CN102942451A - Method for preparing 1,2-diol from oxyalkylene under catalytic action of seleniferous high polymers - Google Patents
Method for preparing 1,2-diol from oxyalkylene under catalytic action of seleniferous high polymers Download PDFInfo
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- CN102942451A CN102942451A CN2012105247834A CN201210524783A CN102942451A CN 102942451 A CN102942451 A CN 102942451A CN 2012105247834 A CN2012105247834 A CN 2012105247834A CN 201210524783 A CN201210524783 A CN 201210524783A CN 102942451 A CN102942451 A CN 102942451A
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Abstract
The invention relates to a method for preparing 1,2-diol from oxyalkylene under the catalytic action of seleniferous high polymers, belonging to the technical field of chemical synthesis of an important organic intermediate 1,2-diol. The method comprises the following steps: by using oxydol as an oxidizer and seleniferous high polymers as a catalyst, reacting at 15-80 DEG C in the presence of a solvent; and after the reaction finishes, carrying out simple filtration to recover the seleniferous high polymer catalyst, distilling the filtrate to respectively recover the unreacted raw materials and solvent, and purifying the product. The method is efficient, clean and environment-friendly, and has the advantage of simple reaction system composition; and the catalyst is stable, and is easy to recover.
Description
Technical field
The present invention relates to important organic intermediate---the chemosynthesis technical field of 1,2-glycol.
Background technology
1,2-glycol is the class important compound in the Chemical Manufacture.For example 1, the 2-cyclohexanediol is an important intermediate of organic synthesis, can be used for synthesizing polyester, diacrylate, epoxy resin diluent, pyrocatechol etc.
1,2-glycol can prepare by olefin oxidation.For example, 1,2-cyclohexanediol can be prepared by tetrahydrobenzene: at first obtain epoxy compounds through oxidation, again through final 1, the 2-cyclohexanediol that generates of hydrolysis.Yet the method often needs to use chemical oxidizing agent when cyclohexene oxide, such as metachloroperbenzoic acid (MCPBA).Reaction also will generate a large amount of by products except generating product, Atom economy is poor.It is as follows that epoxidation of cyclohexene prepares the reaction mechanism of 1,2-cyclohexanediol:
Recently, take hydrogen peroxide (being commonly called as hydrogen peroxide) as oxygenant, selenium compound obtained certain research as the method for catalyzer direct oxidation alkene.The method mild condition, reaction system is simple, and productive rate is higher, therefore, has potential using value.For example, the people such as Santi are reported under the diselenide catalysis, and alkene can by hydrogen peroxide oxidation, generate 1,2-glycol (Santoro S; Santi C; Sabatini M; Testaferri L; Tiecco M. Eco-friendly olefin dihydroxylation catalyzed by diphenyl diselenide. Advanced Synthesis ﹠amp; Catalysis, 2008,350:2881-2884.).With diphenyl disenenide ether (PhSe)
2Be catalyzer, acetonitrile CH
3CN is that the reaction formula under the solvent situation is as follows:
Yet different from pharmaceutical industry as the intermediate in the large Chemical Manufacture, the price of glycol is not high.And the selenium element, as one of rare and scatter element, difficult acquisition.The selenium-containing compound price is higher.Even if that uses catalytic amount contains the selenium catalyzer, the cost of this reaction also is the selling price that is higher than product usually.Therefore, the method for the small molecules selenium-containing compound catalyzed alkene oxidation that document is reported only limits to theoretical investigation, can not be applied to actual production.
Summary of the invention
The object of the present invention is to provide convenient a kind of method that contains synthetic 1, the 2-glycol of selenium superpolymer catalyzing hydrogen peroxide olefin oxide of producing, can reducing the catalyzer use cost.
The present invention is take alkene as raw material, take hydrogen peroxide as oxygenant, to contain the selenium superpolymer as catalyzer, under 15～80 ℃ of temperature, reacting in the presence of the solvent, after finishing, reaction contains selenium superpolymer catalyzer by filtered and recycled, by the distillation reclaim respectively unreacted raw material and solvent after, obtain 1,2-glycol; The mol ratio of described hydrogen peroxide and alkene is 0.5～2: 1; Describedly contain that the molar fraction of selenium element and alkene is 0.1%～5.0% in the selenium superpolymer.
Utilization of the present invention contains the oxidation of selenium superpolymer catalyzed alkene, and its novelty is: (1) regulates and control out optimum reaction condition by experiment, so that catalyst levels is reduced to 0.1～5 mol%, greatly reduces the use cost of catalyzer; (2) the selenium catalyzer that is carried on the superpolymer is insoluble in reaction solution, therefore, can recycle by filtering easily after reaction finishes, and further reduces reaction cost; (3) among the present invention, the recycling flow process of catalyzer is simple.
In addition, alkene of the present invention is a kind of of tetrahydrobenzene, vinylbenzene, chlorallylene, vinyl carbinol or derivatives thereof.Preferred loaded by polystyrene selenous acid.
Oxygenant of the present invention is that concentration of volume percent is 10%～50% aqueous hydrogen peroxide solution.Wherein preferred concentration is 27.5%.
The selenium superpolymer that contains of the present invention is in selenium methyl, selenium alkyl, selenium aryl, selenium sodium, selenous acid or the selenite that is carried on the polystyrene any one.
Described solvent is any one in acetonitrile, water, ethanol or the acetic acid.Preferred acetonitrile.
Described reaction is that lower and temperature is to carry out under 20～30 ℃ of conditions often pressing.
Described distillation is to steam solvent first under normal pressure and 80～100 ℃ of conditions, then is decompressed to 1～50mmHg, and steams product under 70～160 ℃ of conditions.Selected pressure and temperature depends on the boiling point of related compound.
Utilization of the present invention contains the oxidation of selenium superpolymer catalyzed alkene and prepares 1,2-glycol, the method cleaning, environmental protection, atom economy.And can come decrease catalyzer use cost by recycled for multiple times.
Embodiment
The following examples are set forth in more detail to the present invention, rather than limitation of the invention further.
Embodiment 1
In a 100mL round-bottomed flask, add 16.4g(0.2 mol) tetrahydrobenzene, 1.34 gram loaded by polystyrene selenous acid (cat A) (1% is crosslinked, and selenium element charge capacity is 1.45mmol/g, and the use molar ratio of amounting to selenium element and tetrahydrobenzene is 1%), 20 mL acetonitriles stir 10min.Add again the volume percentage and be 27.5% superoxol 25g(0.2mol), 30 ℃ are stirred 24h.Filtering separation contained the selenium superpolymer after reaction finished, and filtrate steams solvent acetonitrile and water first in 80～100 ℃ of distillations of normal pressure; Decompression step by step to 15 mmHg after being cooled to below 50 ℃ begins heating after vacuum is stable, collect 110～120 ℃ cut, steams 1,2-cyclohexanediol 19.3g.Productive rate 95%.
But the follow-up also recirculation of selenium superpolymer catalyzer that contains of Separation and Recovery is used catalyzer 9 times.Experimental result is as shown in table 1.
Table 1 selenium catalyst recovery is utilized situation
| Cycle index | 1 | 2 | 3 | 4 | 5 |
| Product yield (unit: %) | 93 | 90 | 86 | 84 | 91 |
| Cycle index | 6 | 7 | 8 | 9 | 10 |
| Product yield (unit: %) | 85 | 87 | 80 | 82 | 78 |
Embodiment 2
Be catalyzer (detailed structure is seen following formula) with the other kinds selenium superpolymer that contains, other conditions are with embodiment 1, and experimental result is as shown in table 2.
Table 2 different catalysts is on the impact of productive rate
| Catalyzer | catB | catC | catD | catE | catF | catG | catH |
| Product yield (unit: %) | 32 | 31 | 28 | 89 | 85 | 30 | 36 |
The result shows that loaded by polystyrene selenous acid (catA) catalytic effect is best.
The selenium superpolymer that contains involved in the present invention is the selenium compound that is carried on the polystyrene, its preparation method can be with reference to the Ming doctor's Diplomarbeit of disclosed Zhejiang University xuwei " preparation of loaded by polystyrene organoselenium reagent and the application in organic synthesis thereof " in 2005, its molecular structure example following (ball of black represents polystyrene chain):
Embodiment 3
Substitute acetonitrile with other solvents, other conditions are with embodiment 1, and experimental result sees Table 3.
Table 3 different solvents is on the impact of productive rate
| Solvent | Ethanol | Water | Acetic acid |
| Product yield (unit: %) | 89 | 55 | 76 |
Experimental result shows that acetonitrile is optimum solvent.
Embodiment 4
Take embodiment 1 disclosed reaction as the basis, the present invention has also investigated the effect of this reaction under differing temps.This reaction all can be carried out at 15～80 ℃, wherein with 30 ℃ of the bests as a result, the results are shown in Table 4.
Table 4 differential responses temperature is on the impact of productive rate
| Temperature (unit: ℃) | 15 | 25 | 60 | 80 |
| Product yield (unit: %) | 70 | 93 | 89 | 76 |
Embodiment 5
The present invention has also investigated the reaction effect of different catalysts consumption, and other condition the results are shown in Table 5 with embodiment 1.Experimental result shows catalyst levels 1 mol% best results (pressing the selenium element calculates) (embodiment 1).
Table 5 different catalysts consumption is on the impact of productive rate
| Catalyst levels (mol% is based on tetrahydrobenzene) | 5 | 0.5 | 0.1 |
| Product yield (unit: %) | 85 | 93 | 88 |
Embodiment 6
By changing the consumption of solvent, the contriver has also studied the impact of reaction solution concentration on reaction, and other condition is with embodiment 1, and the result is as shown in table 6, shows reaction density 10M best (embodiment 1).
Table 6 differential responses liquid concentration is on the impact of productive rate
| Reaction solution concentration/M | 1 | 2 | 5 | 15 | 20 |
| Product yield/% | 79 | 84 | 88 | 83 | 75 |
Embodiment 7
Hydrogen peroxide concentration also has certain influence to reaction, and the contriver is studied this, and other condition is with embodiment 1, and the result is as shown in table 7.The result represents hydrogen peroxide concentration 27.5% the best (embodiment 1)
The different hydrogen peroxide concentrations of table 7 are on the impact of productive rate
| Hydrogen peroxide concentration/% | 10 | 30 | 50 |
| Product yield/% | 56 | 91 | 78 |
Embodiment 8
The hydrogen peroxide consumption also has certain influence to reaction result, and the contriver has carried out certain research to this, and all the other conditions are with embodiment 1(hydrogen peroxide/tetrahydrobenzene 1:1).The result is as shown in table 8:
The different hydrogen peroxide consumptions of table 8 are on the impact of productive rate
| Hydrogen peroxide mole number/tetrahydrobenzene mole number | 0.5:1 | 0.8:1 | 1.2:1 | 1.5:1 | 2.0:1 |
| Product yield/% | 40 | 72 | 94 | 96 | 98 |
As seen from the above table, the excessive productive rate that improves of hydrogen peroxide, but for the consideration of safety and cost two aspects, hydrogen peroxide still will use the 1:1 amount.In embodiment 1, reaction finishes post analysis detection hydrogen peroxide and has consumed idle most.
Embodiment 9
The present invention has also checked a series of other alkene, and the result shows that the method range of application is wider, applicable to other a series of alkene.As shown in table 9:
The oxidation of table 9 different alkene
| Alkene | Vinylbenzene | Vinyl carbinol | Chlorallylene | To bromstyrol | Cyclopentenes |
| Glycol productive rate/% | 87 | 71 | 87 | 76 | 90 |
Claims (10)
1. one kind contains that olefin oxide prepares 1 under the catalysis of selenium superpolymer, the method of 2-glycol, it is characterized in that: take alkene as raw material, take hydrogen peroxide as oxygenant, to contain the selenium superpolymer as catalyzer, under 15～80 ℃ of temperature, reacting in the presence of the solvent, after finishing, reaction contains selenium superpolymer catalyzer by filtered and recycled, by the distillation reclaim respectively unreacted raw material and solvent after, obtain 1,2-glycol; The mol ratio of described hydrogen peroxide and alkene is 0.5～2: 1; Describedly contain that the molar fraction of selenium element and alkene is 0.1%～5.0% in the selenium superpolymer.
2. preparation method according to claim 1 is characterized in that: described alkene is a kind of of tetrahydrobenzene, vinylbenzene, chlorallylene, vinyl carbinol or derivatives thereof.
3. preparation method according to claim 1, it is characterized in that: described oxygenant is that concentration of volume percent is 10%～50% aqueous hydrogen peroxide solution.
4. preparation method according to claim 3, it is characterized in that: the concentration of described aqueous hydrogen peroxide solution is 27.5%.
5. preparation method according to claim 1 is characterized in that: the described selenium superpolymer that contains is in selenium methyl, selenium alkyl, selenium aryl, selenium sodium, selenous acid or the selenite that is carried on the polystyrene any one.
6. preparation method according to claim 5, it is characterized in that: the described selenium superpolymer that contains is the loaded by polystyrene selenous acid.
7. preparation method according to claim 1, it is characterized in that: described solvent is any one in acetonitrile, water, ethanol or the acetic acid.
8. preparation method according to claim 7, it is characterized in that: described solvent is acetonitrile.
9. preparation method according to claim 1 is characterized in that: described reaction is to be to carry out under 20～30 ℃ of conditions pressing normal lower and temperature.
10. preparation method according to claim 1 is characterized in that: described distillation is to steam solvent first under normal pressure and 80～100 ℃ of conditions, then is decompressed to 1～50mmHg, and steams product under 70～160 ℃ of conditions.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447204A (en) * | 2013-09-12 | 2015-03-25 | 中国科学院大连化学物理研究所 | Preparation method of diol |
| CN104892403A (en) * | 2015-06-08 | 2015-09-09 | 扬州大学 | Synthetic method of benzoic anhydride |
| CN106432739A (en) * | 2016-09-18 | 2017-02-22 | 扬州大学 | Method for synthesizing selenium-containing high polymer |
| CN110102345A (en) * | 2019-05-15 | 2019-08-09 | 扬州大学 | The synthetic method of the catalyst of copolymer containing selenium of catalytic olefin oxidations cracking |
| CN113773418A (en) * | 2021-10-22 | 2021-12-10 | 扬州大学 | Polystyrene selenizing method using diselenide as selenium source |
Citations (1)
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| CN102503774A (en) * | 2011-10-20 | 2012-06-20 | 江苏扬农化工集团有限公司 | Method for synthesizing 1,2-cyclohexanediol by cyclohexene under selenium catalysis |
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2012
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Patent Citations (1)
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| CN102503774A (en) * | 2011-10-20 | 2012-06-20 | 江苏扬农化工集团有限公司 | Method for synthesizing 1,2-cyclohexanediol by cyclohexene under selenium catalysis |
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| GERD-JAN TEN BRINK等: "Selenium catalysed oxidations with aqueous hydrogen peroxide. Part I: epoxidation reactions in homogeneous solution", 《J. CHEM. SOC., PERKIN TRANS. 1》 * |
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| TRUC M. NGUYEN等: "A Novel Reactivity of SeO2 with 1,3-Dienes: Formation of syn 1,2- and 1,4-Diols via a Facile C-Se Bond Oxidation", 《ORG. LETT.》 * |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447204A (en) * | 2013-09-12 | 2015-03-25 | 中国科学院大连化学物理研究所 | Preparation method of diol |
| CN104447204B (en) * | 2013-09-12 | 2016-01-13 | 中国科学院大连化学物理研究所 | A kind of method preparing glycol |
| CN104892403A (en) * | 2015-06-08 | 2015-09-09 | 扬州大学 | Synthetic method of benzoic anhydride |
| CN106432739A (en) * | 2016-09-18 | 2017-02-22 | 扬州大学 | Method for synthesizing selenium-containing high polymer |
| CN106432739B (en) * | 2016-09-18 | 2019-03-29 | 扬州大学 | A method of synthesis high polymer containing selenium |
| CN110102345A (en) * | 2019-05-15 | 2019-08-09 | 扬州大学 | The synthetic method of the catalyst of copolymer containing selenium of catalytic olefin oxidations cracking |
| CN110102345B (en) * | 2019-05-15 | 2021-09-10 | 扬州大学 | Synthetic method of selenium-containing copolymer catalyst for catalyzing olefin oxidative cracking |
| CN113773418A (en) * | 2021-10-22 | 2021-12-10 | 扬州大学 | Polystyrene selenizing method using diselenide as selenium source |
| CN113773418B (en) * | 2021-10-22 | 2024-03-08 | 扬州大学 | Polystyrene selenizing method using diselenide as selenium source |
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