A method for synthesizing high-purity 3-aminopropanol

Abstract

The application discloses a kind of synthesis methods of high-purity 3-amino propanol, it is related to organic synthesis technical field, the synthesis method of 3-amino propanol includes: adding 3-hydroxy propionitrile, liquid ammonia, catalyst and solvent to reaction kettle, hydrogen is inhaled and catalytic hydrogenation reaction is carried out, after reaction, product is separated and purified, and 3-amino propanol is obtained;The application is by using high-purity 3-hydroxy propionitrile as raw material and the screening of catalyst, so that the purity of 3-amino propanol reaches 99.9%.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and specifically to a method for synthesizing high-purity 3-aminopropanol. Background Technology

[0002] 3-Aminopropanol is an important organic synthetic intermediate widely used in the pharmaceutical, cosmetic, and chemical industries. Using 3-aminopropanol as a raw material, it can be used to synthesize antitumor drugs such as cyclophosphamide, cardiovascular drugs such as serotonin, and precursors of vitamin B5. It can also be used to prepare moisturizers, surfactants, preservatives, and dye and coating additives.

[0003] The existing methods for synthesizing 3-aminopropanol mainly include the following: (1) Catalytic hydrogenation method using 3-hydroxypropionitrile as raw material. Under the catalysis of Raney nickel, 3-hydroxypropionitrile reacts with liquid ammonia and hydrogen to generate 3-aminopropanol. (2) Hydrogenation-hydrolysis method using 3-methoxypropionitrile as raw material. 3-methoxypropionitrile reacts with hydrogen to generate 3-methoxypropylamine, which is then hydrolyzed to obtain 3-aminopropanol. (3) Chlorination-ammonolysis method using 1,3-propanediol as raw material. 1,3-propanediol reacts with hydrogen chloride to generate 3-chloropropanol, which is then ammonolyzed to obtain 3-aminopropanol. (4) Hydration-catalytic hydrogenation method using acrylonitrile as raw material. Acrylonitrile undergoes hydration to generate 3-hydroxypropionitrile, which is then catalytically hydrogenated to obtain 3-aminopropanol. Among them, the catalytic hydrogenation method using 3-hydroxypropionitrile as a raw material is currently the most widely used industrial route for the synthesis of 3-aminopropanol, but its post-processing is complex and the product purity is low. To obtain high-purity 3-hydroxypropionitrile while controlling costs, the synthesis process of 3-hydroxypropionitrile needs to be improved. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a method for synthesizing high-purity 3-aminopropanol. By using high-purity 3-hydroxypropionitrile as raw material and screening catalysts, the purity of the product 3-aminopropanol can reach more than 99.9%.

[0005] The technical problem to be solved by this invention is achieved by the following technical solution:

[0006] A method for synthesizing high-purity 3-aminopropanol involves adding 3-hydroxypropionitrile, liquid ammonia, a catalyst, and a solvent to a reaction vessel, introducing hydrogen gas to carry out a catalytic hydrogenation reaction, and separating and purifying the product after the reaction to obtain 3-aminopropanol.

[0007] Furthermore, the catalyst is Raney nickel. Even further, the Raney nickel contains ≥90 wt% nickel and ≤10 wt% aluminum.

[0008] Furthermore, the solvent includes, but is not limited to, at least one of methanol, ethanol, acetone, and chloroform, with methanol being preferred.

[0009] Furthermore, the purity of the 3-hydroxypropionitrile is not less than 99%. In this invention, high-purity 3-hydroxypropionitrile is used as the raw material.

[0010] Furthermore, the molar ratio of 3-hydroxypropionitrile to liquid ammonia is 1:(1~2).

[0011] Furthermore, the amount of the catalyst used is 1 to 5% of the mass of 3-hydroxypropionitrile.

[0012] Furthermore, the reaction temperature of the catalytic hydrogenation reaction is 80~120℃, and the reaction pressure is 5~25 MPa.

[0013] Furthermore, the separation and purification process includes filtration, crude distillation, and distillation. Filtration is used to remove the catalyst. Crude distillation aims to preliminarily separate and purify the target product, removing solvents and low-boiling-point impurities through distillation. Distillation aims to achieve efficient separation by utilizing the differences in boiling points of the components in the mixture, thereby improving the purity of the target product.

[0014] Furthermore, the purity of the 3-aminopropanol is not less than 99.9%.

[0015] In this invention, liquid ammonia is used as a reaction solvent to provide a suitable polar environment, which promotes the effective contact between 3-hydroxypropionitrile and hydrogen on the catalyst surface; the weakly alkaline environment provided by liquid ammonia helps to stabilize the activity of the catalyst; the presence of ammonia can also reduce the formation of by-products and improve the selectivity and yield of the target product 3-aminopropanol.

[0016] The beneficial effects of this invention are:

[0017] (1) The present invention uses high-purity 3-hydroxypropionitrile as raw material to control the introduction of impurities from the source, thereby improving the purity of 3-aminopropanol;

[0018] (2) The present invention uses a novel catalyst to reduce the amount of byproducts generated and reduce the difficulty of purifying 3-aminopropanol;

[0019] (3) The present invention can obtain 3-aminopropanol with a purity of over 99.9% after distillation, which meets the threshold of high-end pharmaceutical intermediates. Attached Figure Description

[0020] Figure 1 The image shows the HPLC chromatogram of 3-aminopropanol prepared in Example 1. Detailed Implementation

[0021] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below with reference to specific embodiments and illustrations.

[0022] The raw material 3-hydroxypropionitrile used in the following examples and comparative examples was purchased from Anqing Xinfu Chemical Co., Ltd., with a purity of 99%.

[0023] Example 1

[0024] 3-hydroxypropionitrile (711 g, 10 mol), liquid ammonia (341 g, 20 mol), 25 g Raney nickel (Hangzhou Fangsheng New Materials Co., Ltd., model FSC-4110), and 500 mL methanol were added to a reaction vessel. Hydrogen gas was introduced, and the reaction was carried out at 95℃ and 5 MPa for 2 h. After the reaction was completed, the reaction solution was filtered, and the filtrate was subjected to crude distillation to recover methanol. The filtrate was then subjected to fractional distillation (reflux ratio 3:1) to obtain 3-aminopropanol. The yield was 94.5%, and the purity was 99.91%.

[0025] Example 2

[0026] 711 g (10 mol) of 3-hydroxypropionitrile, 170 g (10 mol) of liquid ammonia, 15 g of Raney nickel (Hangzhou Fangsheng New Materials Co., Ltd., model FSC-2110), and 500 mL of methanol were added to a reaction vessel. Hydrogen gas was introduced, and the reaction was carried out at 80 °C and 15 MPa for 3 h. After the reaction was completed, the reaction solution was filtered, and the filtrate was subjected to crude distillation to recover methanol. The filtrate was then subjected to fractional distillation (reflux ratio 4:1) to obtain 3-aminopropanol. The yield was 93.6%, and the purity was 99.90%.

[0027] Example 3

[0028] 711 g (10 mol) of 3-hydroxypropionitrile, 255 g (15 mol) of liquid ammonia, 35 g of Raney nickel (Hangzhou Fangsheng New Materials Co., Ltd., model FSC-3110), and 500 mL of methanol were added to a reaction vessel. Hydrogen gas was introduced, and the reaction was carried out at 120 °C and 10 MPa for 2 h. After the reaction was completed, the reaction solution was filtered, and the filtrate was subjected to crude distillation to recover methanol. The filtrate was then subjected to fractional distillation (reflux ratio 3:1) to obtain 3-aminopropanol. The yield was 94.8%, and the purity was 99.92%.

[0029] Comparative Example 1

[0030] 3-Aminopropanol was synthesized according to the method in Example 1, except that the catalyst was replaced with Raney nickel (model RaneCAT-1200) from Shanghai Xunkai Chemical Technology Co., Ltd.

[0031] 711 g (10 mol) of 3-hydroxypropionitrile, 341 g (20 mol) of liquid ammonia, 25 g of Raney nickel (Shanghai Xunkai Chemical Technology Co., Ltd., model RaneCAT-1200), and 500 mL of methanol were added to a reaction vessel. Hydrogen gas was introduced, and the reaction was carried out at 95 °C and 5 MPa for 2 h. After the reaction was completed, the reaction solution was filtered, and the filtrate was subjected to crude distillation to recover methanol. The filtrate was then subjected to fractional distillation (reflux ratio 3:1) to obtain 3-aminopropanol. The yield was 90.4%, and the purity was 98.72%.

[0032] Comparative Example 2

[0033] 3-Aminopropanol was synthesized according to the method in Example 1, except that the catalyst was replaced with Raney nickel (model RCF-CF-80-4) from Jiangsu Raney Metal Technology Co., Ltd.

[0034] 711 g (10 mol) of 3-hydroxypropionitrile, 341 g (20 mol) of liquid ammonia, 25 g of Raney nickel (Jiangsu Raney Metal Technology Co., Ltd., model RCF-CF-80-4), and 500 mL of methanol were added to a reaction vessel. Hydrogen gas was introduced, and the reaction was carried out at 95 °C and 5 MPa for 2 h. After the reaction was completed, the reaction solution was filtered, and the filtrate was subjected to crude distillation to recover methanol. The filtrate was then subjected to fractional distillation (reflux ratio 3:1) to obtain 3-aminopropanol. The yield was 91.3%, and the purity was 98.45%.

[0035] As can be seen from Examples 1-3 and Comparative Examples 1-2, different types of Raney nickel have different catalytic properties. High-performance Raney nickel catalysts can be obtained through screening, thereby improving the yield and purity of 3-aminopropanol.

[0036] This invention also provides a method for synthesizing high-purity 3-aminopropanol, wherein 3-hydroxypropionitrile, liquid ammonia, catalyst and solvent are added to a reaction vessel, hydrogen is introduced to carry out a catalytic hydrogenation reaction, and the product is separated and purified after the reaction to obtain 3-aminopropanol.

[0037] Furthermore, the catalyst is composed of Raney nickel and butyltin mercaptan in a mass ratio of (9~9.5):(0.5~1). Even further, the Raney nickel contains ≥90wt% nickel and ≤10wt% aluminum.

[0038] Furthermore, the solvent includes, but is not limited to, at least one of methanol, ethanol, acetone, and chloroform, with methanol being preferred.

[0039] Furthermore, the purity of the 3-hydroxypropionitrile is not less than 99%. In this invention, high-purity 3-hydroxypropionitrile is used as the raw material.

[0040] Furthermore, the molar ratio of 3-hydroxypropionitrile to liquid ammonia is 1:(1~2).

[0041] Furthermore, the amount of the catalyst used is 1 to 5% of the mass of 3-hydroxypropionitrile.

[0042] Furthermore, the reaction temperature of the catalytic hydrogenation reaction is 80~120℃, and the reaction pressure is 5~25 MPa.

[0043] Furthermore, the separation and purification process includes filtration, crude distillation, and distillation. Filtration is used to remove the catalyst. Crude distillation aims to preliminarily separate and purify the target product, removing solvents and low-boiling-point impurities through distillation. Distillation aims to achieve efficient separation by utilizing the differences in boiling points of the components in the mixture, thereby improving the purity of the target product.

[0044] Furthermore, the purity of the 3-aminopropanol is not less than 99.9%.

[0045] In this invention, liquid ammonia is used as a reaction solvent to provide a suitable polar environment, which promotes the effective contact between 3-hydroxypropionitrile and hydrogen on the catalyst surface; the weakly alkaline environment provided by liquid ammonia helps to stabilize the activity of the catalyst; the presence of ammonia can also reduce the formation of by-products and improve the selectivity and yield of the target product 3-aminopropanol.

[0046] The raw material 3-hydroxypropionitrile used in the following examples and comparative examples was purchased from Anqing Xinfu Chemical Co., Ltd., with a purity of 99%.

[0047] Example 4

[0048] 3-Aminopropanol was synthesized according to the method of Example 1, except that the catalyst was replaced with Raney nickel FSC-4110 and butyl thiotin in a mass ratio of 9:1.

[0049] 3-hydroxypropionitrile (711 g, 10 mol), liquid ammonia (341 g, 20 mol), 22.5 g Raney nickel (Hangzhou Fangsheng New Materials Co., Ltd., model FSC-4110), 2.5 g butyltin mercaptan, and 500 mL methanol were added to a reaction vessel. Hydrogen gas was introduced, and the reaction was carried out at 95℃ and 5 MPa for 2 h. After the reaction was completed, the reaction solution was filtered, and the filtrate was subjected to crude distillation to recover methanol. The filtrate was then distilled (reflux ratio 3:1) to obtain 3-aminopropanol. The yield was 97.2%, and the purity was 99.93%.

[0050] Example 5

[0051] 3-Aminopropanol was synthesized according to the method of Example 1, except that the catalyst was replaced with Raney nickel FSC-4110 and butyl thiotin in a mass ratio of 9.5:0.5.

[0052] 711 g (10 mol) of 3-hydroxypropionitrile, 341 g (20 mol) of liquid ammonia, 23.75 g of Raney nickel (Hangzhou Fangsheng New Material Co., Ltd., model FSC-4110), 1.25 g of butyltin mercaptan, and 500 mL of methanol were added to a reaction vessel. Hydrogen gas was introduced, and the reaction was carried out at 95 °C and 5 MPa for 2 h. After the reaction was completed, the reaction solution was filtered, and the filtrate was subjected to crude distillation to recover methanol. The filtrate was then subjected to fractional distillation (reflux ratio 3:1) to obtain 3-aminopropanol. The yield was 96.8%, and the purity was 99.92%.

[0053] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A method for synthesizing high-purity 3-aminopropanol, characterized in that: 3-hydroxypropionitrile, liquid ammonia, catalyst and solvent were added to the reaction vessel, and hydrogen gas was introduced to carry out catalytic hydrogenation reaction. After the reaction was completed, the product was separated and purified to obtain 3-aminopropanol.

2. The method for synthesizing high-purity 3-aminopropanol according to claim 1, characterized in that: The catalyst is Raney nickel.

3. The method for synthesizing high-purity 3-aminopropanol according to claim 2, characterized in that: The Raney nickel contains ≥90wt% nickel and ≤10wt% aluminum.

4. The method for synthesizing high-purity 3-aminopropanol according to claim 1, characterized in that: The solvent is at least one of methanol, ethanol, acetone, and chloroform.

5. The method for synthesizing high-purity 3-aminopropanol according to claim 1, characterized in that: The purity of the 3-hydroxypropionitrile is not less than 99%.

6. The method for synthesizing high-purity 3-aminopropanol according to claim 1, characterized in that: The molar ratio of 3-hydroxypropionitrile to liquid ammonia is 1:(1~2).

7. The method for synthesizing high-purity 3-aminopropanol according to claim 1, characterized in that: The amount of catalyst used is 1 to 5% of the mass of 3-hydroxypropionitrile.

8. The method for synthesizing high-purity 3-aminopropanol according to claim 1, characterized in that: The reaction temperature of the catalytic hydrogenation reaction is 80~120℃, and the reaction pressure is 5~25 MPa.

9. The method for synthesizing high-purity 3-aminopropanol according to claim 1, characterized in that: The separation and purification process includes filtration, crude evaporation, and distillation.

10. The method for synthesizing high-purity 3-aminopropanol according to claim 1, characterized in that: The purity of the 3-aminopropanol is not less than 99.9%.

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