CN109516919B - Preparation method of tri (2-aminoethyl) amine - Google Patents
Preparation method of tri (2-aminoethyl) amine Download PDFInfo
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- CN109516919B CN109516919B CN201811607623.XA CN201811607623A CN109516919B CN 109516919 B CN109516919 B CN 109516919B CN 201811607623 A CN201811607623 A CN 201811607623A CN 109516919 B CN109516919 B CN 109516919B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/08—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
Abstract
The invention discloses a preparation method of tri (2-aminoethyl) amine, belonging to the technical field of compound preparation, which takes triethanolamine as an initial raw material, firstly, the triethanolamine, thionyl chloride and a catalyst DMF are placed in a reactor, tri (2-chloroethyl) amine hydrochloride is generated under the heating condition, then the purified tri (2-chloroethyl) amine hydrochloride and ammonia water are dissolved in an organic solvent and placed in the reactor, the tri (2-aminoethyl) amine hydrochloride is obtained by reaction under the heating condition, and finally the tri (2-aminoethyl) amine hydrochloride and sodium hydroxide are reacted to obtain the tri (2-aminoethyl) amine; the method has the advantages of short reaction route and strong controllability.
Description
Technical Field
The invention relates to the technical field of compound preparation, in particular to the technical field of synthesis of aliphatic nitrogen tritium tetramine, and specifically relates to a preparation method of tri (2-aminoethyl) amine.
Background
Tris (2-aminoethyl) amine, of the formula:
the aliphatic nitrogen tritium tetramine can be used in research and industrial fields of chelating agents, corrosion inhibitors, resin curing agents, catalysts, organic intermediates and the like, and the tri (2-aminoethyl) amine is an important organic polyamine compound in aliphatic nitrogen tritium tetramine compounds. The outstanding structural characteristics are that four nitrogen atoms with strong coordination ability in molecules can be mixed with a plurality of transition metal atoms (such as Cd)2+、Zn2+、Mn2+Etc.) to form a stable chelate having a bicyclic structure.
Aliphatic nitrogen tritium tetramine such as tris (2-aminoethyl) amine is used for synthesizing phosphorus-containing bicyclic organic nonionic superbases, and is the strongest organic nonionic superbase having a phosphorus atom as the center, which has been found so far. Are successfully used in many organic synthesis reactions as excellent alkaline reagents or phosphorus ligands. However, the traditional synthesis process has the defects of more raw materials, complex operation, low yield and the like, and toxic by-products harmful to human bodies and the environment can be generated.
Disclosure of Invention
The invention aims to provide a preparation method of tri (2-aminoethyl) amine, which has the advantages of simple process, mild reaction, environmental protection and safety.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention comprises the following steps:
(1) preparation of the first intermediate: triethanolamine and thionyl chloride are used as initial raw materials, and are heated and reacted under the action of a catalyst to generate a first intermediate tri (2-chloroethyl) amine hydrochloride;
(2) preparation of the second intermediate: separating and purifying the first intermediate tris (2-chloroethyl) amine hydrochloride, dissolving the first intermediate in an organic solvent, adding ammonia water into the organic solvent, and reacting to generate a second intermediate tris (2-aminoethyl) amine hydrochloride;
(3) preparation of a target product: and (3) separating and purifying the second intermediate tri (2-aminoethyl) amine hydrochloride, adding a strong base solution, adjusting the pH value to 9-11, reacting completely to obtain a reaction solution containing a target product, and separating and purifying the reaction solution to obtain the tri (2-aminoethyl) amine.
As a further improvement of the invention, the catalyst in the step (1) is DMF.
As a further improvement of the invention, the organic solvent in the step (2) is absolute ethyl alcohol.
As a further improvement of the invention, the strong alkaline solution is a sodium hydroxide solution.
As a further improvement of the invention, the specific process of the step (1) is as follows: and (2) placing triethanolamine and DMF (dimethyl formamide) in a mass ratio of 1: 1-2 into a reactor, slowly dropwise adding a thionyl chloride solution while stirring, and after dropwise adding, carrying out reflux reaction at the temperature of 70 ℃ for 6-8h to obtain a first intermediate tris (2-chloroethyl) amine hydrochloride.
As a further improvement of the invention, the separation and purification process of the first intermediate tris (2-chloroethyl) amine hydrochloride is as follows: and (3) carrying out reduced pressure rotary evaporation on the generated first intermediate tris (2-chloroethyl) amine hydrochloride, removing the residual thionyl chloride solution, dissolving the tris (2-chloroethyl) amine hydrochloride by using absolute ethyl alcohol, refrigerating to separate out a solid, and carrying out suction filtration treatment on the refrigerated solution to obtain a white crystal of the second intermediate tris (2-chloroethyl) amine hydrochloride.
As a further improvement of the method, in the step (2), the molar ratio of the tris (2-chloroethyl) amine hydrochloride to the ammonia water is 1: 10-40, and the reaction time is 6-8 h.
As a further improvement of the invention, the separation and purification process of the second intermediate, namely the hydrochloride of the tri (2-aminoethyl) amine, comprises the following steps: and (3) carrying out reduced pressure rotary evaporation on the reaction liquid obtained in the step (2), removing residual ammonia water, adding absolute ethyl alcohol to dissolve, refrigerating to separate out ammonium chloride solid, carrying out suction filtration, and collecting filtrate to obtain the tris (2-aminoethyl) amine hydrochloride solution.
As a further improvement of the invention, the reaction solution is distilled under reduced pressure, and the fraction collected at the temperature of 5kPa, 140 ℃ and 150 ℃ is the tri (2-aminoethyl) amine.
The synthetic route of the invention is as follows:
compared with the prior art, the invention has the following technical effects:
the invention provides a new method for synthesizing tri (2-aminoethyl) amine, which takes triethanolamine as a raw material to synthesize the tri (2-aminoethyl) amine by a three-step method, wherein the reaction product of each step is single, no redundant byproduct is generated, the separation and purification are convenient, the convenience is provided for the next reaction, the yield of the target product is higher, the synthetic route is simple, the process flow is short, the selected raw material is cheap and easy to obtain, and the production cost is low; hair brushThe synthesis of the Mintris (2-chloroethyl) amine hydrochloride intermediate has no large amount of SO2And HCl gas is released, the reaction is mild, and the harm to human bodies and the environment is low.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
45.45g of triethanolamine solution and 90g of DMF are respectively added into a 1000ml three-neck flask, stirred, and 150g of thionyl chloride solution is slowly dripped into the reagent, and the dripping speed is controlled to be 1 second per drop. White solid is generated at first along with gas, and after the dripping is finished, the white solid disappears and the solution is clear. Stirring was continued for 7 hours. And after the reaction is finished, carrying out reduced pressure rotary evaporation on the generated tris (2-chloroethyl) amine hydrochloride, removing the residual thionyl chloride solution, dissolving the tris (2-chloroethyl) amine hydrochloride by using 300ml of absolute ethyl alcohol, refrigerating to separate out a solid, and carrying out suction filtration on the refrigerated solution to obtain a white tris (2-chloroethyl) amine hydrochloride crystal.
130g of ammonia water was added to a 250ml three-necked flask, and 48.2g of the above tris (2-chloroethyl) amine hydrochloride was dissolved in 100g of ethanol, stirred, heated in an oil bath at 70 ℃ under reflux, and reacted under reflux for 7 hours. The color of the reaction solution gradually changed from colorless to dark brown. And after the reaction is finished, removing the solvent and the residual ammonia water by rotary evaporation to obtain a dark brown viscous substance, dissolving 100ml of absolute ethyl alcohol, refrigerating to separate out an ammonium chloride solid, performing suction filtration, collecting filtrate, adding a proper amount of sodium hydroxide, adjusting the pH to be about 10, reacting to obtain tris (2-aminoethyl) amine, performing reduced pressure distillation, and collecting a fraction at the temperature of 140-150 ℃ of 5kp to obtain tris (2-aminoethyl) amine. Through weighing and calculation, the yield of the tri (2-aminoethyl) amine is 92.3 percent.
Example 2:
75.75g of triethanolamine solution and 75g of DMF are respectively added into a 1000ml three-neck flask, stirred, 250g of thionyl chloride solution is slowly dripped into the reagent, and the dripping speed is controlled to be 1 second per drop. White solid is generated at first along with gas, and after the dripping is finished, the white solid disappears and the solution is clear. Stirring was continued for 7 hours. And after the reaction is finished, carrying out reduced pressure rotary evaporation on the generated tris (2-chloroethyl) amine hydrochloride, removing the residual thionyl chloride solution, dissolving the tris (2-chloroethyl) amine hydrochloride by using 500ml of absolute ethyl alcohol, refrigerating to separate out a solid, and carrying out suction filtration on the refrigerated solution to obtain a white tris (2-chloroethyl) amine hydrochloride crystal.
210g of ammonia water was charged into a 250ml three-necked flask, 48.2g of the above tris (2-chloroethyl) amine hydrochloride was dissolved in 100g of ethanol, stirred, heated in an oil bath at 70 ℃ under reflux, and reacted under reflux for 7 hours. The color of the reaction solution gradually changed from colorless to dark brown. After the reaction is finished, the solvent and the residual ammonia water are removed by rotary evaporation to obtain a dark brown sticky substance. Dissolving 100ml of absolute ethyl alcohol, refrigerating to separate out ammonium chloride solid, carrying out suction filtration, collecting filtrate, adding a proper amount of sodium hydroxide, adjusting the pH to be about 10, reacting to obtain tris (2-aminoethyl) amine, carrying out reduced pressure distillation, and collecting the fraction at the temperature of 140-150 ℃ of 5kp to obtain tris (2-aminoethyl) amine. The yield of tris (2-aminoethyl) amine was 82.24% by weight and calculation.
Example 3:
60.6g of triethanolamine solution and 90g of DMF are respectively added into a 1000ml three-neck flask, stirred, 200g of thionyl chloride solution is slowly dripped into the reagent, and the dripping speed is controlled to be 1 second per drop. White solid is generated at first along with gas, and after the dripping is finished, the white solid disappears and the solution is clear. Stirring was continued for 7 hours. And after the reaction is finished, carrying out reduced pressure rotary evaporation on the generated tris (2-chloroethyl) amine hydrochloride, removing the residual thionyl chloride solution, dissolving the tris (2-chloroethyl) amine hydrochloride by using 500ml of absolute ethyl alcohol, refrigerating to separate out a solid, and carrying out suction filtration on the refrigerated solution to obtain a white tris (2-chloroethyl) amine hydrochloride crystal.
210g of ammonia water was charged into a 250ml three-necked flask, 48.2g of the above tris (2-chloroethyl) amine hydrochloride was dissolved in 100g of ethanol, stirred, heated in an oil bath at 70 ℃ under reflux, and reacted under reflux for 7 hours. The color of the reaction solution gradually changed from colorless to dark brown. After the reaction is finished, the solvent and the residual ammonia water are removed by rotary evaporation to obtain a dark brown sticky substance. Dissolving 100ml of absolute ethyl alcohol, refrigerating to separate out ammonium chloride solid, carrying out suction filtration, collecting filtrate, adding a proper amount of sodium hydroxide, adjusting the pH to be about 10, reacting to obtain tris (2-aminoethyl) amine, carrying out reduced pressure distillation, and collecting the fraction at the temperature of 140-150 ℃ of 5kp to obtain tris (2-aminoethyl) amine. The yield of tris (2-aminoethyl) amine was 84.80% by weight and calculation.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (1)
1. A preparation method of tri (2-aminoethyl) amine is characterized by comprising the following steps:
respectively taking 45.45g of triethanolamine solution and 90g of DMF, adding the triethanolamine solution and the DMF into a 1000ml three-neck flask, stirring, taking 150g of thionyl chloride solution, slowly dropwise adding the thionyl chloride solution into the reagent, controlling the dropwise adding speed to be 1 second per drop, initially generating white solid accompanied with gas, disappearing the white solid after dropwise adding, clarifying the solution, continuously stirring for 7 hours, decompressing and rotatably steaming generated tris (2-chloroethyl) amine hydrochloride after reaction is finished, removing the residual thionyl chloride solution, dissolving the tris (2-chloroethyl) amine hydrochloride by 300ml of absolute ethyl alcohol, separating out the solid after refrigeration, and performing suction filtration on the refrigerated solution to obtain tris (2-chloroethyl) amine hydrochloride white crystals;
adding 130g of ammonia water into a 250ml three-neck flask, dissolving 48.2g of the tris (2-chloroethyl) amine hydrochloride in 100g of ethanol, stirring, heating in an oil bath at 70 ℃, keeping the solution refluxing, carrying out reflux reaction for 7 hours, gradually changing the color of the reaction solution from colorless to dark brown, after the reaction is finished, carrying out rotary evaporation to remove the solvent and the residual ammonia water to obtain a dark brown viscous substance, dissolving the dark brown viscous substance in 100ml of absolute ethanol, refrigerating to separate out ammonium chloride solid, carrying out suction filtration, collecting filtrate, adding a proper amount of sodium hydroxide, adjusting the pH to about 10, reacting to obtain tris (2-aminoethyl) amine, carrying out reduced pressure distillation, and collecting the fraction at 5kp and 140-150 ℃ as tris (2-aminoethyl) amine.
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| CN109438252B (en) * | 2018-12-27 | 2021-12-14 | 安徽工业大学科技园有限公司 | Synthesis process of tri (2-aminoethyl) amine |
| CN109912428B (en) * | 2019-04-23 | 2022-02-22 | 长江大学 | Preparation method of N-alkylated triamino star ultra-low molecular inhibitor |
| CN115448845A (en) * | 2022-10-22 | 2022-12-09 | 大连双硼医药化工有限公司 | Process method for synthesizing tri (2-aminoethyl) amine |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001187751A (en) * | 1999-12-28 | 2001-07-10 | Nippon Shokubai Co Ltd | New tren derivative and method for producing the same |
| CN103265677A (en) * | 2008-05-30 | 2013-08-28 | 东曹株式会社 | Process for producing hydroxyalkyltriethylenediamine compound, and catalyst composition for the production of polyurethane resin using the hydroxyalkyltriethylenediamine compound |
| CN104341333A (en) * | 2014-10-29 | 2015-02-11 | 北京华睿鼎信科技有限公司 | Preparation method of Pramiracetam sulfate |
| CN108084033A (en) * | 2017-12-29 | 2018-05-29 | 山东诚汇双达药业有限公司 | A kind of preparation method of N, N- diethyl ethylenediamine |
| CN109438252A (en) * | 2018-12-27 | 2019-03-08 | 安徽工大化工科技有限公司 | A kind of synthesis technology of three (2- amino-ethyl) amine |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE0302090D0 (en) * | 2003-07-16 | 2003-07-16 | Astrazeneca Ab | Chemical compounds |
| RU2470017C2 (en) * | 2007-06-08 | 2012-12-20 | Янссен Фармацевтика Н.В. | Piperidine/piperazine derivatives |
-
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- 2018-12-27 CN CN201811607623.XA patent/CN109516919B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001187751A (en) * | 1999-12-28 | 2001-07-10 | Nippon Shokubai Co Ltd | New tren derivative and method for producing the same |
| CN103265677A (en) * | 2008-05-30 | 2013-08-28 | 东曹株式会社 | Process for producing hydroxyalkyltriethylenediamine compound, and catalyst composition for the production of polyurethane resin using the hydroxyalkyltriethylenediamine compound |
| CN104341333A (en) * | 2014-10-29 | 2015-02-11 | 北京华睿鼎信科技有限公司 | Preparation method of Pramiracetam sulfate |
| CN108084033A (en) * | 2017-12-29 | 2018-05-29 | 山东诚汇双达药业有限公司 | A kind of preparation method of N, N- diethyl ethylenediamine |
| CN109438252A (en) * | 2018-12-27 | 2019-03-08 | 安徽工大化工科技有限公司 | A kind of synthesis technology of three (2- amino-ethyl) amine |
Non-Patent Citations (2)
| Title |
|---|
| 三( 2-氨基乙基)胺合成方法的改进;吴伟，等;《化学试剂》;20101130;第32卷(第11期);第1.2节 * |
| 三(2-氨基乙基)胺盐酸盐的合成;樊有恒，等;《化学试剂》;20140731;第36卷(第7期);第659-660页 * |
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