CN106543051A - A kind of preparation method of Aromatic Sulfide class compound - Google Patents
A kind of preparation method of Aromatic Sulfide class compound Download PDFInfo
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- CN106543051A CN106543051A CN201610921087.5A CN201610921087A CN106543051A CN 106543051 A CN106543051 A CN 106543051A CN 201610921087 A CN201610921087 A CN 201610921087A CN 106543051 A CN106543051 A CN 106543051A
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- 0 CC(C)C=CCC(*C=C1)C(Sc2c(C)cccc2)=C1OC Chemical compound CC(C)C=CCC(*C=C1)C(Sc2c(C)cccc2)=C1OC 0.000 description 1
- QQWMAKPWKUGZCV-UHFFFAOYSA-N CNC(C=Cc1ccccc1C1)=C1Sc(cc1)ccc1OC Chemical compound CNC(C=Cc1ccccc1C1)=C1Sc(cc1)ccc1OC QQWMAKPWKUGZCV-UHFFFAOYSA-N 0.000 description 1
- JMXIUEIWYYWGDE-UHFFFAOYSA-N COc1ccc(cccc2)c2c1Sc(cc1)ccc1Br Chemical compound COc1ccc(cccc2)c2c1Sc(cc1)ccc1Br JMXIUEIWYYWGDE-UHFFFAOYSA-N 0.000 description 1
- RBEHDQQNMUIHOL-UHFFFAOYSA-N COc1ccc(cccc2)c2c1Sc(cc1)ccc1F Chemical compound COc1ccc(cccc2)c2c1Sc(cc1)ccc1F RBEHDQQNMUIHOL-UHFFFAOYSA-N 0.000 description 1
- SKAWGXTUIZGACB-UHFFFAOYSA-N COc1ccc(cccc2)c2c1Sc1ccccc1 Chemical compound COc1ccc(cccc2)c2c1Sc1ccccc1 SKAWGXTUIZGACB-UHFFFAOYSA-N 0.000 description 1
- SVMKBRYXYNLVQY-UHFFFAOYSA-N Cc(cc1)ccc1Sc(c1ccccc1cc1)c1OC Chemical compound Cc(cc1)ccc1Sc(c1ccccc1cc1)c1OC SVMKBRYXYNLVQY-UHFFFAOYSA-N 0.000 description 1
Classifications
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of Aromatic Sulfide class compound, its step is：Substrate A, substrate B and acid are added in reactor, ionic liquid are added as reaction dissolvent, heated and stirred reaction；After reaction terminates, products therefrom is extracted with organic solvent, revolving removes solvent, Jing column chromatographies or is recrystallized to give product.The present invention has advantages below：(1) reaction is carried out in ionic liquid, glyoxaline ion liquid as reaction medium have the advantages that inexpensively, low volatility and recyclable；(2) reaction condition is gentle and need not add the reagents such as other metallic catalysts, reducing agent；(3) reaction yield is high, workable, can be used for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of Aromatic Sulfide class compound, belongs to organic synthesis field.
Background technology
Aromatic Sulfide is widely used in medicine, macromolecule material as the important organic synthesiss of a class and medicinal intermediates
The fields such as material, pesticide, fuel oil additive and lube oil additive.In existing thioether synthetic method, in most cases all
The use of the severe toxicity such as mercaptan, thiophenol, malodorous chemicals can be related to, meanwhile, do not meet the theme of Green Chemistry instantly yet.
Patent CN104725172A discloses a kind of synthetic method of aryl thioethers class compound, be in reaction dissolvent,
With aryl or enylthio Sulfateses derivant and boric acid or boric acid fat or borate family derivant as reaction raw materials, in metal
Under copper catalyst effect, reaction obtains polysubstituted aryl thioethers class compound.This method uses metal catalytic in operation
Agent, while adding part and oxidant, system is excessively complicated, and does not meet the requirement of production energy-saving.
The synthetic method of aryl thioethers class compound disclosed in patent CN103848767A, is in reaction dissolvent, with virtue
Base iodide or aryl trifluoromethayl sulfonic acid esters derivative, are reaction raw materials with halogenated alkane, with Na2S2O3For sulfiding reagent,
Under metal palladium catalyst effect, reaction obtains polysubstituted aryl thioethers class compound.Noble metal, work are adopted in catalytic process
Production cost will certainly be raised in industry production process, while the loss of noble metal there is also problem with recovery.
Patent CN102516139A discloses a kind of synthetic method of phenyl sulfide compound, reaction medium be 1- alkyl-
3- methyl imidazolium tetrafluoroborates or 1- alkyl -3- Methylimidazole. hexafluorophosphoric acid ionic liquids, the catalyst used is solid
Acid.Costly, preparation process is also relatively complicated for ionic liquid price described in this method, while the deactivation prob of solid acid is also more
Seriously.
The content of the invention
It is an object of the invention to provide a kind of preparation method of Aromatic Sulfide class compound.
To achieve these goals, the present invention provides following technical solution：
A kind of preparation method of asymmetric Aromatic Sulfide, comprises the following steps that：
Substrate A, substrate B and acid are added in reactor, ionic liquid are added as reaction dissolvent, heated and stirred reaction；
After reaction terminates, products therefrom is extracted with organic solvent, revolving removes solvent, Jing column chromatographies or is recrystallized to give product, wherein,
The structural formula of ionic liquid is as follows：
In above-mentioned steps, substrate A is one of following arbitrary structures compound：
In above-mentioned steps, substrate B is benzene sulfinic acid sodium salt, SPTS, adjacent toluenesulfinic acid sodium, 2,4,6- front threes
Benzene sulfinic acid sodium salt, to fluorine benzene sulfinic acid sodium salt, to chlorobenzene sulfinic acid sodium, to bromine benzene sulfinic acid sodium salt, bromophenyl sulfinic acid sodium, to methoxy
In base benzene sulfinic acid sodium salt any one.
In above-mentioned steps, 1～3 times for substrate A mole of substrate B addition.
In above-mentioned steps, acid is hydrochloric acid, sulphuric acid, p-methyl benzenesulfonic acid or oxalic acid.
In above-mentioned steps, 1.5～3 times for substrate B mole of sour addition.
In above-mentioned steps, the ratio of ionic liquid and substrate B is 0.3～0.5mL/mmol.
In above-mentioned steps, heating-up temperature is more than 80 DEG C；Response time is 3～20h.
Compared with prior art, the present invention has advantages below：(1) reaction is carried out in ionic liquid, imidazole-like ionic
Liquid as reaction medium have the advantages that inexpensively, low volatility and recyclable；(2) reaction condition is gentle and need not add other
The reagents such as metallic catalyst, oxidant；(3) reaction yield is high, workable, can be used for industrialized production.
Specific embodiment
Embodiment 1：
Take 0.5mmol beta naphthals (72.1mg) respectively, 0.75mmol benzene sulfinic acid sodium salts (123.1mg), to toluenesulfinic acid
Sodium (133.6mg), adjacent toluenesulfinic acid sodium (133.6mg), 2,4,6- front three benzene sulfinic acid sodium salts (154.7mg), to fluorobenzene Asia sulphur
Sour sodium (136.6mg), to chlorobenzene sulfinic acid sodium (149.0mg), to bromine benzene sulfinic acid sodium salt (180.8mg) or to methoxybenzene Asia sulphur
One kind in sour sodium (145.6mg), 1.2mmol hydrochloric acid (36.5% hydrochloric acid, 102.6 μ L) add 0.5mL ions in pressure pipe
Liquid, reacts 6h at 80 DEG C, and after reaction terminates, after adding 2mL ethyl acetate to extract three times, revolving removes organic solvent, leads to
Cross post layer silica gel, obtain target product 1a-1h, yield is as follows to be respectively 94%, 96%, 97%, 94%, 98%, 98%,
96%th, 99%.
Embodiment 2：
Take 0.5mmol 2- methoxynaphthalenes (79.1mg) respectively, it is 0.75mmol benzene sulfinic acid sodium salts (123.1mg), sub- to toluene
Sodium sulfonate (133.6mg), adjacent toluenesulfinic acid sodium (133.6mg), to fluorine benzene sulfinic acid sodium salt (136.6mg), to bromobenzene sulfinic acid
Sodium (180.8mg) or to the one kind in methoxyl group benzene sulfinic acid sodium salt (145.6mg), 1.2mmol hydrochloric acid (36.5% hydrochloric acid, 102.6 μ
L) in pressure pipe, 0.5mL ionic liquids are added, 6h is reacted at 80 DEG C, after reaction terminates, add the extraction of 2mL ethyl acetate
After three times, revolving removes organic solvent, by post layer silica gel, obtains target product 2a -2f, and yield is as follows to be respectively
100%th, 96%, 95%, 94%, 97%, 97%.
Embodiment 3：
0.5mmol1,3,5- trimethoxy-benzenes (84.1mg), 1,2,3- trimethoxy-benzenes (84.1mg), 3,4,5- are taken respectively
One kind in trimethoxytoluene (94.1mg), 3,5- trimethoxy-anilines (76.6mg) or 2- amino naphthalenes (71.6mg),
0.75mmol SPTS (133.6mg), 1.2mmol hydrochloric acid (36.5% hydrochloric acid, 102.6 μ L) are added in pressure pipe
0.5mL ionic liquids, react 6h at 80 DEG C, and after reaction terminates, after adding 2mL ethyl acetate to extract three times, revolving removing has
Machine solvent, by post layer silica gel, obtains target product 3a-3f, and yield is 92%, 87%, 84%, 52%, 37%, 94%.
Embodiment 4：
0.5mmol3,5-trimethoxytoluene (76.1mg), 1,3-dimethoxy benzene (69.1mg) or 1,3-two are taken respectively
One kind in ethoxybenzene (83.1mg), 0.75mmol is to methoxyl group benzene sulfinic acid sodium salt (145.6mg), 1.2mmol hydrochloric acid
(36.5% hydrochloric acid, 102.6 μ L) adds 0.5mL ionic liquids in pressure pipe, and 6h is reacted at 120 DEG C, after reaction terminates, plus
Enter 2mL ethyl acetate extract three times after, revolving remove organic solvent, by post layer silica gel, obtain target product 4a-4c, yield
For 88%, 86%, 91%.
Embodiment 5:
Take 0.5mmol beta naphthals (72.1mg) respectively, 0.75mmol benzene sulfinic acid sodium salts (123.1mg), 1.5mmol is to first
Benzenesulfonic acid adds 0.5mL ionic liquids in pressure pipe, and 6h is reacted at 80 DEG C, after reaction terminates, adds 2mL ethyl acetate
After extraction three times, revolving removes organic solvent, by post layer silica gel, obtains target product 1a, and yield is as follows to be respectively
93%.
Embodiment 6:
0.5mmol beta naphthals (72.1mg), 0.75mmol benzene sulfinic acid sodium salts (123.1mg), 1.5mmol oxalic acid are taken respectively
In pressure pipe, 0.5mL ionic liquids are added, 6h is reacted at 80 DEG C, after reaction terminates, add 2mL ethyl acetate extraction three
After secondary, revolving removes organic solvent, by post layer silica gel, obtains target product 1a, and yield is as follows to be respectively 94%.
Embodiment 7:
0.5mmol beta naphthals (72.1mg), 0.75mmol benzene sulfinic acid sodium salts (123.1mg), 1.5mmol sulphuric acid are taken respectively
In pressure pipe, 0.5mL ionic liquids are added, 6h is reacted at 80 DEG C, after reaction terminates, add 2mL ethyl acetate extraction three
After secondary, revolving removes organic solvent, by post layer silica gel, obtains target product 1a, and yield is as follows to be respectively 91%.
Embodiment 8:
Take 0.5mmol beta naphthals (72.1mg) respectively, 0.75mmol benzene sulfinic acid sodium salts (123.1mg), 1.5mmolHCl in
In pressure pipe, 0.5mL ionic liquids are added, 3h is reacted at 80 DEG C, after reaction terminates, add 2mL ethyl acetate to extract three times
Afterwards, revolving removes organic solvent, by post layer silica gel, obtains target product 1a, and yield is as follows to be respectively 93%.
Knowable to above-described embodiment, the invention provides a kind of preparation method of Aromatic Sulfide class compound, the method profit
With the cheap ionic liquid of cleaning as reaction system；Reaction condition is gentle and need not add other metallic catalysts, oxidant
Deng reagent；Reaction yield is high, workable, can be used for industrialized production.
Claims (8)
1. a kind of preparation method of asymmetric Aromatic Sulfide, it is characterised in that by substrate A, substrate B and acid mixing, with ionic liquid
Body stirs temperature reaction as reaction dissolvent；After reaction terminates, products therefrom is extracted with organic solvent, revolving removes solvent, Jing
Column chromatography is recrystallized to give product, wherein, the structural formula of ionic liquid is as follows：
2. the preparation method of asymmetric Aromatic Sulfide as claimed in claim 1, it is characterised in that substrate A is arbitrarily tied for following
One of structure compound：
3. the preparation method of asymmetric Aromatic Sulfide as claimed in claim 1, it is characterised in that substrate B be benzene sulfinic acid sodium salt,
SPTS, adjacent toluenesulfinic acid sodium, 2,4,6- front three benzene sulfinic acid sodium salts, to fluorine benzene sulfinic acid sodium salt, to chlorobenzene Asia sulphur
Sour sodium, to bromine benzene sulfinic acid sodium salt, bromophenyl sulfinic acid sodium, in methoxyl group benzene sulfinic acid sodium salt any one.
4. the preparation method of asymmetric Aromatic Sulfide as claimed in claim 1, it is characterised in that substrate B addition is substrate A
1～3 times of mole.
5. the preparation method of asymmetric Aromatic Sulfide as claimed in claim 1, it is characterised in that acid is hydrochloric acid, sulphuric acid, to first
In benzenesulfonic acid and oxalic acid any one.
6. the preparation method of asymmetric Aromatic Sulfide as claimed in claim 1, it is characterised in that sour addition is rubbed for substrate B
1.5～3 times of that amount.
7. the preparation method of asymmetric Aromatic Sulfide as claimed in claim 1, it is characterised in that ionic liquid and substrate B
Ratio is 0.3～0.5mL/mmol.
8. the preparation method of asymmetric Aromatic Sulfide as claimed in claim 1, it is characterised in that reaction temperature be 80 DEG C with
On；Response time is 3～20h.
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Citations (4)
| 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 |
| CN103804249A (en) * | 2014-01-27 | 2014-05-21 | 中国人民解放军63975部队 | Synthetic method of aryl-alkyl thioether compound |
| CN104387303A (en) * | 2014-10-31 | 2015-03-04 | 华东师范大学 | Aryl-aryl, aryl-alkyl and alkyl-alkyl asymmetric persulfides and synthesis method thereof |
| CN105837480A (en) * | 2016-03-31 | 2016-08-10 | 南京理工大学 | Preparation method for asymmetric aromatic thioether |
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2016
- 2016-10-21 CN CN201610921087.5A patent/CN106543051B/en not_active Expired - Fee Related
Patent Citations (4)
| 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 |
| CN103804249A (en) * | 2014-01-27 | 2014-05-21 | 中国人民解放军63975部队 | Synthetic method of aryl-alkyl thioether compound |
| CN104387303A (en) * | 2014-10-31 | 2015-03-04 | 华东师范大学 | Aryl-aryl, aryl-alkyl and alkyl-alkyl asymmetric persulfides and synthesis method thereof |
| CN105837480A (en) * | 2016-03-31 | 2016-08-10 | 南京理工大学 | Preparation method for asymmetric aromatic thioether |
Non-Patent Citations (5)
| Title |
|---|
| CONG-RONG LIU 等: "Byproduct promoted regioselective sulfenylation of indoles with sulfinic acids", 《ORGANIC & BIOMOLECULAR CHEMISTRY》 * |
| DINGYI WANG 等: "Iodine-mediated thiolation of phenol/phenylamine derivatives and sodium arylsulfinates in neat water", 《RSC ADVANCES》 * |
| FUHONG XIAO 等: "Chemoselective cross-coupling reaction of sodium sulfinates with phenols under aqueous conditions", 《GREEN CHEMISTRY》 * |
| RAJJAKFUR RAHAMAN 等: "Microwave-assisted regioselective sulfenylation of indoles under solvent- and metal-free conditions", 《RSC ADVANCES》 * |
| YINGCAI DING: "Generation of thioethers via direct C–H functionalization with sodium benzenesulfinate as a sulfur source", 《ORGANIC & BIOMOLECULAR CHEMISTRY》 * |
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Granted publication date: 20181002 Termination date: 20201021 |