CN103435649B - A kind of Bidentate phosphine functionalization ionic liquid and synthetic method thereof - Google Patents
A kind of Bidentate phosphine functionalization ionic liquid and synthetic method thereof Download PDFInfo
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- CN103435649B CN103435649B CN201310331153.XA CN201310331153A CN103435649B CN 103435649 B CN103435649 B CN 103435649B CN 201310331153 A CN201310331153 A CN 201310331153A CN 103435649 B CN103435649 B CN 103435649B
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- ionic liquid
- bidentate phosphine
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Abstract
The invention discloses a kind of Bidentate phosphine functionalization ionic liquid, this ionic liquid has following general structure:
wherein, R
1for phenyl or oxyethyl group, R
2for phenyl or oxyethyl group, X is (CF
3sO
2)
2n or PF
6, n is 2,3,4 or 5; The synthetic method of this Bidentate phosphine functionalization ionic liquid utilizes Microwave-assisted firing catalyzed reaction, substantially reduce the reaction times, improve speed of reaction, it is a kind of synthetic method that is simple, economic, Bidentate phosphine functionalization ionic liquid efficiently, adopt the productive rate of the Bidentate phosphine functionalization ionic liquid of the method synthesis higher, reach as high as 89.5%.Bidentate phosphine functionalization ionic liquid provided by the invention is with a wide range of applications in the association areas such as rare earth ion separating and extracting, polymer composite and lithium ion battery production.
Description
Technical field
The present invention relates to a kind of ionic liquid, be specifically related to a kind of Bidentate phosphine functionalization ionic liquid and synthetic method thereof.
Background technology
Ionic liquid is one (< 100 DEG C) salt of being in a liquid state at low temperatures.This makes it and traditional organic solvent have a great difference, and it has many new advantageous properties, as steam force down, non-volatile, nontoxic, nonflammable explosive, not oxidizable, there is higher thermostability, mix with multiple organic solvent.Nearly ten years, ionic liquid has been widely used in the research and development of the related fields such as organic synthesis, electrochemistry, chemical separating and Polymer materialspreparation.
A relatively new research field to the research of ionic liquid.At present, what ionic liquid preparation adopted mostly is traditional heating means.Often reach tens hours, even tens hours with the reaction times required for traditional method synthesis ionic liquid, also have the problems such as mol ratio excessive between reactant.The longer reaction times is not only consuming time, easily produces too much by product simultaneously and can bring very large difficulty to abstraction and purification, and excessive mol ratio brings very large difficulty also to the isolation andpurification of product, indirectly adds cost.
Summary of the invention
Technical problem to be solved by this invention is, for the deficiencies in the prior art, provides a kind of Bidentate phosphine functionalization ionic liquid and simple, economic, efficient synthetic method thereof.
The present invention for solving the problems of the technologies described above adopted technical scheme is: a kind of Bidentate phosphine functionalization ionic liquid, and this ionic liquid has following general structure:
Wherein, R
1for phenyl or oxyethyl group, R
2for phenyl or oxyethyl group, X is (CF
3sO
2)
2n or PF
6, n is 2,3,4 or 5.
A kind of synthetic method of Bidentate phosphine functionalization ionic liquid, comprise the following steps: by imidazoles and bromo alkyl diphenyl phosphine oxide, bromo alkyl phenyl-phosphonic acid ethyl ester or bromo alkyl diethyl phosphonate are dissolved in organic solvent with the mol ratio of 1:2 ~ 4, add water soluble carbonate again, then be positioned in microwave reaction device and carry out microwave reaction, microwave power is 280 ~ 500W, temperature of reaction is 80 ~ 110 DEG C, reaction times is 5 ~ 40min, crude product is obtained after reaction, remove unreacted raw material, add negative ion exchanger in the crude product, carry out negative ion exchange, obtain Bidentate phosphine functionalization ionic liquid.
Preferably, described organic solvent is alcoholic solvent.
Preferably, described alcoholic solvent is ethanol, propyl alcohol or butanols.
Preferably, described water soluble carbonate is K
2cO
3, Na
2cO
3or Cs
2cO
3.
Preferably, described negative ion exchanger is Li (CF
3sO
2)
2n or KPF
6.
Compared with prior art, advantage of the present invention is as follows: the invention provides a kind of novel Bidentate phosphine functionalization ionic liquid, its synthetic method utilizes Microwave-assisted firing catalyzed reaction, substantially reduce the reaction times, improve speed of reaction, be a kind of synthetic method that is simple, economic, Bidentate phosphine functionalization ionic liquid efficiently, adopt the productive rate of the Bidentate phosphine functionalization ionic liquid of the method synthesis higher, reach as high as 89.5%.Bidentate phosphine functionalization ionic liquid provided by the invention is with a wide range of applications in the association areas such as rare earth ion separating and extracting, polymer composite and lithium ion battery production.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: respectively by imidazoles (1.31g, 19.3mmol), 2-bromoethyl diethyl phosphoric acid (9.46g, 38.6mmol), K
2cO
3(2.93g, 21.2mmol) joins and is equipped with in two neck round-bottomed flasks of 100mL ethanol; Then this two necks round bottom flask is entered in microwave reactor to carry out microwave reaction, microwave power is 280W, and temperature of reaction is 80 DEG C, microwave continuous radioreaction 5min, in reaction process, carry out magnetic agitation and condensing reflux, reaction terminates rear filtration and obtains crude product; Revolve except after the etoh solvent in crude product, add deionized water dissolving crude product, by ethyl acetate washed product four to five times to remove unreacted raw material; Add KPF in the crude product afterwards
6(3.91g, 21.2mmol), as negative ion exchanger, stirring at room temperature 3h carries out negative ion exchange, then adds CH
2cl
2extraction product, separatory, uses deionized water wash CH
2cl
2organic phase three to four times, adds anhydrous MgSO
4drying, filters, revolves and desolventize CH
2cl
2, then 70 DEG C of vacuum-drying 3h, obtain product 1,3-bis-(2-diethyl phosphoric acid) ethyl imidazol(e) hexafluorophosphate 3.19g, productive rate 30.5%.
Embodiment 2: respectively by imidazoles (1.31g, 19.3mmol), 3-Bromopropyl diethyl phosphoric acid (11.01g, 42.5mmol), K
2cO
3(2.93g, 21.2mmol) joins and is equipped with in two neck round-bottomed flasks of 100mL ethanol; Then this two necks round bottom flask is entered in microwave reactor to carry out microwave reaction, microwave power is 300W, and temperature of reaction is 90 DEG C, microwave continuous radioreaction 10min, in reaction process, carry out magnetic agitation and condensing reflux, reaction terminates rear filtration and obtains crude product; Revolve except after the etoh solvent in crude product, add deionized water dissolving crude product, by ethyl acetate washed product four to five times to remove unreacted raw material; Add Li (CF in the crude product afterwards
3sO
2)
2n (6.09g, 21.2mmol) is as negative ion exchanger, and stirring at room temperature 3h carries out negative ion exchange, then adds CH
2cl
2extraction product, separatory, uses deionized water wash CH
2cl
2organic phase three to four times, adds anhydrous MgSO
4drying, filters, revolves and desolventize CH
2cl
2, then 70 DEG C of vacuum-drying 3h, obtain two (trifluoromethyl sulfonyl) inferior amine salt 7.49g of product 1,3-bis-(3-diethyl phosphoric acid) propyl imidazole, productive rate 55.0%.
Embodiment 3: respectively by imidazoles (1.31g, 19.3mmol), 4-bromobutyl phosphenylic acid ethyl ester (23.56g, 77.2mmol), K
2cO
3(2.93g, 21.2mmol) joins and is equipped with in two neck round-bottomed flasks of 100mL ethanol; Then this two necks round bottom flask is entered in microwave reactor to carry out microwave reaction, microwave power is 450W, and temperature of reaction is 95 DEG C, microwave continuous radioreaction 20min, in reaction process, carry out magnetic agitation and condensing reflux, reaction terminates rear filtration and obtains crude product; Revolve except after the etoh solvent in crude product, add deionized water dissolving crude product, by ethyl acetate washed product four to five times to remove unreacted raw material; Add Li (CF in the crude product afterwards
3sO
2)
2n (6.09g, 21.2mmol) is as negative ion exchanger, and stirring at room temperature 3h carries out negative ion exchange, then adds CH
2cl
2extraction product, separatory, uses deionized water wash CH
2cl
2organic phase three to four times, adds anhydrous MgSO
4drying, filters, revolves and desolventize CH
2cl
2, then 70 DEG C of vacuum-drying 3h, obtain two (trifluoromethyl sulfonyl) inferior amine salt 12.13g of product 1,3-bis-(4-phosphenylic acid ethyl ester) butyl imidazole, productive rate 78.8%.
Embodiment 4: respectively by imidazoles (1.31g, 19.3mmol), 5-bromo amyl group diphenyl phosphine oxide (13.56g, 38.6mmol), K
2cO
3(2.93g, 21.2mmol) joins and is equipped with in two neck round-bottomed flasks of 100mL ethanol; Then this two necks round bottom flask is entered in microwave reactor to carry out microwave reaction, microwave power is 480W, and temperature of reaction is 100 DEG C, microwave continuous radioreaction 30min, in reaction process, carry out magnetic agitation and condensing reflux, reaction terminates rear filtration and obtains crude product; Revolve except after the etoh solvent in crude product, add deionized water dissolving crude product, by ethyl acetate washed product four to five times to remove unreacted raw material; Add KPF in the crude product afterwards
6(3.91g, 21.2mmol), as negative ion exchanger, stirring at room temperature 3h carries out negative ion exchange, then adds CH
2cl
2extraction product, separatory, uses deionized water wash CH
2cl
2organic phase three to four times, adds anhydrous MgSO
4drying, filters, revolves and desolventize CH
2cl
2, then 70 DEG C of vacuum-drying 3h, obtain product 1,3-bis-(5-diphenyl phosphine oxide) amyl group limidazolium hexafluorophosphate 11.49g, productive rate 78.9%.
Embodiment 5: respectively by imidazoles (1.31g, 19.3mmol), 2-bromoethyl diethyl phosphoric acid (9.46g, 38.6mmol), K
2cO
3(2.93g, 21.2mmol) joins and is equipped with in two neck round-bottomed flasks of 100mL ethanol; Then this two necks round bottom flask is entered in microwave reactor to carry out microwave reaction, microwave power is 500W, and temperature of reaction is 110 DEG C, microwave continuous radioreaction 40min, in reaction process, carry out magnetic agitation and condensing reflux, reaction terminates rear filtration and obtains crude product; Revolve except after the etoh solvent in crude product, add deionized water dissolving crude product, by ethyl acetate washed product four to five times to remove unreacted raw material; Add Li (CF in the crude product afterwards
3sO
2)
2n (6.09g, 21.2mmol) is as negative ion exchanger, and stirring at room temperature 3h carries out negative ion exchange, then adds CH
2cl
2extraction product, separatory, uses deionized water wash CH
2cl
2organic phase three to four times, adds anhydrous MgSO
4drying, filters, revolves and desolventize CH
2cl
2, then 70 DEG C of vacuum-drying 3h, obtain two (trifluoromethyl sulfonyl) inferior amine salt g of product 1,3-bis-(2-diethyl phosphoric acid) ethyl imidazol(e), productive rate 89.5%.
Embodiment 6: respectively by imidazoles (1.31g, 19.3mmol), 3-Bromopropyl diethyl phosphoric acid (11.01g, 42.5mmol), K
2cO
3(2.93g, 21.2mmol) joins and is equipped with in two neck round-bottomed flasks of 100mL ethanol; Then this two necks round bottom flask is entered in microwave reactor to carry out microwave reaction, microwave power is 280W, and temperature of reaction is 80 DEG C, microwave continuous radioreaction 5min, in reaction process, carry out magnetic agitation and condensing reflux, reaction terminates rear filtration and obtains crude product; Revolve except after the etoh solvent in crude product, add deionized water dissolving crude product, by ethyl acetate washed product four to five times to remove unreacted raw material; Add KPF in the crude product afterwards
6(3.91g, 21.2mmol), as negative ion exchanger, stirring at room temperature 3h carries out negative ion exchange, then adds CH
2cl
2extraction product, separatory, uses deionized water wash CH
2cl
2organic phase three to four times, adds anhydrous MgSO
4drying, filters, revolves and desolventize CH
2cl
2, then 70 DEG C of vacuum-drying 3h, obtain product 1,3-bis-(3-diethyl phosphoric acid) propyl imidazole hexafluorophosphate 6.54g, productive rate 50.0%.
Embodiment 7: respectively by imidazoles (1.31g, 19.3mmol), 4-bromobutyl phosphenylic acid ethyl ester (23.56g, 77.2mmol), K
2cO
3(2.93g, 21.2mmol) joins and is equipped with in two neck round-bottomed flasks of 100mL ethanol; Then this two necks round bottom flask is entered in microwave reactor to carry out microwave reaction, microwave power is 300W, and temperature of reaction is 90 DEG C, microwave continuous radioreaction 10min, in reaction process, carry out magnetic agitation and condensing reflux, reaction terminates rear filtration and obtains crude product; Revolve except after the etoh solvent in crude product, add deionized water dissolving crude product, by ethyl acetate washed product four to five times to remove unreacted raw material; Add KPF in the crude product afterwards
6(3.91g, 21.2mmol), as negative ion exchanger, stirring at room temperature 3h carries out negative ion exchange, then adds CH
2cl
2extraction product, separatory, uses deionized water wash CH
2cl
2organic phase three to four times, adds anhydrous MgSO
4drying, filters, revolves and desolventize CH
2cl
2, then 70 DEG C of vacuum-drying 3h, obtain product 1,3-bis-(4-phosphenylic acid ethyl ester) butyl imidazole hexafluorophosphate 8.53g, productive rate 66.7%.
Embodiment 8: respectively by imidazoles (1.31g, 19.3mmol), 5-bromo amyl group diphenyl phosphine oxide (13.56g, 38.6mmol), K
2cO
3(2.93g, 21.2mmol) joins and is equipped with in two neck round-bottomed flasks of 100mL ethanol; Then this two necks round bottom flask is entered in microwave reactor to carry out microwave reaction, microwave power is 450W, and temperature of reaction is 95 DEG C, microwave continuous radioreaction 20min, in reaction process, carry out magnetic agitation and condensing reflux, reaction terminates rear filtration and obtains crude product; Revolve except after the etoh solvent in crude product, add deionized water dissolving crude product, by ethyl acetate washed product four to five times to remove unreacted raw material; Add Li (CF in the crude product afterwards
3sO
2)
2n (6.09g, 21.2mmol) is as negative ion exchanger, and stirring at room temperature 3h carries out negative ion exchange, then adds CH
2cl
2extraction product, separatory, uses deionized water wash CH
2cl
2organic phase three to four times, adds anhydrous MgSO
4drying, filters, revolves and desolventize CH
2cl
2, then 70 DEG C of vacuum-drying 3h, obtain two (trifluoromethyl sulfonyl) inferior amine salt 13.6g of product 1,3-bis-(5-diphenyl phosphine oxide) amyl group imidazoles, productive rate 79.2%.
Embodiment 9: respectively by imidazoles (1.31g, 19.3mmol), 2-bromoethyl diethyl phosphoric acid (10.41g, 42.5mmol), K
2cO
3(2.93g, 21.2mmol) joins and is equipped with in two neck round-bottomed flasks of 100mL ethanol; Then this two necks round bottom flask is entered in microwave reactor to carry out microwave reaction, microwave power is 480W, and temperature of reaction is 100 DEG C, microwave continuous radioreaction 30min, in reaction process, carry out magnetic agitation and condensing reflux, reaction terminates rear filtration and obtains crude product; Revolve except after the etoh solvent in crude product, add deionized water dissolving crude product, by ethyl acetate washed product four to five times to remove unreacted raw material; Add KPF in the crude product afterwards
6(3.91g, 21.2mmol), as negative ion exchanger, stirring at room temperature 3h carries out negative ion exchange, then adds CH
2cl
2extraction product, separatory, uses deionized water wash CH
2cl
2organic phase three to four times, adds anhydrous MgSO
4drying, filters, revolves and desolventize CH
2cl
2, then 70 DEG C of vacuum-drying 3h, obtain product 1,3-bis-(2-diethyl phosphoric acid) ethyl imidazol(e) hexafluorophosphate 8.38g, productive rate 80.1%.
Embodiment 10: respectively by imidazoles (1.31g, 19.3mmol), 3-Bromopropyl diethyl phosphoric acid (54.47g, 77.2mmol), K
2cO
3(2.93g, 21.2mmol) joins and is equipped with in two neck round-bottomed flasks of 100mL ethanol; Then this two necks round bottom flask is entered in microwave reactor to carry out microwave reaction, microwave power is 500W, and temperature of reaction is 110 DEG C, microwave continuous radioreaction 40min, in reaction process, carry out magnetic agitation and condensing reflux, reaction terminates rear filtration and obtains crude product; Revolve except after the etoh solvent in crude product, add deionized water dissolving crude product, by ethyl acetate washed product four to five times to remove unreacted raw material; Add Li (CF in the crude product afterwards
3sO
2)
2n (6.09g, 21.2mmol) is as negative ion exchanger, and stirring at room temperature 3h carries out negative ion exchange, then adds CH
2cl
2extraction product, separatory, uses deionized water wash CH
2cl
2organic phase three to four times, adds anhydrous MgSO
4drying, filters, revolves and desolventize CH
2cl
2, then 70 DEG C of vacuum-drying 3h, obtain two (trifluoromethyl sulfonyl) inferior amine salt 11.17g of product 1,3-bis-(3-diethyl phosphoric acid) propyl imidazole, productive rate 82.0%.
From above embodiment 1 ~ 10, the productive rate of the synthetic method of Bidentate phosphine functionalization ionic liquid of the present invention is higher, reaches as high as 89.5%.
Claims (6)
1. a Bidentate phosphine functionalization ionic liquid, is characterized in that this ionic liquid has following general structure:
Wherein, R
1for phenyl or oxyethyl group, R
2for phenyl or oxyethyl group, X is (CF
3sO
2)
2n or PF
6, n is 2,3,4 or 5.
2. the synthetic method of a Bidentate phosphine functionalization ionic liquid as claimed in claim 1, it is characterized in that comprising the following steps: by imidazoles and bromo alkyl diphenyl phosphine oxide, bromo alkyl phenyl-phosphonic acid ethyl ester or bromo alkyl diethyl phosphonate are dissolved in organic solvent with the mol ratio of 1:2 ~ 4, add water soluble carbonate again, then be positioned in microwave reaction device and carry out microwave reaction, microwave power is 280 ~ 500W, temperature of reaction is 80 ~ 110 DEG C, reaction times is 5 ~ 40min, crude product is obtained after reaction, remove unreacted raw material, add negative ion exchanger in the crude product, carry out negative ion exchange, obtain Bidentate phosphine functionalization ionic liquid.
3. the synthetic method of a kind of Bidentate phosphine functionalization ionic liquid according to claim 2, is characterized in that described organic solvent is alcoholic solvent.
4. the synthetic method of a kind of Bidentate phosphine functionalization ionic liquid according to claim 3, is characterized in that described alcoholic solvent is ethanol, propyl alcohol or butanols.
5. the synthetic method of a kind of Bidentate phosphine functionalization ionic liquid according to claim 2, is characterized in that described water soluble carbonate is K
2cO
3, Na
2cO
3or Cs
2cO
3.
6. the synthetic method of a kind of Bidentate phosphine functionalization ionic liquid according to any one of claim 2 ~ 5, is characterized in that described negative ion exchanger is Li (CF
3sO
2)
2n or KPF
6.
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| FR3035880B1 (en) * | 2015-05-07 | 2017-06-02 | Commissariat Energie Atomique | USE OF NOVEL COMPOUNDS FOR THE SELECTIVE EXTRACTION OF RARE EARTHS FROM AQUEOUS SOLUTIONS COMPRISING PHOSPHORIC ACID AND METHOD OF EXTRACTING THE SAME |
| CN104926869B (en) * | 2015-06-30 | 2018-04-27 | 宁波大学 | A kind of bidentate difunctionalization imidazole type ion liquid and preparation method thereof |
| CN106397499A (en) * | 2016-08-31 | 2017-02-15 | 宁波美康生物科技股份有限公司 | Preparation method of 2,3,4-triacetyl-1-(2-chloro-4-nitro-phenyl)-alpha-L-fucopyranoside |
| CN111151297B (en) * | 2020-01-19 | 2021-03-16 | 山东新和成精化科技有限公司 | Catalyst for phosgenation reaction and phosgenation reaction method |
| CN115611941A (en) * | 2022-09-16 | 2023-01-17 | 哈尔滨工程大学 | Oxyphosphatidyl pyridine ionic liquid and preparation method and application thereof |
| CN116675954B (en) * | 2023-08-03 | 2023-10-31 | 长春工业大学 | Phosphorus and nitrogen-containing ionic liquid/epoxy resin composite material and preparation method thereof |
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| CN101857608A (en) * | 2010-05-28 | 2010-10-13 | 中国科学院过程工程研究所 | Imidazole ionic liquid phosphine ligand and application of coordination compound thereof in hydroesterification |
| CN102690291A (en) * | 2012-01-17 | 2012-09-26 | 青岛科技大学 | Imidazole ionic liquid supported chiral phosphine ligands and preparation method thereof |
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| CN101857608A (en) * | 2010-05-28 | 2010-10-13 | 中国科学院过程工程研究所 | Imidazole ionic liquid phosphine ligand and application of coordination compound thereof in hydroesterification |
| CN102690291A (en) * | 2012-01-17 | 2012-09-26 | 青岛科技大学 | Imidazole ionic liquid supported chiral phosphine ligands and preparation method thereof |
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