CN100513394C - Ketopyrrolidine sulfurate in liquid and its prpearing method - Google Patents
Ketopyrrolidine sulfurate in liquid and its prpearing method Download PDFInfo
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- CN100513394C CN100513394C CNB2007100272839A CN200710027283A CN100513394C CN 100513394 C CN100513394 C CN 100513394C CN B2007100272839 A CNB2007100272839 A CN B2007100272839A CN 200710027283 A CN200710027283 A CN 200710027283A CN 100513394 C CN100513394 C CN 100513394C
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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 such as Cole in 2002
Acidic ionic liquids and their use as dual solvent-catalysts.J.Am.Chem.Soc.2002,124,5962-5963) reported first functionalized ion liquid synthetic, this of band sulfonic acid group on the imidazoles Huo quaternary phosphine positively charged ion
Acidic ion liquid can be applicable to esterification, becomes acid catalyzed reactions such as ether, pinacol rearrangement.(CN1379005, CN1405140 CN1528733) successively disclose double as catalyzer and solvent to He Mingyuan etc.
Acidic ion liquid [Hmim] BF4 is in 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.[Esterification of aliphatic acids with olefin promoted by such as Gu Yanlong
Acidic ionic liquids.Joumal of Molecular Catalysis A:Chemical 212 (2004) 71-75] introduce the acidic ion liquid of sulfonic acid group on the synthetic imidazole ring, 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.[Novel such as Gui Jianzhou
Acidic ionic liquid as efficient and reusable catalystsystem for esterification.Catalysis Communications.5 (2004), 473-477] reported the imidazoles and the quaternary ammonium hydrogensulfates ionic liquid that have sulfonic acid group.Wang Tao etc. (CN 1594280) 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 (CN 1646540) discloses and has contained just like side chains such as sulfonic groups
The imidazoles of acid groups, quaternary ammonium, quaternary alkylphosphonium salt ionic liquid.Yu Shitao etc. (CN 1903824) 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 that Deng You congruence (CN 1772739) has at first proposed with the protonated lactan of N-
Acidic ion liquid 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.(CN 1880303, CN1880295) disclose a kind of pyrrolidone ionic liquid and the application in the catalytic hydroxy acid esterifying reaction thereof respectively, and ionic liquid is that the pyrrolidone that replaces with the protonated N-alkyl of N-is cationic for Fang Yanxiong etc.
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, be have stronger
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 is made up of positively charged ion and negatively charged ion.Wherein positively charged ion has following chemical structure of general formula (1):
N=3 or 4 wherein; R is alkyl or the vinyl of H or C1～C12; Negatively charged ion is 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: 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.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 the acid accordingly of above-mentioned pyrrolidone sulfonate ion liquid negatively charged ion, 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 stronger
Acidity so be particularly suitable for the solvent and the catalyzer of double as acid catalyzed reaction, replaces the vitriol oil and poisonous, the volatile organic solvent of 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 HCl 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 (2)
1. a pyrrolidone sulfonate ion liquid is made up of positively charged ion and negatively charged ion, it is characterized in that wherein positively charged ion has following chemical structure of general formula (1):
N=3 or 4 wherein; R is alkyl or the vinyl of H or C1～C12; Negatively charged ion is chlorine, bromine, iodine, sulfate radical, bisulfate ion, nitrate radical, tetrafluoroborate, tosic acid root, trifluoromethanesulfonic acid root or 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; Described 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; Described reactant acid is and the acid accordingly of the described negatively charged ion of claim 1, is hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, Tetrafluoroboric acid, sulfuric acid, nitric acid, tosic acid, trifluoromethanesulfonic acid or trifluoroacetic acid.
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Cited By (1)
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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 |
| CN102872911B (en) * | 2012-10-23 | 2015-04-08 | 吴峰 | Fatty acid preparation method |
| CN104084234B (en) * | 2014-07-16 | 2016-01-20 | 沈阳工业大学 | A kind of PVPP is catalyst based and preparation method thereof |
| CN104892426B (en) * | 2015-05-29 | 2018-01-30 | 江苏亚邦染料股份有限公司 | A kind of method using pyrrolidinone compounds ionic liquid as the nitroanthraquinone of catalyst preparation 1 |
| 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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| CN113788775B (en) * | 2021-09-03 | 2023-04-07 | 南昌大学 | Sulfonic acid functionalized pyrrolidone ionic liquid catalyst, and preparation method and application thereof |
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Cited By (2)
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| TWI565737B (en) * | 2015-12-16 | 2017-01-11 | 財團法人工業技術研究院 | Porous hydrophobic fluorine-containing polymer membrane and production methods thereof |
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