CN104356015B - A kind of synthetic method of aminopolycarboxylate compounds's ethylene glycol bis (2-amino-ethyl ether) nitrilotriacetic - Google Patents
A kind of synthetic method of aminopolycarboxylate compounds's ethylene glycol bis (2-amino-ethyl ether) nitrilotriacetic Download PDFInfo
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- CN104356015B CN104356015B CN201410691669.XA CN201410691669A CN104356015B CN 104356015 B CN104356015 B CN 104356015B CN 201410691669 A CN201410691669 A CN 201410691669A CN 104356015 B CN104356015 B CN 104356015B
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Abstract
The invention discloses the synthetic method of a kind of aminopolycarboxylate compounds's ethylene glycol bis (2-amino-ethyl ether) nitrilotriacetic.The technical scheme adopted is: be first dissolved in appropriate warm water by ethylene glycol bis (2-amino-ethyl ether) tetraacethyl, add rare-earth oxide, and heated and stirred backflow 3 ~ 4h, obtains H
3eg3a-Re
2o
3complex solution, drip organic amine regulator solution pH value to 5.0 ~ 6.0 time, concentrated by solution, leave standstill, cross leaching filtrate, in filtrate, drip sodium hydroxide solution, regulate pH to 12.0 ~ 13.0, alkalization destroys H
3eg3a-Re
2o
3mixture.Leave standstill, filter, in filtrate, drip concentrated hydrochloric acid regulate pH to 2.0 ~ 3.0, obtain a large amount of white H
3eg3a precipitates.The inventive method is simply novel, and cost is low, and does not have by product generation to cause environmental pollution.
Description
Technical field
The invention belongs to organic synthesis field, relate to a kind of unsaturated asymmetric aminopolycarboxylate compounds's ethylene glycol bis (2-amino-ethyl ether) nitrilotriacetic (H particularly
3eg3a) synthetic method.
Background technology
The synthesis of aminopolycarboxylate compounds is for many years one of more interested research topic of many chemists with research and development always.Aminopolycarboxylate compounds is widely used in the fields such as biomedicine (preparing targeted drug etc.), pharmacy (synthesizing antineoplastic medicament and antidote etc.), agricultural (being applied to chemistry and biosensor etc.) and environment measuring (fluorescent probe etc.).Therefore the novel method researching and developing synthesizing amino multi-carboxylic acid compounds is quite necessary.
At present, the kind studying the aminopolycarboxylate compounds of saturated symmetry is in the world abundanter, but the kind of unsaturated asymmetric aminopolycarboxylate compounds is but very limited.In organic synthesis, the synthetic method of the aminopolycarboxylate compounds of saturated symmetry has a lot, in order to improve productive rate, often all can add excessive bromo carboxylic acid or chlorinated carboxylic acid, the productive rate of saturated symmetrical amino polyacid compound can be improved by this mode to a certain extent.But for the synthesis of unsaturated asymmetric aminopolycarboxylate compounds, due to its group, to be in symmetrical position chemical property identical, the synthesis step of usual asymmetric aminopolycarboxylate compounds is comparatively loaded down with trivial details but also can produce a large amount of by product.If it is very large that present stage wants to obtain certain specific unsaturated asymmetric aminopolycarboxylate compounds's difficulty, as ethylenediamine triacetic acid, ethylenediamine-N,N'-diacetic acid(EDDA) and quadrol one acetic acid etc., this is also that on market, unsaturated asymmetric aminopolycarboxylate compounds's price is high, and we are difficult to the reason of having bought.Therefore the synthetic method researching and developing new unsaturated asymmetric aminopolycarboxylate compounds be highly significant with the direction of scientific rersearch of prospect.
Summary of the invention
In order to solve the difficult problem that the unsaturated asymmetric aminopolycarboxylate compounds of synthesis exists, it is a kind of simple novel to the invention provides, and cost is low, and does not have by product to generate the synthetic method that can't cause the unsaturated asymmetric aminopolycarboxylate compounds of environmental pollution.
The technical solution used in the present invention is: a kind of aminopolycarboxylate compounds's ethylene glycol bis (2-amino-ethyl ether) nitrilotriacetic (H
3eg3a) synthetic method, method is as follows:
1) by ethylene glycol bis (2-amino-ethyl ether) tetraacethyl (H
4egta) be dissolved in appropriate warm water, add rare-earth oxide, mixture stirs lower reflux 3 ~ 4h, and cooling, drips By Amine Solutions regulator solution pH value to 5.0 ~ 6.0, concentrated by solution, obtain concentrated solution in solution;
2) left standstill by concentrated solution, filter, get filtrate, in filtrate, drip mineral alkali, regulator solution pH, to 12.0 ~ 13.0, leaves standstill, and filters, gets filtrate; In filtrate, drip hydrochloric acid conditioning solution pH again to 2.0 ~ 3.0, cross leaching precipitation, precipitate through washing and drying, obtain target product.
Above-mentioned aminopolycarboxylate compounds's ethylene glycol bis (2-amino-ethyl ether) nitrilotriacetic (H
3eg3a), ethylene glycol bis (2-amino-ethyl ether) tetraacethyl (H
4egta) be 2:1 with the mol ratio of rare-earth oxide.
Above-mentioned aminopolycarboxylate compounds's ethylene glycol bis (2-amino-ethyl ether) nitrilotriacetic (H
3eg3a), described rare-earth oxide is Yb
2o
3, Eu
2o
3or Tb
2o
3.
Above-mentioned aminopolycarboxylate compounds's ethylene glycol bis (2-amino-ethyl ether) nitrilotriacetic (H
3eg3a), described organic amine is methylamine or or quadrol.
Above-mentioned aminopolycarboxylate compounds's ethylene glycol bis (2-amino-ethyl ether) nitrilotriacetic (H
3eg3a), described mineral alkali is sodium hydroxide or potassium hydroxide.
In the present invention, first by ethylene glycol bis (2-amino-ethyl ether) tetraacethyl (H
4egta) with rare-earth oxide (Re
2o
3: Eu
2o
3, Tb
2o
3and Yb
2o
3) reacted by reflux, reaction solution passes through to regulate pH to 5.0 ~ 6.0, by the H of reaction
3eg3a-Re
2o
3mixture and unconverted H
4egta-Re
2o
3mixture separately.When pH is 5.0 ~ 6.0, unconverted H
4egta-Re
2o
3mixture with precipitation forms filtering, thus obtains the H in solution
3eg3a-Re
2o
3mixture.Above-mentioned solution is passed through regulator solution pH to 12.0 ~ 13.0, alkalization destroys H
3eg3a-Re
2o
3mixture.By leaving standstill, filter, removing rare-earth oxide obtains Na
3eg3a solution.Pass through regulator solution pH again to 2.0 ~ 3.0, obtain a large amount of white H
3eg3a precipitates.
The invention has the beneficial effects as follows: the present invention, only just can make ethylene glycol bis (2-amino-ethyl ether) tetraacethyl (H by simple stirring heating backflow with the method for regulator solution pH
4egta) take off a carboxylic acid, obtain product-ethylene glycol bis (the 2-amino-ethyl ether) nitrilotriacetic (H wanted
3eg3a), and by product can not be supervened, the reactant rare-earth oxide (Re of recovery
2o
3) can reuse.Compared with the synthetic method of the method adopted in the present invention and traditional decarboxylic reaction or unsaturated asymmetric aminopolycarboxylate compounds, have simple, fast, the features such as environmental protection.
The aminopolycarboxylate compounds H of the present invention's synthesis
3eg3a, has unsaturated unsymmetrical structure, aminopolycarboxylate compounds H
3eg3a contains unsubstituted hydrogen atom, and these hydrogen atoms can be replaced by some functional groups or biomolecules is modified, and can be applied to many fields according to this special property.Such as, (1) human body is at Pb
2+after poisoning, usual EDTA is as toxinicide, but it is too large to see EDTA macromolecule water-solubility as from pharmacokinetic property, not easily crosses over cytolemma, and Pb
2+mainly be present in cell, want effectively to remove heavy metal ion poisonous in body, should require that toxinicide can enter in cell.Therefore only have to introduce and have the fat-soluble of fat-soluble group increase toxinicide, toxinicide just has the ability of crossing over cytolemma just can effectively detoxify, the H of the present invention's synthesis
3have a unsubstituted hydrogen atom in eg3a, the chloro fat alkane can introducing long-chain increases that it is fat-soluble, its permeate through cell membranes is entered in cell and detoxifies.Meanwhile, also can improve its identification to each metal ion species by this method, select and binding ability.(2) the unsaturated asymmetric aminopolycarboxylate compounds H of the present invention's synthesis
3eg3a can connect a kind of anti-tumor drug on its unsubstituted hydrogen, therefore can become and carry the optimum carrier that these antitumor drugs with Diagnosis and Treat effect enter human body.The amino polyacid part meanwhile connecting antitumor drug is combined with the rare earth radioactive metal with Diagnosis and Treat function again, make it enter human body discharge safely again with the form stable of title complex, use this method will obtain having the antitumor drug of monitoring and treatment tumour cell double effects.(3) the unsaturated asymmetric aminopolycanboxylic acid of the present invention's synthesis can connect with the suitable biomolecules with orientating function, form directed delivery system thus reach the Diagnosis and Treat object of expection, thus form the targeted drug with particular diagnostic therapeutic action, make it in the process of synthesis targeted drug, have potential using value.(4) the unsaturated asymmetric aminopolycanboxylic acid of the present invention's synthesis can connect the group of the phenyl ring heterocycle containing fluorescent characteristic in the above to change the fluorescence activity of itself, can be applicable to prepare fluorescent probe and biosensor etc.In sum, the unsaturated asymmetric aminopolycarboxylate compounds of the present invention's synthesis is widely used in above-mentioned field.
Accompanying drawing explanation
Fig. 1 .H
3the schema of eg3a building-up reactions.
Fig. 2. rare-earth oxide (Eu
2o
3, Tb
2o
3and Yb
2o
3) H under existent condition
4egta decarboxylation explanatory view.
Fig. 3. rare-earth oxide (Eu
2o
3, Tb
2o
3, Yb
2o
3) H under existent condition
4egta decarboxylic reaction mechanism figure.
Fig. 4 .H
3the molecular structure (being obtained by monocrystalline-x diffraction data) of eg3a.
Fig. 5 .H
4the molecular structure (being obtained by monocrystalline-x diffraction data) of egta.
Embodiment
Embodiment 1 is by synthesis H
3eg3a-Eu
2o
3mixture obtains H
3eg3a
H
3eg3a-Eu
2o
3the synthesis of mixture: by the H taken
4egta (1.9017g, 5.00mmol) joins in the warm water of 100mL, then adds Eu to it
2o
3powder (0.8798g, 2.50mmol), by above-mentioned mixing solutions reflux 3 ~ 4h in magnetic stirring apparatus, until solution becomes clear, cooling.In solution, drip ethylenediamine solution, adjust ph is to 6.0.Solution is concentrated into 25.00mL, leaves standstill, now unconverted H
4egta-Eu
2o
3mixture exists with precipitation forms, filters, removes unconverted H
4egta-Eu
2o
3mixture, gets filtrate, is mainly H in filtrate
3eg3a-Eu
2o
3mixture.
H
3the synthesis of eg3a: drip sodium hydroxide solution in filtrate, regulate pH to 12.0 ~ 13.0, alkalization destroys H
3eg3a-Eu
2o
3mixture.Leave standstill, cross leaching filtrate, obtain Na
3eg3a solution, then in solution, drip concentrated hydrochloric acid adjustment pH to 2.0 ~ 3.0, obtain a large amount of white H
3eg3a precipitates.Finally by filtration, washing, dry, obtain white product H
3eg3a.Productive rate is 83%.
To products therefrom (H
3eg3a) cultivate monocrystalline, measure through infrared (IR) spectrum and x-ray single crystal diffraction, draw the molecular structure of white product as shown in Figure 4.Infrared (IR) spectroscopic data: ν (C-N)=1134cm
-1, ν (C=O)=1744cm
-1, ν
a(OCO)=1640cm
-1, ν
as(OCO)=1403cm
-1, ν (O-H)=3422cm
-1with ν (N-H)=2952cm
- 1.Bond distance's data are in table 1.
In contrast, equally to reactant (H
4egta) cultivate monocrystalline, measure through infrared (IR) spectrum and x-ray single crystal diffraction, show that molecular structure as shown in Figure 5.Infrared (IR) data: ν (C-N)=1133cm
-1, ν (C=O)=1738cm
- 1, ν
a(OCO)=1593cm
-1, ν
as(OCO)=1411cm
-1with ν (O-H)=3491cm
-1.Bond distance's data are in table 2.
Table 1H
3eg3a bond distance's data
Table 2H
4egta bond distance's data
Embodiment 2 is by synthesis H
3eg3a-Tb
2o
3mixture obtains H
3eg3a
H
3eg3a-Tb
2o
3the synthesis of mixture: by the H taken
4egta (1.9017g, 5.00mmol) joins in the warm water of 100mL, then adds Tb to it
2o
3powder (0.9146g, 2.50mmol), by above-mentioned mixing solutions reflux 3 ~ 4h in magnetic stirring apparatus, until solution becomes clear, cooling.In solution, drip ethylenediamine solution, adjust ph is to 6.0.Solution is concentrated into 25.00mL, leaves standstill, now unconverted H
4egta-Tb
2o
3mixture exists with precipitation forms, filters, removes unconverted H
4egta-Tb
2o
3mixture, gets filtrate.
H
3the synthesis of eg3a: drip sodium hydroxide solution in filtrate, regulate pH to 12.0 ~ 13.0, alkalization destroys H
3eg3a-Tb
2o
3mixture.Leave standstill, filter, obtain Na
3eg3a solution, then in filtrate, drip concentrated hydrochloric acid adjustment pH to 2.0 ~ 3.0, obtain a large amount of white H
3eg3a precipitates.Finally by filtration, washing, dry, obtain white product H
3eg3a.Productive rate is 87%.
To products therefrom (H
3eg3a) cultivate monocrystalline, carry out infrared (IR) spectrum and x-ray single crystal diffraction mensuration.Infrared (IR) spectroscopic data: ν (C-N)=1134cm
-1, ν (C=O)=1744cm
-1, ν
a(OCO)=1640cm
-1, ν
as(OCO)=1403cm
-1, ν (O-H)=3422cm
-1with ν (N-H)=2952cm
-1.Measure bond distance by x-ray single crystal diffraction, measure according to infrared (IR) spectrum and x-ray single crystal diffraction, show that molecular structure as shown in Figure 4.
In contrast, equally to reactant (H
4egta) cultivate monocrystalline, measure through infrared (IR) spectrum and x-ray single crystal diffraction, show that molecular structure as shown in Figure 5.
Embodiment 3 is by synthesis H
3eg3a-Yb
2o
3mixture obtains H
3eg3a
H
3eg3a-Yb
2o
3the synthesis of mixture: by the H taken
4egta (1.9017g, 5.00mmol) joins in the warm water of 100mL, then adds Yb to it
2o
3powder (0.9852g, 2.50mmol), by above-mentioned mixing solutions reflux 3 ~ 4h in magnetic stirring apparatus, until solution becomes clear, cooling.In solution, drip methylamine solution, adjust ph is to 6.0.Solution is concentrated into 25.00mL, leaves standstill, now unconverted H
4egta-Yb
2o
3mixture exists with precipitation forms, filters, removes unconverted H
4egta-Yb
2o
3mixture, gets filtrate.
H
3the synthesis of eg3a: drip potassium hydroxide solution in filtrate, regulate pH to 12.0 ~ 13.0, alkalization destroys H
3eg3a-Yb
2o
3mixture.Leave standstill, filter, obtain K
3eg3a solution, then in filtrate, drip concentrated hydrochloric acid adjustment pH to 2.0 ~ 3.0, obtain a large amount of white H
3eg3a precipitates.Finally by filtration, washing, dry, obtain white product H
3eg3a.Productive rate is 91%.
To products therefrom (H
3eg3a) cultivate monocrystalline, measure through infrared (IR) spectrum and x-ray single crystal diffraction, show that molecular structure as shown in Figure 4.
In contrast, equally to reactant (H
4egta) cultivate monocrystalline, measure through infrared (IR) spectrum and x-ray single crystal diffraction, show that molecular structure as shown in Figure 5.
Embodiment 4 simultaneous test
1, rare-earth oxide is changed into Sm
2o
3
By the H taken
4egta (1.9017g, 5.00mmol) joins in the warm water of 100mL, then adds Sm to it
2o
3powder (0.8720g, 2.50mmol), by above-mentioned mixing solutions, in magnetic stirring apparatus, reflux 3 ~ 4h is until solution becomes clear, and cooling, in solution, drip ethylenediamine solution, adjust ph is to 6.0.Solution is concentrated into 25.00mL, leaves standstill, now produce a large amount of precipitation, cross leaching filtrate, then in filtrate, drip sodium hydroxide solution, regulate pH to 12.0 ~ 13.0.Leave standstill, cross leaching filtrate, then in filtrate, drip concentrated hydrochloric acid adjustment pH to 2.0 ~ 3.0, obtain a small amount of white precipitate.Finally by filtration, washing, dry, obtain white product.
Monocrystalline is cultivated to white product, carries out infrared (IR) spectrum and x-ray single crystal diffraction mensuration.
Infrared (IR) data: ν (C-N)=1133cm
-1, ν (C=O)=1738cm
-1, ν
a(OCO)=1593cm
-1, ν
as(OCO)=1411cm
-1with ν (O-H)=3491cm
-1.
Bond distance is measured by x-ray single crystal diffraction.According to infrared spectra and x-ray single crystal diffraction measurement result, the molecular structure of white product as shown in Figure 5, illustrates that obtain is H
4egta, but not H
3eg3a.
2, rare-earth oxide is changed into Gd
2o
3
By the H taken
4egta (1.9017g, 5.00mmol) joins in the warm water of 100mL, then adds Gd to it
2o
3powder (0.9063g, 2.50mmol), by above-mentioned mixing solutions, in magnetic stirring apparatus, reflux 3 ~ 4h is until solution becomes clear, and cooling, in solution, drip ethylenediamine solution, adjust ph is to 6.0.Solution is concentrated into 25.00mL, leaves standstill, now produce a large amount of precipitation, cross leaching filtrate, then in filtrate, drip sodium hydroxide solution, regulate pH to 12.0 ~ 13.0.Leave standstill, cross leaching filtrate, then in filtrate, drip concentrated hydrochloric acid adjustment pH to 2.0 ~ 3.0, obtain a small amount of white precipitate.Finally by filtration, washing, dry, obtain white product.
Monocrystalline is cultivated to white product, carries out infrared (IR) spectrum and x-ray single crystal diffraction and measure, according to the molecular structure of measurement result white product as shown in Figure 5, illustrate that obtain is H
4egta, but not H
3eg3a.
3, rare-earth oxide is changed into Er
2o
3
By the H taken
4egta (1.9017g, 5.00mmol) joins in the warm water of 100mL, then adds Er to it
2o
3powder (0.9563g, 2.50mmol), by above-mentioned mixing solutions, in magnetic stirring apparatus, reflux 3 ~ 4h is until solution becomes clear, and cooling, in solution, drip ethylenediamine solution, adjust ph is to 6.0.Solution is concentrated into 25.00mL, leaves standstill, now produce a large amount of precipitation, cross leaching filtrate, in filtrate, drip sodium hydroxide solution, regulate pH to 12.0 ~ 13.0, leave standstill, cross leaching filtrate, then in filtrate, drip concentrated hydrochloric acid adjustment pH to 2.0 ~ 3.0, obtain a small amount of white precipitate.Finally by filtration, washing, dry, obtain white product.
Monocrystalline is cultivated to white product, carries out infrared (IR) spectrum and x-ray single crystal diffraction and measure, according to the molecular structure of measurement result white product as shown in Figure 5, illustrate that obtain is H
4egta, but not H
3eg3a.
By the above embodiments 1-3 and contrast experiment, the rare-earth oxide when selecting is only had to be Yb
2o
3, Eu
2o
3and Tb
2o
3during wherein a kind of, under common heated and stirred backflow, H
4egta is meeting and rare-earth oxide (Re
2o
3) produce H
3eg3a-Re
2o
3mixture.Only have when wherein one exists these three kinds of rare-earth oxides, the H containing four carboxylic acids
4egta just can take off a hydroxy-acid group.These three kinds of rare-earth oxides are only had to have catalytic decarboxylation performance to aminopolycarboxylate compounds.
Claims (4)
1. a synthetic method for aminopolycarboxylate compounds's ethylene glycol bis (2-amino-ethyl ether) nitrilotriacetic, is characterized in that method is as follows:
1) ethylene glycol bis (2-amino-ethyl ether) tetraacethyl is dissolved in appropriate warm water, add rare-earth oxide, mixture stirs lower reflux 3 ~ 4h, cooling, By Amine Solutions regulator solution pH value to 5.0 ~ 6.0 are dripped in solution, solution is concentrated, obtains concentrated solution; Wherein, described rare-earth oxide is Yb
2o
3, Eu
2o
3or Tb
2o
3;
2) left standstill by concentrated solution, filter, get filtrate, in filtrate, drip mineral alkali, regulator solution pH, to 12.0 ~ 13.0, leaves standstill, and filters, gets filtrate; In filtrate, drip hydrochloric acid conditioning solution pH again to 2.0 ~ 3.0, cross leaching precipitation, precipitate through washing and drying, obtain target product.
2. according to the synthetic method of aminopolycarboxylate compounds's ethylene glycol bis according to claim 1 (2-amino-ethyl ether) nitrilotriacetic, it is characterized in that: the mol ratio of ethylene glycol bis (2-amino-ethyl ether) tetraacethyl and rare-earth oxide is 2:1.
3., according to the synthetic method of aminopolycarboxylate compounds's ethylene glycol bis according to claim 1 (2-amino-ethyl ether) nitrilotriacetic, it is characterized in that: described organic amine is methylamine or quadrol.
4., according to the synthetic method of aminopolycarboxylate compounds's ethylene glycol bis according to claim 1 (2-amino-ethyl ether) nitrilotriacetic, it is characterized in that: described mineral alkali is sodium hydroxide or potassium hydroxide.
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Citations (3)
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|---|---|---|---|---|
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| EP2371869A1 (en) * | 2010-03-30 | 2011-10-05 | Evonik Stockhausen GmbH | A process for the production of a superabsorbent polymer |
| CN103025654A (en) * | 2009-12-29 | 2013-04-03 | 蒙特克莱尔州立大学 | Methods of preparation and use of chelating agent modified graphene oxides |
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| JP2002020358A (en) * | 2000-07-07 | 2002-01-23 | Kansai Tlo Kk | New water-soluble chiral shift reagent comprising complex of rare earth metal with amino acid derivative ligand and optically resolving agent comprising the complex |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4352751A (en) * | 1979-09-10 | 1982-10-05 | Analytical Radiation Corporation | Species-linked diamine triacetic acids and their chelates |
| CN103025654A (en) * | 2009-12-29 | 2013-04-03 | 蒙特克莱尔州立大学 | Methods of preparation and use of chelating agent modified graphene oxides |
| EP2371869A1 (en) * | 2010-03-30 | 2011-10-05 | Evonik Stockhausen GmbH | A process for the production of a superabsorbent polymer |
| CN102869689A (en) * | 2010-03-30 | 2013-01-09 | 赢创德固赛有限公司 | A process for the production of a superabsorbent polymer |
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