CN111233781A - Method for catalyzing molecular oxygen oxidation in aqueous phase to generate 2-hydroxyphenoloxazin-3-one compounds - Google Patents
Method for catalyzing molecular oxygen oxidation in aqueous phase to generate 2-hydroxyphenoloxazin-3-one compounds Download PDFInfo
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Abstract
本发明提供了一种水相中催化分子氧氧化生成2‑羟基酚噁嗪‑3‑酮类化合物的方法，以没食子酸为催化剂，金属盐为助催化剂，在氧气或空气环境中，使邻氨基苯酚类化合物与邻苯二酚类化合物在水相中、碱存在条件下反应，生成2‑羟基酚噁嗪‑3‑酮类化合物。本发明反应在水相中进行，无需添加其它有机溶剂；催化剂简单，催化活性高，反应效率高；合成工艺简捷，废物少，环境友好，具有较强的工业应用前景。
The invention provides a method for catalyzing the oxidation of molecular oxygen in an aqueous phase to generate 2-hydroxyphenoxazine-3-ketone compounds. Gallic acid is used as a catalyst and a metal salt is used as a co-catalyst. In an oxygen or air environment, ozone is produced. Aminophenol compounds and catechol compounds react in the aqueous phase in the presence of alkali to generate 2-hydroxyphenoxazine-3-one compounds. The reaction of the invention is carried out in the aqueous phase without adding other organic solvents; the catalyst is simple, the catalytic activity is high, the reaction efficiency is high; the synthesis process is simple, the waste is less, the environment is friendly, and it has strong industrial application prospects.
Description
技术领域technical field
本发明涉及有机杂环化合物合成技术领域，具体涉及一种水相中催化分子氧氧化生成2-羟基酚噁嗪-3-酮类化合物的方法。The invention relates to the technical field of organic heterocyclic compound synthesis, in particular to a method for catalyzing the oxidation of molecular oxygen in an aqueous phase to generate 2-hydroxyphenoloxazin-3-one compounds.
背景技术Background technique
酚噁嗪酮生物碱在自然界中分布广泛，被认为是一类独特的天然三环杂环化合物。研究发现，酚噁嗪酮类化合物具有广泛的药物特性，包括抗肿瘤、抗病毒、抗炎、抗菌、抗阿尔茨海默病等等。因此，药物化学研究常将酚噁嗪酮用作新药的母核结构。其中，2-羟基酚噁嗪-3-酮类化合物备受关注。Phenoxazinone alkaloids are widely distributed in nature and are considered to be a unique class of natural tricyclic heterocyclic compounds. Studies have found that phenoloxazinones have a wide range of drug properties, including anti-tumor, anti-viral, anti-inflammatory, antibacterial, anti-Alzheimer's disease and so on. Therefore, phenoloxazinone is often used as the core structure of new drugs in medicinal chemistry research. Among them, 2-hydroxyphenoloxazin-3-one compounds have attracted much attention.
文献报道的2-羟基酚噁嗪-3-酮类化合物的合成不多。C. W. Bird等使用2-硝基二苯醚化合物为原料，经还原环合和去亚甲基化反应合成了2-羟基酚噁嗪-3-酮类化合物[Tetrahedron, 36(4), 529-33; 1980]。此法反应步骤多，应用价值不高。The synthesis of 2-hydroxyphenoloxazin-3-one compounds reported in the literature is not much. C.W.Bird et al. used 2-nitrodiphenyl ether compounds as raw materials, and synthesized 2-hydroxyphenoloxazin-3-one compounds through reductive cyclization and demethylation [Tetrahedron, 36(4), 529- 33; 1980]. This method has many reaction steps and has little application value.
由邻氨基苯酚类化合物与邻苯二酚类化合物氧化缩合环化反应，生成2-羟基酚噁嗪-3-酮类化合物的方法最为简单高效（见式1），但文献报道此类合成方法今发现一例。H.W. Wanzlick等报道，在乙酸中6-乙酰基邻氨基苯酚与邻苯二酚可由K3Fe(CN)6氧化生成9-乙酰基-2-羟基酚噁嗪-3-酮[Angewandte Chemie, 76(8), 313-20; 1964]。此方法使用计量的氧化剂，且在有机溶剂中进行，后处理繁琐，成本高，难以避免含盐废水的产生，从而限制了这些方法的使用。Oxidative condensation cyclization of o-aminophenols and catechols to generate 2-hydroxyphenoloxazin-3-ones is the most simple and efficient method (see formula 1), but the literature reports such synthesis methods Found a case today. HW Wanzlick et al. reported that 6-acetyl-o-aminophenol and catechol can be oxidized by K 3 Fe(CN) 6 in acetic acid to generate 9-acetyl-2-hydroxyphenoloxazin-3-one [Angewandte Chemie, 76 (8), 313-20; 1964]. This method uses a metered oxidant and is carried out in an organic solvent. The post-treatment is cumbersome and costly, and it is difficult to avoid the generation of salty wastewater, thus limiting the use of these methods.
式1。Formula 1.
发明内容SUMMARY OF THE INVENTION
本发明提出了一种水相中天然没食子酸和金属盐组合催化分子氧氧化邻氨基苯酚类化合物与邻苯二酚类化合物氧化缩合环化反应生成2-羟基酚噁嗪-3-酮类化合物的方法，该方法该法是在水相中反应，无需另外添加有机溶剂。The invention proposes a combination of natural gallic acid and metal salt in water phase to catalyze molecular oxygen oxidation of o-aminophenol compounds and catechol compounds to oxidative condensation cyclization to generate 2-hydroxyphenoloxazin-3-one compounds The method of this method is to react in the aqueous phase without adding an additional organic solvent.
实现本发明的技术方案是：The technical scheme that realizes the present invention is:
一种水相中催化分子氧氧化生成2-羟基酚噁嗪-3-酮类化合物的方法，以没食子酸为催化剂，金属盐为助催化剂，在氧气或空气环境中，使邻氨基苯酚类化合物与邻苯二酚类化合物在水相中、碱存在条件下反应，生成2-羟基酚噁嗪-3-酮类化合物。A method for catalyzing the oxidation of molecular oxygen in an aqueous phase to generate 2-hydroxyphenoloxazin-3-one compounds, using gallic acid as a catalyst and a metal salt as a co-catalyst, in an oxygen or air environment, the o-aminophenol compounds are It reacts with catechol compounds in aqueous phase and in the presence of alkali to generate 2-hydroxyphenoloxazin-3-one compounds.
所述助催化剂金属盐的金属为Cu、Fe、Co、Mn中的任意一种，酸根离子为醋酸根、碳酸根、盐酸根、硫酸根中的任意一种。所述金属盐可以是其中一种或两种以上任意组合。The metal of the promoter metal salt is any one of Cu, Fe, Co, and Mn, and the acid ion is any one of acetate, carbonate, hydrochloride, and sulfate. The metal salt may be one or any combination of two or more of them.
所述碱为NaOH、Na2CO3、NaHCO3、KOH、K2CO3或KHCO3中的任意一种。The base is any one of NaOH, Na 2 CO 3 , NaHCO 3 , KOH, K 2 CO 3 or KHCO 3 .
所述邻氨基苯酚类化合物为邻氨基苯酚和取代的邻氨基苯酚。The o-aminophenol compounds are o-aminophenol and substituted o-aminophenol.
所述邻苯二酚类化合物为邻苯二酚或取代的邻苯二酚。The catechol compound is catechol or substituted catechol.
所述邻氨基苯酚类化合物与邻苯二酚类化合物的摩尔比为1：（0.9-1.2）。The molar ratio of the o-aminophenol compound to the catechol compound is 1:(0.9-1.2).
所述催化剂没食子酸的用量为邻氨基苯酚类化合物物质的量的0.01-10%，所述助催化剂的用量为邻氨基苯酚类化合物物质的量的0.01-10%，所述水的用量为邻氨基苯酚类化合物质量的2-60倍，碱为邻氨基苯酚类化合物的0.05-1当量。The consumption of the catalyst gallic acid is 0.01-10% of the amount of the o-aminophenol compound material, the consumption of the cocatalyst is 0.01-10% of the amount of the o-aminophenol compound material, and the consumption of the water is o-aminophenol. The mass of the aminophenol compound is 2-60 times, and the base is 0.05-1 equivalent of the o-aminophenol compound.
所述反应氧气分压为0.1-1.0 MPa、温度为10-60℃、反应时间为2-50小时。The reaction oxygen partial pressure is 0.1-1.0 MPa, the temperature is 10-60° C., and the reaction time is 2-50 hours.
所述反应氧气分压为0.2-0.3 MPa、温度为10-40℃、反应时间为4-20小时。The reaction oxygen partial pressure is 0.2-0.3 MPa, the temperature is 10-40° C., and the reaction time is 4-20 hours.
所述合成2-羟基酚噁嗪-3-酮类化合物的方法，反应在水相中进行，无需添加其它有机溶剂。In the method for synthesizing 2-hydroxyphenoloxazin-3-one compounds, the reaction is carried out in an aqueous phase without adding other organic solvents.
本发明中，以没食子酸为催化剂，金属盐为助催化剂，直接投入使用。用于催化剂的没食子酸和助催化剂金属盐可以直接购买相应的化工产品。In the present invention, gallic acid is used as a catalyst, and a metal salt is used as a co-catalyst, which is directly put into use. The gallic acid and cocatalyst metal salts used in the catalyst can be directly purchased from the corresponding chemical products.
本发明在使用过程中，反应效果随催化剂和助催化剂用量增加而提高，但催化剂用量增加生产成本也随之增加，过量的催化剂会带来分离困难。催化剂的用量为邻氨基苯酚类化合物质量的0.01-10%，优选0.03-2%。助催化剂的用量为邻氨基苯酚类化合物质的量的0.01-5%，优选0.03-1%。During the use process of the present invention, the reaction effect is improved with the increase of the catalyst and the co-catalyst dosage, but the production cost also increases with the increase of the catalyst dosage, and the excess catalyst will bring about the difficulty of separation. The dosage of the catalyst is 0.01-10% of the mass of the o-aminophenol compound, preferably 0.03-2%. The amount of the co-catalyst is 0.01-5% of the mass of the o-aminophenol compound, preferably 0.03-1%.
本发明的方法在水相中进行，水的用量增加会降低反应液粘稠度而提高搅拌效果，进而提高反应效果，但水的用量过大会降低催化体系的浓度而降低反应效率，增加能源消耗。水的用量为邻氨基苯酚类化合物质量的2-60倍，优选10-40倍。The method of the present invention is carried out in the water phase, and the increase in the amount of water will reduce the viscosity of the reaction solution and improve the stirring effect, thereby improving the reaction effect, but if the amount of water is too large, the concentration of the catalytic system will be reduced, the reaction efficiency will be reduced, and the energy consumption will be increased. . The amount of water used is 2-60 times the mass of the o-aminophenol compound, preferably 10-40 times.
本发明中合成反应结束后，后处理工艺过程没有特别限定，产物分离提纯可以通过以下方法进行：氧化反应结束后，放置冷却，通过萃取、蒸馏，再经重结晶，得到产物。In the present invention, after the synthesis reaction is completed, the post-processing process is not particularly limited, and the product separation and purification can be carried out by the following methods: after the oxidation reaction is completed, place it to cool, extract, distill, and then recrystallize to obtain the product.
本发明的有益效果是：反应在水相中进行，无需添加其它有机溶剂；催化剂简单，催化活性高，反应效率高；合成工艺简捷，废物少，环境友好，具有较强的工业应用前景。The beneficial effects of the invention are as follows: the reaction is carried out in the water phase without adding other organic solvents; the catalyst is simple, the catalytic activity is high, and the reaction efficiency is high;
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only These are some embodiments of the present invention, and for those of ordinary skill in the art, other drawings can also be obtained from these drawings without creative effort.
图1是实施例1制备的2-羟基酚噁嗪-3-酮的1HNMR谱图；Fig. 1 is the 1 HNMR spectrum of 2-hydroxyphenoloxazin-3-one prepared in Example 1;
图2是实施例1制备的2-羟基酚噁嗪-3-酮的13HNMR谱图；Fig. 2 is the 13 HNMR spectrum of 2-hydroxyphenoloxazin-3-one prepared in Example 1;
图3是实施例2制备的1-甲基-2-羟基酚噁嗪-3-酮的1HNMR谱图；Fig. 3 is the 1 HNMR spectrum of 1-methyl-2-hydroxyphenoloxazin-3-one prepared in Example 2;
图4是实施例2制备的1-甲基-2-羟基酚噁嗪-3-酮的13HNMR谱图。FIG. 4 is a 13 HNMR spectrum of 1-methyl-2-hydroxyphenoloxazin-3-one prepared in Example 2. FIG.
具体实施方式Detailed ways
下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例1Example 1
2-羟基酚噁嗪-3-酮的合成：Synthesis of 2-hydroxyphenoloxazin-3-one:
在150 mL的反应釜中，投入2.18 g邻氨基苯酚、1.88 g邻苯二酚、2.2 mg没食子酸、0.3g硫酸铁、0.25 g碳酸铜、80 mg NaOH和60 mL水；搅拌下加热升温至40℃，通入氧气，保持反应釜内压强为0.3 MPa，反应20小时后停止反应，冷却至室温，3 × 15 mL乙酸乙酯萃取，合并乙酸乙酯层，旋蒸去除乙酸乙酯，剩余固体用异丙醇重结晶，抽滤，烘干，得黑色固体3.6g，产品经NMR（见附图）、MS等方法确定结构为2-羟基酚噁嗪-3-酮，收率为87 %，液相色谱仪分析产物纯度为98%。In a 150 mL reaction kettle, put 2.18 g o-aminophenol, 1.88 g catechol, 2.2 mg gallic acid, 0.3 g iron sulfate, 0.25 g copper carbonate, 80 mg NaOH and 60 mL water; 40°C, feed oxygen, keep the pressure in the reactor at 0.3 MPa, stop the reaction after 20 hours of reaction, cool to room temperature, extract with 3 × 15 mL of ethyl acetate, combine the ethyl acetate layers, and remove the ethyl acetate by rotary evaporation. The solid was recrystallized with isopropanol, filtered with suction, and dried to obtain 3.6 g of black solid. The product was determined to be 2-hydroxyphenoloxazin-3-one by methods such as NMR (see the accompanying drawings) and MS, and the yield was 87 %, and the purity of the product analyzed by liquid chromatography was 98%.
实施例2Example 2
1-甲基-2-羟基酚噁嗪-3-酮的合成：Synthesis of 1-methyl-2-hydroxyphenoloxazin-3-one:
在150 mL的反应釜中，投入1.23 g 2-氨基苯酚、0.94 g 3-甲基邻苯二酚、123 mg没食子酸、2.4 mg氯化钴、9.9 mg醋酸锰、1.38 g K2CO3和55 mL水；搅拌下保温15℃，压入空气，保持反应釜内压强为0.1 MPa，反应2小时后停止反应，冷却至室温，3 × 15 mL乙酸乙酯萃取，合并乙酸乙酯层，旋蒸去除乙酸乙酯，剩余固体用异丙醇重结晶，抽滤，烘干，得黑色固体2.0 g，产品经NMR（见附图）、MS等方法确定结构为7-甲基-2-羟基酚噁嗪-3-酮，收率为92%，液相色谱仪分析产物纯度为97 %。In a 150 mL reaction kettle, put 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 of K 2 CO 3 and 55 mL of water; keep the temperature at 15°C under stirring, press into air, keep the pressure in the reactor at 0.1 MPa, stop the reaction after 2 hours of reaction, cool to room temperature, extract with 3 × 15 mL of ethyl acetate, combine the ethyl acetate layers, spin The ethyl acetate was removed by evaporation, the remaining solid was recrystallized with isopropanol, suction filtered, and dried to obtain 2.0 g of black solid. The product was determined to be 7-methyl-2-hydroxyl by methods such as NMR (see the accompanying drawings) and MS. Phenoxazin-3-one, the yield is 92%, and the product purity analyzed by liquid chromatograph is 97%.
按实施例1相同的方法合成其它2-羟基酚噁嗪-3-酮类化合物，其各种反应条件和反应结果见表1。Synthesize other 2-hydroxyphenoloxazin-3-one compounds in the same manner as in Example 1. Various reaction conditions and reaction results are shown in Table 1.
表1 不同条件下合成各种2-羟基酚噁嗪-3-酮类化合物Table 1 Synthesis of various 2-hydroxyphenoloxazin-3-ones under different conditions
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the scope of the present invention. within the scope of protection.
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