CN101974029A - Method for preparing phosphorylethanolamine compound - Google Patents
Method for preparing phosphorylethanolamine compound Download PDFInfo
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- CN101974029A CN101974029A CN 201010523933 CN201010523933A CN101974029A CN 101974029 A CN101974029 A CN 101974029A CN 201010523933 CN201010523933 CN 201010523933 CN 201010523933 A CN201010523933 A CN 201010523933A CN 101974029 A CN101974029 A CN 101974029A
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- phosphorylethanolamine
- preparing
- phosphorus oxychloride
- phosphoric acid
- solution
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Abstract
The invention relates to a method for preparing a phosphorylethanolamine compound, which belongs to the technical field of biochemistry. The method comprises the following steps of: adding ethanolamine or ethanolamine solution into one of phosphorus pentoxide, the solution of phosphoric acid, phosphorus oxychloride or the solution of phosphorus oxychloride at a certain reaction temperature to form a reaction mixture; heating the reaction mixture for vacuum-drying by using a direct program to form phosphorylethanolamine or phosphorylethanolamine hydrochloride; and dissolving the reaction product into water in a certain amount and then adding ethanolamine or the ethanolamine solution, wherein the mass ratio of the reaction product to the water in the certain amount is 1:1-100. As the water serves as a solvent, the method of the invention ensures high yield, vast raw material sources, low production cost, simple, safe and rational process, short production cycle and high purity of the prepared product, and avoids wastewater, waste gases and waste residues.
Description
Technical field
The present invention relates to a kind of method for preparing the phosphorylethanolamine compound, belong to technological field of biochemistry.
Background technology
Phosphorylethanolamine is divided into phosphoric acid Monoethanolamine MEA BASF (CAS:1071-23-4), p diethylaminobenzoic acid hydramine (CAS:6094-81-1) and nitranol (CAS:29901-63-1) by structure.Wherein the phosphoric acid Monoethanolamine MEA BASF claims 2-monoethanolamine dihydrogen phosphoric acid ester, 2-monoethanolamine phosphoric acid ester, thanomin phosphoric acid ester, o-phosphorylethanolamine, phosphoric acid again, 2-amino ethyl ester, Phosphoethanolamine, phosphoric acid cholamine, 2-aminoethyl dihydrogen phosphoric acid ester, cholamine phosphoric acid, colamine phosphoric acid etc.
The phosphorylethanolamine compounds is widely used in biotechnology, medicine and other fields, can also be as fodder additives, special lubricant etc.Disclosed synthetic method and the technology about the phosphorylethanolamine compounds mainly is to be raw material with phosphoric acid and thanomin, at first the two is mixed with certain density solution respectively with solvent, after the two is blended in and reacts in the solvent, filtration obtains thanomin phosphoric acid salt, at last again in organic solvent high temperature dehydration obtain phosphorylethanolamine; Perhaps phosphoric acid and thanomin reaction in aromatic hydrocarbons (as benzene,toluene,xylene etc.), bicyclic hydrocarbon, halohydrocarbon and organic solvents such as high boiling ether and ketone obtains phosphorylethanolamine through processes such as azeotropic, high temperature dewater, make with extra care then, as US 2,730, and 542; Tetrahedron Letters, (24), 1913-1916,1975; PL 196501, and its reaction process as the formula (1).Cause thus that above method exists that raw material is single, complex process, step is many, the cycle is long, productive rate low (44%～80%), problems such as by product is many, purity is low, cost is high, serious three wastes.
In the two-step reaction of preparation phosphorylethanolamine, all need a large amount of solvents: in the first step reaction, thanomin phosphoric acid salt is when organic solvent deposit comes out, heavy metals such as mineral ion in the reaction system such as lead are also separated out with precipitation, cause the richness of impurity long-pending, these impurity enter follow-up reaction thereupon, and in the reaction of second step, can't directly remove, the product quality is descended, then need to adopt gac etc. to carry out further purification process for improving quality, increase cost and quantity of three wastes, reduced productive rate simultaneously; The same richness of impurity in the organic solvent that the reaction of second step is used is amassed in end product, and product quality is further descended.In addition, owing to used a large amount of organic solvents in producing, cause production environment poor, the three wastes are many, the cost height.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming of prior art, a kind of method for preparing the phosphorylethanolamine compound is proposed, this method yield height, raw material sources are wide, production cost is low, the no three wastes, simple and safe reasonable, with short production cycle, the prepared product purity height of technology.
The objective of the invention is to be achieved through the following technical solutions.
A kind of method for preparing the phosphorylethanolamine compound of the present invention, wherein the structural formula of phosphorylethanolamine compound is as the formula (2):
Wherein, R
1Be H or H
2N-CH
2-CH
2, R
2Be H or H
2N-CH
2-CH
2, x is 0,1,2 or 3;
The concrete steps of this method are:
1) under certain temperature of reaction with thanomin (HOCH
2CH
2NH
2) or ethanolamine solutions join in the reactant, obtain reaction mixture;
2) will obtain phosphorylethanolamine or phosphorylethanolamine hydrochloride after the reaction mixture process straight line program intensification vacuum-drying then;
Can earlier reactant be dissolved in a certain amount of water in the step 1), and then add thanomin (HOCH
2CH
2NH
2) or ethanolamine solutions; The mass ratio of reactant and a certain amount of water is 1: 1～100;
Reactant in the step 1) is Vanadium Pentoxide in FLAKES (P
2O
5), phosphoric acid (H
3PO
4) solution, phosphorus oxychloride (POCl
3) or phosphorus oxychloride (POCl
3) a kind of in the solution;
Phosphoric acid (H
3PO
4) solvent in the solution is water or high boiling solvent, high boiling solvent is preferably ketone; Phosphoric acid (H
3PO
4) concentration of solution is 1%～85%;
Phosphorus oxychloride (POCl
3) solvent in the solution is aromatic hydrocarbons, bicyclic hydrocarbon, carbon atom a kind of or its mixture in the halohydrocarbon between 1～4, high boiling point ether, high boiling point ketone or the ester of carbon atom between 1～7; Wherein, aromatic hydrocarbons is preferably benzene, toluene or dimethylbenzene; Phosphorus oxychloride (POCl
3) concentration of solution is 1%～99%;
Solvent in the step 1) in the ethanolamine solutions be aromatic hydrocarbons, bicyclic hydrocarbon, carbon atom the halohydrocarbon between 1～4, high boiling point ether, high boiling point ketone, carbon atom at ester between 1～7 or carbon atom a kind of or its mixture in the alcohol between 1～7; Wherein, aromatic hydrocarbons is preferably benzene, toluene or dimethylbenzene; The concentration of ethanolamine solutions is 1%～99%;
Reactant is Vanadium Pentoxide in FLAKES (P in the step 1)
2O
5) time, the Vanadium Pentoxide in FLAKES (P of adding
2O
5) with the mol ratio of thanomin be 1: 2.0～6.0;
Reactant is phosphoric acid (H in the step 1)
3PO
4) during solution, the phosphoric acid (H of adding
3PO
4) with the mol ratio of thanomin be 1: 1.0～3.0;
Reactant is phosphorus oxychloride (POCl in the step 1)
3) or phosphorus oxychloride (POCl
3) during solution, the phosphorus oxychloride (POCl of adding
3) with the mol ratio of thanomin be 1: 1.0～3.0;
Certain temperature of reaction is-20～100 ℃ in the step 1);
The time that adds in the step 1) is that 5min is to 72h;
Step 2) the temperature programming scope is-20～250 ℃ in, and the heating-up time is 0.5～72h;
Step 2) vacuum drying vacuum tightness is 0～101.18*10 in
5KPa.
Beneficial effect
The present invention makees solvent by water, and this method yield height, raw material sources are wide, production cost is low, the no three wastes, simple and safe reasonable, with short production cycle, the prepared product purity height of technology.
Embodiment
Below in conjunction with embodiment the present invention is further described, but protection scope of the present invention is not limited to this.
Embodiment 1
Add 50kg water in the 100L reactor, after being warming up to 80 ℃, the Vanadium Pentoxide in FLAKES 14.2kg of adding 100%, add 100% thanomin 12.2kg then, be-dewatered more than the 0.098kPa 2 hours in vacuum tightness, be warming up to 100 ℃ again, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ in vacuum tightness are respectively-the above vaccum dewatering of 0.098kPa 2 hours, to lump then and be-more than the 0.098kPa dry 2 hours in 160 ℃ of vacuum tightnesss again after pulverizing, obtain phosphoric acid Monoethanolamine MEA BASF white solid powder 27.1kg, 236.6～237.6 ℃ of fusing points, productive rate 96%, purity 〉=99.3%.
Embodiment 2
Phosphoric acid (the H of adding 85% in the 1000L reactor
3PO
4) aqueous solution 500kg, room temperature adds 100% thanomin 265kg (61.05), intensification degree to 80 ℃, be-dewatered more than the 0.098kPa 2 hours in vacuum tightness, be warming up to 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ then and be-vaccum dewatering 2 hours respectively more than the 0.098kPa in vacuum tightness, to lump and be-more than the 0.098kPa dry 2 hours in 160 ℃ of vacuum tightnesss again after pulverizing, obtain phosphoric acid Monoethanolamine MEA BASF white solid powder 593kg, 239.8～242 ℃ of fusing points, productive rate 97%, purity 99.5%.
Embodiment 3
The toluene solution 61.4kg of the phosphorus oxychloride of adding 50% in the 100L reactor, and then add 100% thanomin 12.2kg, 80 ℃ of vacuum tightnesss be-kept 2 hours more than the 0.098kPa, be warming up to 100 ℃ then, 120 ℃, 140 ℃, 160 ℃, 180 ℃ be-kept respectively more than the 0.098kPa 2 hours in vacuum tightness, the tail gas condensation gets hydrochloride aqueous solution, to lump and be-0.098kPa dry 2 hours down in 160 ℃ of vacuum tightnesss again after pulverizing, obtain phosphoric acid ethanolamine hydrochloride white solid powder 32.3kg, 247.5～248.9 ℃ of fusing points, productive rate 91%, purity 〉=99.0%.
Embodiment 4
Add 5.0kg water in the 10L reactor, be warming up to 80 ℃ after, add 100% Vanadium Pentoxide in FLAKES (P
2O
5) 1.42kg, the thanomin 2.44kg (61.05) of adding 100% after stirring, 100 ℃ dewatered 2 hours, heat up again 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ and be-above the vaccum dewatering of 0.098kPa 2 hours in vacuum tightness respectively, to lump then and be-more than the 0.098kPa dry 2 hours in 160 ℃ of vacuum tightnesss again after pulverizing, obtain p diethylaminobenzoic acid hydramine white solid powder 3.46kg, productive rate 94%, purity 〉=99.3%.
Embodiment 5
Phosphoric acid (the H of adding 85% in the 10L reactor
3PO
4) aqueous solution 2.3kg, the thanomin 2.44kg of adding 100%, intensification degree to 60 ℃, be-dewatered more than the 0.098kPa 2 hours in vacuum tightness, be warming up to 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ then and be-vaccum dewatering 2 hours respectively more than the 0.098kPa in vacuum tightness, will lump is-drying 2 hours more than the 0.098kPa in 160 ℃ of vacuum tightnesss after pulverizing again, obtains p diethylaminobenzoic acid hydramine white solid powder 3.54kg, productive rate 96%, purity 〉=99.0%.
Embodiment 6
The toluene solution 3.07kg of the phosphorus oxychloride of adding 50% in the 10L reactor, and then add 100% thanomin 1.22kg, 80 ℃ of vacuum tightnesss be-kept 2 hours more than the 0.098kPa, being warming up to 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ then be-kept respectively more than the 0.098kPa 2 hours in vacuum tightness, the tail gas condensation gets hydrochloride aqueous solution, to lump and be-0.098kPa dry 2 hours down in 160 ℃ of vacuum tightnesss again after pulverizing, obtain p diethylaminobenzoic acid alcohol hydrochloride white solid powder 4.10kg, productive rate 93%, purity 〉=98.0%.
Embodiment 7
Add 4.0kg water in the 10L reactor, after being warming up to 80 ℃, the Vanadium Pentoxide in FLAKES 1.42kg of adding 100%, add 100% thanomin 3.66kg then, be-dewatered more than the 0.098kPa 2 hours in vacuum tightness, be warming up to 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ again and be-above the vaccum dewatering of 0.098kPa 2 hours in vacuum tightness respectively, obtain nitranol 4.32kg, productive rate 95%, purity 〉=99.3%.
Embodiment 8
Phosphoric acid (the H of adding 85% in the 10L reactor
3PO
4) aqueous solution 2.50kg, room temperature adds 100% thanomin 3.97kg, intensification degree to 60～80 ℃, be-dewatered more than the 0.098kPa 2 hours in vacuum tightness, be warming up to 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ then and be-vaccum dewatering 2 hours respectively more than the 0.098kPa in vacuum tightness, obtain nitranol 4.77kg, productive rate 97%, purity 〉=99.5%.
Embodiment 9
The toluene solution 30.7kg of the phosphorus oxychloride of adding 50% in the 100L reactor, and then add 100% thanomin 18.3kg, 80 ℃ of vacuum tightnesss be-kept 2 hours more than the 0.098kPa, be warming up to 100 ℃ then, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ be-kept respectively more than the 0.098kPa 2 hours in vacuum tightness, the tail gas condensation gets hydrochloride aqueous solution, to lump and be-0.098kPa dry 2 hours down in 160 ℃ of vacuum tightnesss again after pulverizing, obtain nitranol hydrochloride white solid powder 49.6kg, 210～211 ℃ of fusing points, productive rate 94%, purity 〉=99.0%.
Embodiment 10
Add the phosphoric acid ethanolamine hydrochloride that obtains among 2L water and the 3.55kg embodiment 3 in the 10L reactor, vigorous stirring adds the 2.1kg triethylamine after making its dissolving again, continued vigorous stirring 30 minutes, be warming up to 80 ℃ and remove unnecessary triethylamine and water, then solid is pulverized, add 3L toluene vigorous stirring, leave standstill, filter toluene wash filter cake three times, each 500ml, 100 ℃ of vacuum tightness is-0.098kPa dry 2 hours down, obtain phosphoric acid Monoethanolamine MEA BASF white solid powder 2.54kg, 236～237 ℃ of fusing points, productive rate 90%, purity 〉=98.0%.
Claims (10)
1. method for preparing the phosphorylethanolamine compound, wherein the structural formula of phosphorylethanolamine compound is as the formula (2):
Wherein, R
1Be H or H
2N-CH
2-CH
2, R
2Be H or H
2N-CH
2-CH
2, x is 0,1,2 or 3;
The concrete steps that it is characterized in that this method are:
1) under certain temperature of reaction, thanomin or ethanolamine solutions are joined in the reactant, obtain reaction mixture;
2) will obtain phosphorylethanolamine or phosphorylethanolamine hydrochloride after the reaction mixture process straight line program intensification vacuum-drying then;
Reactant is a kind of in Vanadium Pentoxide in FLAKES, phosphoric acid solution, phosphorus oxychloride or the phosphorus oxychloride solution in the step 1).
2. a kind of method for preparing the phosphorylethanolamine compound according to claim 1 is characterized in that: earlier reactant is dissolved in a certain amount of water in the step 1), and then adds thanomin or ethanolamine solutions; The mass ratio of reactant and a certain amount of water is 1: 1～100.
3. a kind of method for preparing the phosphorylethanolamine compound according to claim 1 is characterized in that: the solvent in the phosphoric acid solution is water or high boiling solvent; The concentration of phosphoric acid solution is 1%～85%;
Solvent in the phosphorus oxychloride solution is aromatic hydrocarbons, bicyclic hydrocarbon, carbon atom a kind of or its mixture in the halohydrocarbon between 1～4, high boiling point ether, high boiling point ketone or the ester of carbon atom between 1～7; The concentration of phosphorus oxychloride solution is 1%～99%;
Solvent in the ethanolamine solutions be aromatic hydrocarbons, bicyclic hydrocarbon, carbon atom the halohydrocarbon between 1～4, high boiling point ether, high boiling point ketone, carbon atom at ester between 1～7 or carbon atom a kind of or its mixture in the alcohol between 1～7; The concentration of ethanolamine solutions is 1%～99%.
4. a kind of method for preparing the phosphorylethanolamine compound according to claim 3, it is characterized in that: the high boiling solvent in the phosphoric acid solution is preferably ketone, and the aromatic solvent in the phosphorus oxychloride solution is preferably a kind of in benzene, toluene or the dimethylbenzene; Aromatic solvent in the ethanolamine solutions is preferably a kind of in benzene, toluene or the dimethylbenzene.
5. a kind of method for preparing the phosphorylethanolamine compound according to claim 1 is characterized in that: when reactant was Vanadium Pentoxide in FLAKES, the Vanadium Pentoxide in FLAKES of adding and the mol ratio of thanomin were 1: 2.0～6.0.
6. a kind of method for preparing the phosphorylethanolamine compound according to claim 1 is characterized in that: when reactant was phosphoric acid solution, the phosphoric acid of adding and the mol ratio of thanomin were 1: 1.0～3.0.
7. a kind of method for preparing the phosphorylethanolamine compound according to claim 1 is characterized in that: when reactant was phosphorus oxychloride or phosphorus oxychloride solution, the phosphorus oxychloride of adding and the mol ratio of thanomin were 1: 1.0～3.0.
8. a kind of method for preparing the phosphorylethanolamine compound according to claim 1 is characterized in that: certain temperature of reaction is-20～100 ℃ in the step 1), and the time of adding is that 5min is to 72h.
9. a kind of method for preparing the phosphorylethanolamine compound according to claim 1 is characterized in that: step 2) in the temperature programming scope be-20～250 ℃, the heating-up time is 0.5～72h.
10. a kind of method for preparing the phosphorylethanolamine compound according to claim 1 is characterized in that: step 2) in vacuum drying vacuum tightness be 0～101.18*10
5KPa.
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|---|---|---|---|
| CN 201010523933 CN101974029B (en) | 2010-10-29 | 2010-10-29 | Method for preparing phosphorylethanolamine compound |
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| CN101974029A true CN101974029A (en) | 2011-02-16 |
| CN101974029B CN101974029B (en) | 2012-07-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206600A (en) * | 2017-07-03 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of preparation method of phosphorous copolymerization flame-proof polylactic acid fiber |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2730542A (en) * | 1951-06-25 | 1956-01-10 | Ferrari Vittorio Emiliano | Process for preparing ethanol-2-aminophosphoric acid |
| CN1150391A (en) * | 1994-04-20 | 1997-05-21 | 耐克麦德瑟鲁塔公司 | Dendrimeric compounds |
-
2010
- 2010-10-29 CN CN 201010523933 patent/CN101974029B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2730542A (en) * | 1951-06-25 | 1956-01-10 | Ferrari Vittorio Emiliano | Process for preparing ethanol-2-aminophosphoric acid |
| CN1150391A (en) * | 1994-04-20 | 1997-05-21 | 耐克麦德瑟鲁塔公司 | Dendrimeric compounds |
Non-Patent Citations (1)
| Title |
|---|
| 《Polymer Degradation and Stability》 20071231 A. Toldy，et al Intrinsically flame retardant epoxy resin e Fire performance and background e Part I 2223e2230 1-10 , 2 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206600A (en) * | 2017-07-03 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of preparation method of phosphorous copolymerization flame-proof polylactic acid fiber |
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