CN104151466A - Method for environmentally preparing novel material capable of splitting chiral binaphthol from L-phenylalanine - Google Patents
Method for environmentally preparing novel material capable of splitting chiral binaphthol from L-phenylalanine Download PDFInfo
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- CN104151466A CN104151466A CN201410363134.XA CN201410363134A CN104151466A CN 104151466 A CN104151466 A CN 104151466A CN 201410363134 A CN201410363134 A CN 201410363134A CN 104151466 A CN104151466 A CN 104151466A
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Abstract
The invention relates to a method for environmentally preparing a novel material capable of splitting chiral binaphthol from L-phenylalanine. The method comprises the following steps: firstly, preparing N-methylacryloyl-L-phenylalanine methyl ester (A-L-M) in ionic liquid-1-ethyl-3-methylimidazole ethyl sulfate from L-phenylalanine; secondly, adding prepared A-L-M and a certain quantity of yttrium trifluoromethanesulfonate into ionic liquid-hexanolactam-tetrabutylammonium bromide, selecting and using a proper initiator, and obtaining a poly(A-L-M) material with a regular main chain in an inert atmosphere. According to the method, a preparation process is simple and good in repeatability, the used raw material-L-phenylalanine is wide in source and good in environmental compatibility, a reaction medium-ionic liquid is harmless to a human body and environment and can be recycled, and the prepared novel material is relatively high in yield, good in economic benefit and suitable for large-scale industrialized production.
Description
Technical field
The invention belongs to technical field of material, relate to a kind of method of utilizing the novel material of the detachable chiral binaphthol of the green preparation of L-Phe.
Background technology
Chipal compounds dinaphthol BINOL(1,1'-union-2-naphthol) and R, two kinds of enantiomorphs of S-BINOL are particularly widely used at aspects such as preparing chiral medicinal, agricultural chemicals and foodstuff additive in asymmetric synthesis.Especially take a series of high chirality efficiency catalyzer and the chiral ligand that these two kinds of different enantiomorphs prepare as basis, for a large amount of asymmetric medicines synthetic provides a high yield, highly selective, approach cheaply, the application of the fractionation of dinaphthol in asymmetric synthesis more and more paid attention to.
At present, the material of domestic and international detachable dinaphthol mainly contains following several: (1) dinaphthol matrix material, for example Toda F is at < < Topics in Current Chemistry > > magazine 2005,254, in 1-40, utilize dinaphthol to be prepared into 1,1'-union-2-naphthol-Me by chemical method
4n
+cl
-composite materials splits dinaphthol.(2) chiral stationary phase, such as Weng Wen etc. at < < applied chemistry > > 2004,31,853-855 has reported and has utilized L-TARTARIC ACID type chiral stationary phase under positive condition, to realize the fractionation to dinaphthol.(3) phosphoric acid ester, Fabbn D is at < < Journal of organic chemistry > >, 2013,78,4895-4904 has reported with α-phenylethylamine and as resolution reagent, dinaphthol phosphoric acid ester has been split, again the hydrolysis of dinaphthol phosphoric acid ester is obtained to dinaphthol, thereby reached the chiral separation to dinaphthol.But the preparation method of existing fractionation material need to carry out under strict laboratory equipment and process control condition, and complex process, productive rate is low, reaction medium is used a large amount of poisonous organic solvents, human body and environment are caused damage, thereby greatly limited detachable dinaphthol material in the widespread use of production field, be difficult to realize industrialization.
Zhao Haili etc. are at < < chemical progress > >, 2009,10,2077-2083 has reported that ionic liquid has the incomparable excellent properties of many conventional solvent as " green " solvent, in fields such as organic synthesis, catalysis, the separation of liquid liquid and extractions, causes broad research.Ionic liquid has tasteless, ordorless, pollution-free, nonflammable, be easy to product separation, easily reclaim, can repeated multiple times recycle, most inorganics, organism, polymer being had to the very advantage such as strong solubility, become a kind of novel eco-friendly " green medium ", is the ideal substitute of organic solvent.
Wei etc. are at < < Journal of Polymer Science:Part A:Polymer Chemistry > > 2010,48,5411-5418 has reported that chiral monomer prepares main chain regular polymer under the catalysis of trifluoromethanesulfonic acid rare-earth salts, due to its space behavior having, can be used for chiral separation, preparation process is simple, there is larger application prospect, but its reaction raw materials used source is limited, and biocompatibility is poor.
Summary of the invention
The object of the invention is to for the preparation of the existing material for resolving chiral dinaphthol complicated, productive rate is low, industrial production poor operability, prepare the required raw materials cost of detachable material high, Environmental compatibility is poor, originate limited, reaction medium is used a large amount of poisonous organic solvents, human body and environment are produced to dysgenic problem, provide a kind of preparation process simple, reproducible, productive rate is high, prepared using the Nature extensively exists, can prepare from organism, the L-Phe that Environmental compatibility is good, reaction medium utilizes reusable, the ionic liquid of environmental protection is prepared the method for the novel material of resolving chiral dinaphthol.
N-methacryloyl-L-Phe methyl esters (A-L-M) that the present invention utilizes L-Phe to prepare in ionic liquid; under trifluoromethanesulfonic acid yttrium exists; ionic liquid is that reaction medium has been prepared the regular polymethyl acylphenylalanines methyl esters poly(A-L-M of main chain); between this material and dinaphthol molecule, produce hydrogen bond and space behavior, thereby reach the effect that can split dinaphthol.
Ionic liquid generally refers to the liquid being comprised of organic ionic compounds completely, sometimes, also referred to as ionic liquid, (referring to, Li Da etc., hexanolactam-Tetrabutyl amonium bromide class ionic liquid absorbs SO to the liquid of the similarity also organic ionic compounds and amides organism being formed
2the research of efficiency, environmental science and management, 2011,7,84).
Polymethyl acylphenylalanines methyl esters, is characterized in that, its number-average molecular weight between 1.5 ten thousand to 30,000, molecular weight distribution M
w/ M
n=1.30～1.50; Its repeating unit is:
Preferably, described polymethyl acylphenylalanines methyl esters is the regular polymkeric substance of main chain, and main polymer chain is complete is m/r=70/30-65/35 with (m) part and same (r) part ratio.
The present invention also provides the preparation method of described polymethyl acylphenylalanines methyl esters.
A preparation method for the novel material of resolving chiral dinaphthol, is characterized in that comprising the steps:
(1) preparation of N-methacryloyl-L-Phe methyl esters (A-L-M) under ionic liquid
Under-5 ℃ of-0 ℃ of ice baths, sulfur oxychloride is slowly joined in the mixing solutions of methyl alcohol and L-Phe, stir after 2～3h, rise to 60-65 ℃ of stirring 2～5h and obtain mixed solution, the L-Phe methyl ester hydrochloride obtaining after revolving steaming joins in the ionic liquid 1-ethyl-3-methylimidazole sulfovinic acid that contains triethylamine;
Under-5 ℃ of-0 ℃ of ice baths, slowly drip methacrylic chloride, stir to move on to after 1～3h and under room temperature, stir 2～5h and obtain mixing solutions, after extracting, be dried, revolving steaming, obtain chiral monomer A-L-M;
(2) the preparation material poly(A-L-M of detachable chiral binaphthol under ionic liquid)
The A-L-M of preparation in step (1) and trifluoromethanesulfonic acid yttrium are joined in the ionic liquid that the hexanolactam-Tetrabutyl amonium bromide by 1:1-2:1 mol ratio forms.Stirring at room 0.5-1 hour, adds initiator, and under protection of inert gas atmosphere, 60-65 ℃ of reaction 20-28h, obtains polymers soln; Above-mentioned solution washing, the centrifugal polymkeric substance obtaining are dissolved with 10～30mL tetrahydrofuran (THF); pour in 200～600mL varsol; by solid suction filtration, the oven dry of separating out, obtain the regular poly-N-methacryloyl-L-Phe methyl esters poly(A-L-M of main chain) material.
Preferably, the mass ratio of the L-Phe described in step (1), methyl alcohol, sulfur oxychloride is 1:(10～30): (1.5～7).
Preferably, the mass ratio of the L-Phe methyl ester hydrochloride described in step (1), methacrylic chloride, San Yi An ﹑ 1-ethyl-3-methylimidazole sulfovinic acid is 1:(1.5～3): (3～9): (25～30).
Preferably, the mass ratio of the A-L-M ﹑ trifluoromethanesulfonic acid Yi ﹑ hexanolactam-Tetrabutyl amonium bromide described in step (2) is 1:(0.05～0.25): (5～8).
The described initiator of step (2) is Diisopropyl azodicarboxylate or ammonium persulphate, and the mass ratio of initiator and A-L-M is (0.03～0.07): 1.
The described rare gas element of step (2) is nitrogen or argon gas.
The described varsol of step (2) is a kind of or mixture in sherwood oil, hexane, heptane, hexanaphthene.
Poly-N-methacryloyl-L-Phe methyl esters poly(A-L-M of preparation) material main chain regularity as shown in Figure 3, by the integral area of 1.1～1.9 ppm place polymkeric substance is analyzed, main polymer chain is complete is m/r=70/30 with (m) part and same (r) part ratio, main chain regularity is high, prepared poly(A-L-M) be that (analytical procedure is with reference to < < Journal of Polymer Science:Part A:Polymer Chemistry > > 2002 for the regular material of main chain, 40, 2496-2500).The measuring method of its molecular-weight average and distribution thereof adopts traditional gel permeation chromatography-laser light scattering combined instrument, take tetrahydrofuran (THF) as solvent, and polystyrene is standard test.
Effect proof experiment 1:
Utilize nuclear magnetic resonance spectrometer, by polymer materials poly(A-L-M) and dinaphthol (R, S-BINOL) be dissolved in deuterochloroform and characterize, using and investigate the evident characteristics of polymkeric substance to dinaphthol: by the chloroformic solution of deuteration containing 0.016g dinaphthol as blank, and containing 0.02g poly(A-L-M) and the chloroformic solution of deuteration that mixes of 0.016g dinaphthol contrast.Nuclear magnetic spectrogram as shown in Figure 1
Fig. 1 (b) represents the dinaphthol nuclear magnetic spectrum as blank, (a) represents polymkeric substance and the mixed nuclear magnetic spectrum of dinaphthol.
As shown in Fig. 1 (b), dinaphthol-OH is single spike at 5.0 places, after Fig. 1 (a) polymkeric substance mixes with dinaphthol, the peak of 5.0 places-OH produce and split minute (+,-difference corresponding R, S-BINOL), because polymkeric substance produces hydrogen bond and space behavior to dinaphthol, hydroxyl peak is split minute, thereby can be proved that polymkeric substance has fractionation effect to dinaphthol.
Effect proof experiment 2:
1.0g polymer materials is filled in the Glass tubing that internal diameter is 10mm, and the bed volume (BV) that makes packed column is 3mL.Making concentration is that the R-BINOL solution of 0.20g/L is with 4BVh
-1flow velocity adverse current by packed column, with the interval of 2BV, collect effluent liquid, utilize ultraviolet spectrophotometer to measure the concentration of R-BIONL in effluent liquid, draw dynamic bind curve.Adopt same procedure, make the S-BINOL solution of 0.20g/L with 4BVh
-1flow velocity adverse current by packed column, with the interval of 2BV, collect effluent liquid, measure the concentration of S-BINOL in effluent liquid, draw dynamic bind curve.
As shown in Figure 2, R-BINOL solution starts to reveal in 66BV, and S-BINOL solution starts to reveal in 73BV, and both differ 7BV; The penetration volume of R-BINOL solution is 84BV, and the penetration volume of S-BINOL solution is 95BV, and both differ 9BV.
By above data, poly-(A-L-M can be described) material shows respectively different identification selection and binding ability to S-BINOL and R-BINOL, and therefore can be used as and split R, the material of S-BINOL.
Compared with prior art, the invention has the advantages that:
Adopt method of the present invention, compare with the preparation process of existing fractionation material, simple, reproducible, can be for industrial scale operation.
The raw materials used L-Phe of the inventive method can extract from organism, originates very extensive, and Environmental compatibility is good, pollution-free.
The inventive method reaction medium used is ionic liquid, compares with traditional organic solvent, and it is to human body and environmentally friendly, recyclable.
It is gentle that the inventive method is prepared the required reaction conditions of polymer materials, easy handling.
The material productive rate that the material of detachable dinaphthol prepared by the inventive method is prepared than traditional method is high, compares with traditional organic solvent method, can improve productive rate 10-15 percentage point.
Accompanying drawing explanation
Fig. 1 is blank dinaphthol, the mixed collection of illustrative plates of polymkeric substance and dinaphthol.
Fig. 2 is the material poly(A-L-M of detachable chiral binaphthol) dynamic bind curve to R-BIONL and S-BINOL.
Fig. 3 is poly-N-methacryloyl-L-Phe methyl esters poly(A-L-M) nmr spectrum of material.
specific implementation method
By specific embodiment, foregoing of the present invention is made to further description below, but this should be interpreted as to content of the present invention only limits to following example.
Embodiment 1
(1) preparation of N-methacryloyl-L-Phe methyl esters (A-L-M) under ionic liquid
Under 0 ℃ of ice bath, the sulfur oxychloride of 2.5g is slowly joined in the mixing solutions of 15g methyl alcohol and 1.3g L-Phe, stir after 2h, rise to 65 ℃ of stirring 2h and obtain mixed solution, after revolving steaming, the 1.5g L-Phe methyl ester hydrochloride obtaining is joined in the 38g ionic liquid 1-ethyl-3-methylimidazole sulfovinic acid that contains 6g triethylamine.Under 0 ℃ of ice bath, slowly drip 3g methacrylic chloride, stir to move on to after 1h and under room temperature, stir 2h and obtain mixing solutions, through extract, be dried, revolve steaming, obtain chiral monomer A-L-M;
(2) the preparation material poly(A-L-M of detachable chiral binaphthol under ionic liquid)
The 0.3g A-L-M of preparation in step (1) and 0.03g trifluoromethanesulfonic acid yttrium are joined to 2g in the ionic liquid that the hexanolactam-Tetrabutyl amonium bromide of 2:1 mol ratio forms.Stirring at room half hour,, add initiator Diisopropyl azodicarboxylate 0.015g, and under nitrogen protection atmosphere, 65 ℃ of reaction 24h, obtain polymers soln; Above-mentioned solution washing, the centrifugal polymkeric substance obtaining are dissolved with 10mL tetrahydrofuran (THF), pour in 200mL sherwood oil, suction filtration, oven dry, obtain the regular poly-N-methacryloyl-L-Phe methyl esters poly(A-L-M of main chain) material, (molecular weight M
n=24000, molecular weight distribution M
w/ M
n=1.37), productive rate 75%.Main polymer chain is complete is m/r=69/31 with (m) part and same (r) part ratio.
Embodiment 2
(1) preparation of N-methacryloyl-L-Phe methyl esters (A-L-M) under ionic liquid
Under 0 ℃ of ice bath, the sulfur oxychloride of 6g is slowly joined in the mixing solutions of 60g methyl alcohol and 2g L-Phe, stir after 2.5h, rise to 65 ℃ of stirring 2.5h and obtain mixed solution, after revolving steaming, the 2g L-Phe methyl ester hydrochloride obtaining is joined in the 53g ionic liquid 1-ethyl-3-methylimidazole sulfovinic acid that contains 12g triethylamine.Under 0 ℃ of ice bath, slowly drip 4.5g methacrylic chloride, stir to move on to after 2h and under room temperature, stir after 3h to mixing solutions, through extract, be dried, revolve steaming, obtain chiral monomer A-L-M;
(2) the preparation material poly(A-L-M of detachable chiral binaphthol under ionic liquid)
The 0.5g A-L-M of preparation in step (1) and 0.075g trifluoromethanesulfonic acid yttrium are joined to 4g in the ionic liquid that the hexanolactam-Tetrabutyl amonium bromide of 1:1 mol ratio forms.Stirring at room half hour,, add initiator azo two isobutyl 0.03g, and under nitrogen protection atmosphere, 60 ℃, reaction 24h, obtains polymers soln; Above-mentioned solution washing, the centrifugal polymkeric substance obtaining are dissolved with 20mL tetrahydrofuran (THF), pour in 400mL sherwood oil, suction filtration, oven dry, obtain the regular poly-N-methacryloyl-L-Phe methyl esters poly(A-L-M of main chain) material (molecular weight M
n=24500, molecular weight distribution M
w/ M
n=1.44), productive rate 78%.Main polymer chain is complete is m/r=66/34 with (m) part and same (r) part ratio.
Embodiment 3
(1) preparation of N-methacryloyl-L-Phe methyl esters (A-L-M) under ionic liquid
Under 0 ℃ of ice bath, the sulfur oxychloride of 24g slowly joins in the mixing solutions of 80g methyl alcohol and 4g L-Phe, stir after 3h, rise to 65 ℃ of stirring 5h and obtain mixed solution, after revolving steaming, the 5g L-Phe methyl ester hydrochloride obtaining is joined in the 90g ionic liquid 1-ethyl-3-methylimidazole sulfovinic acid that contains 40g triethylamine.Under 0 ℃ of ice bath, slowly drip 15g methacrylic chloride, stir to move on to after 3h and under room temperature, stir 5h and obtain mixing solutions, through extract, be dried, revolve steaming, obtain chiral monomer A-L-M;
(2) the preparation material poly(A-L-M of detachable chiral binaphthol under ionic liquid)
The 0.8g A-L-M of preparation in step (1) and 0.16g trifluoromethanesulfonic acid yttrium are joined to 6g in the ionic liquid that the hexanolactam-Tetrabutyl amonium bromide of 3:2 mol ratio forms.Stirring at room half hour,, add initiator ammonium persulfate 0.056g, and under nitrogen protection atmosphere, 60 ℃, reaction 24h, obtains polymers soln; Above-mentioned solution washing, the centrifugal polymkeric substance obtaining are dissolved with 30mL tetrahydrofuran (THF), pour in 600mL sherwood oil, suction filtration, oven dry, obtain the regular poly-N-methacryloyl-L-Phe methyl esters poly(A-L-M of main chain) material (molecular weight M
n=25000, molecular weight distribution M
w/ M
n=1.50), productive rate 77%.Main polymer chain is complete is m/r=67/33 with (m) part and same (r) part ratio.
Claims (9)
1. a polymethyl acylphenylalanines methyl esters, is characterized in that, its number-average molecular weight between 1.5 ten thousand to 30,000, molecular weight distribution M
w/ M
n=1.30～1.50; Its repeating unit is:
?。
2. polymethyl acylphenylalanines methyl esters as claimed in claim 1 is the regular polymkeric substance of main chain, it is characterized in that, main polymer chain is complete is m/r=70/30-65/35 with (m) part and same (r) part ratio.
3. the preparation method of polymethyl acylphenylalanines methyl esters as claimed in claim 1 or 2, comprises the steps:
(1) preparation of N-methacryloyl-L-Phe methyl esters (A-L-M)
Under-5 ℃ of-0 ℃ of ice baths, sulfur oxychloride is slowly joined in the mixing solutions of methyl alcohol and L-Phe, stir after 2～3h, rise to 60-65 ℃ of stirring 2～5h and obtain mixed solution, the L-Phe methyl ester hydrochloride obtaining after revolving steaming joins in the ionic liquid 1-ethyl-3-methylimidazole sulfovinic acid that contains triethylamine;
Under-5 ℃ of-0 ℃ of ice baths, slowly drip methacrylic chloride, stir to move on to after 1～3h and under room temperature, stir 2～5h and obtain mixing solutions, after extracting, be dried, revolving steaming, obtain chiral monomer A-L-M;
(2) the preparation material poly(A-L-M of detachable chiral binaphthol)
The A-L-M of preparation in step (1) and trifluoromethanesulfonic acid yttrium are joined in the ionic liquid that the hexanolactam-Tetrabutyl amonium bromide by 1:1-2:1 mol ratio forms; Stirring at room 0.5-1 hour, adds initiator, and under protection of inert gas atmosphere, 60-65 ℃ of reaction 20-28h, obtains polymers soln; Above-mentioned solution washing, the centrifugal polymkeric substance obtaining are dissolved with 10～30mL tetrahydrofuran (THF); pour in 200～600mL varsol; by solid suction filtration, the oven dry of separating out, obtain the regular poly-N-methacryloyl-L-Phe methyl esters poly(A-L-M of main chain) material.
4. the preparation method of polymethyl acylphenylalanines methyl esters as claimed in claim 3, is characterized in that, the mass ratio of the described L-Phe of step (1), methyl alcohol, sulfur oxychloride is 1:(10～30): (1.5～7).
5. the preparation method of polymethyl acylphenylalanines methyl esters as claimed in claim 3; it is characterized in that, the mass ratio of the described L-Phe methyl ester hydrochloride of step (1), methacrylic chloride, San Yi An ﹑ 1-ethyl-3-methylimidazole sulfovinic acid is 1:(1.5～3): (3～9): (25～30).
6. the preparation method of polymethyl acylphenylalanines methyl esters as claimed in claim 3; it is characterized in that, the mass ratio of A-L-M ﹑ trifluoromethanesulfonic acid Yi ﹑ hexanolactam-Tetrabutyl amonium bromide that step (2) is described is 1:(0.05～0.25): (5～8).
7. the preparation method of polymethyl acylphenylalanines methyl esters as claimed in claim 3; it is characterized in that; the described initiator of step (2) is Diisopropyl azodicarboxylate or ammonium persulphate, and the mass ratio of initiator and A-L-M is (0.03～0.07): 1.
8. the preparation method of polymethyl acylphenylalanines methyl esters as claimed in claim 3, is characterized in that, the described rare gas element of step (2) is nitrogen or argon gas.
9. the preparation method of polymethyl acylphenylalanines methyl esters as claimed in claim 3, is characterized in that, the described varsol of step (2) is a kind of or mixture in sherwood oil, hexane, heptane, hexanaphthene.
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Cited By (3)
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| CN106631847A (en) * | 2016-12-26 | 2017-05-10 | 徐州得铸生物科技有限公司 | Synthesis process of preservative intermediate compound phenylalanine ethyl ester sorbate |
| CN113024434A (en) * | 2019-12-24 | 2021-06-25 | 上海科胜药物研发有限公司 | Preparation method of brivaracetam intermediate |
| CN114534311A (en) * | 2021-08-26 | 2022-05-27 | 昆明医科大学 | Sulfur spacer arm (R) -BIONL CSP filler and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106631847A (en) * | 2016-12-26 | 2017-05-10 | 徐州得铸生物科技有限公司 | Synthesis process of preservative intermediate compound phenylalanine ethyl ester sorbate |
| CN106631847B (en) * | 2016-12-26 | 2018-09-28 | 上海博栋化学科技有限公司 | A kind of synthesis technology of preservative intermediate sorbic acid phenylalanine ethyl ester |
| CN113024434A (en) * | 2019-12-24 | 2021-06-25 | 上海科胜药物研发有限公司 | Preparation method of brivaracetam intermediate |
| CN114534311A (en) * | 2021-08-26 | 2022-05-27 | 昆明医科大学 | Sulfur spacer arm (R) -BIONL CSP filler and preparation method thereof |
| CN114534311B (en) * | 2021-08-26 | 2023-08-25 | 昆明医科大学 | Sulfur spacer arm (R) -BIONL CSP filler and preparation method thereof |
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