##

[0702] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: transformation of vanillin to 2-methoxyhydroquinone (reaction 8.1) by treatment with hydrogen peroxide and base at 0-60° C., preferably between 25-40° C. 2-methoxyhydroquinone is oxidized to 2-methoxy-5-hydroxybenzoquinone (reaction 8.2) with an oxidation agent such as but not limited to oxygen, hydrogen peroxide, manganese dioxide, sodium hypochlorite, cerium ammonium nitrate or potassium permanganate optionally in the presence of a catalyst.

[0703] In some embodiments, 2-Methoxybenzoquinone is reacted with acetic anhydride (reaction 8.3) in the presence of acid such as but not limited to sulfuric acid, hydrochloric acid, phosphorus acid, triflic acid or organic acids such as acetic acid to give 5-methoxybenzene-1,2,4-triyl triacetate. 5-methoxybenzene-1,2,4-triyl triacetate is treated with acidic or alkaline aqueous, methanolic or acetone solution to yield 5-methoxybenzene-1,2,4-triol (reaction 8.4). 5-methoxybenzene-1,2,4-triol was oxidized to 2-hydroxy-5-methoxycyclohexa-2,5-diene-1,4-dione (reaction 8.5) in the presence of oxidation agent such as but not limited to oxygen, hydrogen peroxide, manganese dioxide, sodium hypochlorite, cerium ammonium nitrate or potassium permanganate optionally in the presence of a catalyst. Then 2-hydroxy-5-methoxycyclohexa-2,5-diene-1,4-dione was reacted with 3,4-diaminobenzene-1-sulfonic acid (reaction 8.6) at 20-200° C., preferably between 30-100° C. to give 8-hydroxy-7-methoxyphenazine-2-sulfonic acid.

Example 13

[0704] ##STR00071##

[0705] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a cyclization reaction with benzofuroxanes. In some embodiments, Benzofuroxan is reacted with 2-methoxyhydroquinone (reaction 9.1) in the presence of a base such as but not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethyl amine or sodium methylate at 0-120° C., preferably between 20-80° C. to yield 3-methoxy-5,10-dioxo-phenazin-2-ol. 3-methoxy-5,10-dioxo-phenazin-2-ol is reduced to 3-methoxyphenazin-2-ol (reaction 9.2) by treatment with reagents such as but not limited to trifluoroacetic anhydride and sodium iodide in acetonitrile at rt, or titanium(IV)-chloride and tin(II)-chloride in acetonitrile at rt, or titanium(IV)-chloride and sodium iodide in acetonitrile at 30° C., or aqueous sodium hydrosulfite and sodium hydroxide at rt, or zinc in aqueous sodium hydroxide solution, or tin(II)-chloride in hydrochloric acid, or by catalytic reduction with sodium hydrophosphite over palladium on carbon (5%) in THF/water at rt, or by hydrogenation with catalytic palladium on charcoal (10% Pd) or Raney nickel (2-10%) under hydrogen (1-5 bar) in EtOH or MeOH.

##STR00072##

[0706] In some embodiments, benzofuroxan is reacted with 3,4-dihydroxybenzoic acid (reaction 9.3) in the presence of a base such as but not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethyl amine or sodium methylate at 0-120° C., preferably between 20-80° C. to yield the mixture of 4-hydroxy-5,10-dioxo-phenazine-2-carboxylic acid and 4-hydroxy-5,10-dioxo-phenazine-1-carboxylic acid. The mixture of 4-hydroxy-5,10-dioxo-phenazine-2-carboxylic acid and 4-hydroxy-5,10-dioxo-phenazine-1-carboxylic acid was reduced to 4-hydroxyphenazine-2-carboxylic acid and 4-hydroxyphenazine-1-carboxylic acid (reaction 9.4) by treatment with reagents such as but not limited to trifluoroacetic anhydride and sodium iodide in acetonitril at rt, or titanium(IV)-chloride and tin(li)-chloride in acetonitrile at rt, or titanium(IV)-chloride and sodium iodide in acetonitrile at 30° C., or aqueous sodium hydrosulfite and sodium hydroxide at rt, or zinc in aqueous sodium hydroxide solution, or tin(II)-chloride in hydrochloric acid, or by catalytic reduction with sodium hydrophosphite over palladium on carbon (5%) in THE/water at rt, or by hydrogenation with catalytic palladium on charcoal (10% Pd) or Raney nickel (2-10%) under hydrogen (1-5 bar) in EtOH or MeOH.

##STR00073##

[0707] In some embodiments, 4-amino-3-methoxy-5-nitrobenzoic acid was oxidized with an oxidation agent (reaction 9.5) such as but not limited to sodium hypochlorite in alkaline solution at 0-100° C. preferably at 10-60° C. or with Phi(OAc).sub.2 at 20-80° C. to give 7-methoxy-3-oxo-2,1,3λ.sup.5-benzoxadiazole-5-carboxylic acid. Then 7-methoxy-3-oxo-2,1,3λ.sup.5-benzoxadiazole-5-carboxylic acid was reacted with 2-methoxyhydroquinone (reaction 9.6) in the presence of a base such as but not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethyl amine or sodium methylate at 0-120° C., preferably between 20-80° C. to yield 8-hydroxy-4,7-dimethoxy-5,10-dioxo-phenazine-2-carboxylic acid. 8-hydroxy-4,7-dimethoxy-5,10-dioxo-phenazine-2-carboxylic acid was reduced to 8-hydroxy-4,7-dimethoxyphenazine-2-carboxylic acid (reaction 9.7) by treatment with reagents such as but not limited to trifluoroacetic anhydride and sodium iodide in acetonitril at rt, or titanium(IV)-chloride and tin(II)-chloride in acetonitrile at rt, or titanium(IV)-chloride and sodium iodide in acetonitrile at 30° C., or aqueous sodium hydrosulfite and sodium hydroxide at rt, or zinc in aqueous sodium hydroxide solution, or tin(l)-chloride in hydrochloric acid, or by catalytic reduction with sodium hydrophosphite over palladium on carbon (5%) in THE/water at rt, or by hydrogenation with catalytic palladium on charcoal (10% Pd) or Raney nickel (2-10%) under hydrogen (1-5 bar) in EtOH or MeOH.

##STR00074##

[0708] In some embodiments, 2-Nitroaniline was converted to 4-amino-3-nitrobenzene-1-sulfonic acid (reaction 9.8) by treatment with sulfuric acid or oleum at 30-200° C., preferably 50-120° C. The resulting 4-amino-3-nitrobenzene-1-sulfonic acid is oxidized with an oxidation agent (reaction 9.9) such as but not limited to sodium hypochlorite in alkaline solution at 0-100° C. preferably at 10-60° C. or with PhI(OAc).sub.2 at 20-80° C. to give 3-oxo-2,1,3λ.sup.5-benzoxadiazole-5-sulfonic acid. 3-oxo-2,1,3λ.sup.5-benzoxadiazole-5-sulfonic acid was reacted with 2-methoxyhydroquinone (reaction 9.10) in the presence of a base such as but not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethyl amine or sodium methylate at 0-120° C., preferably between 20-80° C. to yield 8-hydroxy-7-methoxy-5,10-dioxo-5λ.sup.5,10λ.sup.5-phenazine-2-sulfonic acid. 8-hydroxy-7-methoxy-5,10-dioxo-5λ.sup.5,10λ.sup.5-phenazine-2-sulfonic acid was reduced to 8-hydroxy-7-methoxyphenazine-2-sulfonic acid (reaction 9.11) by treatment with reagents such as but not limited to trifluoroacetic anhydride and sodium iodide in acetonitril at rt, or titanium(IV)-chloride and tin(II)-chloride in acetonitrile at rt, or titanium(IV)-chloride and sodium iodide in acetonitrile at 30° C., or aqueous sodium hydrosulfite and sodium hydroxide at rt, or zinc in aqueous sodium hydroxide solution, or tin(II)-chloride in hydrochloric acid, or by catalytic reduction with sodium hydrophosphite over palladium on carbon (5%) in THF/water at rt, or by hydrogenation with catalytic palladium on charcoal (10% Pd) or Raney nickel (2-10%) under hydrogen (1-5 bar) in EtOH or MeOH.

Example 14

[0709] ##STR00075##

[0710] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a cyclization reaction with benzofuroxanes. In some embodiments, Methyl 4-hydroxy-3-methoxybenzoate is nitrated (reaction 10.1) with but not limited to nitric acid in combination with or without nitrous acid under cooling at least at 0° C., at least 10° C., at least 20° C. under room temperature, or under heating at least at 30° C., at least 50° C., at least 70° C., at least 100° C., at least 120° C., at least 150° C. Methyl 4-hydroxy-3-methoxy-5-nitrobenzoate is reacted with ammonia in water or methanol at 50-300° C., preferably 100-200° C. to give methyl 4-amino-3-methoxy-5-nitrobenzoate (reaction 10.2). Methyl 4-hydroxy-3-methoxy-5-nitrobenzoate is oxidized with an oxidation agent (reaction 10.3) such as but not limited to sodium hypochlorite in alkaline solution at 0-100° C. preferably at 10-60° C. or with PhI(OAc).sub.2 at 20-80° C. to give methyl 7-methoxy-3-oxo-2,1,3λ.sup.5-benzoxadiazole-5-carboxylate. 7-methoxy-3-oxo-2,1,3λ.sup.5-benzoxadiazole-5-carboxylate is reacted with 2-methoxyhydroquinone (reaction 10.4) was reacted with 2-methoxyhydroquinone (reaction 10.4) in the presence of a base such as but not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethyl amine or sodium methylate at 0-120° C., preferably between 20-80° C. to yield methyl 8-hydroxy-4,7-dimethoxy-5,10-dioxo-5λ.sup.5,10λ.sup.5-phenazine-2-carboxylate. Methyl 8-hydroxy-4,7-dimethoxy-5,10-dioxo-5λ.sup.5,10λ.sup.5-phenazine-2-carboxylate was reduced to methyl 8-hydroxy-4,7-dimethoxyphenazine-2-carboxylate (reaction 10.5) by treatment with reagents such as but not limited to trifluoroacetic anhydride and sodium iodide in acetonitril at rt, or titanium(V)-chloride and tin(II)-chloride in acetonitrile at rt, or titanium(IV)-chloride and sodium iodide in acetonitrile at 30° C., or aqueous sodium hydrosulfite and sodium hydroxide at rt, or zinc in aqueous sodium hydroxide solution, or tin(II)-chloride in hydrochloric acid, or by catalytic reduction with sodium hydrophosphite over palladium on carbon (5%) in THE/water at rt, or by hydrogenation with catalytic palladium on charcoal (10% Pd) or Raney nickel (2-10%) under hydrogen (1-5 bar) in EtOH or MeOH. Methyl 8-hydroxy-4,7-dimethoxyphenazine-2-carboxylate was hydrolized to 8-hydroxy-4,7-dimethoxyphenazine-2-carboxylic acid by treatment with alkaline aqueous solution at 20-100° C., preferably 20-70° C.

Example 15

[0711] ##STR00076##

[0712] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, comprising: a dimerization of 2-aminocyclobenzoquinones. In some embodiments, Vanillin is nitrated (reaction 11.1) with but not limited to nitric acid in combination with or without nitrous acid under cooling at least at 0° C., at least 10° C., at least 20° C. under room temperature, or under heating at least at 30° C., at least 50° C., at least 70° C., at least 100° C., at least 120° C., at least 150° C. 4-hydroxy-3-methoxy-5-nitrobenzaldehyde was reduced to 3-amino-4-hydroxy-5-methoxybenzaldehyde (reaction 11.2)) by treatment with an reducing agent such as SnCl.sub.2 in water/methanol mixture, or with iron in ammonium chloride solution, or with iron in acetic acid/ethanol mixture, or with zinc in ammonium chloride solution, or by hydrogenation with a catalyst such as but not limited to Pd, Pt, Ni, Rh or Ru between 20-150° C., preferably between 20-100° C. 3-amino-4-hydroxy-5-methoxybenzaldehyde is oxidized to 2-amino-6-methoxybenzene-1,4-diol (reaction 11.3) with hydrogen peroxide solution in presence of base such as but not limited to sodium hydroxide or potassium hydroxide or by sodium percarbonate solution. In some embodiments, 4-hydroxy-3-methoxy-5-nitrobenzaldehyde is oxidized to 2-methoxy-6-nitrobenzene-1,4-diol (reaction 11.4) with hydrogen peroxide solution in presence of base such as but not limited to sodium hydroxide or potassium hydroxide or by sodium percarbonate solution. 2-methoxy-6-nitrobenzene-1,4-diol was reduced to 2-amino-6-methoxybenzene-1,4-diol (reaction 11.5) by treatment with an reducing agent such as SnCl.sub.2 in water/methanol mixture, or with iron in ammonium chloride solution, or with iron in acetic acid/ethanol mixture, or with zinc in ammonium chloride solution, or by hydrogenation with a catalyst such as but not limited to Pd, Pt, Ni, Rh or Ru between 20-150° C., preferably between 20-100° C. Then 2-amino-6-methoxybenzene-1,4-diol was oxidized to 2-amino-6-methoxycyclohexa-2,5-diene-1,4-dione (reaction 11.6) with an oxidation agent such as but not limited to oxygen, hydrogen peroxide, manganese dioxide, sodium hypochlorite, cerium ammonium nitrate or potassium permanganate optionally in the presence of a catalyst. 2-amino-6-methoxycyclohexa-2,5-diene-1,4-dione was dimerized to 4,9-dimethoxyphenazine-2,7-diol (reaction 11.7) in the presence of a catalyst such as but not limited to trifluoroacetic acid, H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, acetic acid, p-toluenesulfonic acid between 0-100° C., preferably 0-50° C., more preferably between 10-30° C.

Example 16

[0713] ##STR00077##

[0714] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a dimerization of 2-aminocyclobenzoquinones. In some embodiments, vanillin is converted to 2-methoxyhydroquinone (reaction 12.1) by treatment with hydrogen peroxide and base at 0-60° C., preferably between 25-40° C. 2-methoxyhydroquinone is oxidized to 2-methoxy-5-hydroxybenzoquinone (reaction 12.2) with an oxidation agent such as but not limited to oxygen, hydrogen peroxide, manganese dioxide, sodium hypochlorite, cerium ammonium nitrate or potassium permanganate optionally in the presence of a catalyst. 2-Methoxybenzoquinone is reacted with ammonia to give 2-aminobenzoquinone (reaction 12.3) at 20-200° C., preferably 20-100° C. Then 2-aminobenzoquinone was dimerized to phenazine-2,7-diol (reaction 12.4) in the presence of a catalyst such as but not limited to trifluoroacetic acid, H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, acetic acid, p-toluenesulfonic acid between 0-100° C., preferably 0-50° C., more preferably between 10-30° C.

Example 17

[0715] ##STR00078##

[0716] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a condensation of 2-aminocyclobenzoquinones with 3,4-diaminobenzene-1-sulfonic acid. In some embodiments, 2-Methoxybenzoquinone is treated with dimethylamine at 20-100° C., preferably 20-50° C. to give 2-(dimethylamino)-5-methoxycyclohexa-2,5-diene-1,4-dione (reaction 13.1). Then 2-(dimethylamino)-5-methoxycyclohexa-2,5-diene-1,4-dione is reacted with 3,4-diaminobenzene-1-sulfonic acid (reaction 13.2) at 20-200° C., preferably between 30-100° C. to give 7-(dimethylamino)-8-hydroxyphenazine-2-sulfonic acid. In some embodiments, 2-Methoxybenzoquinone is reacted with dimethylamine (reaction 13.3) at 20-100° C., preferably 20-60° C. to give 2,5-bis(dimethylamino)benzene-1,4-diol. Then 2,5-bis(dimethylamino)benzene-1,4-diol is converted to 7-(dimethylamino)-8-hydroxyphenazine-2-sulfonic acid (reaction 13.4) by a condensation reaction with 3,4-diaminobenzene-1-sulfonic acid at 20-200° C., preferably between 30-100° C.

##STR00079##

[0717] In some embodiments, 2-Methoxybenzoquinone is treated with other amines such as, but not limited to 2-(methylamino)ethan-1-ol, to give 2-amino-5-methoxycyclohexa-2,5-diene-1,4-dione (reaction 13.5) at 20-100° C., preferably 20-50° C. Then these amines are condensed with 3,4-diaminobenzene-1-sulfonic acid (reaction 13.6) at 20-200° C., preferably between 30-100° C. to give the 8-hydroxy-7-aminophenazine-2-sulfonic acid.

Example 18

[0718] ##STR00080##

[0719] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a dimerization of 2-methoxycyclohexanol. In some embodiments, vanillic acid is hydrogenated to 4-hydroxy-3-methoxycyclohexane-1-carboxylic acid (reaction 14.1) using a catalyst such as but not limited to Pd, Pt, Ni, Co, Rh or Ru under 10-200 bar H.sub.2, preferably 10-100 bar H.sub.2 pressure between 50-250° C., preferably between 80-200° C. Then 4-hydroxy-3-methoxycyclohexane-1-carboxylic acid is dimerized to 1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylic acid (reaction 14.2) by treatment with ammonia optionally in presence of transition metal catalyst such as but not limited to Iridium and its complexes. 1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylic acid is converted to phenazine-2,7-dicarboxylic acid (reaction 14.3) by treatment with a catalyst such as but not limited to palladium on carbon between 50-300° C., preferably 100-200° C.

Example 19

[0720] ##STR00081##

[0721] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a dimerization starting from the protocatechuic acid. In some embodiments, Vanillin is converted to 3,4-dihydroxybenzoic acid (reaction 15.1) by treatment with KOH/NaOH at 150-300° C., preferably 190-245° C. under air. In the following reaction 3,4-dihydroxybenzoic acid is hydrogenated to give 3,4-dihydroxycyclohexane-1-carboxylic acid (reaction 15.2) using a catalyst such as but not limited to Pd, Pt, Ni, Co, Rh or Ru under 10-200 bar H.sub.2, preferably 10-100 bar H.sub.2 pressure between 50-250° C., preferably between 80-200° C. 3,4-dihydroxycyclohexane-1-carboxylic acid was dimerized to 1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylic acid (reaction 15.3) by treatment with ammonia optionally in presence of transition metal catalyst such as but not limited to Iridium and its complexes. 1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylic acid is converted to phenazine-2,7-dicarboxylic acid (reaction 15.4) by treatment with a catalyst such as but not limited to palladium on carbon between 50-300° C., preferably 100-200° C.

##STR00082##

[0722] In some embodiments, 3,4-dihydroxybenzoic acid is oxidized to 3,4-dioxocyclohexa-1,5-diene-1-carboxylic acid (reaction 15.5) with an oxidation agent such as but not limited to oxygen, hydrogen peroxide, manganese dioxide, sodium hypochlorite, cerium ammonium nitrate or potassium permanganate optionally in the presence of a catalyst. Then 3,4-dioxocyclohexa-1,5-diene-1-carboxylic acid is reacted with 3,4-diaminobenzoic acid (reaction 15.6) at 20-200° C., preferably 20-140° C. to yield a mixture of phenazine-2,7-dicarboxylic acid and phenazine-2,8-dicarboxylic acid.

Example 20

[0723] ##STR00083##

[0724] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a dimerization of 4-nitrosophenols. In some embodiments, 2-Methoxybenzoquinone is converted to 2-methoxy-4-nitrosophenol (reaction 16.1) by treatment with hydroxylamine or its salt in presence of a base such as but not limited to sodium acetate, sodium carbonate or sodium hydroxide at temperatures from 0° C.-100° C., preferably 0° C.-60° C. Then 2-methoxy-4-nitrosophenol is dimerized to 3,8-dimethoxy-5,10-dioxo-phenazine-2,7-diol (reaction 16.2) optionally in the presence of a catalyst such as but not limited to trifluoroacetic acid, H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, acetic acid, p-toluenesulfonic acid between 0-150° C., preferably 0-100° C. 3,8-dimethoxy-5,10-dioxo-phenazine-2,7-diol is reduced to 3,8-dimethoxyphenazine-2,7-diol (reaction 16.3) by treatment with reagents such as but not limited to trifluoroacetic anhydride and sodium iodide in acetonitril at rt, or titanium(IV)-chloride and tin(II)-chloride in acetonitrile at rt, or titanium(IV)-chloride and sodium iodide in acetonitrile at 30° C., or aqueous sodium hydrosulfite and sodium hydroxide at rt, or zinc in aqueous sodium hydroxide solution, or tin(II)-chloride in hydrochloric acid, or by catalytic reduction with sodium hydrophosphite over palladium on carbon (5%) in THF/water at rt, or by hydrogenation with catalytic palladium on charcoal (10% Pd) or Raney nickel (2-10%) under hydrogen (1-5 bar) in EtOH or MeOH.

##STR00084##

[0725] In some embodiments, 5-Aminovanillic acid is oxidized to 4-hydroxy-3-methoxy-5-nitrosobenzoic acid (reaction 16.4) using a oxidation reagent such as but not limited to hydrogen peroxide, oxone, Ph.sub.2Se.sub.2, oxygen, perbenzoic acid, 3-chloro-benzenecarboperoxoic acid optionally in the presence of a catalyst such as but not limited to KI, Na.sub.2WO.sub.4, (n-Bu.sub.3Sn).sub.2WO.sub.4, phosphotungstic acid, CpMo(CO).sub.3(CCPh), MoO.sub.3, methyltrioxorhenium(VII)) and additive (phosphoric acid, NBu.sub.4Br) at 0° C.-150° C., preferably 0° C. to 100° C. Then 4-hydroxy-3-methoxy-5-nitrosobenzoic acid is dimerized to 4,9-dihydroxy-3,8-dimethoxy-5,10-dioxo-phenazine-1,6-dicarboxylic acid (reaction 16.5) by treatment optionally in the presence of a catalyst such as but not limited to trifluoroacetic acid, H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, acetic acid, p-toluenesulfonic acid between 0-150° C., preferably 0-100° C. 4,9-dihydroxy-3,8-dimethoxy-5,10-dioxo-phenazine-1,6-dicarboxylic acid was reduced to 4,9-dihydroxy-3,8-dimethoxyphenazine-1,6-dicarboxylic acid (reaction 16.6) by treatment with reagents such as but not limited to trifluoroacetic anhydride and sodium iodide in acetonitril at rt, or titanium(IV)-chloride and tin(I)-chloride in acetonitrile at rt, or titanium(IV)-chloride and sodium iodide in acetonitrile at 30° C., or aqueous sodium hydrosulfite and sodium hydroxide at rt, or zinc in aqueous sodium hydroxide solution, or tin(II)-chloride in hydrochloric acid, or by catalytic reduction with sodium hydrophosphite over palladium on carbon (5%) in THF/water at rt, or by hydrogenation with catalytic palladium on charcoal (10% Pd) or Raney nickel (2-10%) under hydrogen (1-5 bar) in EtOH or MeOH.

##STR00085##

[0726] In some embodiments, 4-hydroxy-3-methoxy-5-nitrosobenzoic is reacted with catechol (reaction 16.7) by treatment optionally in the presence of a catalyst such as but not limited to trifluoroacetic acid, H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, acetic acid, p-toluenesulfonic acid between 0-150° C., preferably 0-100° C. to yield 2-hydroxy-6-methoxy-3-oxo-3H-phenoxazine-8-carboxylic acid. Then 2-hydroxy-6-methoxy-3-oxo-3H-phenoxazine-8-carboxylic acid is reacted with ammonia (R═H) or primary amine (reaction 16.8) between 20-250° C., preferably between 50-200° C. and at 0-150 bar preferably 0-100 bar to yield the corresponding phenazine.

Example 21

[0727] ##STR00086##

[0728] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, comprising: a dimerization of 2-aminocyclohexanones. In some embodiments, vanillic acid is reacted with an alcohol such as but not limited to methanol (reaction 17.1) in some embodiments, in the presence of a catalyst, such as but not limited to H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, CH.sub.3COOH between 20-150° C., preferably between 20-100° C. most preferably between 30-70° C. to give methyl 4-hydroxy-3-methoxybenzoate. Then methyl 4-hydroxy-3-methoxybenzoate is hydrogenated to methyl 3-methoxy-4-oxocyclohexane-1-carboxylate (reaction 17.2) using a doped metal catalyst such as but not limited to Pd, Pt, Ni, Co, Rh or Ru under 10-200 bar H.sub.2, preferably 10-100 bar H.sub.2 pressure between 50-250° C., preferably between 80-200° C. Methyl 3-methoxy-4-oxocyclohexane-1-carboxylate is hydrolyzed to 3-methoxy-4-oxocyclohexane-1-carboxylic acid (reaction 17.3) by treatment with aqueous alkaline solution at 20-120° C., preferably 20-90° C. In the following step 3-methoxy-4-oxocyclohexane-1-carboxylic acid is converted to 3-amino-4-oxocyclohexane-1-carboxylic acid by treatment with ammonia (reaction 17.4) at 20-200° C., preferably 20-100° C. 3-amino-4-oxocyclohexane-1-carboxylic acid is dimerized to 1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylic acid (reaction 17.5) by treatment optionally in the presence of a catalyst such as but not limited to trifluoroacetic acid, H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, acetic acid, p-toluenesulfonic acid between 0-100° C., preferably 0-50° C., most preferably between 10-30° C. 1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylic acid is converted to phenazine-2,7-dicarboxylic acid (reaction 17.6) by treatment with a catalyst such as but not limited to palladium on carbon between 50-300° C., preferably 100-200° C.

Example 22

[0729] ##STR00087##

[0730] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a dimerization of 2-aminocyclohexanones. In some embodiments, Vanillin is reacted with ethylene glycol (reaction 18.1) by treatment optionally in the presence of a catalyst such as but not limited to trifluoroacetic acid, H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, acetic acid, p-toluenesulfonic acid between 0-100° C., preferably 0-50° C., most preferably between 10-30° C. 4-(1,3-dioxolan-2-yl)-2-methoxyphenol is hydrogenated to 4-(1,3-dioxolan-2-yl)-2-methoxycyclohexan-1-one (reaction 18.2) using doped catalyst such as but not limited to Pd, Pt, Ni, Co, Rh or Ru under 10-200 bar H.sub.2, preferably 10-100 bar H.sub.2 pressure between 50-250° C., preferably between 80-200° C. In the following step 4-(1,3-dioxolan-2-yl)-2-methoxycyclohexan-1-one is converted to 2-amino-4-(1,3-dioxolan-2-yl)cyclohexan-1-one by treatment with ammonia (reaction 18.3) at 20-200° C., preferably 20-100° C. 2-amino-4-(1,3-dioxolan-2-yl)cyclohexan-1-one is dimerized to 3,8-bis(1,3-dioxolan-2-yl)-1,2,3,4,4a,6,7,8,9,9a-decahydrophenazine (reaction 18.4) optionally in the presence of a catalyst such as but not limited to trifluoroacetic acid, H.sub.2SO.sub.4, HC, H.sub.3PO.sub.4, acetic acid, p-toluenesulfonic acid between 0-100° C., preferably 0-50° C., most preferably between 10-30° C. 3,8-bis(1,3-dioxolan-2-yl)-1,2,3,4,4a,6,7,8,9,9a-decahydrophenazine is converted to 1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarbaldehyde (reaction 18.5) optionally in the presence of a catalyst such as but not limited to trifluoroacetic acid, H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, acetic acid, p-toluenesulfonic acid between 0-100° C., preferably 0-50° C., most preferably between 10-30° C. 1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarbaldehyde is oxidized to 1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylic acid (reaction 18.6) using an oxidation reagent such as but not limited to hydrogen peroxide, oxone, oxygen, sodium hypochlorite, potassium permanganate or manganese dioxide optionally in the presence of a catalyst at 0° C.-150° C., preferably 0° C. to 100° C. 1,2,3,4,5a,6,7,8,9,10a-decahydrophenazine-2,7-dicarboxylic acid is converted to phenazine-2,7-dicarboxylic acid (reaction 18.7) by treatment with a catalyst such as but not limited to palladium on carbon between 50-300° C., preferably 100-200° C. In some embodiments, reaction 18.6. and reaction 18.7 are done in a single step.

Example 23

[0731] ##STR00088##

[0732] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, comprising: an electrooxidation of a monomer. In some embodiments, 2-Methoxyhydroquinone is converted to 2,5-dihydroxybenzoquinone by electrochemical oxidation (reaction 19.1) with a suitable electrode, such as but not limited to PbO2/Pb as an anode and an electrolyte such as but not limited to sulfuric acid and acetic acid or a mixture thereof. 2,5-dihydroxybenzoquinone is condensed with 3,4-diaminobenzene-1-sulfonic acid (reaction 19.2) at 20-150° C., preferably 23-100° C., more preferably 40-80° C. to give 7,8-dihydroxyphenazine-2-sulfonic acid.

##STR00089##

[0733] In some embodiments, vanillic acid is decarboxylated to 2-methoxyphenol (reaction 19.3) exemplary but not limited to by treatment with sodium hydroxide in 2-ethoxy-ethanol at 100-150° C., or with enzymes (e.g. decarboxylase) at 20-40° C., or with copper dichloride in water at 150-250° C., or with hydrogen chloride at 150-250° C. Then 2-methoxyphenol is converted to 2-hydroxycyclohexa-2,5-diene-1,4-dione (reaction 19.4) by electrochemical oxidation with a suitable electrode, such as but not limited to PbO2/Pb as an anode and an electrolyte such as but not limited to sulfuric acid and acetic acid or a mixture thereof. 2-hydroxycyclohexa-2,5-diene-1,4-dione is condensed with 3,4-diaminobenzene-1-sulfonic acid (reaction 19.5) at 20-150° C., preferably 23-100° C., more preferably 40-80° C. to give 7,8-dihydroxyphenazine-2-sulfonic acid.

Example 24

[0734] ##STR00090##

[0735] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a condensation of a 2-nitrophenol and a 2-aminophenol, known as the Wohl-Aue-reaction. In some embodiments, methyl 4-hydroxy-3-methoxybenzoate is nitrated (reaction 20.1) with but not limited to nitric acid in combination with or without nitrous acid under cooling at least at 0° C., at least 10° C., at least 20° C. under room temperature, or under heating at least at 30° C., at least 40° C., at least 50° C., at least 60° C., at least 70° C., at least 80° C., at least 90° C., at least 100° C., at least 110° C., at least 120° C., at least 130° C., at least 140° C., at least 150° C. Methyl 4-hydroxy-3-methoxy-5-nitrobenzoate is reduced to methyl 3-amino-4-hydroxy-5-methoxybenzoate (reaction 20.2) by treatment with an reducing agent such as SnCl.sub.2 in water/methanol mixture, or with iron in ammonium chloride solution, or with iron in acetic acid/ethanol mixture, or with zinc in ammonium chloride solution, or by hydrogenation with a catalyst such as but not limited to Pd, Pt, Ni, Rh or Ru between 20-150° C., preferably between 20-100° C. Then Methyl 4-hydroxy-3-methoxy-5-nitrobenzoate is reacted with methyl 3-amino-4-hydroxy-5-methoxybenzoate at 50-300° C., preferably at 100-250° C., more preferably at 100-200° C. to give dimethyl 4,9-dihydroxy-3,8-dimethoxyphenazine-1,6-dicarboxylate (reaction 20.3). Finally, Dimethyl 4,9-dihydroxy-3,8-dimethoxyphenazine-1,6-dicarboxylate is hydrolyzed to, 9-dihydroxy-3,8-dimethoxyphenazine-1,6-dicarboxylic acid (reaction 20.4) by treatment with aqueous alkaline solution at 20-120° C., preferably 20-90° C.

Example 25

[0736] ##STR00091##

[0737] In some embodiments, vanillic acid is treated with ammonia (reaction 21.1) at 10-300 bar, preferably at 10-200 bar, more preferably at 10-50 bar, optionally in the presence of catalyst such as but not limited to Mo, W, Ir, Ru, Pd, Pt, aluminum oxide, H-151 alumina, palladium on carbon, zeolite, copper (1) oxide at 30-400° C., preferably at 40-300° C., most preferably at 50-200° C. to give 3,4-diaminobenzoic acid. Then 4-amino-3-methoxybenzoic acid is nitrated (reaction 21.2) with but not limited to nitric acid in combination with or without nitrous acid under cooling at least at 0° C., at least 10° C., at least 20° C. under room temperature, or under heating at least at 30° C., at least 50° C., at least 70° C., at least 100° C., at least 120° C., at least 150° C. to give 4-amino-3-methoxy-5-nitrobenzoic acid. 4-amino-3-methoxy-5-nitrobenzoic acid is reduced to 3,4-diamino-5-methoxybenzoic acid (reaction 21.3) by treatment with an reducing agent such as SnCl.sub.2 in water/methanol mixture, or with iron in ammonium chloride solution, or with iron in acetic acid/ethanol mixture, or with zinc in ammonium chloride solution, or by hydrogenation with a catalyst such as but not limited to Pd, Pt, Ni, Rh or Ru between 20-150° C., preferably between 20-100° C. 3,4-diamino-5-methoxybenzoic acid is dimerized (reaction 21.4) in the presence of an oxidation reagent such as, but not limited to iron(III) chloride, hydrogen peroxide, potassium persulfate, silver(I) oxide, oxygen, optionally with a catalyst at 20-150° C., preferably 20-100° C. to give 7,8-diamino-4,9-dimethoxyphenazine-2-carboxylic acid.

Example 26

[0738] ##STR00092##

[0739] Another method of obtaining phenazines or phenazine derived structures from monomers that originate from lignin, is disclosed comprising: a treatment of monomers with ammonia under pressure. In some embodiments, vanillic acid is treated with ammonia (reaction 22.1) at 10-300 bar, preferably at 10-200 bar, more preferably at 10-100 bar, optionally in the presence of catalyst such as but not limited to Mo, W, Ir, Ru, Pd, Pt, aluminum oxide, H-151 alumina, palladium on carbon, zeolite, copper (1) oxide at 30-400° C., preferably at 50-300° C. to give 4,4′-azanediylbis(3-methoxybenzoic acid). 4,4′-azanediylbis(3-methoxybenzoic acid) is then nitrated (reaction 22.2) with but not limited to nitric acid in combination with or without nitrous acid under cooling at least at 0° C., at least 10° C., at least 20° C. under room temperature, or under heating at least at 30° C., at least 50° C., at least 70° C., at least 100° C., at least 120° C., at least 150° C. to give 4,4′-azanediylbis(3-methoxy-5-nitrobenzoic acid). 4,4′-azanediylbis(3-methoxy-5-nitrobenzoic acid) is cyclized to 4-methoxyphenazine-2,7-dicarboxylic acid (reaction 22.3) by treatment with an reducing agent such as but not limited to hydrazine hydrate, sodium borohydride, hydrogen, and base such as KOH or sodium ethanolate, with a catalyst such as Pd, Pt, Ni or Ru between 20-150° C., preferably between 20-100° C.

Example 27

[0740] ##STR00093##

[0741] Another method of obtaining phenazines or phenazine derived structures from monomers, is disclosed comprising: a dimerization of 2-aminocyclohexanones. In some embodiments, maleic anhydride is reacted with butadiene (reaction 23.1) in presence of catalyst (Lewis acids, metal complexes) between 20-200° C., preferably 50-120° C. to give cyclohex-4-ene-1,2-dicarboxylic acid. Cyclohex-4-ene-1,2-dicarboxylic acid is converted to 4-(acetyloxy)cyclohex-4-ene-1,2-dicarboxylic acid (reaction 23.2) with acetic acid optionally in presence of catalyst (iron(III) triflate). 4-(acetyloxy)cyclohex-4-ene-1,2-dicarboxylic acid is reacted with nitric acid in acetic anhydride to give 4-nitro-5-oxocyclohexane-1,2-dicarboxylic acid (reaction 23.3) at 20-100° C. 4-nitro-5-oxocyclohexane-1,2-dicarboxylic acid is reduced to 4-amino-5-oxocyclohexane-1,2-dicarboxylic acid (reaction 23.4) by treatment with an reducing agent such as SnCl.sub.2 in water/methanol mixture, or with iron in ammonium chloride solution, or with iron in acetic acid/ethanol mixture, or with zinc in ammonium chloride solution, or by hydrogenation with a catalyst such as but not limited to Pd, Pt, Ni, Rh or Ru between 20-150° C., preferably between 20-100° C. Then 4-amino-5-oxocyclohexane-1,2-dicarboxylic acid was dimerized to 1,2,3,4,4a,6,7,8,9,9a-decahydrophenazine-2,3,7,8-tetracarboxylic acid (reaction 23.5) in the presence of a catalyst such as but not limited to trifluoroacetic acid, H.sub.2SO.sub.4, HCl, H.sub.3PO.sub.4, acetic acid, p-toluenesulfonic acid between 0-100° C., preferably 0-50° C., more preferably between 10-30° C. In some embodiments, the reaction 23.5 is spontaneous. 1,2,3,4,4a,6,7,8,9,9a-decahydrophenazine-2,3,7,8-tetracarboxylic acid is converted to phenazine-2,3,7,8-tetracarboxylic acid (reaction 23.6) by treatment with a catalyst such as but not limited to palladium on carbon between 50-300° C., preferably 100-200° C.

Example 28

[0742] For electrochemical characterization, a small laboratory cell is used. A graphite felt (with an area of 6 cm.sup.2, 6 mm in thickness, supplier: SGL GFA 6EA) is employed as both the positive and negative electrode, and a cation exchange membrane (630K or 620PE, supplier: fumatech) is used to separate the positive and negative electrolytes. The membrane is conditioned in 0.5 M KOH/NaOH (50/50) for at least 150 h prior to each test. Electrolyte volumes range from 12 to 50 mL. The electrolytes are pumped by peristaltic pumps (Drifton BT100-1L, Cole Parmer Ismatec MCP and BVP Process IP 65) at a rate of 24 mL/min to the corresponding electrodes, respectively. Electrochemical testing is performed on a BaSyTec (BaSyTec GmbH, 89176 Asselfingen, Germany) or a Bio-Logic (Bio-Logic Science Instruments, Seyssinet-Pariset 38170, France) battery test system by polarization curves, which are recorded in the charged state by galvanostatic holds and constant-current charge-discharge cycles. For cycling, the cell is charged at a current density of 25 mA/cm.sup.2 up to 1.7 V and discharged at the same current density down to 0.8 V cut-off.

[0743] The results of the electrochemical experiments using [K.sub.4Fe(CN).sub.6] as a posolyte and a phenazine derivative (phenazine derivatives substituted by hydroxyl, methoxysulfonic acid and/or sulfonated alkoxy groups) are shown by FIG. 3. The voltage is shown as a function of time (over various charge/discharge cycles). Peak voltage values of up to 1.6 V are observed.