CN101648894A - N,N,N,N-tetramethylethylenediamine sulphonate ionic liquid and preparation method thereof - Google Patents
N,N,N,N-tetramethylethylenediamine sulphonate ionic liquid and preparation method thereof Download PDFInfo
- Publication number
- CN101648894A CN101648894A CN200910035216A CN200910035216A CN101648894A CN 101648894 A CN101648894 A CN 101648894A CN 200910035216 A CN200910035216 A CN 200910035216A CN 200910035216 A CN200910035216 A CN 200910035216A CN 101648894 A CN101648894 A CN 101648894A
- Authority
- CN
- China
- Prior art keywords
- acid
- ionic liquid
- tetramethylethylenediamine
- ethylene diamine
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides N,N,N,N-tetramethylethylenediamine sulphonate ionic liquid and a preparation method thereof, belonging to the technical field of organic chemical synthesis. The preparation method of the ionic liquid comprises the following steps: using N,N,N,N-tetramethylethylenediamine and sultone to react at room temperature in the presence of acetone and absolute ethanol to obtain N,N,N,N-tetramethylethylenediamine sulphonate inner salt, and then using N,N,N,N-tetramethylethylenediamine sulphonate inner salt to react with inorganic acid or organic acid to obtain disulfonic acid groupacidic ionic liquid with N,N,N,N-tetramethylethylenediamine cationic group. The prepared ionic liquid can be used as the catalyst or solvent of organic reactions, in particular to the catalytic reaction of inorganic acid or organic acid; compared with the existing monosulfonic group acidic ionic liquid used as catalyst, the N,N,N,N-tetramethylethylenediamine sulphonate ionic liquid has higher catalytic activity, less dosage, less loss in cycle use, higher product yield and more environmentally friendly.
Description
Technical field:
The invention belongs to the organic chemistry synthesis technical field, be specifically related to a kind of N, N, N, N-Tetramethyl Ethylene Diamine sulfonate ion liquid and preparation method thereof.
Background technology:
Nowadays, the economical acidic ion liquid of non-imidazoles that exploitation has prospects for commercial application, comprise bronsted acid ionic liquid and lewis acidity ionic liquid, become the focus of functionalized ion liquid research field, receive domestic and international chemical research person's concern, obtained certain achievement.(CN101024625A such as Huang Baohua, CN101024613A) in water or under condition of no solvent, pyrrolidone acid inner salt and equimolar acid have been obtained pyrrolidone sulfonate ion liquid at 0～120 ℃ of stirring reaction 2～48h, and it has been realized the esterification of acid alcohol as catalyzer, solvent and dewatering agent.Zhou Xiaomei, Zhang Haibo etc. (CN101050205A) have synthesized the ionic liquid that contains cation radical of piperazidine, and this ionic liquid is not only made gas absorbent and liquid extraction in the separation engineering mutually again, can also be as ionogen in electrochemistry.In addition, for reducing the expense of preparation acidic ion liquid, improve the catalytic activity of acidic ion liquid, thereby accelerate ionic liquid industrialization paces, seek novel, efficient, inexpensive acidic ion liquid and also received concern especially.(Mannich reaction in waterusing acidic ionic liquid as recoverable and reusable catalyst such as Fang Dong, Catalysis Letters, 116 (2007), 76-80) synthesized a kind of sulfonic 3-alkyl quaternary ammonium salts ionic liquid that has, and it has successfully been applied in the Mannich reaction.The contriver also with (CN1698929A) synthetic functionalized ion liquid of alcoholamine carboxylate such as Zhang Suojiang as catalyst Knoevenagel condensation reaction (Knoevenagel condensation reaction catalyzed by task-specific ionic liquidunder solvent-free conditions, Catalysis Communications, 9 (2008), 1571～1574).
The acid ionic liquid of sulfonate extensively applies in the various acid catalyzed reactions owing to itself have preferably stability and catalytic activity.But because smaller for the ionic liquid acid number that only has a sulfonic acid group, therefore the amount that in use needs is bigger, and it is also bigger to cause it to recycle middle loss amount, has increased use cost.
Summary of the invention:
The objective of the invention is to overcome exist in the prior art acidic ion liquid big as the catalyzer usage quantity, recycle in shortcomings such as loss is big, uneconomical, and provide a kind of N of high catalytic activity, N, N, N-Tetramethyl Ethylene Diamine sulfonate ion liquid and preparation method thereof.
The N that the present invention is prepared, N, N, the structural formula of N-Tetramethyl Ethylene Diamine sulfonate ion liquid is:
N is 3 or 4 in the formula, X
-A kind of in bisulfate ion, dihydrogen phosphate, trifluoroacetic acid root, acetate moiety, formate or the tosic acid root.
Ionic liquid of the present invention prepares by the following method:
In acetone or dehydrated alcohol with N, N, N, N-Tetramethyl Ethylene Diamine and sultone are to react under 1: 2 the ratio room temperature in molar ratio, preparation N, N, N, N-Tetramethyl Ethylene Diamine acid inner salt is then with N, N, N, N-Tetramethyl Ethylene Diamine acid inner salt and mineral acid or organic acid are that 1: 2 ratio is carried out acidifying in molar ratio, obtain corresponding N, N, N, N-Tetramethyl Ethylene Diamine sulfonate ion liquid.Its preparation process is specific as follows:
The first step prepares N, N, N, N-Tetramethyl Ethylene Diamine acid inner salt
According to N, N, N, N-Tetramethyl Ethylene Diamine and sultone are that 1: 2 ratio takes by weighing in molar ratio, stirring reaction 12-24h under the room temperature obtains white solid, suction filtration in acetone or dehydrated alcohol, respectively wash solid 3 times with acetone or dehydrated alcohol, anhydrous diethyl ether then, 50 ℃ of following vacuum-drying 48h get N, N, N, N-Tetramethyl Ethylene Diamine acid inner salt.
Synthetic N of second step, N, N, N-Tetramethyl Ethylene Diamine sulfonate ion liquid
According to N, N, N, N-Tetramethyl Ethylene Diamine acid inner salt and mineral acid or organic acid are that 1: 2 ratio takes by weighing in molar ratio, solvent-free, stirring reaction 24～48h under 80～120 ℃ of conditions gets a liquid of vicidity, with washed with dichloromethane 3 times, promptly can obtain corresponding ionic liquid at 60～80 ℃ of following vacuum-drying 24h then.
Wherein used sultone is 1 in the reaction, 3-propane sultone or 1,4-butane sultone; Used mineral acid or organic acid are a kind of in the vitriol oil, phosphoric acid, trifluoroacetic acid, glacial acetic acid, formic acid or the tosic acid.
The present invention makes catalyzer with the acidic ion liquid that has occurred and reaction process relatively has following characteristics:
1, ion liquid acid number height, the catalytic activity height, the reaction consumption is few;
2, ionic liquid can be recycled, and loss amount is less in the working cycle;
3, thermostability height, heat decomposition temperature is more than 200 ℃;
4, wide as catalyzer and the spendable scope of green solvent.
Embodiment:
Embodiment 1:N, N, N, the preparation of N-tetramethyl--two (3-sulfonic acid propyl group) quadrol inner salt
Under room temperature, the agitation condition, with 0.2mol 1, the mixed liquid of 3-propane sultone and 30mL acetone slowly is added drop-wise to and contains 0.1molN, N, N, in N-Tetramethyl Ethylene Diamine and the 50mL acetone mixed solution, last 30min, very fast adularescent solid is separated out, behind the 12h, filter, the gained white solid is respectively washed 3 times 50 ℃ of following vacuum-drying 24h with acetone, anhydrous diethyl ether.
Embodiment 2:N, N, N, the preparation of N-tetramethyl--two (4-sulfonic acid butyl) quadrol inner salt
Under room temperature, the agitation condition, with 0.2mol 1, the mixed liquid of 4-butane sultone and 30mL acetone slowly is added drop-wise to and contains 0.1molN, N, N, in N-Tetramethyl Ethylene Diamine and the 50mL acetone mixed solution, last 30min, behind the 24h, filter, the gained white solid is respectively washed 3 times with acetone, anhydrous diethyl ether, filter 50 ℃ of following vacuum-drying 24h.
Embodiment 3:[hydrogen sulfate] [tetramethyl--two (3-sulfonic acid propyl group) quadrol] ionic liquid
With 0.1mol embodiment 1 prepared N, N, N, N-tetramethyl--two (3-sulfonic acid propyl group) quadrol inner salt and 0.2mol
The vitriol oil joins in the 250mL there-necked flask that has stirring rod, prolong, after reacting 24h under 120 ℃, with washed with dichloromethane 3 times, 80 ℃ of following vacuum-drying 24h can get heavy-gravity [hydrogen sulfate] [tetramethyl--two (3-sulfonic acid propyl group) quadrol] ionic liquid then.
Embodiment 4:[biphosphate] [tetramethyl--two (3-sulfonic acid propyl group) quadrol] ionic liquid
With 0.1mol embodiment 1 prepared N, N, N, N-tetramethyl--two (3-sulfonic acid propyl group) quadrol inner salt and 0.2mol strong phosphoric acid join in the 250mL there-necked flask that has stirring rod, prolong, after reacting 24h under 100 ℃, with washed with dichloromethane 3 times, 80 ℃ of following vacuum-drying 24h can get [biphosphate] [tetramethyl--two (3-sulfonic acid propyl group) quadrol] ionic liquid then.
Embodiment 5:[hydrogen sulfate] [tetramethyl--two (4-sulfonic acid butyl) quadrol] ionic liquid
With 0.1mol embodiment 2 prepared N, N, N, N-tetramethyl--two (4-sulfonic acid butyl) the quadrol inner salt and the 0.2mol vitriol oil join in the 250mL there-necked flask that has stirring rod, prolong, after reacting 24h under 120 ℃, with washed with dichloromethane 3 times, 80 ℃ of following vacuum-drying 24h can get heavy-gravity [hydrogen sulfate] [tetramethyl--two (4-sulfonic acid butyl) quadrol] ionic liquid then.
Embodiment 6:[biphosphate] [tetramethyl--two (4-sulfonic acid butyl) quadrol] ionic liquid
With 0.1mol embodiment 2 prepared N, N, N, N-tetramethyl--two (4-sulfonic acid butyl) quadrol inner salt and 0.2mol strong phosphoric acid join in the 250mL there-necked flask that has stirring rod, prolong, after reacting 24h under 100 ℃, with washed with dichloromethane 3 times, 80 ℃ of following vacuum-drying 24h can get [biphosphate] [tetramethyl--two (4-sulfonic acid butyl) quadrol] ionic liquid then.
Embodiment 7:[trifluoroacetic acid] [tetramethyl--two (4-sulfonic acid butyl) quadrol] ionic liquid
With 0.1mol embodiment 2 prepared N, N, N, N-tetramethyl--two (4-sulfonic acid butyl) quadrol inner salt and 0.2mol trifluoroacetic acid join the 250mL there-necked flask that has stirring rod, prolong, after reacting 12h under 80 ℃, with washed with dichloromethane 3 times, 60 ℃ of following vacuum-drying 24h can get [trifluoroacetic acid] [tetramethyl--two (4-sulfonic acid butyl) quadrol] ionic liquid then.
Embodiment 8:[hydrogen sulfate] [tetramethyl--two (4-sulfonic acid butyl) quadrol] ionic liquid is used for catalytic esterification
In having the 50mL single port bottle of stirrer, prolong, add the ionic liquid that 0.01mol propyl carbinol, 0.02mol glacial acetic acid and 3mmol embodiment 3 make, 110 ℃ of following stirring reaction 2h, being cooled to the room temperature afterreaction is divided into two-layer, lower floor is the mixture of ionic liquid and water, n-butyl acetate and the unreacted raw material of upper strata for generating.The upper strata is through 10%NaHCO
3Behind the solution washing, the gas-chromatography calculated yield is 95%.Lower floor's ionic liquid can recycle after removing water under reduced pressure.
Claims (4)
1, a kind of N, N, N, N-Tetramethyl Ethylene Diamine sulfonate ion liquid, its structural formula is as follows:
N is 3 or 4 in the formula; X-is a kind of in bisulfate ion, dihydrogen phosphate, trifluoroacetic acid root, acetate moiety, formate or the tosic acid root.
2, the described preparation method of ionic liquid of a kind of claim 1, it is characterized in that this preparation method is: in acetone or dehydrated alcohol with N, N, N, N-Tetramethyl Ethylene Diamine and sultone are to react under 1: 2 the ratio room temperature in molar ratio, prepare N, N, N, N-Tetramethyl Ethylene Diamine acid inner salt, then with N, N, N, N-Tetramethyl Ethylene Diamine acid inner salt and mineral acid or organic acid are that 1: 2 ratio is carried out acidifying in molar ratio under 90～120 ℃, obtain corresponding N, N, N, N-Tetramethyl Ethylene Diamine sulfonate ion liquid.
3, method according to claim 2 is characterized in that used sultone is 1,3-propane sultone or 1,4-butane sultone.
4, method according to claim 2 is characterized in that used mineral acid or organic acid are a kind of in the vitriol oil, strong phosphoric acid, trifluoroacetic acid, acetate, formic acid, the tosic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910035216A CN101648894A (en) | 2009-09-24 | 2009-09-24 | N,N,N,N-tetramethylethylenediamine sulphonate ionic liquid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910035216A CN101648894A (en) | 2009-09-24 | 2009-09-24 | N,N,N,N-tetramethylethylenediamine sulphonate ionic liquid and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101648894A true CN101648894A (en) | 2010-02-17 |
Family
ID=41671246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910035216A Pending CN101648894A (en) | 2009-09-24 | 2009-09-24 | N,N,N,N-tetramethylethylenediamine sulphonate ionic liquid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101648894A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060715A (en) * | 2010-12-22 | 2011-05-18 | 南京大学 | Double quaternary ammonium carboxylate functional ionic liquid and preparation method thereof |
| CN102070462A (en) * | 2011-01-20 | 2011-05-25 | 中国科学院过程工程研究所 | Ethylenediamine-nitrophenol type ionic liquids and preparation method thereof |
| CN102964277A (en) * | 2012-12-17 | 2013-03-13 | 江南大学 | Preparation method of N,N-dimethyl-N-fatty alcohol polyethenoxy ether-base sulfopropyl lycine |
| CN102993059A (en) * | 2012-12-17 | 2013-03-27 | 江南大学 | Preparation method of N, N-dimethyl-N-fatty alcohol-polyoxyethylene ether hydroxypropyl sulpho glycine betaine |
| CN103934023A (en) * | 2014-04-25 | 2014-07-23 | 中国石油大学(华东) | Ionic liquid catalyst for C5/C6 alkane isomerization and preparation and using method of catalyst |
| CN103936768A (en) * | 2014-04-30 | 2014-07-23 | 安徽工业大学 | Green catalysis preparation method of thiazole[3,2-alpha] pyridine derivative |
| CN104876932A (en) * | 2015-05-12 | 2015-09-02 | 安徽工业大学 | Method for efficient catalytic synthesis of 2H-indole [2,1-b] phthalazine-1,6,11(13H) triketone |
| CN104892540A (en) * | 2015-05-20 | 2015-09-09 | 安徽工业大学 | Simple preparation method of naphthoxazine ketone derivative |
| CN105732439A (en) * | 2016-03-21 | 2016-07-06 | 闽江学院 | Multi-sulfonic-acid-group acidic functionalized ionic liquid and preparation method thereof |
| CN106543096A (en) * | 2016-10-25 | 2017-03-29 | 安徽工业大学 | A kind of method that catalysis prepares naphthalene oxazine ketone derivatives |
| CN107376994A (en) * | 2017-07-21 | 2017-11-24 | 闽江学院 | B/L bisgallic acid heteropoly acid ion hybrids and its preparation method and application |
| US20230272258A1 (en) * | 2022-02-25 | 2023-08-31 | Saudi Arabian Oil Company | Ionic liquid monomer for synthesis of friction reducer and methods thereof |
-
2009
- 2009-09-24 CN CN200910035216A patent/CN101648894A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060715A (en) * | 2010-12-22 | 2011-05-18 | 南京大学 | Double quaternary ammonium carboxylate functional ionic liquid and preparation method thereof |
| CN102070462A (en) * | 2011-01-20 | 2011-05-25 | 中国科学院过程工程研究所 | Ethylenediamine-nitrophenol type ionic liquids and preparation method thereof |
| CN102964277A (en) * | 2012-12-17 | 2013-03-13 | 江南大学 | Preparation method of N,N-dimethyl-N-fatty alcohol polyethenoxy ether-base sulfopropyl lycine |
| CN102993059A (en) * | 2012-12-17 | 2013-03-27 | 江南大学 | Preparation method of N, N-dimethyl-N-fatty alcohol-polyoxyethylene ether hydroxypropyl sulpho glycine betaine |
| CN103934023A (en) * | 2014-04-25 | 2014-07-23 | 中国石油大学(华东) | Ionic liquid catalyst for C5/C6 alkane isomerization and preparation and using method of catalyst |
| CN103934023B (en) * | 2014-04-25 | 2016-02-03 | 中国石油大学(华东) | For ionic-liquid catalyst and the preparation and application thereof of C5/C6 alkane isomerization |
| CN103936768B (en) * | 2014-04-30 | 2015-12-02 | 安徽工业大学 | A kind of green catalysis prepares the method for thiazole also [3,2-α] pyridine derivate |
| CN103936768A (en) * | 2014-04-30 | 2014-07-23 | 安徽工业大学 | Green catalysis preparation method of thiazole[3,2-alpha] pyridine derivative |
| CN104876932A (en) * | 2015-05-12 | 2015-09-02 | 安徽工业大学 | Method for efficient catalytic synthesis of 2H-indole [2,1-b] phthalazine-1,6,11(13H) triketone |
| CN104876932B (en) * | 2015-05-12 | 2017-03-29 | 安徽工业大学 | A kind of efficient catalytic synthesizes the method for 2H indole [2,1 b] phthalazines 1,6,11 (13H) triketone |
| CN104892540A (en) * | 2015-05-20 | 2015-09-09 | 安徽工业大学 | Simple preparation method of naphthoxazine ketone derivative |
| CN105732439A (en) * | 2016-03-21 | 2016-07-06 | 闽江学院 | Multi-sulfonic-acid-group acidic functionalized ionic liquid and preparation method thereof |
| CN105732439B (en) * | 2016-03-21 | 2017-07-07 | 闽江学院 | A kind of multi-sulfonic functionalized acidic ionic liquid and preparation method thereof |
| CN106543096A (en) * | 2016-10-25 | 2017-03-29 | 安徽工业大学 | A kind of method that catalysis prepares naphthalene oxazine ketone derivatives |
| CN106543096B (en) * | 2016-10-25 | 2019-01-04 | 安徽工业大学 | A kind of method that catalysis prepares naphtho- oxazines ketone derivatives |
| CN107376994A (en) * | 2017-07-21 | 2017-11-24 | 闽江学院 | B/L bisgallic acid heteropoly acid ion hybrids and its preparation method and application |
| CN107376994B (en) * | 2017-07-21 | 2020-07-31 | 闽江学院 | B/L double-acid heteropoly acid ion hybrid and preparation method and application thereof |
| US20230272258A1 (en) * | 2022-02-25 | 2023-08-31 | Saudi Arabian Oil Company | Ionic liquid monomer for synthesis of friction reducer and methods thereof |
| US11746274B1 (en) * | 2022-02-25 | 2023-09-05 | Saudi Arabian Oil Company | Ionic liquid monomer for synthesis of friction reducer and methods thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101648894A (en) | N,N,N,N-tetramethylethylenediamine sulphonate ionic liquid and preparation method thereof | |
| CN102120728B (en) | Sulfonic- functionalized caprolactam acidic ion liquid and preparation method thereof | |
| CN101348487A (en) | Preparation of multi-sulfonic functional ion liquid | |
| CN108084120B (en) | It is used to prepare the difunctional solid catalyst of soda acid and its preparation method and application of 5 hydroxymethyl furfural | |
| CN101348448A (en) | Preparation of ion liquid having B acid center and L acid center | |
| CN104072471B (en) | A kind of green catalysis prepares the method for 14-aryl-14H-dibenzo [a, j] oxa anthracenes derivative | |
| CN102558572B (en) | Method for preparing xylogen acetylated derivative in ionic liquid solvent | |
| CN102212046A (en) | Catalytic system for synthesizing 5-hydroxymethylfurfural by dehydration of sugar or polysaccharide | |
| CN102060738A (en) | Ionic liquid combining B acid site and L acid site as well as preparation method and application thereof | |
| CN103694203B (en) | Method of catalyzing fructose by cellulose base sulfonic acid catalyst to prepare 5-hydroxymethyl furfural | |
| CN103381373A (en) | Magnetic nano imidazolium-based ionic liquid catalyst and method for catalyzed synthesis of polyoxymethylene dimethyl ether through same | |
| CN103506156A (en) | Heterogeneous acid catalyst and preparation method and application thereof | |
| CN107790178B (en) | Based on three (2,4,6- trimethoxyphenyl) phosphine ionic-liquid catalysts and preparation method thereof | |
| CN102259025B (en) | Catalyst for preparing cyclohexanol by hydration of cyclohexene as well as preparation method and application method thereof | |
| CN102040545A (en) | Acidic room-temperature ionic liquid using acidic functional tetraalkylguanidine as cations and preparation method thereof | |
| CN105112170A (en) | Method for preparing biodiesel through sulfonic acid type phosphotungstic acid ionic liquid in catalysis mode | |
| CN103521263A (en) | Morpholine salt ionic liquid catalyst and preparation method and application thereof | |
| CN112939798B (en) | Preparation method of amantadine | |
| CN111036294A (en) | Polyacid site ionic liquid catalyst based on polyethyleneimine and preparation method and application thereof | |
| CN101880228A (en) | Clean preparation method for butyl acetate | |
| CN102249863B (en) | Method for preparing benzenediol by phenol hydroxylation | |
| CN103012215B (en) | Azo dodecanedioic acid dialkyl ester preparation method | |
| CN111001440A (en) | Polyacid site ionic liquid catalyst and preparation method and application thereof | |
| CN109847798A (en) | A kind of preparation method of solid type ionic-liquid catalyst | |
| CN104971772A (en) | Preparation method of sulfonic acid and thioether synergistic hybrid graphene catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20100217 |