CN1676514A - 1-di-ester-base-3-alkyl imidazo ion liquid and its preparing method - Google Patents

1-di-ester-base-3-alkyl imidazo ion liquid and its preparing method Download PDF

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CN1676514A
CN1676514A CN 200510032669 CN200510032669A CN1676514A CN 1676514 A CN1676514 A CN 1676514A CN 200510032669 CN200510032669 CN 200510032669 CN 200510032669 A CN200510032669 A CN 200510032669A CN 1676514 A CN1676514 A CN 1676514A
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acid esters
dibasic acid
base
ion liquid
imidazoles
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CN1676514B (en
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李雪辉
耿卫国
王乐夫
潘微平
段红丽
张磊
李谦和
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South China University of Technology SCUT
Hunan University of Technology
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Abstract

This invention is 1-diester-3-alkylimidazole ion liquor and its making method. This method is that imidazole and non-saturable diester with double keys react to get 1-diester-imidazole, then 1-diester-imidazole reacts alkylogen to get 1-diester-3-alkylimidazole halide ion liquor. In addition, exchange the anion of 1-diester-3-alkylimidazole halide ion liquor with other anions to get series 1-diester-3-alkylimidazole ion liquor. This invention has low cost, simple making procedure, and is suitable for lager scale of production.

Description

1-dibasic acid esters base-3-alkyl imidazo ion liquid and preparation method thereof
Technical field
The present invention relates to new chemical material and preparing technical field thereof, specifically be meant a kind of 1-dibasic acid esters base-3-alkyl imidazo ion liquid and preparation method thereof.
Background technology
In recent years, as a class green solvent and a catalyzer, ionic liquid obtains the extensive concern of domestic and international research institution and enterprise, and ionic liquid is widely used in having functions such as solvent, catalyzer in reactions such as organic synthesis, electrochemistry, chemical separation and petrochemical complex and the process.Because that ionic liquid has is non-volatile, do not have vapour pressure, liquid temperature regional extent extensively, etc. characteristics, with using traditional organic technology to compare, use ion liquid system to be considered to eco-friendly technological process.P.Wasserscheid and T.Welton mentioned in its being entitled as in the 7th～8 page of Ionic Liquids in Synthesis one book of writing, the compounds that ionic liquid is made up of zwitterion, present ion liquid positively charged ion mainly contains quaternary ammonium alkyl ion, alkyl quaternary phosphine ion, alkyl substituted imidazole ion and alkyl substituted pyridines ion four classes, and negatively charged ion mainly contains Cl -, Br -, CH 3COO -, HSO 4 -, CF 3COO -, BF 4 -, PF 6 -Or NO 3 -Deng, by the various combination of zwitterion, mix ionic liquid with different physics, chemical property.How ring synthetic L-sulforamidate type chiral ionic liquid (Chinese invention patents such as unit, publication number CN1383920A), synthetic diacetone acrylic amide type ionic liquid (Chinese invention patent such as He Mingyuan, publication number CN1385243A), synthetic such as Zhang Jun contains the ionic liquid (Chinese invention patent of unsaturated double-bond, publication number CN1417407A), synthetic hexaalkylguanidium salts ionic liquid (Chinese invention patent, publication number CN1491939A) such as Zhang Suobo etc.The synthetic ion liquid method that has ester group of Britain Green Chemistry magazine 2004 the 6th phases the 166th～175 page of report is that employing 1-Methylimidazole and halogen ester are raw material, direct reaction synthesizes 1-ester group-3-Methylimidazole ionic liquid, and aspect such as substituting group number all exists different greatly with the present invention on method reaction raw materials, reaction scheme and the imidazole ring of this report; The ion liquid method that the preparation of Britain Chem.Commun. magazine the 2038th～2039 page of report in 2003 contains ester group is under the pyridine katalysis, Methylimidazole and Tetrafluoroboric acid is reacted, and then react with butyl acrylate, obtains ion liquid compound.Similarly, this method aspect such as ester group substituting group number on reaction raw materials, reaction scheme and imidazole ring all exists different greatly with the present invention; Simultaneously, closing the 1-dibasic acid esters base-3-alkyl imidazo ion liquid preparation method that contains involved in the present invention does not appear in the newspapers so far.The preparation technology of the 1-dibasic acid esters base-3-alkyl imidazo ion liquid that the present invention relates to is simple, by the method that the present invention relates to, can prepare serial novel 1-dibasic acid esters base-3-alkyl imidazo ion liquid compound.
Summary of the invention
Purpose of the present invention is exactly in order to solve above-mentioned the deficiencies in the prior art part, and a kind of 1-dibasic acid esters base-3-alkyl imidazo ion liquid and preparation method thereof is provided.
The object of the invention is achieved through the following technical solutions:
Described a kind of 1-dibasic acid esters base-3-alkyl imidazo ion liquid, its structural formula is as follows:
Figure A20051003266900041
R wherein 1Be dibasic acid esters base with following structure:
Figure A20051003266900042
m＝1～10；x＝1～8，x+y＜10；
R 2Be the straight chained alkyl that contains 1～10 carbon atom, X -Be Cl -, Br -, BF 4 -, PF 6 -, CH 3COO -, CF 3COO -, CF 3SO 3 -Or NO 3 -
The preparation method of described a kind of 1-dibasic acid esters base-3-alkyl imidazo ion liquid comprises the steps and processing condition
(1) is solvent with toluene or acetone, under the backflow situation,, obtains 1-dibasic acid esters base imidazoles imidazoles and the unsaturated dibasic acid esters reaction that contains two keys 12～24 hours; Wherein, the mol ratio of imidazoles and unsaturated dibasic acid esters is 1: 1～1: 1.5;
(2) in alcoholic solution, 1-dibasic acid esters base imidazoles and haloalkane were reacted 12～24 hours at 25～80 ℃, pass through the volatilizable component of pressure reducing and steaming again, just obtain 1-dibasic acid esters base-3-alkyl imidazo ion liquid; Wherein, the mol ratio of 1-dibasic acid esters base imidazoles and haloalkane is 1: 1～1: 2.
In addition, with 1-dibasic acid esters base-3-alkyl substituted imidazole ionic liquid with contain and BF 4 -, PF 6 -, CH 3COO -, CF 3COO -, CF 3SO 3-or NO 3 -After anionic sylvite or sodium salt mix, the powerful stirring, after reacting completely, repeatedly through halogen freezing, that remove by filter generation, underpressure distillation removes and desolvates, and can obtain serial 1-dibasic acid esters base-3-alkyl imidazo ion liquid.
The present invention compared with prior art has following advantage and beneficial effect:
1, the present invention is to provide serial novel ion liquid, developed the ionic liquid new variety;
2,, can prepare serial 1-dibasic acid esters base-3-alkyl imidazo ion liquid by method provided by the invention;
3, of the present invention preparation is simple, and suitable large-scale industrial production.
Description of drawings
Fig. 1 is an ion liquid chemical structural formula of the present invention.
Embodiment
Synthesizing of embodiment 1:1-(two-2-ethyl butyrate base)-3-ethyl imidazol(e) bromide ion liquid
Get the 1mol imidazoles and be dissolved in 200ml toluene, add the 1.1mol diethyl maleate, refluxed 24 hours, the pressure reducing and steaming solvent obtains 1-(two-2-ethyl butyrate base) imidazoles, add an amount of dehydrated alcohol and monobromethane (mol ratio of the monobromethane of adding and 1-(two-2-ethyl butyrate base) imidazoles is 2: 1) then, stir and also react 12h at normal temperatures, pressure reducing and steaming volatile component, just obtain 1-(two-2-ethyl butyrate base)-3-ethyl imidazol(e) bromide, productive rate is 95%, and reaction equation is:
Embodiment 2:1-(two-2-butyl butyrate base)-3-decyl imidazolium chloride is ion liquid synthetic
Get the 1mol imidazoles and be dissolved in 200ml acetone, add the 1.1mol dibutyl maleate, refluxed 24 hours, the volatilizable thing of pressure reducing and steaming, obtain 1-(two-2-butyl butyrate base) imidazoles, add an amount of anhydrous normal butyl alcohol and 1-chlorodecane (mol ratio of the 1-chlorodecane of adding and 1-(two-2-butyl butyrate base) imidazoles is 1.3: 1) then, stirring is also reacted 12h under 80 ℃ of temperature, pressure reducing and steaming ethanol, just obtain 1-(two-2-butyl butyrate base)-3-decyl imidazolium chloride ionic liquid, productive rate is 90%, and reaction equation is:
Embodiment 3:1-(two-5-methyl caprate base)-3-amyl group imidazolium chloride is ion liquid synthetic
Get the 1mol imidazoles and be dissolved in 200ml acetone, add 1.1mol 5-octene dicarboxylic acid dimethyl ester, refluxed 24 hours, the pressure reducing and steaming non-volatile matter, obtain 1-(two-5-methyl caprate base) imidazoles, add an amount of anhydrous methanol and chloropentane then, the chloropentane that adds and the mol ratio of 1-(two-5-methyl caprate base) imidazoles are 1: 1, stir and reaction 12h under 60 ℃, pressure reducing and steaming methyl alcohol, just obtain 1-(two-5-methyl caprate base)-3-amyl group imidazolium chloride ionic liquid, productive rate is 85%, and reaction equation is:
Embodiment 4; 1-(two-2-ethyl butyrate base)-3-ethyl imidazol(e) hexafluorophosphate is ion liquid synthetic
Get among the embodiment 1 1-(two-2-ethyl butyrate the base)-3-ethyl imidazol(e) bromide 0.1mol of preparation and mix with the methylene dichloride that contains 0.1 mole of phosphofluoric acid, stir 5h, dry organic phase also steams solvent, obtain 1-(two-2-ethyl butyrate base)-3-ethyl imidazol(e) hexafluorophosphate ionic liquid, productive rate is 90%.
Synthesizing of embodiment 5:1-(two-2-butyric acid-ethoxycarbonyl)-3-ethyl imidazol(e) tetrafluoroborate ion liquid
Get among the embodiment 1 1-(two-2-ethyl butyrate base)-0.1 mole of the 3-ethyl imidazol(e) bromide of preparation and mix with the methylene dichloride that contains 0.1 mole of sodium tetrafluoroborate, stir 5h, dry organic phase also steams solvent, just obtain 1-(two-2-butyric acid-ethoxycarbonyl)-3-ethyl imidazol(e) tetrafluoroborate, productive rate is 88%.
Embodiment 6:1-(two-2-ethyl butyrate base)-3-ethyl imidazol(e) fluoroform sulphonate is ion liquid synthetic
Get among the embodiment 1 1-(two-2-ethyl butyrate base)-0.1 mole of the 3-ethyl imidazol(e) bromide of preparation and mix with the methylene dichloride that contains 0.1 mole of trifluoromethanesulfonic acid sodium, stir 5h, dry organic phase also steams solvent, just obtain 1-(two-2-ethyl butyrate base)-3-ethyl imidazol(e) fluoroform sulphonate ionic liquid, productive rate is 95%.
Synthesizing of embodiment 7:1-(two-2-ethyl butyrate base)-3-ethyl imidazol(e) acetate ionic liquid
Get among the embodiment 1 1-(two-2-ethyl butyrate base)-0.1 mole of the 3-ethyl imidazol(e) bromide of preparation and mix with the methylene dichloride that contains 0.1 molar sodium acetate, stir 5h, dry organic phase also steams solvent, 1-(two-2-ethyl butyrate base)-3-ethyl imidazol(e) acetate ionic liquid, productive rate is 95%.
Synthesizing of embodiment 8:1-(two-2-ethyl butyrate base)-3-butyl imidazole nitrate ion liquid
Get among the embodiment 1 1-(two-2-ethyl butyrate base)-0.1 mole of the 3-ethyl imidazol(e) bromide of preparation and mix with the methylene dichloride that contains 0.1 molar nitric acid sodium, stir 5h, dry organic phase also steams solvent, 1-(two-2-ethyl butyrate base)-3-ethyl imidazol(e) nitrate ion liquid, productive rate is 95%.

Claims (5)

1,1-dibasic acid esters base-3-alkyl imidazo ion liquid has following chemical structure of general formula:
Figure A2005100326690002C1
2, according to the described 1-dibasic acid esters base of claim 1-3-alkyl imidazo ion liquid, it is characterized in that R 1For having the dibasic acid esters base of following structure:
Wherein, m, x and y are natural number, m=1～10; X=1～8, x+y＜10.
3, according to the described 1-dibasic acid esters base of claim 1-3-alkyl imidazo ion liquid, it is characterized in that R 2It is the straight chained alkyl that contains 1～10 carbon atom.
4, according to the described 1-dibasic acid esters base of claim 1-3-alkyl imidazo ion liquid, it is characterized in that X -Be Cl -, Br -, BF 4 -, PF 6 -, CH 3COO -, CF 3COO -, CF 3SO 3 -Or NO 3 -
5, the preparation method of the described 1-dibasic acid esters base of claim 1-3-alkyl imidazo ion liquid is characterized in that, comprises the steps and processing condition:
(1) is solvent with toluene or acetone, under the backflow situation,, obtains 1-dibasic acid esters base imidazoles imidazoles and the unsaturated dibasic acid esters reaction that contains two keys 12～24 hours; Wherein, the mol ratio of imidazoles and unsaturated dibasic acid esters is 1: 1～1: 1.5;
(2) in alcoholic solution, 1-dibasic acid esters base imidazoles and haloalkane were reacted 12～24 hours at 25～80 ℃, pass through the volatilizable component of pressure reducing and steaming again, just obtain 1-dibasic acid esters base-3-alkyl imidazo ion liquid; Wherein, the mol ratio of 1-dibasic acid esters base imidazoles and haloalkane is 1: 1～1: 2.
CN 200510032669 2005-01-04 2005-01-04 1-di-ester-base-3-alkyl imidazo ion liquid and its preparing method Expired - Fee Related CN1676514B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102558063A (en) * 2012-01-06 2012-07-11 河南科技大学 Preparing method of 1, 3-four carboxylic acid ester ionic liquid
CN110204689A (en) * 2019-06-19 2019-09-06 南京工业大学 Toughening imidazole epoxy resin latent curing agent and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102558063A (en) * 2012-01-06 2012-07-11 河南科技大学 Preparing method of 1, 3-four carboxylic acid ester ionic liquid
CN110204689A (en) * 2019-06-19 2019-09-06 南京工业大学 Toughening imidazole epoxy resin latent curing agent and preparation method thereof
CN110204689B (en) * 2019-06-19 2021-11-30 南京工业大学 Toughening imidazole epoxy resin latent curing agent and preparation method thereof

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