技术领域technical field
本发明属于有机合成及催化领域，具体涉及一种绿色氧化合成甘油醛的方法。The invention belongs to the field of organic synthesis and catalysis, in particular to a method for green oxidation synthesis of glyceraldehyde.
背景技术Background technique
甘油醛是最早发现的一种光学活性醛糖化合物,分子中含有一对手性碳原子,即D型与L型光学异构体,常用作标定碳水化合物构型的标准。外消旋体D,L-甘油醛具有抗糖酵解作用,是一种很好的血糖保护剂，同时作为一种重要的有机合成中间体，在医药，农业化学品和天然产物合成中占有相当重要的地位，在有机合成中可以作为手性源进行不对称合成，特别是其含有活泼的官能团—醛基，可以产生多种类型的衍生物，因此在手性药物的开发中具有十分重要的意义。在食品医药及化工行业中,主要作为一种廉价的手性诱导单体用于手性分子的合成用来合成一些手性药物和具有光学活性的天然产物的重要前体。Glyceraldehyde is the earliest discovered optically active aldose compound, which contains a pair of chiral carbon atoms, that is, D-type and L-type optical isomers, and is often used as a standard for calibrating carbohydrate configurations. Racemate D, L-glyceraldehyde has anti-glycolysis effect and is a good blood sugar protective agent. At the same time, as an important organic synthesis intermediate, it occupies an important role in the synthesis of medicine, agricultural chemicals and natural products. Quite an important position, it can be used as a chiral source in organic synthesis for asymmetric synthesis, especially it contains active functional groups-aldehyde groups, which can produce various types of derivatives, so it is very important in the development of chiral drugs meaning. In the food, medicine and chemical industries, it is mainly used as a cheap chiral-inducing monomer for the synthesis of chiral molecules and is used as an important precursor for the synthesis of some chiral drugs and optically active natural products.
甘油醛的传统生产方法主要是以甘油为原料，通过化学氧化法合成甘油醛，常用的氧化剂一般为：过氧化氢、过氧酸、稀硝酸、氧化铬、活性二氧化锰、二甲亚砜等作为氧化剂来制备甘油醛。但过氧化氢、过氧酸等均为强氧化剂,易燃、易爆,存在运输、贮存等问题，氧化铬、二甲亚砜等对环境污染问题，因此探求高效率、低成本、对环境友好的新制备方法仍然是当前研究的重要目标。反应式如下：The traditional production method of glyceraldehyde mainly uses glycerol as raw material to synthesize glyceraldehyde through chemical oxidation method. Commonly used oxidants are: hydrogen peroxide, peroxyacid, dilute nitric acid, chromium oxide, active manganese dioxide, dimethyl sulfoxide etc. as an oxidizing agent to prepare glyceraldehyde. However, hydrogen peroxide and peroxyacid are strong oxidants, flammable and explosive, and there are problems such as transportation and storage. Chromium oxide and dimethyl sulfoxide have environmental pollution problems. Therefore, it is necessary to seek high efficiency, low cost, and environmental protection. Friendly new preparation methods are still an important goal of current research. The reaction formula is as follows:
有文献报道用Lewis酸无水ZnCl2作为催化脱水剂,D-甘露醇与丙酮缩合反应合成二异亚丙基缩合物,然后用NaIO4氧化断键制备D-(R)-甘油醛缩丙酮,再脱去丙酮制备甘油醛。该方法具有产率高、价廉、环境友好等优点。但由于原料价格较高、反应步骤复杂等缺点，不适于工业化生产选用。反应如下：It has been reported in the literature that using Lewis acid anhydrous ZnCl2 as a catalytic dehydrating agent, D-mannitol and acetone were condensed to synthesize diisopropylidene condensate, and then NaIO4 was used to oxidatively break bonds to prepare D-(R)-glyceraldehyde acetone , and then remove acetone to prepare glyceraldehyde. The method has the advantages of high yield, low cost, and environmental friendliness. However, due to the disadvantages of high raw material prices and complicated reaction steps, it is not suitable for industrial production. The response is as follows:
也有文献报道以甘油为原料采用间接电氧化法合成甘油醛，该法虽然具有反应步骤简单、产品收率高等特点，但反应中能耗较大，且需要膜分离等，也不适合工业化生产。本发明克服现有技术的不足，开发出一种富勒烯氧化锌硒(C60/ZnO/Se)复合材料作为催化剂，催化甘油、甘油醇缩丙酮在氧气存在下，温和地转化为甘油醛、甘油醛缩丙酮，该反应操作简便、条件温和、转化率和选择性高、对环境无污染、绿色环保、易于工业化大生产。There are also reports in the literature that glycerol is used as a raw material to synthesize glyceraldehyde by indirect electrooxidation. Although this method has the characteristics of simple reaction steps and high product yield, the energy consumption in the reaction is relatively large, and membrane separation is required, so it is not suitable for industrial production. The present invention overcomes the deficiencies in the prior art and develops a fullerene zinc oxide selenium (C60 /ZnO/Se) composite material as a catalyst to catalyze glycerol and glyceryl acetal to be gently converted into glyceraldehyde in the presence of oxygen 1. Glyceraldehyde acetone, the reaction is simple to operate, mild in conditions, high in conversion rate and selectivity, non-polluting to the environment, green and environmentally friendly, and easy for industrialized large-scale production.
发明内容Contents of the invention
本发明提供一种富勒烯氧化锌硒(C60/ZnO/Se)复合材料，其特征在于所述富勒烯氧化锌硒复合材料的制备方法包括如下步骤：The invention provides a fullerene zinc oxide selenium (C60 /ZnO/Se) composite material, which is characterized in that the preparation method of the fullerene zinc oxide selenium composite material comprises the following steps:
(1)将富勒烯、锌盐溶液、氨水混合均匀后，升温至120-130℃反应18-20h后，自然降至室温后，经后处理得富勒烯氧化锌(C60/ZnO)材料；(1) Mix fullerene, zinc salt solution, and ammonia water evenly, raise the temperature to 120-130°C and react for 18-20 hours, then cool down to room temperature naturally, and post-process to obtain fullerene zinc oxide (C60 /ZnO) Material;
(2)将步骤(1)得到的富勒烯氧化锌(C60/ZnO)材料加入体积分数为5％-10％的乙醇溶液中搅拌10-15min后，加入含硒的水合肼，继续搅拌10-15min后，升温至160-180℃反应12-16h后，自然冷却至室温，经后处理即得所述富勒烯氧化锌硒(C60/ZnO/Se)复合材料。(2) Add the fullerene zinc oxide (C60 /ZnO) material obtained in step (1) into an ethanol solution with a volume fraction of 5%-10% and stir for 10-15min, then add selenium-containing hydrazine hydrate and continue stirring After 10-15 minutes, the temperature is raised to 160-180° C. for 12-16 hours, and then naturally cooled to room temperature, and after post-treatment, the fullerene zinc oxide selenium (C60 /ZnO/Se) composite material is obtained.
步骤(1)中每克富勒烯使用锌盐2-3mmol，锌盐与氨水的摩尔比为1：1.2-1.5，锌盐溶液的浓度为1-2mol/L，氨水的浓度为1mol/L；所述富勒烯优选C60、C70中的一种或两种混合；所述锌盐选自氯化锌、硝酸锌、硫酸锌或其水合物中的一种或几种。In step (1), 2-3mmol of zinc salt is used per gram of fullerene, the molar ratio of zinc salt to ammonia is 1:1.2-1.5, the concentration of zinc salt solution is 1-2mol/L, and the concentration of ammonia is 1mol/L ; The fullerene is preferably C60 , C70 in one or a mixture of two; the zinc salt is selected from one or more of zinc chloride, zinc nitrate, zinc sulfate or hydrate thereof.
步骤(2)中每克富勒烯氧化锌(C60/ZnO)材料使用乙醇溶液120-180mL，使用含硒的水合肼10-15mL；所述含硒的水合肼为每毫升水合肼中含硒6-10mg。In step (2), 120-180mL of ethanol solution is used for each gram of fullerene zinc oxide (C60 /ZnO) material, and 10-15mL of selenium-containing hydrazine hydrate is used; the selenium-containing hydrazine hydrate contains Selenium 6-10mg.
本发明所述步骤(1)、(2)的反应优选在高压反应釜中进行；步骤(1)、(2)所述后处理为过滤、沉淀用去离子水、乙醇洗涤后，于60-80℃下真空干燥6-10h。The reaction of steps (1) and (2) of the present invention is preferably carried out in an autoclave; step (1), (2) described aftertreatment is after filtration, precipitation with deionized water, ethanol washing, in 60- Vacuum dry at 80°C for 6-10h.
本发明的另一实施方案提供一种富勒烯氧化锌硒(C60/ZnO/Se)复合材料的制备方法，其特征在于包括如下步骤：Another embodiment of the present invention provides a kind of preparation method of fullerene zinc oxide selenium (C60 /ZnO/Se) composite material, it is characterized in that comprising the following steps:
(1)将富勒烯、锌盐溶液、氨水混合均匀后，升温至120-130℃反应18-20h后，自然降至室温后，经后处理得富勒烯氧化锌(C60/ZnO)材料；(1) Mix fullerene, zinc salt solution, and ammonia water evenly, raise the temperature to 120-130°C and react for 18-20 hours, then cool down to room temperature naturally, and post-process to obtain fullerene zinc oxide (C60 /ZnO) Material;
(2)将步骤(1)得到的富勒烯氧化锌(C60/ZnO)材料加入体积分数为5％-10％的乙醇溶液中搅拌10-15min后，加入含硒的水合肼，继续搅拌10-15min后，升温至160-180℃反应12-16h后，自然冷却至室温，经后处理即得所述富勒烯氧化锌硒(C60/ZnO/Se)复合材料。(2) Add the fullerene zinc oxide (C60 /ZnO) material obtained in step (1) into an ethanol solution with a volume fraction of 5%-10% and stir for 10-15min, then add selenium-containing hydrazine hydrate and continue stirring After 10-15 minutes, the temperature is raised to 160-180° C. for 12-16 hours, and then naturally cooled to room temperature, and after post-treatment, the fullerene zinc oxide selenium (C60 /ZnO/Se) composite material is obtained.
步骤(1)中每克富勒烯使用锌盐2-3mmol，锌盐与氨水的摩尔比为1：1.2-1.5，锌盐溶液的浓度为1-2mol/L，氨水的浓度为1mol/L；所述富勒烯优选C60、C70中的一种或两种混合；所述锌盐选自氯化锌、硝酸锌、硫酸锌或其水合物中的一种或几种。In step (1), 2-3mmol of zinc salt is used per gram of fullerene, the molar ratio of zinc salt to ammonia is 1:1.2-1.5, the concentration of zinc salt solution is 1-2mol/L, and the concentration of ammonia is 1mol/L ; The fullerene is preferably C60 , C70 in one or a mixture of two; the zinc salt is selected from one or more of zinc chloride, zinc nitrate, zinc sulfate or hydrate thereof.
步骤(2)中每克富勒烯氧化锌(C60/ZnO)材料使用乙醇溶液120-180mL，使用含硒的水合肼10-15mL；所述含硒的水合肼为每毫升水合肼中含硒6-10mg。In step (2), 120-180mL of ethanol solution is used for each gram of fullerene zinc oxide (C60 /ZnO) material, and 10-15mL of selenium-containing hydrazine hydrate is used; the selenium-containing hydrazine hydrate contains Selenium 6-10mg.
本发明所述步骤(1)、(2)的反应优选在高压反应釜中进行；步骤(1)、(2)所述后处理为过滤、沉淀用去离子水、乙醇洗涤后，于60-80℃下真空干燥6-10h。The reaction of steps (1) and (2) of the present invention is preferably carried out in an autoclave; step (1), (2) described aftertreatment is after filtration, precipitation with deionized water, ethanol washing, in 60- Vacuum dry at 80°C for 6-10h.
本发明的另一实施方案提供上述富勒烯氧化锌硒(C60/ZnO/Se)复合材料作为催化剂的应用，优选作为氧化反应催化剂的应用。Another embodiment of the present invention provides the application of the above-mentioned fullerene zinc oxide selenium oxide (C60 /ZnO/Se) composite material as a catalyst, preferably as an oxidation reaction catalyst.
本发明的另一实施方案提供上述富勒烯氧化锌硒(C60/ZnO/Se)复合材料在选择性氧化伯羟基中的应用，优选在选择性氧化伯羟基为醛基中的应用。Another embodiment of the present invention provides the application of the above-mentioned fullerene zinc oxide selenium oxide (C60 /ZnO/Se) composite material in the selective oxidation of primary hydroxyl groups, preferably in the selective oxidation of primary hydroxyl groups into aldehyde groups.
本发明的另一实施方案提供上述富勒烯氧化锌硒(C60/ZnO/Se)复合材料在制备甘油醛中的应用。Another embodiment of the present invention provides the application of the above fullerene zinc oxide selenium oxide (C60 /ZnO/Se) composite material in the preparation of glyceraldehyde.
本发明的另一实施方案提供上述富勒烯氧化锌硒(C60/ZnO/Se)复合材料在催化氧化甘油制备甘油醛中的应用。Another embodiment of the present invention provides the application of the above fullerene zinc oxide selenium (C60 /ZnO/Se) composite material in the catalytic oxidation of glycerin to prepare glyceraldehyde.
本发明的另一实施方案提供上述富勒烯氧化锌硒(C60/ZnO/Se)复合材料在制备甘油醛缩丙酮中的应用。Another embodiment of the present invention provides the application of the above fullerene zinc oxide selenium (C60 /ZnO/Se) composite material in the preparation of glyceraldehyde acetal.
本发明的另一实施方案提供上述富勒烯氧化锌硒(C60/ZnO/Se)复合材料在催化氧化甘油醇缩丙酮制备甘油醛缩丙酮中的应用。Another embodiment of the present invention provides the application of the above-mentioned fullerene zinc oxide selenium (C60 /ZnO/Se) composite material in the preparation of glyceraldehyde acetal by catalyzing the oxidation of glycerol acetal.
本发明的另一实施方案提供一种甘油醛的制备方法，其特征在于包括如下步骤：Another embodiment of the present invention provides a kind of preparation method of glyceraldehyde, it is characterized in that comprising the steps:
向甘油水溶液中加入适量的上述富勒烯氧化锌硒(C60/ZnO/Se)复合材料，升温至45-50℃后，通入氧气，反应5-8小时后，离心除去富勒烯氧化锌硒(C60/ZnO/Se)复合材料，上清液经减压蒸馏除水后，加入无水乙醇结晶，过滤、洗涤、干燥即得甘油醛。Add an appropriate amount of the above-mentioned fullerene zinc oxide selenium (C60 /ZnO/Se) composite material to the glycerin aqueous solution, heat up to 45-50°C, feed oxygen, react for 5-8 hours, and centrifuge to remove the fullerene oxidation. Zinc selenium (C60 /ZnO/Se) composite material, the supernatant liquid is distilled under reduced pressure to remove water, then added absolute ethanol to crystallize, filtered, washed and dried to obtain glyceraldehyde.
其中，甘油水溶液的浓度为0.4-0.6mol/L，富勒烯氧化锌硒(C60/ZnO/Se)复合材料的用量为每摩尔甘油使用40-50mg富勒烯氧化锌硒(C60/ZnO/Se)复合材料；氧气的流速为120-150mL/min。Wherein, the concentration of the aqueous glycerol solution is 0.4-0.6mol/L, and the consumption of the fullerene zinc selenium oxide (C60 /ZnO/Se) composite material is 40-50 mg of fullerene zinc selenium oxide (C60 /ZnO/Se) per mole of glycerin. ZnO/Se) composite material; the flow rate of oxygen is 120-150mL/min.
上述制备方法中，甘油醛的收率在90％以上。In the above preparation method, the yield of glyceraldehyde is above 90%.
本发明的另一技术方案提供一种甘油醛缩丙酮的制备方法，其特征在于包括如下步骤：Another technical scheme of the present invention provides a kind of preparation method of glyceraldehyde acetone, it is characterized in that comprising the steps:
将甘油醇缩丙酮溶于丙酮中加入适量的上述富勒烯氧化锌硒(C60/ZnO/Se)复合材料，室温下，通入氧气反应，直至反应液中无甘油醇缩丙酮，离心除去富勒烯氧化锌硒(C60/ZnO/Se)复合材料，上清液经减压浓缩、干燥即得甘油醛缩丙酮。Dissolve glyceryl acetone in acetone and add an appropriate amount of the above-mentioned fullerene zinc oxide selenium (C60 /ZnO/Se) composite material. At room temperature, feed oxygen to react until there is no glycerol acetal in the reaction solution, and then remove it by centrifugation. Fullerene zinc oxide selenium (C60 /ZnO/Se) composite material, the supernatant is concentrated under reduced pressure and dried to obtain glyceraldehyde acetonide.
其中，富勒烯氧化锌硒(C60/ZnO/Se)复合材料的用量为每摩尔甘油醇缩丙酮使用25-30mg富勒烯氧化锌硒(C60/ZnO/Se)复合材料；氧气的流速为180-200mL/min。丙酮的用量以能充分混匀反应物为宜，优选每摩尔甘油醇缩丙酮使用1.5-2.0L丙酮。Wherein, the consumption of fullerene zinc oxide selenium (C60 /ZnO/Se) composite material is that every mole of glyceryl acetal uses 25-30mg fullerene zinc oxide selenium (C60 /ZnO/Se) composite material; The flow rate is 180-200 mL/min. The amount of acetone should be enough to fully mix the reactants, preferably 1.5-2.0L of acetone per mole of glycerol acetone.
上述制备甘油醛缩丙酮的反应为绿色反应，反应结束后(反应时间优选20-24小时)无需复杂的纯化操作，只需通过离心去除反应催化剂——富勒烯氧化锌硒(C60/ZnO/Se)复合材料，上清液浓缩、干燥即可得到高纯度甘油醛缩丙酮(HPLC纯度在98.6％以上)。The above-mentioned reaction for preparing glyceraldehyde acetone is a green reaction. After the reaction (reaction time is preferably 20-24 hours), no complicated purification operation is required, and the reaction catalyst—fullerene zinc selenium oxide (C60 /ZnO /Se) composite material, the supernatant is concentrated and dried to obtain high-purity glycerol aldehyde acetone (HPLC purity above 98.6%).
本发明的优点在于：本发明克服现有技术的不足，开发出一种富勒烯氧化锌硒(C60/ZnO/Se)复合材料作为催化剂，催化甘油、甘油醇缩丙酮在氧气存在下，温和地转化为甘油醛、甘油醛缩丙酮，该反应操作简便、条件温和、转化率和选择性高、对环境无污染、绿色环保、易于工业化大生产。The advantages of the present invention are: the present invention overcomes the deficiencies in the prior art, and develops a fullerene zinc oxide selenium (C60 /ZnO/Se) composite material as a catalyst to catalyze glycerin and glycerol acetal under the presence of oxygen, Mild conversion into glyceraldehyde and glyceraldehyde acetone, the reaction is simple to operate, mild in conditions, high in conversion rate and selectivity, non-polluting to the environment, green and environmentally friendly, and easy for industrialized large-scale production.
附图说明Description of drawings
图1本发明制备甘油醛的简易反应装置图；Fig. 1 present invention prepares the simple and easy reaction device diagram of glyceraldehyde;
图2产品A、B的SEM图。Figure 2 SEM images of products A and B.
具体实施方式Detailed ways
为了便于对本发明的进一步理解，下面提供的实施例对其做了更详细的说明。但是这些实施例仅供更好的理解发明而并非用来限定本发明的范围或实施原则，本发明的实施方式不限于以下内容。In order to facilitate a further understanding of the present invention, the examples provided below illustrate it in more detail. However, these examples are only for a better understanding of the invention and are not used to limit the scope or implementation principle of the invention, and the embodiments of the invention are not limited to the following content.
实施例1Example 1
(1)取C60富勒烯(1.0g)、1mol/L的硝酸锌溶液(2mL)、1mol/L的氨水(2.4mL)于高压釜中混合均匀后，升温至120-125℃反应20h后，自然降至室温后，过滤、沉淀用去离子水、乙醇洗涤后，于80℃下真空干燥6h得富勒烯氧化锌(C60/ZnO)材料(以下简称产品a)；(1) Take C60 fullerene (1.0g), 1mol/L zinc nitrate solution (2mL), and 1mol/L ammonia water (2.4mL) in an autoclave and mix them evenly, then raise the temperature to 120-125°C for 20h After that, after naturally cooling down to room temperature, filter and precipitate, wash with deionized water and ethanol, and vacuum-dry at 80°C for 6 hours to obtain a fullerene zinc oxide (C60 /ZnO) material (hereinafter referred to as product a);
(2)取产品a(1.0g)加入体积分数为10％的乙醇溶液(120mL)中搅拌10-15min后，加入含硒的水合肼(15mL，含硒150mg)，继续搅拌10-15min后，升温至175-180℃反应12h后，自然冷却至室温，过滤、沉淀用去离子水、乙醇洗涤后，于70℃下真空干燥10h即得所述富勒烯氧化锌硒(C60/ZnO/Se)复合材料(以下简称产品A)。(2) Take product a (1.0 g) and add it into 10% ethanol solution (120 mL) by volume fraction and stir for 10-15 min, then add selenium-containing hydrazine hydrate (15 mL, containing 150 mg selenium), and continue stirring for 10-15 min, Raise the temperature to 175-180°C for 12 hours, then naturally cool to room temperature, filter, wash the precipitate with deionized water and ethanol, and vacuum dry at 70°C for 10 hours to obtain the fullerene zinc selenium oxide (C60 /ZnO/ Se) Composite material (hereinafter referred to as product A).
实施例2Example 2
(1)取C70富勒烯(1.0g)、2mol/L的硫酸锌溶液(1.5mL)、1mol/L的氨水(4.5mL)于高压釜中混合均匀后，升温至125-130℃反应18h后，自然降至室温后，过滤、沉淀用去离子水、乙醇洗涤后，于60℃下真空干燥10h得富勒烯氧化锌(C70/ZnO)材料(以下简称产品b)；(1) Take C70 fullerene (1.0g), 2mol/L zinc sulfate solution (1.5mL), and 1mol/L ammonia water (4.5mL) in an autoclave, mix them evenly, and heat up to 125-130°C for reaction After 18 hours, cool down to room temperature naturally, filter, precipitate, wash with deionized water and ethanol, and vacuum-dry at 60°C for 10 hours to obtain a fullerene zinc oxide (C70 /ZnO) material (hereinafter referred to as product b);
(2)取产品b(1.0g)加入体积分数为5％的乙醇溶液(180mL)中搅拌10-15min后，加入含硒的水合肼(10mL，含硒60mg)，继续搅拌10-15min后，升温至160-165℃反应16h后，自然冷却至室温，过滤、沉淀用去离子水、乙醇洗涤后，于80℃下真空干燥6h即得所述富勒烯氧化锌硒(C70/ZnO/Se)复合材料(以下简称产品B)。(2) Take product b (1.0g) and add it into ethanol solution (180mL) with a volume fraction of 5% and stir for 10-15min, then add selenium-containing hydrazine hydrate (10mL, containing 60mg selenium), and continue stirring for 10-15min, After raising the temperature to 160-165°C for 16 hours, cool naturally to room temperature, filter, wash the precipitate with deionized water and ethanol, and vacuum-dry at 80°C for 6 hours to obtain the fullerene zinc selenium oxide (C70 /ZnO/ Se) Composite material (hereinafter referred to as product B).
实施例3Example 3
(1)取石墨烯(1.0g)、1mol/L的硝酸锌溶液(2mL)、1mol/L的氨水(2.4mL)于高压釜中混合均匀后，升温至120-125℃反应20h后，自然降至室温后，过滤、沉淀用去离子水、乙醇洗涤后，于80℃下真空干燥6h得石墨烯氧化锌材料(以下简称产品c)；(1) After mixing graphene (1.0g), 1mol/L zinc nitrate solution (2mL), and 1mol/L ammonia water (2.4mL) in an autoclave, heat up to 120-125°C for 20 hours, and then naturally After cooling down to room temperature, filter and precipitate, wash with deionized water and ethanol, and vacuum-dry at 80°C for 6 hours to obtain a graphene zinc oxide material (hereinafter referred to as product c);
(2)取产品c(1.0g)加入体积分数为10％的乙醇溶液(120mL)中搅拌10-15min后，加入含硒的水合肼(15mL，含硒150mg)，继续搅拌10-15min后，升温至175-180℃反应12h后，自然冷却至室温，过滤、沉淀用去离子水、乙醇洗涤后，于70℃下真空干燥10h得石墨烯氧化锌硒复合材料(以下简称产品C)。(2) Take product c (1.0g) and add it into 10% ethanol solution (120mL) by volume fraction and stir for 10-15min, then add selenium-containing hydrazine hydrate (15mL, containing 150mg selenium), and continue stirring for 10-15min, After heating up to 175-180°C for 12 hours, cool naturally to room temperature, filter and precipitate, wash with deionized water and ethanol, and vacuum-dry at 70°C for 10 hours to obtain a graphene zinc oxide selenium composite material (hereinafter referred to as product C).
实施例4Example 4
取氧化锌(1.0g)加入体积分数为10％的乙醇溶液(120mL)中搅拌10-15min后，加入含硒的水合肼(15mL，含硒150mg)，继续搅拌10-15min后，升温至175-180℃反应12h后，自然冷却至室温，过滤、沉淀用去离子水、乙醇洗涤后，于70℃下真空干燥10h得产品D。Take zinc oxide (1.0g) and add it to 10% ethanol solution (120mL) and stir for 10-15min, then add selenium-containing hydrazine hydrate (15mL, containing 150mg selenium), continue stirring for 10-15min, then heat up to 175 After reacting at -180°C for 12 hours, cool naturally to room temperature, filter, wash the precipitate with deionized water and ethanol, and vacuum-dry at 70°C for 10 hours to obtain product D.
实施例5Example 5
向甘油水溶液(0.4mol/L，500mL)中加入产品A(8mg)，升温至45-50℃后，通入氧气(流速为150mL/min)，反应5小时后，离心除去产品A，上清液经减压蒸馏除水后，加入无水乙醇结晶，过滤、洗涤、干燥即得甘油醛(16.4g，收率为91.0％)，结构确证数据与已知报道一致。Add product A (8mg) to glycerol aqueous solution (0.4mol/L, 500mL), heat up to 45-50°C, feed oxygen (flow rate 150mL/min), react for 5 hours, centrifuge to remove product A, supernatant After the liquid was distilled under reduced pressure to remove water, absolute ethanol was added to crystallize, filtered, washed, and dried to obtain glyceraldehyde (16.4 g, yield 91.0%), and the structure confirmation data was consistent with known reports.
实施例6Example 6
向甘油水溶液(0.6mol/L，500mL)中加入产品B(15mg)，升温至45-50℃后，通入氧气(流速为120mL/min)，反应8小时后，离心除去产品B，上清液经减压蒸馏除水后，加入无水乙醇结晶，过滤、洗涤、干燥即得甘油醛(24.4g，收率为90.2％)，结构确证数据与已知报道一致。Add product B (15mg) to glycerol aqueous solution (0.6mol/L, 500mL), heat up to 45-50°C, feed oxygen (flow rate: 120mL/min), react for 8 hours, centrifuge to remove product B, supernatant After the solution was distilled under reduced pressure to remove water, absolute ethanol was added to crystallize, filtered, washed, and dried to obtain glyceraldehyde (24.4 g, yield 90.2%), and the structure confirmation data was consistent with known reports.
实施例7Example 7
按照实施例5记载的方法，分别采用产品a、b、c、C、D替代产品A，反应5小时后取上清液，采用高效液相色谱通过外标法进行定量分析，色谱条件：采用Aminex HPX-87H色谱柱，柱温60℃，以0.01mol/L的H2SO4溶液作为流动相，流速0.5mL/min，紫外检测器(UVD)和示差折光检测器(RID)串联使用。结果表明仅在使用产品C的反应上清液中检测到15％的甘油醛、13％的1,3-二羟基丙酮；使用产品a、b、c、D的反应上清液中只检测到甘油，未发现甘油醛。According to the method described in Example 5, product a, b, c, C, D are respectively used to replace product A, and after 5 hours of reaction, the supernatant is taken, and high performance liquid chromatography is used for quantitative analysis by external standard method, chromatographic conditions: adopt Aminex HPX-87H chromatographic column, column temperature 60°C, 0.01mol/L H2 SO4 solution as mobile phase, flow rate 0.5mL/min, ultraviolet detector (UVD) and differential refractive index detector (RID) used in series. The results showed that only 15% of glyceraldehyde and 13% of 1,3-dihydroxyacetone were detected in the reaction supernatant using product C; only detected in the reaction supernatant using products a, b, c, and D Glycerin, glyceraldehyde not found.
实施例8Example 8
将甘油醇缩丙酮(0.1mol)溶于丙酮(150mL)中加入产品A(2.5mg)，室温下，通入氧气反应(流速为200mL/min)，直至反应液中无甘油醇缩丙酮(反应约24小时)，离心除去产品A，上清液经减压浓缩、干燥即得甘油醛缩丙酮(12.9g，HPLC纯度为98.6％)，结构确证数据与已知报道一致。Dissolve glyceryl acetone (0.1mol) in acetone (150mL) and add product A (2.5mg). About 24 hours), the product A was removed by centrifugation, and the supernatant was concentrated under reduced pressure and dried to obtain glyceraldehyde acetone (12.9 g, HPLC purity: 98.6%), and the structure confirmation data was consistent with known reports.
实施例9Example 9
将甘油醇缩丙酮(0.1mol)溶于丙酮(200mL)中加入产品B(3mg)，室温下，通入氧气反应(流速为180mL/min)，直至反应液中无甘油醇缩丙酮(反应约20小时)，离心除去产品B，上清液经减压浓缩、干燥即得甘油醛缩丙酮(12.8g，HPLC纯度为98.8％)，结构确证数据与已知报道一致。Dissolve glyceryl acetonide (0.1mol) in acetone (200mL) and add product B (3mg). 20 hours), centrifuged to remove product B, and the supernatant was concentrated under reduced pressure and dried to obtain glyceraldehyde acetone (12.8 g, HPLC purity: 98.8%), and the structure confirmation data was consistent with known reports.
实施例10Example 10
按照实施例8记载的方法，分别采用产品a、b、c、C、D替代产品A，反应24小时后取上清液，采用高效液相色谱通过外标法进行定量分析，结果发现使用产品a、b、c、D的反应上清液中未检测到甘油醛缩丙酮，使用产品C的反应上清液中检测到甘油醛缩丙酮，但是仍有大量甘油醇缩丙酮未反应。According to the method described in Example 8, products a, b, c, C, and D were used to replace product A respectively, and the supernatant was taken after 24 hours of reaction, and quantitative analysis was carried out by high performance liquid chromatography by external standard method. It was found that the product Glycerol aldehyde acetonide was not detected in the reaction supernatants of a, b, c, and D, and glycerol aldehyde acetonide was detected in the reaction supernatant of product C, but there were still a large amount of glycerol acetone unreacted.
| Application Number | Priority Date | Filing Date | Title |
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| CN201810472194.3ACN108686682B (en) | 2018-05-16 | 2018-05-16 | Green oxidation synthesis method of glyceraldehyde |
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| CN201810472194.3ACN108686682B (en) | 2018-05-16 | 2018-05-16 | Green oxidation synthesis method of glyceraldehyde |
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| CN108686682B CN108686682B (en) | 2020-08-25 |
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| CN201810472194.3AActiveCN108686682B (en) | 2018-05-16 | 2018-05-16 | Green oxidation synthesis method of glyceraldehyde |
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