CN108484568A - A method of with the single thiocarbonic acid acrylic ester of ionic liquid-catalyzed preparation - Google Patents
A method of with the single thiocarbonic acid acrylic ester of ionic liquid-catalyzed preparation Download PDFInfo
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- CN108484568A CN108484568A CN201810295844.1A CN201810295844A CN108484568A CN 108484568 A CN108484568 A CN 108484568A CN 201810295844 A CN201810295844 A CN 201810295844A CN 108484568 A CN108484568 A CN 108484568A
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- Prior art keywords
- acrylic ester
- acid acrylic
- thiocarbonic acid
- ionic liquid
- butyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
- C07D327/04—Five-membered rings
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of in the ionic liquid-catalyzed method for preparing single thiocarbonic acid acrylic ester, and using carbonyl sulfide and propylene oxide as raw material, using ionic liquid as catalyst, single thiocarbonic acid acrylic ester is obtained by the reaction in this method in autoclave.The ionic-liquid catalyst that the present invention develops has the advantages that high activity, highly selective, the selectivity and conversion ratio for improving carbonyl sulfide, by being evaporated under reduced pressure in the reusable reaction for synthesizing single thiocarbonic acid acrylic ester with propylene oxide in carbonyl sulfide of catalyst after purification；The single thiocarbonic acid acrylic ester process of present invention preparation is simple, and easy to operate, reaction condition is mild, and reaction rate is fast, reaction process environmental protection.
Description
Technical field
The invention belongs to heterogeneous catalysis field technical fields, and in particular to a kind of with the single thio carbon of ionic liquid-catalyzed preparation
The method of acid propylene ester.
Background technology
Ring list sulfocarbonate is potential polar non-solute, drug synthesis intermediate, and prepares high refractive power and refer to
The monomer etc. of number resin Polythiocarbonate.Therefore the synthesis of research ring list sulfocarbonate has important value.
Carbonyl sulfide is atmosphere pollution, and is industrial waste gas, but it is also a kind of important chemical synthesis raw material, profit
Ring list sulfocarbonate is prepared with carbonyl sulfide and epoxide reaction, it is valuable on the one hand can to efficiently use carbonyl sulfide synthesis
The Organic chemical products of value；On the other hand this reaction has very high Atom economy, meets green chemistry principles.
Inventor has found that five-membered ring list sulfocarbonate can be logical by carbonyl sulfide and epoxyalkane in experimental study
Cross cycloaddition reaction realization, such as 107619405 A of CN, in the patent using chiral (R)-propylene oxide with carbonyl sulfide in gold
(R)-mono- thiocarbonic acid acrylic ester is formed under the catalysis of Chinine and organic amine；It is disclosed using epoxy in 107721973 A of CN
Propane carbonyl sulfide is prepared under the catalysis of the Titanium Sieve Molecular Sieve for removing template agent removing and Titanium Sieve Molecular Sieve containing template
Single thiocarbonic acid acrylic ester.Catalyst will be used by preparing single sulfocarbonate, and in all multi-catalysts for being catalyzed this reaction, from
Development and application is not yet received in sub- liquid catalyst.Ionic-liquid catalyst because of itself unique performance, increasingly by
The attention of people.Ionic liquid be made of organic cation and organic or inorganic anion, in room temperature or near room temperature temperature
The lower salt in liquid condition of degree.In the ionic liquid of document report, ionic liquid is mainly quaternary ammonium salt, quaternary alkylphosphonium salt, miaow
The ionic liquid etc. that the cation of azoles and pyridine is formed with inorganic anion.Compared with traditional catalyst, ionic liquid is made
For homogeneous catalyst, the yield of target product and selectivity is made all to improve a lot.Homogeneous catalyst is relative to heterogeneous catalysis
Have many advantages, such as that high activity, highly selective and reaction condition are mild for agent, inventor is in view of ionic liquid is as catalyst
Many advantages, be applied to carbonyl sulfide and propylene oxide coupled reaction and prepare in the reacting of single sulfocarbonate, invention
It is effectively catalyzed the technology path of the reaction.
Invention content
The purpose of the present invention is to provide a kind of in the ionic liquid-catalyzed method for preparing single thiocarbonic acid acrylic ester.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
A method of with the single thiocarbonic acid acrylic ester of ionic liquid-catalyzed preparation, using carbonyl sulfide and propylene oxide as raw material,
Using ionic liquid as catalyst, single thiocarbonic acid acrylic ester is obtained by the reaction in autoclave, chemical equation is such as（1）Formula institute
Show：
（1）Formula
The list thiocarbonic acid acrylic ester is the mixture of structural formula 1 and structural formula 2 in chemical equation.
Preferably, the concrete operations of the present invention in the ionic liquid-catalyzed method for preparing single thiocarbonic acid acrylic ester walk
It is rapid as follows：
The propylene oxide of certain mass is added in autoclave, 0.1 ~ 5% ratio that weight is added in propylene oxide is added
Ionic-liquid catalyst under uniform stirring, is passed through 0.5 ~ 5.0 MPa carbonyl sulfides, reacts 1 ~ 24 hour, obtain at 50 ~ 150 DEG C
Crude product, through being evaporated under reduced pressure up to product list thiocarbonic acid acrylic ester.
Preferably, the ionic liquid described in step is 1- butyl -3- methylimidazole bromines borate, 1- butyl -3- methyl
Imidazoles borofluoride, 1- butyl -3- methylimidazoles fluorophosphate, 1- ethyl-3-methylimidazoles borofluoride, normal-butyl pyridine fluorine
One or two kinds of mixtures of borate.
Preferably, carbonyl sulfide pressure is 1.0 ~ 3.0 MPa in the step, temperature is 60 ~ 100 DEG C, reaction time 1
~ 6 hours.
The present invention compared with prior art, has the following advantages that：
1. the ionic-liquid catalyst that the present invention develops has the advantages that high activity, highly selective, the choosing of carbonyl sulfide is improved
Selecting property and conversion ratio synthesize single sulphur in carbonyl sulfide by the way that the catalyst of vacuum distillation after purification is reusable with propylene oxide
For in the reaction of propene carbonate.
2. simple operations are easy in building-up process of the present invention, reaction condition is mild, and reaction rate is fast, reaction process environmental protection.
Description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of 3 products therefrom of embodiment.
Specific implementation mode
In order to make the objectives, technical solutions and advantages of the present invention clearer, With reference to embodiment, to this
Invention is further described.It should be understood that these descriptions are merely illustrative, and it is not intended to limit the scope of the present invention.
Embodiment 1
2 grams of propylene oxide are added in 10ml autoclaves, 1- butyl -3- methyl miaows are added by the 2% of propylene oxide quality
Azoles bromine borate ion liquid catalyst under uniform stirring, is passed through carbonyl sulfide to 2 MPa pressure, it is small that 1 is reacted at 100 DEG C
When, it slowly deflates after being cooled to room temperature, crude product liquid is obtained by filtration, obtain single thiocarbonic acid acrylic ester through vacuum distillation, pass through
Nucleus magnetic hydrogen spectrum measures yield, and single thiocarbonic acid acrylic ester products collection efficiency result is as shown in table 1 below.
Embodiment 2
2 grams of propylene oxide are added in 10ml autoclaves, 1- butyl -3- methyl is added by the 0.5% of propylene oxide quality
Imidazoles borofluoride ion liquid catalyst under uniform stirring, is passed through carbonyl sulfide to 3 MPa pressure, it is small that 2 is reacted at 80 DEG C
When, it slowly deflates after being cooled to room temperature, crude product liquid is obtained by filtration, obtain single thiocarbonic acid acrylic ester through vacuum distillation, pass through
Nucleus magnetic hydrogen spectrum measures yield, and single thiocarbonic acid acrylic ester products collection efficiency result is as shown in table 1 below.
Embodiment 3
2 grams of propylene oxide are added in 10ml autoclaves, 1- butyl -3- methyl is added by the 0.1% of propylene oxide quality
Imidazoles fluorophosphate ionic-liquid catalyst under uniform stirring, is passed through carbonyl sulfide to 5 MPa pressure, it is small that 6 is reacted at 70 DEG C
When, it slowly deflates after being cooled to room temperature, crude product liquid is obtained by filtration, obtain single thiocarbonic acid acrylic ester through vacuum distillation, pass through
Nucleus magnetic hydrogen spectrum measures yield, and single thiocarbonic acid acrylic ester products collection efficiency result is as shown in table 1 below.
Embodiment 4
2 grams of propylene oxide are added in 10ml autoclaves, 1- ethyl -3- methyl miaows are added by the 1% of propylene oxide quality
Azoles borofluoride ion liquid catalyst under uniform stirring, is passed through carbonyl sulfide to 1 MPa pressure, it is small that 3 is reacted at 60 DEG C
When, it slowly deflates after being cooled to room temperature, crude product liquid is obtained by filtration, obtain single thiocarbonic acid acrylic ester through vacuum distillation, pass through
Nucleus magnetic hydrogen spectrum measures yield, and single thiocarbonic acid acrylic ester products collection efficiency result is as shown in table 1 below.
Embodiment 5
2 grams of propylene oxide are added in 10ml autoclaves, normal-butyl pyridine fluoboric acid is added by the 5% of propylene oxide quality
Ionic liquid catalyst under uniform stirring, is passed through carbonyl sulfide to 2 MPa pressure, reacts 5 hours, be cooled at 90 DEG C
It slowly deflates after room temperature, crude product liquid is obtained by filtration, obtain single thiocarbonic acid acrylic ester through vacuum distillation, surveyed through nucleus magnetic hydrogen spectrum
Volume production rate, single thiocarbonic acid acrylic ester products collection efficiency result are as shown in table 1 below.
Table 1：The test result of the reaction product of Examples 1 to 5.
Note：The yield of structural formula 1 and 2 products specifically refers to after removing whole solvents and monomer, according to nuclear-magnetism hydrogen
The molar ratio of proton in spectrum on the methine of two kinds of products is calculated, and the two yield summation regards 100% as.
The product nucleus magnetic hydrogen spectrum figure obtained in embodiment 3 is as shown in Figure 1, each proton peak is respectively at product 1 and 2 in Fig. 1
On proton correspond to, such as peak a and b correspond to methine protons and methene proton on product 1 respectively.Two kinds of products rub
You are also equal to the molar ratio of two kinds of methene protons than being equal to the molar ratio of two kinds of methine protons on spectrogram simultaneously.
Although embodiments of the present invention are described in detail, it should be understood that, without departing from the present invention's
In the case of spirit and scope, can embodiments of the present invention be made with various changes, replacement and change.
Claims (5)
1. a kind of in the ionic liquid-catalyzed method for preparing single thiocarbonic acid acrylic ester, it is characterised in that：With carbonyl sulfide and ring
Ethylene Oxide is raw material, and using ionic liquid as catalyst, single thiocarbonic acid acrylic ester, chemistry side are obtained by the reaction in autoclave
Formula is such as（1）Shown in formula：
（1）Formula
It is described list thiocarbonic acid acrylic ester be（1）The mixture of structural formula 1 and structural formula 2 in formula.
2. according to the method described in claim 1, it is characterized in that：The method is as follows：In autoclave
Propylene oxide is added, ionic-liquid catalyst is added in 0.1 ~ 5% ratio that weight is added by propylene oxide, logical under uniform stirring
Enter 0.5 ~ 5.0 MPa carbonyl sulfides, reacted 1 ~ 24 hour at 50 ~ 150 DEG C, obtain crude product, through being evaporated under reduced pressure up to product list
Thiocarbonic acid acrylic ester.
3. method according to claim 1 or 2, it is characterised in that：The ionic liquid is 1- butyl -3- methylimidazole bromines
Borate, 1- butyl -3- methylimidazoles borofluoride, 1- butyl -3- methylimidazoles fluorophosphate, 1- ethyl-3-methylimidazoles
One or two kinds of mixtures of borofluoride, normal-butyl pyridine borofluoride.
4. method according to claim 1 or 2, it is characterised in that：The ionic liquid is 1- butyl -3- methylimidazole fluorine
Borate.
5. method according to claim 1 or 2, it is characterised in that：1.0 ~ 3.0 MPa carbonyl sulfides are passed through, 60 ~ 100
It is reacted 1 ~ 6 hour at DEG C.
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| CN201810295844.1A CN108484568A (en) | 2018-04-04 | 2018-04-04 | A method of with the single thiocarbonic acid acrylic ester of ionic liquid-catalyzed preparation |
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| CN201810295844.1A CN108484568A (en) | 2018-04-04 | 2018-04-04 | A method of with the single thiocarbonic acid acrylic ester of ionic liquid-catalyzed preparation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108640899A (en) * | 2018-05-10 | 2018-10-12 | 杭州普力材料科技有限公司 | A kind of preparation method of list thiocarbonic acid acrylic ester |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153104A (en) * | 2015-08-18 | 2015-12-16 | 广西大学 | Method for synthesizing propylene carbonate |
| CN107721973A (en) * | 2017-09-25 | 2018-02-23 | 常熟理工学院 | A kind of method for preparing single thiocarbonic acid propylene |
-
2018
- 2018-04-04 CN CN201810295844.1A patent/CN108484568A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153104A (en) * | 2015-08-18 | 2015-12-16 | 广西大学 | Method for synthesizing propylene carbonate |
| CN107721973A (en) * | 2017-09-25 | 2018-02-23 | 常熟理工学院 | A kind of method for preparing single thiocarbonic acid propylene |
Non-Patent Citations (2)
| Title |
|---|
| JIAJIAN PENG等: ""Cycloaddition of carbon dioxide to propylene oxide catalyzed by ionic liquids"", 《NEW J. CHEM》 * |
| VITTHAL B等: ""Bifunctional Ionic Liquids for the Multitask Fixation of Carbon Dioxide into Valuable Chemicals"", 《CHEMCATCHEM》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108640899A (en) * | 2018-05-10 | 2018-10-12 | 杭州普力材料科技有限公司 | A kind of preparation method of list thiocarbonic acid acrylic ester |
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