CN101759615A - Method for synthesizing a variety of thiophenols by one-step method - Google Patents
Method for synthesizing a variety of thiophenols by one-step method Download PDFInfo
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- CN101759615A CN101759615A CN201010300717A CN201010300717A CN101759615A CN 101759615 A CN101759615 A CN 101759615A CN 201010300717 A CN201010300717 A CN 201010300717A CN 201010300717 A CN201010300717 A CN 201010300717A CN 101759615 A CN101759615 A CN 101759615A
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Abstract
The invention relates to a method for synthesizing a variety of thiophenols by a one-step method, belonging to the technical field of chemistry / chemical engineering. 2,4 - di-tert-butyl phenol acts with sulfur chloride in a solvent to be synthesized to the thiophenols. The method is characterized by comprising the following steps: in a petroleum ether solvent, firstly dissolving out a thiophenol, filtering, evaporating a filter liquor, removing the petroleum ether solvent, and then recrystallizing to obtain the mixture of other thiophenols. With simple operation and low cost, the method adopting the petroleum ether solvent has no toxic and side effect, safety, environment protection and easy industrial production.
Description
Technical field
The present invention relates to the method for the synthetic multiple thiophenols of a kind of single stage method, belong to chemistry/chemical technology field.
Background technology
The thiophenols series products comprises monothio alkylphenol and dithio alkylphenol etc., is widely used in the petroleum industry field as a kind of efficient Hinered phenols antiaging agent.Since contain simultaneously in its molecule the hindered phenol unit and-the S-unit, make it have the dual function of radical scavenger and hydrogen peroxide decomposition agent simultaneously.Compare with common oxidation inhibitor, thiobisphenol kind antioxidant intramolecularly has more-the S-unit, thereby is the better intramolecularly complex type antioxidant of a kind of antioxidant effect.It also can use with UV light absorber, metal passivator, carbon black etc., has good synergistic effect, minimum to the influence of the electrical property of goods simultaneously, so in the polyolefins material, in the rubber item and in synthetic Gum Rosin product, all be widely used.
United States Patent (USP) 4877902 has been reported dialkyl phenol and the reaction of sulfur monochloride in nitroparaffins and acetonitrile mixed solvent, its main products is two alkylphenols of dithio and trithio and as the production process of solid rapid subsidence from reactant, its the highest solid yield is 83.8%, but the product in the solvent does not illustrate how to collect.United States Patent (USP) 4898980 reported with toluene and done under the situation of solvent, 2, and the method for 4-di-tert-butylphenol and sulfur monochloride reaction, the recrystallization solvent recrystallization is made with acetonitrile in reaction soln distillation back, dithio product purity height, but yield also only is 69.3%.More than two reports used hypertoxic solvent second eyeball, the toxicity of toluene and Nitromethane 99Min. is also bigger, the price comparison costliness makes it lose industrialized the operation.It is big to the solubleness of monothio thing that toluene is made solvent, and in toluene, obtain pure monothio thing and be not easy, the energy height that needs during distillation, color is deep when causing product to be separated out in recrystallization solvent, needs repeatedly washing.
Summary of the invention
The object of the present invention is to provide the method for the synthetic multiple thiophenols of a kind of single stage method, simple to operate, cost is low, and has no side effect, safety and environmental protection.
The method of the synthetic multiple thiophenols of single stage method of the present invention, by 2, it is synthetic that 4-DI-tert-butylphenol compounds and sulfur monochloride react in solvent, it is characterized in that in petroleum ether solvent, carrying out, at first separate out monothio phenol, filtration with filtrate evaporative removal petroleum ether solvent after, carry out the mixture that recrystallization obtains other thiophenols again, as dithio phenol, trithio phenol and tetrathio phenol etc.
Suitable synthesis condition control is as follows:
Synthesis temperature is-5～5 ℃;
Building-up process needs to stir, and guarantees that not precipitating (resultant does not sink to the bottom) gets final product.
In synthetic, 2,4-DI-tert-butylphenol compounds and sulfur monochloride are got the raw materials ready according to reactional equation and are got final product.
2, the mass volume ratio of 4-DI-tert-butylphenol compounds and sherwood oil is 1: (2～7), preferred 1: (3～5).
Recrystallization need use recrystallization solvent, and recrystallization solvent uses the first alcohol and water.Product is in methyl alcohol behind the crystallization-stable, and gradation changes the polarity of water gradually with less water, makes the further crystallization of product up to complete crystallization.The first alcohol and water also can be further purified various products as recrystallization solvent.
The present invention utilizes the difference in solubility of petroleum ether solvent to various products, after building-up reactions finishes, at first monothio part is obtained by filtering mode, after filtrate is removed sherwood oil by distillation, utilizing alcohol and water to carry out recrystallization again handles, obtaining with dithio phenol is the main mixture that contains trithio phenol etc. again, and total yield of products can reach more than 90%.
The inventive method adopts single stage method, and simple to operate, cost is low, and has adopted petroleum ether solvent, has no side effect, and safety and environmental protection is easy to suitability for industrialized production.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
In being housed, 1000 milliliters of four-hole glass flask of stirring, thermowell and constant pressure funnel add 100 grams 2,4-DI-tert-butylphenol compounds raw material, 400 milliliters of sherwood oils, with icy salt solution cooling and maintain the temperature at-5～5 ℃, under the whipped state, be added drop-wise in the reaction flask with being added in the gram sulfur monochloride of 33.9 in the dropping funnel and 100 milliliters of sherwood oil mixtures in 2 hours, continue to stir 3 hours.Filtration drying obtains monothio phenol 25.4 grams.After the filtrate vacuum steams sherwood oil, add crystallization filtration under 100 milliliters of whipped states of methyl alcohol, add entry adjusting solvent polarity continuation crystallization filtration after distilling a little methyl alcohol, drying obtains the mixture of dithio phenol, trithio phenol and some other oligomeric sulfo-product, total yield of products 93.9%.
Embodiment 2
In being housed, 1000 milliliters of four-hole glass flask of stirring, thermowell and constant pressure funnel add 100 grams 2,4-DI-tert-butylphenol compounds raw material, 350 milliliters of sherwood oils, with icy salt solution cooling and keep 5～5 ℃ of temperature, under the whipped state, be added drop-wise in the reaction flask with being added in the gram sulfur monochloride of 33.9 in the dropping funnel and 100 milliliters of sherwood oil mixtures in 2 hours, continue to stir 3 hours.Filtration drying obtains monothio phenol 23.5 grams.After the filtrate vacuum steams sherwood oil, add 100 milliliters of stirred crystallization of methyl alcohol and filter, slowly add water after distilling a little methyl alcohol, regulate solvent polarity gradually, recrystallization, the mixture that filter, drying obtains dithio phenol, trithio phenol and some other oligomeric sulfo-product.Total yield of products 94.7%.
Claims (7)
1. the method for the synthetic multiple thiophenols of a single stage method, by 2, it is synthetic that 4-DI-tert-butylphenol compounds and sulfur monochloride react in solvent, it is characterized in that in petroleum ether solvent, carrying out, at first separate out monothio phenol, filtration with filtrate evaporative removal petroleum ether solvent after, carry out the mixture that recrystallization obtains other thiophenols again.
2. the method for the synthetic multiple thiophenols of single stage method according to claim 1 is characterized in that synthesis temperature is 5～5 ℃.
3. the method for the synthetic multiple thiophenols of single stage method according to claim 1 is characterized in that building-up process needs to stir.
4. according to the method for claim 1, the synthetic multiple thiophenols of 2 or 3 described single stage method, it is characterized in that 2, the mass volume ratio of 4-DI-tert-butylphenol compounds and sherwood oil is 1: (2～7).
5. the method for the synthetic multiple thiophenols of single stage method according to claim 4 is characterized in that 2, and the mass volume ratio of 4-DI-tert-butylphenol compounds and sherwood oil is 1: (3～5).
6. the single stage method synthesis method of multiple thiophenols according to claim 4 is characterized in that recrystallization need use recrystallization solvent, and recrystallization solvent uses the first alcohol and water.
7. the single stage method synthesis method of multiple thiophenols according to claim 6 is characterized in that product in methyl alcohol behind the crystallization-stable, and gradation changes the polarity of water gradually with less water, makes the further crystallization of product up to complete crystallization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010300717A CN101759615A (en) | 2010-01-26 | 2010-01-26 | Method for synthesizing a variety of thiophenols by one-step method |
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| CN201010300717A CN101759615A (en) | 2010-01-26 | 2010-01-26 | Method for synthesizing a variety of thiophenols by one-step method |
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| CN101759615A true CN101759615A (en) | 2010-06-30 |
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| CN201010300717A Pending CN101759615A (en) | 2010-01-26 | 2010-01-26 | Method for synthesizing a variety of thiophenols by one-step method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050960A (en) * | 2010-11-30 | 2011-05-11 | 胥乾 | Efficient scrap rubber regeneration activator and preparation method thereof |
| CN103333093A (en) * | 2013-06-17 | 2013-10-02 | 温州大学 | Synthesis method of 1-arylsulfenylnaphthalene compound |
| CN103333092A (en) * | 2013-06-17 | 2013-10-02 | 温州大学 | Synthesis method of 1-thiophenyl-2-isonaphthol compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1145630B (en) * | 1958-03-12 | 1963-03-21 | Ethyl Corp | Process for the preparation of antioxidant, alkyl-substituted bis (4-hydroxyphenyl) sulfides |
| GB1153269A (en) * | 1967-05-12 | 1969-05-29 | Lubrizol Corp | Method For Preparing Phenol Sulfides |
| US4740578A (en) * | 1984-12-24 | 1988-04-26 | Seitetsu Kagaku Co., Ltd | Process for producing polythiobisphenols and process for producing mercaptophenols by the hydrogenolysis of the same |
| US4898980A (en) * | 1988-06-29 | 1990-02-06 | Ciba-Geigy Corporation | Process for preparing dithiobisphenols |
-
2010
- 2010-01-26 CN CN201010300717A patent/CN101759615A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1145630B (en) * | 1958-03-12 | 1963-03-21 | Ethyl Corp | Process for the preparation of antioxidant, alkyl-substituted bis (4-hydroxyphenyl) sulfides |
| GB1153269A (en) * | 1967-05-12 | 1969-05-29 | Lubrizol Corp | Method For Preparing Phenol Sulfides |
| US4740578A (en) * | 1984-12-24 | 1988-04-26 | Seitetsu Kagaku Co., Ltd | Process for producing polythiobisphenols and process for producing mercaptophenols by the hydrogenolysis of the same |
| US4898980A (en) * | 1988-06-29 | 1990-02-06 | Ciba-Geigy Corporation | Process for preparing dithiobisphenols |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050960A (en) * | 2010-11-30 | 2011-05-11 | 胥乾 | Efficient scrap rubber regeneration activator and preparation method thereof |
| CN103333093A (en) * | 2013-06-17 | 2013-10-02 | 温州大学 | Synthesis method of 1-arylsulfenylnaphthalene compound |
| CN103333092A (en) * | 2013-06-17 | 2013-10-02 | 温州大学 | Synthesis method of 1-thiophenyl-2-isonaphthol compound |
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Application publication date: 20100630 |