ES2819599B2 - 2,6-DIHYDROXYANTHRAQUINONE SYNTHESIS PROCEDURE - Google Patents
2,6-DIHYDROXYANTHRAQUINONE SYNTHESIS PROCEDURE Download PDFInfo
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- APAJFZPFBHMFQR-UHFFFAOYSA-N anthraflavic acid Chemical compound OC1=CC=C2C(=O)C3=CC(O)=CC=C3C(=O)C2=C1 APAJFZPFBHMFQR-UHFFFAOYSA-N 0.000 title claims description 53
- 238000000034 method Methods 0.000 title claims description 14
- 230000015572 biosynthetic process Effects 0.000 title claims description 9
- 238000003786 synthesis reaction Methods 0.000 title claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- WQOWBWVMZPPPGX-UHFFFAOYSA-N 2,6-diaminoanthracene-9,10-dione Chemical compound NC1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 WQOWBWVMZPPPGX-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012954 diazonium Substances 0.000 claims description 4
- 150000001989 diazonium salts Chemical class 0.000 claims description 4
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 238000006193 diazotization reaction Methods 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000007886 mutagenicity Effects 0.000 description 3
- 231100000299 mutagenicity Toxicity 0.000 description 3
- 230000003389 potentiating effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 101000725148 Rattus norvegicus Cytochrome P450 1A2 Proteins 0.000 description 2
- MSSUFHMGCXOVBZ-UHFFFAOYSA-N anthraquinone-2,6-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 MSSUFHMGCXOVBZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002595 magnetic resonance imaging Methods 0.000 description 2
- 239000003471 mutagenic agent Substances 0.000 description 2
- 231100000707 mutagenic chemical Toxicity 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 description 1
- 150000005421 3-hydroxybenzoic acid derivatives Chemical class 0.000 description 1
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- 229940076442 9,10-anthraquinone Drugs 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- JBBHFHMVEOHFRE-UHFFFAOYSA-N anthracene-2,6-diol Chemical compound C1=C(O)C=CC2=CC3=CC(O)=CC=C3C=C21 JBBHFHMVEOHFRE-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 230000002790 anti-mutagenic effect Effects 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001086 cytosolic effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- 230000003228 microsomal effect Effects 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000004342 trihydroxyanthraquinones Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/16—Quinones the quinoid structure being part of a condensed ring system containing three rings
- C07C50/18—Anthraquinones, i.e. C14H8O2
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
DESCRIPCIÓNDESCRIPTION
PROCEDIMIENTO DE SÍNTESIS DE 2,6-DIHIDROXIANTRAQUINONA2,6-DIHYDROXYANTRAQUINONE SYNTHESIS PROCEDURE
La presente invención se refiere a un procedimiento de síntesis del compuesto 2,6 dihidroxiantraquinona, también conocido como ácido antraflávico.The present invention relates to a process for the synthesis of the compound 2,6-dihydroxyanthraquinone, also known as anthraflavic acid.
La 2,6-dihidroxiantraquinona, cuya estructura se muestra a continuación en la fórmula (I), es un compuesto bien conocido y de uso en muy diversas aplicaciones.2,6-Dihydroxyanthraquinone, the structure of which is shown below in formula (I), is a well-known compound used in many different applications.
Así, por ejemplo, es un inhibidor específico muy potente de la actividad del citocromo P-448 (“Anthraflavic acid is a potent and specific inhibitor of cytochrome P-448 activity”, Andrew D. Ayrton et. al, Biochimica et Biophysica Acta (BBA) - Protein Structure and Molecular Enzymology, Volume 916, Cap. 3, diciembre 1987, pp.328-331).Thus, for example, it is a very potent specific inhibitor of cytochrome P-448 activity ("Anthraflavic acid is a potent and specific inhibitor of cytochrome P-448 activity", Andrew D. Ayrton et. Al, Biochimica et Biophysica Acta ( BBA) - Protein Structure and Molecular Enzymology, Volume 916, Ch. 3, December 1987, pp. 328-331).
Este compuesto también posee propiedades antimutagénicas, inhibiendo la mutagenicidad de ciertos mutágenos presentes en los alimentos. A este respecto, en el artículo “Anthraflavic acid inhibits the mutagenicity of the food mutagen IQ: Mechanism of action” (Andrew D. Ayrton et. al, Mutation Research Letters, volumen 207, cap. 3-4, 1988, pp. 121-125) los autores concluyen que en un potente inhibidor de la mutagenicidad de las imidazolquinolinas debido a su capacidad para inhibir sus rutas de activación microsomales y citosólicas.This compound also has antimutagenic properties, inhibiting the mutagenicity of certain mutagens present in food. In this regard, in the article "Anthraflavic acid inhibits the mutagenicity of the food mutagen IQ: Mechanism of action" (Andrew D. Ayrton et. Al, Mutation Research Letters, volume 207, chap. 3-4, 1988, pp. 121 -125) the authors conclude that it is a potent inhibitor of the mutagenicity of imidazolquinolines due to its ability to inhibit their microsomal and cytosolic activation pathways.
Entre sus aplicaciones industriales se puede citar su uso en la preparación de poliésteres aromáticos termotrópicos fácilmente procesables y de alta estabilidad térmica (US4224433A), como precursor en la preparación de antraceno-2,6-diol, a su vez precursor de materiales semiconductores orgánicos (Jie Li et al., “Aromatic Extension at 2,6-Positions of Anthracene toward an Elegant Strategy for Organic Semiconductors with Efficient Charge Transport and Strong Solid State Emission”, en Am. Chem. Soc. 2017, 139, 48, pp.17261-17264), en la obtención de cristales líquidos (US7211641B2) o en aplicaciones electroquímicas (US6712949B2) y baterías de flujo (US20180375142A1).Among its industrial applications can be mentioned its use in the preparation of easily processable thermotropic aromatic polyesters with high thermal stability (US4224433A), as a precursor in the preparation of anthracene-2,6-diol, in turn a precursor of organic semiconductor materials ( Jie Li et al., “Aromatic Extension at 2,6-Positions of Anthracene toward an Elegant Strategy for Organic Semiconductors with Efficient Charge Transport and Strong Solid State Emission”, in Am. Chem. Soc. 2017, 139, 48, pp. 17261-17264), in obtaining liquid crystals (US7211641B2) or in electrochemical applications (US6712949B2) and flow batteries (US20180375142A1).
Si bien la 2,6-dihidroxiantraquinona es un producto disponible actualmente en el mercado (CAS No.: 84-60-6), por ejemplo de Sigma-Aldrich, su coste es excesivamente elevado para su uso en aplicaciones que requieren grandes cantidades de producto. While 2,6-dihydroxyanthraquinone is currently a commercially available product (CAS No .: 84-60-6), for example from Sigma-Aldrich, its cost is too high for use in applications requiring large amounts of product.
Habitualmente, la forma de preparación de la 2,6-dihidroxiantraquinona consiste en la sulfonación directa de la 9,10-antraquinona, producto muy fácilmente disponible por oxidación del antraceno, la cual proporciona, en ausencia de sales de mercurio, una mezcla de ácidos sulfónicos, a partir de la cual el ácido 2,6-antraquinona disulfónico necesita ser purificado (J. Chem. Soc. 1915, 2178). La posterior fusión alcalina de este diácido proporciona la 2,6-dihidroxiantraquinona.Usually, the form of preparation of 2,6-dihydroxyanthraquinone consists of the direct sulfonation of 9,10-anthraquinone, a product very easily available by oxidation of anthracene, which provides, in the absence of mercury salts, a mixture of acids sulfonic, from which 2,6-anthraquinone disulfonic acid needs to be purified (J. Chem. Soc. 1915, 2178). Subsequent alkaline fusion of this diacid provides 2,6-dihydroxyanthraquinone.
La SU159861 también describe un método de producción de ácido antraflávico por saponificación del ácido 2,6-antraquinona disulfónico con una disolución acuosa de hidróxido de sodio a una temperatura de 200-220°C sin que se produzca sobreoxidación y se generen derivados de trihidroxiantraquinona.SU159861 also describes a method for the production of anthraflavic acid by saponification of 2,6-anthraquinone disulfonic acid with an aqueous solution of sodium hydroxide at a temperature of 200-220 ° C without over-oxidation occurring and the generation of trihydroxyanthraquinone derivatives.
Alternativamente, la 2,6-dihidroxiantraquinona también se puede preparar a partir de derivados de ácido 3-hidroxibenzoico empleando como paso clave la reacción de Friedel-Crafts. Sin embargo, también se obtienen productos regioisómeros que necesitan de una posterior purificación. El documento JP63091347 describe un proceso para obtener 2,6-dihidroxiantraquinona a partir de ácido m-hidroxibenzoico y cloruro de benzoílo por condensación en presencia de un catalizador ácido. El documento JP60136533 describe un procedimiento para purificar 2,6-dihidroxiantraquinona por disolución en una solución acuosa de un hidróxido alcalino, precipitación de la sal alcalina de la 2,6-dihidroxiantraquinona y acidificación.Alternatively, 2,6-dihydroxyanthraquinone can also be prepared from 3-hydroxybenzoic acid derivatives using the Friedel-Crafts reaction as a key step. However, regioisomeric products are also obtained that require further purification. JP63091347 describes a process for obtaining 2,6-dihydroxyanthraquinone from m-hydroxybenzoic acid and benzoyl chloride by condensation in the presence of an acid catalyst. JP60136533 describes a process for purifying 2,6-dihydroxyanthraquinone by dissolving in an aqueous solution of an alkali hydroxide, precipitation of the alkaline salt of 2,6-dihydroxyanthraquinone and acidification.
A la vista de lo anteriormente citado, sería deseable disponer de un método de síntesis de 2,6-dihidroxiantraquinona que no tuviera las desventajas de conllevar procesos adicionales, por ejemplo, los de purificación antes mencionados, que resultan muy costosos, desde el punto de vista económico, y muy tediosos en su aplicación.In view of the above, it would be desirable to have a 2,6-dihydroxyanthraquinone synthesis method that does not have the disadvantages of involving additional processes, for example, the aforementioned purification processes, which are very expensive, from the point of view of economic view, and very tedious in its application.
Por tanto, el objeto de la invención es proporcionar un nuevo procedimiento de síntesis de 2,6-dihidroxiantraquinona que no conlleve etapas adicionales y que permita obtener dicho compuesto de forma selectiva y sin necesidad de purificación adicional. Therefore, the object of the invention is to provide a new synthesis process for 2,6-dihydroxyanthraquinone that does not involve additional steps and that allows to obtain said compound selectively and without the need for additional purification.
Para la síntesis de 2,6-dihidroxiantraquinona, de fórmula (I), de acuerdo con el procedimiento de la invención el compuesto de fórmula (II), 2,6-diaminoantraquinona,For the synthesis of 2,6-dihydroxyanthraquinone, of formula (I), according to the process of the invention the compound of formula (II), 2,6-diaminoanthraquinone,
se somete a una diazotación de los grupos amino por tratamiento con nitrito sódico en medio ácido sulfúrico, obteniéndose la sal de diazonio de fórmula (III) como producto intermedio,it is subjected to a diazotization of the amino groups by treatment with sodium nitrite in sulfuric acid medium, obtaining the diazonium salt of formula (III) as an intermediate product,
sal de diazonio de fórmula (III) que entonces se somete a reacción con agua a 100 °C para obtener la 2,6-dihidroxiantraquinona, de fórmula (I)diazonium salt of formula (III) which is then reacted with water at 100 ° C to obtain 2,6-dihydroxyanthraquinone, of formula (I)
Dado que el producto de partida en el procedimiento aquí descrito es el compuesto de fórmula (II), 2,6-diaminoantraquinona, un producto comercial (CAS No. 131-14-6) significativamente más económico que la 2,6-dihidroxiantraquinona, la invención permite llegar al compuesto de fórmula (I) de forma sencilla, selectiva y sin pasos de procesado posterior y, por lo tanto, viable a escala industrial.Since the starting product in the process described here is the compound of formula (II), 2,6-diaminoanthraquinone, a commercial product (CAS No. 131-14-6) significantly cheaper than 2,6-dihydroxyanthraquinone, The invention makes it possible to arrive at the compound of formula (I) in a simple, selective and without subsequent processing steps and, therefore, feasible on an industrial scale.
A continuación se describe la invención en base a los siguientes ejemplos de realización y figuras, en las cuales: The invention is described below based on the following embodiments and figures, in which:
Fig. 1: Caracterización de la 2,6-dihidroxiantraquinona sintetizada según el procedimiento de la invención mediante resonancia magnética de protón (1H-RMN en dmso-d6).Fig. 1: Characterization of 2,6-dihydroxyanthraquinone synthesized according to the method of the invention by proton magnetic resonance imaging ( 1 H-NMR in dmso-d 6 ).
Fig. 2: Caracterización de la 2,6-dihidroxiantraquinona sintetizada según el procedimiento de la invención mediante resonancia magnética de carbono (13C-RMN en dmso-d6).Fig. 2: Characterization of 2,6-dihydroxyanthraquinone synthesized according to the method of the invention by carbon magnetic resonance imaging ( 13 C-NMR in dmso-d 6 ).
Ejemplo 1: Síntesis de 2,6-dihidroxiantraquinonaExample 1: Synthesis of 2,6-dihydroxyanthraquinone
Se disuelven 10 g (42 mmol) de 2,6-diaminoantraquinona en ácido sulfúrico al 96% (110 ml) en un matraz de fondo redondo de 250 ml y la disolución se enfría a 0 °C en un baño de hielo. A continuación se añaden lentamente 6,7 g (97 mmol) de nitrito sódico y se deja agitando a temperatura ambiente durante 3 horas y media. Seguidamente, se vierte la mezcla de reacción sobre hielo picado (500 g). La disolución resultante se calienta a reflujo en un baño de aceite (temperatura del baño: 105 °C) durante 2 horas, observándose la formación de un precipitado de color amarillo oscuro. La mezcla se deja enfriar hasta temperatura ambiente y el sólido resultante se filtra en placa filtrante y se lava con agua destilada (200 ml). El sólido obtenido se deja secar en una estufa a 60 °C. Se obtiene 2,6-dihidroxiantraquinona con un rendimiento de aproximadamente el 95% como un sólido amarillo oscuro cuyos espectros de RMN se muestran en la Fig. 1 y 2, demostrando una pureza similar a la de una muestra comercial (Aldrich).10 g (42 mmol) of 2,6-diaminoanthraquinone is dissolved in 96% sulfuric acid (110 ml) in a 250 ml round bottom flask and the solution is cooled to 0 ° C in an ice bath. Then 6.7 g (97 mmol) of sodium nitrite are slowly added and the mixture is left stirring at room temperature for 3.5 hours. The reaction mixture is then poured onto crushed ice (500 g). The resulting solution is refluxed in an oil bath (bath temperature: 105 ° C) for 2 hours, observing the formation of a dark yellow precipitate. The mixture is allowed to cool to room temperature and the resulting solid is filtered through a filter plate and washed with distilled water (200 ml). The solid obtained is left to dry in an oven at 60 ° C. 2,6-Dihydroxyanthraquinone is obtained in a yield of approximately 95% as a dark yellow solid whose NMR spectra are shown in Fig. 1 and 2, demonstrating a purity similar to that of a commercial sample (Aldrich).
1H-NMR (300 MHz, dmso-de) 5 (ppm) 10,98 (s, 2H), 8,04 (d, J = 8,5 Hz, 2H), 7,47 (d, J = 2,4 Hz, 2H), 7,18 (dd, J = 8,5, 2,4 Hz, 2H). 1H-NMR (300 MHz, dmso-d e ) 5 (ppm) 10.98 (s, 2H), 8.04 (d, J = 8.5 Hz, 2H), 7.47 (d, J = 2 , 4Hz, 2H), 7.18 (dd, J = 8.5, 2.4Hz, 2H).
13C-NMR (75,4 MHz, dmso-de): 5 (ppm) 181,3 (2 x C), 163,1 (2 x C), 135,5 (2 x C), 13C-NMR (75.4 MHz, dmso-d e ): 5 (ppm) 181.3 (2 x C), 163.1 (2 x C), 135.5 (2 x C),
129,7 (2 x CH), 125,3 (2 x C), 120,9 (2 x CH), 112,2 (2 x CH). 129.7 (2 x CH), 125.3 (2 x C), 120.9 (2 x CH), 112.2 (2 x CH).
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