CN104693054A - L-amino acid sulfate type chiral ionic liquid and preparation method thereof - Google Patents
L-amino acid sulfate type chiral ionic liquid and preparation method thereof Download PDFInfo
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- CN104693054A CN104693054A CN201310646619.5A CN201310646619A CN104693054A CN 104693054 A CN104693054 A CN 104693054A CN 201310646619 A CN201310646619 A CN 201310646619A CN 104693054 A CN104693054 A CN 104693054A
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Abstract
The invention relates to an L-amino acid sulfate type chiral ionic liquid and a preparation method thereof, and belongs to the technical field of a new chemical material and its preparation. L-amino acid is prepared into a water solution, and the water solution is fully reacted with sulfuric acid with a concentration of 98% to obtain the L-amino acid sulfate type chiral ionic liquid. The prepared L-amino acid sulfate type chiral ionic liquid has the characteristics of the ionic liquid, and has the characteristics of chiral compounds, during reaction, no pollutant is emitted, no by-product is produced, product purity is high, cost is low, and the prepared L-amino acid sulfate type chiral ionic liquid is suitable for large-scale industrial production and application, and is likely to become an important new material in green chemical industry aspects in future.
Description
Technical field
The present invention relates to a kind of ionic liquid and preparation method thereof, especially a kind of novel chiral ionic liquid of L-sulforamidate type and the preparation method of this chiral ionic liquid, belong to new chemical material and preparing technical field thereof.
Background technology
In recent years, ionic liquid causes extensive concern as green solvent or catalyzer, is common in some chemical reaction processes such as organic synthesis, chemical separation, electrochemistry, has solvent catalyst double function characteristic.Li Ruxiong etc. are at " chemical reagent ", 2001,23 (4), speak of in one literary composition of 211st ~ 215 pages " synthesis of ionic liquid and application ", the positively charged ion of current ionic liquid has 4 classes: quaternary ammonium alkyl salt ion, alkyl quaternary microcosmic salt ion, alkyl for imidazol ion, alkyl for pyridinium ion; Negatively charged ion mainly contains cr
-, Br
-, BF
4 -, PF
6 -, (CF
3sO
3)
2n
-, CF
3cOO
-deng.By the various combination between these positively charged ion and negatively charged ion, mix the ionic liquid differed from one another, but there is not yet report so far about L-sulforamidate type ionic liquid involved in the present invention.And these ionic liquids have a something in common to be, the ionic liquid reported does not have the characteristic of chiral material in the past, namely do not have chiral catalysis characteristic, chiral separation characteristic and chirality banyan agent characteristic, therefore they are not chiral ionic liquids.And chiral material refers to a type objects that can not carry out mirror image coincide, the stereoselectivity of chiral material in molecule based on asymmetric induction plays an important role in Synthetic Organic Chemistry, but usually said chiral material, the such as liquid state range without ionic liquid is wide, steam forces down, good conductivity, wider electrochemical window, strong polarity, and to the dissolving of Cucumber and the selectivity of catalysis.At present, relevant L-sulforamidate type chiral ionic liquid there is not yet report, and its preparation method is also that the present invention mentions first.Also there is some weak points in the preparation of ionic liquid in the past: scarcity of raw material, and cost is higher, is generally more than 2 times of conventional organic solvent; It is more difficult to prepare, purifying products difficulty, is not suitable for large-scale industrial production application; Usually and aluminum chloride coupling, easily pollute, affect its application in green chemical industry.
Summary of the invention
The object of the invention is the good characteristic providing a kind of existing chiral material, has again the L-sulforamidate type chiral ionic liquid of ionic liquid desirable features, and provides the preparation method of this kind of ionic liquid.
L-sulforamidate type chiral ionic liquid provided by the invention, its structural formula is as follows:
[amino acid]
m[SO4]
n
According to the cationic valent difference of different L-amino acid, wherein m span is 1-2, n span is between 1-3, i.e. m=2 and n==l when L-amino acid cationic compound valency is 1, the m=1 when L-amino acid cationic compound valency is 2 and n bucket, the m=2 dawn n=3 when L-amino acid cationic compound valency is 3, the m=l when L-amino acid cationic compound valency is 4 and n=2.
The preparation method of L-sulforamidate type chiral ionic liquid provided by the invention is:
L-amino acid is made into the aqueous solution, stir while drip the sulfuric acid that concentration is 98%, wherein the mol ratio of L-amino acid and the vitriol oil is that z is when to work as L-amino acid cationic compound valency be 1, mol ratio is 2:1, when L amino acid cationic compound valency is 2, mol ratio is 1:1 when to work as L-amino acid cationic compound valency be 3, and mol ratio is 2:3, when L-amino acid sun from
When sub-valency is 4, mol ratio is 1:2, fully after reaction, is evaporated by water, obtains final product L-sulforamidate type chiral ionic liquid.Reaction formula is expressed as:
m[amino acid]+n]
2SO4→[amino acid]
m[SO4]
n
One of the L-sulforamidate type chiral ionic liquid that the present invention relates to, wherein L-amino acid [amino acid] is preferably: L-Ala [Ala], α-amino-isovaleric acid [Val], leucine [Leu], glycine [Gly], enzyme propylhomoserin [Tyr], L-glutamic acid [Glu], proline(Pro) [Pro], Methionin [Lys], Histidine [] is] and arginine [Arg].That is the L-sulforamidate type chiral ionic liquid that the present invention relates to is preferably: L-Ala vitriol chiral ionic liquid [Ala]
2sO
4, α-amino-isovaleric acid vitriol chiral ionic liquid [Val]
2sO4, leucine vitriol chiral ionic liquid [Leu] SO
4, Triglycine sulfate chiral ionic liquid [Gly] SO
4, enzyme propylhomoserin vitriol chiral ionic liquid [Tyr] SO
4, L-glutamic acid vitriol chiral ionic liquid [Glu] SO
4, proline(Pro) vitriol chiral ionic liquid [Pro] SO
4, lysine sulfate chiral ionic liquid [LyS] SO
4, Histidine vitriol chiral ionic liquid [His]
2sO
4with arginine vitriol chiral ionic liquid [Arg] [SO
4]
2one of.
L-sulforamidate type chiral ionic liquid [aminoacid] m [SO of the present invention
4] n preparation method preferred version is: the L-amino acid in preparation method is used respectively L-Ala [Ala], α-amino-isovaleric acid [Val], leucine [Leu], glycine [Gly], enzyme propylhomoserin [Tyr], L-glutamic acid [Glu], proline(Pro) [Pro], Methionin [Lys], Histidine [] is] and arginine [Arg]
One of replace, obtain the L-sulforamidate type chiral ionic liquid of required preparation.
Except above-mentioned vitriol and preparation thereof, other sulforamidate be made up of L monoamino-acids such as such as tryptophanes is also tested.Most of new compound fusing point is lower, generally at about 20 DEG C, has several below 80 DEG C.The specific conductivity recording them 60 DEG C time is in 10
3-10
4between (unit is μ S/cm), follow universal law equally, with temperature raise specific conductivity in rising trend, increasing degree is different.And record ionic liquid refractive index at such a temperature between 1.4-1.5.Obtained the thermal stability data of a series of new compound by the TG/SDTA851e differential thermal analyzer of Mettler company, known great majority all show good thermostability, start to decompose more than 200 DEG C, and this depends on the characteristic of each amino acid itself.By using the viscosity determinator of RVT-TB, RVT-TE, RVT2 type, record result under normal temperature 10
2-10
3between cP (except solid-state), viscosity difference in size is larger.
L-sulforamidate chiral ionic liquid provided by the present invention has following beneficial effect:
(1) there is while there is the characteristic of ionic liquid the characteristic of chiral material, as the characteristic etc. of: chiral separation, chiral catalysis and the agent of chirality banyan, and these characteristics are that usual ionic liquid figure scope is wide, steam forces down, good conductivity, wider electrochemical window, by force polarity, and to the dissolving of Cucumber and the selectivity of catalysis, and these are not available for general chiral material.
The preparation method of L-sulforamidate type chiral ionic liquid provided by the present invention has following unusual effect:
(1) raw material obtains comparatively easily, and also inexpensively, therefore preparation cost is low for price;
(2) neutralization reaction, preparation is simple, and required equipment is few, and just can obtain very pure product without the need to crossing multioperation, suitable large-scale industrial production application;
(3) preparation process does not discharge pollutants, no coupling product, belongs to the Green synthesis process of atom economy;
(4) fusing point of design-adjustable product and Acid-Base strengths in preparation process, only has ionic liquid containing aluminum chloride before this point.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but be not limited only to this.
Embodiment 1: L-Ala vitriol chiral ionic liquid
Take 5.00g L-Ala (gill biochemical corp, Shanghai purchases for 0.056mo1, purity more than 99%) put into fill 50ml distill H
2in the beaker of O, drip 98%H while stirring
2sO
4(analytical pure), H
2sO
4consumption is 2.81g (0.028mo1), namely the mol ratio of reaction raw materials is 2:1, this transparent mixed solution is continued at room temperature to stir 1 hour, proceed to rotary evaporation, evaporate between 40 DEG C ~ 50 DEG C and anhydrate, be warming up to 80 ~ 85 DEG C of evaporations 2 hours subsequently, finally obtain a water white transparency L-Ala vitriol chiral ionic liquid.Reaction formula is:
2Ala+H
2SO
4→[Ala]
2SO
4
Embodiment 2: pay propylhomoserin vitriol chiral ionic liquid
Take 5.00g to pay propylhomoserin (gill biochemical corp, Shanghai purchases for 0.043mo1, purity more than 99%) and put into the beaker filling 50ml distilled water, drip 98%H while stirring
2sO
4(analytical pure), H
2sO
4consumption is 2.19 (0.021mol), and namely the mol ratio of reaction raw materials is 2:1.This transparent mixed solution is continued at room temperature to stir 1 hour, proceeds to Rotary Evaporators, evaporate between 40 DEG C ~ 50 DEG C and anhydrate, be warming up to 80 DEG C-85 DEG C evaporations 2 hours subsequently, finally obtain a water white transparency and pay propylhomoserin vitriol chiral ionic liquid.Reaction formula is:
2Val+H
2SO
4→[Val]
2SO
4
Embodiment 3: leucine vitriol chiral ionic liquid
Take 5.00g leucine (gill biochemical corp, Shanghai purchases for 0.038mo l, purity more than 99%) and put into the beaker filling 50ml distilled water, drip 98%H while stirring
2sO
4(analytical pure), H
2sO
4consumption is 1.9g (0.019mo1), and namely the mol ratio of reaction raw materials is 2:1.This transparent mixed solution is continued at room temperature to stir 1 hour, proceeds to Rotary Evaporators, evaporate between 40 DEG C ~ 50 DEG C and anhydrate, be warming up to 80 DEG C ~ 85 DEG C evaporations 2 hours subsequently, finally obtain a water white transparency leucine vitriol chiral ionic liquid.Reaction formula is:
2Leu+H
2SO
4→[Leu]
2SO
4。
Claims (4)
1. the present invention relates to a kind of L sulforamidate type chiral ionic liquid, it is characterized in that structural formula is as follows:
[amino acid]
m[SO
4]
n
According to the cationic valent difference of different L-amino acid, wherein m span is 1-2, n span is between 1-3, i.e. m=2 and n=l when L-amino acid cationic compound valency is 1, the m=l when L-amino acid cationic compound valency is 2 and n=l, the m=2 when L-amino acid cationic compound valency is 3 and n=3, the m=1 when L-amino acid cationic compound valency is 4 and n=2.
2. the present invention relates to a kind of preparation method of L-sulforamidate type chiral ionic liquid, it is characterized in that preparation process is as follows:
Amino acid is made into the aqueous solution, stir while drip the sulfuric acid that concentration is 98%, wherein the mol ratio of L-amino acid and the vitriol oil is that z is when to work as L-amino acid cationic compound valency be 1, mol ratio is 2:1, the m when L-amino acid cationic compound valency is 2, mol ratio is 1:1, when L-amino acid cationic compound valency is 3, mol ratio is that 2:3. is when to work as L-amino acid cationic compound valency be 4, mol ratio is 1:2, after abundant reaction, water is evaporated, obtains final product L-sulforamidate type chiral ionic liquid.
3. L-sulforamidate type chiral ionic liquid as claimed in claim 1, is characterized in that described L-amino acid ion is z L-Ala ion, α-amino-isovaleric acid ion, leucine ion, glycine ion, cruel propylhomoserin ion, ionotropic glutamate, proline(Pro) ion, Methionin ion, one of Histidine ion and arginine ion.
4. L-sulforamidate type chiral ionic liquid preparation method as claimed in claim 2, is characterized in that described L-amino acid is selected from L-Ala, α-amino-isovaleric acid, leucine, glycine, cruel propylhomoserin, L-glutamic acid, proline(Pro), Methionin, one of Histidine and arginine.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380417A (en) * | 2016-08-29 | 2017-02-08 | 唐山师范学院 | Amino-acid ester bromide type chiral ionic liquid and preparation method thereof |
| CN106397239A (en) * | 2016-08-29 | 2017-02-15 | 唐山师范学院 | Amino acid ester cationic chiral ionic liquid and preparation method thereof |
-
2013
- 2013-12-04 CN CN201310646619.5A patent/CN104693054A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380417A (en) * | 2016-08-29 | 2017-02-08 | 唐山师范学院 | Amino-acid ester bromide type chiral ionic liquid and preparation method thereof |
| CN106397239A (en) * | 2016-08-29 | 2017-02-15 | 唐山师范学院 | Amino acid ester cationic chiral ionic liquid and preparation method thereof |
| CN106380417B (en) * | 2016-08-29 | 2018-07-20 | 唐山师范学院 | Amino-acid ester bromination salt form chiral ionic liquid and preparation method thereof |
| CN106397239B (en) * | 2016-08-29 | 2018-07-20 | 唐山师范学院 | Amino-acid ester cationic chiral ionic liquid and preparation method thereof |
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Application publication date: 20150610 |