CN101723864A - Method for preparing p-tert-butyl o-nitrothiophenol - Google Patents
Method for preparing p-tert-butyl o-nitrothiophenol Download PDFInfo
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- CN101723864A CN101723864A CN200810224132A CN200810224132A CN101723864A CN 101723864 A CN101723864 A CN 101723864A CN 200810224132 A CN200810224132 A CN 200810224132A CN 200810224132 A CN200810224132 A CN 200810224132A CN 101723864 A CN101723864 A CN 101723864A
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Abstract
The invention relates to the synthesis field of chemical intermediates and discloses a method for directly preparing p-tert-butyl o-nitrothiophenol. In the method, with o-nitrothiophenol or 2,2'-binitro diphenyl disulfide as the raw material, the p-tert-butyl o-nitrothiophenol and the derivatives thereof are obtained through tert-butylation reaction. The method is characterized by easily obtained raw materials, short reaction route, higher relative reaction yield and easy realization of large-scale production.
Description
Technical field
The present invention relates to the synthetic field of chemical intermediate, be the method for a kind of direct preparation to the tert-butyl o nitro thiophenol, described method is with adjacent nitro thiophenol or 2, and 2 '-dinitrobenzene diphenyl disulfide is a raw material, through tertiary butyl reaction, obtain the tert-butyl o nitro thiophenol.
Background technology
To the tert-butyl o nitro thiophenol is a kind of important synthesis material, is mainly used in numerous areas such as the monomer of medicine intermediate, sensitive materials, electrochromism display material, electrolytic polymerization and extraction agent intermediate.And its preparation method is few, main have a document [Journal of Organic Chemistry, 1980,45 (21), 4216] Bao Dao synthetic route is to be raw material to the tert-butyl o nitrophenols, through the function conversion of a series of complexity, phenolic hydroxyl group is converted to the phenol sulfydryl, specifically reacts See Figure:
This method is at present main to tert-butyl o nitro thiophenol preparation method, but problems such as that this method also has is long such as raw materials cost height, difficult acquisition, reaction scheme, the difficult grasp of reaction conditions, yield are low, based on reducing reaction cost, improve reaction yield and the consideration that improves raw material sources, the inventor develops the synthesis technique new to the tert-butyl o nitro thiophenol.
The chemicals ortho-nitrophenyl thiophenols or 2 of the present invention to obtain in a large number easily, 2 '-dinitrobenzene diphenyl disulfide is a raw material, through tertiary butyl reaction, directly obtain corresponding to tert-butyl o nitro thiophenol or 4,4 '-di-t-butyl-2,2 '-dinitrobenzene diphenyl disulfide, wherein 4,4 '-di-t-butyl-2,2 '-dinitrobenzene diphenyl disulfide can obtain target product to the tert-butyl o nitro thiophenol through a simple processing of step.Because reaction raw materials all is the chemicals that obtain easily, from raw materials cost with regard to more dominant.And reaction scheme is short, the relative response yield is higher and be easy to realize large-scale production.
Summary of the invention
Among the present invention respectively with adjacent nitro thiophenol or 2,2 '-dinitrobenzene diphenyl disulfide is a raw material, through tertiary butyl reaction, directly obtain corresponding to tert-butyl o nitro thiophenol or 4,4 '-di-t-butyl-2,2 '-dinitrobenzene diphenyl disulfide, wherein 4,4 '-di-t-butyl-2,2 '-dinitrobenzene diphenyl disulfide need be through obtaining tert-butyl o nitro thiophenol metal-salt after corresponding the processing or directly carrying out downstream application.Concrete reaction is as follows:
X is a hydrogen atom in the formula.Catalysts is one or more in the phosphoric acid, boron trifluoride, aluminum chloride, zinc chloride, strong acidic ion resin (as 001 * 1,001 * 2,001 * 3,001 * 4,001 * 7,001 * 7FC, 001 * 7MB, 001 * 8, the strongly acidic styrene type cation exchange resin of the trade mark such as 001 * 10 and 001 * 16 and the large hole strong acid styrene system cation exchange resin of the trades mark such as D001, D001FC and DOO1SC), preferably phosphoric acid and boron trifluoride.Tertiary butyl source comprises iso-butylene, the trimethyl carbinol, t-butyl methyl ether, tertiary butyl ethyl ether, tertiary butyl chloride or tert.-butyl bromide, preferred iso-butylene or tertiary butyl chloride.Temperature of reaction-30-160 ℃, preferred 0-140 ℃ was reacted preferred 1～4 hour 0.1-10 hour down.
After tertiary butyl reaction was complete, reaction was cooled to room temperature, and organic phase generally layering can occur mutually with catalyzer, separated organic phase and also was dissolved in the organic solvent, this solution with water washing, anhydrous magnesium sulfate drying.Revolve to steam to remove and desolvate, refining through aftertreatment, obtain corresponding 4-position tert-butylation compound: to tert-butyl o nitro thiophenol or 4,4 '-di-t-butyl-2,2 '-dinitrobenzene diphenyl disulfide.Solvent is selected toluene, benzene, methylene dichloride, chloroform, ethyl acetate, chlorobenzene, tetracol phenixin, Nitromethane 99Min. etc. for use, preferred toluene or methylene dichloride.
Wherein with 2,2 '-dinitrobenzene diphenyl disulfide is the product 4 that raw material obtains through tertiary butyl reaction, 4 '-di-t-butyl-2,2 '-dinitrobenzene diphenyl disulfide can obtain by the method for alkaline lysis tert-butyl o nitro thiophenol an alkali metal salt, and acidified then technology such as refining obtains the tert-butyl o nitro thiophenol.The solvent of alkaline lysis reaction is one or more in methyl alcohol, ethanol, Virahol, butanols (comprising propyl carbinol, isopropylcarbinol and the trimethyl carbinol), amylalcohol, tetrahydrofuran (THF), dioxane and the water, preferably water and methyl alcohol.The alkali that reaction is used comprises one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, yellow soda ash and the salt of wormwood, preferential sodium hydroxide.Temperature of reaction 0-130 ℃, preferred 30-80 ℃ was reacted preferred 0.5～2 hour 0.1-10 hour down.After alkaline lysis reaction is finished, gained to tert-butyl o nitro thiophenol metal-salt system, generally use acid to carry out acidifying, the acid that acidifying is used is non-oxidizing acids such as dilute sulphuric acid, hydrochloric acid, phosphoric acid, acetate, preferably hydrochloric acid.Adjustment system slightly acidic has the 4-tertiary butyl-2-nitro thiophenol to separate out.If the organic solvent amount is more, can under decompression, remove an amount of organic solvent by Bamboo, leave standstill crystallization, obtain the 4-tertiary butyl-pure product of 2-nitro thiophenol, yield is higher than 90%.
Above-mentioned gained to tert-butyl o nitro thiophenol metal-salt system directly and the halohydrocarbon or derivatives thereof play the S-alkylated reaction, obtain corresponding derived product to tert-butyl o oil of mirbane thioether.
The present invention is described in detail for following examples, but the scope that the present invention is contained is not limited in this:
Embodiment 1
In reactor, add 10 moles of ortho-nitrophenyl thiophenols, keep zero degree and constantly stirring, to wherein slowly adding 300 gram BF
3/ H
3PO
4Composite catalyst and 11 moles of iso-butylenes.4 hours reaction times was warming up to 70-75 ℃ after finishing, continued stirring reaction 2 hours.Be cooled to room temperature, organic phase layering occurs mutually with catalyzer, separates organic phase and is dissolved in 500 milliliters of toluene.This toluene solution washs 4 times with 1000 ml waters, anhydrous magnesium sulfate drying.Revolve to steam and remove toluene, residuum underpressure distillation (80-100 ℃/1 mmhg) obtains product to the tert-butyl o nitro thiophenol, productive rate 70%.
Embodiment 2
In 250 milliliters of stirred autoclaves, add 50 gram ortho-nitrophenyl thiophenols, 10 gram strong acidic ion resins (macropore vinylbenzene-Vinylstyrene sulfonic acid ion exchange resin), be decompressed to 200 mmhg, it is 120 ℃ that system is kept temperature of reaction, in 1 hour 180 milliliters of t-butyl methyl ether is joined in the reactor.Back insulation reaction 2h finishes.Be cooled to room temperature, add methylene dichloride 100ml dissolving, organic phase 20ml water washing 4 times, anhydrous magnesium sulfate drying.Revolve to steam to remove and desolvate, obtain the thick product of tert-butyl o nitro thiophenol, crude product yield 68%.
Embodiment 3
In reactor, add 10 mole 4,4 '-di-t-butyl-2,2 '-dinitrobenzene diphenyl sulfide is kept zero degree and constantly stirring, to wherein slowly adding 150 gram AlCl
3, 620g (10.9 moles) isobutyl chloride.Be warming up to 0-10 degree stirring reaction 2h after finishing.Be warming up to the 70-75 degree, continue stirring reaction 2h.Be cooled to room temperature, add 500 milliliters of methylene dichloride, and with 100 milliliters of extractions.Merge organic phase and wash anhydrous magnesium sulfate drying 4 times with 1000 ml waters.Revolve to steam to remove and desolvate, obtain 4,4 '-di-t-butyl-2, the thick product of 2 '-dinitrobenzene diphenyl sulfide, crude product yield 78%.
In reaction flask, add 20 ml methanol, 6 mmoles 4,4 '-di-t-butyl-2,2 '-dinitrobenzene diphenyl sulfide is at N
2Be heated with stirring to backflow under the atmosphere, drip the solution that 0.96 gram (24 mmole) sodium hydroxide and 4 ml waters are made into, reacted 0.5 hour.Cooling is filtered.Bamboo desolvates Xia the Zai decompression, obtains the 4-tertiary butyl-2-nitro thiophenol sodium, after acidifying is refining, obtains the 4-tertiary butyl-2-nitro thiophenol, yield 95%.
Reference example
After the 4-tertiary butyl among the embodiment 3-2-nitro thiophenol sodium solvent evaporated, refining without acidifying, directly add 15 ml waters, 12 mmole iso-octyl bromines and 0.10 gram TEBA, 60 ℃ of reactions 0.5 hour, solution was changed into light yellowly in the process by scarlet, and separates out solid.Solid is collected in cooling.Product Glacial acetic acid recrystallization gets yellow needle-like crystal iso-octyl to tert-butyl o oil of mirbane thioether, yield 93.5%.
Claims (10)
1. preparation method to the tert-butyl o nitro thiophenol, it is characterized in that: with the ortho-nitrophenyl thiophenol is raw material, through tertiary butyl reaction, directly obtains the tert-butyl o nitro thiophenol.
2. a kind of preparation method to the tert-butyl o nitro thiophenol according to claim 1 is characterized in that: the used catalysts of tertiary butyl reaction is one or more in phosphoric acid, boron trifluoride, aluminum chloride, zinc chloride, the strong acidic ion resin etc.
3. a kind of preparation method to the tert-butyl o nitro thiophenol according to claim 1 is characterized in that: the tertiary butyl source of tertiary butyl reaction is selected from iso-butylene, the trimethyl carbinol, t-butyl methyl ether, tertiary butyl ethyl ether, tertiary butyl chloride and tert.-butyl bromide.
4. a kind of preparation method to the tert-butyl o nitro thiophenol according to claim 1 is characterized in that: the tertiary butyl reaction temperature is preferably 0-140 ℃ for-30-160 ℃.
5. preparation method to the tert-butyl o nitro thiophenol, it is characterized in that: with 2,2 '-dinitrobenzene diphenyl disulfide is a raw material, carry out tertiary butyl reaction, obtain 4,4 '-di-t-butyl-2,2 '-dinitrobenzene diphenyl disulfide, method by alkaline lysis obtains tert-butyl o nitro thiophenol metal-salt, acidified then refining obtaining the tert-butyl o nitro thiophenol.
6. the preparation method to the tert-butyl o nitro thiophenol as claimed in claim 5 is characterized in that: the used catalysts of tertiary butyl reaction is one or more in phosphoric acid, boron trifluoride, aluminum chloride, zinc chloride, the strong acidic ion resin etc.
7. the preparation method to the tert-butyl o nitro thiophenol as claimed in claim 5 is characterized in that: the tertiary butyl source of tertiary butyl reaction is selected from iso-butylene, the trimethyl carbinol, t-butyl methyl ether, tertiary butyl ethyl ether, tertiary butyl chloride and tert.-butyl bromide.
8. the preparation method to the tert-butyl o nitro thiophenol as claimed in claim 5 is characterized in that: the tertiary butyl reaction temperature is preferably 0-140 ℃ for-30-160 ℃.
9. the preparation method to the tert-butyl o nitro thiophenol as claimed in claim 5 is characterized in that: the alkali that the alkaline lysis reaction is used comprises one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, yellow soda ash and the salt of wormwood.
10. the preparation method to the tert-butyl o nitro thiophenol as claimed in claim 5 is characterized in that: the alkaline lysis temperature of reaction is 0-130 ℃, preferred 30-80 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558000A (en) * | 2011-12-25 | 2012-07-11 | 聊城大学 | Rubber peptizer intermediate 2,2'-dinitro-diphenyl disulfide and preparation method thereof |
| CN110746280A (en) * | 2019-10-14 | 2020-02-04 | 湖北荆洪生物科技股份有限公司 | Synthesis method of 4-tert-butyl benzaldehyde |
-
2008
- 2008-10-17 CN CN200810224132A patent/CN101723864A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558000A (en) * | 2011-12-25 | 2012-07-11 | 聊城大学 | Rubber peptizer intermediate 2,2'-dinitro-diphenyl disulfide and preparation method thereof |
| CN110746280A (en) * | 2019-10-14 | 2020-02-04 | 湖北荆洪生物科技股份有限公司 | Synthesis method of 4-tert-butyl benzaldehyde |
| CN110746280B (en) * | 2019-10-14 | 2022-10-11 | 湖北荆洪生物科技股份有限公司 | Synthesis method of 4-tert-butyl benzaldehyde |
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Application publication date: 20100609 |