CN101024625A - Ketopyrrolidine sulfurate in liquid and its prpearing method - Google Patents
Ketopyrrolidine sulfurate in liquid and its prpearing method Download PDFInfo
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- CN101024625A CN101024625A CN 200710027283 CN200710027283A CN101024625A CN 101024625 A CN101024625 A CN 101024625A CN 200710027283 CN200710027283 CN 200710027283 CN 200710027283 A CN200710027283 A CN 200710027283A CN 101024625 A CN101024625 A CN 101024625A
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Abstract
The invention relates to a general expression of pyrrolidone sulfonate ion liquid, and n=3 or 4, R is alkyl or ethenyl of H or C1-C12, B- is chlorine, bromine, iodine, sulfate radical, hydrogen sulfate radical, nitrate radical, 4- fluoroboric acid radical, paratoluenesulfonic acid radical, fluoroform sulfonic acid, and trifluoroacetic acid radical. The invention also relates to the manufacture method that includes the following steps: whisking and reacting for 2-48 hours in pyrrolidone sulfonic acid inner salt and equal mol acid at 0-120 degree centigrade to gain pyrrolidone sulfosalt salt ion. The liquid could be used as catalyst or solvent for organic chemical reaction. It has the advantages of low raw material cost, low toxin, environment protection, high yield and high purity.
Description
Technical field
The invention belongs to chemical material and preparing technical field thereof, be specifically related to a kind of pyrrolidone sulfonate ion liquid and preparation method thereof.
Technical background
Ionic liquid is the special liquid melting salt of a class, be by organic cation and the ionic compound that under room temperature or nearly room temperature, is in a liquid state inorganic or that organic anion constitutes, as a kind of eco-friendly solvent and catalyzer, have good physicochemical property and can modify, the zwitterion structure of modulation, and can recycle, be subjected to each field scholar's extensive concern in recent years.Ion liquid research is expanded to fields such as functional materials, electric light and photoelectric material, storage of solar energy, life science rapidly from Green Chemistry chemical industry and catalytic field.And the synthetic of novel ion liquid is one of the core of whole ionic liquid research and important prerequisite of realization ionic liquid research Sustainable development.Utilizing ion liquid designability to satisfy the ionic liquid that specificity requires through design is exactly the ionic liquid of functionalization, comprises at physical properties () functionalization and at the functionalization of chemical property (polarity, acidity, chirality, coordination ability, solvability) for example: flowability, transmissibility, liquid scope.The various functional groups of grafting in ionic liquid realize ion liquid functionalization to satisfy specific demand, are the forward positions of current ionic liquid research.
Develop the research focus that the functionalization acidic ionic liquid body with prospects for commercial application has become organic chemistry acid catalyzed reaction field at present, obtained a series of achievements.(Novel Br nsted acidic ionic liquids and their use as dual solvent-catalysts.J.Am.Chem.Soc.2002 such as Cole in 2002,124,5962-5963) reported first functionalized ion liquid synthetic of band sulfonic acid group on the imidazoles Huo quaternary phosphine positively charged ion, this Br nsted acidic ion liquid can be applicable to esterification, becomes acid catalyzed reactions such as ether, pinacol rearrangement.(CN1528733) priority discloses Br nsted acidic ion liquid [Hmim] BF of double as catalyzer and solvent to He Mingyuan etc. for CN1379005, CN1405140
4In a step oligomerisation of iso-butylene and the application of esterification.Kou Yuan etc. [acidic ion liquid of functionalization. petrochemical complex .2004,33 (4), 297-302] synthesized the functionalization acidic ionic liquid body that connects carboxyl on the positively charged ion.Introduce the acidic ion liquid of sulfonic acid group on the synthetic imidazole ring of Gu Yanlong etc. [Esterification of aliphatic acids with olefin promoted byBr nsted acidic ionic liquids.Journal of Molecular Catalysis A:Chemical 212 (2004) 71-75], propose on another N of ionic liquid positively charged ion alkyl chain length the transformation efficiency and the selectivity of the esterification of lipid acid and alkene all had bigger influence.Gui Jianzhou etc. [Novel Br nsted acidic ionic liquid as efficient and reusable catalystsystem for esterification.Catalysis Communications.5 (2004), 473-477] have reported imidazoles and the quaternary ammonium hydrogensulfates ionic liquid that has sulfonic acid group.Wang Tao etc. (CN1594280) connect sulfonic acid group on the N of pyridine ring, obtain a kind of tart pyridine-sulfonic acid salt ion liquid, can be used for the acid catalyzed reaction that esterification, Beckman rearrangement, carbonylation or dehydration of alcohols become ether.J.H. little Davis (CN1646540) discloses imidazoles, quaternary ammonium, the quaternary alkylphosphonium salt ionic liquid that contains just like side chain Br nsted acid groups such as sulfonic groups.Yu Shitao etc. (CN1903824) are applied to the synthetic of bialkyl ortho phthalate to pyridine and the imidazole ion liquid that sulfonic group replaces.Li Xuehui etc. [acid characterization of many carboxyls imidazole ion liquid. Acta PhySico-Chimica Sinica .2006,22 (2), 230-23] synthesized the acidic ion liquid of the many carboxyl-functionals of imidazoles, and its acidity is characterized.
Seeking the positively charged ion raw material that constitutes novel ion liquid also receives much concern.It is cationic Br nsted acidic ion liquid that Deng You congruence (CN1772739) has at first proposed with the protonated lactan of N-, can be applicable to acid catalyzed reaction.Zhou Xiaohai etc. (CN1775753) have synthesized a kind of N with surfactant properties, N-dialkyl group-2-Pyrrolidone quaternary ammonium salt ionic liquid.(CN1880303 such as Fang Yanxiong, CN1880295) disclose a kind of pyrrolidone ionic liquid and the application in the catalytic hydroxy acid esterifying reaction thereof respectively, ionic liquid is that the pyrrolidone that replaces with the protonated N-alkyl of N-is cationic Br nsted acidic ion liquid.Yu Shitao etc. (CN1903824) mention that also 2-oxo-pyrrolidine (being N-Methyl pyrrolidone) ionic liquid can be applicable to the synthetic of bialkyl ortho phthalate.2-Pyrrolidone also claims butyrolactam.These novel lactan ionic liquid at room temperature are compared with imidazoles, pyridines ionic liquid, and raw materials cost is low, and toxicity is low, readily biodegradable, thereby more friendly to environment.
The pyrrolidone sulfonate ion liquid that the present invention relates to is different from above-mentioned disclosed ionic liquid, has introduced the alkylsulphonic acid group on the N of pyrrolidone sulfonate ion liquid cation, is to have strong Br nsted tart functionalization acidic ionic liquid body.
Summary of the invention
The object of the present invention is to provide and a kind of tart pyrrolidone sulfonate ion liquid and preparation method thereof is stablized, is to water.
A kind of pyrrolidone sulfonate ion liquid of the present invention has following chemical structure of general formula (1):
N=3 or 4 wherein; R is alkyl or the vinyl of H or C1～C12; B
-Be chlorine, bromine, iodine, sulfate radical, bisulfate ion, nitrate radical, tetrafluoroborate, tosic acid root, trifluoromethanesulfonic acid root, trifluoroacetic acid root.
The invention provides the preparation method of above-mentioned pyrrolidone sulfonate ion liquid (1): in water or under condition of no solvent, pyrrolidone acid inner salt and equimolar acid 0～120 ℃ of stirring reaction 2～48 hours; After reaction finishes, need or not need underpressure distillation to dewater, get pyrrolidone sulfonate ion liquid (1).
Described pyrrolidone acid inner salt has following chemical structure of general formula (2):
N=3 or 4 wherein.R is alkyl or the vinyl of H or C1～C12.
Described reactant acid is hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, Tetrafluoroboric acid, sulfuric acid, nitric acid, tosic acid, trifluoromethanesulfonic acid, trifluoroacetic acid.
Pyrrolidone sulfonate ion liquid that the present invention relates to and preparation method thereof is compared with background technology, and beneficial effect is:
1) pyrrolidone sulfonate ion liquid is stable to water, has water-soluble, acid, dehydration property, can be used as the catalyzer or the solvent of organic chemical reactions.Owing to have strong Br nsted acidity, so be particularly suitable for the solvent and the catalyzer of double as acid catalyzed reaction, the vitriol oil and poisonous, the volatile organic solvent that replace severe corrosive, improve activity of such catalysts and stability, improve the selectivity of reaction, simplify the sepn process of product, can reuse through simple process.
2) with existing imidazoles, pyridines sulfonate ion liquid phase ratio, the preparation raw materials cost is lower; Toxicity is low; Readily biodegradable, more friendly to environment.
3) product yield height, the purity height, and also the preparation method is simple, is easy to realize.Can be used for mass preparation.
Embodiment
(R is H to embodiment 1:0.1mol 2-Pyrrolidone propane sulfonic acid inner salt, n=3) waits a mole H with containing
2SO
4The vitriol oil directly mix, in 120 ℃ of stirring reactions 2 hours, vacuum-drying, 2-Pyrrolidone propane sulfonate ([C
3SO
3HPn]
+HSO
4 -) (R is H to ionic liquid, n=3).This ionic liquid is stable to water, has water-soluble, acid, dehydration property, can be particularly useful for acid catalyzed reaction as the solvent and the catalyzer of organic chemical reactions, and is reusable.
(R is H to embodiment 2:0.1mol 2-Pyrrolidone butane acid inner salt, n=4) directly mixes with equimolar trifluoroacetic acid, and 80 ℃ of stirring reactions 8 hours, vacuum-drying got 2-Pyrrolidone butane sulfonate [C
4SO
3HPn]
+CF
3COO
-(R is H to ionic liquid, n=4).This ionic liquid is stable to water, has water-soluble, acid, dehydration property, can be particularly useful for acid catalyzed reaction as the solvent and the catalyzer of organic chemical reactions, and is reusable.
Embodiment 3:0.1mol N-Methyl pyrrolidone propane sulfonic acid inner salt directly mixes with equimolar tosic acid, in 100 ℃ of stirring reactions 24 hours, vacuum-drying, N-Methyl pyrrolidone propane sulfonate ([C
3SO
3HmPn]
+CH
3(C
6H
4) SO
3 -) ionic liquid.This ionic liquid is stable to water, has water-soluble, acid, dehydration property, can be particularly useful for acid catalyzed reaction as the solvent and the catalyzer of organic chemical reactions, and is reusable.
Embodiment 4:0.1mol N-ethyl pyrrolidone propane sulfonic acid inner salt waits a mole HBF with containing
4Fluoroboric acid (40wt%) directly mix, 0～5 ℃ of stirring reaction 48 hours, after underpressure distillation dewaters N-ethyl pyrrolidone propane sulfonate ([C
3SO
3HePn]
+BF
4 -) ionic liquid.This ionic liquid is stable to water, has water-soluble, acid, dehydration property, can be particularly useful for acid catalyzed reaction as the solvent and the catalyzer of organic chemical reactions, and is reusable.
Embodiment 5:0.1mol N-propyl pyrrole alkane ketone butane acid inner salt directly mixes with equimolar trifluoromethanesulfonic acid, in 100 ℃ of stirring reactions 24 hours, vacuum-drying, N-propyl pyrrole alkane ketone butane sulfonate ([C
4SO
3HpPn]
+CF
3SO
3-) ionic liquid.This ionic liquid is stable to water, has water-soluble, acid, dehydration property, can be particularly useful for acid catalyzed reaction as the solvent and the catalyzer of organic chemical reactions, and is reusable.
Embodiment 6:0.1mol N-butyl pyrrolidine ketone propane sulfonic acid inner salt waits a mole HNO with containing
3Nitric acid (49wt%) directly mix, 0～5 ℃ of stirring reaction 48 hours, after underpressure distillation dewaters N-butyl pyrrolidine ketone propane sulfonate ([C
3SO
3HbPn]
+NO
3 -) ionic liquid.This ionic liquid is stable to water, has water-soluble, acid, dehydration property, can be particularly useful for acid catalyzed reaction as the solvent and the catalyzer of organic chemical reactions, and is reusable.
Embodiment 7:0.1mol N-octylpyrrolidone butane acid inner salt directly mixes with the Hydrogen bromide (48wt%) of mole HBr such as containing, 0～5 ℃ of stirring reaction 48 hours, after underpressure distillation dewaters N-octylpyrrolidone butane sulfonate ([C
4SO
3HC
8Pn]
+Br
-) ionic liquid.This ionic liquid has water-soluble, acid, dehydration property, can be particularly useful for acid catalyzed reaction as the solvent and the catalyzer of organic chemical reactions, and is reusable.
Embodiment 8:0.1mol N-dodecyl pyrrolidone propane sulfonic acid inner salt directly mixes with the hydrochloric acid (37wt%) of mole HCI such as containing, 0～5 ℃ of stirring reaction 48 hours, after underpressure distillation dewaters N-dodecyl pyrrolidone propane sulfonate ([C
3SO
3HC
12Pn]
+Cl
-) ionic liquid.This ionic liquid has water-soluble, acid, dehydration property, can be particularly useful for acid catalyzed reaction as the solvent and the catalyzer of organic chemical reactions, and is reusable.
Embodiment 9:0.1mol N-vinyl pyrrolidone butane acid inner salt waits a mole H with containing
2SO
4The vitriol oil directly mix, in 100 ℃ of stirring reactions 24 hours, vacuum-drying, N-vinyl pyrrolidone butane sulfonate ([C
4SO
3HVPn]
+HSO
4 -) ionic liquid.This ionic liquid has water-soluble, acid, dehydration property, can be particularly useful for acid catalyzed reaction as the solvent and the catalyzer of organic chemical reactions, and is reusable.
Embodiment 10:0.1mol N-Methyl pyrrolidone butane acid inner salt directly mixes with the hydroiodic acid HI (57wt%) of mole HI such as containing, 0～5 ℃ of stirring reaction 48 hours, after underpressure distillation dewaters N-Methyl pyrrolidone butane sulfonate ([C
4SO
3HmPn]
+I
-) ionic liquid.This ionic liquid has water-soluble, acid, dehydration property, can be particularly useful for acid catalyzed reaction as the solvent and the catalyzer of organic chemical reactions, and is reusable.
Claims (4)
1. pyrrolidone sulfonate ion liquid is characterized in that having following chemical structure of general formula (1):
N=3 or 4 wherein; R is alkyl or the vinyl of H or C1～C12; B
-Be chlorine, bromine, iodine, sulfate radical, bisulfate ion, nitrate radical, tetrafluoroborate, tosic acid root, trifluoromethanesulfonic acid root, trifluoroacetic acid root.
2. preparation method of ionic liquid as claimed in claim 1 is characterized in that: in water or under condition of no solvent, pyrrolidone acid inner salt and equimolar acid 0～120 ℃ of stirring reaction 2～48 hours; After reaction finishes, need or not need underpressure distillation to dewater, get pyrrolidone sulfonate ion liquid (1).
3. preparation method of ionic liquid as claimed in claim 2 is characterized in that the pyrrolidone acid inner salt has following chemical structure of general formula (2):
N=3 or 4 wherein; R be H or C1～C12 alkyl or vinyl.
4. preparation method of ionic liquid as claimed in claim 2 is characterized in that described reactant acid is hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, Tetrafluoroboric acid, sulfuric acid, nitric acid, tosic acid, trifluoromethanesulfonic acid, trifluoroacetic acid.
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| CN102643708A (en) * | 2012-04-13 | 2012-08-22 | 广州市联诺化工科技有限公司 | High-oil-content environment-friendly aqueous cutting fluid and preparing method thereof |
| CN102784664A (en) * | 2011-05-19 | 2012-11-21 | 常州市华润复合材料有限公司 | Catalytic composition containing ionic liquid and application thereof |
| CN102872911A (en) * | 2012-10-23 | 2013-01-16 | 吴峰 | Ion liquid catalyst and fatty acid preparation method |
| CN104084234A (en) * | 2014-07-16 | 2014-10-08 | 沈阳工业大学 | Crosslinked polyethylene pyrrolidone based catalyst and preparation method thereof |
| CN104892426A (en) * | 2015-05-29 | 2015-09-09 | 江苏亚邦染料股份有限公司 | Method for preparing 1-nitroanthraquinone by using pyrrolidinone ionic liquid as catalyst |
| CN105669512A (en) * | 2016-01-05 | 2016-06-15 | 南通职业大学 | Pyrrolidone ionic liquid and oil product desulphurization method using it |
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| CN113788775A (en) * | 2021-09-03 | 2021-12-14 | 南昌大学 | Sulfonic acid functionalized pyrrolidone ionic liquid catalyst and preparation method and application thereof |
| CN116371467A (en) * | 2023-03-17 | 2023-07-04 | 中国石油大学(华东) | Preparation method and application of solid acid catalyst loaded with acidic ionic liquid |
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| EP1556390A4 (en) * | 2002-04-05 | 2007-12-26 | Univ South Alabama | Functionalized ionic liquids, and methods of use thereof |
| CN1880295A (en) * | 2005-06-17 | 2006-12-20 | 广东工业大学 | Method for catalyzing alcohol acid esterification using ion liquid |
| CN1903824A (en) * | 2006-08-03 | 2007-01-31 | 青岛科技大学 | Clean esterification method for producing bialkyl ortho phthalate |
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| WO2014063582A1 (en) * | 2012-10-23 | 2014-05-01 | Wu Feng | Ionic liquid catalyst and fatty acid preparation method |
| CN102872911B (en) * | 2012-10-23 | 2015-04-08 | 吴峰 | Fatty acid preparation method |
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| CN104892426A (en) * | 2015-05-29 | 2015-09-09 | 江苏亚邦染料股份有限公司 | Method for preparing 1-nitroanthraquinone by using pyrrolidinone ionic liquid as catalyst |
| CN105669512A (en) * | 2016-01-05 | 2016-06-15 | 南通职业大学 | Pyrrolidone ionic liquid and oil product desulphurization method using it |
| CN107511176A (en) * | 2017-08-15 | 2017-12-26 | 常州大学 | A kind of method of iron-based pyrrolidonium ionic liquids catalysis unsaturated alkyl ester hydrosilylation |
| CN107511176B (en) * | 2017-08-15 | 2020-02-14 | 常州大学 | Method for catalyzing hydrosilylation reaction of unsaturated alkyl ester by iron-based pyrrolidone ionic liquid |
| CN109609285A (en) * | 2018-12-13 | 2019-04-12 | 云南师范大学 | A kind of preparation method of fatty acid mixed |
| CN113788775A (en) * | 2021-09-03 | 2021-12-14 | 南昌大学 | Sulfonic acid functionalized pyrrolidone ionic liquid catalyst and preparation method and application thereof |
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