CN108686682B - Green oxidation synthesis method of glyceraldehyde - Google Patents

Abstract

The invention relates to a method for synthesizing glyceraldehyde by green oxidation, which specifically includes the following steps: adding an appropriate amount of fullerene zinc selenium oxide (C ₆₀ /ZnO/Se) composite material into an aqueous glycerol solution, and after heating to 45-50° C., Oxygen was introduced, and after 5-8 hours of reaction, the fullerene zinc selenium oxide (C ₆₀ /ZnO/Se) composite material was removed by centrifugation. and drying to obtain glyceraldehyde.

Description

A kind of method of green oxidation synthesizing glyceraldehyde

technical field

The invention belongs to the field of organic synthesis and catalysis, and in particular relates to a method for synthesizing glyceraldehyde by green oxidation.

Background technique

Glyceraldehyde is an optically active aldose compound first discovered, and its molecule contains a chiral carbon atom, namely D- and L-optical isomers, and is often used as a standard for the calibration of carbohydrate configurations. Racemic D, L-glyceraldehyde has anti-glycolytic effect and is a good blood sugar protectant. At the same time, as an important organic synthesis intermediate, it occupies a position in the synthesis of medicine, agricultural chemicals and natural products. It has a very important position and can be used as a chiral source for asymmetric synthesis in organic synthesis. Especially, it contains an active functional group - aldehyde group, 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 an inexpensive chiral inducing monomer for the synthesis of chiral molecules and is an important precursor for the synthesis of some chiral drugs and optically active natural products.

The traditional production method of glyceraldehyde mainly uses glycerol as raw material, and synthesizes glyceraldehyde by chemical oxidation method. The commonly used oxidants are generally: hydrogen peroxide, peroxyacid, dilute nitric acid, chromium oxide, active manganese dioxide, dimethyl sulfoxide etc. as an oxidant to prepare glyceraldehyde. However, hydrogen peroxide, peroxyacid, etc. are strong oxidants, which are flammable and explosive, and have problems such as transportation and storage. Chromium oxide and dimethyl sulfoxide pollute the environment. Therefore, high efficiency, low cost, and environmental Friendly new preparation methods remain an important goal of current research. The reaction formula is as follows:

It has been reported in the literature that using Lewis acid anhydrous ZnCl ₂ as a catalytic dehydrating agent, D-mannitol and acetone are condensed to synthesize diisopropylidene condensate, and then NaIO ₄ is used for oxidative bond cleavage to prepare D-(R)-glyceraldehyde acetal. , and then remove acetone to prepare glyceraldehyde. This method has the advantages of high yield, low cost, and environmental friendliness. However, due to the disadvantages of high raw material price and complicated reaction steps, it is not suitable for industrial production selection. The reaction is as follows:

There are also literature reports that glyceraldehyde is synthesized by indirect electro-oxidation method using glycerol as a raw material. 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, which is not suitable for industrial production. The invention overcomes the deficiencies of the prior art and develops a fullerene zinc oxide selenium (C ₆₀ /ZnO/Se) composite material as a catalyst, which catalyzes the gentle conversion of glycerol and glycerol acetal into glyceraldehyde in the presence of oxygen , glyceraldehyde acetone, the reaction is easy to operate, mild conditions, high conversion rate and selectivity, no pollution to the environment, green environmental protection, easy to industrialized production.

SUMMARY OF THE INVENTION

The invention provides a fullerene zinc selenium oxide (C ₆₀ /ZnO/Se) composite material, which is characterized in that the preparation method of the fullerene zinc selenium oxide composite material comprises the following steps:

(1) After mixing the fullerene, zinc salt solution and ammonia water uniformly, the temperature is raised to 120-130°C for 18-20h, and after naturally cooling to room temperature, the fullerene zinc oxide (C ₆₀ /ZnO) is obtained by post-processing. Material;

(2) adding the fullerene zinc oxide (C ₆₀ /ZnO) material obtained in step (1) into an ethanol solution with a volume fraction of 5%-10% and stirring for 10-15min, adding selenium-containing hydrazine hydrate, and continuing to stir After 10-15 minutes, the temperature is raised to 160-180° C. and reacted for 12-16 hours, then naturally cooled to room temperature, and the fullerene zinc selenium oxide (C ₆₀ /ZnO/Se) composite material is obtained after post-treatment.

In step (1), every gram of fullerene uses zinc salt 2-3mmol, the mol ratio of zinc salt and ammoniacal liquor is 1:1.2-1.5, the concentration of zinc salt solution is 1-2mol/L, and the concentration of ammoniacal liquor is 1mol/L The fullerene is preferably one or a mixture of C ₆₀ and C ₇₀ ; the zinc salt is selected from one or more of zinc chloride, zinc nitrate, zinc sulfate or its hydrate.

In step (2), 120-180 mL of ethanol solution is used for each gram of fullerene zinc oxide (C ₆₀ /ZnO) material, and 10-15 mL of selenium-containing hydrazine hydrate is used; Selenium 6-10mg.

The reactions of the steps (1) and (2) of the present invention are preferably carried out in a high-pressure reactor; the post-treatment in the steps (1) and (2) is filtration, precipitation after washing with deionized water and ethanol, and then in 60- Vacuum dry at 80°C for 6-10h.

Another embodiment of the present invention provides a preparation method of a fullerene zinc oxide selenium (C ₆₀ /ZnO/Se) composite material, which is characterized by comprising the following steps:

(1) After mixing the fullerene, zinc salt solution and ammonia water uniformly, the temperature is raised to 120-130°C for 18-20h, and after naturally cooling to room temperature, the fullerene zinc oxide (C ₆₀ /ZnO) is obtained by post-processing. Material;

(2) adding the fullerene zinc oxide (C ₆₀ /ZnO) material obtained in step (1) into an ethanol solution with a volume fraction of 5%-10% and stirring for 10-15min, adding selenium-containing hydrazine hydrate, and continuing to stir After 10-15 minutes, the temperature is raised to 160-180° C. and reacted for 12-16 hours, then naturally cooled to room temperature, and the fullerene zinc selenium oxide (C ₆₀ /ZnO/Se) composite material is obtained after post-treatment.

In step (1), every gram of fullerene uses zinc salt 2-3mmol, the mol ratio of zinc salt and ammoniacal liquor is 1:1.2-1.5, the concentration of zinc salt solution is 1-2mol/L, and the concentration of ammoniacal liquor is 1mol/L The fullerene is preferably one or a mixture of C ₆₀ and C ₇₀ ; the zinc salt is selected from one or more of zinc chloride, zinc nitrate, zinc sulfate or its hydrate.

In step (2), 120-180 mL of ethanol solution is used for each gram of fullerene zinc oxide (C ₆₀ /ZnO) material, and 10-15 mL of selenium-containing hydrazine hydrate is used; Selenium 6-10mg.

The reactions of the steps (1) and (2) of the present invention are preferably carried out in a high-pressure reactor; the post-treatment in the steps (1) and (2) is filtration, precipitation after washing with deionized water and ethanol, and then in 60- Vacuum dry at 80°C for 6-10h.

Another embodiment of the present invention provides the application of the above-mentioned fullerene zinc oxide selenium (C ₆₀ /ZnO/Se) composite material as a catalyst, preferably as an oxidation reaction catalyst.

Another embodiment of the present invention provides the application of the above-mentioned fullerene zinc selenium oxide (C ₆₀ /ZnO/Se) composite material in the selective oxidation of primary hydroxyl groups, preferably in the selective oxidation of primary hydroxyl groups to aldehyde groups.

Another embodiment of the present invention provides the application of the above-mentioned fullerene zinc oxide selenium (C ₆₀ /ZnO/Se) composite material in the preparation of glyceraldehyde.

Another embodiment of the present invention provides the application of the above-mentioned fullerene zinc selenium oxide (C ₆₀ /ZnO/Se) composite material in catalytic oxidation of glycerol to prepare glyceraldehyde.

Another embodiment of the present invention provides the application of the above-mentioned fullerene zinc oxide selenium (C ₆₀ /ZnO/Se) composite material in the preparation of glyceraldehyde acetal.

Another embodiment of the present invention provides the application of the above-mentioned fullerene zinc selenium oxide (C ₆₀ /ZnO/Se) composite material in catalytic oxidation of glycerol acetal to prepare glyceraldehyde acetal.

Another embodiment of the present invention provides a kind of preparation method of glyceraldehyde, it is characterized in that comprising the following steps:

Add an appropriate amount of the above-mentioned fullerene zinc selenium oxide (C ₆₀ /ZnO/Se) composite material to the glycerin aqueous solution, heat up to 45-50 ° C, introduce oxygen, react for 5-8 hours, and remove the fullerene oxidation by centrifugation. For zinc selenium (C ₆₀ /ZnO/Se) composite material, the supernatant is distilled under reduced pressure to remove water, then crystallized with absolute ethanol, filtered, washed and dried to obtain glyceraldehyde.

Wherein, the concentration of the glycerin aqueous solution is 0.4-0.6 mol/L, and the dosage of the fullerene zinc oxide selenium (C ₆₀ /ZnO/Se) composite material is 40-50 mg of fullerene zinc oxide selenium (C ₆₀ /ZnO/Se) per mole of glycerol. ZnO/Se) composite; the flow rate of oxygen was 120-150 mL/min.

In the above preparation method, the yield of glyceraldehyde is above 90%.

Another technical scheme of the present invention provides a kind of preparation method of glyceraldehyde acetone, which is characterized in that comprising the following steps:

Dissolving glycerol acetal in acetone, adding an appropriate amount of the above-mentioned fullerene zinc oxide selenium (C ₆₀ /ZnO/Se) composite material, at room temperature, introducing oxygen to react until there is no glycerol acetal in the reaction solution, and removing by centrifugation Fullerene zinc selenium oxide (C ₆₀ /ZnO/Se) composite material, the supernatant is concentrated under reduced pressure and dried to obtain glyceraldehyde acetal.

Wherein, the dosage of fullerene zinc oxide selenium (C ₆₀ /ZnO/Se) composite material is 25-30 mg of fullerene zinc oxide selenium (C ₆₀ /ZnO/Se) composite material per mole of glycerol acetal; The flow rate was 180-200 mL/min. The dosage of acetone is suitable for fully mixing the reactants, preferably 1.5-2.0L of acetone is used per mole of glycerol acetal.

The above-mentioned reaction for preparing glyceraldehyde acetal is a green reaction, and after the reaction is finished (preferably 20-24 hours of reaction time), no complicated purification operation is required, and the reaction catalyst-fullerene zinc selenium oxide (C ₆₀ /ZnO) only needs to be removed by centrifugation. /Se) composite material, the supernatant is concentrated and dried to obtain high-purity glyceraldehyde acetal (HPLC purity is above 98.6%).

The advantages of the present invention are: the present invention overcomes the deficiencies of the prior art, and develops a fullerene zinc oxide selenium (C ₆₀ /ZnO/Se) composite material as a catalyst to catalyze glycerol and glycerol acetal in the presence of oxygen. Gently converted into glyceraldehyde and glyceraldehyde acetone, the reaction is easy to operate, mild conditions, high conversion rate and selectivity, no pollution to the environment, green and environmental protection, and easy for industrialized large-scale production.

Description of drawings

Fig. 1 is a simple reaction device diagram for preparing glyceraldehyde of the present invention;

Figure 2 SEM images of products A and B.

Detailed ways

In order to facilitate the further understanding of the present invention, the following examples are provided to describe it in more detail. However, these examples are only for better understanding of the invention and are not used to limit the scope or implementation principles of the present invention, and the embodiments of the present invention are not limited to the following contents.

Example 1

(1) Mix C ₆₀ fullerene (1.0g), 1mol/L zinc nitrate solution (2mL), and 1mol/L ammonia water (2.4mL) in an autoclave, and then heat it up to 120-125℃ for 20h After filtration and precipitation, washed with deionized water and ethanol, and vacuum-dried at 80°C for 6 hours to obtain fullerene zinc oxide (C ₆₀ /ZnO) material (hereinafter referred to as product a);

(2) Add product a (1.0 g) into ethanol solution (120 mL) with a volume fraction of 10%, and stir for 10-15 min. The temperature was raised to 175-180°C for 12h, then cooled to room temperature naturally, filtered and washed with deionized water and ethanol for precipitation, and then vacuum-dried at 70°C for 10h to obtain the fullerene zinc selenium oxide (C ₆₀ /ZnO/ Se) composite material (hereinafter referred to as product A).

Example 2

(1) After taking C ₇₀ fullerene (1.0g), 2mol/L zinc sulfate solution (1.5mL), 1mol/L ammonia water (4.5mL) and mixing them in the autoclave, the temperature was raised to 125-130°C for reaction After 18 hours, it was naturally lowered to room temperature, filtered and precipitated, washed with deionized water and ethanol, and then vacuum-dried at 60°C for 10 hours to obtain a fullerene zinc oxide (C ₇₀ /ZnO) material (hereinafter referred to as product b);

(2) Add product b (1.0 g) into 5% ethanol solution (180 mL) and stir for 10-15 min, add selenium-containing hydrazine hydrate (10 mL, selenium-containing 60 mg), and continue stirring for 10-15 min. The temperature was raised to 160-165°C for 16h, then cooled to room temperature naturally, filtered, washed with deionized water and ethanol for precipitation, and vacuum-dried at 80°C for 6h to obtain the fullerene zinc selenium oxide (C ₇₀ /ZnO/ Se) composite material (hereinafter referred to as product B).

Example 3

(1) After taking graphene (1.0g), 1mol/L zinc nitrate solution (2mL), and 1mol/L ammonia water (2.4mL) and mixing them in the autoclave, the temperature was raised to 120-125°C and reacted for 20h. After cooling to room temperature, filtration and precipitation were washed with deionized water and ethanol, and then vacuum-dried at 80°C for 6 hours to obtain graphene zinc oxide material (hereinafter referred to as product c);

(2) Add product c (1.0 g) into ethanol solution (120 mL) with a volume fraction of 10%, and stir for 10-15 min, add selenium-containing hydrazine hydrate (15 mL, 150 mg of selenium), and continue stirring for 10-15 min. After heating to 175-180°C for 12h, it was naturally cooled to room temperature, filtered, washed with deionized water and ethanol for precipitation, and vacuum-dried at 70°C for 10h to obtain graphene zinc oxide selenium composite material (hereinafter referred to as product C).

Example 4

Take zinc oxide (1.0g) and add it to 10% ethanol solution (120mL), stir for 10-15min, add selenium-containing hydrazine hydrate (15mL, selenium-containing 150mg), continue stirring for 10-15min, then heat up to 175 After reacting at -180°C for 12h, it was naturally cooled to room temperature, filtered and precipitated, washed with deionized water and ethanol, and then vacuum-dried at 70°C for 10h to obtain product D.

Example 5

Add product A (8mg) to glycerol aqueous solution (0.4mol/L, 500mL), after warming up to 45-50 ℃, feed oxygen (flow rate is 150mL/min), after 5 hours of reaction, remove product A by centrifugation, supernatant After the liquid was distilled under reduced pressure to remove water, anhydrous ethanol was added for crystallization, filtered, washed and dried to obtain glyceraldehyde (16.4 g, yield 91.0%).

Example 6

Add product B (15mg) to glycerol aqueous solution (0.6mol/L, 500mL), after warming up to 45-50 ℃, feed oxygen (flow rate is 120mL/min), after 8 hours of reaction, centrifugally remove product B, supernatant After the liquid was distilled under reduced pressure to remove water, anhydrous ethanol was added for crystallization, filtered, washed and dried to obtain glyceraldehyde (24.4 g, yield 90.2%). The structural confirmation data was consistent with known reports.

Example 7

According to the method described in Example 5, products a, b, c, C, and D were respectively used to replace product A, and the supernatant was taken after 5 hours of reaction, and high-performance liquid chromatography was used to carry out quantitative analysis by external standard method. Chromatographic conditions: using Aminex HPX-87H chromatographic column, column temperature 60 ℃, with 0.01mol/L H ₂ SO ₄ solution as mobile phase, flow rate 0.5 mL/min, ultraviolet detector (UVD) and refractive index detector (RID) were 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 the reaction supernatant using products a, b, c, and D was detected Glycerol, no glyceraldehyde was found.

Example 8

Dissolve glycerol acetal (0.1mol) in acetone (150mL) and add product A (2.5mg), at room temperature, feed oxygen to react (flow rate is 200mL/min), until there is no glycerol acetal (reaction) in the reaction solution. About 24 hours), product A was removed by centrifugation, and the supernatant was concentrated under reduced pressure and dried to obtain glyceraldehyde acetal (12.9 g, HPLC purity 98.6%), and the structural confirmation data was consistent with known reports.

Example 9

Dissolve glycerol acetal (0.1mol) in acetone (200mL) and add product B (3mg), at room temperature, feed oxygen to react (flow rate is 180mL/min), until there is no glycerol acetal in the reaction solution (reaction about 20 hours), product B was removed by centrifugation, and the supernatant was concentrated under reduced pressure and dried to obtain glyceraldehyde acetal (12.8 g, HPLC purity 98.8%), and the structural confirmation data was consistent with known reports.

Example 10

According to the method described in Example 8, products a, b, c, C, and D were respectively used to replace product A, and the supernatant was taken after 24 hours of reaction, and high-performance liquid chromatography was used to carry out quantitative analysis by external standard method, and it was found that the product was used Glyceraldehyde acetal is not detected in the reaction supernatants of a, b, c, and D, and glyceraldehyde acetal is detected in the reaction supernatants of product C, but a large amount of glycerol acetal is still unreacted.

Claims (3)

1. A preparation method of glyceraldehyde is characterized by comprising the following steps:

adding proper amount of fullerene zinc oxide selenium C into glycerol aqueous solution₆₀Heating the/ZnO/Se composite material to 45-50 ℃, introducing oxygen, reacting for 5-8 hours, centrifuging to remove fullerene, zinc oxide and selenium C₆₀the/ZnO/Se composite material is prepared by distilling the supernatant fluid under reduced pressure to remove water, adding absolute ethyl alcohol for crystallization, filtering, washing and drying to obtain glyceraldehyde; the fullerene zinc oxide selenium C₆₀The preparation method of the/ZnO/Se composite material comprises the following steps: (1) uniformly mixing fullerene, zinc salt solution and ammonia water, heating to 120-130 ℃, reacting for 18-20h, naturally cooling to room temperature, and performing post-treatment to obtain fullerene zinc oxide C₆₀a/ZnO material; (2) the fullerene zinc oxide C obtained in the step (1)₆₀Adding ZnO material into 5-10% ethanol solution, stirring for 10-15min, adding hydrazine hydrate containing selenium, stirring for 10-15min, heating to 160-180 deg.C, reacting for 12-16h, naturally cooling to room temperature, and post-treating to obtain the fullerene zinc oxide selenium C₆₀a/ZnO/Se composite material.

2. The method according to claim 1, wherein the concentration of the aqueous glycerol solution is 0.4 to 0.6mol/L, and the fullerene zinc selenide C is₆₀The dosage of the/ZnO/Se composite material is 40-50mg of fullerene zinc oxide selenium C per mol of glycerol₆₀a/ZnO/Se composite material.

3. The method of claim 1, wherein the flow rate of oxygen is 120-150 mL/min.

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