CN111233781B - Method for generating 2-hydroxyphenol oxazine-3-ketone compound by catalyzing oxidation of molecular oxygen in water phase - Google Patents
Method for generating 2-hydroxyphenol oxazine-3-ketone compound by catalyzing oxidation of molecular oxygen in water phase Download PDFInfo
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001882 dioxygen Inorganic materials 0.000 title claims abstract description 14
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- -1 o-aminophenol compound Chemical class 0.000 claims abstract description 43
- CDAWCLOXVUBKRW-UHFFFAOYSA-N ortho-hydroxyaniline Natural products NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008346 aqueous phase Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229940074391 gallic acid Drugs 0.000 claims abstract description 10
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 150000005837 radical ions Chemical class 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000012071 phase Substances 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- PGSWEKYNAOWQDF-UHFFFAOYSA-N 3-methylcatechol Chemical compound CC1=CC=CC(O)=C1O PGSWEKYNAOWQDF-UHFFFAOYSA-N 0.000 description 2
- FBXGQDUVJBKEAJ-UHFFFAOYSA-N 4h-oxazin-3-one Chemical compound O=C1CC=CON1 FBXGQDUVJBKEAJ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FIZIRKROSLGMPL-UHFFFAOYSA-N phenoxazin-1-one Chemical class C1=CC=C2N=C3C(=O)C=CC=C3OC2=C1 FIZIRKROSLGMPL-UHFFFAOYSA-N 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- NLLYXOVHEQVWJF-UHFFFAOYSA-N 1-(3-amino-2-hydroxyphenyl)ethanone Chemical compound CC(=O)C1=CC=CC(N)=C1O NLLYXOVHEQVWJF-UHFFFAOYSA-N 0.000 description 1
- HRKCYKFBXMHXMG-UHFFFAOYSA-N 4H-oxazin-3-one phenol Chemical class C1(=CC=CC=C1)O.O1NC(CC=C1)=O HRKCYKFBXMHXMG-UHFFFAOYSA-N 0.000 description 1
- 230000007131 anti Alzheimer effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 150000004395 organic heterocyclic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
- C07D265/38—[b, e]-condensed with two six-membered rings
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- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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Abstract
The invention provides a method for generating 2-hydroxyphenol oxazine-3-ketone compounds by catalyzing molecular oxygen oxidation in an aqueous phase, which takes gallic acid as a catalyst and metal salt as a cocatalyst, and leads an o-aminophenol compound and a catechol compound to react in the aqueous phase in the presence of alkali in an oxygen or air environment to generate the 2-hydroxyphenol oxazine-3-ketone compounds. The reaction is carried out in a water phase, and other organic solvents are not required to be added; the catalyst is simple, the catalytic activity is high, and the reaction efficiency is high; simple synthesis process, less waste, environment friendliness and stronger industrial application prospect.
Description
Technical Field
The invention relates to the technical field of synthesis of organic heterocyclic compounds, in particular to a method for generating 2-hydroxyphenol oxazine-3-ketone compounds by catalyzing oxidation of molecular oxygen in a water phase.
Background
The phenoxazinone alkaloids are widely distributed in nature and are considered as a unique natural tricyclic heterocyclic compound. The research finds that the phenol oxazinone compounds have wide drug properties, including anti-tumor, anti-virus, anti-inflammatory, antibacterial, anti-Alzheimer disease and the like. Therefore, the pharmaceutical chemistry research often uses phenoxazinones as the parent core structure of new drugs. Among them, 2-hydroxyphenol oxazine-3-one compounds are attracting much attention.
The synthesis of 2-hydroxyphenol oxazine-3-ketone compounds reported in the literature is not many. C.W. Bird et al used 2-nitro diphenyl ether compound as raw material, and synthesized 2-hydroxyphenol oxazine-3-ketone compound by reduction cyclization and demethylation reaction [ Tetrahedron, 36(4), 529-33; 1980 ]. The method has multiple reaction steps and low application value.
The method for generating the 2-hydroxyphenol oxazine-3-ketone compound by the oxidative condensation cyclization reaction of the o-aminophenol compound and the o-dihydroxybenzene compound is the simplest and most efficient (see formula 1), but the literature reports that one example of the synthetic method is found. H.W. Wanzlick et al report that 6-acetyl ortho aminophenol and catechol in acetic acid can be extracted from K3Fe(CN)6Oxidation to 9-acetyl-2-hydroxyphenol oxazin-3-one [ Angewandte Chemie, 76(8), 313-20; 1964]. The method uses a metered oxidant, is carried out in an organic solvent, has complicated post-treatment and high cost, and is difficult to avoid the generation of salt-containing wastewater, thereby limiting the use of the methods.
Formula 1.
Disclosure of Invention
The invention provides a method for generating 2-hydroxyphenol oxazine-3-ketone compounds by oxidizing o-aminophenol compounds and oxidizing, condensing and cyclizing o-catechol compounds by using natural gallic acid and metal salt combined catalysis molecules in a water phase.
The technical scheme for realizing the invention is as follows:
a method for generating 2-hydroxyphenol oxazine-3-ketone compounds by catalyzing molecular oxygen oxidation in an aqueous phase comprises the steps of reacting an o-aminophenol compound and a catechol compound in the presence of alkali in the aqueous phase in an oxygen or air environment by using gallic acid as a catalyst and metal salt as a cocatalyst to generate the 2-hydroxyphenol oxazine-3-ketone compounds.
The metal of the promoter metal salt is any one of Cu, Fe, Co and Mn, and the acid radical ion is any one of acetate, carbonate, hydrochloride and sulfate. The metal salt may be one or any combination of two or more thereof.
The alkali is NaOH and Na2CO3、NaHCO3、KOH、K2CO3Or KHCO3Any one of them.
The o-aminophenol compound is o-aminophenol and substituted o-aminophenol.
The catechol compound is catechol or substituted catechol.
The mol ratio of the o-aminophenol compound to the o-catechol compound is 1: (0.9-1.2).
The dosage of the catalyst gallic acid is 0.01-10% of the quantity of the o-aminophenol compound, the dosage of the cocatalyst is 0.01-10% of the quantity of the o-aminophenol compound, the dosage of the water is 2-60 times of the quantity of the o-aminophenol compound, and the alkali is 0.05-1 equivalent of the o-aminophenol compound.
The reaction oxygen partial pressure is 0.1-1.0 MPa, the temperature is 10-60 ℃, and the reaction time is 2-50 hours.
The reaction oxygen partial pressure is 0.2-0.3 MPa, the temperature is 10-40 ℃, and the reaction time is 4-20 hours.
The method for synthesizing the 2-hydroxyphenol oxazine-3-ketone compound has the advantages that the reaction is carried out in a water phase, and other organic solvents are not required to be added.
In the invention, gallic acid is used as a catalyst, and metal salt is used as a cocatalyst, and the catalyst is directly put into use. The gallic acid and the metal salt of the cocatalyst used for the catalyst can be directly purchased into corresponding chemical products.
In the using process of the invention, the reaction effect is improved along with the increase of the using amount of the catalyst and the cocatalyst, but the production cost is increased along with the increase of the using amount of the catalyst, and the separation is difficult due to the excessive catalyst. The amount of the catalyst is 0.01 to 10%, preferably 0.03 to 2% by mass of the o-aminophenol compound. The amount of the cocatalyst is 0.01-5%, preferably 0.03-1% of the amount of the o-aminophenol compound.
The method is carried out in the water phase, the increase of the water consumption can reduce the viscosity of the reaction solution and improve the stirring effect, thereby improving the reaction effect, but the excessive water consumption can reduce the concentration of the catalytic system and reduce the reaction efficiency, and increase the energy consumption. The amount of water used is 2 to 60 times, preferably 10 to 40 times, the amount of the o-aminophenol compound.
After the synthesis reaction is finished, the post-treatment process is not particularly limited, and the product can be separated and purified by the following method: and after the oxidation reaction is finished, standing and cooling, extracting, distilling, and recrystallizing to obtain the product.
The invention has the beneficial effects that: the reaction is carried out in a water phase, and other organic solvents are not required to be added; the catalyst is simple, the catalytic activity is high, and the reaction efficiency is high; simple synthesis process, less waste, environment friendliness and stronger industrial application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic representation of 2-hydroxyphenol oxazin-3-one prepared in example 11HNMR spectrogram;
FIG. 2 is a drawing of 2-hydroxyphenol oxazin-3-one prepared in example 113HNMR spectrogram;
FIG. 3 is a drawing showing the preparation of 1-methyl-2-hydroxyphenol oxazin-3-one prepared in example 21HNMR spectrogram;
FIG. 4 is a drawing of 1-methyl-2-hydroxyphenol oxazin-3-one prepared in example 213HNMR spectrogram.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
Synthesis of 2-hydroxyphenol oxazine-3-one:
in a 150 mL reaction vessel, 2.18 g of ortho-aminophenol, 1.88 g of catechol, 2.2 mg of gallic acid, 0.3 g of ferric sulfate, 0.25 g of copper carbonate, 80 mg of NaOH and 60 mL of water were put; heating to 40 ℃ under stirring, introducing oxygen, keeping the pressure in the reaction kettle at 0.3 MPa, stopping the reaction after 20 hours of reaction, cooling to room temperature, extracting with 3X 15 mL of ethyl acetate, combining ethyl acetate layers, removing ethyl acetate by rotary evaporation, recrystallizing the residual solid with isopropanol, filtering, drying to obtain 3.6 g of black solid, determining the product to be 2-hydroxyphenol oxazine-3-one by methods such as NMR (shown in the attached drawing) and MS, wherein the yield is 87%, and the purity of the product is 98% as analyzed by a liquid chromatograph.
Example 2
Synthesis of 1-methyl-2-hydroxyphenol oxazine-3-one:
into a 150 mL reaction vessel were charged 1.23 g of 2-aminophenol, 0.94 g of 3-methylcatechol, 123 mg of gallic acid, 2.4 mg of cobalt chloride, 9.9 mg of manganese acetate, 1.38 g K2CO3And 55 mL of water; keeping the temperature at 15 ℃ while stirring, pressing air in, keeping the pressure in the reaction kettle at 0.1 MPa, stopping the reaction after 2 hours of reaction, cooling to room temperature, extracting with 3X 15 mL ethyl acetate, combining ethyl acetate layers, removing ethyl acetate by rotary evaporation, recrystallizing the residual solid with isopropanol, filtering, drying to obtain 2.0 g of black solid, determining the product to be 7-methyl-2-hydroxyphenol oxazine-3-one by the methods of NMR (shown in the attached drawing), MS and the like, wherein the yield is 92%, and the purity of the product analyzed by a liquid chromatograph is 97%.
Other 2-hydroxyphenol oxazin-3-one compounds were synthesized in the same manner as in example 1, and their various reaction conditions and reaction results are shown in Table 1.
TABLE 1 Synthesis of various 2-hydroxyphenol oxazine-3-ones under different conditions
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A method for generating 2-hydroxyphenol oxazine-3-ketone compounds by catalyzing oxidation of molecular oxygen in an aqueous phase is characterized by comprising the following steps: reacting an o-aminophenol compound and an o-catechol compound in an aqueous phase in the presence of alkali in an oxygen or air environment by using gallic acid as a catalyst and a metal salt as a cocatalyst to generate a 2-hydroxyphenol oxazine-3-ketone compound.
2. The method for catalyzing the oxidation of molecular oxygen to generate 2-hydroxyphenol oxazin-3-one compounds in aqueous phase according to claim 1, characterized in that: the metal of the promoter metal salt is any one of Cu, Fe, Co and Mn, and the acid radical ion is any one of acetate, carbonate, hydrochloride and sulfate.
3. The method for catalyzing the oxidation of molecular oxygen to generate 2-hydroxyphenol oxazin-3-one compounds in aqueous phase according to claim 1, characterized in that: the alkali is NaOH and Na2CO3、NaHCO3、KOH、K2CO3Or KHCO3Any one of them.
4. The method for catalyzing the oxidation of molecular oxygen to generate 2-hydroxyphenol oxazin-3-one compounds in aqueous phase according to claim 1, characterized in that: the o-aminophenol compound is o-aminophenol and substituted o-aminophenol.
5. The method for catalyzing the oxidation of molecular oxygen to generate 2-hydroxyphenol oxazin-3-one compounds in aqueous phase according to claim 1, characterized in that: the catechol compound is catechol or substituted catechol.
6. The method for catalyzing the oxidation of molecular oxygen to generate 2-hydroxyphenol oxazin-3-one compounds in aqueous phase according to claim 1, characterized in that: the mol ratio of the o-aminophenol compound to the o-catechol compound is 1: (0.9-1.2).
7. The method for catalyzing the oxidation of molecular oxygen to generate 2-hydroxyphenol oxazin-3-one compounds in aqueous phase according to claim 1, characterized in that: the dosage of the catalyst gallic acid is 0.01-10% of the quantity of the o-aminophenol compound, the dosage of the cocatalyst is 0.01-10% of the quantity of the o-aminophenol compound, the dosage of the water is 2-60 times of the quantity of the o-aminophenol compound, and the alkali is 0.05-1 equivalent of the o-aminophenol compound.
8. The method for catalyzing the oxidation of molecular oxygen to generate 2-hydroxyphenol oxazin-3-one compounds in aqueous phase according to claim 1, characterized in that: the reaction oxygen partial pressure is 0.1-1.0 MPa, the temperature is 10-60 ℃, and the reaction time is 2-50 hours.
9. The method for catalyzing the oxidation of molecular oxygen to generate 2-hydroxyphenol oxazin-3-one compounds in aqueous phase according to claim 8, characterized in that: the reaction oxygen partial pressure is 0.2-0.3 MPa, the temperature is 10-40 ℃, and the reaction time is 4-20 hours.
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| CN1524859A (en) * | 2003-09-17 | 2004-09-01 | 中山大学 | Phenoxazones, preparing process and pharmaceutical uses thereof |
| WO2020035548A2 (en) * | 2018-08-14 | 2020-02-20 | Cmblu Projekt Ag | Redox-active compounds and uses thereof |
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| CN1524859A (en) * | 2003-09-17 | 2004-09-01 | 中山大学 | Phenoxazones, preparing process and pharmaceutical uses thereof |
| WO2020035548A2 (en) * | 2018-08-14 | 2020-02-20 | Cmblu Projekt Ag | Redox-active compounds and uses thereof |
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