CN107400074A - A kind of method of one pot process dimethyl diselenide ether - Google Patents
A kind of method of one pot process dimethyl diselenide ether Download PDFInfo
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- CN107400074A CN107400074A CN201710742804.2A CN201710742804A CN107400074A CN 107400074 A CN107400074 A CN 107400074A CN 201710742804 A CN201710742804 A CN 201710742804A CN 107400074 A CN107400074 A CN 107400074A
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- C07C391/00—Compounds containing selenium
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Abstract
The invention discloses a kind of method of one pot process dimethyl diselenide ether.The method of described one pot process dimethyl diselenide ether is to be stirred the ethanol solution of borohydride salts with elemental selenium at a temperature of 0 ~ 90 DEG C, add the mixture of ethanol and dimethyl carbonate, under stirring condition 1 ~ 2h of reaction is carried out at 0 ~ 90 DEG C, filter, the distilled water of 0.1 ~ 5 times of filtrate volume is added in filtrate, 1 ~ 3h is stood, then with petroleum ether extraction, merge petroleum ether layer, it is object dimethyl diselenide ether that steaming petroleum ether, which obtains salmon liquid,.
Description
Technical field
The invention belongs to selenium technical field of chemistry, and in particular to a kind of method of one pot process dimethyl diselenide ether.
Background technology
Organic Selenium chemistry is since the 1980s, and with deepening continuously for research, the speed of development is gradually accelerated.
Research process find that some organic selenium compounds can resist cancer, antitumor, anti-oxidant etc..Therefore, the research and development of selenium medicine into
For a study hotspot of medical field.To 20 end of the centurys, biological study field has carried out substantial amounts of research to selenium, and obtains
Many great scientific achievements, greatly accelerate the research and development speed of selenium medicine, just having synthesized four major classes at that time has bioactivity
Organic selenium compounds, be selenide, diselenide, selenium cyanogen and heterocycle containing selenium respectively.Diselenide is important during organic synthesis
Intermediate, its application is more extensive than other three class, and dibenzyl diselenide can be applied to the production of rubber, light guide as a kind of modifying agent
Also there is the participation of dibenzyl diselenide in the solid phase separation of material；The precursor of semi-conducting material can be replaced with two pyridine diselenides；
Some diselenides can be used as sterilizing and sterilize.Due to containing special chemical bond-selenium selenium key on diselenide molecule, in diselenide
With important bioactivity, diselenide can anti-aging, anti-inflammatory, antiviral etc., there is important medical value.
A variety of selenium-containing compounds are disclosed in the prior art, and these compounds all there is good application to dive in multiple fields
Power and value.Therefore, to the synthetic method of these new compounds and known selenium compound, people have carried out unremitting grind
Study carefully, especially the synthesis to selenide compounds, explored a plurality of synthetic route and method at present.
CN101274908A discloses a kind of synthetic method of Organic Selenium ether compound, and methods described is in torpescence gas
Body (such as nitrogen, carbon dioxide) protection under conditions of, using halides and two selenium compounds as raw material, the cerium salt of tetravalence and
The system of the metals such as zinc, iron, magnesium, aluminium composition, such as the O/Zn systems of Ce (SO 4) 2 4H 2, Ce (NO 3) 4/Al
System is catalyst, heating stirring certain time, synthesizes selenide compound.The methods described reaction time is short, yield is high, accessory substance
Less, it is environmentally friendly, it is a kind of method that efficiently easily one kettle way prepares unsymmetrical selenides.
CN1663950A disclose it is a kind of synthesize dibenzyl diselenide method, methods described be with aromatic aldehyde, selenium and
Water is raw material, is passed through carbon monoxide, in organic solvent, 50-100 DEG C of stirring 5-15 hour, is cooled to room temperature, ether extraction
Take, remove the solvent in extract under reduced pressure, obtain product dibenzyl diselenide, this method is to be reacted at ambient pressure, operation
Easy and products collection efficiency is high.
CN1724517A discloses a kind of method for preparing alkyl diselenide, and methods described is in CO ventilation bubblings
Under the conditions of, with fatty aldehyde or aliphatic ketone, selenium and water raw material, so as to which alkyl diselenide be prepared by single step reaction.The party
Method convenient post-treatment, synthesis under normal pressure, it is easy to operate, be not added with any auxiliary reagent, there is good operability and controlling.
CN103724246A discloses a kind of synthetic method of Aryl elemental selenium compound, and the synthetic method is with copper
Compound is as catalyst, in the presence of oxidant and organic ligand, by arylboronic acid compound and simple substance in reaction dissolvent
Selenium Se reacts, and the Aryl elemental selenium compound is made in a step.The synthetic method is simple to operate, catalytic efficiency is good
Well, the purity of product is higher, has good scientific research value and industrial prospect.
CN103739536A discloses a kind of synthetic method of diaryl diselenide compound, and the synthetic method includes
In the presence of alkali and N- N-halosuccinimides, at 40-80 DEG C, aryl boric acid and elemental selenium Se react and
Diaryl diselenide compound has been made.The synthetic method has many advantages, such as, as temperature is low, process is easily controllable, product
Yield and purity are higher etc..
CN10224969A discloses a kind of phenyl-(3- aryl 2-2 acrylic) selenide compounds and preparation method thereof institute
It is that in organic solvent, reaction temperature is -10 DEG C~50 DEG C, with [Ir (COD) Cl] 2 and chiral ligand to state preparation method
The iridium complex of effect generation is catalyst, and allyl carbonate esters compound and the reaction of selenophenol sodium salt, reaction carry out 6-48
After hour, the selenide compounds are made.Compared with prior art, methods described reaction condition is gentle, reaction yield is preferable,
Regioselectivity is high.
As described above, a variety of methods for preparing diaryliodonium are disclosed in the prior art, but these methods are present necessarily
The defects of, such as atom utilization is not ideal enough, yield is not high, the reaction time is long, it is poisonous to also need to use sometimes and to environment
Harmful halide reagent (such as chlorine, bromine).
For these reasons, synthesis Organic Selenium class compound efficiently, gentle, easy and good functional group compatibility is explored,
The new method of especially alkyl selenide ether compound still has great importance, and still suffers from the necessity for continuing to study and exploring,
This is also exactly the basis that the present invention is accomplished and power place.
The content of the invention
It is an object of the invention to provide a kind of method of one pot process dimethyl diselenide ether.
The object of the present invention is achieved like this, is by the ethanol solution and elemental selenium of borohydride salts at a temperature of 0 ~ 90 DEG C
It is stirred, adds the mixture of ethanol and dimethyl carbonate, carry out 1 ~ 2h of reaction under stirring condition at 0 ~ 90 DEG C, filters,
The distilled water of 0.1 ~ 5 times of filtrate volume is added in filtrate, stands 1 ~ 3h, then with petroleum ether extraction, merges petroleum ether layer, boils off
It is object dimethyl diselenide ether that petroleum ether, which obtains salmon liquid,.
The method of synthesis dimethyl diselenide ether of the present invention is efficiently, gentle, easy and functional group compatibility is good, with it
He compares synthetic method, and reactions steps of the present invention are brief, reaction condition is gentle, yield is high, green, is adapted to extensive raw
Production.
Embodiment
With reference to embodiment, the present invention is further illustrated, but the present invention is not any limitation as in any way,
Based on present invention teach that any conversion or replacement made, belong to protection scope of the present invention.
The method of one pot process dimethyl diselenide ether of the present invention, it is by borohydride salts at a temperature of 0 ~ 90 DEG C
Ethanol solution is stirred with elemental selenium, is added the mixture of ethanol and dimethyl carbonate, is entered under stirring condition at 0 ~ 90 DEG C
Row 1 ~ 2h of reaction, filters, the distilled water of 0.1 ~ 5 times of filtrate volume is added in filtrate, stand 1 ~ 3h, then with petroleum ether extraction,
Merge petroleum ether layer, it is object dimethyl diselenide ether that steaming petroleum ether, which obtains salmon liquid,.
Described borohydride salts are the one or more in hydroboration metal salt.
Described borohydride salts are sodium borohydride or potassium borohydride.
The mass concentration of the ethanol solution of described borohydride salts is 95 ~ 99.9%.
The mol ratio of borohydride salts and elemental selenium is 1 ~ 20 in the ethanol solution of borohydride salts:1~5.
Described ethanol and the mixture of dimethyl carbonate form the volume ratio of ethanol and dimethyl carbonate in mixed system
For 1:1~100.
Described ethanol and the mixture of dimethyl carbonate form the volume ratio of ethanol and dimethyl carbonate in mixed system
For 1:5~10.
The temperature of mixed system reaction is 50 DEG C.
Distilled water addition is 1 ~ 2.5 times of filtrate volume.
Embodiment 1
16g selenium grain is taken, 20g sodium borohydrides are sequentially placed into three-neck flask, the second that injection 150ml has crossed in 30 DEG C of heating water baths
Alcohol and dimethyl carbonate mixed liquor（Its mixed proportion is 55ml：95ml）, treat that solution is added dropwise, reaction temperature be warming up to 50
DEG C, at such a temperature after the reaction completely of selenium grain, sustained response 1.5 hours, filter.It is small that filtrate adds 150ml distilled water standing 1
When, filtrate is extracted with petroleum ether, until water layer is close to colourless.Merge petroleum ether layer, 19.1g oranges are obtained after steaming petroleum ether
Red liquid is dimethyl diselenide ether, yield 95.5%.
Embodiment 2
20g selenium grain is taken, 15g sodium borohydrides are sequentially placed into three-neck flask, the second that injection 150ml has crossed in 50 DEG C of heating water baths
Alcohol and dimethyl carbonate mixed liquor（Its mixed proportion is 1ml：100ml）, treat that solution is added dropwise, reaction temperature be warming up to 90
DEG C, at such a temperature after the reaction completely of selenium grain, sustained response 1 hour, filter.It is small that filtrate adds 100ml distilled water standing 1
When, filtrate is extracted with petroleum ether, until water layer is close to colourless.Merge petroleum ether layer, 19.8g oranges are obtained after steaming petroleum ether
Red liquid is dimethyl diselenide ether, yield 97.2%.
Embodiment 3
15g selenium grain is taken, 20g potassium borohydrides are sequentially placed into three-neck flask, the second that injection 150ml has crossed in 50 DEG C of heating water baths
Alcohol and dimethyl carbonate mixed liquor（Its mixed proportion is 10ml：50ml）, treat that solution is added dropwise, reaction temperature be warming up to 40
DEG C, at such a temperature after the reaction completely of selenium grain, sustained response 2 hours, filter.It is small that filtrate adds 200ml distilled water standing 1
When, filtrate is extracted with petroleum ether, until water layer is close to colourless.Merge petroleum ether layer, 21.1g oranges are obtained after steaming petroleum ether
Red liquid is dimethyl diselenide ether, yield 98.1%.
Embodiment 4
5g selenium grain is taken, 15g potassium borohydrides are sequentially placed into three-neck flask, the second that injection 100ml has crossed in 60 DEG C of heating water baths
Alcohol and dimethyl carbonate mixed liquor（Its mixed proportion is 10ml：100ml）, treat that solution is added dropwise, reaction temperature be warming up to
80 DEG C, at such a temperature after the reaction completely of selenium grain, sustained response 1.5 hours, filter.Filtrate adds 100ml distilled water and stands 3
Hour, filtrate is extracted with petroleum ether, until water layer is close to colourless.Merge petroleum ether layer, 16.1g is obtained after steaming petroleum ether
Salmon liquid is dimethyl diselenide ether, yield 95.9%.
Embodiment 5
10g selenium grain is taken, 15g potassium borohydrides are sequentially placed into three-neck flask, the second that injection 80ml has crossed in 20 DEG C of heating water baths
Alcohol and dimethyl carbonate mixed liquor（Its mixed proportion is 50ml：50ml）, treat that solution is added dropwise, reaction temperature be warming up to 60
DEG C, at such a temperature after the reaction completely of selenium grain, sustained response 1.5 hours, filter.It is small that filtrate adds 150ml distilled water standing 2
When, filtrate is extracted with petroleum ether, until water layer is close to colourless.Merge petroleum ether layer, 22.5g oranges are obtained after steaming petroleum ether
Red liquid is dimethyl diselenide ether, yield 98.9%.
Embodiment 6
25g selenium grain is taken, 10g potassium borohydrides are sequentially placed into three-neck flask, the second that injection 120ml has crossed in 30 DEG C of heating water baths
Alcohol and dimethyl carbonate mixed liquor（Its mixed proportion is 50ml：50ml）, treat that solution is added dropwise, reaction temperature be warming up to 70
DEG C, at such a temperature after the reaction completely of selenium grain, sustained response 2 hours, filter.It is small that filtrate adds 100ml distilled water standing 1.5
When, filtrate is extracted with petroleum ether, until water layer is close to colourless.Merge petroleum ether layer, 24.8g oranges are obtained after steaming petroleum ether
Red liquid is dimethyl diselenide ether, yield 97.7%.
Claims (9)
- A kind of 1. method of one pot process dimethyl diselenide ether, it is characterised in that be by borohydride salts at a temperature of 0 ~ 90 DEG C Ethanol solution is stirred with elemental selenium, is added the mixture of ethanol and dimethyl carbonate, is entered under stirring condition at 0 ~ 90 DEG C Row 1 ~ 2h of reaction, filters, the distilled water of 0.1 ~ 5 times of filtrate volume is added in filtrate, stand 1 ~ 3h, then with petroleum ether extraction, Merge petroleum ether layer, it is object dimethyl diselenide ether that steaming petroleum ether, which obtains salmon liquid,.
- 2. the preparation method of high-purity nm selenium material according to claim 1, it is characterised in that described borohydride salts are One or more in hydroboration metal salt.
- 3. the preparation method of high-purity nm selenium material according to claim 1 or 2, it is characterised in that described borohydride salts For sodium borohydride or potassium borohydride.
- 4. the preparation method of high-purity nm selenium material according to claim 1, it is characterised in that described borohydride salts The mass concentration of ethanol solution is 95 ~ 99.9%.
- 5. the preparation method of high-purity nm selenium material according to claim 1, it is characterised in that the ethanol of borohydride salts is molten The mol ratio of borohydride salts and elemental selenium is 1 ~ 20 in liquid:1~5.
- 6. the preparation method of high-purity nm selenium material according to claim 1, it is characterised in that described ethanol and carbonic acid It is 1 that the mixture of dimethyl ester, which forms the volume ratio of ethanol and dimethyl carbonate in mixed system,:1~100.
- 7. the preparation method of the high-purity nm selenium material according to claim 1 or 6, it is characterised in that described ethanol and carbon It is 1 that the mixture of dimethyl phthalate, which forms the volume ratio of ethanol and dimethyl carbonate in mixed system,:5~10.
- 8. the preparation method of high-purity nm selenium material according to claim 1, it is characterised in that the temperature of mixed system reaction Spend for 50 DEG C.
- 9. the preparation method of high-purity nm selenium material according to claim 1, it is characterised in that distilled water addition is filter 1 ~ 2.5 times of liquid product.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735130A (en) * | 2010-01-15 | 2010-06-16 | 广州九益生物技术有限公司 | Method for preparing dimethyl diselenide |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735130A (en) * | 2010-01-15 | 2010-06-16 | 广州九益生物技术有限公司 | Method for preparing dimethyl diselenide |
Non-Patent Citations (4)
| Title |
|---|
| ALAIN KRIEF, 等: "Condition-driven selective syntheses of dialkyl diselenides involving elemental selenium and sodium borohydride", 《SYNLETT》 * |
| LUDWIG SYPER, 等: "The convenient syntheses of organoselenium reagents", 《SYNTHESIS》 * |
| 张小梅，等: "简易方法制备二甲基二硒", 《广州化工》 * |
| 杨祥良，等: "一种合成二硒化钠和有机二硒化物的新方法", 《无机化学学报》 * |
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Effective date of registration: 20191104 Address after: Room 305, building a, innovation and entrepreneurship center, 227 Zixi Avenue, Chuxiong hi tech Zone, Chuxiong Yi Autonomous Prefecture, Yunnan Province Applicant after: Chuxiong hi tech Zone nuclear degree selenium rich Biotechnology Development Co., Ltd. Address before: Panlong District Jinchen Street Village 650000 Yunnan city of Kunming Province, a 31 Building 5 Applicant before: Yunnan Nuclear Biological Industry Development Co., Ltd. |
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