CN101058560A - Acidic ionic liquid based on 1-methyl-3-benzyl imidazole cation, synthetic method and use - Google Patents
Acidic ionic liquid based on 1-methyl-3-benzyl imidazole cation, synthetic method and use Download PDFInfo
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Abstract
The invention discloses an acid ion liquid and synthesizing method and application based on 1-methyl-3-benzyl imidazole cation, which is 1-methyl imidazole benzyl methylation organic cation, wherein the inorganic/organic anion is BF4<->,HSO4<->, H2PO4<->, p-CH3C6H4SO<3->, CF3COO<-> and ClCH2COO<->, wherein the ion liquid is liquid phase under indoor temperature, which can repair structure as mother compound due to leading functional group into structure, such as benzene ring, methylene and so on; the BrPhinsted acid can be repeating ring, reacting dielectric and reacting catalytic, which can be used to synthesize important perfume and solvent.
Description
Technical field
The present invention relates to a kind of based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid and preparation method and use thereof.
Background technology
Normal temperature ionic liquid or title ionic liquid at room temperature or room temperature fused salt abbreviate ionic liquid as.Refer in room temperature or be in a liquid state during near normal temperature by organic cation and salt inorganic or that organic anion is formed.Since Wilkes et al in 1992 has reported first based on the cationic ionic liquid of Methylimidazole: since the emimBF4, ionic liquid has obtained swift and violent development.It is novel as a kind, green, designability, material with special physico-chemical property, its application promptly forwards organic synthesis to from initial electrochemistry, research report emerge in multitude functionalized (or functionalization) and task specificity ionic liquid as the promotor of the medium of organic reaction and reaction, it is the new research focus of ionic liquid, they are to be connected on the positively charged ion or negatively charged ion of ionic liquid having the form of functionalized group with covalent linkage, further increase ionic liquid in the Application in Chemistry field, and shown very strong purposes specificity, specific aim.Because the special status of acid in organic reaction, people are developed and the tart ionic liquid such as Lewis is acid and Br nsted acidic ion liquid.It is ion liquid a kind of that Br nsted acidic ion liquid belongs to the task specificity, and it is meant the ionic liquid of having introduced Br nsted acidic functionality on the positively charged ion of ionic liquid or negatively charged ion.Because it is non-volatile that it has, adapt to wide, non-corrosiveness, with non-polar organic solvent advantageous property such as do not dissolve each other mutually, become the reaction medium and the catalysts that have development prospect in the reaction of having of acid catalysis.Alkylated reaction and Mannich reaction as the dimerization phenol of Fischer esterification aldolization vinyl toluene.Compare Br nsted acidic ion liquid with traditional organic/inorganic acid or Lewis acidic ion liquid and have (1) environmental friendliness, safety; (2) water, air had stability; (3) synthetic simple and direct, convenient; (4) acidity can be regulated; (5) reaction product is easy to separate from ionic liquid; (6) ionic liquid advantage such as can be recycled.
Benzoic ether is important industrial solvent and synthetic perfume, purposes is very extensive, its classical synthetic method is phenylformic acid and alcohol direct esterification in the presence of protonic acid (particularly sulfuric acid), or utilize Benzoyl chloride and alcohol to react, or utilizing methyl benzoate and alcohol to carry out transesterify and synthesize. protonic acid has severe corrosive and easily causes the generation of side reaction, and also there is the problem of all many-sides such as raw material sources, production cost, environment in additive method.In the face of urgent day by day environment and economic pressures, development " green ", efficient, economic esterification process have feasibility with urgent.
Summary of the invention
The object of the invention is, designed and synthesized out six kinds based on 1-methyl-cationic acidic ion liquid of 3-benzyl imidazole and preparation method and use, inorganic/organic anion that the positively charged ion of ionic liquid is the methylated organic cation of 1-Methylimidazole benzyl, joined is followed successively by: BF
4 -, HSO
4 -, H
2PO
4 -, p-CH
3C
6H
4SO
3 -, CF
3COO
-, ClCH
2COO
-Six kinds of negatively charged ion.Resulting ionic liquid all at room temperature is liquid phase, owing in its structure, there are site such as phenyl ring, the methylene radical etc. that can facilitate the introduction of functional group, it can be used as parent compound and makes further structure repair, thereby obtains the ionic liquid that structure is more novel, purposes is various.This is synthetic to be the starting raw material of reaction with 1-Methylimidazole, benzyl chloride, corresponding organic/inorganic acid, makes through quaternary ammoniated, ion-exchange two steps reaction.Wherein in quaternary ammonium reaction, reaction is chosen in low temperature, room temperature, three stages of heating condition respectively to be carried out, and is aided with means such as nitrogen, lucifuge, has improved the productive rate of reaction effectively, has especially obtained high-purity and the good chlorizate 1a of outward appearance.For ion exchange reaction, adopt that to have done with the methylene dichloride be the liquid phase synthesizing method of reaction medium, and will be reflected under low temperature and the reflux state respectively and carry out, overcoming traditional anionic salt exchanging is reaction raw materials, many deficiencies of the metathesis process that carries out at acetone, methyl alcohol isopolarity solvent, improved utilization ratio of raw materials, shortened the reaction times, high yield, the highly purified product ion liquid 2a-f that obtains.
Because all Br nsted acidity of synthetic ionic liquid, it can be used as and can repeat the reaction medium and the catalysts that encircle, use, is used for the synthetic of methyl benzoate, ethyl benzoate, three kinds of important spices comparatively commonly used of the positive butyl ester of phenylformic acid and solvent.Be reflected at alcohol/acid/, temperature 80-110 ℃, just can obtain two kinds of product esters under time 4-6 hour the condition greater than 85% productive rate from liquid (mol ratio)=1: 1: 0.5.The characteristics of reaction are that the separation of mild condition, productive rate height, particularly product is very convenient, owing to generate product ester and ion liquid immiscible property, finish the afterreaction system in reaction and are divided into two-phase: product ester phase, ionic liquid phase.The product ester can adopt the method for inclining to add to separate easily, and ionic liquid phase can obtain regeneration, recycle and catalytic activity only has decline slightly through simple and direct processing.Thereby the green that has realized methyl benzoate, ethyl benzoate, phenylformic acid positive butyl ester is synthetic.
Employing of the present invention is quaternary ammoniated, ion-exchange two step method synthetic is based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid 2a-2f, follows these steps to carry out:
The synthesizing chlorinated thing 1a of step 1:
With 1-Methylimidazole, benzyl chloride is the starting raw material of reaction, add non-polar organic solvent toluene or dimethylbenzene, earlier at low temperatures 0-5 ℃ reacted 8 hours, after go under the room temperature reaction 24 hours, at last 65-75 ℃ of following reacting by heating 24 hours, the gained muriate is the weak yellow liquid of good fluidity, has water absorbability;
Step 2 is synthesized ionic liquid 2a-2f:
Step 1 synthetic muriate is reacted with Tetrafluoroboric acid or sulfuric acid or phosphoric acid or tosic acid or trifluoroacetic acid or 1-Mono Chloro Acetic Acid respectively, reaction is solvent with the methylene dichloride, react down at 0-5 ℃ earlier and spend the night, reflux then, and blasted nitrogen reaction 24 hours, can obtain based on 1-methyl-3-benzyl imidazole positively charged ion Br nsted acidic ion liquid, be flaxen oily matter with Tetrafluoroboric acid or trifluoroacetic acid or 1-chloroacetate reaction gained ionic liquid wherein; Reacting the gained ionic liquid with tosic acid is yellow thickness oily matter; With sulfuric acid reaction gained ionic liquid be white thickness oily matter; With phosphatase reaction gained ionic liquid be that pistac is than thickness oily matter;
The chemical structure of synthetic ionic liquid 2a-2f is:
Based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid, the selected inorganic/organic anion that matches is followed successively by: BF
4 -, HSO
4 -, H
2PO
4 -, p-CH
3C
6H
4SO
3 -, CF
3COO
-, ClCH
2COO
-Six kinds of negatively charged ion.
A kind of synthetic method based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid follows these steps to carry out:
Synthesizing chlorinated thing 1a
A, earlier reaction substrate 1-Methylimidazole is dissolved in toluene, the dimethylbenzene non-polar solvent, open stir treat that it fully dissolves after, reaction system is placed ice-water bath, slowly drip the normal benzyl chloride of 1.1-1.15 at low temperatures, reacted 8 hours;
B, insulation reaction are spent the night, and reaction was warmed up to 65-75 ℃ of reaction 24 hours after 24 hours under the room temperature, and thin-layer chromatography is followed the tracks of reaction, and reaction system is under the nitrogen environment and under the lucifuge condition and reacts;
C, aftertreatment: earlier the temperature of reaction mixture is reduced to room temperature, reaction system will be divided into two-phase, lower floor's yellow oily of system is the crude product for generating mutually, the upper strata is that reaction solvent reaches excessive and unreacted reaction raw materials mutually, separating funnel leaves standstill phase-splitting, collection obtains crude product, and solvent recuperation is applied mechanically;
D, crude product are successively with ether or ethyl acetate organic solvent thorough washing, and 70-85 ℃ of following vacuum-drying 8 hours, obtaining outward appearance was flaxen at room temperature mobile better liquid target muriate 1a;
Synthetic ionic liquid 2a-2f
E, the synthetic muriate is mixed stirring with methylene chloride, after the question response system becomes homogeneous phase, reaction system is put into ice-water bath, when temperature of charge was reduced to 0-5 ℃, beginning slowly dripped equivalent Tetrafluoroboric acid or sulfuric acid or phosphoric acid or tosic acid or trifluoroacetic acid or 1-Mono Chloro Acetic Acid insulation reaction and spends the night;
F, with reaction system under reflux state and blasted nitrogen reaction 24 hours, can obtain based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid, be flaxen oily matter with Tetrafluoroboric acid or trifluoroacetic acid or 1-chloroacetate reaction gained ionic liquid wherein; Reacting the gained ionic liquid with tosic acid is yellow thickness oily matter; With sulfuric acid reaction gained ionic liquid be white thickness oily matter; With phosphatase reaction gained ionic liquid be that pistac is than thickness oily matter.
A kind of based on the purposes of the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid as preparation methyl benzoate or ethyl benzoate or the positive butyl ester spices of phenylformic acid.
Br nsted acidic ion liquid prepares methyl benzoate, wherein the material ratio mol ratio: phenylformic acid: methyl alcohol: ionic liquid=1: 1: 0.5-1, and temperature of reaction is 80 ± 5 ℃, the reaction times is 4 hours;
Product postprocessing: after reaction finishes, reaction system was left standstill 8 hours, after treating fully to be separated, the separating funnel phase-splitting, obtain product organic ester phase, ionic liquid phase, ionic liquid phase fully extracts with anhydrous diethyl ether 3 * 15ml, merges extraction phase, ester phase, carefully is rotated evaporation process and obtains the product methyl benzoate.
Phenylformic acid and the methyl alcohol esterification result in ionic liquid
| Ionic liquid | Methyl benzoate productive rate (%) |
| | 70.1 88.7 85.4 76.5 92.3 84.2 |
Annotate: productive rate is in thick ester
Br nsted acidic ion liquid prepares ethyl benzoate, wherein the material ratio mol ratio: phenylformic acid: acetate: ionic liquid=1: 1: 0.5-1, and temperature of reaction is 100 ± 5 ℃, the reaction times is 4 hours;
Product postprocessing: after reaction finishes, reaction system was left standstill more than 8 hours, after treating fully to be separated, use the separating funnel phase-splitting, obtain product organic ester phase, ionic liquid phase, ionic liquid phase fully extracts with anhydrous diethyl ether 3 * 15ml, merges extraction phase, organic ester phase, carefully is rotated evaporation process and obtains the product ethyl benzoate.
Phenylformic acid and the ethanol esterification result in ionic liquid
| Ionic liquid | Ethyl benzoate productive rate (%) |
| | 67.4 84.6 85.3 73.6 91.2 80.5 |
Annotate: productive rate is in thick ester
Br nsted acidic ion liquid prepares the positive butyl ester of phenylformic acid, wherein material ratio mol ratio: phenylcarbinol: butanic acid: ionic liquid=1: 1.5: 0.5-1, and temperature of reaction is 110 ± 5 ℃, the reaction times is 6 hours;
Product postprocessing: reaction is left standstill reaction system more than 8 hours after finishing, and after treating fully to be separated, the separating funnel phase-splitting obtains product ester phase, ionic liquid phase.Ionic liquid phase fully extracts with anhydrous diethyl ether 3 * 15ml, merges extraction phase, ester phase, carefully is rotated evaporation process and obtains the positive butyl ester of product phenylformic acid.
Phenylformic acid and the propyl carbinol esterification result in ionic liquid
| Ionic liquid | The positive butyl ester productive rate of phenylformic acid (%) |
| | 63.8 84.6 81.2 73 88.9 82 |
Annotate: productive rate is in thick ester
Employing is that methyl benzoate, the ethyl benzoate of reaction medium and catalysts, synthetic its reaction equation of green of the positive butyl ester of phenylformic acid are based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid:
Wherein
Synthetic method based on 1-methyl-cationic acidic ion liquid of 3-benzyl imidazole of the present invention, it is synthetic by following two-step synthesis
Quaternary ammoniated:
Earlier reaction substrate 1-Methylimidazole is dissolved in such as: in the non-polar solvents such as toluene, dimethylbenzene, open stir treat that it fully dissolves after, reaction system is placed ice-water bath, begin slowly to drip excessive slightly benzyl chloride at low temperatures.Drip complete insulation reaction and spend the night, reaction was warmed up to 65-75 ℃ of reaction 24 hours (thin-layer chromatography is followed the tracks of reaction, and reaction system is under the nitrogen environment and under the lucifuge condition and reacts) and finishes after 24 hours under the room temperature.Aftertreatment: earlier the temperature of reaction mixture is reduced to room temperature, at this moment reaction system will be divided into two-phase, lower floor's yellow oily of system is the crude product for generating mutually, the upper strata is that reaction solvent reaches reaction raw materials excessive and the end reaction mutually, separating funnel leaves standstill phase-splitting, collection obtains crude product, and solvent recuperation is applied mechanically.Crude product is used organic solvent thorough washing such as ether or ethyl acetate successively, and at last 70～85 ℃ of following vacuum-dryings more than 8 hours, obtaining outward appearance is flaxen at room temperature mobile better liquid target compound (representing with 1a), productive rate＞92%.
Ion-exchange:
Claim anionresin or replacement(metathesis)reaction again, traditional method is that the excessive anion salt that will exchange of employing is a reaction raw materials, reacts in polar solvent such as anhydrous methanol, acetone etc.Weak point be long reaction time, prepared using insufficient, be difficult to the salt that generates from ionic liquid, separate and cause the product purification difficulty because the stronger solvability of ionic liquid makes.The anionic organic or inorganic acid that we have designed exchanging in this is synthetic is the liquid phase synthesizing method of reaction medium as reaction raw materials, with methylene dichloride or acetone, improve utilization ratio of raw materials, reduced the reaction times, because reaction is chosen in reflux state and carries out, and the employing that in reactive system, blasts these measures of nitrogen can be in time, effectively by product HCl gas is discharged from reactive system, thereby obtained the good product ion liquid of purity and outward appearance and (used 2a, 2b, 2c, 2d, 2e, 2f represents).
In the there-necked flask of being furnished with acid gas absorption bottle and nitrogen bottom insert canal, muriate 1a is dissolved in a large amount of methylene dichloride, acetone, or in other polar solvent, under low temperature and intensive agitation condition, slowly dripping the mineral acid of equivalent or organic acid (adopting the method that the short run gradation adds by need for solid-state organic acid such as tosic acid or 1-Mono Chloro Acetic Acid) dropwises, elder generation's insulation reaction is spent the night, after be warming up to reflux state and be blown into the nitrogen (HCl that absorbs in the NaOH Titrable acid gas absorption bottle, follow the tracks of the degree that reaction is carried out) aftertreatment: revolve steaming earlier except that desolvating and obtain crude product, crude product obtains final ionic liquid product through vacuum-drying again.The ionic liquid situation of gained is as follows: ionic liquid 2a outward appearance is: flaxen oily matter, productive rate 95%;
Ionic liquid 2c outward appearance is: pistac is than thickness oily matter, productive rate 98.7%;
Table 1: the ion liquid table that recycles
| Recycle number of times | Acid | Alcohol | Ionic liquid | Acid/alcohol/ionic liquid (mol ratio) | Temperature of reaction (℃) | Reaction times (h) | Productive rate [a] (％) | ||
| 1 2 3 1 2 3 1 2 3 | Phenylamino benzoic acid formic acid phenylamino benzoic acid formic acid phenylamino benzoic acid formic acid phenylamino benzoic acid formic acid benzoic acid | Methyl alcohol methyl alcohol methanol/ethanol ethanol ethanol n-butanol n-butanol n- | | 2b | 2b | 1∶1∶0.5 1∶1∶0.5 1∶1∶0.5 1∶1∶0.5 1∶1∶0.5 1∶1∶0.5 1∶1∶0.5 1∶1∶0.5 1∶1∶0.5 | 80 80 80 100 100 100 110 110 110 | 4 4 4 4 4 4 6 6 6 | 87.4 87 85.3 85.1 84.2 83.7 81.4 80.2 79.6 |
[a] productive rate is in thick ester
The synthetic method of methyl benzoate of the present invention, ethyl ester, positive butyl ester is undertaken by following method.
In the there-necked flask of being furnished with magnetic agitation, reflux exchanger, add ionic liquid, phenylformic acid, the alcohol that measures successively, be reflected in the oil bath and carry out.Interior temperature control finished (reaction process is followed the tracks of in the timing sampling analysis) aftertreatment in 4-6 hour 80-110 ℃ of reaction: reaction finishes the back because product ester and ion liquid immiscible, make reaction system become two-phase, the product ester (includes ionic liquid with ionic liquid phase, unreacted raw material, the water that generates, a spot of product ester) thus the separation of product can adopt and incline to method easily, for the product ester that fully obtains generating with recycle ionic liquid, use ether, organic solvent extraction ionic liquid phase such as ethyl acetate merge extraction phase and promptly obtain the product ester with ester is careful mutually except that desolvating.
Ion liquid regeneration:
Ionic liquid phase is joined in the organic solvents such as a large amount of ether, ethyl acetate, be heated under the reflux state thorough washing more than 4 hours, except that after desolvating, ionic liquid phase is dry more than 8 hours under condition under 80-85 ℃, high vacuum, can recirculation use, the catalytic activity of reaction has decline slightly.(the results are shown in Table 2)
Of the present invention have following advantage based on 1-methyl-cationic acidic ion liquid of 3-benzyl imidazole:
Adopt starting raw material inexpensive, that be easy to get: 1-Methylimidazole, benzyl chloride, mineral acid/organic acid have obtained the target acidic ion liquid through simple and direct reaction high yield of two steps;
The selection of reaction conditions and design have been guaranteed good purity, productive rate and the outward appearance of product ion liquid;
From the ion liquid chemical structure that obtains as seen, set out thus and can make further structural modification, as introducing-SO on phenyl ring ionic liquid
3H etc.;
Since the synthetic ionic liquid have acid its can be used as synthesizing benzoic acids methyl esters, ethyl ester, positive butyl ester effectively, reaction medium and the catalyzer that can be recycled.Reaction has that productive rate height, reaction conditions gentleness, product are easy to separate, ionic liquid is regenerated easy reusable characteristics, realized that " green " of methyl benzoate, ethyl ester, positive butyl ester is synthetic.
Description of drawings
Fig. 1 is an ionic liquid synthetic route chart of the present invention
Embodiment
Embodiment 1 ionic liquid 2b's is synthetic
Synthesizing chlorinated thing 1a
A, in being furnished with churned mechanically 50ml there-necked flask, earlier the 1-Methylimidazole of reaction substrate 5g is dissolved in 25ml toluene, open stir make reactant become homogeneous phase after, reactant is placed ice-water bath, drip 1.15 normal benzyl chlorides during with 0 ℃, reacted 8 hours;
B, insulation reaction are spent the night, and reaction was warmed up to 65 ℃ of reactions 24 hours after 24 hours under the room temperature, and thin-layer chromatography is followed the tracks of reaction, and reaction system is under the nitrogen environment and under the lucifuge condition and reacts;
C, aftertreatment: earlier the temperature of reaction mixture is reduced to room temperature, reaction system will be divided into two-phase, lower floor's yellow oily of system is the crude product for generating mutually, the upper strata is that reaction solvent reaches excessive and unreacted reaction raw materials mutually, separating funnel leaves standstill phase-splitting, collection obtains crude product, and solvent recuperation is applied mechanically;
D, crude product are used ethyl acetate organic solvent thorough washing successively, and 70 ℃ of following vacuum-dryings 8 hours, obtaining target muriate 1a was the good weak yellow liquid of room temperature current downflow, has water absorbability, productive rate 95%;
Ir data (KBr, v/cm
-1): 3,032 2,853 2,110 1,645 1,568 14,561,161 1,086 866 725;
Proton nmr spectra data (400MHz, D
2O): 8.74 (d, 1H), 7.41-7.51 (m, 7H), 5.38 (s, 2H), 3.88 (s, 3H);
Synthetic ionic liquid 2b
E, in the 50ml there-necked flask of being furnished with magnetic agitation, reflux exchanger, acid gas absorption bottle, add successively 25ml methylene dichloride, 5g muriate 1a (0.0231mol) open stir the question response system and become homogeneous phase after, reaction system is put into ice-water bath, at interior temperature drop during to 0-5 ℃, beginning slowly drips the vitriol oil of equivalent, and insulation reaction is spent the night;
F, reaction system are under reflux state and blast nitrogen reaction and finished in 24 hours, and can obtain outward appearance is flaxen oily product 2b 6.11g, productive rate 99% based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid 2b.
Ir data (KBr v/cm
-1): 3108,2970,2857,2325,2100,1642,1500,1446,1210,872,745,710.
Proton nmr spectra data (400MHz, D
2O): 8.74 (d, 1H), 7.41-7.51 (m, 7H), 5.38 (s, 2H), 3.88 (s, 3H).
Embodiment 2 ionic liquid 2c's is synthetic
Synthesizing chlorinated thing 1a
A, in being furnished with churned mechanically 50ml there-necked flask, earlier the 1-Methylimidazole of reaction substrate 5g is dissolved in 25ml toluene, open stir make reactant become homogeneous phase after, reactant is placed ice-water bath, drip 1.10 normal benzyl chlorides during with 0 ℃, reacted 8 hours;
B, insulation reaction are spent the night, and reaction was warmed up to 70 ℃ of reactions 24 hours after 24 hours under the room temperature, and thin-layer chromatography is followed the tracks of reaction, and reaction system is under the nitrogen environment and under the lucifuge condition and reacts;
C, aftertreatment: earlier the temperature of reaction mixture is reduced to room temperature, reaction system will be divided into two-phase, lower floor's yellow oily of system is the crude product for generating mutually, the upper strata is that reaction solvent reaches excessive and unreacted reaction raw materials mutually, separating funnel leaves standstill phase-splitting, collection obtains crude product, and solvent recuperation is applied mechanically;
D, crude product are used ethyl acetate organic solvent thorough washing successively, and 70 ℃ of following vacuum-dryings 8 hours, obtaining target muriate 1a was the good weak yellow liquid of room temperature current downflow, has water absorbability, productive rate 95%;
Synthetic ionic liquid 2c
E, in the 50ml there-necked flask of being furnished with magnetic agitation, reflux exchanger, acid gas absorption bottle, add successively 25ml methylene dichloride, 5g muriate 1a (0.0231mol) open stir the question response system and become homogeneous phase after, reaction system is put into ice-water bath, at interior temperature drop during to 0-5 ℃, beginning slowly drips the phosphoric acid of equivalent, and insulation reaction is spent the night;
F, reaction system are under reflux state and blast nitrogen reaction and finished in 24 hours, and can obtain outward appearance is flaxen oily product 2c, productive rate 98.5% based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid 2c.
Ir data (KBr v/cm
-1): 3065,2973,2868,2340,1639,1490,1455.8,1207,875,750,701.
Proton nmr spectra data (400MHz, D
2O): 8.74 (d, 1H), 7.41-7.51 (m, 7H), 5.38 (s, 2H), 3.88 (s, 3H).
Embodiment 3 ionic liquid 2e's is synthetic
Synthesizing chlorinated thing 1a
A, in being furnished with churned mechanically 50ml there-necked flask, earlier the 1-Methylimidazole of reaction substrate 5g is dissolved in 25ml dimethylbenzene, after unlatching is stirred and is made reactant become homogeneous phase, reactant is placed ice-water bath, drip 1.12 normal benzyl chlorides during with 1 ℃, reacted 8 hours;
B, insulation reaction are spent the night, and reaction was warmed up to 72 ℃ of reactions 24 hours after 24 hours under the room temperature, and thin-layer chromatography is followed the tracks of reaction, and reaction system is under the nitrogen environment and under the lucifuge condition and reacts;
C, aftertreatment: earlier the temperature of reaction mixture is reduced to room temperature, reaction system will be divided into two-phase, lower floor's yellow oily of system is the crude product for generating mutually, the upper strata is that reaction solvent reaches excessive and unreacted reaction raw materials mutually, separating funnel leaves standstill phase-splitting, collection obtains crude product, and solvent recuperation is applied mechanically;
D, crude product are used ethyl acetate organic solvent thorough washing successively, and 75 ℃ of following vacuum-dryings 8 hours, obtaining target muriate 1a was the good weak yellow liquid of room temperature current downflow, has water absorbability, productive rate 95%;
Synthetic ionic liquid 2e
E, in the 50ml there-necked flask of being furnished with magnetic agitation, reflux exchanger, acid gas absorption bottle, add successively 25ml methylene dichloride, 5g muriate 1a (0.0231mol) open stir the question response system and become homogeneous phase after, reaction system is put into ice-water bath, when interior temperature drop to 1 ℃, beginning slowly drips the trifluoroacetic acid of equivalent, and insulation reaction is spent the night;
F, reaction system are under reflux state and blast nitrogen reaction and finished in 24 hours, and can obtain outward appearance is flaxen oily product 2e, productive rate 98.5% based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid 2c.
Ir data (KBr v/cm
-1): 3122,2953,2930,2578,1688,1489,1456.6,1210,1120,825,745,680.
Proton nmr spectra data (400MHz, D
2O): 8.74 (d, 1H), 7.41-7.51 (m, 7H), 5.38 (s, 2H), 3.88 (s, 3H).
Embodiment 4 ionic liquid 2d's is synthetic
Synthesizing chlorinated thing 1a
A, in being furnished with churned mechanically 50ml there-necked flask, earlier the 1-Methylimidazole of reaction substrate 5g is dissolved in 25ml dimethylbenzene, after unlatching is stirred and is made reactant become homogeneous phase, reactant is placed ice-water bath, drip 1.12 normal benzyl chlorides during with 1 ℃, reacted 8 hours;
B, insulation reaction are spent the night, and reaction was warmed up to 72 ℃ of reactions 24 hours after 24 hours under the room temperature, and thin-layer chromatography is followed the tracks of reaction, and reaction system is under the nitrogen environment and under the lucifuge condition and reacts;
C, aftertreatment: earlier the temperature of reaction mixture is reduced to room temperature, reaction system will be divided into two-phase, lower floor's yellow oily of system is the crude product for generating mutually, the upper strata is that reaction solvent reaches excessive and unreacted reaction raw materials mutually, separating funnel leaves standstill phase-splitting, collection obtains crude product, and solvent recuperation is applied mechanically;
D, crude product are used ether organic solvent thorough washing successively, and 80 ℃ of following vacuum-dryings 8 hours, obtaining target muriate 1a was the good weak yellow liquid of room temperature current downflow, has water absorbability, productive rate 95%;
Synthetic ionic liquid 2d
E, in the 50ml there-necked flask of being furnished with magnetic agitation, reflux exchanger, acid gas absorption bottle, add successively 25ml methylene dichloride, 5g muriate 1a (0.0231mol) open stir the question response system and become homogeneous phase after, reaction system is put into ice-water bath, when interior temperature drop to 1 ℃, begin the solid phase tosic acid of slow gradation dropping equivalent, insulation reaction is spent the night;
F, reaction system are under reflux state and blast nitrogen reaction and finished in 24 hours, and can obtain outward appearance is faint yellow thickness oily product 2d, productive rate 98% based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid 2d.
Ir data (KBr v/cm
-1): 3127,3058,2963,2860,2588,2426,1625,1490.5,1454,1392,816,750,682.
Proton nmr spectra data (400MHz, D
2O): 8.74 (d, 1H), 7.41-7.51 (m, 7H), 7.06-8.11 (q, 4H), 5.38 (s.2H) 3.88 (s, 3H), 1.35 (t, 3H).
Embodiment 5 ionic liquid 2f's is synthetic
Synthesizing chlorinated thing 1a
A, in being furnished with churned mechanically 50ml there-necked flask, earlier the 1-Methylimidazole of reaction substrate 5g is dissolved in 25ml toluene, open stir make reactant become homogeneous phase after, reactant is placed ice-water bath, drip 1.14 normal benzyl chlorides during with 1 ℃, reacted 8 hours;
B, insulation reaction are spent the night, and reaction was warmed up to 75 ℃ of reactions 24 hours after 24 hours under the room temperature, and thin-layer chromatography is followed the tracks of reaction, and reaction system is under the nitrogen environment and under the lucifuge condition and reacts;
C, aftertreatment: earlier the temperature of reaction mixture is reduced to room temperature, reaction system will be divided into two-phase, lower floor's yellow oily of system is the crude product for generating mutually, the upper strata is that reaction solvent reaches excessive and unreacted reaction raw materials mutually, separating funnel leaves standstill phase-splitting, collection obtains crude product, and solvent recuperation is applied mechanically;
D, crude product are used ethyl acetate organic solvent thorough washing successively, and 85 ℃ of following vacuum-dryings 8 hours, obtaining target muriate 1a was the good weak yellow liquid of room temperature current downflow, has water absorbability, productive rate 95%;
Synthetic ionic liquid 2f
E, in the 50ml there-necked flask of being furnished with magnetic agitation, reflux exchanger, acid gas absorption bottle, add successively 25ml methylene dichloride, 5g muriate 1a (0.0231mol) open stir the question response system and become homogeneous phase after, reaction system is put into ice-water bath, when interior temperature drop to 1 ℃, beginning slowly drips the 1-Mono Chloro Acetic Acid of equivalent, and insulation reaction is spent the night;
F, reaction system are under reflux state and blast nitrogen reaction and finished in 24 hours, and can obtain outward appearance is flaxen oily product 2f, productive rate 97% based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid 2f.
Ir data (KBr v/cm
-1): 3122,3053,2928,2587,2523,1696,1734,1642,1490,1456,1162,770,704.
Proton nmr spectra data (400MHz, D
2O): 8.77 (d, 1H), 7.41-7.51 (m, 7H), 5.41 (s, 2H), 4.33 (s.2H), 3.88 (s, 3H).
Embodiment 6 ionic liquid 2a's is synthetic
Synthesizing chlorinated thing 1a
A, in being furnished with churned mechanically 50ml there-necked flask, earlier the 1-Methylimidazole of reaction substrate 5g is dissolved in 25ml toluene, open stir make reactant become homogeneous phase after, reactant is placed ice-water bath, drip 1.12 normal benzyl chlorides during with 1 ℃, reacted 8 hours;
B, insulation reaction are spent the night, and reaction was warmed up to 75 ℃ of reactions 24 hours after 24 hours under the room temperature, and thin-layer chromatography is followed the tracks of reaction, and reaction system is under the nitrogen environment and under the lucifuge condition and reacts;
C, aftertreatment: earlier the temperature of reaction mixture is reduced to room temperature, reaction system will be divided into two-phase, lower floor's yellow oily of system is the crude product for generating mutually, the upper strata is that reaction solvent reaches excessive and unreacted reaction raw materials mutually, separating funnel leaves standstill phase-splitting, collection obtains crude product, and solvent recuperation is applied mechanically;
D, crude product are used ethyl acetate organic solvent thorough washing successively, and 78 ℃ of following vacuum-dryings 8 hours, obtaining target muriate 1a was the good weak yellow liquid of room temperature current downflow, has water absorbability, productive rate 95%;
Synthetic ionic liquid 2a
E, in the 50ml there-necked flask of being furnished with magnetic agitation, reflux exchanger, acid gas absorption bottle, add successively 25ml methylene dichloride, 5g muriate 1a (0.0231mol) open stir the question response system and become homogeneous phase after, reaction system is put into ice-water bath, when interior temperature drop to 1 ℃, beginning slowly drips the Tetrafluoroboric acid of equivalent, and insulation reaction is spent the night;
F, reaction system are under reflux state and blast nitrogen reaction and finished in 24 hours, and can obtain outward appearance is flaxen oily product 2a, productive rate: 95% based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid 2a.
Ir data (KBr v/cm
-1): 3055,2960,1638,1590,1490,1460,1065,754,709.
Proton nmr spectra data (400MHz, D
2O): 8.74 (d, 1H), 7.41-7.51 (m, 7H), 5.38 (s, 2H), 3.88 (s, 3H).
Synthesizing of embodiment 7 methyl benzoate
Add 2.2g ionic liquid 2b, 2g phenylformic acid, 0.55g methyl alcohol successively in being furnished with magnetic agitation, reflux exchanger, 25ml there-necked flask, behind the thorough mixing reactant being placed oil bath, controlled temperature finished 80 ± 2 ℃ of reactions in 4 hours.(the timing sampling gas chromatographic analysis is followed the tracks of reaction and carried out) leaves standstill a few hours, and reaction system is rendered as two-phase.The upper strata is a product ester phase, and lower floor is an ionic liquid phase.Inclining upper strata ester phase, and lower floor's ionic liquid phase fully extracts three times with the 15ml ether, merges ester phase and extraction phase, carefully revolves steaming, removes ether and obtains product jasmal 2.0g productive rate 88.7%.
Synthesizing of embodiment 8 ethyl benzoates
Is being furnished with magnetic agitation, reflux exchanger, add 2.2g ionic liquid 2b in the 25ml there-necked flask successively, 2g phenylcarbinol 0.75g ethanol, open to stir and at room temperature mix earlier, at this moment reaction system becomes homogeneous phase, afterwards reactant is placed oil bath, controlled temperature finished (the timing sampling gas chromatographic analysis is followed the tracks of reaction and carried out) in 4 hours and leaves standstill a few hours 110 ± 2 ℃ of reactions, reaction system is rendered as two-phase, the upper strata is a product ester phase, and lower floor is an ionic liquid phase, inclines to upper strata ester phase, lower floor's ionic liquid phase fully extracts three times with the 15ml ether, merge ester phase and extraction phase, carefully revolve steaming, remove ether and obtain product benzyl propionate 2.1g productive rate 84.6%.
Synthesizing of the positive butyl ester of embodiment 9 phenylformic acid
Is being furnished with magnetic agitation, reflux exchanger, add 2.2g ionic liquid 2b in the 25ml there-necked flask successively, 2g phenylcarbinol 1.22g propyl carbinol, open to stir and at room temperature mix earlier, at this moment reaction system becomes homogeneous phase, afterwards reactant is placed oil bath, controlled temperature finished (the timing sampling gas chromatographic analysis is followed the tracks of reaction and carried out) in 4 hours and leaves standstill a few hours 110 ± 2 ℃ of reactions, reaction system is rendered as two-phase, the upper strata is a product ester phase, and lower floor is an ionic liquid phase, inclines to upper strata ester phase, lower floor's ionic liquid phase fully extracts three times with the 15ml ether, merge ester phase and extraction phase, carefully revolve steaming, remove ether and obtain product benzyl propionate 2.4g productive rate 82.7%.
Claims (5)
1, quaternary ammoniated, the ion-exchange two step method synthetic of a kind of employing is characterized in that following these steps to carrying out based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid 2a-2f:
The synthesizing chlorinated thing 1a of step 1:
With 1-Methylimidazole, benzyl chloride is the starting raw material of reaction, add non-polar organic solvent toluene or dimethylbenzene, earlier at low temperatures 0-5 ℃ reacted 8 hours, after go under the room temperature reaction 24 hours, at last 65-75 ℃ of following reacting by heating 24 hours, the gained muriate is the weak yellow liquid of good fluidity, has water absorbability;
Step 2 is synthesized ionic liquid 2a-2f:
Step 1 synthetic muriate is reacted with Tetrafluoroboric acid or sulfuric acid or phosphoric acid or tosic acid or trifluoroacetic acid or 1-Mono Chloro Acetic Acid respectively, reaction is solvent with the methylene dichloride, react down at 0-5 ℃ earlier and spend the night, reflux then, and blasted nitrogen reaction 24 hours, can obtain based on 1-methyl-3-benzyl imidazole positively charged ion Br nsted acidic ion liquid, be flaxen oily matter with Tetrafluoroboric acid or trifluoroacetic acid or 1-chloroacetate reaction gained ionic liquid wherein; Reacting the gained ionic liquid with tosic acid is yellow thickness oily matter; With sulfuric acid reaction gained ionic liquid be white thickness oily matter; With phosphatase reaction gained ionic liquid be that pistac is than thickness oily matter;
The chemical structure of synthetic ionic liquid 2a-2f is:
2, according to claim 1 based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid, it is characterized in that the selected inorganic/organic anion that matches is followed successively by: BF
4 -, HSO
4 -, H
2PO
4 -, p-CH
3C
6H
4SO
3 -, CF
3COO
-, ClCH
2COO
-Six kinds of negatively charged ion.
3, a kind of synthetic method based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid is characterized in that following these steps to carrying out:
Synthesizing chlorinated thing 1a
A, earlier reaction substrate 1-Methylimidazole is dissolved in the non-polar solvents such as toluene, dimethylbenzene, open stir treat that it fully dissolves after, reaction system is placed ice-water bath, slowly drip the normal benzyl chloride of 1.1-1.15 at low temperatures, reacted 8 hours;
B, insulation reaction are spent the night, and reaction was warmed up to 65-75 ℃ of reaction 24 hours after 24 hours under the room temperature, and thin-layer chromatography is followed the tracks of reaction, and reaction system is under the nitrogen environment and under the lucifuge condition and reacts;
C, aftertreatment: earlier the temperature of reaction mixture is reduced to room temperature, reaction system will be divided into two-phase, lower floor's yellow oily of system is the crude product for generating mutually, the upper strata is that reaction solvent reaches excessive and unreacted reaction raw materials mutually, separating funnel leaves standstill phase-splitting, collection obtains crude product, and solvent recuperation is applied mechanically;
D, crude product are successively with ether or ethyl acetate organic solvent thorough washing, and 70-85 ℃ of following vacuum-drying 8 hours, obtaining outward appearance was flaxen at room temperature mobile better liquid target muriate 1a;
Synthetic ionic liquid 2a-2f
E, the synthetic muriate is mixed stirring with methylene chloride, after the question response system becomes homogeneous phase, reaction system is put into ice-water bath, when temperature of charge was reduced to 0-5 ℃, beginning slowly dripped equivalent Tetrafluoroboric acid or sulfuric acid or phosphoric acid or tosic acid or trifluoroacetic acid or 1-Mono Chloro Acetic Acid insulation reaction and spends the night;
F, with reaction system under reflux state and blasted nitrogen reaction 24 hours, can obtain based on the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid, be flaxen oily matter with Tetrafluoroboric acid or trifluoroacetic acid or 1-chloroacetate reaction gained ionic liquid wherein; Reacting the gained ionic liquid with tosic acid is yellow thickness oily matter; With sulfuric acid reaction gained ionic liquid be white thickness oily matter; With phosphatase reaction gained ionic liquid be that pistac is than thickness oily matter.
4, a kind of based on the purposes of the 1-methyl-cationic Br of 3-benzyl imidazole nsted acidic ion liquid as preparation methyl benzoate or ethyl benzoate or the positive butyl ester spices of phenylformic acid.
5, the Br nsted acidic ion liquid according to claim 4 prepares the positive butyl ester of methyl benzoate or ethyl benzoate or phenylformic acid, material ratio mol ratio wherein: phenylformic acid: methyl alcohol or ethanol or propyl carbinol: ionic liquid=1: 1: 0.5-1, temperature of reaction is 80-110 ± 5 ℃, and the reaction times is 4-6 hour;
Product postprocessing: after reaction finishes, reaction system was left standstill 8 hours, after treating fully to be separated, the separating funnel phase-splitting, obtain product organic ester phase, ionic liquid phase, ionic liquid phase fully extracts with anhydrous diethyl ether 3 * 15ml, merges extraction phase, ester phase, carefully is rotated evaporation process and obtains the positive butyl ester of product methyl benzoate or ethyl benzoate or phenylformic acid.
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