CN101033210A - Functionalization acidic ionic liquid based on pyridine cation and its synthetic method and application - Google Patents
Functionalization acidic ionic liquid based on pyridine cation and its synthetic method and application Download PDFInfo
- Publication number
- CN101033210A CN101033210A CN 200710100464 CN200710100464A CN101033210A CN 101033210 A CN101033210 A CN 101033210A CN 200710100464 CN200710100464 CN 200710100464 CN 200710100464 A CN200710100464 A CN 200710100464A CN 101033210 A CN101033210 A CN 101033210A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- reaction
- acid
- hours
- phase
- 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.)
- Granted
Links
Images
Landscapes
- Pyridine Compounds (AREA)
Abstract
This invention relates to a functional acidity ionic solution based on pyridine cations, its synthesizing method and its usage, which applies pyridine benzyl chloride as the start raw material of reactions and adds nonpolarity organic solvent to get a water absorption white crystal of a chloride, then takes the synthesized chloride, tetrafluoroboracic acid, H2SO4, H3PO4, toluene-p-sulfonic acid, trifluoroacetic acid or 1-chloroactic acid as the materials and adds a solvent to flow back and penetrate N2 for reaction to get the functional acid ionic solution based on pyridine cations, which is taken as the reaction medium and reaction catalyst to prepare two spices of acetic benzyl and methyl acetic benzyl to realize green synthesization of them.
Description
Technical field
The present invention relates to a kind of functionalization acidic ionic liquid and synthetic method and application based on pyridylium, because inherent Br nsted of these ionic liquid institutes or Lewis acidity, its can be used as the Fisher esterification effectively, reaction medium and the catalysts that can be recycled.
Background technology
The normal temperature ionic liquid or claim ionic liquid at room temperature room temperature fused salt (abbreviating ionic liquid as) is meant 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 in 1992 has reported first based on Methylimidazole since the cationic ionic liquid emimBF4, ionic liquid has obtained swift and violent development.Its as kind novel, green, designability, material with special physico-chemical property, its application promptly forwards organic synthesis to from initial electrochemistry, as the research report emerge in multitude of the promotor of the medium of organic reaction and reaction, the special physico-chemical property of its performance can reduce following some:
(1) strong protonic acid; Proton in the ionic liquid has than the stronger acidity of proton in sulfuric acid or the hydrofluoric acid.
(2) in ionic liquid, help the generation of positive ion and increase its life-span.
(3) ionic liquid has shown strong polarity and weak coordination ability and has been very beneficial for stationary phase as the metal composite catalyzer.
(4) ionic liquid has thermostability, and being close to can be in vapour pressure of disregarding and powerful dissolving power.
(5) polarity has the catalystic converter system of using by the present ionic liquid of the adjustability of the different companion ion of conversion has: 1) homogeneous reaction system: reaction substrate and catalyzer all are dissolved in the ionic liquid; 2) homogeneous reaction system: ionic liquid is reacted as the medium of reaction and catalyzer such as Friedel-Craft simultaneously; 3) biphasic reaction system: catalyzer is present in one mutually with ionic liquid, and the substrate of reaction and product are present in another mutually or opposite; 4) three-phase reaction system: ionic liquid and catalyzer one mutually, reaction substrate and reaction product are present in organic phase, the salt that reaction generates etc. is present in water.
Enter 21st century, " Green Chemistry " becomes the developing direction of various countries' chemistry and chemical industry, and the people's Search green chemistry that appears as of ionic liquid has been opened up a new world.Functionalized (or functionalization) and task specificity ionic liquid, it is the new research focus of ionic liquid, they give to be changed the positively charged ion of group or negatively charged ion and match with corresponding positive (the moon) and form having the official, its pointed and narrow spectrum characteristic becomes a novel method in the organic synthesis.
But at present most of ionic liquid of report still are based on the imidazole type ionic liquid of glyoxaline cation, and based on the pyridine type ionic liquid phase of pyridylium to less.Can have following advantage than the former pyridine type ionic liquid: 1) the synthetic starting raw material is easy to obtain more, and cheap.2) can avoid the deficiency of some imidazole type ionic liquid.Acid problem as H on the C-2 position on the imidazole ring.3) having more structural changes and structural modification.(all can introduce various functionalized substituting groups easily on N atom and the pyridine ring) is nearest, and the pyridyl ionic liquid has attracted more and more researchists' attention, the report of the functionalized pyridyl ionic liquid of a large amount of novel structures occurred, and its structure is:
These ionic liquid not only can be full of prospect as reaction medium and catalyzer in numerous known organic reactions, and have also represented good growth momentum in asymmetry catalysis transforms.But be not difficult from its structural formula to find that this this report pyridyl ionic liquid substantially all is that functionalized straight-chain paraffin is incorporated on N atom or the pyridine ring, and as the report of the introducing of aryl substituent seldom.
The acid of acetate benzyl, the acid of propionic acid benzyl are as two kinds of important spices comparatively commonly used, and its production method is as follows at present: 1) equal phase synthesi: adopt homogeneous catalyst, as the vitriol oil or tosic acid etc.Its deficiency is that side reaction is many, and production unit is had corrodibility, the product postprocessing difficulty, and a large amount of salt waste that produces in the production causes environmental pollution.2) heterogeneous synthesis method: adopt the catalyst system as reaction such as acidic resins, immobilization mineral acid, heteropolyacid.Its deficiency is the production cost height, and the catalyzer instability has corrodibility.In the middle of aftertreatment, need to use a large amount of volatile organic solvents in addition.Thereby the green synthesis techniques that develops jasmal, benzyl propionate has feasibility with urgent.
The present invention has selected the model reaction of the esterification of phenylcarbinol and acetate, propionic acid as research.Under the reaction conditions of gentleness highly selective, high yield obtained target product, thereby the green that has realized jasmal, two kinds of spices of benzyl propionate is synthetic.
Summary of the invention
The object of the invention is, has designed and synthesized out six kinds based on the cationic functionalization acidic ionic liquid of pyridyl, and the organic anion that the positively charged ion of ionic liquid is the methylated organic cation of pyridine 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, exist and to facilitate the introduction of functional group such as phenyl ring, methylene radical etc., 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 pyridine, benzyl chloride, corresponding organic 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 at low temperature respectively and return under the attitude 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 the acidity that the synthetic ionic liquid is shown, it can be used as reaction medium and the catalysts that can be recycled, and is used for the synthetic of jasmal, two kinds of important spices comparatively commonly used of benzyl propionate.Be reflected at material ratio: alcohol/acid/ionic liquid (mol ratio)=1: 1.5: 0.5,80,110 ℃ of temperature of reaction just can obtain two kinds of product esters with the productive rate greater than 85% under the condition in 4 hours reaction times.The characteristics of reaction are that the separation of mild condition, productive rate height, particularly product is very convenient, owing to generate the immiscible property of product ester and ionic liquid, finish the afterreaction system in reaction and are divided into two-phase: product ester phase, ionic liquid phase.The product ester can method easily add to be separated with inclining, 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 jasmal, benzyl propionate is synthetic
The research of employing two step method has synthesized the functionalization acidic ionic liquid based on pyridylium, the synthetic of this ionic liquid at first is synthesizing chlorinated thing (representing with 1a), with pyridine, benzyl chloride is the starting raw material of reaction, with non-polar organic solvent toluene or dimethylbenzene is reaction medium, can obtain muriate 1a productive rate 92%; The resynthesis ionic liquid (is used 2a, 2b, 2c, 2d, 2e, 2f represents), with synthetic muriate 1a respectively with Tetrafluoroboric acid or sulfuric acid or phosphoric acid or tosic acid or trifluoroacetic acid or 1-chloroacetate reaction, reaction is a medium with the methylene dichloride, is refluxing and is blasting the functionalization acidic ionic liquid that reaction can obtain based on pyridylium in 24 hours under the reaction conditions of nitrogen, wherein reacting the ionic liquid that obtains with Tetrafluoroboric acid is flaxen oily matter, productive rate 95%; The ionic liquid that obtains with sulfuric acid reaction is flaxen oily matter, productive rate 99%; The ionic liquid that obtains with phosphatase reaction is flaxen oily matter, productive rate 98.5%; The ionic liquid that obtains with the trifluoroacetic acid reaction is flaxen oily matter, productive rate 98.5%; The ionic liquid that obtains with the 1-chloroacetate reaction is flaxen oily matter, and productive rate 97% is yellow thickness oily matter with tosic acid reaction gained ionic liquid, productive rate 98%.The present invention is based on the purposes of the functionalization acidic ionic liquid of pyridylium as preparation jasmal, two kinds of spices of benzyl propionate; Having proposed a kind of is the jasmal of reaction medium and catalysts, the new synthetic method of benzyl propionate with the pyridyl acidic ionic liquid.
A kind of functionalization acidic ionic liquid that adopts quaternary ammoniated, ion-exchange two step method synthetic based on pyridylium of the present invention, press routine step and carry out:
The synthesizing chlorinated thing of step 1: with pyridine, benzyl chloride is the starting raw material of reaction, add non-polar organic solvent toluene or dimethylbenzene, earlier low temperature 0-5 ℃ of reaction 8 hours, after go under the room temperature reaction 24 hours, reacting by heating 24 hours under 60-65 ℃ of condition at last, the gained muriate is the high-hydroscopicity white crystal, fusing point: 125-128 ℃;
Step 2 is synthesized ionic liquid: 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 the functionalization acidic ionic liquid based on pyridylium, be flaxen oily matter with Tetrafluoroboric acid or sulfuric acid or phosphoric 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;
The chemical structure of synthetic ionic liquid is:
Organic cation is the positively charged ion of pyridine benzyl methyl derivatize.
The selected 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 of the functionalization acidic ionic liquid based on pyridylium follows these steps to carry out:
Synthesizing chlorinated thing
A, with the pyridine behind non-polar organic solvent toluene or dimethylbenzene and the purifying mix to stir make reactant become homogeneous phase after, reactant is placed ice-water bath, in the time of 0-5 ℃, drip the normal benzyl chloride of 1.1-1.15 and reacted 8 hours;
B, with the reactant incubated overnight, at room temperature reacted then 24 hours, be warming up to 65-70 ℃ of reaction 24 hours again, reaction needs to carry out under lucifuge and nitrogen protection environment, after reaction finished, cooling was fully separated out crude product;
After c, crude product carry out suction filtration, ethyl acetate thorough washing successively, obtained product in 8 hours in 70 ℃ of following vacuum-dryings, target compound is the high-hydroscopicity white crystal, fusing point: 125-128 ℃;
Synthetic ionic liquid
D, 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;
E, with reaction system under reflux state and blasted nitrogen reaction 24 hours, can obtain the functionalization acidic ionic liquid based on pyridylium, be flaxen oily matter with Tetrafluoroboric acid or sulfuric acid or phosphoric 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.
A kind of functionalization acidic ionic liquid based on pyridylium is as the purposes of preparation jasmal, two kinds of spices of benzyl propionate, and wherein the synthetic method of jasmal is:
Molar ratio of material: phenylcarbinol: glacial acetic acid: ionic liquid=1: 1.5: 0.5;
Temperature of reaction is 80 ± 2 ℃, 4 hours reaction times;
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 ester phase and ionic liquid phase, ionic liquid phase is fully extracted with anhydrous diethyl ether or ethyl acetate, merge extraction phase and ester mutually, be rotated evaporation process and obtain the product jasmal;
Recycling of ionic liquid: the ionic liquid after will extracting joins in a large amount of anhydrous diethyl ethers, remain on the fully reaction phase-splitting after 6-8 hour down of fierce reflux conditions, ionic liquid phase revolve earlier steam tell solvent after, ℃ dry down more than 8 hours in 5-10mmHg vacuum tightness, 80-85 again, ionic liquid promptly can be recycled, and its catalytic reaction activity has decline slightly.
The synthetic method of benzyl propionate:
Reaction mass mol ratio: phenylcarbinol: propionic acid: ionic liquid=1: 1.5: 0.5;
Temperature of reaction is 110 ± 2 ℃, 4 hours reaction times;
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 ester phase and ionic liquid phase, ionic liquid phase is fully extracted with anhydrous diethyl ether, merge extraction phase and ester mutually, carefully be rotated evaporation process and obtain the product jasmal;
Recycling of ionic liquid: the ionic liquid after will extracting joins in a large amount of anhydrous diethyl ethers, remain on the fully reaction phase-splitting after 6-8 hour down of fierce reflux conditions, ionic liquid phase revolve earlier steam tell solvent after, ℃ dry down more than 8 hours in 5-10mmHg vacuum tightness, 80-85 again, ionic liquid promptly can be recycled, and the catalytic activity of its esterification has decline slightly.
The synthetic method of the functionalization acidic ionic liquid based on pyridine of the present invention, it is synthetic by following two-step synthesis
1) quaternary ammoniated:
Earlier reaction substrate pyridine (need make purification process before using) 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 the slowly excessive slightly benzyl chloride of dropping at low temperatures.Drip complete insulation reaction and spend the night, reaction was warmed up to 65-75 degree reaction 24 hours (TLC follows 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 with the interior temperature drop of reaction system to room temperature, crude product is fully separated out, filter to collect and to obtain crude product, crude product again with organic solvent thorough washing such as ether or ethyl acetate to remove residual last reaction raw materials, obtain muriate (representing) in vacuum-drying at last with 1a.
2) 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 at polar solvent. weak point is that long reaction time, prepared using are insufficient, product purification is difficult.The anionic acid that we have designed exchanging in this is synthetic is the liquid phase synthesizing method of reaction medium as reaction raw materials, methylene dichloride, improve utilization ratio of raw materials, reduced the reaction times, because reaction is chosen in reflux state and carries out, and in reactive system, blast these measures of nitrogen adopt work can be in time, effectively by product HCl gas is discharged from reactive system, (use 2a, 2b thereby obtained the good product ion liquid of purity and outward appearance, 2c, 2d, 2e, 2f represents).
In being furnished with the there-necked flask that acid gas absorption bottle and nitrogen inserts bottom tube, muriate 1a is dissolved in a large amount of methylene dichloride, at low temperatures with the intensive agitation condition under, slowly drip the mineral acid or the organic acid of equivalent.(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) dripped and finished, insulation reaction is spent the night, 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 product through vacuum-drying again.
Employing is the jasmal of reaction medium and catalysts, the green synthesis method of benzyl propionate based on the cationic functionalization acidic ionic liquid of pyridyl.Reaction equation is:
Phenylcarbinol and the acetate esterification result in the pyridyl functionalization acidic ionic liquid
| Ionic liquid | Jasmal productive rate (%) |
| | 84.5 92.6 86.5 87.1 92.0 90.6 |
Annotate: productive rate is in thick ester
Phenylcarbinol and the propionic acid esterification result in the pyridyl functionalization acidic ionic liquid
| Ionic liquid | Benzyl propionate productive rate (%) |
| | 67.4 87 82.3 77.6 92 84 |
Annotate: productive rate is in thick ester
Of the present invention based on pyridylium functionalization acidic ionic liquid and the synthetic method of jasmal, benzyl propionate be:
In the there-necked flask of being furnished with magnetic agitation, reflux exchanger, add ionic liquid, phenylcarbinol, the acid 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 hours 80 ± 2 ℃ of reactions: reaction finishes the back because product ester and ionic liquid immiscible, make reaction system become two-phase, the product ester can be adopted with separating of ionic liquid phase thereby product and incline to method easily, for the product ester that fully obtains generating with recycle ionic liquid, use organic solvent extraction ionic liquid phase such as ether, ethyl acetate, merge extraction phase and promptly obtain product jasmal or benzyl propionate except that desolvating with ester is careful mutually.
Ionic liquid phase earlier with organic solvents such as ether, ethyl acetate under reflux state behind the thorough washing, dry more than 8 hours under condition under 80-85 ℃, high vacuum again, can recirculation use, the catalytic reaction activity of ionic liquid has decline slightly.
The situation that recycles of ionic liquid
| Recycle number of times | Alcohol | Acid | Ionic liquid | Alcohol/acid/ionic liquid (mol ratio) | Temperature of reaction (℃) | Reaction times (h) | Productive rate (%) | ||
| 1 2 3 1 2 3 | Phenylcarbinol phenylcarbinol phenylcarbinol phenylcarbinol phenylcarbinol phenylcarbinol | Acetate acetate acetate propionic acid propionic acid | | 2b | 2b | 1∶1.5∶0.5 1∶1.5∶0.5 1∶1.5∶0.5 1∶1.5∶0.5 1∶1.5∶0.5 1∶1.5∶0.5 | 80 80 80 110 110 110 | 4 4 4 4 4 4 | 91.2 87 89.4 84 85.2 81 |
Productive rate is in thick ester
The present invention has following advantage:
Adopt starting raw material inexpensive, that be easy to get: pyridine, benzyl chloride, mineral acid/organic acid have obtained the objective function acidic ionic 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 chemical structure of the ionic liquid that obtains as seen, set out thus and can make further structural modification, as introducing-SO on phenyl ring ionic liquid
3H or the like.
Since the synthetic ionic liquid have acid its can be used as synthetic benzyl acetate, benzyl propionate 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 jasmal, benzyl propionate 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
Muriate 1a's is synthetic:
In being furnished with churned mechanically 50ml there-necked flask, add the pyridine behind 25ml toluene, the 5g purifying successively, open stir make reactant become homogeneous phase after, reactant is placed ice-water bath, drip 1.15 normal benzyl chlorides reactions 8 hours during with 0-5 ℃;
With the reactant incubated overnight, at room temperature reacted then 24 hours, be warming up to the 65-70 reaction again and finished in 24 hours, be reflected under lucifuge and the nitrogen environment and carry out, cooling is fully separated out crude product;
Carry out suction filtration successively, use ethyl acetate organic solvent thorough washing, 70 ℃ of following vacuum-dryings obtained product in 8 hours, and the gained muriate is the high-hydroscopicity white crystal, and fusing point: 125-128 ℃, productive rate 92%.
Ir data (KBr ν/cm
-1): 3127,3036,2963,1630,1489,1454,1159,770.
Proton nmr spectra data (400MHz, D
2O): δ 8.95 (d, J=5.2Hz, 2H), 8.60 (m, 1H), 8.11 (m, J=7.2Hz 2H), 7.52-7.56 (m, 5H), 5.86 (s, 2H).
In the 50ml there-necked flask of being furnished with magnetic agitation, reflux exchanger, acid gas absorption bottle, add the 25ml methylene dichloride successively, 5g muriate 1a (0.0231mol) opens stirring, after the question response system becomes homogeneous phase, reaction system is put into ice-water bath, at interior temperature drop during to 0-5 ℃, beginning slowly drips the equivalent vitriol oil, and insulation reaction is spent the night;
Under reflux state and blasted nitrogen reaction 24 hours, can obtain outward appearance is flaxen oily product 2b 6.11g, productive rate: 99% the acid HSO of the functionalization based on pyridylium with reaction system
4 - Ionic liquid 2b.
Ir data (KBr ν/cm
-1): 3128,2970,2857,2338,1642,1500,1456,1210,882,755,709.
Proton nmr spectra data (400MHz, D
2O): δ 8.95 (d, J=5.2Hz, 2H), 8.60 (m, 1H), 8.11 (m, J=7.2Hz 2H), 7.52-7.56 (m, 5H), 5.86 (s, 2H).
Embodiment 2 ionic liquid 2c's is synthetic
Muriate 1a's is synthetic:
In being furnished with churned mechanically 50ml there-necked flask, add the pyridine behind 25ml toluene, the 5g purifying successively, open stir make reactant become homogeneous phase after, reactant is placed ice-water bath, drip 1.10 normal benzyl chlorides reactions 8 hours during with 0-5 ℃;
With the reactant incubated overnight, at room temperature reacted then 24 hours, be warming up to 65-70 reaction end (be reflected under lucifuge and the nitrogen environment and carry out) in 24 hours cooling again crude product is fully separated out;
Carry out suction filtration successively, use ethyl acetate organic solvent thorough washing, 70 ℃ of following vacuum-dryings obtained product in 8 hours, and the gained muriate is the high-hydroscopicity white crystal, and fusing point: 125-128 ℃, productive rate 92%.
Ionic liquid 2c's is synthetic:
In the 50ml there-necked flask of being furnished with magnetic agitation, reflux exchanger, acid gas absorption bottle, add the 25ml methylene dichloride successively, 5g muriate 1a (0.0231mol) opens stirring, after the question response system becomes homogeneous phase, reaction system is put into ice-water bath, at interior temperature drop during to 0-5 ℃, beginning slowly drips equivalent phosphoric acid, and insulation reaction is spent the night;
Under reflux state and blasted nitrogen reaction 24 hours, can obtain outward appearance is flaxen oily product 2c, productive rate: 98.5% the acid H of the functionalization based on pyridylium with reaction system
2PO
4 -Ionic liquid 2c.
Ir data (KBr ν/cm
-1): 3057,2963,2858,2330,1632,1490,1456,1207,877,750,704
1HNMR(400MHz，D
2O)：δ8.95(d，J＝5.2Hz，2H)，8.60(m，1H)，8.11(m，J＝7.2Hz 2H)，7.52-7.56(m，5H)，5.86(s，2H)
Embodiment 3 ionic liquid 2e's is synthetic
Muriate 1a's is synthetic:
In being furnished with churned mechanically 50ml there-necked flask, add the pyridine behind 25ml dimethylbenzene, the 5g purifying successively, open stir make reactant become homogeneous phase after, reactant is placed ice-water bath, drip 1.13 normal benzyl chlorides reactions 8 hours during with 0-5 ℃;
With the reactant incubated overnight, at room temperature reacted then 24 hours, be warming up to 65-70 reaction end (be reflected under lucifuge and the nitrogen environment and carry out) in 24 hours cooling again crude product is fully separated out;
Carry out suction filtration successively, use ethyl acetate organic solvent thorough washing, 70 ℃ of following vacuum-dryings obtained product in 8 hours, and the gained muriate is the high-hydroscopicity white crystal, and fusing point: 125-128 ℃, productive rate 92%.
Ionic liquid 2e's is synthetic:
In the 50ml there-necked flask of being furnished with magnetic agitation, reflux exchanger, acid gas absorption bottle, add the 25ml methylene dichloride successively, 5g muriate 1a (0.0231mol) opens stirring, after the question response system becomes homogeneous phase, reaction system is put into ice-water bath, at interior temperature drop during to 0-5 ℃, beginning slowly drips the equivalent trifluoroacetic acid, and insulation reaction is spent the night;
Under reflux state and blasted nitrogen reaction 24 hours, can obtain outward appearance is flaxen oily product 2e, productive rate: 98.5% the acid CF of the functionalization based on pyridylium with reaction system
3COO
- Ionic liquid 2e.
Ir data: (KBr ν/cm
-1) 3132,3056,2963,2860,2580,2099,1689.5,1489.9,1456.6,1200,1127,825,750,685.
Proton nmr spectra data (400MHz, D
2O): δ 8.95 (d, J=5.2Hz, 2H), 8.60 (m, 1H), 8.11 (m, J=7.2Hz 2H), 7.52-7.56 (m, 5H), 5.86 (s, 2H)
Embodiment 4 ionic liquid 2d's is synthetic
Muriate 1a's is synthetic:
In being furnished with churned mechanically 50ml there-necked flask, add the pyridine behind 25ml toluene, the 5g purifying successively, open stir make reactant become homogeneous phase after, reactant is placed ice-water bath, drip 1.12 normal benzyl chlorides reactions 8 hours during with 0-5 ℃;
With the reactant incubated overnight, at room temperature reacted then 24 hours, be warming up to 65-70 reaction end (be reflected under lucifuge and the nitrogen environment and carry out) in 24 hours cooling again crude product is fully separated out;
Carry out suction filtration successively, use ethyl acetate organic solvent thorough washing, 70 ℃ of following vacuum-dryings obtained product in 8 hours, and the gained muriate is the high-hydroscopicity white crystal, and fusing point: 125-128 ℃, productive rate 92%.
Ionic liquid 2d's is synthetic:
In the 50ml there-necked flask of being furnished with magnetic agitation, reflux exchanger, acid gas absorption bottle, add the 25ml methylene dichloride successively, 5g muriate 1a (0.0231mol) opens stirring, after the question response system becomes homogeneous phase, reaction system is put into ice-water bath, at interior temperature drop during to 0-5 ℃, gradation adds equivalent solid phase toluenesulphonic acids, and insulation reaction is spent the night;
Under reflux state and blasted nitrogen reaction 24 hours, can obtain outward appearance is faint yellow thickness oily product 2d, productive rate: 98% the acid p-CH of the functionalization based on pyridylium with reaction system
3C
6H
4SO
3 -Ionic liquid 2b.
Ir data: (KBr ν/cm
-1) 3131,3058,2963,2927,2860,2588,2426,1632,1490.5,1455,1388,818,750,683.
Proton nmr spectra data (400MHz, D
2O) δ 8.95 (d, J=5.2Hz, 2H), 8.60 (m, 1H), 8.11 (m, J=7.2Hz, 2H), 7.52-7.56 (m, 5H), 7.06-8.11 (q, 4H), 5.86 (s, 2H), 1.35 (t, 3H).
Embodiment 5 ionic liquid 2f's is synthetic
Muriate 1a's is synthetic:
In being furnished with churned mechanically 50ml there-necked flask, add the pyridine behind 25ml dimethylbenzene, the 5g purifying successively, open stir make reactant become homogeneous phase after, reactant is placed ice-water bath, drip 1.15 normal benzyl chlorides reactions 8 hours during with 0-5 ℃;
With the reactant incubated overnight, at room temperature reacted then 24 hours, be warming up to 65-70 reaction end (be reflected under lucifuge and the nitrogen environment and carry out) in 24 hours cooling again crude product is fully separated out;
Carry out suction filtration successively, use ethyl acetate organic solvent thorough washing, 70 ℃ of following vacuum-dryings obtained product in 8 hours, and the gained muriate is the high-hydroscopicity white crystal, and fusing point: 125-128 ℃, productive rate 92%.
Ionic liquid 2f's is synthetic:
In the 50ml there-necked flask of being furnished with magnetic agitation, reflux exchanger, acid gas absorption bottle, add the 25ml methylene dichloride successively, 5g muriate 1a (0.0231mol) opens stirring, after the question response system becomes homogeneous phase, reaction system is put into ice-water bath, at interior temperature drop during to 0-5 ℃, gradation adds equivalent solid phase 1-Mono Chloro Acetic Acid, and insulation reaction is spent the night;
Under reflux state and blasted nitrogen reaction 24 hours, can obtain outward appearance is flaxen oily product 2f, productive rate: 97% the acid ClCH of the functionalization based on pyridylium with reaction system
2COO
- Ionic liquid 2f.
Ir data: (KBr ν/cm
-1) 3128,3053,2928,2587,2533.5,1975,1737,1632,1489,1456,1162,770,747,704.
Proton nmr spectra data: (400MHz, D
2O) δ 8.95 (d, J=5.2Hz, 2H), 8.60 (m, 1H), 8.11 (m, J=7.2Hz, 2H), 7.52-7.56 (m, 5H), 5.86 (s, 2H), 4.32 (s, 3H).
Embodiment 6 ionic liquid 2a's is synthetic
Muriate 1a's is synthetic:
In being furnished with churned mechanically 50ml there-necked flask, add the pyridine behind 25ml toluene, the 5g purifying successively, open stir make reactant become homogeneous phase after, reactant is placed ice-water bath, drip 1.15 normal benzyl chlorides reactions 8 hours during with 0-5 ℃;
With the reactant incubated overnight, at room temperature reacted then 24 hours, be warming up to 65-70 reaction end (be reflected under lucifuge and the nitrogen environment and carry out) in 24 hours cooling again crude product is fully separated out;
Carry out suction filtration successively, use ethyl acetate organic solvent thorough washing, 70 ℃ of following vacuum-dryings obtained product in 8 hours, and the gained muriate is the high-hydroscopicity white crystal, and fusing point: 125-128 ℃, productive rate 92%.
In the 50ml there-necked flask of being furnished with magnetic agitation, reflux exchanger, acid gas absorption bottle, add the 25ml methylene dichloride successively, 5g muriate 1a (0.0231mol) opens stirring, after the question response system becomes homogeneous phase, reaction system is put into ice-water bath, at interior temperature drop during to 0-5 ℃, beginning slowly drips the equivalent Tetrafluoroboric acid, and insulation reaction is spent the night;
Under reflux state and blasted nitrogen reaction 24 hours, product ion liquid 2a is faint yellow oily thing, productive rate 95% with reaction system.
Ir data: (KBr ν/cm
-1) 3075,3060,1683,5190,1490,1460,1065,754,709.
Proton nmr spectra data: (400MHz, D
2O) δ 8.95 (d, J=5.2Hz, 2H), 8.60 (m, 1H), 8.11 (m, J=7.2Hz, 2H), 7.52-7.56 (m, 5H), 5.86 (s, 2H), 4.32 (s, 3H).
Synthesizing of embodiment 7 jasmals
Add 2.42g ionic liquid 2b, 2g phenylcarbinol, 1.63g glacial acetic acid 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;
(timing sampling GC analyzes to follow the tracks of to react and carries 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, inclines to 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 2.6g productive rate 92.6%;
Ionic liquid after the extraction is joined in a large amount of anhydrous diethyl ethers, remain on the fully reaction phase-splitting after 6-8 hour down of fierce reflux conditions, ionic liquid phase revolve earlier steam tell solvent after, ℃ dry down more than 8 hours in 5-10mmHg vacuum tightness, 80-85 again, ionic liquid promptly can be recycled, and its catalytic reaction activity has decline slightly.
Synthesizing of embodiment 8 benzyl propionates
Is being furnished with magnetic agitation, reflux exchanger, add 2.42g ionic liquid 2b in the 25ml there-necked flask successively, 2g phenylcarbinol 2.2g propionic acid, 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 (timing sampling GC analyzes to follow the tracks of to react and carries 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 2.65g productive rate 87%.
Ionic liquid after the extraction is joined in a large amount of anhydrous diethyl ethers, remain on the fully reaction phase-splitting after 6-8 hour down of fierce reflux conditions, ionic liquid phase revolve earlier steam tell solvent after, ℃ dry down more than 8 hours in 5-10mmHg vacuum tightness, 80-85 again, ionic liquid promptly can be recycled, and the catalytic activity of its reaction has decline slightly.
Claims (5)
1, a kind of functionalization acidic ionic liquid that adopts quaternary ammoniated, ion-exchange two step method synthetic based on pyridylium is characterized in that following these steps to carrying out:
The synthesizing chlorinated thing of step 1: with pyridine, benzyl chloride is the starting raw material of reaction, add non-polar organic solvent toluene or dimethylbenzene, earlier low temperature 0-5 ℃ of reaction 8 hours, after go under the room temperature reaction 24 hours, reacting by heating 24 hours under 60-65 ℃ of condition at last, the gained muriate is the high-hydroscopicity white crystal, fusing point: 125-128 ℃;
Step 2 is synthesized ionic liquid: 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 the functionalization acidic ionic liquid based on pyridylium, be flaxen oily matter with Tetrafluoroboric acid or sulfuric acid or phosphoric 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; The chemical structure of synthetic ionic liquid is:
2, the functionalization acidic ionic liquid based on pyridylium according to claim 1 is characterized in that organic cation is the positively charged ion of pyridine benzyl methyl derivatize.
3, the functionalization acidic ionic liquid based on pyridylium according to claim 2 is characterized in that the selected 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.
4, a kind of synthetic method of the functionalization acidic ionic liquid based on pyridylium is characterized in that following these steps to carrying out:
Synthesizing chlorinated thing
A, with the pyridine behind non-polar organic solvent toluene or dimethylbenzene and the purifying mix to stir make reactant become homogeneous phase after, reactant is placed ice-water bath, in the time of 0-5 ℃, drip the normal benzyl chloride of 1.1-1.15 and reacted 8 hours;
B, with the reactant incubated overnight, at room temperature reacted then 24 hours, be warming up to 65-70 ℃ of reaction 24 hours again, reaction needs to carry out under lucifuge and nitrogen protection environment, after reaction finished, cooling was fully separated out crude product;
After c, crude product carry out suction filtration, ethyl acetate thorough washing successively, obtained product in 8 hours in 70 ℃ of following vacuum-dryings, target compound is the high-hydroscopicity white crystal, fusing point: 125-128 ℃;
Synthetic ionic liquid
D, 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;
E, with reaction system under reflux state and blasted nitrogen reaction 24 hours, can obtain the functionalization acidic ionic liquid based on pyridylium, be flaxen oily matter with Tetrafluoroboric acid or sulfuric acid or phosphoric 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.
5, a kind of functionalization acidic ionic liquid based on pyridylium is as the purposes of preparation jasmal, two kinds of spices of benzyl propionate, and wherein the synthetic method of jasmal is:
Molar ratio of material: phenylcarbinol: glacial acetic acid: ionic liquid=1: 1.5: 0.5;
Temperature of reaction is 80 ± 2 ℃, 4 hours reaction times;
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 ester phase and ionic liquid phase, ionic liquid phase is fully extracted with anhydrous diethyl ether or ethyl acetate, merge extraction phase and ester mutually, be rotated evaporation process and obtain the product jasmal;
Recycling of ionic liquid: the ionic liquid after will extracting joins in a large amount of anhydrous diethyl ethers, remain on the fully reaction phase-splitting after 6-8 hour down of fierce reflux conditions, ionic liquid phase revolve earlier steam tell solvent after, ℃ dry down more than 8 hours in 5-10mmHg vacuum tightness, 80-85 again, ionic liquid promptly can be recycled, and its catalytic reaction activity has decline slightly.
The synthetic method of benzyl propionate:
Reaction mass mol ratio: phenylcarbinol: propionic acid: ionic liquid=1: 1.5: 0.5;
Temperature of reaction is 110 ± 2 ℃, 4 hours reaction times;
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 ester phase and ionic liquid phase, ionic liquid phase is fully extracted with anhydrous diethyl ether, merge extraction phase and ester mutually, carefully be rotated evaporation process and obtain the product jasmal;
Recycling of ionic liquid: the ionic liquid after will extracting joins in a large amount of anhydrous diethyl ethers, remain on the fully reaction phase-splitting after 6-8 hour down of fierce reflux conditions, ionic liquid phase revolve earlier steam tell solvent after, ℃ dry down more than 8 hours in 5-10mmHg vacuum tightness, 80-85 again, ionic liquid promptly can be recycled, and the catalytic activity of its esterification has decline slightly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710100464XA CN101033210B (en) | 2007-04-06 | 2007-04-06 | Functionalized acidic ionic liquid based on pyridine cation and its synthetic method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710100464XA CN101033210B (en) | 2007-04-06 | 2007-04-06 | Functionalized acidic ionic liquid based on pyridine cation and its synthetic method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101033210A true CN101033210A (en) | 2007-09-12 |
| CN101033210B CN101033210B (en) | 2010-08-11 |
Family
ID=38729975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710100464XA Expired - Fee Related CN101033210B (en) | 2007-04-06 | 2007-04-06 | Functionalized acidic ionic liquid based on pyridine cation and its synthetic method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101033210B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041606A (en) * | 2012-12-18 | 2013-04-17 | 苏州锦富新材料股份有限公司 | Method for cleansing ionic liquid |
| CN108558662A (en) * | 2018-05-16 | 2018-09-21 | 浙江工业大学 | A kind of method that multi-sulfonic functional ion liquid catalyzes and synthesizes isopropyl palmitate |
| CN113481247A (en) * | 2021-07-20 | 2021-10-08 | 广东浠芮生物科技有限责任公司 | Preparation method of medium-carbon-chain triglyceride |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320962B (en) * | 2011-07-18 | 2013-10-02 | 旭阳化学技术研究院有限公司 | Method for catalytic synthesis of methyl propionate |
-
2007
- 2007-04-06 CN CN200710100464XA patent/CN101033210B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041606A (en) * | 2012-12-18 | 2013-04-17 | 苏州锦富新材料股份有限公司 | Method for cleansing ionic liquid |
| CN103041606B (en) * | 2012-12-18 | 2016-03-02 | 苏州锦富新材料股份有限公司 | A kind of purification method of ionic liquid |
| CN108558662A (en) * | 2018-05-16 | 2018-09-21 | 浙江工业大学 | A kind of method that multi-sulfonic functional ion liquid catalyzes and synthesizes isopropyl palmitate |
| CN108558662B (en) * | 2018-05-16 | 2021-05-07 | 浙江工业大学 | Method for catalytically synthesizing isopropyl palmitate by multi-sulfonic functional ionic liquid |
| CN113481247A (en) * | 2021-07-20 | 2021-10-08 | 广东浠芮生物科技有限责任公司 | Preparation method of medium-carbon-chain triglyceride |
| CN113481247B (en) * | 2021-07-20 | 2022-03-18 | 广东浠芮生物科技有限责任公司 | Preparation method of medium-carbon-chain triglyceride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101033210B (en) | 2010-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101058560A (en) | Acidic ionic liquid based on 1-methyl-3-benzyl imidazole cation, synthetic method and use | |
| CN1046265C (en) | Process for the production of plasticizer and polyol esters | |
| JP4418432B2 (en) | Production method of biodiesel oil | |
| CN101037431A (en) | Method for synthesizing cricoid carbonate by addition reaction of carbon dioxide and epoxy compound ring | |
| CN101033210A (en) | Functionalization acidic ionic liquid based on pyridine cation and its synthetic method and application | |
| CN1396919A (en) | Synthesis of 3,6-dialkyl-5,6-dihydro-4-hydroxy-pyran-2-one | |
| CN1293026C (en) | Process for perparation of (R)-2-alkyl-3-phenyl-1-propanols | |
| CN100345821C (en) | Process for preparation of iopamidol and new intermediates therein | |
| CN1765503A (en) | Quarternary ammonium salt of quinine compound, its preparation method and use | |
| CN102513155B (en) | Ionic liquid supported molecular sieve catalyst for synthesizing biodiesel fuel and preparation method of catalyst | |
| CN104860980A (en) | Ezetimibe synthesis intermediate and preparation method and application thereof | |
| CN1976891A (en) | Method for producing optically active alfa-fluorocarboxylic ester derivative | |
| CN102069010B (en) | Montmorillonite catalyst used in preparation of cyclic carbonate | |
| CN113087740B (en) | Preparation method and application of organotin ionic liquid catalyst | |
| CN112321475B (en) | Gamma-amino acid analogue and synthetic method thereof | |
| CN104086458A (en) | Preparation method for isocyanate ethyl methacrylate | |
| CN1684934A (en) | Process for preparing fluorocarboxylic acids | |
| CN104370953B (en) | (R)-tert-butyl dimethyl siloxy-glutaric acid monoester preparation method | |
| Mohammadi-Aghdam et al. | One-pot synthesis of highly regioselective β-azido alcohols catalyzed by Brønsted acidic ionic liquids | |
| CN101066947A (en) | Br phi nsted acid ionic liquid based on 2,4-dicarboxyl pyridine cation and its synthesis process | |
| CN1339022A (en) | Production of esters | |
| Ooi et al. | anti‐Selective Asymmetric Synthesis of β‐Hydroxy‐α‐amino Acid Esters by the in situ Generated Chiral Quaternary Ammonium Fluoride‐Catalyzed Mukaiyama‐Type Aldol Reaction | |
| Chen et al. | Asymmetric Michael addition of trisubstituted carbanion to nitroalkenes catalyzed by sodium demethylquinine salt in water | |
| CN1810761A (en) | Alkyl fatty ester preparing process | |
| CN1757638A (en) | Imidazole type functional ion liquid having N-substituted amide structure fragment, and its prepn. method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100811 Termination date: 20140406 |