CN102127038B - Method for synthetizing mono-thioether compound - Google Patents
Method for synthetizing mono-thioether compound Download PDFInfo
- Publication number
- CN102127038B CN102127038B CN201110022751XA CN201110022751A CN102127038B CN 102127038 B CN102127038 B CN 102127038B CN 201110022751X A CN201110022751X A CN 201110022751XA CN 201110022751 A CN201110022751 A CN 201110022751A CN 102127038 B CN102127038 B CN 102127038B
- Authority
- CN
- China
- Prior art keywords
- solvent
- compound
- disulfide compound
- carbon monoxide
- water
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for synthetizing mono-thioether compound. The technical scheme adopted by the invention is as follows: in the presence of carbon monoxide and water, disulfide compound and halogenated hydrocarbon compound are used as raw materials, selenium is used as catalyst, organic base or inorganic base is used as cocatalyst or any cocatalyst is not added, the raw materials react in organic solvent at 20-100 DEG C under atmospheric pressure for 1-24 hours, the product is cooled to the room temperature, then carbon monoxide is displaced by air, stirring is performed for 0.2-2 hours, filtration is performed, distilled water and cyclohexane are used to extract the filtrate, and the solvent in the extract liquor is distilled out through reduced pressure distillation to obtain the target product. The method is convenient and safe to operate, adopts one-pot reaction, has common raw materials, no pollution, high selectivity and high yield; and the catalyst can be separated and recycled after the reaction.
Description
Technical field
The invention belongs to the field of chemical synthesis, relating to disulfide compound and halohydrocarbon particularly is raw material, utilizes carbon monoxide and water, through the method for the synthetic single thio-ether type compounds of selenium catalyzed reaction.
Background technology
Single thio-ether type compounds is important fine chemical material and organic synthesis intermediate.Thioether is the raw material of organic synthesis, is again good solvent and extraction agent, is used for extracting rare metal and precious metal (like Au, Pd, Ag etc.).Thioether is widely used in organic synthesis, medicine, agricultural chemicals, dyestuff and the foodstuff additive field; Thioether still is one type of important spices simultaneously; Furfuryl sulfide has coffee or sesame oil fragrance, and furfuryl group amyl group thioether has fruital, and furfuryl group benzyl thioether has burnt coffee perfume.Thioether can be synthetic by several different methods: the compound method of more early stage classics is for being that solvent reaction gets by potassium sulphide (or sodium) with the absolute ethyl alcohol with halohydrocarbon or sulfuric ester, but this method long reaction time, preparation condition is harshness; The method that grew up afterwards also has: phase-transfer catalysis synthesis method, the microwave radiation synthesis method of dipping reagent method, use phase-transfer catalyst.Above compound method general operation method is comparatively complicated, and reaction conditions requires comparatively strict.
Summary of the invention
The object of the present invention is to provide the method for the synthetic single thio-ether type compounds of a kind of selenium catalysis that reaction conditions is gentle under normal pressure, cost is low.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is following: in the presence of carbon monoxide and water, disulfide compound and halogenated hydrocarbon compound are raw material; Selenium is catalyzer, and organic bases or mineral alkali are promotor, or does not add any promotor; Under normal pressure, 20 ~ 100 ℃ were reacted 1 ~ 24 hour, and were cooled to room temperature in organic solvent; Carbon monoxide is switched to air, stirred 0.2 ~ 2 hour, filter; With zero(ppm) water and hexanaphthene extraction, underpressure distillation steams the solvent in the extraction liquid to filtrating, obtains title product respectively.Reaction formula is following:
R, R ' are aromatic group, heterocyclic group or alkyl; X is Cl, Br, I or OTs (tosic acid base);
Wherein: the mol ratio of disulfide compound and halogenated hydrocarbon compound is 1:2 ~ 1:3; The mole dosage of selenium is 1 ~ 20% of a disulfide compound; The mol ratio of disulfide compound and water is 1:1 ~ 1:100; The mole dosage of organic bases or mineral alkali is 0 ~ 200% of a disulfide compound.
Above-mentioned mineral alkali is one or more a mixture of sodium hydroxide, Pottasium Hydroxide, yellow soda ash, sodium hydrogencarbonate; Above-mentioned organic bases is sodium acetate, potassium acetate, triethylamine, aniline, pyridine, 4-picoline, 1, the mixture of one or more in 5-diaza-bicyclo [5.4.0]-5-undecylene (DBU) and the N-crassitude.
Carbon monoxide also can use the industrial carbon monoxide tail gas that contains air, nitrogen, carbonic acid gas, water vapour, and wherein the content sum of nitrogen, carbonic acid gas, water vapour is smaller or equal to 95% of TV, and air content is less than 30%.
Said organic solvent is one or more polarity or nonpolar inert solvent; Said polar solvent is THF, methylene dichloride, N; Dinethylformamide (DMF), N; N-N,N-DIMETHYLACETAMIDE (DMAC), DMSO 99.8MIN. (DMSO), glycol ether, ethylene glycol diethyl ether, N-formyl piperidine (FP), dioxane, crown ether or acetone, non-polar solvent is toluene, YLENE, normal hexane or benzene.
The present invention has following advantage:
1. the present invention is a synthesis under normal pressure, one pot reaction, and facility investment is few, and is easy to operate and safe.
2. cost is low.Raw material is simple, be easy to get, and only uses the lower nonmetal selenium of price to be catalyzer.
3. environmentally friendly.It is green reaction that the present invention does not have the three wastes, has reached the requirement of cleaner production, helps large-scale industrial production.
4. the reaction process difficulty is low.The present invention is easy and simple to handle, and product separates with the postorder of catalyzer easily.
5. good economy performance.The present invention reacts and selects row high, and adopting nonmetal selenium is catalyzer, and catalytic selectivity can reach more than 99%.
6. has phase transfer function.In catalyzed reaction of the present invention; Solid selenium powder catalyzer is insoluble in the reaction system before the reaction beginning; The selenium of solid phase changes the active specy that is dissolved in reaction system into and carries out the homogeneous catalyzed reaction in reaction process; After reaction ended, catalyzer was separated out with the solid phase selenium powder again, very easyly separated with product.Therefore, the present invention combines the advantage of homogeneous catalysis and heterogeneous catalyst.
Embodiment
Following instance is to detailed description of the present invention, rather than limitation of the present invention.
Embodiment 1
Be equipped with one and add furfuryl disulfide ether (2mmol), bromo pentane (4.2mmol), selenium powder (0.2mmol), H in the 100ml there-necked flask of stirrer, prolong
2O (50 mmol), NaOAC (1.25mmol) and solvent DMF (20ml) continue to feed carbon monoxide, under the normal pressure; Be heated to the 90oC stirring reaction 5 hours, be cooled to room temperature after, carbon monoxide is switched to air; Stir after 0.5-1 hour, filter out selenium powder, filtrating is respectively with zero(ppm) water and hexanaphthene extraction; Underpressure distillation steams the solvent in the extraction liquid, obtains title product, yield 80.9%.
Embodiment 2
Method is with embodiment 1, and is following for the yield of different substrates, and product verifies that through nuclear-magnetism structural formula is following
Embodiment 3
Method only changes the consumption of catalyzer selenium with embodiment 1, and yield is following:
| The consumption of selenium (mmol) | 0.02 | 0.10 | 0.16 | 0.20 | 0.24 | 0.30 | 0.40 |
| Hundred parts of the relative furfuryl disulfide ether of selenium are compared % | 1 | 5 | 8 | 10 | 12 | 15 | 20 |
| Yield % | 74 | 85 | 90 | 80.9 | 89 | 87 | 90 |
Embodiment 4
Method only changes the consumption of water with embodiment 1, and yield is following:
| The consumption of water (mmol) | 2.0 | 10 | 20 | 40 | 50 | 100 | 200 |
| The mol ratio of furfuryl disulfide ether and water | 1:1 | 1:5 | 1:10 | 1:20 | 1:25 | 1:50 | 1:100 |
| Yield % | 67.1 | 74.5 | 78.4 | 79.9 | 80.9 | 80.4 | 80.3 |
Embodiment 5
Method only changes the consumption of sodium acetate with embodiment 1, and yield is following:
| The consumption of sodium acetate (mmol) | 0 | 0.8 | 1.6 | 2.0 | 2.8 | 3.6 | 4.0 |
| The sodium acetate consumption is that hundred parts of disulfide compound compare % | 0 | 40 | 80 | 100 | 140 | 180 | 200 |
| Yield % | 53 | 79 | 80 | 80 | 80 | 80 | 80 |
Embodiment 6
The consumption of promotor and organic solvent is following, and experimental technique and other condition are with embodiment 1, and yield is following:
Embodiment 7
Method is with embodiment 1, and is following for the yield in differing temps and reaction times:
| Temperature of reaction ( oC） | 20 | 50 | 70 | 90 | 100 |
| Reaction times (hr) | 24 | 5 | 5 | 5 | 3 |
| Yield % | 45 | 66 | 81 | 80.9 | 80 |
Embodiment 8
One be equipped with add in the 100ml there-necked flask of stirrer, prolong to nitro phenylbenzene disulfide (2mmol),
Bromo pentane (4.2mmol), selenium powder (0.2mmol), H
2O (50mmol), NaOAC (1.25mmol) and solvent DMF (20ml) continue to feed carbon monoxide, then are heated to the 90oC stirring reaction 5 hours; After being cooled to room temperature, carbon monoxide is switched to-air, stir after 0.5-1 hour; Filter out selenium powder, with zero(ppm) water and hexanaphthene extraction, underpressure distillation steams the solvent in the extraction liquid to filtrating respectively; Obtain title product, yield 82.9%.
Product is following through nuclear-magnetism checking structural formula:
Claims (4)
1. the method for a synthetic single thio-ether type compounds, it is characterized in that: in the presence of carbon monoxide and water, be raw material with disulfide compound and halogenated hydrocarbon compound, selenium is catalyzer; Organic bases or mineral alkali are promotor, or do not add any promotor, in organic solvent; Under normal pressure, 20 ~ 100 ℃ were reacted 1 ~ 24 hour, and were cooled to room temperature; Carbon monoxide is switched to air, stirred 0.2 ~ 2 hour, filter; With zero(ppm) water and hexanaphthene extraction, underpressure distillation steams the solvent in the extraction liquid to filtrating, obtains title product respectively; Wherein:
The mol ratio of disulfide compound and halogenated hydrocarbon compound is 1:2 ~ 1:3;
The mole dosage of selenium is 1 ~ 20% of a disulfide compound;
The mol ratio of disulfide compound and water is 1:1 ~ 1:100;
The mole dosage of organic bases or mineral alkali is 0 ~ 200% of a disulfide compound;
The structural formula of described disulfide compound is:
, R is aromatic group, heterocyclic group or alkyl;
The structural formula of described halogenated hydrocarbon compound is:
; R ' is aromatic group, heterocyclic group or alkyl, and X is Cl, Br, I or p-toluenesulfonyl oxygen base.
2. according to the method for the described synthetic single thio-ether type compounds of claim 1, it is characterized in that: said mineral alkali is one or more a mixture of sodium hydroxide, Pottasium Hydroxide, yellow soda ash and sodium hydrogencarbonate; Said organic bases is sodium acetate, potassium acetate, triethylamine, aniline, pyridine, 4-picoline, 1, the mixture of one or more in 5-diaza-bicyclo [5.4.0]-5-undecylene and the N-crassitude.
3. according to the method for the described synthetic single thio-ether type compounds of claim 1, it is characterized in that: described organic solvent is polar solvent and/or non-polar solvent.
4. according to the method for the described synthetic single thio-ether type compounds of claim 1; It is characterized in that: described solvent is THF, methylene dichloride, N; One or more mixing of dinethylformamide, DMAC N,N, DMSO 99.8MIN., glycol ether, ethylene glycol diethyl ether, N-formyl piperidine, dioxane, crown ether or acetone; Or described solvent is one or more mixing of toluene, YLENE, normal hexane or benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110022751XA CN102127038B (en) | 2011-01-20 | 2011-01-20 | Method for synthetizing mono-thioether compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110022751XA CN102127038B (en) | 2011-01-20 | 2011-01-20 | Method for synthetizing mono-thioether compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102127038A CN102127038A (en) | 2011-07-20 |
| CN102127038B true CN102127038B (en) | 2012-08-01 |
Family
ID=44265349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110022751XA Expired - Fee Related CN102127038B (en) | 2011-01-20 | 2011-01-20 | Method for synthetizing mono-thioether compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102127038B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041236A (en) * | 2018-01-15 | 2019-07-23 | 天津师范大学 | The synthetic method of thio-ether type compounds |
| CN108774098A (en) * | 2018-05-17 | 2018-11-09 | 广东工业大学 | A kind of thio-ether type compounds and its synthetic method and application |
| CN113481379B (en) * | 2021-06-18 | 2022-08-12 | 金川集团股份有限公司 | Method for removing impurities by using palladium extracting agent |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19824488A1 (en) * | 1998-06-02 | 1999-12-09 | Bayer Ag | Process for the preparation of perfluoroalkyl aryl sulfides and new perfluoroalkyl aryl sulfides |
| CN101186591A (en) * | 2007-12-24 | 2008-05-28 | 辽宁大学 | Method for synthesizing symmetrical dibenzyldithioether compounds |
| CN101619034B (en) * | 2009-07-28 | 2012-07-25 | 辽宁大学 | Diselenide compound synthesis method |
-
2011
- 2011-01-20 CN CN201110022751XA patent/CN102127038B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102127038A (en) | 2011-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103418438A (en) | Nitrogen-impurity carbene-class palladium catalyst and preparation method and application thereof | |
| CN107235923B (en) | Preparation method of 3-aryl quinoxalinone derivatives | |
| CN101619034B (en) | Diselenide compound synthesis method | |
| CN101274915B (en) | Method for synthesizing isoxazole | |
| CN102381950B (en) | Catalytic oxidation method for preparing vanillin | |
| CN102127038B (en) | Method for synthetizing mono-thioether compound | |
| CN102643237B (en) | Method for preparing 1H-imidazole-4-formic acid | |
| CN103183686A (en) | Preparation method of 7beta-amino-7lapha-methoxy-3-cephem compound | |
| CN112047842A (en) | 1, 4-diene compound and preparation method and application thereof | |
| CN109988143B (en) | Method for preparing functionalized chiral cyclic carbonate through biomass polyol | |
| CN111777564A (en) | Method for synthesizing quinazolinone compound through photocatalytic alcohol oxidation in aqueous phase | |
| CN108299466B (en) | Improved dolutegravir synthesis method | |
| CN102675162B (en) | Method for synthesizing CLT acid | |
| CN111454222B (en) | Synthesis method of 2,4- (1H, 3H) -quinazolinedione and derivatives thereof | |
| CN1295209C (en) | Method of synthesizing hydrodiazo kind compound | |
| CN115340475B (en) | Preparation method of 1-diphenyl diazene oxide or derivative thereof | |
| CN113666827B (en) | Synthetic method of fluxapyroxad intermediate | |
| CN115340469B (en) | Preparation method of diphenyl diazene or derivative thereof | |
| CN109503532A (en) | A kind of 3- phenyl -3- Benzylbenzofuran ketone compounds and its high-efficiency synthesis method | |
| CN108299236B (en) | Synthetic method of alpha-cyanoacrylate compound | |
| CN1951914A (en) | Process for synthesis of symmetrical aryl urea compound | |
| CN114082442B (en) | Succinimidyl ionic liquid and method for synthesizing quinazoline-2, 4 (1H, 3H) -diketone by using same as catalyst | |
| CN108947928B (en) | Nitrogen, oxygen and oxygen-containing tri-substituted six-membered ring lactone compound and preparation method and application thereof | |
| CN109020922B (en) | Preparation method of cyclic sulfonamide compound | |
| CN115340474B (en) | Application of zirconium hydroxide as catalyst in catalyzing aniline or derivative thereof to prepare 1-diphenyl diazene oxide or derivative thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120801 Termination date: 20150120 |
|
| EXPY | Termination of patent right or utility model |