• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    2,6-Dihydroxyanthraquinone synthesis procedure. The invention provides a new process for the synthesis of 2,6-dihydroxyanthraquinone from 2,6-diaminoanthraquinone that makes it possible to obtain said compound selectively and without the need for additional purification. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2819599A1
    申请号:ES201930914
    申请日:2019-10-15
    公开日:2021-04-16
    发明作者:
    申请人:Energy Storage Solutions S L；Universidad de Burgos；
    IPC主号:
    专利说明:

    [0004] The present invention relates to a process for the synthesis of the compound 2,6-dihydroxyanthraquinone, also known as anthraflavic acid.
    [0006] 2,6-dihydroxyanthraquinone, the structure of which is shown below in formula (I), is a well-known compound used in many different applications.
    [0010] 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).
    [0012] 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.
    [0014] Its industrial applications include its use in the preparation of thermotropic aromatic polyesters that are easily processable and 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).
    [0016] 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.
    [0017] Usually, the preparation form of 2,6-dihydroxyanthraquinone consists of the direct sulfonation of 9,10-anthraquinone, a product that is 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.
    [0019] 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.
    [0021] 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.
    [0023] In view of the aforementioned, 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.
    [0025] 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.
    [0026] 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,
    [0031] it is subjected to 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,
    [0036] diazonium salt of formula (III) which is then reacted with water at 100 ° C to obtain the 2,6-dihydroxyanthraquinone, of formula (I)
    [0040] 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 post-processing steps and, therefore, feasible on an industrial scale.
    [0042] The invention is described below based on the following embodiments and figures, in which:
    [0043] 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 ).
    [0045] 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 ).
    [0047] Example 1: Synthesis of 2,6-dihydroxyanthraquinone
    [0049] 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 on 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 approximately 95% yield 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).
    [0051] 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).
    [0053] 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),
    [0054] 129.7 (2 x CH), 125.3 (2 x C), 120.9 (2 x CH), 112.2 (2 x CH).
    权利要求:
    Claims (2)
    [1]
    1. Procedure for the synthesis of 2,6-dihydroxyanthraquinone, of formula (I),

    [2]
    2 . 2,6-dihydroxyanthraquinone synthesis process according to claim 1, wherein the sulfuric acid medium is a concentrated 96% sulfuric acid solution.
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    同族专利:
    公开号 | 公开日
    ES2819599B2|2021-11-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS60136533A|1983-12-23|1985-07-20|Mitsui Toatsu Chem Inc|Purification of 2,6-dioxyanthraquinone|
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