Synthesis method of 3, 3 '-diaminodipropylamine

Abstract

The invention discloses a synthesis method of 3, 3 '-diaminodipropylamine, which comprises the following steps: step a, hydroxylamine hydrochloride and acrylonitrile are subjected to an addition reaction in a solvent A under the action of alkali, the reaction temperature is room temperature to reflux temperature, and after full reaction, an intermediate 1 is obtained through post-treatment; and b, introducing hydrogen into the intermediate 1 in a solvent B, carrying out hydrogenation reduction reaction under the action of a catalyst at the reaction temperature of 0-50 DEG C and the hydrogen pressure of 3-10 MPa, and carrying out after-treatment after full reaction to obtain the final product 3, 3 '-diaminodipropylamine, the catalyst is one or more of Raney nickel, palladium carbon and ruthenium carbon. The method has the advantages of simple steps, green and efficient reaction, few side reactions, high product yield and high purity; and the required reagents are all industrial products, are simple and easy to obtain, and are easy for industrial production. # imgabs0 #

Description

Technical Field

[0001] The invention relates to a method for synthesizing 3,3'-diaminodipropylamine. Background Art

[0002] 3,3'-Diaminodipropylamine, also known as dipropylenetriamine, norspermamine, etc., can be used as a synthetic unit of polymer materials, and is also a raw material for a variety of defoaming agents and antistatic agents. It can also be used to synthesize a variety of multidentate ligands and is widely used in the chemical and pharmaceutical industries.

[0003]

[0004] At present, the method for producing 3,3'-diaminodipropylamine mainly uses ammonia as a raw material to react with acrylonitrile and then separates it by hydrogenation.

[0005] Method 1: Patent CN101817753A reports a method of using liquid ammonia and acrylonitrile to prepare the intermediate N-(3-aminopropyl)-1,3-propylenediamine, and then obtaining 3,3'-diaminodipropylamine with a total yield of more than 80% by nickel-catalyzed hydrogenation.

[0006]

[0007] Method 2: Patent CN101111468A reports a method for preparing 3,3'-diaminodipropylamine by reacting 1,3-propylenediamine with hydrogen under palladium-carbon catalysis.

[0008]

[0009] Method 3: Patent CN116003268A reports a method of using 1,3-propylenediamine as a raw material, reacting with acrylonitrile to obtain an intermediate 3-[(3-aminopropyl)amino]propionitrile, and then hydrogenating it over ruthenium carbon to obtain 3,3'-diaminodipropylamine.

[0010]

[0011] In summary, although the current method for preparing 3,3'-diaminodipropylamine has a high conversion rate, the by-products in the reaction are difficult to avoid, and the molecular structure of the by-products is similar to that of the product, and the purification cost is high. Therefore, it is of great significance to develop a synthetic method with both high conversion rate and selectivity. Summary of the invention

[0012] The invention aims to provide a method for synthesizing high-purity 3,3'-diaminodipropylamine, which has simple steps, green and efficient reaction, few side reactions, high product yield and purity, and required reagents are all industrial products, which are easy to obtain and easy to industrialize.

[0013] In order to achieve the above-mentioned invention object, the present invention adopts the following technical scheme:

[0014] The present invention provides a method for synthesizing 3,3'-diaminodipropylamine, which comprises the following steps:

[0015]

[0016] Step a: Hydroxylamine hydrochloride and acrylonitrile react in solvent A under the action of a base at a temperature ranging from room temperature to reflux temperature, and after sufficient reaction, post-treatment is performed to obtain intermediate 1;

[0017] Step b: Into the intermediate 1 in solvent B, hydrogen is introduced, and a hydrogenation reduction reaction is carried out in the presence of a catalyst, the reaction temperature is 0 to 50° C., the hydrogen pressure is 3 to 10 MPa, and after sufficient reaction, post-treatment is performed to obtain the final product 3,3'-diaminodipropylamine; the catalyst is one or more of Raney nickel, palladium carbon, and ruthenium carbon.

[0018] Preferably, the solvent A in step a is one or more of methanol, ethanol and isopropanol. Further preferably, in step a, the solvent A is methanol.

[0019] Preferably, the alkali in step a is one or more of sodium hydroxide, potassium hydroxide, sodium methoxide, and sodium ethoxide. Further preferably, in step a, the alkali is sodium hydroxide.

[0020] Preferably, in step a, the molar ratio of hydroxylamine hydrochloride to alkali and acrylonitrile is 1:1-1.5:2-4, more preferably 1:1-1.2:3-4.

[0021] Preferably, in step a, the feed ratio of hydroxylamine hydrochloride to solvent is 1 g: 14-18 mL.

[0022] Preferably, step a is specifically implemented as follows: hydroxylamine hydrochloride, solvent A and a base are added to a reaction vessel, stirred at room temperature for 15 to 25 minutes, a large amount of sodium chloride solid is generated, and then acrylonitrile is slowly added dropwise at room temperature, stirred and heated to reflux reaction after the addition is completed, and TLC iodine cylinder color development is performed to monitor until the substrate disappears, and after the reaction is completed, the intermediate 1 is obtained by post-treatment. It is further preferred that the post-treatment adopts the following operation: the obtained reaction mixture is cooled to room temperature, the solvent is removed, dichloromethane is added, the filtered solid is dissolved, the filtrate is evaporated under reduced pressure at room temperature to remove dichloromethane, and the residue is frozen and crystallized to obtain the intermediate 1.

[0023] Preferably, the solvent B in step b is one or more of methanol, ethanol and water. More preferably, the solvent B is methanol.

[0024] Preferably, in step b, the catalyst is palladium carbon, and the amount used is 5 to 15% wt of the mass of the intermediate 1.

[0025] Preferably, in step b, the feed ratio of the intermediate 1 to the solvent is 1 g: 5-15 mL.

[0026] Preferably, in step b, the reaction temperature is 0-5°C, and the hydrogen pressure is 7-9 MPa. The reaction ends when the hydrogen is no longer absorbed.

[0027] Preferably, in step b, the post-treatment is carried out in the following manner: filtering the obtained reaction mixture to recover the catalyst, distilling off the solvent under reduced pressure, and performing vacuum distillation to obtain 3,3'-diaminodipropylamine.

[0028] Compared with the prior art, the present invention has the following beneficial effects: the present invention has simple steps, green and efficient reactions, few side reactions, high yield and high purity of the obtained products; and the required reagents are all industrial products, which are simple and easy to obtain and easy to industrialize. DETAILED DESCRIPTION

[0029] The technical solution of the present invention is further described below with reference to specific embodiments, but the protection scope of the present invention is not limited thereto.

[0030] If no specific conditions are specified in the examples of the present invention, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be obtained by conventional technical means or purchased commercially.

[0031] Embodiment 1:

[0032] Hydroxylamine hydrochloride (12 g, 172.7 mmol), 200 mL of methanol and sodium hydroxide (6.9 g, 172.7 mmol) were added to a 500 mL three-necked flask and stirred at room temperature for 20 min. A large amount of sodium chloride solid was produced. Acrylonitrile (27.5 g, 519 mmol) was then slowly added dropwise at room temperature. After the addition was completed, the mixture was stirred and the temperature was raised to reflux for reaction. The TLC iodine cylinder was used for color development to monitor until the substrate disappeared. The reaction mixture was cooled to room temperature, methanol was evaporated under reduced pressure at room temperature, 100 mL of dichloromethane was added to dissolve the filtered solid, and dichloromethane was evaporated from the filtrate under reduced pressure at room temperature. The residue was frozen and crystallized to obtain 21.4 g of a light yellow solid (mp: 35-37 ° C, lit: 37-38 ° C). The thus obtained 21.4 g (intermediate 1) was dissolved in 200 mL of methanol, palladium carbon (2.14 g, 10% wt.) was added, hydrogen was introduced into the reactor at a hydrogen pressure of 8 MPa, and the reaction was carried out at 0-5°C for 15 h without hydrogen absorption. The pressure was released, and the reaction liquid was filtered to recover the catalyst. After the filtrate was decompressed to remove methanol, 18 g of pure colorless 3,3'-diaminodipropylamine was obtained by vacuum distillation (the retention time of GC analysis was consistent with that of the standard, GC purity was 99.9%, and the total yield of two steps was 80%).

[0033] Embodiment 2:

[0034] Hydroxylamine hydrochloride (10 g, 143.9 mmol), 150 mL of methanol and sodium hydroxide (6.1 g, 152.5 mmol) were added to a 500 mL three-necked flask and stirred at room temperature for 18 min. A large amount of sodium chloride solid was produced. Acrylonitrile (30.5 g, 575 mmol) was then slowly added dropwise at room temperature. After the addition was completed, the mixture was stirred and the temperature was raised to reflux for reaction. The TLC iodine cylinder was used for color development and monitoring until the substrate disappeared. The reaction mixture was cooled to room temperature, methanol was evaporated under reduced pressure at room temperature, 100 mL of dichloromethane was added to dissolve the filtered solid, and dichloromethane was evaporated under reduced pressure from the filtrate at room temperature. The residue was frozen and crystallized to obtain 18.6 g of a light yellow solid (mp: 36-37 ° C). 18.6 g (intermediate 1) thus obtained was dissolved in 180 mL of methanol, palladium carbon (2.79 g, 15% wt.) was added, hydrogen was introduced into the reactor at a hydrogen pressure of 5 MPa, and the reaction was carried out at 0-5°C for 18 h until no more hydrogen was absorbed. The pressure was released, and the reaction liquid was filtered to recover the catalyst. After the filtrate was decompressed to remove methanol, 16 g of pure colorless 3,3'-diaminodipropylamine was obtained by vacuum distillation (the retention time of GC analysis was consistent with that of the standard, GC purity was 99.9%, and the total yield of two steps was 85%).

[0035] Embodiment 3:

[0036] Hydroxylamine hydrochloride (15 g, 215.8 mmol), 250 mL of methanol and sodium hydroxide (8.7 g, 217.5 mmol) were added to a 500 mL three-necked flask and stirred at room temperature for 25 min. A large amount of sodium chloride solid was produced. Acrylonitrile (34.9 g, 658 mmol) was then slowly added dropwise at room temperature. After the addition was completed, the mixture was stirred and the temperature was raised to reflux for reaction. The TLC iodine cylinder was used for color development and monitoring until the substrate disappeared. The reaction mixture was cooled to room temperature, methanol was evaporated under reduced pressure at room temperature, 120 mL of dichloromethane was added to dissolve the filtered solid, and dichloromethane was evaporated under reduced pressure from the filtrate at room temperature. The residue was frozen and crystallized to obtain 27.3 g of a light yellow solid (mp: 36-37 ° C). 27.3 g (intermediate 1) thus obtained was dissolved in 250 mL of methanol, palladium carbon (1.36 g, 5% wt.) was added, hydrogen was introduced into the reactor at a hydrogen pressure of 9 MPa, and the reaction was carried out at 0-5°C for 15 h until no more hydrogen was absorbed. The pressure was released, and the reaction liquid was filtered to recover the catalyst. After the filtrate was decompressed to remove methanol, 23 g of pure colorless 3,3'-diaminodipropylamine was obtained by vacuum distillation (the retention time of GC analysis was consistent with that of the standard, GC purity was 99.9%, and the total yield of two steps was 81%).

Claims

1. A method for synthesizing 3,3'-diaminodipropylamine, characterized in that: The synthesis method comprises the following steps: Step a: Hydroxylamine hydrochloride and acrylonitrile react in solvent A under the action of a base at a temperature ranging from room temperature to reflux temperature, and after sufficient reaction, post-treatment is performed to obtain intermediate 1; Step b: Into the intermediate 1 in solvent B, hydrogen is introduced, and a hydrogenation reduction reaction is carried out in the presence of a catalyst, the reaction temperature is 0 to 50° C., the hydrogen pressure is 3 to 10 MPa, and after sufficient reaction, post-treatment is performed to obtain the final product 3,3'-diaminodipropylamine; the catalyst is one or more of Raney nickel, palladium carbon, and ruthenium carbon.

2. The synthesis method according to claim 1, characterized in that: The solvent A in step a is one or more of methanol, ethanol and isopropanol.

3. The synthesis method according to claim 1, characterized in that: The base in step a is one or more of sodium hydroxide, potassium hydroxide, sodium methoxide and sodium ethoxide.

4. The synthesis method according to claim 1, characterized in that: In step a, the molar ratio of hydroxylamine hydrochloride to alkali and acrylonitrile is 1:1-1.5:2-4.

5. The synthesis method according to claim 4, characterized in that: In step a, the molar ratio of hydroxylamine hydrochloride to alkali and acrylonitrile is 1:1-1.2:3-4.

6. The synthesis method according to claim 1, characterized in that: Step a is specifically implemented as follows: hydroxylamine hydrochloride, solvent A and a base are added to a reaction container, and stirred at room temperature for 15 to 25 minutes, at which time a large amount of sodium chloride solid is produced, and then acrylonitrile is slowly added dropwise at room temperature. After the addition is completed, the temperature is raised to reflux for reaction with stirring, and TLC iodine cylinder color development is performed to monitor until the substrate disappears. After the reaction is completed, intermediate 1 is obtained by post-treatment.

7. The synthesis method according to claim 1, characterized in that: The solvent B in step b is one or more of methanol, ethanol and water.

8. The synthesis method according to claim 1, characterized in that: In step b, the catalyst is palladium carbon, and the amount used is 5-15%wt of the mass of the intermediate 1.

9. The synthesis method according to claim 1, characterized in that: In step b, the reaction temperature is 0-5° C. and the hydrogen pressure is 7-9 MPa.

Images