CN106977434A - A kind of preparation method of β alkoxies sulfide compound - Google Patents
A kind of preparation method of β alkoxies sulfide compound Download PDFInfo
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- CN106977434A CN106977434A CN201710181811.XA CN201710181811A CN106977434A CN 106977434 A CN106977434 A CN 106977434A CN 201710181811 A CN201710181811 A CN 201710181811A CN 106977434 A CN106977434 A CN 106977434A
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- sulfide compound
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- alkoxy sulfide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/16—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
- C07C323/20—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
- C07D317/56—Radicals substituted by sulfur atoms
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention discloses a kind of preparation method of β alkoxies sulfide compound, its step is：Using glyoxaline ion liquid as reaction medium, sodium arylsulfinate, fragrant alkene, fatty alcohol and acid are sequentially added, heating stirring reacts 8 14 h；After reaction terminates, products therefrom is extracted with organic solvent, revolving removes solvent, through column chromatography or is recrystallized to give product.Compared with prior art, its remarkable advantage is the present invention：(1) glyoxaline ion liquid as reaction medium have the advantages that inexpensively, it is low volatility, nonflammable and recyclable；(2) reaction condition is more gentle, and reaction reagent is cheap, without using transition-metal catalyst and reducing agent；(3) course of reaction is odorless, and reaction yield is higher, workable.
Description
Technical field
The invention belongs to environment-friendly organic synthesis technical field, and in particular to one kind passes through by solvent of glyoxaline ion liquid
The method that addition substitution reaction synthesizes β-alkoxy sulfide compound.
Background technology
Glyoxaline ion liquid not only has the excellent physical property that general ionic liquid is possessed, such as low melting point, height
Boiling point, low-steam pressure and good dissolubility, are also a kind of green solvent, with more easily prepared, and structure is easy to regulation and control etc.
Advantage, is also to be applied to industrialized ionic liquid earliest.It is widely used in biomass dissolving and extracted, organic synthesis, work
Industry catalysis and biomedicine field etc..
Organic sulfur compound illustrates it in terms of medicine, agronomy, biology, organic functional material and is increasingly widely applied
Prospect, wherein β-alkoxy Aromatic Sulfide are the important organic sulfur compounds of a class, are many biological and medicinal activity molecule syntheses
Important intermediate.It has been reported that the preparation method of β-alkoxy sulfide compound substantially have following several：(1) it is sub- with aryl
Sulfonic acid is that sulphur source synthesizes β-alkoxy sulfide compound (Org.Biomol.Chem.2016,14,5136) in toluene solvant；
(2) equivalent dimethyl sulfoxide is added by sulphur source of disulfide and β-alkoxy sulfide compound is synthesized under the conditions of microwave radiation
(J.Org.Chem.2015,80,2120)；(3) β-alkoxy sulphur is synthesized in dichloroethane solvent by sulphur source of arylsulfonyl hydrazine
Ether compound (Chem.Commun.2014,50,2111).But these methods are equally with there are problems that, as reaction is needed
Use the iodide and organic solvent of toxic and volatile.
The content of the invention
It is an object of the invention to provide a kind of preparation method of β-alkoxy sulfide compound, its side reaction is less, yield
Higher, reaction medium can be recycled, it is to avoid used in iodide catalyst, and course of reaction and to be joined without transition metal
With the requirement to equipment is not also high, realizes the concept of Green Chemistry.
Realizing the technical solution of the object of the invention is：The preparation method of a kind of β-alkoxy sulfide compound, by virtue
Alkene, sodium arylsulfinate and fatty alcohol are sequentially added in reaction vessel, are added glyoxaline ion liquid as solvent, are added acid
Reacted；Reaction adds ethyl acetate after terminating, and ionic liquid is reclaimed by point liquid, and gained ethyl acetate phase revolving removes molten
Agent, β-alkoxy sulfide compound is obtained through column chromatography silica gel.
In the step, sodium arylsulfinate be SPTS, benzene sulfinic acid sodium salt, p-nitrophenyl sulfinic acid sodium,
To one kind in methoxyl group benzene sulfinic acid sodium salt.
In the step, described fragrant alkene is styrene, p-methylstyrene, to trifluoromethy styrene, 3,4- (Asias
Methylenedioxy group) one kind in styrene.
In the step, described fatty alcohol is one kind in methanol or ethanol.
In the step, the mol ratio of described fragrant alkene, sodium arylsulfinate and alcohol is 1:1:2~1:2:3.
In the step, described acid is one kind in hydrochloric acid, sulfuric acid, phosphoric acid, and sour amount is 2~3 times of equivalents of fragrant alkene.
In the step, described glyoxaline ion liquid is [Omim] Br.
In the step, described reaction temperature is 80~120 DEG C；The described reaction time is 8~14h.
The present invention compared with prior art, there is following outstanding feature：
(1) glyoxaline ion liquid as reaction medium have the advantages that inexpensively, it is low volatility, nonflammable and recyclable；
(2) reaction condition is more gentle, and reaction reagent is cheap, without using transition-metal catalyst and volatile, poisonous
Iodide etc.；
(3) course of reaction is odorless, and reaction yield is high, workable, with certain industrial prospect.
Embodiment
Below by embodiment, the present invention will be further described in detail.
Embodiment 1
The reactant that the present embodiment is used is styrene, SPTS and methanol, and molecular weight is respectively 104,178
With 32.
By 0.5mmol styrene, 0.75mmol SPTSs, 1.5mmol methanol is successively added to the resistance to of 10mL
In pressure pipe, then 1mL ionic liquids [Omim] Br is taken into pressure pipe, instill hydrochloric acid (HCl content 1.5mmol) solution rear enclosed resistance to
Pressure pipe, in being reacted 12 hours at 100 DEG C, reaction terminates rear mixture and is down to room temperature, and recovery ionic liquid is extracted with ethyl acetate,
Purified after obtained extract concentration through silica gel column chromatography, obtain product 1a, yield 85%.
Embodiment 2
The reactant that the present embodiment is used is styrene, to methoxyl group benzene sulfinic acid sodium salt and ethanol, and molecular weight is respectively
104th, 194 and 46.
By 0.5mmol styrene, 0.75mmol is successively added to 10mL to methoxyl group benzene sulfinic acid sodium salt, 1.5mmol ethanol
Pressure pipe in, then take 1mL ionic liquids [Omim] Br into pressure pipe, instill after hydrochloric acid (HCl content 1.5mmol) solution and seal
Pressure pipe is closed, in being reacted 12 hours at 100 DEG C, reaction terminates rear mixture and is down to room temperature, and recovery ion is extracted with ethyl acetate
Liquid, purifies through silica gel column chromatography after obtained extract concentration, obtains product 1b, yield 88%.
Embodiment 3
The reactant that the present embodiment is used is styrene, p-nitrophenyl sulfinic acid sodium and ethanol, molecular weight is respectively 104,
209 and 46.
By 0.5mmol styrene, 0.75mmol p-nitrophenyl sulfinic acid sodium, 1.5mmol ethanol is successively added to 10mL's
In pressure pipe, then 1mL ionic liquids [Omim] Br is taken into pressure pipe, instill hydrochloric acid (HCl content 1.5mmol) solution rear enclosed
Pressure pipe, in being reacted 12 hours at 100 DEG C, reaction terminates rear mixture and is down to room temperature, and recovery ionic liquid is extracted with ethyl acetate
Body, purifies through silica gel column chromatography after obtained extract concentration, obtains product 1c, yield 73%.
Embodiment 4
The reactant that the present embodiment is used is to trifluoromethy styrene, benzene sulfinic acid sodium salt and ethanol, molecular weight difference
For 172,164 and 46.
By 0.5mmol to trifluoromethy styrene, 0.75mmol benzene sulfinic acid sodium salts, 1.5mmol ethanol is successively added to
In 10mL pressure pipe, then 1mL ionic liquids [Omim] Br is taken into pressure pipe, instill hydrochloric acid (HCl content 1.5mmol) solution
Rear enclosed pressure pipe, in being reacted 12 hours at 100 DEG C, reaction terminates rear mixture and is down to room temperature, and recovery is extracted with ethyl acetate
Ionic liquid, purifies through silica gel column chromatography after obtained extract concentration, obtains product 1d, yield 68%.
Embodiment 5
The reactant that the present embodiment is used is 3,4- (methylene-dioxy) styrene, benzene sulfinic acid sodium salt and ethanol, molecular weight
Respectively 148,164 and 46.
By 0.5mmol 3,4- (methylene-dioxy) styrene, 0.75mmol benzene sulfinic acid sodium salts, 1.5mmol ethanol successively adds
Enter into 10mL pressure pipe, then take 1mL ionic liquids [Omim] Br into pressure pipe, instill hydrochloric acid (HCl content 1.5mmol)
Solution rear enclosed pressure pipe, in being reacted 12 hours at 100 DEG C, reaction terminates rear mixture and is down to room temperature, is extracted with ethyl acetate
Ionic liquid is reclaimed, is purified after obtained extract concentration through silica gel column chromatography, obtains product 1e, yield 83%.
Embodiment 6
The reactant that the present embodiment is used is p-methylstyrene, benzene sulfinic acid sodium salt and ethanol, molecular weight is respectively 118,
164 and 46.
By 0.5mmol p-methylstyrenes, 0.75mmol benzene sulfinic acid sodium salts, 1.5mmol ethanol is successively added to 10mL's
In pressure pipe, then 1mL ionic liquids [Omim] Br is taken into pressure pipe, instill hydrochloric acid (HCl content 1.5mmol) solution rear enclosed
Pressure pipe, in being reacted 12 hours at 100 DEG C, reaction terminates rear mixture and is down to room temperature, and recovery ionic liquid is extracted with ethyl acetate
Body, purifies through silica gel column chromatography after obtained extract concentration, obtains product 1f, yield 76%.
Above-described embodiment is only the explanation to product of the present invention, not makes any formal limitation to the present invention,
Within the scope of not departing from technical scheme, the technology contents of any utilization the disclosure above make simple transformation etc. Tongfang
Case, belongs to protection scope of the present invention.
Claims (9)
1. the preparation method of a kind of β-alkoxy sulfide compound, it is characterised in that by sodium arylsulfinate, fragrant alkene and fatty alcohol
Sequentially add in reaction vessel, add glyoxaline ion liquid as solvent, finally instill hydrochloric acid and reacted；After reaction terminates
Ethyl acetate is added, ionic liquid is reclaimed by point liquid, gained ethyl acetate phase revolving removes solvent, obtained through column chromatography silica gel
β-alkoxy sulfide compound.
2. the preparation method of β according to claim 1-alkoxy sulfide compound, it is characterised in that in the step,
Sodium arylsulfinate be SPTS, benzene sulfinic acid sodium salt, p-nitrophenyl sulfinic acid sodium, in methoxyl group benzene sulfinic acid sodium salt
One kind.
3. the preparation method of β according to claim 1-alkoxy sulfide compound, it is characterised in that in the step,
Fragrant alkene is one kind in styrene, p-methylstyrene, p-trifluoromethylstyrene, 3,4- (methylene-dioxy) styrene.
4. the preparation method of β according to claim 1-alkoxy sulfide compound, it is characterised in that in the step,
Fatty alcohol is one kind in methanol or ethanol, and the mole of fatty alcohol is 2~3 times of equivalents of fragrant alkene.
5. the preparation method of β according to claim 1-alkoxy sulfide compound, it is characterised in that in the step,
Acid is one kind in hydrochloric acid, sulfuric acid, phosphoric acid, and sour mole is 2~3 times of equivalents of fragrant alkene.
6. the preparation method of β according to claim 1-alkoxy sulfide compound, it is characterised in that in the step,
The mol ratio of fragrant alkene and sodium arylsulfinate is 1:1~1:2.
7. a kind of preparation method of β-alkoxy sulfide compound according to claim 1, it is characterised in that the step
In, reaction temperature is 80~120 DEG C.
8. the preparation method of β according to claim 1-alkoxy sulfide compound, it is characterised in that described step
In, the reaction time is 8~14h.
9. the preparation method of β according to claim 1-alkoxy sulfide compound, it is characterised in that described step
In, glyoxaline ion liquid is N, N- Methyl Octyl limidazolium salt.
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| CN201710181811.XA CN106977434A (en) | 2017-03-24 | 2017-03-24 | A kind of preparation method of β alkoxies sulfide compound |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516139A (en) * | 2011-11-02 | 2012-06-27 | 浙江工业大学 | Synthesis method of phenyl sulfide compound |
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- 2017-03-24 CN CN201710181811.XA patent/CN106977434A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516139A (en) * | 2011-11-02 | 2012-06-27 | 浙江工业大学 | Synthesis method of phenyl sulfide compound |
Non-Patent Citations (3)
| Title |
|---|
| DINGYI WANG等: "Three-component oxysulfenylation reaction: two simple and convenient approaches to β-alkoxy sulfides", 《ORGANIC & BIOMOLECULAR CHEMISTRY》 * |
| YA-MEI LIN 等: "Acid/Phosphide-Induced Radical Route to Alkyl and Alkenyl Sulfides and Phosphonothioates from Sodium Arylsulfinates in Water", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
| ZHU-BING XU 等: "Acid-induced chemoselective arylthiolations of electron-rich arenes in ionic liquids from sodium arylsulfinates: the reducibility of halide anions in [Hmim]Br", 《ORGANIC & BIOMOLECULAR CHEMISTRY》 * |
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