CN102153523A - Thiazole amino acid salt type ionic liquid and preparation method thereof - Google Patents
Thiazole amino acid salt type ionic liquid and preparation method thereof Download PDFInfo
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- CN102153523A CN102153523A CN2011100438900A CN201110043890A CN102153523A CN 102153523 A CN102153523 A CN 102153523A CN 2011100438900 A CN2011100438900 A CN 2011100438900A CN 201110043890 A CN201110043890 A CN 201110043890A CN 102153523 A CN102153523 A CN 102153523A
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Abstract
The invention relates to a thiazole amino acid salt type ionic liquid and a preparation method thereof. The ionic liquid has the structural general formula of A<+>B<->, wherein A<+> has a structural general formula containing R1, R2 and R3, and R1, R2 and R3 in the general formula comply to the following rules: (a) at least containing one carbon atom; and (b) at most containing 20 carbon atoms; and B<-> is one of amino acid anions. The preparation method comprises the following steps of: preparing a thiazole non-amino-acid-salt-type ionic liquid; converting the thiazole non-amino-acid-salt-type ionic liquid into a thiazole hydroxide type ionic liquid through anion exchange reaction; and performing neutralization reaction between amino acid and the thiazole hydroxide type ionic liquid to prepare the thiazole amino acid salt type ionic liquid. The thiazole amino acid salt type ionic liquid which has the advantages of environmental friendliness, diversity, strong dissolvability, biocompatibility and the like is a new generation of ionic liquid which is more environmentally friendly and greener and has wide application prospects in pharmaceutical chemistry, organic chemistry and industrial chemistry.
Description
Technical field
The present invention relates to a kind of Chemicals and technology of preparing thereof, be specially a kind of thiazole amino acid salts type ionic liquid and preparation method thereof.
Background technology
In today that environment protection and Sustainable utilization of resources are received much concern, Green Chemistry is the inexorable trend of chemical developer, is one of the important directions of 21 century chemical developer.Traditional chemical reaction and sepn process are owing to use a large amount of volatile organic solvents, environment is caused severe contamination, and Green Chemistry is by design variation route, the methods such as green alternative compounds and starting material, selection effective catalyst of seeking antipollution generation from the source at the source of polluting and characteristic.The substitute medium of exploitation volatile solvent reduces environmental pollution, is the important content of Green Chemistry.And ionic liquid (English is ionic liquid, is abbreviated as IL) is in room temperature or be bordering on the material that is made of ion that is in a liquid state under the room temperature, claims the room temperature melting salt again.Ionic liquid with its good electrical conductivity, wide electrochemical window, negligible vapour pressure, adjustable acid-basicity and to characteristics such as organism, inorganics and superpolymer good solubility or just in electrochemistry, organic synthesis, catalysis, the field such as separate and be widely used, and become the ideal substitute of conventional organic solvents because of its advantage such as environmentally friendly, the research work of carrying out the ionic liquid related fields meets the needs of Green Chemistry development, is the focus of the common concern of countries in the world investigator in recent years.Ion liquid various performances depend on yin, yang ionic structure under the room temperature.In principle, design division's temperature ionic liquid by changing substituting group and the anionic kind on the positively charged ion, can access many kinds of ionic liquid at room temperature, so the kind of ionic liquid at room temperature is numerous as requested.
The amino acid pattern ionic liquid has the ability of stronger formation hydrogen bond, can dissolving DNA, Mierocrystalline cellulose and other carbohydrate, can be used as chiral solvent and new function material, and in life science and medicine industry, will have been widely used.Because it has good biocompatibility, the amino acid pattern ionic liquid is a new generation's ionic liquid friendly more and green more to environment.Fukumoto etc. J.AM.CHEM.SOC. (2005,127,2398-2399) reported that imidazole amino acid salt type is ion liquid synthetic, and a series of ion liquid physicochemical property.Guan Wei etc. Journal of Solution Chemistry (2009,38,1463-1469) reported the thermodynamic property of imidazole amino acid salt ion liquid.Progressively rise about the fundamental research of imidazole amino acid salt ion liquid at present, but also do not have the ion liquid report of thiazole amino acid salts.The kind of horn of plenty amino acid ion liquid, the fundamental research of expansion amino acid ion liquid, we also need to do a large amount of work.Because thiazole amino acid salts type ionic liquid has multiple advantages such as the feature of environmental protection, diversity, strong solubility and biocompatibility, is with a wide range of applications in pharmaceutical chemistry, organic chemistry and technical chemistry.
Summary of the invention
Fundamental research at prior art relatively lacks, and the products obtained therefrom biocompatibility is relatively poor, and technical problem to be solved by this invention is that a kind of novel thiazole amino acid salts type ionic liquid and preparation method thereof is provided.It is low, non-volatile that the type ionic liquid has a cost, and Heat stability is good is easy to characteristics such as practical application.This preparation method has simple to operate, and the product yield height is convenient to characteristics such as industrializing implementation.
The technical scheme that the present invention solves described ionic liquid technical problem is, designs a kind of thiazole amino acid salts type ionic liquid, and this ionic liquid has following general structure: A
+B
-,
Wherein, A
+Have following general structure:
In the general formula: R
1, R
2, R
3Meet following rule:
A) contain 1 carbon atom at least;
B) no more than 20 carbon atoms;
B
-Be selected from a kind of in the amino acid negatively charged ion;
The technical scheme that the present invention solves described ionic liquid preparation method technical problem is: the non-amino acid salts type of preparation thiazole ionic liquid; By anion exchange reaction the non-amino acid salts type of thiazole ionic liquid is converted to thiazole hydroxide type ionic liquid; Prepare thiazole amino acid salts type ionic liquid by the neutralization reaction between amino acid and the thiazole hydroxide type ionic liquid.
Compare with the ionic liquid of prior art, product of the present invention provides a kind of novel ionic liquid, be the ion liquid new variety of a class, such ionic liquid has the thermostability height, easily preparation, characteristics such as non-volatile: the raw material of product of the present invention is easy to get low price simultaneously, therefore preparation cost is low, is easy to promote the use of.
Compare with the ionic liquid preparation method of prior art, the present invention, for example 3-butyl-4-methylthiazol glycinate preparation method of ionic liquid is by selecting for use appropriate solvent and heated and stirred even, shortened the reaction times, at room temperature the reaction times reduces to eight hours, has the reaction times weak point, characteristics such as significantly raise the efficiency, and productive rate can reach 89%, preparation technology is simple simultaneously, required equipment is few, need not multioperation and just can obtain very purified product, suitable large-scale industrial production and application.
The non-amino acid pattern ionic liquid of thiazole of the present invention comprises: 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole hydrochloride, 3-butyl-4-methylthiazol hydrochloride, 3-hydroxyethyl-4-methylthiazol hydrochloride, 3-vinyl-4-methylthiazol hydrochloride, 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole bromate, 3-butyl-4-methylthiazol bromate, 3-hydroxyethyl-4-methylthiazol bromate, 3-vinyl-8 kinds of 4-methylthiazol bromate.Be specially:
The structural formula of described 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole hydrochloride is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1H NMR (300MHz, CDCl
3) δ: 10.54 (s, 1H, N=CH-S), 4.46 (t, 2H, N-CH
2), 3.76 (t, 2H, CH
2-OH), 3.02 (d, 2H, CH
2), 2.46 (d, 3H, CH
3), 1.81 (m, 2H, CH
2), 1.37 (m, 2H, CH
2), 0.91 (t, 3H, CH
3).
The structural formula of described 3-butyl-4-methylthiazol hydrochloride is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1H NMR (300MHz, CDCl
3) δ: 11.12 (s, 1H, N=CH-S), 8.16 (s, 1H, S-CH=C), 4.71 (t, 2H, N-CH
2), 2.61 (s, 3H, CH
3), 1.88 (m, 2H, CH
2), 1.49 (m, 2H, CH
2), 0.91 (t, 3H, CH
3).
The structural formula of described 3-hydroxyethyl-4-methylthiazol hydrochloride is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1H NMR (300MHz, DMSO-d
6) δ: 10.16 (t, 1H, N=CH-S), 8.03 (s, 1H, S-CH=C), 4.56 (t, 2H, N-CH
2), 3.79 (t, 2H, CH2OH), 2.56 (s, 3H, CH
3).
The structural formula of described 3-vinyl-4-methylthiazol hydrochloride is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1H NMR (300MHz, CDCl
3) δ: 11.32 (d, 1H, N=CH-S), 8.12 (s, 1H, S-CH=C), 6.03 (m, 1H, CH=CH
2), 5.45 (d, 2H, N-CH
2), 5.23 (d, 2H, CH=CH
2), 2.62 (s, 3H, CH
3).
The structural formula of described 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole bromate is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1HNMR (300MHz, CDCl3) δ: 10.58 (t, 1H, N=CH-S), 4.50 (t, 2H, N-CH2), 3.76 (t, 2H, CH2-OH), 3.07 (t, 2H, CH2), 2.48 (s, 3H, CH3), 1.84 (m, 2H, CH2), 1.40 (m, 2H, CH2), 0.92 (m, 3H, CH
3).
The structural formula of described 3-butyl-4-methylthiazol bromate is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1H NMR (300MHz, CDCl
3) δ: 11.13 (s, 1H, N=CH-S), 8.14 (s, 1H, S-CH=C), 4.67 (t, 2H, N-CH
2), 2.65 (s, 3H, CH
3), 1.91 (m, 2H, CH
2), 1.45 (m, 2H, CH
2), 0.95 (t, 3H, CH
3).
The structural formula of described 3-hydroxyethyl-4-methylthiazol bromate is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1H NMR (300MHz, DMSO-d
6) δ: 10.12 (t, 1H, N=CH-S), 8.06 (s, 1H, S-CH=C), 4.58 (t, 2H, N-CH
2), 3.82 (t, 2H, CH
2OH), 2.51 (s, 3H, CH
3).
The structural formula of described 3-vinyl-4-methylthiazol bromate is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1H NMR (300MHz, CDCl
3) δ: 11.36 (d, 1H, N=CH-S), 8.10 (s, 1H, S-CH=C), 6.05 (m, 1H, CH=CH
2), 5.48 (d, 2H, N-CH
2), 5.21 (d, 2H, CH=CH
2), 2.66 (s, 3H, CH
3).
Thiazole hydroxide type ionic liquid of the present invention comprises: 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole hydroxide type ionic liquid, 3-butyl-4-methylthiazol hydroxide type ionic liquid, 3-hydroxyethyl-4-methylthiazol hydroxide type ionic liquid, 3-vinyl-4 kinds of 4-methylthiazol hydroxide type ionic liquid;
Described 3-butyl-ion liquid structural formula of 4-methyl-5-(2-hydroxyethyl) thiazole hydroxide type is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1H NMR (300MHz, CDCl
3) δ: 10.52 (s, 1H, N=CH-S), 4.45 (t, 2H, N-CH
2), 3.77 (t, 2H, CH
2-OH), 2.99 (d, 2H, CH
2), 2.49 (d, 3H, CH
3), 1.83 (m, 2H, CH
2), 1.36 (m, 2H, CH
2), 0.94 (t, 3H, CH
3), 3.20 (t, 1H, OH
-).
Described 3-butyl-ion liquid structural formula of 4-methylthiazol hydroxide type is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1H NMR (300MHz, CDCl
3) δ: 11.13 (s, 1H, N=CH-S), 8.18 (s, 1H, S-CH=C), 4.75 (t, 2H, N-CH
2), 2.63 (s, 3H, CH
3), 1.92 (m, 2H, CH
2), 1.51 (m, 2H, CH
2), 0.93 (t, 3H, CH
3), 3.19 (t, 1H, OH
-).
Described 3-hydroxyethyl-ion liquid structural formula of 4-methylthiazol hydroxide type is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1H NMR (300MHz, DMSO-d
6) δ: 10.12 (t, 1H, N=CH-S), 8.06 (s, 1H, S-CH=C), 4.60 (t, 2H, N-CH
2), 3.82 (t, 2H, CH
2OH), 2.59 (s, 3H, CH
3), 3.23 (t, 1H, OH
-).
Described 3-vinyl-ion liquid structural formula of 4-methylthiazol hydroxide type is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1H NMR (300MHz, CDCl
3) δ: 11.31 (d, 1H, N=CH-S), 8.09 (s, 1H, S-CH=C), 6.06 (m, 1H, CH=CH
2), 5.43 (d, 2H, N-CH
2), 5.21 (d, 2H, CH=CH
2), 2.64 (s, 3H, CH
3), 3.18 (t, 1H, OH
-).
According to each described thiazole amino acid salts type ionic liquid of claim 1-12, it is characterized in that described thiazole amino acid salts type ionic liquid is: 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole glycinate type ionic liquid, 3-butyl-4-methylthiazol glycinate type ionic liquid, 3-hydroxyethyl-4-methylthiazol glycinate type ionic liquid, 3-vinyl-4 kinds of 4-methylthiazol glycinate type ionic liquid;
Described 3-butyl-ion liquid structural formula of 4-methyl-5-(2-hydroxyethyl) thiazole glycinate type is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1H NMR (300MHz, CDCl
3) δ: 10.51 (s, 1H, N=CH-S), 4.46 (t, 2H, N-CH
2), 3.78 (t, 2H, CH
2-OH), 3.00 (d, 2H, CH
2), 2.51 (d, 3H, CH
3), 1.82 (m, 2H, CH
2), 1.35 (m, 2H, CH
2), 0.93 (t, 3H, CH
3), 2.70 (2H, s, NH
2CH
2CO
2), 2.52 (2H, m, NH
2CH
2CO
2).
Described 3-butyl-ion liquid structural formula of 4-methylthiazol glycinate type is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1H NMR (300MHz, CDCl
3) δ: 11.12 (s, 1H, N=CH-S), 8.19 (s, 1H, S-CH=C), 4.76 (t, 2H, N-CH
2), 2.62 (s, 3H, CH
3), 1.93 (m, 2H, CH
2), 1.52 (m, 2H, CH
2), 0.94 (t, 3H, CH
3), 2.68 (2H, s, NH
2CH
2CO
2), 2.52 (2H, m, NH
2CH
2CO
2).
Described 3-hydroxyethyl-ion liquid structural formula of 4-methylthiazol glycinate type is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1H NMR (300MHz, DMSO-d
6) δ: 10.13 (t, 1H, N=CH-S), 8.07 (s, 1H, S-CH=C), 4.61 (t, 2H, N-CH
2), 3.83 (t, 2H, CH
2OH), 2.58 (s, 3H, CH
3), 2.68 (2H, s, NH
2CH
2CO
2), 2.51 (2H, m, NH
2CH
2CO
2).
Described 3-vinyl-ion liquid structural formula of 4-methylthiazol glycinate type is:
Its characteristic features is: adopt nuclear magnetic resonance analyser to detect, the parameter of products obtained therefrom is: 1H NMR (300MHz, CDCl
3) δ: 11.32 (d, 1H, N=CH-S), 8.10 (s, 1H, S-CH=C), 6.05 (m, 1H, CH=CH
2), 5.42 (d, 2H, N-CH
2), 5.22 (d, 2H, CH=CH
2), 2.63 (s, 3H, CH
3), 2.68 (2H, s, NH
2CH
2CO
2), 2.52 (2H, m, NH
2CH
2CO
2).
The present invention has designed described thiazole amino acid salts type preparation method of ionic liquid.This preparation method is applicable to thiazole amino acid salts type ionic liquid of the present invention, and concrete technology is: the non-amino acid salts type of preparation thiazole ionic liquid; By anion exchange reaction the non-amino acid salts type of thiazole ionic liquid is converted to thiazole hydroxide type ionic liquid; Prepare thiazole amino acid salts type ionic liquid by the neutralization reaction between amino acid and the thiazole hydroxide type ionic liquid.
The present invention has designed the non-amino acid salts type of described thiazole preparation method of ionic liquid.This preparation method is applicable to the non-amino acid salts type of thiazole of the present invention ionic liquid, concrete technology is: the 4-methylthiazol is mixed by 1: 1～2: 1 mol ratio with 1-chlorobutane, 1-n-butyl bromide, ethylene chlorhydrin, ethylene bromohyrin, chlorallylene, allyl bromide 98 respectively mutually with 4-methyl-5-(2-hydroxyethyl) thiazole, in 12 kinds of mixing solutionss of gained, add 20～40ml acetonitrile respectively as solvent, heated and stirred is even, keep 40～90 ℃ of temperature, react after 2～50 hours, solvent evaporated obtains the described 8 kinds of non-amino acid salts type of thiazole ionic liquids.
The present invention has designed described thiazole hydroxide type preparation method of ionic liquid.This preparation method is applicable to thiazole hydroxide type ionic liquid of the present invention, concrete technology is: 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole hydrochloride, 3-butyl-4-methylthiazol hydrochloride, 3-hydroxyethyl-4-methylthiazol hydrochloride and 3-vinyl-4-methylthiazol hydrochloride are mixed mutually with the mass ratio of pure water by 1: 1～10: 1 respectively, 4 kinds of mixing solutionss of gained are flow through anion-exchange column respectively, dripping the end back washs with pure water, collect washings and obtain 4 kinds of thiazole hydroxide type ionic liquids through purifying, till detecting washings neutrality.
The present invention has designed described thiazole amino acid salts type preparation method of ionic liquid.This preparation method is applicable to thiazole amino acid salts type ionic liquid of the present invention, concrete technology is: 4 kinds of thiazole hydroxide type ionic liquids are mixed by 1: 1～2: 1 mol ratio mutually with glycine, after in ice-water bath, stirring 2～24 hours, 4 kinds of mixing solutionss of gained are revolved to steam in 20～80 ℃ of following vacuum remove moisture, 20～80 ℃ of following vacuum-dryings after 24～48 hours, the acetonitrile that adds 20～40ml is respectively removed unreacted thiazole hydroxide type ionic liquid as solvent, remove residual acetonitrile by rotary evaporation and vacuum-drying, obtain 4 kinds of thiazole amino acid salts type ionic liquids.
The present invention introduces the amino acid negatively charged ion in the ion liquid structure of thiazoles, prepared a series of thiazole type amino acid salts ionic liquids belong to new variety.In the scope of applicant's retrieval, do not see the ion liquid bibliographical information of relevant the type, its preparation method also is that the present invention mentions first.Ionic liquid at room temperature has good conductivity, fusing point is low, electrochemical window is wide and almost do not have multiple advantages such as vapour pressure, is widely used in the numerous areas such as solvent, catalysis, electrochemistry, biological chemistry, the chemistry of complex, extraction and liquid crystal of organic synthesis.Simultaneously amino acid is the basis that makes up the bioactive macromolecule of living organism, is the base mateiral that makes up cell, repair tissue, is all Source of life, so amino acid ion liquid has biocompatibility, is one of more green ionic liquid.Amino acid ion liquid has chirality, and it is synthetic to be used for chirality.So amino acid ion liquid is in biological chemistry, pharmacy, various fields such as zymochemistry and life science have application prospect.Because ionic liquid of the present invention adopts and is easy to obtain on the market and 4-methylthiazol and 4-methyl-5-(2-hydroxyethyl) thiazole of less expensive are synthesis material, and it is low therefore to have a cost, be easy to the advantage of industrialization and practical application again.Among the preparation method of the present invention, with 0.20mol 4-methylthiazol is raw material, adopting 40ml second eyeball is solvent, temperature control stirs reaction in 8 hours in 75 ℃ and finishes substantially, through in ion-exchange process and the amino acid and after the operation, 3-butyl-ion liquid yield of 4-methylthiazol glycinate type is 89%, therefore has the reaction times weak point, solvent for use is few, characteristics such as efficient and productive rate height.
Embodiment
Further narrate the present invention below in conjunction with embodiment.Specific embodiment does not limit claim of the present invention, under the scope of described aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1:
Preparation 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole glycinate type ionic liquid.
Take by weighing 4-methyl-5-(2-hydroxyethyl) thiazole 28.64g (0.20mol) and 1-chlorobutane 18.51g (0.20mol), add the 30ml acetonitrile as solvent, be mixed in the 100ml there-necked flask, under vigorous stirring, heated 48 hours, maintain the temperature at 80 ℃, reaction steams solvent with it with Rotary Evaporators after finishing, use the 20ml washing with acetone, after the oven dry, obtain brown viscous liquid 42.14g, be 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole hydrochloride; Take by weighing 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole hydrochloride 23.58g (0.10mol) and pure water 100g, flow through anion-exchange column behind the uniform mixing, dripping the end back washs with pure water, collect alkaline detergent solution, behind 60ml ethyl acetate extraction three times, rotary evaporation is removed ethyl acetate, use the 20ml washing with acetone, after the oven dry, obtain the 21.08g thick liquid, be 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole hydroxide type ionic liquid; Take by weighing 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole hydroxide type ionic liquid 10.87g (0.05mol) and glycine 6.01g (0.08mol), in ice-water bath, stirred 24 hours behind the uniform mixing, revolve steaming in 60 ℃ of following vacuum and remove moisture, 20～80 ℃ of following vacuum-dryings after 24 hours, the acetonitrile that adds 30ml is removed unreacted 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole hydroxide type ionic liquid as solvent, remove residual acetonitrile by rotary evaporation and vacuum-drying, use the 20ml washing with acetone, after the oven dry, obtain thick liquid 13.53g, be 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole glycinate ionic liquid.
As calculated, productive rate is 79%.The employing nuclear magnetic resonance analyser detects, and the parameter of products obtained therefrom is: 1HNMR (300MHz, CDCl
3) δ: 10.51 (s, 1H, N=CH-S), 4.46 (t, 2H, N-CH
2), 3.78 (t, 2H, CH
2-OH), 3.00 (d, 2H, CH
2), 2.51 (d, 3H, CH
3), 1.82 (m, 2H, CH
2), 1.35 (m, 2H, CH
2), 0.93 (t, 3H, CH
3), 2.70 (2H, s, NH
2CH
2CO
2), 2.52 (2H, m, NH
2CH
2CO
2).
Embodiment 2:
Preparation 3-butyl-4-methylthiazol glycinate type ionic liquid.
Take by weighing 4-methylthiazol 19.83g (0.20mol) and 1-chlorobutane 27.77g (0.30mol), add the 40ml acetonitrile as solvent, be mixed in the 100ml there-necked flask, under vigorous stirring, heated 8 hours, maintain the temperature at 75 ℃, reaction steams solvent with it with Rotary Evaporators after finishing, use the 30ml washing with acetone, after the oven dry, obtain brown viscous liquid 35.56g, be 3-butyl-4-methylthiazol hydrochloride; Take by weighing 3-butyl-4-methylthiazol hydrochloride 19.17g (0.10mol) and pure water 100g, flow through anion-exchange column behind the uniform mixing, dripping the end back washs with pure water, collect alkaline detergent solution, behind 100ml ethyl acetate extraction three times, rotary evaporation is removed ethyl acetate, use the 30ml washing with acetone, after the oven dry, obtain the 17.12g thick liquid, be 3-butyl-4-methylthiazol hydroxide type ionic liquid; Take by weighing 3-butyl-4-methylthiazol hydroxide type ionic liquid 8.66g (0.05mol) and glycine 7.51g (0.10mol), in ice-water bath, stirred 20 hours behind the uniform mixing, revolve steaming in 80 ℃ of following vacuum and remove moisture, 80 ℃ of following vacuum-dryings after 24 hours, the acetonitrile that adds 40ml is removed unreacted 3-butyl-4-methylthiazol hydroxide type ionic liquid as solvent, remove residual acetonitrile by rotary evaporation and vacuum-drying, use the 30ml washing with acetone, after the oven dry, obtain thick liquid 11.2g, be 3-butyl-4-methylthiazol glycinate ionic liquid.
As calculated, productive rate is 89%.The employing nuclear magnetic resonance analyser detects, and the parameter of products obtained therefrom is: 1HNMR (300MHz, CDCl
3) δ: 11.12 (s, 1H, N=CH-S), 8.19 (s, 1H, S-CH=C), 4.76 (t, 2H, N-CH
2), 2.62 (s, 3H, CH
3), 1.93 (m, 2H, CH
2), 1.52 (m, 2H, CH
2), 0.94 (t, 3H, CH
3), 2.68 (2H, s, NH
2CH
2CO
2), 2.52 (2H, m, NH
2CH
2CO
2).
Embodiment 3:
Preparation 3-hydroxyethyl-4-methylthiazol glycinate type ionic liquid.
Take by weighing 4-methylthiazol 19.83g (0.20mol) and ethylene chlorhydrin 32.20g (0.40mol), add the 40ml acetonitrile as solvent, be mixed in the 100ml there-necked flask, under vigorous stirring, heated 24 hours, maintain the temperature at 55 ℃, reaction steams solvent with it with Rotary Evaporators after finishing, use the 30ml washing with acetone, after the oven dry, obtain brown viscous liquid 32.78g, be 3-hydroxyethyl-4-methylthiazol hydrochloride; Take by weighing 3-hydroxyethyl-4-methylthiazol hydrochloride 17.97g (0.10mol) and pure water 100g, flow through anion-exchange column behind the uniform mixing, dripping the end back washs with pure water, collect alkaline detergent solution, behind 30ml ethyl acetate extraction three times, rotary evaporation is removed ethyl acetate, use the 20ml washing with acetone, after the oven dry, obtain the 15.88g thick liquid, be 3-hydroxyethyl-4-methylthiazol hydroxide type ionic liquid; Take by weighing 3-hydroxyethyl-4-methylthiazol hydroxide type ionic liquid 8.06g (0.05mol) and glycine 3.75g (0.05mol), in ice-water bath, stirred 24 hours behind the uniform mixing, revolve steaming in 40 ℃ of following vacuum and remove moisture, 50 ℃ of following vacuum-dryings after 48 hours, the acetonitrile that adds 25ml is removed unreacted 3-hydroxyethyl-4-methylthiazol hydroxide type ionic liquid as solvent, remove residual acetonitrile by rotary evaporation and vacuum-drying, use the 30ml washing with acetone, after the oven dry, obtain liquid 10.51g, be 3-hydroxyethyl-4-methylthiazol glycinate ionic liquid.
As calculated, productive rate is 87%.The employing nuclear magnetic resonance analyser detects, and the parameter of products obtained therefrom is: 1H NMR (300MHz, DMSO-d
6) δ: 10.13 (t, 1H, N=CH-S), 8.07 (s, 1H, S-CH=C), 4.61 (t, 2H, N-CH
2), 3.83 (t, 2H, CH
2OH), 2.58 (s, 3H, CH
3), 2.68 (2H, s, NH
2CH
2CO
2), 2.51 (2H, m, NH
2CH
2CO
2).
Embodiment 4:
Preparation 3-vinyl-4-methylthiazol glycinate type ionic liquid.
Take by weighing 4-methylthiazol 19.83g (0.20mol) and chlorallylene 22.96g (0.30mol), add the 20ml acetonitrile as solvent, be mixed in the 100ml there-necked flask, under vigorous stirring, heated 12 hours, maintain the temperature at 75 ℃, reaction steams solvent with it with Rotary Evaporators after finishing, use the 20ml washing with acetone, after the oven dry, obtain brown viscous liquid 30.18g, be 3-vinyl-4-methylthiazol hydrochloride; Take by weighing 3-vinyl-4-methylthiazol hydrochloride 17.57g (0.10mol) and pure water 100g, flow through anion-exchange column behind the uniform mixing, dripping the end back washs with pure water, collect alkaline detergent solution, behind 60ml ethyl acetate extraction three times, rotary evaporation is removed ethyl acetate, use the 20ml washing with acetone, after the oven dry, obtain the 15.61g thick liquid, be 3-vinyl-4-methylthiazol hydroxide type ionic liquid; Take by weighing 3-vinyl-4-methylthiazol hydroxide type ionic liquid 7.86g (0.05mol) and glycine 6.01g (0.08mol), in ice-water bath, stirred 24 hours behind the uniform mixing, revolve steaming in 60 ℃ of following vacuum and remove moisture, 80 ℃ of following vacuum-dryings after 24 hours, the acetonitrile that adds 30ml is removed unreacted 3-vinyl-4-methylthiazol hydroxide type ionic liquid as solvent, remove residual acetonitrile by rotary evaporation and vacuum-drying, use the 20ml washing with acetone, after the oven dry, obtain liquid 10.49g, be 3-vinyl-4-methylthiazol glycinate ionic liquid.
As calculated, productive rate is 84%.The employing nuclear magnetic resonance analyser detects, and the parameter of products obtained therefrom is: 1HNMR (300MHz, CDCl
3) δ: 11.32 (d, 1H, N=CH-S), 8.10 (s, 1H, S-CH=C), 6.05 (m, 1H, CH=CH
2), 5.42 (d, 2H, N-CH
2), 5.22 (d, 2H, CH=CH
2), 2.63 (s, 3H, CH
3), 2.68 (2H, s, NH
2CH
2CO
2), 2.52 (2H, m, NH
2CH
2CO
2).
Claims (10)
1. thiazole amino acid salts type ionic liquid, this ionic liquid has following general structure: A
+B
-, wherein, A
+Have following general structure:
In the general formula: R
1, R
2, R
3Meet following rule:
A) contain 1 carbon atom at least;
B) no more than 20 carbon atoms;
B-is selected from a kind of in the amino acid negatively charged ion;
The preparation method is: the non-amino acid salts type of preparation thiazole ionic liquid; By anion exchange reaction the non-amino acid salts type of thiazole ionic liquid is converted to thiazole hydroxide type ionic liquid; Prepare thiazole amino acid salts type ionic liquid by the neutralization reaction between amino acid and the thiazole hydroxide type ionic liquid.
2. according to the non-amino acid salts type of the described thiazole of claim 1 ionic liquid, it is characterized in that described R
1, R
2, R
3Be C1～C4 alkyl, straight or branched alkyl, propenyl, phenmethyl or hydroxyethyl; According to the described thiazole hydroxide of claim 1 type ionic liquid, it is characterized in that described R
1, R
2, R
3Be C1～C4 alkyl, straight or branched alkyl, propenyl, phenmethyl or hydroxyethyl; According to the described thiazole amino acid salts of claim 1 type ionic liquid, it is characterized in that described R
1, R
2, R
3Be C1～C4 alkyl, straight or branched alkyl, propenyl, phenmethyl or hydroxyethyl.
3. according to the non-amino acid salts type of the described thiazole of claim 1 ionic liquid, it is characterized in that described B
-Be selected from following anionic a kind of: chlorion, bromide anion, iodide ion, acetate ion, sulfate ion, sulfite ion, nitrate ion, tetrafluoroborate ion, thiocyanate ion, hexafluorophosphoricacid acid ions, tosic acid radical ion or trifluoromethanesulfonic acid radical ion; According to the described thiazole hydroxide of claim 1 type ionic liquid, it is characterized in that described B
-Be hydroxide ion; According to the described thiazole amino acid salts of claim 1 type ionic liquid, it is characterized in that described B
-Be selected from a kind of in the amino acid negatively charged ion; According to the described thiazole amino acid salts of claim 1 type ionic liquid, it is characterized in that described amino acid negatively charged ion is selected from the glycine negatively charged ion, D-L-Ala negatively charged ion, L-L-Ala negatively charged ion, DL-L-Ala negatively charged ion, D-Xie Ansuan negatively charged ion, L-Xie Ansuan negatively charged ion, the DL-valine negatively charged ion, D-leucine negatively charged ion, L-leucine negatively charged ion, DL-leucine negatively charged ion, D-Isoleucine negatively charged ion, L-Isoleucine negatively charged ion, DL-Isoleucine negatively charged ion, D-phenylalanine negatively charged ion, L-phenylalanine negatively charged ion, DL-phenylalanine negatively charged ion, D-halfcystine negatively charged ion, L-halfcystine negatively charged ion, the DL-cysteine negatively charged ion, D-Gelucystine negatively charged ion, L-Gelucystine negatively charged ion, DL-Gelucystine negatively charged ion, D-Threonine negatively charged ion, L-Threonine negatively charged ion, DL-Threonine negatively charged ion, D-L-glutamic acid negatively charged ion, L-L-glutamic acid negatively charged ion, DL-L-glutamic acid negatively charged ion, D-glutamine negatively charged ion, L-glutamine negatively charged ion, DL-glutamine negatively charged ion, D-aspartic acid negatively charged ion, L-aspartic acid negatively charged ion, DL-aspartic acid negatively charged ion, D-l-asparagine negatively charged ion, the altheine negatively charged ion, DL-l-asparagine negatively charged ion, D-methionine(Met) negatively charged ion, L-methionine(Met) negatively charged ion, the DL-methionine negatively charged ion, D-Serine negatively charged ion, L-Serine negatively charged ion, the DL-serine negatively charged ion, D-proline(Pro) negatively charged ion, L-proline(Pro) negatively charged ion, DL-proline(Pro) negatively charged ion, D-tyrosine negatively charged ion, L-tyrosine negatively charged ion, DL-tyrosine negatively charged ion, D-tryptophane negatively charged ion, L-tryptophane negatively charged ion, DL-tryptophane negatively charged ion, D-Methionin negatively charged ion, L-Methionin negatively charged ion, DL-Methionin negatively charged ion, D-arginine negatively charged ion, L-arginine negatively charged ion, DL-arginine negatively charged ion, D-Histidine negatively charged ion, L-Histidine negatively charged ion, the DL-histidine negatively charged ion, D-ornithine negatively charged ion, L-ornithine negatively charged ion, DL-ornithine negatively charged ion, the Beta-alanine negatively charged ion, 2-aminobutyric acid negatively charged ion, 3-aminobutyric acid negatively charged ion, 4-aminobutyric acid negatively charged ion, 2-aminoisobutyric acid anion, 3-aminoisobutyric acid anion, 2-aminovaleric acid negatively charged ion, the 2-aminohexanoic acid negatively charged ion, the 6-aminocaprolc acid negatively charged ion, alpha-amino group phenylpropionic acid negatively charged ion, S-beta-amino phenylpropionic acid negatively charged ion, 3-amino-benzene ethylformic acid negatively charged ion.
4. according to the ion liquid preparation technology of thiazole amino acid salts type described in the claim 1-3 be: the non-amino acid salts type of preparation thiazole ionic liquid; By anion exchange reaction the non-amino acid salts type of thiazole ionic liquid is converted to thiazole hydroxide type ionic liquid; Prepare thiazole amino acid salts type ionic liquid by the neutralization reaction between amino acid and the thiazole hydroxide type ionic liquid.
5. according to the ion liquid preparation technology of the non-amino acid salts type of the thiazole described in the claim 4 be: the 4-methylthiazol is mixed by 1: 1～2: 1 mol ratio with 1-chlorobutane, 1-n-butyl bromide, ethylene chlorhydrin, ethylene bromohyrin, chlorallylene, allyl bromide 98 respectively mutually with 4-methyl-5-(2-hydroxyethyl) thiazole, in 12 kinds of mixing solutionss of gained, add 20～40ml acetonitrile respectively as solvent, heated and stirred is even, keep 40～90 ℃ of temperature, react after 2～50 hours, solvent evaporated obtains the described 8 kinds of non-amino acid salts type of thiazole ionic liquids.
6. according to the ion liquid preparation technology of thiazole hydroxide type described in the claim 4 be: with 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole hydrochloride, 3-butyl-4-methylthiazol hydrochloride, 3-hydroxyethyl-4-methylthiazol hydrochloride mixes with the mass ratio of pure water by 1: 1～10: 1 respectively mutually with 3-vinyl-4-methylthiazol hydrochloride, 4 kinds of mixing solutionss of gained are flow through anion-exchange column respectively from top to bottom, dripping the end back washs with pure water, collect washings and purify and obtain 4 kinds of thiazole hydroxide type ionic liquids, till detecting washings neutrality.
7. according to the ion liquid preparation technology of thiazole amino acid salts type described in the claim 4 be: 4 kinds of thiazole hydroxide type ionic liquids are mixed by 1: 1～2: 1 mol ratio mutually with glycine, after in ice-water bath, stirring 2～24 hours, 4 kinds of mixing solutionss of gained are revolved to steam in 20～80 ℃ of following vacuum remove moisture, 20～80 ℃ of following vacuum-dryings after 24～48 hours, the acetonitrile that adds 20～40ml is respectively removed unreacted thiazole hydroxide type ionic liquid as solvent, remove residual acetonitrile by rotary evaporation and vacuum-drying, obtain 4 kinds of thiazole amino acid salts type ionic liquids.
8. according to the non-amino acid salts type of each described thiazole of claim 1-7 ionic liquid, it is characterized in that the non-amino acid salts type of described thiazole ionic liquid is: 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole hydrochloride, 3-butyl-4-methylthiazol hydrochloride, 3-hydroxyethyl-4-methylthiazol hydrochloride, 3-vinyl-4-methylthiazol hydrochloride, 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole bromate, 3-butyl-4-methylthiazol bromate, 3-hydroxyethyl-4-methylthiazol bromate, 3-vinyl-8 kinds of 4-methylthiazol bromate;
(1) structural formula of described 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole hydrochloride is:
(2) structural formula of described 3-butyl-4-methylthiazol hydrochloride is:
(3) structural formula of described 3-hydroxyethyl-4-methylthiazol hydrochloride is:
(4) structural formula of described 3-vinyl-4-methylthiazol hydrochloride is:
(5) structural formula of described 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole bromate is:
(6) structural formula of described 3-butyl-4-methylthiazol bromate is:
(7) structural formula of described 3-hydroxyethyl-4-methylthiazol bromate is:
(8) structural formula of described 3-vinyl-4-methylthiazol bromate is:
9. according to each described thiazole hydroxide type ionic liquid of claim 1-7, it is characterized in that described thiazole hydroxide type ionic liquid is: 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole hydroxide type ionic liquid, 3-butyl-4-methylthiazol hydroxide type ionic liquid, 3-hydroxyethyl-4-methylthiazol hydroxide type ionic liquid, 3-vinyl-4 kinds of 4-methylthiazol hydroxide type ionic liquid;
(1) described 3-butyl-ion liquid structural formula of 4-methyl-5-(2-hydroxyethyl) thiazole hydroxide type is:
(2) described 3-butyl-ion liquid structural formula of 4-methylthiazol hydroxide type is:
(3) described 3-hydroxyethyl-ion liquid structural formula of 4-methylthiazol hydroxide type is:
(4) described 3-vinyl-ion liquid structural formula of 4-methylthiazol hydroxide type is:
10. according to each described thiazole amino acid salts type ionic liquid of claim 1-7, it is characterized in that described thiazole amino acid salts type ionic liquid is: 3-butyl-4-methyl-5-(2-hydroxyethyl) thiazole glycinate type ionic liquid, 3-butyl-4-methylthiazol glycinate type ionic liquid, 3-hydroxyethyl-4-methylthiazol glycinate type ionic liquid, 3-vinyl-4 kinds of 4-methylthiazol glycinate type ionic liquid;
(1) described 3-butyl-ion liquid structural formula of 4-methyl-5-(2-hydroxyethyl) thiazole glycinate type is:
(2) described 3-butyl-ion liquid structural formula of 4-methylthiazol glycinate type is:
(3) described 3-hydroxyethyl-ion liquid structural formula of 4-methylthiazol glycinate type is:
(4) described 3-vinyl-ion liquid structural formula of 4-methylthiazol glycinate type is:
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105727694A (en) * | 2016-04-07 | 2016-07-06 | 浙江大学 | Method for improving amino functional carbon capture through spatial synergistic effect |
| CN107115892A (en) * | 2017-06-15 | 2017-09-01 | 福州大学 | The vinylthiazole base polymeric ionic liquid of 4 methyl 5 is prepared and applied |
-
2011
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105727694A (en) * | 2016-04-07 | 2016-07-06 | 浙江大学 | Method for improving amino functional carbon capture through spatial synergistic effect |
| CN105727694B (en) * | 2016-04-07 | 2018-05-29 | 浙江大学 | A kind of method that the trapping of amino functional carbon is improved using spatial cooperation effect |
| CN107115892A (en) * | 2017-06-15 | 2017-09-01 | 福州大学 | The vinylthiazole base polymeric ionic liquid of 4 methyl 5 is prepared and applied |
| CN107115892B (en) * | 2017-06-15 | 2019-03-12 | 福州大学 | The preparation of 4- methyl -5- vinylthiazole base polymeric ionic liquid and application |
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